EP0588805B1 - Method of producing bright shaped parts electroplated with zinc or a zinc alloy - Google Patents

Method of producing bright shaped parts electroplated with zinc or a zinc alloy Download PDF

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EP0588805B1
EP0588805B1 EP92909336A EP92909336A EP0588805B1 EP 0588805 B1 EP0588805 B1 EP 0588805B1 EP 92909336 A EP92909336 A EP 92909336A EP 92909336 A EP92909336 A EP 92909336A EP 0588805 B1 EP0588805 B1 EP 0588805B1
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Prior art keywords
zinc
salts
brighteners
alloy
compounds
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German (de)
French (fr)
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EP0588805A1 (en
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Erwin Hahn
Bernhard Dung
Bernd Burkhart
Chung-Ji Tschang
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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 present invention relates to an improved process for the production of shiny galvanized or zinc alloy-coated molded parts by electrolytic deposition of zinc or a zinc alloy from aqueous acidic galvanic baths.
  • a glossy coating is often sought in order to give the galvanized object an advantageous decorative appearance, i.e. in addition to the corrosion-preventing effect, a decorative effect is often desired.
  • the galvanic baths contain certain auxiliaries, because otherwise the zinc coatings resulting from the acidic solution are usually dull and often also irregular.
  • a group of such aids for acidic galvanic baths are, for example, conductive salts which are used to improve the conductivity of the baths, another group of aids are the so-called brighteners.
  • benzylidene acetone (benzal acetone).
  • the present invention was therefore based on the object of replacing gloss agents based on benzylidene acetone in aqueous-acidic, galvanic baths for the deposition of zinc or zinc alloys by other substances which achieve the effectiveness of the known gloss agents but do not adversely affect people's health who handle these substances.
  • Preferred radicals R1 are C1 to C8 alkoxy groups such as n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, 2nd -Ethylhexoxy, octoxy or especially methoxy or ethoxy.
  • Preferred radicals R2 are C1 to C4 alkyl groups such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or especially methyl and C1 to C6 alkoxy groups such as n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy or especially methoxy or ethoxy.
  • the preferred radical Ar is the phenyl group, which can additionally be substituted by one or two methyl, ethyl, methoxy or ethoxy groups, but especially the unsubstituted phenyl group.
  • the compounds I are in the aqueous-acidic galvanic baths according to the invention in an amount of advantageously 0.05 g to 3 g per liter, preferably 0.05 g to 1 g per liter, in particular 0.1 g to 0.7 g per liter , used.
  • the aqueous-acidic galvanic baths according to the invention have the usual compositions with regard to the other components. They contain, for example, 50 to 150 g / l zinc chloride or the equivalent amount of zinc sulfate. If zinc alloys are to be deposited on metallic substrates, for example with cobalt and / or nickel, the baths generally additionally contain 1 to 30 g / l of cobalt and / or nickel sulfate or the equivalent amount of another water-soluble cobalt and / or nickel salt .
  • a suitable conductive salt is potassium chloride, which is usually present in amounts of 100 to 250 g / l in the aqueous acidic electroplating bath.
  • Other conductive salts are, for example, ammonium chloride or sodium chloride, which are usually used in amounts of 10 to 150 g / l.
  • nonionic and anionic surfactants are known for example from GB-PS 1 149 106. These are addition products of ethylene oxide with fatty alcohols, e.g. to C8 to C18 alcohols, or to the addition products of ethylene oxide with phenol or alkylphenols, especially with nonylphenyl. As a rule, 5 to 100 moles of ethylene oxide are added per mole of alcohol or phenol.
  • Suitable anionic surfactants are known, for example, from US Pat. No. 3,787,296. These are mainly sulfated polyethers which can be obtained, for example, by adding ethylene oxide to fatty alcohols, fatty amines, amides of C6 to C10 carboxylic acids and longer-chain fatty acids and subsequent sulfonation. Sulfonates of polyalkylene oxides or block copolymers of ethylene oxide and propylene oxide are also used as anionic surfactants.
  • EP-PS 0 115 020 Another group of anionic surfactants is known from EP-PS 0 115 020. This describes sulfonated and sulfated alkylphenol ethoxylates which, for example, have the general formula II in the R3 C4 to C20 alkyl, X and Y are the groups -SO3H or -SO3Me, where Me is ammonium, alkali metal or an equivalent of alkaline earth metal or zinc, and n is a number from 5 to 50.
  • those sulfonated and sulfated products whose polyether chain contains 1 to 25 propylene oxide or butylene oxide units are also suitable as anionic surfactants.
  • the advantage of the sulfonated and sulfated alkylphenol alkoxylates is that they have an extremely high cloud point, so that the electrolytic deposition of the zinc not only in the usual temperature range of 20 to 30 ° C but also at temperatures above 50 ° C, e.g. can be made in a range of 20 to 70 ° C.
  • the nonionic and anionic surfactants act as auxiliary brighteners and at the same time are solubilizing agents for, for example, the compounds I, which are sparingly soluble in water.
  • surfactants and phenol-formaldehyde condensation products or naphthalenesulfonic acid / formaldehyde condensation products which can also be used as surfactants are usually used in amounts of 1 to 20 g / l, preferably 2 to 15 g / l, in the aqueous-acidic electroplating bath according to the invention.
  • a mixture of several surfactants can also be used.
  • alkali metal or ammonium benzoates such as, in particular, sodium benzoate, in amounts of 1 to 8 g / l, preferably 2 to 6 g / l, can advantageously be used as additional brighteners.
  • the pH of the aqueous-acidic galvanic baths according to the invention is generally between 4 and 5. It is obtained by adding acids, e.g. usual mineral acids such as sulfuric acid or hydrochloric acid.
  • the present application also relates to aqueous acidic galvanic baths for the electrolytic deposition of zinc or a zinc alloy as a glossy coating on moldings, the baths being essential components of one or more zinc salts and optionally salts of the other alloy metals, one or more conductive salts, one or more Contain surfactants and one or more brighteners, characterized by an effective content of the compounds I.
  • the process according to the invention galvanizes molded parts made of metals, mainly iron and steel, in order to protect them against corrosion and at the same time to give them a high gloss.
  • the baths according to the invention used for this purpose provide high-gloss and ductile zinc coatings over the entire range of current density that is technically possible, which correspond in quality to the coatings that are obtainable using benzylidene acetone according to the prior art.
  • the compounds I When handling the compounds I, no health impairments were observed in persons who handle these substances.
  • the compounds I usually have such a low vapor pressure that the possibility of vapors of these compounds being absorbed by the human organism, for example by inhalation, is very low from the outset.
  • composition of bath 1 is a composition of bath 1:
  • composition of bath 2 is Composition of bath 2:
  • the pH of bath 1 was 4.8, the pH of bath 2 was 4.5.
  • the pH was adjusted with dilute hydrochloric acid.
  • the galvanizing of steel sheets took 10 minutes each. It was carried out in a 250 ml Hull cell with 1 ampere at approximately 23 ° C. Blue chromating was carried out after the galvanizing.
  • the quality of the zinc coatings obtained is shown in the following table.

