EP0143919B1 - Alkaline cyanide bath for the electrodeposition of copper-tin-alloy layers - Google Patents

Alkaline cyanide bath for the electrodeposition of copper-tin-alloy layers Download PDF

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Publication number
EP0143919B1
EP0143919B1 EP84110792A EP84110792A EP0143919B1 EP 0143919 B1 EP0143919 B1 EP 0143919B1 EP 84110792 A EP84110792 A EP 84110792A EP 84110792 A EP84110792 A EP 84110792A EP 0143919 B1 EP0143919 B1 EP 0143919B1
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Prior art keywords
copper
general formula
cyanide bath
cyanide
alkaline
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German (de)
French (fr)
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EP0143919A1 (en
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Gerd Hoffacher
Willi Müller
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Evonik Operations GmbH
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Degussa GmbH
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    • 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

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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)

Description

Die Erfindung betrifft ein alkalisch-cyanidisches Bad zur galvanischen Abscheidung blanker bis glänzender Kupfer-Zinn-Legierungsüberzüge, insbesondere Kupfer-Zinn-Legierungsüberzüge mit 45 bis 60 % Kupfer, das 1 bis 60 g/I Kupfer in Form von Kupfercyanid, 7 bis 30 g/I Zinn in Form von Stannat, 0,1 bis 100 g/I eines oder mehrerer Komplexbildner aus der Gruppe Phosphat, Polyphosphat, Phosphonat und Polyoxycarbonsäuren, 1 bis 50 g/I freies Alkalicyanid, 1 bis 50 g/I freies Alkalihydroxid und 0 bis 50 g/I Alkalicarbonat enthält.The invention relates to an alkaline cyanide bath for the electrodeposition of bare to shiny copper-tin alloy coatings, in particular copper-tin alloy coatings with 45 to 60% copper, the 1 to 60 g / l copper in the form of copper cyanide, 7 to 30 g / I tin in the form of stannate, 0.1 to 100 g / I of one or more complexing agents from the group phosphate, polyphosphate, phosphonate and polyoxycarboxylic acids, 1 to 50 g / I free alkali metal cyanide, 1 to 50 g / I free alkali metal hydroxide and 0 contains up to 50 g / l alkali carbonate.

Es ist seit vielen Jahren bekannt, Kupfer-Zinn-Legierungsüberzüge aus galvanischen Bädern abzuscheiden. Insbesondere verwendet man überzüge, die 45 bis 60 % Kupfer enthalten, vorzugsweise 55 bis 60 % Kupfer, da diese einen hellen Silberglanz besitzen und nicht zum Anlaufen neigen. Sie finden daher Verwendung in der dekorativen Galvanotechnik als Ersatz für beispielsweise Silber, Chrom oder Aluminium. Wegen ihrer sehr guten Löteigenschaften, ihrer Abriebbeständigkeit und ihres niedrigen elektrischen Übergangswiderstandes finden Kupfer-Zinn-Legierungsüberzüge aber auch steigende technische Anwendung.It has been known for many years to deposit copper-tin alloy coatings from galvanic baths. In particular, coatings are used which contain 45 to 60% copper, preferably 55 to 60% copper, since these have a light silver luster and do not tend to tarnish. They are therefore used in decorative electroplating to replace silver, chrome or aluminum, for example. Because of their very good soldering properties, their abrasion resistance and their low electrical contact resistance, copper-tin alloy coatings are also used increasingly in technical applications.

Solche Kupfer-Zinn-Legierungen werden überwiegend aus alkalischen, cyanidhaltigen Elektrohyten abgeschieden, die das Zinn als Stannat enthalten. Andere Elektrohyte enthalten Phosphat und Pyrophosphate als Komplexbildner und außerdem Kolloide, wie z. B. Polypeptide als Glanzzusätze (DE-PS 860 300). Diese bekannten Bäder müssen bei hohen, konstanten Temperaturen (65 °C und höher) betrieben werden, um gleichmässige Schichten konstanter Zusammensetzung zu erhalten. Das gleiche gilt auch für die Einstellung der Cyanid- und Hydroxidkonzentration im Bad. Das Arbeiten mit diesen Bädern ist daher schwierig und umständlich.Such copper-tin alloys are mainly deposited from alkaline, cyanide-containing electrohytes, which contain the tin as stannate. Other electrohytes contain phosphate and pyrophosphates as complexing agents and also colloids, such as. B. polypeptides as gloss additives (DE-PS 860 300). These known baths have to be operated at high, constant temperatures (65 ° C. and higher) in order to obtain uniform layers of constant composition. The same applies to the setting of the cyanide and hydroxide concentration in the bath. Working with these baths is therefore difficult and cumbersome.

