EP1114206B1 - Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings - Google Patents

Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings Download PDF

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Publication number
EP1114206B1
EP1114206B1 EP99936607A EP99936607A EP1114206B1 EP 1114206 B1 EP1114206 B1 EP 1114206B1 EP 99936607 A EP99936607 A EP 99936607A EP 99936607 A EP99936607 A EP 99936607A EP 1114206 B1 EP1114206 B1 EP 1114206B1
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Prior art keywords
zinc
bath
bath according
amount
coatings
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German (de)
French (fr)
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EP1114206A1 (en
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Birgit Sonntag
Udo Grieser
Barrie Sydney James
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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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
    • 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
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • Cyanide-free zinc electrolyte baths can be used divide into two bath types, namely into weakly acidic zinc electrolytes (containing zinc chloride or zinc sulfate) and alkaline Zinkatelektrolyte.
  • the ratio of zinc layer thickness in the high current density range to the zinc layer thickness in the low current density range is called layer thickness distribution and should ideally 1.
  • Zinc and zinc alloy baths always have to meet higher demands. Accordingly, a Zinc coating on the object to be coated everywhere have the same layer thickness and a high gloss.
  • a good layer thickness distribution can be achieved by lowering the current yield in the high current density range, while the current efficiency in the low current density range is maintained.
  • the additives proposed so far are disadvantageous however, the tendency that the galvanically generated Flake off zinc layers.
  • the formation of zinc or zinc alloy flaking of the coated substrate, often too referred to as blistering when using Cyanide-free, alkaline baths are a serious problem represents, although no confirmed knowledge regarding the influence of the additives used on the blistering available.
  • the appearance of the blistering works turned out to be particularly disadvantageous because it often takes weeks occurs and therefore often complaints to the coating industry can lead.
  • US Pat. No. 4,030,987 also describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths described which one of the zinc layers should give uniform layer thickness.
  • the invention is therefore based on the object, the shortcomings to overcome the prior art and in particular a aqueous cyanide-free alkaline bath for galvanic deposition to provide zinc and zinc alloy coatings, obtained with the coatings of zinc or zinc alloys can be in which even after long storage none There is a tendency to form flaking.
  • the soluble polymer of the general formula A contained in the bath according to the invention can be obtained by reacting N, N'-bis [3- (dialkylamino) alkyl] ureas with 1, ⁇ -dihaloalkanes.
  • This reaction can be represented by the following reaction scheme, the radicals R 1 -R 4 , X and m and n being as defined above:
  • the implementation of the starting products can, for example, in aqueous solution and carried out at temperatures of 20 to 100 ° C. become.
  • the invention used polymers of formula A are obtained in which the amino urea units by hydrocarbon bridges are connected.
  • the degree of polymerization of these polymers is 2-80.
  • the starting materials of the general formulas D and E are known per se.
  • the diaminoureas of the formula D. are described for example in JP 04-198160.
  • the other starting products for the production of the invention are 1, ⁇ -dihaloalkanes general formula E. Individual examples of these 1, ⁇ -dihaloalkanes are 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane.
  • the polymer of formula A is in the bath according to the invention in an amount of 0.1 to 50 g / l, preferably 0.25 to 10 g / l, contain.
  • the degree of polymerization of polymer A plays a role in avoiding blistering and improving Layer thickness distribution is irrelevant; only the required Solubility of the polymer in the galvanic bath sets an upper limit on the degree of polymerization.
  • the bath contains, as a further additive, a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C.
  • R 6 represents a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
  • the amount of this additional additive in the invention Bath is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.
  • quaternary derivatives of a pyridine-3-carboxylic acid Formula 3 or C are known compounds and for example in B. S. James, M Phil thesis, Aston Univ. 1979 or DE 40 38 721.
  • the production of these derivatives is generally carried out by reacting nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.
  • the addition of the further additive B and / or C results in a further improvement of the layer thickness distribution.
  • Another Advantage of adding the derivatives B and C mentioned to the bath according to the invention is to improve the gloss call.
  • baths according to the invention can additionally the additives A, B and / or C mentioned above also other polymers, such as that in the above-mentioned documents mentioned polymers contain.
  • Zinc baths the usual aqueous alkaline cyanide-free baths, as used to deposit zinc or zinc alloy coatings can be used on different substrates. Standard baths of this type are described, for example, in DE 25 25 264 and US 3,884,774.
  • the baths according to the invention contain the usual sources of zinc ions, such as zinc metal, zinc salts and Zinc oxide, but zinc oxide is preferred, that in alkaline Solution is present as zincate.
  • the concentration of zinc in the baths according to the invention is in the usual range for such baths from 0.2 to 20 g / l, preferably 5 to 20 g / l.
  • zinc alloy coatings from the baths according to the invention to be separated then contain the baths a source of additional metal ions.
  • additional metal ions preferably come Cobalt, nickel, manganese and / or iron ions in Consideration.
  • Suitable salts are nickel sulfate, iron sulfate, Cobalt sulfate and manganese chloride.
  • the concentration of metal ions in the invention Baths can vary and amount within a wide range preferably 0.01 to 100 g / l. Because with different Alloy types also have a different alloy content is necessary, for example, to prevent corrosion improve, this concentration is from metal ion to metal ion different.
  • the baths preferably contain zinc in one Amount of 0.2 to 20 g / l, cobalt in an amount of 10 up to 120 mg / l, nickel in an amount of 0.3 to 3 g / l, manganese in an amount of 10 to 100 g / l and iron in an amount from 10 to 120 mg / l. These concentrations refer to the amount of metal ions contained in the bath. Appropriate Conversions provide the quantities of those to be used Salts of these metals.
  • the additional above Contain metal ions If the baths according to the invention the additional above Contain metal ions, then it is useful to the baths complexing agents also matched to these additional metal ions add to the deposition potential control and a common reduction with the existing ones To allow zinc ions.
  • Chelating agents are preferred as such complexing agents.
  • suitable chelating agents are hydroxycarboxylates, such as sodium gluconate, amino alcohols, such as triethanolamine, Polyamines, such as polyethylene diamine, aminocarboxylates, such as EDTA, Aminophosphonates such as amino-tris (methylenephosphonic acid), and polyhydric alcohols, such as sorbitol or sucrose.
  • the chelating agent can be used individually or as a mixture in the invention Baths may be included, the amount of which is preferably in the range is from 2 to 200 g / l.
  • the baths according to the invention contain - like the corresponding ones Prior art baths - a source of hydroxide ions, preferably an alkali hydroxide.
  • a source of hydroxide ions preferably an alkali hydroxide.
  • potassium hydroxide an increase in the gloss of the zinc layer.
  • the baths according to the invention known levelers, such as 3-mercapto-1,2,4-triazole and / or thiourea, with thiourea being preferred.
  • concentration leveling is the usual concentration of zinc baths and is, for example, 0.01 to 0.50 g / l.
  • Other additives aromatic aldehydes are for the baths according to the invention or their bisulfite adducts.
  • Preferred aromatic aldehydes are selected from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures selected from it.
  • These additives their concentration in the range from 0.005 to 1.0 g / l, preferably from 0.01 to 0.50 g / l, lies, act in a manner known per se as brighteners.
  • a particularly preferred example of such Vanillin is the brightener.
  • the invention Bad as a brightener also other substances, such as Substances selected from the group of sulfur compounds, Aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, Proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof, contain.
  • the baths according to the invention can also be water-softening Contain funds, because the addition of such Sensitivity of the bath according to the invention to foreign metal ions, especially calcium and magnesium from tap water, is reduced.
  • water softening Agents are EDTA, sodium silicates and tartaric acid.
  • customary conductive metal substrates coated with zinc or be provided with a zinc alloy Using the baths according to the invention, customary conductive metal substrates coated with zinc or be provided with a zinc alloy.
  • Another object of the invention is therefore a method for the galvanic deposition of zinc coatings or zinc alloy coatings on conventional substrates, which is characterized in that a bath with the above composition is used as the bath.
  • the coatings are preferably deposited at a current density in the range from 0.01 to 10 A / dm 2 and at a temperature in the range from 15 to 45 ° C.
  • the method according to the invention can be used for mass parts for example as a drum electroplating process and Deposition on larger workpieces as a rack plating process be performed.
  • Anodes are used which can be soluble, such as zinc anodes, which also serve as a source of zinc ions, so that on the Zinc deposited by dissolution of zinc on the cathode Anode is recovered.
  • Anodes such as iron anodes, are used, the zinc ions extracted from the electrolyte to others Need to be added again, e.g. under use a zinc dissolving container.
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
  • a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and 30 ° C for 30 minutes.
  • the steel sheet was rinsed and in a commercially available Blue chromating (Corrotriblue, Atotech) chromated.
  • the Chromated sheet had a standard commercially available.
  • the zinc layer showed no tendency to blister, even tempering in a circulating air cabinet at 220 ° C for 30 minutes and then Quenching in tap water at room temperature resulted not chipping.
  • the Hull cell sheet was rinsed and in a commercially available Yellow chromating (Tridur Yellow Liquid, Atotech) chromated.
  • the chromated sheet had a slight iridescence and standard.
  • the layer thickness distribution was according to that described above Test measured, it was 1.30.
  • the zinc layer showed no signs of blistering, not even after tempering in the recirculating air cabinet for 30 minutes 220 ° C and then quenching in tap water from Room temperature.
  • Steel screws were galvanized in a drum at a current density of 0.1-1 A / dm 2 and room temperature.
  • the shiny zinc layer was very even on the screws spread and showed no tendency to blister, not even in the drying cabinet for 30 minutes at 220 ° C and then quenching in water which Room temperature.
  • a steel sheet (5 cm x 5 cm) was deposited at 3 A / dm 2 and 30 ° C for 30 minutes.
  • a uniform, shiny zinc-nickel layer was deposited.
  • the zinc-nickel layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • the Hull cell sheet was rinsed and in a commercially available Black chromating for zinc-iron layers (Tridur Black Liquid ZnFe, Atotech) chromated.
  • the chromated sheet had a very good black color.
  • the layer thickness distribution was according to that described above Test measured, it was 1.50.
  • the zinc-iron layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and room temperature for 30 minutes.
  • a uniform, shiny zinc-iron-cobalt layer was deposited.
  • the zinc-iron-cobalt layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • a Hull cell sheet was deposited at 1 ampere and room temperature for 15 minutes. The Hull cell sheet was rinsed and lightened in 0.3 vol% HNO 3 for 10 s.
  • the layer thickness distribution was according to that described above Test measured; it was 1.41.
  • the manganese incorporation was measured with XRF at the same positions at which the layer thickness was also measured. At 2.8 A / dm 2 , the manganese content was 5.65%; at 0.5 A / dm 2 the manganese content was 7.81%.
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.