Abstract

PCT No. PCT/EP92/00983 Sec. 371 Date Nov. 9, 1993 Sec. 102(e) Date Nov. 9, 1993 PCT Filed May 6, 1992 PCT Pub. No. WO92/22683 PCT Pub. Date Dec. 23, 1992.The production of shining shaped articles coated with zinc or a zinc alloy by electrodeposition of zinc or a zinc alloy from acidic aqueous electrolytic baths which contain as essential components one or more zinc salts and, where appropriate, salts of the other alloy metals, one or more conducting salts, one or more surfactants and one or more brighteners, entails employing as brighteners compounds of the formula I <IMAGE> I where R1 is C1-C8-alkoxy, phenoxy, benzyloxy, amino, C1-C6-alkylamino or di(C1-C6)alkylamino, R2 is C1-C4-alkyl, phenyl, benzyl or the meanings of R1, and Ar is phenyl or naphthyl which can additionally be substituted by one to three C1-C4-alkyl groups or C1-C4-alkoxy groups.

Description

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung glänzender verzinkter oder mit einer Zinklegierung überzogener Formteile durch elektrolytische Abscheidung von Zink oder einer Zinklegierung aus wäßrig-sauren galvanischen Bädern.The present invention relates to an improved process for the production of shiny galvanized or zinc alloy-coated molded parts by electrolytic deposition of zinc or a zinc alloy from aqueous acidic galvanic baths.

Bei der galvanischen Abscheidung von Zink bzw. Zinklegierungen auf metallischen Substraten aus wäßrig-saurer Lösung wird häufig ein glänzender Überzug angestrebt, um dem verzinkten Gegenstand ein vorteilhaftes dekoratives Aussehen zu verleihen, d.h. es ist oft neben dem korrosionsverhindernden auch ein dekorativer Effekt erwünscht. Um die gewünschten Effekte zu erzielen, ist es unerläßlich, daß die galvanischen Bäder bestimmte Hilfsmittel enthalten, weil andernfalls die aus saurer Lösung entstehenden Zinküberzüge meistens matt und häufig auch noch unregelmäßig anfallen. Eine Gruppe solcher Hilfsmittel für saure galvanische Bäder sind beispielsweise Leitsalze, die zur Verbesserung der Leitfähigkeit der Bäder eingesetzt werden, eine andere Gruppe von Hilfsmitteln sind die sogenannten Glanzbildner.In the galvanic deposition of zinc or zinc alloys on metallic substrates from aqueous-acidic solution, a glossy coating is often sought in order to give the galvanized object an advantageous decorative appearance, i.e. in addition to the corrosion-preventing effect, a decorative effect is often desired. In order to achieve the desired effects, it is essential that the galvanic baths contain certain auxiliaries, because otherwise the zinc coatings resulting from the acidic solution are usually dull and often also irregular. A group of such aids for acidic galvanic baths are, for example, conductive salts which are used to improve the conductivity of the baths, another group of aids are the so-called brighteners.

