EP0115020A2 - Acid galvanic zinc bath - Google Patents

Acid galvanic zinc bath Download PDF

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Publication number
EP0115020A2
EP0115020A2 EP83112804A EP83112804A EP0115020A2 EP 0115020 A2 EP0115020 A2 EP 0115020A2 EP 83112804 A EP83112804 A EP 83112804A EP 83112804 A EP83112804 A EP 83112804A EP 0115020 A2 EP0115020 A2 EP 0115020A2
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Prior art keywords
zinc
formula
hydrogen
radical
surfactant
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German (de)
French (fr)
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EP0115020A3 (en
EP0115020B1 (en
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Norbert Dr. Greif
Knut Dr. Oppenlaender
Albert Dr. Hettche
Christos Dr. Vamvakaris
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BASF SE
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BASF SE
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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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the invention relates to an aqueous acidic galvanic zinc bath which, in addition to the usual additives, such as conductive salts and brighteners, contains certain surfactants.
  • the electrolytic deposition of zinc on metallic substrates from acidic solution depends on several important criteria. Since the resulting zinc coatings are mostly dull and often irregular from acidic solution, so-called brighteners must be present in the baths in addition to the usual conductive salts (to improve the conductivity of the baths), which give the coatings an increased sheen, and which also allow it to work at lower current densities. These brighteners, which can be assigned to a wide variety of chemical substance classes, are often difficult or impossible to dissolve in water and especially salt solutions, so that certain surfactants have to be added to the baths which serve as emulsifiers, which lead to clear, transparent microemulsions. These measures achieve a uniform deposition of the zinc on the substrates.
  • nonionic surfactants have hitherto been used for these purposes, as is known, for example, from GB-PS 1 149 106. Furthermore, from JP-OS 74 89 637 the use of alkyldiphenyloxysulfonic acids is known, the latter of which enable the deposition of relatively uniform zinc layers, but the ductility leaves something to be desired and non-covering coatings result in the low current density range.
  • the aim of the invention was to find a class of surfactants which solubilize the brighteners used well and which, from acidic, galvanic zinc baths which contain the usual additives and also water-insoluble brighteners, can be used to obtain uniform and ductile zinc coatings on metallic substrates, even at low current densities.
  • the subject of the invention is an aqueous, acidic galvanic bath for the electrolytic deposition of zinc, which contains conductive salts, brightening agents and surfactants, which is characterized by a content of a surfactant of the formula I.
  • R 1 is a C 4 - to C 20 -alkyl radical
  • R 2 is the radical R 1 or hydrogen
  • X and Y is a radical of the formula -S0 3 H
  • the hydrogen atom being replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc can and one of the radicals X and Y can be hydrogen
  • n is an integer from 5 to 50
  • the compounds of the formula I as a surfactant in aqueous, acidic galvanic baths for the electrolytic deposition of zinc in the presence of brighteners.
  • R 1 preferably denotes a C 4 to C 15 alkyl radical. Of particular interest from an industrial point of view are C 4 to C 9 alkyl radicals, of which the butyl, tert-butyl, octyl and nonyl radicals should be mentioned specifically.
  • R 2 can have the same meaning as R 1 , preferably R 2 is hydrogen.
  • X and Y are preferably the radical -S0 3 H, the hydrogen atom being replaced by sodium or potassium.
  • n stands for an integer from 5 to 50, preferably 7 to 30.
  • the zinc can be electrolytically used in the bath.
  • an alkali metal ion especially the sodium or potassium ion, is preferably chosen as the metal ion.
  • the surfactants to be used according to the invention are therefore sulfonated and / or sulfated alkylphenol ethoxylates. They can be used individually or in mixtures with known surfactants. Non-ionic surfactants such as pC 4H9 to C 12 H 25 alkylphenol ethoxylates with 10 to 30 ethylene oxide units or ⁇ -naphthol ethoxylates with 5 to 20 ethylene oxide units are particularly suitable as known surfactants. These are expediently used in an amount of 1 to 15 g / l.
  • the zinc baths usually contain brighteners.
  • the brighteners used can be divided into so-called basic brighteners and top brighteners.
  • Polyethyleneimines or their derivatives, for example, are expedient as basic gloss agents.
  • the top brighteners are usually poorly or not at all soluble in the aqueous zinc bath. This includes representatives from a wide variety of substance classes, in particular be voted aromatic or heteroaromatic ketones, as described for example in GB-PS 1 149 106, JP-OS 74 89 637.
  • R 3 is an aromatic or heteroaromatic radical, preferably an optionally alkyl, halogen or nitro-substituted phenyl or thienyl radical and R 4 is C 1 - to C 6 -alkyl, or crude products containing these compounds, and / or o- Chlorobenzaldehyde.
  • the representative class includes:
  • benzal acetone is preferred.
  • o-chlorobenzaldehyde can be used alone or as a mixture with a compound of the formula II as a brightener.
  • the zinc baths appropriately contain brighteners in a total amount of 1 to 10 g / l. They contain lace gloss agents in an amount of 0.1 to 2.0 g / l, preferably 0.1 to 1 g / l.
  • the surfactants to be used according to the invention are present in the baths in an amount of 4 to 30, preferably 5 to 15 g / l.
  • the baths have the usual compositions. They contain e.g. 50 to 150 g / 1 zinc chloride or the equivalent amount of zinc sulfate, 100 to 250 g / 1 potassium chloride (conductive salt), 15 to 25 g / l boric acid, 1 to 8 g / 1 sodium benzoate and ggi. 1 to 4 g / 1 agent to increase the scatter, such as naphthalenesulfonic acid / formaldehyde condensation products.
  • Other baths can also contain 10 to 160 g / l ammonium chloride or sodium chloride. The pH of the baths is usually between 3 and 6.
  • the baths according to the invention provide high-gloss and ductile zinc coatings over the entire current density range.
  • the sheets used are run for 10 minutes in a Hull cell with 1 ampere at room temperature (approx. 23 ° C).
  • an alkylated diphenyl ether disulfonate (commercially available product) was used as the surfactant.
  • the cloud point of the bath at 5 g / 1 and 10 g / l surfactant was above 100 ° C.
  • test plate was run in the Hull cell with 1 A at room temperature (approx. 23 ° C.) for 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Electroplating And Plating Baths Therefor (AREA)
  • Cosmetics (AREA)