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Abstract

An aqueous alkaline cyanide-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces is described, which contains in addition to a source of zinc ions and optionally a source of further metal ions, also hydroxide ions and a polymer of the general formula A that is soluble in the bathas well as optionally conventional additives. The bath may furthermore contain a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and/or a quaternary derivative of a pyridine-3-carboxylic acid of the formula CA process for the galvanic deposition of zinc coatings and zinc alloy coatings using the aforedescribed bath is also described.By using the baths according to the invention it is possible to produce coatings that exhibit a uniform layer thickness combined with a high gloss, and which do not exhibit any tendency to exfoliate.

Description

Zinkabscheidungen aus cyanidischer, alkalischer Lösung dominieren seit vielen Jahren den industriellen Markt. Die immer höheren Auflagen an die Lohngalvaniken bezüglich der Entsorgung alter Zinkelektrolytbäder und die damit einhergehende strenge Kontrolle über das Abwasser führten zu einem verstärkten Interesse an den nicht toxischen, cyanidfreien Zinkelektrolytbädern. Cyanidfreie Zinkelektrolytbäder lassen sich in zwei Badtypen unterteilen, nämlich in schwach saure Zinkelektrolyte (enthaltend Zinkchlorid bzw. Zinksulfat) und alkalische Zinkatelektrolyte.Zinc deposits from cyanide, alkaline solution dominate the industrial market for many years. The always higher requirements for wage electroplating with regard to disposal old zinc electrolyte baths and the accompanying strict control over the wastewater led to an increased Interest in the non-toxic, cyanide-free zinc electrolyte baths. Cyanide-free zinc electrolyte baths can be used divide into two bath types, namely into weakly acidic zinc electrolytes (containing zinc chloride or zinc sulfate) and alkaline Zinkatelektrolyte.

Aus schwach sauren Zinkbädern wird eine gleichmäßig glänzende Zinkschicht abgeschieden, so daß dieses Verfahren schnell einen stärken Marktanteil behaupten konnte. Dieses Verfahren hat jedoch den Nachteil, daß seine Stromausbeute über einen breiten Stromdichtebereich immer 100% beträgt.Weakly acidic zinc baths become evenly shiny Zinc layer deposited, so that this process quickly a could claim stronger market share. This method has the disadvantage, however, that its current efficiency over a wide current density range is always 100%.

Bei Beschichtungsstücken, die eine einfache Form besitzen, mag dies positiv zu bewerten sein, da der Strom ausschließlich zur Abscheidung von Zink verbraucht wird. Doch führt dies bei Beschichtungsteilen, die eine kompliziertere Form besitzen, zu einer dicken Zinkschicht im Bereich hoher Stromdichten und zu sehr dünnen Zinkschichten im Bereich niedriger Stromdichten.For coating pieces that have a simple shape, this may be a positive thing, since the electricity is exclusively is used for the deposition of zinc. But leads this with coating parts that have a more complicated shape have a thick zinc layer in the area of high current densities and too thin zinc layers in the lower area Current densities.

Das Verhältnis von Zinkschichtdicke im hohem Stromdichtebereich zur Zinkschichtdicke im niedrigen Stromdichtebereich wird als Schichtdickeverteilung bezeichnet und sollte im Idealfall 1 betragen. Zink- und Zinklegierungsbäder müssen immer höheren Ansprüchen genüge tun. Dementsprechend soll eine Zinkschicht auf dem zu beschichtenden Gegenstand überall die gleiche Schichtdicke besitzen und einen hohen Glanz aufweisen. Eine gute Schichtdickeverteilung kann erreicht werden durch das Senken der Stromausbeute im hohen Stromdichtebereich, während die Stromausbeute im niedrigen Stromdichtebereich aufrechterhalten bleibt.The ratio of zinc layer thickness in the high current density range to the zinc layer thickness in the low current density range is called layer thickness distribution and should ideally 1. Zinc and zinc alloy baths always have to meet higher demands. Accordingly, a Zinc coating on the object to be coated everywhere have the same layer thickness and a high gloss. A good layer thickness distribution can be achieved by lowering the current yield in the high current density range, while the current efficiency in the low current density range is maintained.

Diese Art des Angleichens der Zinkschichtdicke über einen breiten Stromdichtebereich ist bisher nur durch die Abscheidung von Zink aus alkalischen, cyanidfreien Elektrolyten gelungen. Alkalische Zinkgalvanisierbäder sind allgemein auf der Basis einer wäßrigen Lösung von Zinkationen in Natriumoder Kaliumhydroxid aufgebaut. Durch die Verwendung dieser Bäder ist es möglich, Zinkschichten mit hohem Glanz abzuscheiden (DE 25 25 264, US 3 884 774), jedoch weisen diese Zinkschichten keine gleichmäßige Schichtdickeverteilung auf.This type of adjustment of the zinc layer thickness over one wide current density range is so far only through the deposition of zinc from alkaline, cyanide-free electrolytes. Alkaline zinc plating baths are common on the basis of an aqueous solution of zinc ions in sodium or Potassium hydroxide built up. By using this It is possible for bathrooms to deposit zinc layers with a high gloss (DE 25 25 264, US 3 884 774), however, these have Zinc layers have no uniform layer thickness distribution.

Im Stand der Technik wurden schon zahlreiche Vorschläge gemacht, um die Schichtdickeverteilung der Zinkschichten durch Zugabe geeigneter Additive zu verbessern (US 5 405 523, US 5 435 898, DE 195 09 713, US 4 030 987).Numerous proposals have already been made in the prior art around the layer thickness distribution of the zinc layers To improve the addition of suitable additives (US 5 405 523, US 5 435 898, DE 195 09 713, US 4 030 987).

Bei den bislang vorgeschlagenen Additiven besteht nachteiligerweise jedoch die Neigung, daß die galvanisch erzeugten Zinkschichten abplatzen. Die Bildung von Zink- bzw. Zinklegierungsabplatzern von dem beschichteten Substrat, oft auch als Blasenbildung bezeichnet, stellt bei der Verwendung von cyanidfreien, alkalischen Bädern ein schwerwiegendes Problem dar, wobei noch keine gesicherten Erkenntnisse hinsichtlich dem Einfluß der jeweils verwendeten Zusätze auf die Blasenbildung vorliegen. Die Erscheinung der Blasenbildung wirkt sich als besonders nachteilig aus, weil sie oft erst nach Wochen auftritt und somit häufig zu Reklamationen bei der Beschichterindustrie führen kann. The additives proposed so far are disadvantageous however, the tendency that the galvanically generated Flake off zinc layers. The formation of zinc or zinc alloy flaking of the coated substrate, often too referred to as blistering when using Cyanide-free, alkaline baths are a serious problem represents, although no confirmed knowledge regarding the influence of the additives used on the blistering available. The appearance of the blistering works turned out to be particularly disadvantageous because it often takes weeks occurs and therefore often complaints to the coating industry can lead.

In der US 5 405 523 wird als Zusatz in Zinklegierungsbädern eine Substanz mit dem Handelsnamen Mirapol A 15 und ähnliche Verbindungen beschrieben, die den Glanz von Zinklegierungen verbessern soll.In US 5 405 523 is used as an additive in zinc alloy baths a substance with the trade name Mirapol A 15 and the like Compounds described that have the sheen of zinc alloys should improve.

In der US 5 435 898 wird als Zusatz für Zink- und Zinklegierungsgalvanisierbäder eine ähnliche Verbindung mit dem Handelsnamen Mirapol WT beschrieben, die ebenfalls die Schichtdickeverteilung stark verbessern soll.In US 5 435 898 is used as an additive for zinc and zinc alloy plating baths a similar connection with the trade name Mirapol WT also described the layer thickness distribution should greatly improve.

In der DE 195 09 713 wird ein Diallylammonium-Schwefeldioxid-Copolymer als Zusatz für Zink- und Zinklegierungsgalvanisierbäder beschrieben, welches der Zinkschicht eine gleichmäßige Schichtdicke verleihen soll.DE 195 09 713 describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths described which of the zinc layer is uniform Should give layer thickness.

In der US 4 030 987 wird ebenfalls ein Diallylammonium-Schwefeldioxid-Copolymer als Zusatz für Zink- und Zinklegierungsgalvanisierbäder beschrieben, welches der Zinkschicht eine gleichmäßige Schichtdicke verleihen soll.US Pat. No. 4,030,987 also describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths described which one of the zinc layers should give uniform layer thickness.

Es hat sich herausgestellt, daß die oben beschriebenen Zusätze zu nachteiligen Folgen bei der Abscheidung der Zinkschicht, insbesondere zu einer Blasenbildung der Überzüge, führen.It has been found that the additives described above adverse consequences in the deposition of the zinc layer, especially blistering of the coatings, to lead.