In der US-PS 3 694 330 (1) (Reissue 27 999) werden saure, galvanische Zinkbäder, die Ammoniumsalze und als Glanzbildner aromatische Carbonylverbindungen enthalten, beschrieben. Als letztere werden aromatische Carbonsäuren sowie aromatische Aldehyde und Ketone genannt. Explizit angeführt sind u.a. Zimtsäure, Zimtaldehyd, Benzoesäure, Benzalaceton und Benzoylessigsäureethylester.US Pat. No. 3,694,330 (1) (Reissue 27 999) describes acidic, galvanic zinc baths which contain ammonium salts and aromatic carbonyl compounds as brighteners. Aromatic carboxylic acids and aromatic aldehydes and ketones are mentioned as the latter. The following are explicitly mentioned: Cinnamic acid, cinnamaldehyde, benzoic acid, benzal acetone and ethyl benzoylacetate.

In der US-PS 4 422 908 (2) werden saure, galvanische Zinkbäder, die Sulfamationen und als Glanzbildner aromatische Carbonylverbindungen enthalten, beschrieben. Es werden Aldehyde und Ketone angeführt, darunter als bevorzugte Substanz Benzalaceton.US Pat. No. 4,422,908 (2) describes acidic, galvanic zinc baths which contain sulfamate ions and aromatic carbonyl compounds as brighteners. Aldehydes and ketones are listed, including benzalacetone as the preferred substance.

Der wichtigste Vertreter der Glanzbildner für saure Zinkbäder ist Benzylidenaceton (Benzalaceton). Ein schwerwiegender Nachteil des Benzylidenacetons und auch seiner Homologen ist jedoch die Tatsache, daß diese Verbindungen bei vielen Personen, die damit umgehen, allergische Reaktionen, wie Hautrötungen und Juckreiz, hervorrufen.The most important representative of the brighteners for acidic zinc baths is benzylidene acetone (benzal acetone). A serious disadvantage of benzylidene acetone and its homologues, however, is the fact that these compounds cause allergic reactions such as reddening of the skin and itching in many people who handle it.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Glanzbildner auf Basis von Benzylidenaceton in wäßrig-sauren, galvanischen Bädern zur Abscheidung von Zink oder Zink-Legierungen durch andere Substanzen zu ersetzen, die die Wirksamkeit der bekannten Glanzbildner erreichen, jedoch nicht zu gesundheitlichen Beeinträchtigungen bei Personen führen, die diese Substanzen handhaben.The present invention was therefore based on the object of replacing gloss agents based on benzylidene acetone in aqueous-acidic, galvanic baths for the deposition of zinc or zinc alloys by other substances which achieve the effectiveness of the known gloss agents but do not adversely affect people's health who handle these substances.

Demgemäß wurde ein Verfahren zur Herstellung glänzender verzinkter oder mit einer Zinklegierung überzogener Formteile durch elektrolytische Abscheidung von Zink oder einer Zinklegierung aus wäßrig-sauren galvanischen Bädern, die als wesentliche Bestandteile ein oder mehrere Zinksalze und gegebenenfalls Salze der anderen Legierungsmetalle, ein oder mehrere Leitsalze, ein oder mehrere Tenside und ein oder mehrere Glanzbildner enthalten, gefunden, welches dadurch gekennzeichnet ist, daß man als Glanzbildner Verbindungen der allgemeinen Formel I

Figure imgb0001

in der

R¹
C₁- bis C₈-Alkoxy, Phenoxy, Benzyloxy, Amino, C₁- bis C₆-Alkylamino oder Di(C₁- bis C₆-)alkylamino bedeutet,
R²
C₁- bis C₄-Alkyl, Phenyl, Benzyl oder die unter R¹ aufgeführten Bedeutungen bezeichnet und
Ar
für Phenyl oder Naphthyl, welches zusätzlich durch ein bis drei C₁- bis C₄-Alkylgruppen oder C₁- bis C₄-Alkoxygruppen substituiert sein kann, steht,
einsetzt.Accordingly, a process for the production of shiny, zinc-coated or zinc alloy-coated molded parts by electrolytic deposition of zinc or a zinc alloy from aqueous-acidic galvanic baths, the essential constituents of one or more zinc salts and optionally salts of the other alloy metals, one or more conductive salts or contain more surfactants and one or more brighteners, which is characterized in that compounds of the general formula I are used as brighteners
Figure imgb0001
in the
R¹
C₁- to C₈-alkoxy, phenoxy, benzyloxy, amino, C₁- to C₆-alkylamino or di (C₁- to C₆-) alkylamino,
R²
C₁- to C₄ alkyl, phenyl, benzyl or the meanings listed under R¹ and
Ar
represents phenyl or naphthyl, which may additionally be substituted by one to three C₁ to C₄ alkyl groups or C₁ to C₄ alkoxy groups,
starts.

Bevorzugte Reste R¹ sind C₁- bis C₈-Alkoxygruppen wie n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy, tert.-Butoxy, n-Pentoxy, n-Hexoxy, n-Heptoxy, 2-Ethylhexoxy, Octoxy oder vor allem Methoxy oder Ethoxy.Preferred radicals R¹ are C₁ to C₈ alkoxy groups such as n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, 2nd -Ethylhexoxy, octoxy or especially methoxy or ethoxy.