Abstract

Die Erfindung betrifft ein wäßriges saures galvanisches Bad zur elektrolytischen Abscheidung von Zink, das die üblichen Leitsalze, Glanzbildner und Tenside enthält, mit einen Gehalt an einem Tensid der Formel I <IMAGE> in der R¹ einen C4-bis C20-Alkylrest. R² den Rest R¹ oder Wasserstoff, X und Y einen Rest der Formel -SO3H, wobei das Wasserstoffatom durch ein Alkali-, Erdalkalimetallatom oder ein Äquivalent Zink ersetzt sein kann und einer der Reste X und Y Wasserstoff sein kann, und n eine ganze Zahl von 5 bis 50 bedeuten.The invention relates to an aqueous acidic galvanic bath for the electrodeposition of zinc, which contains the usual conductive salts, brighteners and surfactants, containing a surfactant of the formula I <IMAGE> in which R1 is a C4 to C20 alkyl radical. R² is R¹ or hydrogen, X and Y is a radical of the formula -SO3H, where the hydrogen atom can be replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc and one of the radicals X and Y can be hydrogen, and n is an integer of 5 to 50 mean.

Description

Die Erfindung betrifft ein wäßriges saures galvanisches Zinkbad, das neben den üblichen Zusätzen, wie Leitsalzen und Glanzbildnern, bestimmte Tenside enthält.The invention relates to an aqueous acidic galvanic zinc bath which, in addition to the usual additives, such as conductive salts and brighteners, contains certain surfactants.