Der Erfindung liegt daher die Aufgabe zugrunde, die Mängel des Stands der Technik zu überwinden und insbesondere ein wäßriges cyanidfreies alkalisches Bad zur galvanischen Abscheidung von Zink- und Zinklegierungsüberzügen bereitzustellen, mit dem Überzüge aus Zink- oder Zinklegierungen erhalten werden können, bei denen auch nach längerer Lagerung keine Tendenz zur Bildung von Abplatzern besteht. Dabei sollen die Vorteile dieser Bäder hinsichtlich einer gleichmäßigen Schichtdicke eines hohen Glanzes und der Gleichmäßigkeit der Legierungskomponenten im Überzug über einen breiten Bereich von Stromdichten aufrechterhalten werden. The invention is therefore based on the object, the shortcomings to overcome the prior art and in particular a aqueous cyanide-free alkaline bath for galvanic deposition to provide zinc and zinc alloy coatings, obtained with the coatings of zinc or zinc alloys can be in which even after long storage none There is a tendency to form flaking. The should Advantages of these baths in terms of a uniform Layer thickness of a high gloss and the uniformity of the Alloy components in the coating over a wide range of current densities are maintained.

Es wurde nun gefunden, daß der Zusatz einer speziellen Art von quaternären Ammoniumpolymeren zu wäßrigen alkalischen cyanidfreien Zinkbädern die Schichtdickeverteilung der erhaltenen Überzüge verbessert und die Blasenbildung der Überzüge verringert.It has now been found that the addition of a special species from quaternary ammonium polymers to aqueous alkaline cyanide-free zinc baths the layer thickness distribution of the obtained Coatings improved and the blistering of the coatings reduced.

Gegenstand der Erfindung ist daher ein wäßriges alkalisches cyandifreies Bad zur galvanischen Abscheidung von Zink- öder Zinklegierungsüberzügen auf Substratoberflächen, das dadurch gekennzeichnet ist, daß es

  • (a) eine Zinkionenquelle und gegebenenfalls eine Quelle für weitere Metallionen,
  • (b) Hydroxidionen und
  • (c) ein in dem Bad lösliches Polymeres der allgemeinen Formel A
    Figure 00040001
    worin m den Wert 2 oder 3 hat, n einen Wert von mindestens 2 hat, R1, R2, R3 und R4, die gleich oder verschieden sein können, jeweils für Methyl, Ethyl, Hydroxyethyl stehen, p einen Wert im Bereich von 3 bis 12 hat und X- für Cl-, Br- und/oder I- steht
    sowie gegebenenfalls
  • (d) übliche Additive enthält.
    • The invention therefore relates to an aqueous alkaline, cyano-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces, which is characterized in that it
  • (a) a source of zinc ions and optionally a source of further metal ions,
  • (b) hydroxide ions and
  • (c) a polymer of the general formula A soluble in the bath
    Figure 00040001
    wherein m has the value 2 or 3, n has a value of at least 2, R 1 , R 2 , R 3 and R 4 , which may be the same or different, each represent methyl, ethyl, hydroxyethyl, p a value in the range has from 3 to 12 and X - stands for Cl - , Br - and / or I -
    and if necessary
  • (d) contains common additives.

    • Das in dem erfindungsgemäßen Bad enthaltene lösliche Polymere der allgemeinen Formel A kann durch Umsetzung von N,N'-Bis[3-(dialkylamino)alkyl]harnstoffen mit 1,ω-Dihalogenalkanen erhalten werden. Diese Umsetzung kann durch folgendes Reaktionsschema dargestellt werden, wobei die Reste R1-R4, X sowie m und n wie oben definiert sind:

    Figure 00050001
    The soluble polymer of the general formula A contained in the bath according to the invention can be obtained by reacting N, N'-bis [3- (dialkylamino) alkyl] ureas with 1, ω-dihaloalkanes. This reaction can be represented by the following reaction scheme, the radicals R 1 -R 4 , X and m and n being as defined above:
    Figure 00050001

    Die Umsetzung der Ausgangsprodukte kann beispielsweise in wäßriger Lösung und bei Temperaturen von 20 bis 100°C durchgeführt werden. Auf diese Weise können die erfindungsgemäß verwendeten Polymere der Formel A erhalten werden, bei denen die Aminoharnstoffeinheilen durch Kohlenwasserstoffbrücken verbunden sind. Der Polymerisationsgrad dieser Polymere beträgt 2-80. Die Ausgangsstoffe der allgemeinen Formeln D und E sind an sich bekannt. Die Diaminoharnstoffe der Formel D werden beispielsweise in der JP 04-198160 beschrieben.The implementation of the starting products can, for example, in aqueous solution and carried out at temperatures of 20 to 100 ° C. become. In this way, the invention used polymers of formula A are obtained in which the amino urea units by hydrocarbon bridges are connected. The degree of polymerization of these polymers is 2-80. The starting materials of the general formulas D and E are known per se. The diaminoureas of the formula D. are described for example in JP 04-198160.

    Die weiteren Ausgangsprodukte für die Herstellung der erfindungsgemäß verwendeten Polymeren sind 1,ω-Dihalogenalkane der allgemeinen Formel E. Einzelbeispiele für diese 1,ω-Dihalogenalkane sind 1,3-Dichlorpropan, 1,4-Dichlorbutan, 1,5-Dichlorpentan, 1,6-Dichlorhexan. The other starting products for the production of the invention The polymers used are 1, ω-dihaloalkanes general formula E. Individual examples of these 1, ω-dihaloalkanes are 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane.

    Das Polymere der Formel A ist in dem erfindungsgemäßen Bad in einer Menge von 0,1 bis 50 g/l, vorzugsweise 0,25 bis 10 g/l, enthalten. Der Polymerisationsgrad des Polymeren A spielt für die Vermeidung der Blasenbildung und die Verbesserung der Schichtdickeverteilung keine Rolle; lediglich die erforderliche Löslichkeit des Polymeren in dem galvanischen Bad setzt dem Polymerisationsgrad eine obere Grenze.The polymer of formula A is in the bath according to the invention in an amount of 0.1 to 50 g / l, preferably 0.25 to 10 g / l, contain. The degree of polymerization of polymer A plays a role in avoiding blistering and improving Layer thickness distribution is irrelevant; only the required Solubility of the polymer in the galvanic bath sets an upper limit on the degree of polymerization.

    Gemäß einer bevorzugten Ausführungsform der Erfindung enthält das Bad als weiteres Additiv ein quaternäres Derivat einer Pyridin-3-carbonsäure der Formel B und/oder ein quaternäres Derivat einer Pyridin-3-carbonsäure der Formel C

    Figure 00060001
    Figure 00060002
    worin R6 für einen gesättigten oder ungesättigten, aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen steht.According to a preferred embodiment of the invention, the bath contains, as a further additive, a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C.
    Figure 00060001
    Figure 00060002
    wherein R 6 represents a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.

    Die Menge dieses zusätzlichen Additivs in dem erfindungsgemäßen Bad beträgt 0,005 bis 0,5 g/l, vorzugsweise 0,01 bis 0,2 g/l.The amount of this additional additive in the invention Bath is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.

    Die als weitere Additive in dem erfindungsgemäßen Bad verwendeten quaternären Derivate einer Pyridin-3-carbonsäure der Formel 3 oder C sind an sich bekannte Verbindungen und beispielsweise in B. S. James, M Phil thesis, Aston Univ. 1979 bzw. DE 40 38 721 beschrieben. Die Herstellung dieser Derivate erfolgt im allgemeinen durch Umsetzung von Nicotinsäure mit aliphatischen, aromatischen oder araliphatischen Halogenwasserstoffen.The used as further additives in the bath according to the invention quaternary derivatives of a pyridine-3-carboxylic acid Formula 3 or C are known compounds and for example in B. S. James, M Phil thesis, Aston Univ. 1979 or DE 40 38 721. The production of these derivatives is generally carried out by reacting nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.

    Der Zusatz des weiteren Additivs B und/oder C ergibt eine weitere Verbesserung der Schichtdickeverteilung. Als weiterer Vorteil des Zusatzes der genannten Derivate B und C zu dem erfindungsgemäßen Bad ist die Verbesserung des Glanzes zu nennen.The addition of the further additive B and / or C results in a further improvement of the layer thickness distribution. As another Advantage of adding the derivatives B and C mentioned to the bath according to the invention is to improve the gloss call.

    Schließlich können die erfindungsgemäßen Bäder zusätzlich zu den obengenannten Additiven A, B und/oder C auch weitere Polymere, wie beispielsweise die in den obengenannten Druckschriften genannten Polymere, enthalten.Finally, the baths according to the invention can additionally the additives A, B and / or C mentioned above also other polymers, such as that in the above-mentioned documents mentioned polymers contain.

    Abgesehen von dem erfindungsgemäß erfolgenden Zusatz des Polymeren der allgemeinen Formel A sowie gegebenenfalls des quaternären Derivats einer Pyridin-3-carbonsäure der Formel B und/oder C entsprechen die erfindungsgemäßen cyanidfreien Zinkbäder den üblichen wäßrigen alkalischen cyanidfreien Bädern, wie sie zur Abscheidung von Zink- oder Zinklegierungsüberzügen auf verschiedenen Substraten verwendet werden. Standardbäder dieses Typs werden beispielsweise in DE 25 25 264 und US 3 884 774 beschrieben.Except for the addition of the polymer which is carried out according to the invention of the general formula A and optionally the quaternary derivative of a pyridine-3-carboxylic acid of the formula B. and / or C correspond to the cyanide-free according to the invention Zinc baths the usual aqueous alkaline cyanide-free baths, as used to deposit zinc or zinc alloy coatings can be used on different substrates. Standard baths of this type are described, for example, in DE 25 25 264 and US 3,884,774.