Bevorzugte Reste R² sind C₁- bis C₄-Alkylgruppen wie Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl oder vor allem Methyl und C₁- bis C₆-Alkoxygruppen wie n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy, tert.-Butoxy, n-Pentoxy, n-Hexoxy oder vor allem Methoxy oder Ethoxy.Preferred radicals R² are C₁ to C₄ alkyl groups such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or especially methyl and C₁ to C₆ alkoxy groups such as n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy or especially methoxy or ethoxy.

Bevorzugter Rest Ar ist die Phenylgruppe, welche zusätzlich durch ein oder zwei Methyl-, Ethyl-, Methoxy- oder Ethoxygruppen substituiert sein kann, insbesondere jedoch die unsubstituierte Phenylgruppe.The preferred radical Ar is the phenyl group, which can additionally be substituted by one or two methyl, ethyl, methoxy or ethoxy groups, but especially the unsubstituted phenyl group.

Ganz besonders bevorzugte Verbindungen I sind 2-Benzylidenacetessigsäuremethyl- und -ethylester (R¹ = OCH₃ bzw. OC₂H₅, R² = CH₃, Ar = Ph) sowie 2-Benzyliden-malonsäuredimethyl- und -diethylester (R¹ = R² = OCH₃ bzw. OC₂H₅, Ar = Ph).Very particularly preferred compounds I are 2-benzylideneacetoacetic acid methyl and ethyl esters (R¹ = OCH₃ or OC₂H₅, R² = CH₃, Ar = Ph) and 2-benzylidene-malonate dimethyl and diethyl ester (R¹ = R² = OCH₃ or OC₂H₅, Ar = Ph).

Diese Substanzen sind durch Kondensation aus Benzaldehyd und dem entsprechenden Acetessig- bzw. Malonsäureester leicht und kostengünstig zugänglich. Die Herstellung von Benzyliden-acetessigsäuremethylester wird beispielsweise in der Literaturstelle J. Org. Chem. 1990, Bd. 55, S. 319-324 beschrieben.These substances are easily and inexpensively accessible by condensation from benzaldehyde and the corresponding acetoacetic or malonic ester. The preparation of methyl benzylidene-acetoacetate is described, for example, in J. Org. Chem. 1990, Vol. 55, pp. 319-324.

Die Verbindungen I werden in den erfindungsgemäßen wäßrig-sauren galvanischen Bädern in einer Menge von zweckmäßigerweise 0,05 g bis 3 g pro Liter, vorzugsweise 0,05 g bis 1 g pro Liter, insbesondere 0,1 g bis 0,7 g pro Liter, eingesetzt.The compounds I are in the aqueous-acidic galvanic baths according to the invention in an amount of advantageously 0.05 g to 3 g per liter, preferably 0.05 g to 1 g per liter, in particular 0.1 g to 0.7 g per liter , used.

Es ist selbstverständlich möglich, Mischungen von Verbindungen I als Glanzbildner einzusetzen sowie die Glanzbildner gemäß der Formel I zusammen mit anderen bekannten Glanzbildnern zu verwenden.It is of course possible to use mixtures of compounds I as brighteners and to use the brighteners according to formula I together with other known brighteners.

Die erfindungsgemäßen wäßrig-sauren galvanischen Bäder weisen bezüglich der übrigen Komponenten die üblichen Zusammensetzungen auf. Sie enthalten beispielsweise 50 bis 150 g/l Zinkchlorid oder die äquivalente Menge Zinksulfat. Sofern Legierungen des Zinks beispielsweise mit Kobalt und/oder Nickel auf metallischen Substraten abgeschieden werden sollen, enthalten die Bäder zusätzlich in der Regel 1 bis 30 g/l Kobalt- und/oder Nickelsulfat oder die äquivalente Menge eines anderen wasserlöslichen Kobalt- und/oder Nickelsalzes.The aqueous-acidic galvanic baths according to the invention have the usual compositions with regard to the other components. They contain, for example, 50 to 150 g / l zinc chloride or the equivalent amount of zinc sulfate. If zinc alloys are to be deposited on metallic substrates, for example with cobalt and / or nickel, the baths generally additionally contain 1 to 30 g / l of cobalt and / or nickel sulfate or the equivalent amount of another water-soluble cobalt and / or nickel salt .

Ein weiterer wesentlicher Bestandteil der Bäder sind Leitsalze. Ein geeignetes Leitsalz ist Kaliumchlorid, das in Mengen von üblicherweise 100 bis 250 g/l im wäßrig-sauren galvanischen Bad enthalten ist. Andere Leitsalze sind beispielsweise Ammoniumchlorid oder Natriumchlorid, die üblicherweise in Mengen von 10 bis 150 g/l eingesetzt werden.Another essential component of the baths are conductive salts. A suitable conductive salt is potassium chloride, which is usually present in amounts of 100 to 250 g / l in the aqueous acidic electroplating bath. Other conductive salts are, for example, ammonium chloride or sodium chloride, which are usually used in amounts of 10 to 150 g / l.