Bei der elektrolytischen Abscheidung von Zink auf metallische Substrate aus saurer Lösung, die in den letzten Jahren zunehmende Bedeutung gewonnen hat, kommt es auf mehrere wichtige Kriterien an. Da aus saurer Lösung die entstehenden Zinküberzüge meistens matt und häufig auch unregelmäßig anfallen, müssen in den Bädern neben üblichen Leitsalzen (zur Verbesserung der Leitfähigkeit der Bäder) sogenannte Glanzbildner zugegen sein, die den Überzügen einen erhöhten Glanz verleihen, und die es darüber hinaus auch erlauben, bei geringeren Stromdichten zu arbeiten. Diese Glanzbildner, die den verschiedensten chemischen Stoffklassen zugeordnet werden können, sind häufig in Wasser und vor allem Salzlösungen schwer oder überhaupt nicht löslilch, so daß man den Bädern bestimmte Tenside zusetzen muß, die als Emulgatoren dienen, die zu klaren, duchsichtigen Mikroemulsionen führen. Durch diese Maßnahmen erreicht man eine gleichmäßige Abscheidung des Zinks auf den Substraten. Für diese Zwecke sind bisher eine Reihe von nichtionischen Tensiden eingesetzt worden, wie beispielsweise aus der GB-PS 1 149 106 bekannt ist. Des weiteren ist aus der JP-OS 74 89 637 der Einsatz von Alkyldiphenyloxidsulfonsäuren bekannt, welch letztere zwar eine Abscheidung relativ gleichmäßiger Zinkschichten ermöglichen, wobei jedoch die Duktilität zu wünschen übrig läßt und im niedrigen Stromdichtebereich nichtdeckende Überzüge sich ergeben.The electrolytic deposition of zinc on metallic substrates from acidic solution, which has become increasingly important in recent years, depends on several important criteria. Since the resulting zinc coatings are mostly dull and often irregular from acidic solution, so-called brighteners must be present in the baths in addition to the usual conductive salts (to improve the conductivity of the baths), which give the coatings an increased sheen, and which also allow it to work at lower current densities. These brighteners, which can be assigned to a wide variety of chemical substance classes, are often difficult or impossible to dissolve in water and especially salt solutions, so that certain surfactants have to be added to the baths which serve as emulsifiers, which lead to clear, transparent microemulsions. These measures achieve a uniform deposition of the zinc on the substrates. A number of nonionic surfactants have hitherto been used for these purposes, as is known, for example, from GB-PS 1 149 106. Furthermore, from JP-OS 74 89 637 the use of alkyldiphenyloxysulfonic acids is known, the latter of which enable the deposition of relatively uniform zinc layers, but the ductility leaves something to be desired and non-covering coatings result in the low current density range.

Das Ziel der Erfindung bestand darin, eine Tensidklasse aufzufinden, die die verwendeten Glanzbildner gut solubilisiert und es gestattet, aus sauren, galvanischen Zinkbädern, die übliche Zusätze und auch wasserunlösliche Glanzbildner enthalten, auch mit geringen Stromdichten gleichmäßige und duktile Zinküberzüge auf metallischen Substraten zu erhalten.The aim of the invention was to find a class of surfactants which solubilize the brighteners used well and which, from acidic, galvanic zinc baths which contain the usual additives and also water-insoluble brighteners, can be used to obtain uniform and ductile zinc coatings on metallic substrates, even at low current densities.

Dieses Ziel wurde mit Tensiden erreicht, wie sie gemäß den Patentansprüchen 1 bis 3 definiert sind. Demnach ist Gegenstand der Erfindung ein wäßriges, saures galvanisches Bad zur elektrolytischen Abscheidung von Zink, das Leitsalze, Glanzbilder und Tenside enthält, das gekennzeichnet ist durch einen Gehalt an einem Tensid der Formel I

Figure imgb0001
in der R1 einen C4- bis C20-Alkylrest, R2 den Rest R1 oder Wasserstoff, X und Y einen Rest der Formel -S03H, wobei das Wasserstoffatom durch ein Alkali-, Erdalkalimetallatom oder ein Äquivalent Zink ersetzt sein kann und einer der Reste X und Y Wasserstoff sein kann, und n eine ganze Zahl von 5 bis 50 bedeuten, und die Verwendung der Verbindungen der Formel I als Tensid in wäßrigen, sauren galvanischen Bädern zur elektrolytischen Abscheidung von Zink in Gegenwart von Glanzbildnern.This goal has been achieved with surfactants as defined in claims 1 to 3. Accordingly, the subject of the invention is an aqueous, acidic galvanic bath for the electrolytic deposition of zinc, which contains conductive salts, brightening agents and surfactants, which is characterized by a content of a surfactant of the formula I.
Figure imgb0001
 in which R 1 is a C 4 - to C 20 -alkyl radical, R 2 is the radical R 1 or hydrogen, X and Y is a radical of the formula -S0 3 H, the hydrogen atom being replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc can and one of the radicals X and Y can be hydrogen, and n is an integer from 5 to 50, and the use of the compounds of the formula I as a surfactant in aqueous, acidic galvanic baths for the electrolytic deposition of zinc in the presence of brighteners.