    So enthalten die erfindungsgemäßen Bäder die üblichen Zinkionenquellen, wie beispielsweise Zinkmetall, Zinksalze und Zinkoxid, wobei aber Zinkoxid bevorzugt wird, das in alkalischer Lösung als Zinkat vorliegt.The baths according to the invention contain the usual sources of zinc ions, such as zinc metal, zinc salts and Zinc oxide, but zinc oxide is preferred, that in alkaline Solution is present as zincate.

    Die Konzentration des Zinks in den erfindungsgemäßen Bädern liegt in dem für derartige Bäder üblichen Bereich von 0,2 bis 20 g/l vorzugsweise 5 bis 20 g/l.The concentration of zinc in the baths according to the invention is in the usual range for such baths from 0.2 to 20 g / l, preferably 5 to 20 g / l.

    Wenn aus den erfindungsgemäßen Bädern Überzüge aus Zinklegierungen abgeschieden werden sollen, dann enthalten die Bäder eine Quelle für weitere Metallionen. Als solche kommen vorzugsweise Kobalt-, Nickel-, Mangan- und/oder Eisenionen in Betracht. Vorzugsweise werden als Quellen für diese zusätzlichen Metallionen Salze der entsprechenden Metalle, vorzugsweise der oben beschriebenen Metalle, gegebenenfalls auch im Gemisch, eingesetzt.If zinc alloy coatings from the baths according to the invention to be separated, then contain the baths a source of additional metal ions. As such, preferably come Cobalt, nickel, manganese and / or iron ions in Consideration. Preferably be used as sources for these additional Metal ion salts of the corresponding metals, preferably of the metals described above, optionally also in Mixture used.

    Einzelbeispiele geeigneter Salze sind Nickelsulfat, Eisensulfat, Kobaltsulfat und Manganchlorid.Individual examples of suitable salts are nickel sulfate, iron sulfate, Cobalt sulfate and manganese chloride.

    Die Konzentration der Metallionen in den erfindungsgemäßen Bädern kann innerhalb eines weiten Bereichs variieren und beträgt vorzugsweise 0,01 bis 100 g/l. Da bei unterschiedlichen Legierungstypen auch ein unterschiedlicher Legierungsanteil erforderlich ist, um beispielsweise den Korrosionsschutz zu verbessern, ist diese Konzentration von Metallion zu Metallion verschieden. Vorzugsweise enthalten die Bäder Zink in einer Menge von 0,2 bis 20 g/l, Kobalt in einer Menge von 10 bis 120 mg/l, Nickel in einer Menge von 0,3 bis 3 g/l, Mangan in einer Menge von 10 bis 100 g/l und Eisen in einer Menge von 10 bis 120 mg/l. Diese Konzentrationen beziehen sich auf die in dem Bad enthaltene Menge an Metallionen. Entsprechende Umrechnungen liefern die Mengen der jeweils einzusetzenden Salze dieser Metalle.The concentration of metal ions in the invention Baths can vary and amount within a wide range preferably 0.01 to 100 g / l. Because with different Alloy types also have a different alloy content is necessary, for example, to prevent corrosion improve, this concentration is from metal ion to metal ion different. The baths preferably contain zinc in one Amount of 0.2 to 20 g / l, cobalt in an amount of 10 up to 120 mg / l, nickel in an amount of 0.3 to 3 g / l, manganese in an amount of 10 to 100 g / l and iron in an amount from 10 to 120 mg / l. These concentrations refer to the amount of metal ions contained in the bath. Appropriate Conversions provide the quantities of those to be used Salts of these metals.

    Wenn die erfindungsgemäßen Bäder die obengenannten zusätzlichen Metallionen enthalten, dann ist es zweckmäßig, den Bädern auch auf diese zusätzlichen Metallionen abgestimmte Komplexbildner zuzusetzen, um die Abscheidungspotentiale zu steuern und um eine gemeinsame Reduktion mit den vorhandenen Zinkionen zu ermöglichen.If the baths according to the invention the additional above Contain metal ions, then it is useful to the baths complexing agents also matched to these additional metal ions add to the deposition potential control and a common reduction with the existing ones To allow zinc ions.

    Als solche Kcmplexbildner werden Chelatbildner bevorzugt. Beispiele für geeignete Chelatbildner sind Hydroxycarboxylate, wie Natriumgluconat, Aminoalkohole, wie Triethanolamin, Polyamine, wie Polyethylendiamin, Aminocarboxylate, wie EDTA, Aminophosphonate, wie Amino-tris(methylenphosphonsäure), und mehrwertige Alkohole, wie Sorbit oder Saccharose. Der Chelatbildner kann einzeln oder im Gemisch in den erfindungsgemäßen Bädern enthalten sein, wobei dessen Menge vorzugsweise im Bereich von 2 bis 200 g/l liegt.Chelating agents are preferred as such complexing agents. Examples of suitable chelating agents are hydroxycarboxylates, such as sodium gluconate, amino alcohols, such as triethanolamine, Polyamines, such as polyethylene diamine, aminocarboxylates, such as EDTA, Aminophosphonates such as amino-tris (methylenephosphonic acid), and polyhydric alcohols, such as sorbitol or sucrose. The chelating agent can be used individually or as a mixture in the invention Baths may be included, the amount of which is preferably in the range is from 2 to 200 g / l.

    Die erfindungsgemäßen Bäder enthalten - wie die entsprechenden Bäder des Stands der Technik - eine Hydroxidionenquellen, vorzugsweise ein Alkalihydroxid. Üblicherweise wird Natriumhydroxid in einer Konzentration von 80 bis 250 g/l verwendet; jedoch sind auch andere Alkali- und Erdalkalimetallhydroxide sowie Mischungen davon für den Einsatz in dem erfindungsgemäßen Bad geeignet. So zeigt sich durch Verwendung von z.B. Kaliumhydroxid eine Erhöhung des Glanzes der Zinkschicht.The baths according to the invention contain - like the corresponding ones Prior art baths - a source of hydroxide ions, preferably an alkali hydroxide. Usually sodium hydroxide used in a concentration of 80 to 250 g / l; however, other alkali and alkaline earth metal hydroxides are also and mixtures thereof for use in the invention Bathroom suitable. Thus, by using e.g. potassium hydroxide an increase in the gloss of the zinc layer.

    Weiterhin können die erfindungsgemäßen Bäder bekannte Einebner, wie 3-Mercapto-1,2,4-triazol und/oder Thioharnstoff enthalten, wobei Thioharnstoff bevorzugt wird. Die Konzentration des Einebners ist die übliche Konzentration von Zinkbädern und beträgt beispielsweise 0,01 bis 0,50 g/l. Weitere Zusätze für die erfindungsgemäßen Bäder sind aromatische Aldehyde oder deren Bisulfitaddukte.Furthermore, the baths according to the invention known levelers, such as 3-mercapto-1,2,4-triazole and / or thiourea, with thiourea being preferred. The concentration leveling is the usual concentration of zinc baths and is, for example, 0.01 to 0.50 g / l. Other additives aromatic aldehydes are for the baths according to the invention or their bisulfite adducts.

    Bevorzugte aromatische Aldehyde werden aus der Gruppe 4-Hydroxybenzaldehyd, 4-Hydroxy-3-methoxybenzaldehyd (Vanillin), 3,4-Dimethoxybenzaldehyd, 3,4-Methylendioxybenzaldehyd, 2-Hydroxybenzaldehyd und 4-Hydroxybenzaldehyd oder Gemischen davon ausgewählt. Diese Additive, deren Konzentration im Bereich von 0,005 bis 1,0 g/l, vorzugsweise von 0,01 bis 0,50 g/l, liegt, wirken in an sich bekannter Weise als Glanzbildner. Ein besonders bevorzugtes Beispiel für einen derartigen Glanzbildner ist Vanillin. Daneben kann das erfindungsgemäße Bad als Glanzbildner auch andere Substanzen, wie beispielsweise Substanzen, ausgewählt aus der Gruppe Schwefelverbindungen, Aldehyde, Ketone, Amine, Polyvinylalkohol, Polyvinylpyrrolidon, Proteine oder Reaktionsprodukte von Halogenhydrinen mit aliphatischen oder aromatischen Aminen, Polyaminen oder heterocyclischen Stickstoffverbindungen und Gemische davon, enthalten.Preferred aromatic aldehydes are selected from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures selected from it. These additives, their concentration in the range from 0.005 to 1.0 g / l, preferably from 0.01 to 0.50 g / l, lies, act in a manner known per se as brighteners. A particularly preferred example of such Vanillin is the brightener. In addition, the invention Bad as a brightener also other substances, such as Substances selected from the group of sulfur compounds, Aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, Proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof, contain.

    Schließlich können die erfindungsgemäßen Bäder noch wasserenthärcende Mittel enthalten, da durch derartige Zusätze die Empfindlichkeit des erfindungsgemäßen Bades gegenüber Fremdmetallionen, insbesondere Calcium und Magnesium aus Leitungswasser, verringert wird. Beispiele für derartige wasserenthärtende Mittel sind EDTA, Natriumsilikate und Weinsäure.Finally, the baths according to the invention can also be water-softening Contain funds, because the addition of such Sensitivity of the bath according to the invention to foreign metal ions, especially calcium and magnesium from tap water, is reduced. Examples of such water softening Agents are EDTA, sodium silicates and tartaric acid.

    Unter Verwendung der erfindungsgemäßen Bäder können übliche leitende Substrate aus Metall mit einem Überzug aus Zink oder einer Zinklegierung versehen werden.Using the baths according to the invention, customary conductive metal substrates coated with zinc or be provided with a zinc alloy.