Es war Aufgabe der vorliegenden Erfindung, ein alkalisch-cyanidisches Bad zur galvanischen Abscheidung blanker bis glänzender Kupfer-Zinn-Legierungsüberzüge gemäß Oberbegriff von Anspruch 1 zu entwickeln, das bei niedrigeren Temperaturen betrieben werden kann und bei dem die Überzugzusammensetzung weniger stark von Schwankungen der Badbestandteile abhängig ist.It was an object of the present invention to develop an alkaline cyanide bath for the electrodeposition of bright to shiny copper-tin alloy coatings, which can be operated at lower temperatures and in which the coating composition is less dependent on fluctuations in the bath components is.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Bad noch eine oder mehrere organische Substanzen aus einer oder mehreren der folgenden Gruppen

  • a) Fettsäure-amido-alkyl-dialkylaminoxide der allgemeinen Formel
    • R1―CO―NH(CH2)n―N(R2)n→O, wobei
    • R1 = Alkylgruppe mit 11-17 C-atomen
    • R2 = Alkylgruppe mit 1-5 C-atomen
    • n = 1-30 bedeuten,
  • b) Fettsäure-amido-alkyl-dialkylamin-betaine der allgemeinen Formel
    • R1―CO―NH(CH2)n―+N(R2)2―CH2―COO-, wobei
    • R, = Alkylgruppe mit 11-17 C-atomen
    • R2 = Alkylgruppe mit 1-5 C-atomen
    • n = 1-30 bedeuten,
  • c) Äthoxylierte Naphthole der allgemeinen Formel
    Figure imgb0001
    wobei R1 = H oder O―(CH2CH2O)nH
    • R2 = O-(CH2CH20)nH oder H
    • n = 10, 12 oder 14 bedeuten

in Mengen von 0,05 bis 5 g/I enthält.This object is achieved in that the bath one or more organic substances from one or more of the following groups
  • a) Fatty acid amido-alkyl-dialkylamine oxides of the general formula
    • R 1 ―CO ― NH (CH 2 ) n ―N (R 2 ) n → O, where
    • R 1 = alkyl group with 11-17 carbon atoms
    • R 2 = alkyl group with 1-5 carbon atoms
    • n = 1-30 mean
  • b) fatty acid-amido-alkyl-dialkylamine-betaine of the general formula
    • R 1 ―CO ― NH (CH 2 ) n - + N (R 2 ) 2 ―CH 2 ―COO - , where
    • R, = alkyl group with 11-17 carbon atoms
    • R 2 = alkyl group with 1-5 carbon atoms
    • n = 1-30 mean
  • c) Ethoxylated naphthols of the general formula
    Figure imgb0001
     where R 1 = H or O― (CH 2 CH 2 O) n H
    • R 2 = O- (CH 2 CH 2 0) n H or H
    • n = 10, 12 or 14 mean

contains in amounts of 0.05 to 5 g / l.

Besonders bewährt haben sich die entsprechenden β-Naphthole.The corresponding β-naphthols have proven particularly useful.

Vorzugsweise enthalten die Bäder 1 bis 3 g/I dieser organischen Substanzen aus einer oder mehreren der Gruppen a) bis c).The baths preferably contain 1 to 3 g / l of these organic substances from one or more of groups a) to c).

Die aus solchen Bädern abgeschiedenen Überzüge sind blank, aber noch nicht glänzend. Zur Abscheidung glänzender Kupfer-Zinn-Legierungsüberzüge setzt man dem Bad noch zusätzlich 0,05 bis 2 g/l eines oder mehrerer Glanzmittel zu, ausgewählt aus einer oder mehreren der folgenden Gruppen :