In der Formel I bedeutet R1 vorzugsweise einen C4- bis C15-Alkylrest. Technisch von besonderem Interesse sind C4- bis C9-Alkylreste, von denen der Butyl-, tert.-Butyl-, Octyl- und Nonylrest speziell zu nennen sind. R2 kann dieselbe Bedeutung wie Rl besitzen, vorzugsweise bedeutet R2 Wasserstoff. Bevorzugt bedeuten X und Y den Rest -S03H, wobei das Wasserstoffatom durch Natrium oder Kalium ersetzt ist. n steht für eine ganze Zahl von 5 bis 50, vorzugsweise 7 bis 30. Für den Fall, daß in der -S03H--Gruppe für H Zink steht, kann das Zink in dem Bade elektrolytisch mitverwertet werden. Vorzugsweise wählt man aber als Metallion ein Alkalimetallion, speziell das Natrium- oder Kaliumion.In formula I, R 1 preferably denotes a C 4 to C 15 alkyl radical. Of particular interest from an industrial point of view are C 4 to C 9 alkyl radicals, of which the butyl, tert-butyl, octyl and nonyl radicals should be mentioned specifically. R 2 can have the same meaning as R 1 , preferably R 2 is hydrogen. X and Y are preferably the radical -S0 3 H, the hydrogen atom being replaced by sodium or potassium. n stands for an integer from 5 to 50, preferably 7 to 30. In the event that in the -S0 3 H group stands for H zinc, the zinc can be electrolytically used in the bath. However, an alkali metal ion, especially the sodium or potassium ion, is preferably chosen as the metal ion.

Die erfindungsgemäß zu verwendenen Tenside stellen somit sulfonierte und/oder sulfatierte Alkylphenolethoxylate dar. Sie können einzeln oder in Gemischen mit bekannten Tensiden verwendet werden. Als zusätzliche bekannte Tenside kommen vor allem nichtionische Tenside, wie p-C4H9- bis C12H25-Alkylphenolethoxylate mit 10 bis 30 Ethylenoxideinheiten oder ß-Naphtholethoxylate mit 5 bis 20 Ethylenoxideinheiten in Betracht. Diese werden zweckmäßigerweise in einer Menge von 1 bis 15 g/1 eingesetzt.The surfactants to be used according to the invention are therefore sulfonated and / or sulfated alkylphenol ethoxylates. They can be used individually or in mixtures with known surfactants. Non-ionic surfactants such as pC 4H9 to C 12 H 25 alkylphenol ethoxylates with 10 to 30 ethylene oxide units or β-naphthol ethoxylates with 5 to 20 ethylene oxide units are particularly suitable as known surfactants. These are expediently used in an amount of 1 to 15 g / l.

Die Verbindungen der Formel I sind bekannt oder können nach literaturbekannten Verfahren hergestellt werden.The compounds of the formula I are known or can be prepared by processes known from the literature.

Die Zinkbäder enthalten üblicherweise Glanzbildner. Die verwendeten Glanzbildner können eingeteilt werden in sog. Grundglanzbildner und Spitzenglanzbildner. Als Grundglanzbildner sind zweckmäßig beispielsweise Polyethylenimine oder deren Derivate. Die Spitzenglanzbildner sind in der Regel im wäßrigen Zinkbad schlecht oder überhaupt nicht löslich. Hierzu gehören Vertreter der verschiedensten Stoffklassen, insbesondere bestimmte aromatische oder heteroaromatische Ketone, wie sie beispielsweise in der GB-PS 1 149 106, JP-OS 74 89 637 beschrieben sind.The zinc baths usually contain brighteners. The brighteners used can be divided into so-called basic brighteners and top brighteners. Polyethyleneimines or their derivatives, for example, are expedient as basic gloss agents. The top brighteners are usually poorly or not at all soluble in the aqueous zinc bath. This includes representatives from a wide variety of substance classes, in particular be voted aromatic or heteroaromatic ketones, as described for example in GB-PS 1 149 106, JP-OS 74 89 637.