Ein weiterer wesentlicher Bestandteil der erfindungsgemäßen wäßrig-sauren galvanischen Bäder sind nichtionische und anionische Tenside. Geeignete nichtionische Tenside sind beispielsweise aus der GB-PS 1 149 106 bekannt. Hierbei handelt es sich um Additionsprodukte von Ethylenoxid an Fettalkohole, z.B. an C₈- bis C₁₈-Alkohole, oder um Additionsprodukte von Ethylenoxid an Phenol bzw. Alkylphenole, insbesondere an Nonylphenyl. Pro Mol Alkohol bzw. Phenol werden dabei in der Regel 5 bis 100 Mol Ethylenoxid addiert.Another essential component of the aqueous-acidic galvanic baths according to the invention are nonionic and anionic surfactants. Suitable nonionic surfactants are known for example from GB-PS 1 149 106. These are addition products of ethylene oxide with fatty alcohols, e.g. to C₈ to C₁₈ alcohols, or to the addition products of ethylene oxide with phenol or alkylphenols, especially with nonylphenyl. As a rule, 5 to 100 moles of ethylene oxide are added per mole of alcohol or phenol.

Geeignete anionische Tenside sind beispielsweise aus der US-PS 3 787 296 bekannt. Es handelt sich hierbei hauptsächlich um sulfatierte Polyether, die beispielsweise durch Addition von Ethylenoxid an Fettalkohole, Fettamine, Amide von C₆- bis C₁₀-Carbonsäuren und längerkettige Fettsäuren sowie jeweils nachfolgende Sulfonierung erhältlich sind. Auch Sulfonate von Polyalkylenoxiden oder Blockcopolymerisaten aus Ethylenoxid und Propylenoxid werden als anionische Tenside verwendet.Suitable anionic surfactants are known, for example, from US Pat. No. 3,787,296. These are mainly sulfated polyethers which can be obtained, for example, by adding ethylene oxide to fatty alcohols, fatty amines, amides of C₆ to C₁₀ carboxylic acids and longer-chain fatty acids and subsequent sulfonation. Sulfonates of polyalkylene oxides or block copolymers of ethylene oxide and propylene oxide are also used as anionic surfactants.

Eine weitere Gruppe von anionischen Tensiden ist aus der EP-PS 0 115 020 bekannt. Hierin werden sulfonierte und sulfatierte Alkylphenolethoxylate beschrieben, die beispielsweise die allgemeine Formel II

Figure imgb0002

in der R³ C₄- bis C₂₀-Alkyl, X und Y die Gruppen -SO₃H oder -SO₃Me, wobei Me Ammonium, Alkalimetall oder ein Äquivalent Erdalkalimetall oder Zink bezeichnet, und n eine Zahl von 5 bis 50 bedeuten, haben.Another group of anionic surfactants is known from EP-PS 0 115 020. This describes sulfonated and sulfated alkylphenol ethoxylates which, for example, have the general formula II
Figure imgb0002
in the R³ C₄ to C₂₀ alkyl, X and Y are the groups -SO₃H or -SO₃Me, where Me is ammonium, alkali metal or an equivalent of alkaline earth metal or zinc, and n is a number from 5 to 50.

Außer den Verbindungen der Formel II kommen als anionische Tenside auch solche sulfonierten und sulfatierten Produkte in Betracht, deren Polyetherkette 1 bis 25 Propylenoxid- oder Butylenoxideinheiten enthält.In addition to the compounds of the formula II, those sulfonated and sulfated products whose polyether chain contains 1 to 25 propylene oxide or butylene oxide units are also suitable as anionic surfactants.

Der Vorteil der sulfonierten und sulfatierten Alkylphenolalkoxylate liegt darin, daß sie einen außerordentlich hohen Trübungspunkt aufweisen, so daß die elektrolytische Abscheidung des Zinks nicht nur im sonst üblichen Temperaturbereich von 20 bis 30°C sondern auch noch bei Temperaturen von oberhalb 50°C, z.B. in einem Bereich von 20 bis 70°C, vorgenommen werden kann. Die nichtionischen und anionischen Tenside wirken als Hilfsglanzbildner und sind gleichzeitig Solubilisierungsmittel für beispielsweise die Verbindungen I, die schwer in Wasser löslich sind.The advantage of the sulfonated and sulfated alkylphenol alkoxylates is that they have an extremely high cloud point, so that the electrolytic deposition of the zinc not only in the usual temperature range of 20 to 30 ° C but also at temperatures above 50 ° C, e.g. can be made in a range of 20 to 70 ° C. The nonionic and anionic surfactants act as auxiliary brighteners and at the same time are solubilizing agents for, for example, the compounds I, which are sparingly soluble in water.