  • a) Polyäthylendiamine der allgemeinen Formel H2N-(CH2)n-NH2 mit n = 6-100 bzw. deren Umsetzungsprodukte mit Benzylchlorid oder Epichlorhydrin
  • b) Benzaldehyde mit einer oder mehreren Hydroxy- und/oder Alkoxygruppen am Kern und Zimtaldehyd bzw. deren Umsetzungsprodukte mit Rhodaniden und Sulfiten.
  • c) Äthinole, Äthindiole und deren Äthoxylate und Propoxylate der allgemeinen Formel
  • R1C ≡ C―CH2―OR2
  • mit R1 = H oder CH20R2 und R2 = H, C2H5 oder C3H7
  • d) Benzylpyridincarboxylate der Formel
    Figure imgb0002
The coatings deposited from such baths are shiny, but not yet shiny. To deposit shiny copper-tin alloy coatings, an additional 0.05 to 2 g / l of one or more brighteners, selected from one or more of the following groups, is added to the bath:
  • a) Polyethylenediamines of the general formula H 2 N- (CH 2 ) n- NH 2 with n = 6-100 or their reaction products with benzyl chloride or epichlorohydrin
  • b) Benzaldehydes with one or more hydroxyl and / or alkoxy groups on the core and cinnamaldehyde or their reaction products with rhodanides and sulfites.
  • c) ethynols, ethylenediols and their ethoxylates and propoxylates of the general formula
  • R 1 C ≡ C ― CH 2 ―OR 2
  • with R 1 = H or CH 2 0R 2 and R 2 = H, C 2 H 5 or C 3 H 7
  • d) benzylpyridinecarboxylates of the formula
    Figure imgb0002

Vorzugsweise enthalten die Bäder 0,8 bis 1,5 g/I dieser Glanzmittel. Da die Verbindungen der Gruppe a) und b) in Wasser sehr schwer löslich sind, werden sie vorteilhafterweise erst mit Benzylchlorid oder Epichlorhydrin bzw. Rhodanid oder Sulfit zu wasserlöslichen Verbindungen umgesetzt.The baths preferably contain 0.8 to 1.5 g / l of these brighteners. Since the compounds of group a) and b) are very sparingly soluble in water, they are advantageously first reacted with benzyl chloride or epichlorohydrin or rhodanide or sulfite to give water-soluble compounds.

Die erfindungsgemäßen Bäder können mit unlöslichen Anoden betrieben werden, wie z. B. mit Edelstahlanoden. Die Betriebstemperaturen liegen bei 38 bis 58 °C, die Stromdichten zwischen 0,4 und 3,0 A/dm2 und die pH-Werte zwischen 11,5 und 12,5.The baths of the invention can be operated with insoluble anodes, such as. B. with stainless steel anodes. The operating temperatures are between 38 and 58 ° C, the current densities between 0.4 and 3.0 A / dm 2 and the pH values between 11.5 and 12.5.

Bewährt haben sich Bäder, die 2 bis 10 g Kupfer in Form von Kupfercyanid, 10 bis 20 g/I Zinn in Form von Alkalistannat, 10 bis 50 g/I Komplexbildner, 5 bis 30 g/I freies Alkalicyanid, 5 bis 30 g/I freies Alkalihydroxid, 5 bis 20 g/l Alkalicarbonat, 1 bis 3 g/l der organischen Substanz und 0,8 bis 1,5 g/l Glanzzusatz enthalten.Baths containing 2 to 10 g copper in the form of copper cyanide, 10 to 20 g / l tin in the form of alkali tannate, 10 to 50 g / l complexing agent, 5 to 30 g / l free alkali metal cyanide, 5 to 30 g / I contain free alkali hydroxide, 5 to 20 g / l alkali carbonate, 1 to 3 g / l of the organic substance and 0.8 to 1.5 g / l gloss additive.

Als Glanzzusätze haben sich aus der Gruppe b) z. B. p-Methoxybenzaldehyd (Anisaldehyd), 4-Hydroxy-3-Methoxy-benzaldehyd (Vanillin) und Zimtaldehyd, aus der Gruppe c) z. B. Butin-2-diol-1,4, Butindiolmonopropoxylat, Propargylalkohol und Propargylalkoholmonoäthoxylat als brauchbar erwiesen. Vorteilhafterweise verwendet man jedoch Polyäthylendiamine und Benzylpyridincarboxylate.From group b) z. B. p-methoxybenzaldehyde (anisaldehyde), 4-hydroxy-3-methoxybenzaldehyde (vanillin) and cinnamaldehyde, from group c) z. B. butyne-2-diol-1,4, butynediol monopropoxylate, propargyl alcohol and propargyl alcohol monoethoxylate have been found to be useful. However, it is advantageous to use polyethylene diamines and benzyl pyridine carboxylates.

Folgende Beispiele sollen das erfindungsgemäße Bad näher erläutern.