    Ein weiterer Gegenstand der Erfindung ist daher ein Verfahren zur galvanischen Abscheidung von Zinküberzügen oder von Zinklegierungsüberzügen auf üblichen Substraten, das dadurch gekennzeichnet ist, daß als Bad ein Bad mit der obigen Zusammensetzung verwendet wird. Vorzugsweise erfolgt bei dem erfindungsgemäßen Verfahren die Abscheidung der Überzüge bei einer Stromdichte im Bereich von 0,01 bis 10 A/dm2 sowie bei einer Temperatur im Bereich von 15 bis 45°C.Another object of the invention is therefore a method for the galvanic deposition of zinc coatings or zinc alloy coatings on conventional substrates, which is characterized in that a bath with the above composition is used as the bath. In the method according to the invention, the coatings are preferably deposited at a current density in the range from 0.01 to 10 A / dm 2 and at a temperature in the range from 15 to 45 ° C.

    Das erfindungsgemäße Verfahren kann bei Anwendung für Massenteile beispielsweise als Trommelgalvanisierverfahren und zur Abscheidung auf größeren Werkstücken als Gestellgalvanisierverfahren durchgeführt werden. Dabei werden Anoden verwendet, die löslich sein können, wie beispielsweise Zinkanoden, die gleichzeitig als Zinkionenquelle dienen, damit das auf der Kathode abgeschiedene Zink durch Auflösung von Zink an der Anode zurückgewonnen wird. Andererseits können auch unlösliche Anoden, wie beispielsweise Eisenanoden, eingesetzt werden, wobei die dem Elektrolyten entzogenen Zinkionen auf andere Weise wieder zugesetzt werden müssen, z.B. unter Verwendung eines Zinklösebehälters. The method according to the invention can be used for mass parts for example as a drum electroplating process and Deposition on larger workpieces as a rack plating process be performed. Anodes are used which can be soluble, such as zinc anodes, which also serve as a source of zinc ions, so that on the Zinc deposited by dissolution of zinc on the cathode Anode is recovered. On the other hand, even insoluble ones Anodes, such as iron anodes, are used, the zinc ions extracted from the electrolyte to others Need to be added again, e.g. under use a zinc dissolving container.

    Wie bei der galvanischen Abscheidung üblich, kann auch das erfindungsgemäße Verfahren unter Lufteinblasung, mit Warenbewegung oder ohne Bewegung, betrieben werden, ohne daß sich hierdurch irgendwelche Nachteile für die erhaltenen Überzüge ergeben.As usual with galvanic deposition, this can also be done Method according to the invention with air injection, with goods movement or without movement, without being hereby any disadvantages for the coatings obtained result.

    Die Erfindung wird in den Beispielen erläutert.The invention is illustrated in the examples.

    1. In den Beispielen angewendete Testverfahren1. Test procedures used in the examples 1.1 Blasen-Schnelltest zur Beurteilung der erfindungsgemäß verwendeten polymeren Additive1.1 Rapid bubble test to assess the invention used polymeric additives

    Um die Erscheinung der Blasenbildung zu beobachten, wurde ein eigener Blasen-Schnelltest entwickelt, der die Phänomene aus der Produktion reproduzierbar im Labor nachstellt. Dementsprechend wurde dieser Test so gewählt, daß er alle Eigenschaften, die zu Blasenbildung führen, in sich vereint. Dies ist im besonderen die Beschichtung unter Druckspannung, unter starker Lufteinblasung, bei Raumtemperatur, unter Anwesenheit blasenfördernder Substanzen und mit hoher Schichtdicke. Es ist gelungen, die Erscheinung der Blasenbildung innerhalb von Stunden nach der Beschichtung bei solchen Elektrolyten, die Additive enthalten, die zu Blasenbildung neigen, hervorzurufen.To observe the appearance of blistering, a developed his own rapid bladder test that identified the phenomena reproducibly reproduces production in the laboratory. Accordingly this test was chosen to have all the properties which lead to blistering, united in themselves. This is in particular the coating under compressive stress, under strong air blowing, at room temperature, with presence bubble-promoting substances and with a high layer thickness. It has managed to reduce the appearance of blistering within Hours after coating with such electrolytes that Contain additives that tend to cause blistering.

    Bei dem Blasen-Schnelltest wurde eine Vorrichtung gemäß der Figur sowie folgender Grundelektrolyt verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 1,2 g/l Diallylammonium-Schwefeldioxid-Copolymer (DE 195 09 713, US 4 030 987)
  • 0,19 g/l Umsetzungsprodukt Epichlorhydrin mit Dimethylaminopropylamin (US 3 884 774)
  • 9,2 mg/l N-Benzyl-pyridinium-3-carboxylat
  • 1,25 g/l Trilon D (Trinatriumsalz der Hydroxyethylethylendiamintriessigsäure; Fa. BASF, 40%ige Lösung)
  • 0,1 g/l 3-Mercaptotriazol
    • In the rapid bubble test, a device according to the figure and the following basic electrolyte were used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 1.2 g / l diallylammonium sulfur dioxide copolymer (DE 195 09 713, US 4 030 987)
  • 0.19 g / l reaction product epichlorohydrin with dimethylaminopropylamine (US 3 884 774)
  • 9.2 mg / l N-benzyl-pyridinium-3-carboxylate
  • 1.25 g / l Trilon D (trisodium salt of hydroxyethylethylenediamine triacetic acid; from BASF, 40% solution)
  • 0.1 g / l 3-mercaptotriazole

    • 900 ml der Lösung werden in ein breites 1l-Becherglas gefüllt (Figur). Als Anode dient eine umhüllte Zn-anode. Es wird bei starker Lufteinblasung (1 l/min) gearbeitet, welche aus einem L-förmigen Plastikrohr mit 6 kleinen Löchern (3 auf jeder Seite) unterhalb der eingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gebogen und 35 min bei 2,8 A beschichtet. Das Bad sollte eine Temperatur von 20°C besitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig gerade gebogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werden.900 ml of the solution are poured into a wide 1 liter beaker (figure). A coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.

    1.2 Schichtdickeverteilungstest1.2 Layer thickness distribution test

    Es wird folgender Grundelektrolyt verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
    • The following basic electrolyte is used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3

    • 250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte eine Temperatur von 28°C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren Rand und 2,5 cm vom rechten und linken seitlichen Rand bei hoher (2,8 A/dm2) und niedriger Stromdichte (0,5 A/dm2). Gemessen wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickeverteilung entspricht dem Verhältnis der gemessenen Werte für die Schichtdicke bei hoher (hcd) und niedriger Stromdichte (lcd).
    Schichtdickeverteilung = hcd:lcd    250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. The layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ). XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible. The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
    Layer thickness distribution = hcd: lcd

    2. Herstellungsbeispiele für die erfindungsgemäß verwendeten Polymeren2. Production examples for those used according to the invention polymers 2.1 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Methyl; m = 3; p = 42.1 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 4

    20,0 g (86,8 mmol) N,N'-Bis[3-(dimethylamino)propyl]harnstoff werden in 200 ml Wasser gelöst. Dann werden 11,13 g (86,8 mmol) 1,4-Dichlorbutan zugegeben. Nun wird 8 h unter Rühren auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.20.0 g (86.8 mmol) N, N'-bis [3- (dimethylamino) propyl] urea are dissolved in 200 ml of water. Then 11.13 g (86.8 mmol) 1,4-dichlorobutane added. Now 8 hours with stirring heated to 80 ° C. After cooling, an aqueous one is obtained Polymer solution.

    2.2 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Methyl; m = 3; p = 32.2 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 3

    10,0 g (43,4 mmol) N,N'-Bis[3-(dimethylamino)propyl]harnstoff werden in 100 ml Wasser gelöst. Dann werden 4,95 g (43,4 mmol) 1,3-Dichlorpropan zugegeben. Nun wird 7 h unter Rühren auf 90°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.10.0 g (43.4 mmol) of N, N'-bis [3- (dimethylamino) propyl] urea are dissolved in 100 ml of water. Then 4.95 g (43.4 mmol) 1,3-dichloropropane added. Now 7 h with stirring heated to 90 ° C. After cooling, an aqueous one is obtained Polymer solution.

    2.3 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Methyl; m = 3; p = 62.3 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 6

    20,0 g (86,8 mmol) N,N'-Bis[3-(dimethylamino)propyl]harnstoff und 13,46 g (86,6 mmol) 1,6-Dichlorhexan werden in 50 ml Wasser 17 h auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung. 20.0 g (86.8 mmol) N, N'-bis [3- (dimethylamino) propyl] urea and 13.46 g (86.6 mmol) of 1,6-dichlorohexane in 50 ml of water Heated to 80 ° C for 17 h. After cooling you get one aqueous polymer solution.

    2.4 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Methyl; m = 3; p = 52.4 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 5

    20,0 g (86,8 mmol) N,N'-Bis[3-(dimethylamino)propyl]harnstoff werden in 200 ml Wasser gelöst. Dann werden 12,36 g (86,8 mmol) 1,5-Dichlorpentan zugegeben. Nun wird 17 h unter Rühren auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.20.0 g (86.8 mmol) N, N'-bis [3- (dimethylamino) propyl] urea are dissolved in 200 ml of water. Then 12.36 g (86.8 mmol) 1,5-dichloropentane added. Now 17 h with stirring heated to 80 ° C. After cooling, an aqueous one is obtained Polymer solution.

    2.5 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Ethyl; m = 3; p = 32.5 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = ethyl; m = 3; p = 3

    5,00 g (17,3 mmol) N,N'-Bis[3-(diethylamino)propyl]harnstoff werden in 10 ml Wasser gelöst. Dann werden 1,95 g (17,3 mmol) 1,3-Dichlorpropan zugegeben. Nun wird 16 h unter Rühren auf 100°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.5.00 g (17.3 mmol) N, N'-bis [3- (diethylamino) propyl] urea are dissolved in 10 ml of water. Then 1.95 g (17.3 mmol) 1,3-dichloropropane added. Now open for 16 h with stirring Heated to 100 ° C. After cooling, an aqueous polymer solution is obtained.