Diese in Betracht kommenden Tenside sowie als Tenside auch einsetzbare Phenol-Formaldehyd-Kondensationsprodukte oder Naphthalinsulfonsäure/Formaldehyd-Kondensationsprodukte werden üblicherweise in Mengen von 1 bis 20 g/l, vorzugsweise 2 bis 15 g/l, im erfindungsgemäßen wäßrig-sauren galvanischen Bad angewendet. Man kann auch eine Mischung aus mehreren Tensiden verwenden.These suitable surfactants and phenol-formaldehyde condensation products or naphthalenesulfonic acid / formaldehyde condensation products which can also be used as surfactants are usually used in amounts of 1 to 20 g / l, preferably 2 to 15 g / l, in the aqueous-acidic electroplating bath according to the invention. A mixture of several surfactants can also be used.

Als zusätzliche Glanzbildner können außerdem mit vorteilhafter Wirkung Alkalimetall- oder Ammoniumbenzoate wie insbesondere Natriumbenzoat in Mengen von 1 bis 8 g/l, vorzugsweise 2 bis 6 g/l, eingesetzt werden.In addition, alkali metal or ammonium benzoates such as, in particular, sodium benzoate, in amounts of 1 to 8 g / l, preferably 2 to 6 g / l, can advantageously be used as additional brighteners.

Der pH-Wert der erfindungsgemäßen wäßrig-sauren galvanischen Bäder liegt in der Regel zwischen 4 und 5. Es wird durch Zugabe von Säuren, z.B. üblichen Mineralsäuren wie Schwefelsäure oder Salzsäure, eingestellt.The pH of the aqueous-acidic galvanic baths according to the invention is generally between 4 and 5. It is obtained by adding acids, e.g. usual mineral acids such as sulfuric acid or hydrochloric acid.

Besonders vorteilhafte Ergebnisse bei der Verzinkung werden dann erhalten, wenn man in den erfindungsgemäßen wäßrig-sauren Bädern Natriumbenzoat in einer Menge von 1 bis 8 g/l als zusätzlichen Glanzbildner und gleichzeitig den Methyl- und Ethylester der 2-Benzyliden-acetessigsäure oder der 2-Benzylidenmalonsäure in einer Konzentration von 0,05 g bis 1 g/l, vorzugsweise 0,1 g bis 0,7 g/l, als Glanzbildner einsetzt. Diese Kombinationen haben sich besonders in ammoniumsalzfreien, wäßrig-sauren galvanischen Zinkbädern bewährt.Particularly advantageous results in the galvanizing are obtained if sodium benzoate in an amount of 1 to 8 g / l as additional brightener and at the same time the methyl and ethyl ester of 2-benzylidene-acetic acid or 2- Benzylidene malonic acid in a concentration of 0.05 g to 1 g / l, preferably 0.1 g to 0.7 g / l, is used as a brightener. These combinations have proven particularly useful in ammonium salt-free, aqueous acidic galvanic zinc baths.

Gegenstand der vorliegenden Anmeldung sind auch wäßrig-saure galvanische Bädern zur elektrolytischen Abscheidung von Zink oder einer Zinklegierung als glänzender Überzug auf Formteilen, wobei die Bäder als wesentliche Bestandteile ein oder mehrere Zinksalze und gegebenenfalls Salze der anderen Legierungsmetalle, ein oder mehrere Leitsalze, ein oder mehrere Tenside und ein oder mehrere Glanzbildner enthalten, gekennzeichnet durch einen wirksamen Gehalt an den Verbindungen I.The present application also relates to aqueous acidic galvanic baths for the electrolytic deposition of zinc or a zinc alloy as a glossy coating on moldings, the baths being essential components of one or more zinc salts and optionally salts of the other alloy metals, one or more conductive salts, one or more Contain surfactants and one or more brighteners, characterized by an effective content of the compounds I.

Durch das erfindungsgemäße Verfahren werden Formteile aus Metallen, hauptsächlich Eisen und Stahl, galvanisiert, um sie gegen Korrosion zu schützen und ihnen gleichzeitig einen hohen Glanz zu verleihen. Die hierzu verwendeten erfindungsgemäßen Bäder liefern über den gesamten technisch in Betracht kommenden Stromdichtenbereich hochglänzende und duktile Zinküberzüge, die in der Qualität den Überzügen entsprechen, die unter Verwendung von Benzylidenaceton nach dem Stand der Technik erhältlich sind.The process according to the invention galvanizes molded parts made of metals, mainly iron and steel, in order to protect them against corrosion and at the same time to give them a high gloss. The baths according to the invention used for this purpose provide high-gloss and ductile zinc coatings over the entire range of current density that is technically possible, which correspond in quality to the coatings that are obtainable using benzylidene acetone according to the prior art.

Beim Umgang mit den Verbindungen I wurden keine gesundheitlichen Beeinträchtigungen bei Personen, die diese Substanzen handhaben, beobachtet. Die Verbindungen I weisen in der Regel einen solch geringen Dampfdruck auf, daß die Möglichkeit der Aufnahme von Dämpfen dieser Verbindungen durch den menschlischen Organismus, beispielsweise durch Einatmen, von vornherein sehr gering ist.When handling the compounds I, no health impairments were observed in persons who handle these substances. The compounds I usually have such a low vapor pressure that the possibility of vapors of these compounds being absorbed by the human organism, for example by inhalation, is very low from the outset.