  • 1. Aus einem Bad mit 8,4 g/I Kupfer(I)cyanid, 58 g/I Natriumstannat, 25 g/I Kaliumnatriumtartrat, 25 g/l Tetranatriumdiphosphat, je 20 g/l freies Natriumcyanid und Natriumhydroxid, 15 g/I Natriumcarbonat und 0,3 g/I äthoxyliertes β-Naphthol mit n = 12 (Durchschnittswert) werden bei einer Temperatur von 58 °C und einer Stromdichte von 1 A/dm2 in 50 Minuten 5 µm starke, blanke, weiße Überzüge erhalten, die 53 % Kuper enthalten und nicht anlaufen.
  • 2. Aus einem Bad mit 2,8 g/I Kupfer(I)cyanid, 46,4 g/I Natriumstannat, 25 g/I Kaliumnatriumtartrat, 25 g/I Tetranatriumdiphosphat, je 20 g/I Natriumcyanid und Natriumhydroxid, 15 g/I Natriumcarbonat, 0,3 g/l eines Fettsäure-amido-alkyl-dialkylamin-betains (mit R1 = C15, R2 = Methyl und n = 6) und 1,1 g/I Butin-2-diol-1,4 erhält man bei 42 %C und 1 A/dm2 in einer Stunde 5 µm starke weiße Überzüge, die 49 % Kupfer enthalten und hochglänzend sind.
  • 3. Aus einem Bad mit 2,8 g/I Kupfer(I)cyanid, 46,4 g/l Natriumstannat, 25 g/l Tetranatriumdiphosphat, 25 g/I Dikaliumtartrat, 16 g/I freies Kaliumcyanid, 14 g/I freies Kaliumhydroxid, 1 g/l eines Fettsäure-amido-alkyl-dialkylaminoxides (R1 = C12, R2 = Propyl, n = 4) und 0,7 g/I Benzylpyridincarboxylat wird bei 42 °C mit 1 A/dm2 ein weißer, glänzender Überzug mit einem Kupfergehalt von 50 % abgeschieden.
  • 4. Durch Erhöhung des Cu/Sn-Verhältnisses im Bad lassen sich auch goldgelbe und rosa Kupfer-Zinn-Legierungsüberzüge abscheiden. Aus einem Bad mit 8,4 g/I Kupfer(I)cyanid, 48 g/I Natriumstannat, 40 g/I Dikaliumphosphat, 25 g/I Tetranatriumdiphosphat, 16 g/l Natriumcyanid, 12 g/I Natriumhydroxid, 15 g/I Natriumcarbonat, 2 g/l äthoxyliertes β-Naphthol (mit n = 10) und 0,2 g/I Vanillin erhält man bei 45 °C und 1 A/dm2 goldgelbe, glänzende Überzüge mit 70 % Kupfer.
The following examples are intended to explain the bath according to the invention in more detail.
  • 1. From a bath with 8.4 g / l copper (I) cyanide, 58 g / l sodium stannate, 25 g / l potassium sodium tartrate, 25 g / l tetrasodium diphosphate, each 20 g / l free sodium cyanide and sodium hydroxide, 15 g / l Sodium carbonate and 0.3 g / l of ethoxylated β-naphthol with n = 12 (average value) are obtained at a temperature of 58 ° C and a current density of 1 A / dm 2 in 50 minutes 5 µm thick, bright, white coatings, which Contains 53% copper and does not tarnish.
  • 2. From a bath with 2.8 g / l copper (I) cyanide, 46.4 g / l sodium stannate, 25 g / l potassium sodium tartrate, 25 g / l tetrasodium diphosphate, each 20 g / l sodium cyanide and sodium hydroxide, 15 g / I sodium carbonate, 0.3 g / l of a fatty acid amido-alkyl-dialkylamine betaine (with R 1 = C 15 , R 2 = methyl and n = 6) and 1.1 g / I butyn-2-diol-1 , 4, at 42% C and 1 A / dm 2, 5 µm thick white coatings containing 49% copper and having a high gloss are obtained in one hour.
  • 3. From a bath with 2.8 g / l copper (I) cyanide, 46.4 g / l sodium stannate, 25 g / l tetrasodium diphosphate, 25 g / l dipotassium tartrate, 16 g / l free potassium cyanide, 14 g / l free Potassium hydroxide, 1 g / l of a fatty acid-amido-alkyl-dialkylamine oxide (R 1 = C 12 , R 2 = propyl, n = 4) and 0.7 g / l of benzylpyridinecarboxylate is at 42 A with 1 A / dm 2 white, shiny coating with a copper content of 50% deposited.
  • 4. By increasing the Cu / Sn ratio in the bath, gold-yellow and pink copper-tin alloy coatings can also be deposited. From a bath with 8.4 g / l copper (I) cyanide, 48 g / l sodium stannate, 40 g / l dipotassium phosphate, 25 g / l tetrasodium diphosphate, 16 g / l sodium cyanide, 12 g / l sodium hydroxide, 15 g / l Sodium carbonate, 2 g / l of ethoxylated β-naphthol (with n = 10) and 0.2 g / l of vanillin are obtained at 45 ° C. and 1 A / dm 2 shiny gold-yellow coatings with 70% copper.