    2.6 Herstellung eines Polymeren, bei dem R1, R2, R3, R4 = Methyl; m = 2; p = 32.6 Preparation of a polymer in which R 1 , R 2 , R 3 , R 4 = methyl; m = 2; p = 3

    5,00 g (24,7 mmol) N,N'-Bis[2-(dimethylamino)ethy]harnstoff werden in 10 ml Wasser gelöst. Dann werden 2,79 g (24,7 mmol) 1,3-Dichlorpropan zugegeben. Nun wird 24 h unter Rühren auf 90°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.5.00 g (24.7 mmol) N, N'-bis [2- (dimethylamino) ethy] urea are dissolved in 10 ml of water. Then 2.79 g (24.7 mmol) 1,3-dichloropropane added. Now open for 24 h with stirring 90 ° C heated. After cooling, an aqueous polymer solution is obtained.

    3. Herstellungsbeispiel des quaternären Derivates der Pyridin-3-carbonsäure3. Production example of the quaternary derivative of pyridine-3-carboxylic acid

    Synthese von N,N'-p-Xylylen-bis-(pyridinium-3-carboxylat) (Formel C, R6 = p-Xylylen):
    5,00 g (39,80 mmol) Nicotinsäure werden in 20 ml n-Butanol bei Raumtemperatur vorgelegt, dann werden 5,41 g (19,90 mmol) α,α-'Dibrom-p-xylol bei Raumtemperatur zugegeben. Dann wird 16 h unter Rühren auf 70°C erhitzt, das ausgefallene Produkt abfiltriert, mit 10 ml n-Butanol gewaschen und getrocknet. Man erhält 9,85 g weiße Kristalle, die bei 220°C unter Zersetzung schmelzen.    Synthesis of N, N'-p-xylylene-bis- (pyridinium-3-carboxylate) (Formula C, R 6 = p-xylylene):
    5.00 g (39.80 mmol) of nicotinic acid are placed in 20 ml of n-butanol at room temperature, then 5.41 g (19.90 mmol) of α, α-'dibromo-p-xylene are added at room temperature. The mixture is then heated to 70 ° C. with stirring for 16 h, the precipitated product is filtered off, washed with 10 ml of n-butanol and dried. 9.85 g of white crystals are obtained, which melt at 220 ° C. with decomposition.

    4. Arwendungsbeispiele4. Examples of use Beispiele 1-6:Examples 1-6:

    Es wird jeweils ein Bad mit folgender Zusammensetzung verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 1 g/l Zusatz nach Herstellungsbeispiel 2.1 - 2.6 (berechnet als Festsubstanz)
    • A bath with the following composition is used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 1 g / l additive according to production example 2.1 - 2.6 (calculated as solid substance)

    • 250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte eine Temperatur von 28°C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren Rand und 2,5 cm vom rechten und linken seitlichen Rand bei hoher (2,8 A/dm2) und niedriger Stromdichte (0,5 A/dm2). Gemessen wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickeverteilung entspricht dem Verhältnis der gemessenen Werte für die Schichtdicke bei hoher (hcd) und niedriger Stromdichte (lcd).
    Schichtdickeverteilung = hcd:lcd    250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. The layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ). XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible. The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
    Layer thickness distribution = hcd: lcd

    Die erhaltenen Ergebnisse sind in folgender Tabelle 1 zusammengestellt: Verwendetes Polymeres Schichtdicke hcd Schichtdicke lcd Schichtdickeverteitung R1, R2, R3, R4 = Methyl;
    m = 3; p = 4     6,11 µm 5,38 µm 1,14     R1, R2, R3, R4 = Methyl;
    m = 3; p = 3     6,19 µm 4,15 µm 1,49     R1, R2, R3, R4 = Methyl;
    m = 3; p = 6     4,71 µm 3,50 µm 1,35     R1, R2, R3, R4 = Methyl;
    m = 3; p = 5     5,02 µm 4,03 µm 1,25     R1, R2, R3, R4 = Ethyl;
    m = 3; p = 3     0,76 µm 0,55 µm 1,37     R1, R2, R3, R4 = Methyl;
    m = 2; p = 3     7,70 µm 3,53 µm 2,18     The results obtained are summarized in the following Table 1: Polymer used Layer thickness hcd Layer thickness lcd Schichtdickeverteitung R 1 , R 2 , R 3 , R 4 = methyl;
    m = 3; p = 4     6.11 µm 5.38 µm 1.14     R 1 , R 2 , R 3 , R 4 = methyl;
    m = 3; p = 3     6.19 µm 4.15 µm 1.49     R 1 , R 2 , R 3 , R 4 = methyl;
    m = 3; p = 6     4.71 µm 3.50 µm 1.35     R 1 , R 2 , R 3 , R 4 = methyl;
    m = 3; p = 5     5.02 µm 4.03 µm 1.25     R 1 , R 2 , R 3 , R 4 = ethyl;
    m = 3; p = 3     0.76 µm 0.55 µm 1.37     R 1 , R 2 , R 3 , R 4 = methyl;
    m = 2; p = 3     7.70 µm 3.53 µm 2.18

    Beispiele 7 - 12Examples 7-12

    Es wird ein Bad mit folgender Zusammensetzung verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 1,2 g/l Diallylammonium-Schwefeldioxid-Copolymer (DE 195 09 713, US 4 030 987)
  • 0,19 g/l Umsetzungsprodukt Epichlorhydrin mit Dimethylaminopropylamin (US 3 884 774)
  • 9,2 mg/l N-Benzyl-pyridinium-3-carboxylat
  • 1,25 g/l Trilon D (Trinatriumsalz der Hydroxyethylethylendiamintriessigsäure; Fa. BASF, 40%ige Lösung)
  • 0,1 g/l 3-Mercaptotriazol
  • 1 g/l Zusatz nach Herstellungsbeispiel 2.1 - 2.6 (berechnet als Festsubstanz)
    • A bath with the following composition is used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 1.2 g / l diallylammonium sulfur dioxide copolymer (DE 195 09 713, US 4 030 987)
  • 0.19 g / l reaction product epichlorohydrin with dimethylaminopropylamine (US 3 884 774)
  • 9.2 mg / l N-benzyl-pyridinium-3-carboxylate
  • 1.25 g / l Trilon D (trisodium salt of hydroxyethylethylenediamine triacetic acid; from BASF, 40% solution)
  • 0.1 g / l 3-mercaptotriazole
  • 1 g / l additive according to production example 2.1 - 2.6 (calculated as solid substance)

    • 900 ml der Lösung werden in ein breites 1l-Becherglas gefüllt (Figur). Als Anode dient eine umhüllte Zn-anode. Es wird bei starker Lufteinblasung (1 l/min) gearbeitet, welche aus einem L-förmigen Plastikrohr mit 6 kleinen Löchern (3 auf jeder Seite) unterhalb der eingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gebogen und 35 min bei 2,8 A beschichtet. Das Bad sollte eine Temperatur von 20°C besitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig gerade gebogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werden.900 ml of the solution are poured into a wide 1 liter beaker (figure). A coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.

    Die erhaltenen Ergebnisse sind in Tabelle 2 zusammengestellt: Verwendetes Polymeres Blasenbildung R1, R2, R3, R4 = Methyl; m = 3; p = 4 Keine R1, R2, R3, R4 = Methyl; m = 3; p = 3 Keine R1, R2, R3, R4 = Methyl; m = 3; p = 6 Keine R1, R2, R3, R4 = Methyl; m = 3; p = 5 Keine R1, R2, R3, R4 = Ethyl; m = 3; p = 4 Keine R1, R2, R3, R4 = Methyl; m = 2; p = 3 Keine The results obtained are summarized in Table 2: Polymer used blistering R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 4 No R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 3 No R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 6 No R 1 , R 2 , R 3 , R 4 = methyl; m = 3; p = 5 No R 1 , R 2 , R 3 , R 4 = ethyl; m = 3; p = 4 No R 1 , R 2 , R 3 , R 4 = methyl; m = 2; p = 3 No

    Beispiel 13:Example 13:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zinkschicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 10 g/l ZnO
  • 120 g/l KOH
  • 1 g/l Zusatz nach Herstellungsbeispiel 2.1 (berechnet als Festsubstanz)
  • 20 mg/l N-Benzyl-pyridinium-3-carboxylat
  • 60 mg/l Thioharnstoff
  • 40 mg/l Anisaldehyd (Aktivsubstanz als Bisulfitaddukt)
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition:
  • 10 g / l ZnO
  • 120 g / l KOH
  • 1 g / l additive according to production example 2.1 (calculated as solid substance)
  • 20 mg / l N-benzyl-pyridinium-3-carboxylate
  • 60 mg / l thiourea
  • 40 mg / l anisaldehyde (active substance as bisulfite adduct)

    • Ein Stahlblech (5 cm x 5 cm) wurde bei 2 A/dm2 und 30°C 30 Minuten lang abgeschieden.A steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and 30 ° C for 30 minutes.

    Das Stahlblech wurde gespült und in einer handelsüblichen Blauchromatierung (Corrotriblue, Atotech) chromatiert. Das chromatierte Blech besaß handelsüblichen Standard. Die Zinkschicht zeigte keine Tendenz zur Blasenbildung, selbst Temperung im Umluftschrank bei 220°C für 30 Minuten und anschließendes Abschrecken in Leitungswasser mit Raumtemperatur führte nicht zu Abplatzern.The steel sheet was rinsed and in a commercially available Blue chromating (Corrotriblue, Atotech) chromated. The Chromated sheet had a standard commercially available. The zinc layer showed no tendency to blister, even tempering in a circulating air cabinet at 220 ° C for 30 minutes and then Quenching in tap water at room temperature resulted not chipping.