BeispieleExamples

Die Wirksamkeit der Verbindungen I in wäßrig-sauren galvanischen Bädern zur elektrolytischen Abscheidung von Zink wird anhand von zwei verschiedenen Bädern demonstriert.The effectiveness of the compounds I in aqueous-acidic galvanic baths for the electrolytic deposition of zinc is demonstrated using two different baths.

Zusammensetzung von Bad 1:Composition of bath 1:

Zinkchlorid 100 g/l Kaliumchlorid 200 g/l Borsäure 20 g/l handelsübliches Naphthalinsulfonsäure/Formaldehyd-Kondensationsprodukt 2 g/l Natriumbenzoat 2 g/l handelsüblicher Nonylphenolpolyethylenglykolether mit 20 Ethylenglykol-Einheiten 5 g/l Nonylphenolpolyethylenglykolether, sulfoniert und sulfatiert, mit 10 Ethylenglykol-Einheiten (gemäß EP-PS 0 115 020) 10 g/l
Glanzbildner gemäß Tabelle Zinc chloride 100 g / l Potassium chloride 200 g / l Boric acid 20 g / l commercial naphthalene sulfonic acid / formaldehyde condensation product 2 g / l Sodium benzoate 2 g / l Commercial nonylphenol polyethylene glycol ether with 20 ethylene glycol units 5 g / l Nonylphenol polyethylene glycol ether, sulfonated and sulfated, with 10 ethylene glycol units (according to EP-PS 0 115 020) 10 g / l
Brightener according to the table

Zusammensetzung von Bad 2:Composition of bath 2:

Zinkchlorid 100 g/l Ammoniumchlorid 140 g/l Natriumbenzoat 6 g/l handelsüblicher Nonylphenolpolyethylenglykolether mit 20 Ethylenglykol-Einheiten 10 g/l Nonylphenolpolyethylenglykolether, sulfoniert und sulfatiert, mit 10 Ethylenglykol-Einheiten (gemäß EP-PS 0 115 020) 10 g/l
Glanzbildner gemäß Tabelle
Der pH-Wert des Bades 1 betrug 4,8, der pH-Wert des Bades 2 betrug 4,5. Die Einstellung des pH-Wertes erfolgte jeweils mit verdünnter Salzsäure. Die Verzinkung von Stahlblechen dauerte jeweils 10 Minuten. Sie wurde in einer 250-ml-Hull-Zelle mit 1 Ampere bei ca. 23°C durchgeführt. Im Anschluß an die Verzinkung wurde eine Blauchromatierung vorgenommen. Zinc chloride 100 g / l Ammonium chloride 140 g / l Sodium benzoate 6 g / l Commercial nonylphenol polyethylene glycol ether with 20 ethylene glycol units 10 g / l Nonylphenol polyethylene glycol ether, sulfonated and sulfated, with 10 ethylene glycol units (according to EP-PS 0 115 020) 10 g / l
Brightener according to the table
The pH of bath 1 was 4.8, the pH of bath 2 was 4.5. The pH was adjusted with dilute hydrochloric acid. The galvanizing of steel sheets took 10 minutes each. It was carried out in a 250 ml Hull cell with 1 ampere at approximately 23 ° C. Blue chromating was carried out after the galvanizing.

Die Qualität der erhaltenen Zinküberzüge ist der folgenden Tabelle zu entnehmen. Glanz und Duktilität der galvanischen Überzüge wurde visuell beurteilt, dabei bedeuten die Noten
1 = schlecht, 2 = gering, 3 = mäßig, 4 = gut und 5 = sehr gut.The quality of the zinc coatings obtained is shown in the following table. The gloss and ductility of the galvanic coatings was assessed visually, the marks mean
1 = bad, 2 = low, 3 = moderate, 4 = good and 5 = very good.

Man erkennt, daß die Wirkung der erfindungsgemäß eingesetzten Verbindungen I der sehr guten Wirkung von Benzylidenaceton mindestens gleichkommt. Tabelle Glanzbildner in wäßrig-sauren galvanischen Bädern Bsp. Nr. Glanzbildner Bad-Nr. Ergebnis Substanz Konz. [g/l] Glanz Duktilität 1 Benzylidenacetessig-säureethylester 0,4 1 4-5 5 2 Benzylidenacetessig-säureethylester 0,4 2 3-4 3 3 Benzylidenacetessig-säuremethylester 0,4 1 4-5 5 4 Benzylidenacetessig-säuremethylester 0,4 2 3-4 3 5 Benzylidenmalonsäuredimethylester 0,4 1 4-5 5 6 Benzylidenmalonsäuredimethylester 0,4 2 4 3 7 Benzylidenmalonsäurediethylester 0,6 1 4 5 Zum Vergleich: A Benzylidenaceton 0,4 1 4 5 B Benzylidenaceton 0,4 2 3-4 3 It can be seen that the action of the compounds I used according to the invention is at least equivalent to the very good action of benzylidene acetone. table Brightener in aqueous acidic galvanic baths Example No. Brightener Bathroom no. Result substance Conc. [G / l] shine Ductility 1 Ethyl benzylidene acetoacetate 0.4 1 4-5 5 2nd Ethyl benzylidene acetoacetate 0.4 2nd 3-4 3rd 3rd Methyl benzylidene acetoacetate 0.4 1 4-5 5 4th Methyl benzylidene acetoacetate 0.4 2nd 3-4 3rd 5 Dimethyl benzylidene malonate 0.4 1 4-5 5 6 Dimethyl benzylidene malonate 0.4 2nd 4th 3rd 7 Diethyl benzylidene malonate 0.6 1 4th 5 For comparison: A Benzylidene acetone 0.4 1 4th 5 B Benzylidene acetone 0.4 2nd 3-4 3rd