Es sind dies zum Beispiel Verbindungen der Formel II

Figure imgb0002
in der R3 einen aromatischen oder heteroaromatischen Rest, vorzugsweise einen gegebenenfalls alkyl-, halogen- oder nitrosubstituierten Phenyl-oder Thienylrest bedeutet und R4 für C1- bis C6-Alkyl stehen, oder diese Verbindungen enthaltende Rohprodukte, und/oder o-Chlorbenzaldehyd.These are, for example, compounds of the formula II
Figure imgb0002
 in which R 3 is an aromatic or heteroaromatic radical, preferably an optionally alkyl, halogen or nitro-substituted phenyl or thienyl radical and R 4 is C 1 - to C 6 -alkyl, or crude products containing these compounds, and / or o- Chlorobenzaldehyde.

Diese Verbindungsklasse umfaßt im Vertreter wie:

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
 The representative class includes:
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013

Davon ist das Benzalaceton bevorzugt. Darüber hinaus kann als Glanzbildner o-Chlorbenzaldehyd allein oder in Mischung mit einer Verbindung der Formel II verwendet werden.Of these, benzal acetone is preferred. In addition, o-chlorobenzaldehyde can be used alone or as a mixture with a compound of the formula II as a brightener.

Die Zinkbäder enthalten Glanzbildner zweckmäßig in einer Gesamtmenge von 1 bis 10 g/l. Sie enthalten Spitzenglanzbildner in einer Menge von 0,1 bis 2,0 g/l, vorzugsweise 0,1 bis 1 g/l.The zinc baths appropriately contain brighteners in a total amount of 1 to 10 g / l. They contain lace gloss agents in an amount of 0.1 to 2.0 g / l, preferably 0.1 to 1 g / l.

Die erfindungsgemäß zu verwendenden Tenside sind in den Bädern in einer Menge von 4 bis 30, vorzugsweise 5 bis 15 g/1 enthalten.The surfactants to be used according to the invention are present in the baths in an amount of 4 to 30, preferably 5 to 15 g / l.

Im übrigen weisen die Bäder die üblichen Zusammensetzungen auf. Sie enthalten z.B. 50 bis 150 g/1 Zinkchlorid oder die äquivalente Menge Zinksulfat, 100 bis 250 g/1 Kaliumchlorid (Leitsalz), 15 bis 25 g/l Borsäure, 1 bis 8 g/1 Natriumbenzoat und ggi. 1 bis 4 g/1 Agens zur Erhöhung der Streuung, wie Naphthalinsulfonsäure/Formaldehyd-Kondensationsprodukte. Andere Bäder können auch 10 bis 160 g/l Ammoniumchlorid oder Natriumchlorid enthalten. Der pH-Wert der Bäder liegt in der Regel bei pH 3 bis 6.Otherwise, the baths have the usual compositions. They contain e.g. 50 to 150 g / 1 zinc chloride or the equivalent amount of zinc sulfate, 100 to 250 g / 1 potassium chloride (conductive salt), 15 to 25 g / l boric acid, 1 to 8 g / 1 sodium benzoate and ggi. 1 to 4 g / 1 agent to increase the scatter, such as naphthalenesulfonic acid / formaldehyde condensation products. Other baths can also contain 10 to 160 g / l ammonium chloride or sodium chloride. The pH of the baths is usually between 3 and 6.

Die erfindungsgemäßen Bäder liefern über den gesamten Stromdichtenbereich hochglänzende und duktile Zinküberzüge.The baths according to the invention provide high-gloss and ductile zinc coatings over the entire current density range.

Die nun folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

BeispieleExamples

In galvanischen Bädern der folgenden Zusammensetzung werden die Eigenschaften der erfindungsgemäßen Tenside aufgezeigt. Das mit (+) gekennzeichnete Beispiel mit einer Verbindung der Formel I, in der X und Y ein Wasserstoffatom bedeuten, dient dem Vergleich.

Figure imgb0014
Bad 3:

  • Dieses Bad entspricht Bad 1, jedoch enthält es neben 10 g/1 erfindungsgemäßem Tensid zusätzlich 5 g/1 Tensid entsprechend der Tabelle Beispiel 1 (Vergleich).
The properties of the surfactants according to the invention are shown in electroplating baths of the following composition. The example marked with (+) with a compound of formula I, in which X and Y represent a hydrogen atom, serves for comparison.
Figure imgb0014
 Bathroom 3:
  • This bath corresponds to bath 1, but in addition to 10 g / 1 of the surfactant according to the invention, it additionally contains 5 g / 1 of surfactant according to the table in Example 1 (comparison).