    Beispiel 14:Example 14:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zinkschicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 12,5 g/l ZnO
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 2 g/l Zusatz nach Herstellungsbeispiel 2.2 (berechnet als Festsubstanz)
  • 25 mg/l N-Benzyl-pyridinium-3-carboxylat
  • 100 mg/l 3-Mercaptotriazol
  • 50 mg/l p-Hydroxybenzaldehyd (Aktivsubstanz als Bisulfitaddukt)
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition:
  • 12.5 g / l ZnO
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 2 g / l additive according to production example 2.2 (calculated as solid substance)
  • 25 mg / l N-benzyl-pyridinium-3-carboxylate
  • 100 mg / l 3-mercaptotriazole
  • 50 mg / l p-hydroxybenzaldehyde (active substance as bisulfite adduct)

    • Ein Hullzellblech wurde bei 1 Ampere und Raumtemperatur 15 Minuten lang abgeschieden.A Hull cell sheet became 15 at 1 ampere and room temperature Deposited for minutes.

    Das Hullzellblech wurde gespült und in einer handelsüblichen Gelbchromatierung (Tridur Gelb Liquid, Atotech) chromatiert. Das chromatierte Blech besaß eine geringfügige Irisierung und handelsüblichen Standard.The Hull cell sheet was rinsed and in a commercially available Yellow chromating (Tridur Yellow Liquid, Atotech) chromated. The chromated sheet had a slight iridescence and standard.

    Die Schichtdickeverteilung wurde nach dem oben beschriebenen Test gemessen, sie betrug 1,30.The layer thickness distribution was according to that described above Test measured, it was 1.30.

    Die Zinkschicht zeigte keine Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluftschrank bei 220°C und anschließendem Abschrecken in Leitungswasser von Raumtemperatur.The zinc layer showed no signs of blistering, not even after tempering in the recirculating air cabinet for 30 minutes 220 ° C and then quenching in tap water from Room temperature.

    Beispiel 15:Example 15:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zinkschicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 18,5 g/l ZnO
  • 115 g/l NaOH
  • 1,5 g/l Zusatz nach Herstellungsbeispiel 2.5 (berechnet als Festsubstanz)
  • 25 mg/l N,N'-p-Xylylen-bis-(pyridinium-3-carboxylat)
  • 70 mg/l Thioharnstoff
  • 60 mg/l Vanillin (Aktivsubstanz als Bisulfitaddukt)
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition:
  • 18.5 g / l ZnO
  • 115 g / l NaOH
  • 1.5 g / l additive according to production example 2.5 (calculated as solid substance)
  • 25 mg / l N, N'-p-xylylene-bis- (pyridinium-3-carboxylate)
  • 70 mg / l thiourea
  • 60 mg / l vanillin (active substance as bisulfite adduct)

    • Schrauben aus Stahl wurden in einer Trommel bei einer Stromdichte von 0,1 - 1 A/dm2 und Raumtemperatur galvanisiert.Steel screws were galvanized in a drum at a current density of 0.1-1 A / dm 2 and room temperature.

    Anschließend wurde gespült und in einer handelsüblichen Gelbchromatierung (Tridur Gelb Liquid, Atotech) chromatiert. Die chromatierten Schrauben besaßen handelsüblichen Standard. It was then rinsed and in a commercially available yellow chromating (Tridur Yellow Liquid, Atotech) chromated. The Chromated screws were standard.

    Die glänzende Zinkschicht war auf den Schrauben sehr gleichmäßig verteilt und zeigte keine Tendenz zur Blasenbildung, selbst nicht bei Temperung für 30 Minuten auf 220°C im Trokkenschrank und anschließendem Abschrecken in Wasser, welches Raumtemperatur besitzt.The shiny zinc layer was very even on the screws spread and showed no tendency to blister, not even in the drying cabinet for 30 minutes at 220 ° C and then quenching in water which Room temperature.

    Beispiel 16:Example 16:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Nickel-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 10 g/l ZnO
  • 8 g/l NiSO4 6 H2O
  • 120 g/l NaOH
  • 30 g/l Triethanolamin
  • 1,5 g/l Zusatz nach Herstellungsbeispiel 2.4 (berechnet als Festsubstanz)
  • 50 mg/l Veretriumaldehyd (Aktivsubstanz als Bisulfitaddukt)
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-nickel layer. The electrolyte had the following composition:
  • 10 g / l ZnO
  • 8 g / l NiSO 4 6 H 2 O
  • 120 g / l NaOH
  • 30 g / l triethanolamine
  • 1.5 g / l additive according to preparation example 2.4 (calculated as solid substance)
  • 50 mg / l veretrium aldehyde (active substance as bisulfite adduct)

    • Ein Stahlblech (5 cm x 5 cm) wurde bei 3 A/dm2 und 30°C 30 Minuten lang abgeschieden. Es wurde eine gleichmäßige, glänzende Zink-Nickel-Schicht abgeschieden.A steel sheet (5 cm x 5 cm) was deposited at 3 A / dm 2 and 30 ° C for 30 minutes. A uniform, shiny zinc-nickel layer was deposited.

    Die Zink-Nickel-Schicht zeigte keine Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluftschrank bei 220°C und anschließendem Abschrecken in Leitungswasser von Raumtemperatur.The zinc-nickel layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.

    Beispiel 17:Example 17:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Eisen-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 15 g/ ZnO
  • 120 g/l NaOH
  • 60 mg/l Eisen (als FeSO4 ·7 H2O)
  • 25 g/l Natriumglukonat
  • 2 g/l Zusatz nach Herstellungsbeispiel 2.2 (berechnet als Festsubstanz)
  • 200 mg/l 3-Mercaptotriazol
  • 40 mg/l Heliotropin (Aktivsubstanz als Bisulfitaddukt)
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron layer. The electrolyte had the following composition:
  • 15 g / ZnO
  • 120 g / l NaOH
  • 60 mg / l iron (as FeSO 4 · 7 H 2 O)
  • 25 g / l sodium gluconate
  • 2 g / l additive according to production example 2.2 (calculated as solid substance)
  • 200 mg / l 3-mercaptotriazole
  • 40 mg / l heliotropin (active substance as bisulfite adduct)

    • Ein Hullzellblech wurde bei Ampere und Raumtemperatur 15 Minuten lang abgeschieden.A Hull cell sheet became 15 at amperes and room temperature Deposited for minutes.

    Das Hullzellblech wurde gespült und in einer handelsüblichen Schwarzchromatierung für Zink-Eisen-Schichten (Tridur Schwarz Liquid ZnFe, Atotech) chromatiert. Das chromatierte Blech besaß eine sehr gute Schwarzfärbung.The Hull cell sheet was rinsed and in a commercially available Black chromating for zinc-iron layers (Tridur Black Liquid ZnFe, Atotech) chromated. The chromated sheet had a very good black color.

    Die Schichtdickeverteilung wurde nach dem oben beschriebenen Test gemessen, sie betrug 1,50.The layer thickness distribution was according to that described above Test measured, it was 1.50.

    Die Zink-Eisen-Schicht zeigte keine Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluftschrank bei 220°C und anschließendem Abschrecken in Leitungswasser von Raumtemperatur.The zinc-iron layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.

    Beispiel 18:Example 18:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Eisen-Kobalt-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 12,5 g/l ZnO
  • 110 g/l NaOH
  • 30 mg/l Eisen (als FeSO4 · 7 H2O)
  • 30 mg/l Kobalt (als CoSO4 · 7 H2O)
  • 25 g/l Natriumglukonat
  • 2 g/l Zusatz nach Herstellungsbeispiel 2.3 (berechnet als Festsubstanz)
  • 100 mg/l 3-Mercaptotriazol
  • 25 mg/l N-Benzyl-pyridinium-3-carboxylat
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron-cobalt layer. The electrolyte had the following composition:
  • 12.5 g / l ZnO
  • 110 g / l NaOH
  • 30 mg / l iron (as FeSO 4 · 7 H 2 O)
  • 30 mg / l cobalt (as CoSO 4 · 7 H 2 O)
  • 25 g / l sodium gluconate
  • 2 g / l additive according to production example 2.3 (calculated as solid substance)
  • 100 mg / l 3-mercaptotriazole
  • 25 mg / l N-benzyl-pyridinium-3-carboxylate

    • Ein Stahlblech (5 cm x 5 cm) wurde bei 2 A/dm2 und Raumtemperatur 30 Minuten lang abgeschieden. Es wurde eine gleichmäßige, glänzende Zink-Eisen-Kobalt-Schicht abgeschieden.A steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and room temperature for 30 minutes. A uniform, shiny zinc-iron-cobalt layer was deposited.

    Die Zink-Eisen-Kobalt-Schicht zeigte keine Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluftschrank bei 220°C und anschließendem Abschrecken in Leitungswasser von Raumtemperatur.The zinc-iron-cobalt layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.

    Beispiel 19:Example 19:

    Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Mangan-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:

  • 15 g/l ZnO
  • 120 g/l NaOH
  • 40 g/l MnCl2 · 4 H2O
  • 40 g/l Natriumglukonat
  • 4 g/l Ascorbinsäure
  • 2 g/l Zusatz nach Herstellungsbeispiel 2.1 (berechnet als Festsubstanz)
  • 100 mg/l 3-Mercapto-1,2,4-triazol
  • 20 mg/l N-Benzyl-pyridinium-3-carboxylat
    • An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-manganese layer. The electrolyte had the following composition:
  • 15 g / l ZnO
  • 120 g / l NaOH
  • 40 g / l MnCl 2 .4 H 2 O
  • 40 g / l sodium gluconate
  • 4 g / l ascorbic acid
  • 2 g / l additive according to production example 2.1 (calculated as solid substance)
  • 100 mg / l 3-mercapto-1,2,4-triazole
  • 20 mg / l N-benzyl-pyridinium-3-carboxylate

    • Ein Hullzellblech wurde bei 1 Ampere und Raumtemperatur 15 Minuten lang abgeschieden. Das Hullzellblech wurde gespült und 10 s in 0,3 Vol% HNO3 aufgehellt.A Hull cell sheet was deposited at 1 ampere and room temperature for 15 minutes. The Hull cell sheet was rinsed and lightened in 0.3 vol% HNO 3 for 10 s.