Claims (5)

1. An alkaline-cyanide bath for the electrolytic deposition of bright to lustrous copper tin alloy coatings, in particular copper tin alloy coatings with from 45 to 60 % of copper which contains from 1 to 60 g/I of copper in the form of copper cyanide, from 7 to 30 g/I of tin in the form of alkali stannate, from 0.1 to 100 g/I of one or more complex forming agents from the group comprising phosphate, polyphosphate, phosphonate and polyoxycarboxylic acids, from 1 to 50 g/I of free alkali metal cyanide, from 1 to 50 g/I of free alkali hydroxide and from 0 to 50 g/I, characterised in that it additionally contains one or more organic substances from one or more of the following groups :
a) fatty acid amido alkyl dialkyl amine oxides corresponding to the general formula R1CO―NH(CH2)n―N(R2)2→O, wherein
R1 represents an alkyl group containing from 11 to 17 C-atoms
R2 represents an alkyl group containing from 1 to 5 C-atoms
n represents from 1 to 30,
b) fatty acid amido alkyl dialkyl amine betaines corresponding to the general formula
Figure imgb0006
wherein
R1 represents an alkyl group containing from 11 to 17 C-atoms
R2 represents an alkyl group containing from 1 to 5 C-atoms n represents from 1 to 30,
c) ethoxylated naphthols corresponding to the general formula
Figure imgb0007
wherein R1 represents H or O(CH2―CH2O)nH
R2 represents O(CH2CH20)nH or H
n represents 10, 12 or 14

in quantities of from 0.05 to 5 g/I.
2. An alkaline cyanide bath according to claim 1, characterised in that it contains ethoxylated ß-naphthols corresponding to the general formula
Figure imgb0008
wherein n represents 10, 12, 14.
3. An alkaline cyanide bath according to claims 1 and 2, characterised in that it contains from 1 to 3 g/I of the organic substances.
4. An alkaline cyanide bath for the electrolytic deposition of lustrous copper-tin alloy coatings according to claims 1 to 3, characterised in that it additionally contains from 0.05 to 2 g/I of one or more polishing agents selected from one or more of the following groups
a) polyethylene diamines corresponding to the general formula H2N―(CH2)n―NH2 wherein n represents 6 to 100 or the reaction products thereof with benzyl chloride or epichlorohydrin,
b) benzaldehydes containing one or more hydroxy and/or alkoxy groups at the nucleus and cinnamic aldehyde or the reaction products thereof with rhodanides and sulphites,
c) ethinols, ethine diols and the ethoxylates and propoxylates thereof corresponding to the general formula
R1C ≡ C―CH2OR2
wherein R1 represents H or CH20R2 and R2 represents H, C2H5, C3H7
d) benzylpyridine carboxylates corresponding to the formula
Figure imgb0009
5. An alkaline cyanide bath according to claims 1 to 4 characterised in that it contains from 0.8 to 1.5 g/I of polishing additive.
EP84110792A 1983-11-02 1984-09-11 Alkaline cyanide bath for the electrodeposition of copper-tin-alloy layers Expired EP0143919B1 (en)

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DE3339541A DE3339541C2 (en) 1983-11-02 1983-11-02 Alkaline-cyanide bath for the galvanic deposition of copper-tin alloy coatings
DE3339541 1983-11-02

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EP0143919B1 true EP0143919B1 (en) 1987-07-29

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EP (1) EP0143919B1 (en)
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DE3465114D1 (en) 1987-09-03
DE3339541C2 (en) 1986-08-07
EP0143919A1 (en) 1985-06-12
US4605474A (en) 1986-08-12
US4565608A (en) 1986-01-21
HK57089A (en) 1989-07-21
JPH06104914B2 (en) 1994-12-21
BR8405398A (en) 1985-09-03
JPS60114589A (en) 1985-06-21
DE3339541A1 (en) 1985-05-15

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