Die eingesetzten Bleche werden 10 Minuten in einer Hullzelle mit 1 Ampere bei Raumtemperatur (ca. 23°C) gefahren.

Figure imgb0015
The sheets used are run for 10 minutes in a Hull cell with 1 ampere at room temperature (approx. 23 ° C).
Figure imgb0015

Vergleichsbeispiel 13Comparative Example 13

In einem Bad der Zusammensetzung 3 wurde als Tensid ein alkyliertes Diphenylether-disulfonat (handelsübliches Produkt) eingesetzt. Der Trübungspunkt des Bades bei 5 g/1 und 10 g/l Tensid lag über 100°C.In a bath of composition 3, an alkylated diphenyl ether disulfonate (commercially available product) was used as the surfactant. The cloud point of the bath at 5 g / 1 and 10 g / l surfactant was above 100 ° C.

Ein Testblech wurde 10 Min. in der Hullzelle mit 1 A bei Raumtemperatur (ca. 23°C) darin-gefahren.A test plate was run in the Hull cell with 1 A at room temperature (approx. 23 ° C.) for 10 minutes.

Neben geringem Glanz (Note 2) und Schleier wurde eine sehr schlechte Duktilität (Note 1) der Abscheidungen beobachtet. Im niedrigen Stromdichtebereich konnten keine deckenden Überzüge erzielt werden.In addition to low gloss (grade 2) and fog, very poor ductility (grade 1) of the deposits was observed. No covering coatings could be achieved in the low current density range.

Claims (5)

1. Wäßriges saures galvanisches Bad zur elektrolytischen Abscheidung von Zink, das Leitsalze, Glanzbildner und Tenside enthält, gekennzeichnet durch einen Gehalt an einem Tensid der Formel I
Figure imgb0016
in der R1 einen C4- bis C20-Alkylrest, R2 den Rest R1 oder Wasserstoff, X und Y einen Rest der Formel -SO3H, wobei das Wasserstoffatom durch ein Alkali-, Erdalkalimetallatom oder ein Äquivalent Zink ersetzt sein kann und einer der Reste X und Y Wasserstoff sein kann, und n eine ganze Zahl von 5 bis 50 bedeuten.1. Aqueous acidic galvanic bath for the electrolytic deposition of zinc, which contains conductive salts, brighteners and surfactants, characterized by a content of a surfactant of the formula I.
Figure imgb0016
 in which R 1 is a C 4 to C 20 alkyl radical, R 2 is R 1 or hydrogen, X and Y is a radical of the formula -SO 3 H, the hydrogen atom being replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc can and one of the radicals X and Y can be hydrogen, and n is an integer from 5 to 50. 2. Bad gemäß Anspruch 1, enthaltend ein Tensid der Formel I, in der R2 für Wasserstoff steht.2. Bath according to claim 1, containing a surfactant of formula I, in which R 2 is hydrogen. 3. Bad gemäß Anspruch 1 oder 2, enthaltend ein Tensid der Formel I, in der X und Y den Rest -S03H, wobei das Wasserstoffatom durch ein Alkali-, Erdalkalimetallatom oder ein Äquivalent Zink ersetzt sein kann, bedeuten.3. Bath according to claim 1 or 2, containing a surfactant of the formula I in which X and Y represent the radical -S03H, where the hydrogen atom can be replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc. 4. Bad nach Anspruch 1 bis 3, enthaltend als Glanzbildner eine Verbindung der Formel II
Figure imgb0017
in der R3 einen gegebenenfalls substituierten aromatischen oder heteroaromatischen Rest und R4 C1- bis C6-Alkyl bedeuten, und/oder o-Chlorbenzaldehyd.4. Bath according to claim 1 to 3, containing as a brightener a compound of formula II
Figure imgb0017
 in which R 3 is an optionally substituted aromatic or heteroaromatic radical and R 4 is C 1 -C 6 -alkyl, and / or o-chlorobenzaldehyde. 5. Verwendung einer Verbindung der Formel I
Figure imgb0018
in der R1 einen C4- bis C20-Alkylrest, R 2 den Rest R1 oder Wasserstoff, X und Y einen Rest der Formel -S03H, wobei das Wasserstoffatom durch ein Alkali-, Erdalkalimetallatom oder ein Äquivalent Zink ersetzt sein kann und einer der Reste X und Y Wasserstoff sein kann, und n eine ganze Zahl von 5 bis 50 bedeuten, als Tensid in wäßrigen, sauren galvanischen Bädern zur elektrolytischen Abscheidung von Zink in Gegenwart von Glanzbildnern.5. Use of a compound of formula I.
Figure imgb0018
 in which R 1 is a C4 to C20 alkyl radical, R 2 is R 1 or hydrogen, X and Y is a radical of the formula -S0 3 H, where the hydrogen atom can be replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc and one of the radicals X and Y can be hydrogen, and n is an integer from 5 to 50, as a surfactant in aqueous, acidic galvanic baths for the electrodeposition of zinc in the presence of brighteners.
EP83112804A 1982-12-29 1983-12-20 Acid galvanic zinc bath Expired EP0115020B1 (en)