Claims (6)

  1. A process for the production of shining shaped articles coated with zinc or a zinc alloy by electrodeposition of zinc or a zinc alloy from acidic agueous electrolytic baths which contain as essential components one or more zinc salts and, where appropriate, salts of the other alloy metals, one or more conducting salts, one or more surfactants and one or more brighteners, which comprises employing as brighteners compounds of the formula I
    Figure imgb0004
     where
    R¹   is C₁-C₈-alkoxy, phenoxy, benzyloxy, amino, C₁-C₆-alkylamino or di(C₁-C₆)alkylamino,
    R²   is C₁-C₄-alkyl, phenyl, benzyl or the meanings of R¹, and
    Ar   is phenyl or naphthyl which can additionally be substituted by one to three C₁-C₄-alkyl groups or C₁-C₄-alkoxy groups.
  2. A process for the production of shining shaped articles coated with zinc or a zinc alloy as claimed in claim 1, wherein compounds I where
    R¹   is C₁-C₈-alkoxy,
    R²   is C₁-C₄-alkyl or C₁-C₆-alkoxy, and
    Ar   is phenyl which can additionally be substituted by one or two methyl, ethyl, method or ethoxy groups,
    are employed as brighteners.
  3. A process for the production of shining shaped articles coated with zinc or a zinc alloy as claimed in claim 1, wherein the compounds I are employed in an amount of from 0.05 g to 3 g per liter of the acidic aqueous electrolytic bath.
  4. A process for the production of shining shaped articles coated with zinc or a zinc alloy as claimed in claim 1, wherein alkali metal or ammonium benzoates are employed as additional brighteners.
  5. The use of compounds I as claimed in claim 1 as brighteners in acidic aqueous electrolytic baths which contain as essential components one or more zinc salts and, where appropriate, salts of other alloy metals, one or more conducting salts, one or more surfactants and one or more brighteners, for the electrodeposition of zinc or a zinc alloy as shining coating on shaped articles.
  6. An acidic aqueous electrolytic bath for the electrodeposition of zinc or a zinc alloy as shining coating on shaped articles, where the bath contains as essential components one or more zinc salts and, where appropriate, salts of the other alloy metals, one or more conducting salts, one or more surfactants and one or more brighteners, with an effective content of compounds I as claimed in claim 1.
EP92909336A 1991-06-12 1992-05-06 Method of producing bright shaped parts electroplated with zinc or a zinc alloy Expired - Lifetime EP0588805B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4119341A DE4119341A1 (en) 1991-06-12 1991-06-12 METHOD FOR THE PRODUCTION OF GLAZING PLATED OR WITH ZINC ALLOYED TOOLS
DE4119341 1991-06-12
PCT/EP1992/000983 WO1992022683A1 (en) 1991-06-12 1992-05-06 Method of producing bright shaped parts electroplated with zinc or a zinc alloy

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EP0588805A1 EP0588805A1 (en) 1994-03-30
EP0588805B1 true EP0588805B1 (en) 1995-08-02

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DE4413251A1 (en) * 1994-04-16 1995-10-19 Basf Ag Process for producing bright galvanized or zinc alloy coated molded parts
DE4446329A1 (en) * 1994-12-23 1996-06-27 Basf Ag Salts of aromatic hydroxyl compounds and their use as brighteners
WO2001002627A1 (en) * 1999-07-06 2001-01-11 Dunigan, Frank, C. Method and electroplating solution for plating antimony and antimony alloy coatings

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1521029C3 (en) * 1966-05-28 1984-01-19 Dr.-Ing. Max Schlötter GmbH & Co KG, 7340 Geislingen Acid galvanic bright zinc bath
US4422908A (en) * 1981-11-23 1983-12-27 E. I. Du Pont De Nemours & Co. Zinc plating
US4528075A (en) * 1984-09-07 1985-07-09 Basf Wyandotte Corporation Solubilization of benzylidene acetone in zinc electroplating baths

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DE59203126D1 (en) 1995-09-07
ES2075696T3 (en) 1995-10-01
WO1992022683A1 (en) 1992-12-23
ATE125888T1 (en) 1995-08-15
JPH06508180A (en) 1994-09-14
KR940701467A (en) 1994-05-28
DE4119341A1 (en) 1992-12-17
EP0588805A1 (en) 1994-03-30
TW219954B (en) 1994-02-01

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