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DE19823248503 DE3248503A1 (en) 1982-12-29 1982-12-29 ACID GALVANIC ZINC BATH
DE3248503 1982-12-29

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EP0115020A3 EP0115020A3 (en) 1984-10-03
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2564487A1 (en) * 1984-05-21 1985-11-22 Omi Int Corp AQUEOUS ACID ZINC ELECTROLYTE AND ELECTROLYTIC ZINC DEPOSITION METHOD
EP0244685A1 (en) * 1986-04-24 1987-11-11 BASF Aktiengesellschaft Aqueous acid galvanic bath

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DE3432956A1 (en) * 1984-09-06 1986-03-13 Schering AG, 1000 Berlin und 4709 Bergkamen SULFATES AND SULPHO DERIVATIVES OF THE SS - NAPHTHOLPOLYGLYCOLAETHER AND ACID ZINKBAEDER CONTAINING THESE COMPOUNDS
US5616232A (en) * 1994-09-28 1997-04-01 Nippon Steel Corporation Process for producing zinc-chromium alloy-electroplated steel plate
US6143160A (en) * 1998-09-18 2000-11-07 Pavco, Inc. Method for improving the macro throwing power for chloride zinc electroplating baths
JP6676550B2 (en) 2014-07-04 2020-04-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Additive for alkaline zinc plating
CN107709627B (en) 2015-06-25 2020-07-28 巴斯夫欧洲公司 Additive for alkaline galvanization
CN111118555A (en) * 2020-01-17 2020-05-08 浙江金欣新材料科技股份有限公司 Water-soluble electroplating brightener and preparation method thereof

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DE1521029A1 (en) * 1966-05-28 1969-07-24 Max Schloetter Fabrik Fuer Gal Acid galvanic bright zinc bath
FR2086320A1 (en) * 1970-04-24 1971-12-31 Uemura Kogyo Kk

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GB1327303A (en) * 1971-03-23 1973-08-22 Cruickshanks Ltd M T Acidic zinc electroplating bath

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DE1521029A1 (en) * 1966-05-28 1969-07-24 Max Schloetter Fabrik Fuer Gal Acid galvanic bright zinc bath
FR2086320A1 (en) * 1970-04-24 1971-12-31 Uemura Kogyo Kk

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2564487A1 (en) * 1984-05-21 1985-11-22 Omi Int Corp AQUEOUS ACID ZINC ELECTROLYTE AND ELECTROLYTIC ZINC DEPOSITION METHOD
GB2159179A (en) * 1984-05-21 1985-11-27 Omi Int Corp Carrier brighteners for acid zinc electrolytes
GB2159179B (en) * 1984-05-21 1989-03-30 Omi Int Corp Carrier brighteners for acid zinc electrolytes
EP0244685A1 (en) * 1986-04-24 1987-11-11 BASF Aktiengesellschaft Aqueous acid galvanic bath

Also Published As

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EP0115020A3 (en) 1984-10-03
EP0115020B1 (en) 1987-04-08
DE3248503A1 (en) 1984-07-05
DE3370835D1 (en) 1987-05-14
US4496439A (en) 1985-01-29

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