    Die Schichtdickeverteilung wurde nach dem oben beschriebenen Test gemessen; sie betrug 1,41.The layer thickness distribution was according to that described above Test measured; it was 1.41.

    Der Manganeinbau wurde an den gleichen Positionen mit XRF gemessen, an denen auch die Schichtdickemessung erfolgte. Bei 2,8 A/dm2 betrug der Gehalt an Mangan 5,65%; bei 0,5 A/dm2 betrug der Mangangehalt 7,81%.The manganese incorporation was measured with XRF at the same positions at which the layer thickness was also measured. At 2.8 A / dm 2 , the manganese content was 5.65%; at 0.5 A / dm 2 the manganese content was 7.81%.

    Vergleichsbeispiele 1 - 4:Comparative Examples 1-4:

    Es wird ein Bad mit folgender Zusammensetzung verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 1 g/l Zusatz der in den genannten Druckschriften beschriebenen Additive (berechnet als Festsubstanz)
    • A bath with the following composition is used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 1 g / l addition of the additives described in the publications mentioned (calculated as solid substance)

    • 250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte eine Temperatur von 28°C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren Rand und 2,5 cm vom rechten und linken seitlichen Rand bei hoher (2,8 A/dm2) und niedriger Stromdichte (0,5 A/dm2). Gemessen wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickeverteilung entspricht dem Verhältnis der gemessenen Werte für die Schichtdicke bei hoher (hcd) und niedriger Stromdichte (lcd).
    Schichtdickeverteilung = hcd:lcd    250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. The layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ). XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible. The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
    Layer thickness distribution = hcd: lcd

    Die erhaltenen Ergebnisse sind in folgender Tabelle 3 zusammengestellt. Verwendetes Polymeres Schichtdicke hcd Schichtdicke lcd Schichtdickeverteilung Umsetzungsprodukt Epichlorhydrin mit Imidazol
    DE 25 25 264     11,0 µm 3,80 µm 2,90     Umsetzungsprodukt Epichlorhydrin mit Dimethylaminopropylamin
    US 3 884 774     8,65 µm 2,70 µm 3,20     Mirapol WT
    US 5 435 898     5,89 µm 4,17 µm 1,41     Diallylammonium-Schwefeldioxid-Copolymer
    DE 195 09 713     7,10 µm 2,58 µm 2,75     The results obtained are summarized in Table 3 below. Polymer used Layer thickness hcd Layer thickness lcd Film thickness distribution Reaction product epichlorohydrin with imidazole
    DE 25 25 264     11.0 µm 3.80 µm 2.90     Reaction product epichlorohydrin with dimethylaminopropylamine
    US 3,884,774     8.65 µm 2.70 µm 3.20     Mirapol WT
    US 5,435,898     5.89 µm 4.17 µm 1.41     Diallylammonium sulfur dioxide copolymer
    DE 195 09 713     7.10 µm 2.58 µm 2.75

    Vergleichsbeispiele 5 - 6:Comparative Examples 5-6:

    Es wird ein Bad mit folgender Zusammensetzung verwendet:

  • 10 g/l Zn
  • 130 g/l NaOH
  • 20 g/l Na2CO3
  • 1,2 g/l Diallylammonium-Schwefeldioxid-Copolymer (DE 195 09 713, US 4 030 987)
  • 0,19 g/l Umsetzungsprodukt Epichlorhydrin mit Dimethylaminopropylamin (US 3 884 774)
  • 9,2 mg/l N-Benzyl-pyridinium-3-carboxylat
  • 1,25 g/l Trilon D (Fa. BASF, 40%ige Lösung)
  • 0,1 g/l 3-Mercaptotriazol
  • 1 g/l Zusatz der in den genannten Druckschriften beschriebenen Additive (berechnet als Festsubstanz)
    • A bath with the following composition is used:
  • 10 g / l Zn
  • 130 g / l NaOH
  • 20 g / l Na 2 CO 3
  • 1.2 g / l diallylammonium sulfur dioxide copolymer (DE 195 09 713, US 4 030 987)
  • 0.19 g / l reaction product epichlorohydrin with dimethylaminopropylamine (US 3 884 774)
  • 9.2 mg / l N-benzyl-pyridinium-3-carboxylate
  • 1.25 g / l Trilon D (from BASF, 40% solution)
  • 0.1 g / l 3-mercaptotriazole
  • 1 g / l addition of the additives described in the publications mentioned (calculated as solid substance)

    • 900 ml der Lösung werden in ein breites 11-Becherglas gefüllt (Figur). Als Anode dient eine umhüllte Zn-anode. Es wird bei starker Lufteinblasung (1 l/min) gearbeitet, welche aus einem L-förmigen Plastikrohr mit 6 kleinen Löchern (3 auf jeder Seite) unterhalb der eingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gebogen und 35 min bei 2,8 A beschichtet. Das Bad sollte eine Temperatur von 20°C besitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HNO3 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig gerade gebogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werden.900 ml of the solution are poured into a wide 11-beaker (figure). A coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures. The sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.

    Die erhaltenen Ergebnisse sind in Tabelle 4 zusammengestellt: Verwendetes Polymeres Blasenbildung Mirapol WT
    US 5 435 898     Stark innerhalb von 3 d     Diallylammonium-Schwefeldioxid-Copolymer
    DE 195 09 713     Sofort sehr stark     The results obtained are summarized in Table 4: Polymer used blistering Mirapol WT
    US 5,435,898     Strong within 3 d     Diallylammonium sulfur dioxide copolymer
    DE 195 09 713     Immediately very strong

    Claims (32)

    1. An aqueous, alkaline, cyanide-free bath for electrodeposition of zinc or zinc alloy coatings on substrate surfaces, wherein it contains
      (a) a zinc ion source and optionally a source of further metal ions,
      (b) hydroxide ions and
      (c) a polymer of the general formula A soluble in the bath
      Figure 00320001
      in which m has the value 2 or 3, n a value of at least 2, R1, R2, R3 and R4, which may be identical or different, each denote methyl, ethyl or hydroxyethyl, p has a value in the range from 3 to 12 and X- denotes Cl-, Br- and/or I-
      optionally together with
      (d) conventional additives.
    2. A bath according to claim 1, characterised in that in the general formula A n has a value in the range from 2 to 80, preferably from 3 to 20.
    3. A bath according to claim 1 or 2, characterised in that the polymer of formula A soluble in the bath is present in an amount of from 0.1 to 50 g/l, preferably 0.25 to 10 g/l.
    4. A bath according to any one of claims 1 to 3, characterised in that it further contains a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and/or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C
      Figure 00330001
      Figure 00330002
      wherein R6 denotes a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical with 1 to 12 carbon atoms.
    5. A bath according to claim 4, characterised in that the quaternary derivative of pyridine-3-carboxylic acid of the formula B and/or C is present in an amount of from 0.005 to 0.5 g/l, preferably of from 0.01 to 0.2 g/l.
    6. A bath according to any one of claims 1 to 5, characterised in that the zinc ion source is zinc oxide.
    7. A bath according to any one of claims 1 to 6, characterised in that the concentration of zinc ions amounts to from 0.2 to 20 g/l.
    8. A bath according to any one of claims 1 to 7, characterised in that the further metal ions are cobalt, nickel, manganese and/or iron ions.
    9. A bath according to claim 8, characterised in that the zinc is present in an amount of from 0.2 to 20 g/l, the cobalt in an amount of from 10 to 120 mg/l, the nickel in an amount of from 0.3 to 3 g/l, the manganese in an amount of from 10 to 100 g/l and the iron in an amount of from 10 to 120 mg/l.
    10. A bath according to any one of claims 1 to 9, characterised in that the alkali is sodium hydroxide.
    11. A bath according to claim 10, characterised in that the sodium hydroxide is present in an amount of from 80 to 250 g/l.
    12. A bath according to any one of claims 1 to 9, characterised in that the alkali is potassium hydroxide.
    13. A bath according to claim 12, characterised in that the potassium hydroxide is present in an amount of from 80 to 250 g/l.
    14. A bath according to any one of claims 1 to 13, characterised in that it contains as additive a brightener from the group containing sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinylpyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof.
    15. A bath according to claim 14, characterised in that it contains as additive an aromatic aldehyde or a bisulfite adduct thereof.
    16. A bath according to claim 15, characterised in that the aromatic aldehyde is selected from the group comprising 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures thereof.
    17. A bath according to claim 15 or 16, characterised in that the aromatic aldehyde is present in an amount of from 0.005 to 1.0 g/l, preferably of from 0.01 to 0.50 g/l.
    18. A bath according to any one of claims 1 to 17, characterised in that it further contains a complexing agent or a water-softening agent.
    19. A bath according to claim 18, characterised in that it contains a chelating agent as complexing agent.
    20. A bath according to claim 19, characterised in that the chelating agent is selected from the group comprising hydroxycarboxylates, aminoalcohols, polyamines; aminocarboxylates, aminophosphonates and polyhydric alcohols together with mixtures thereof.
    21. A bath according to claim 18 or 19, characterised in that the chelating agent is present in an amount of from 2 to 200 g/l.
    22. A bath according to any one of claims 1 to 21, characterised in that it further contains a sulfur compound as levelling agent.
    23. A bath according to claim 22, characterised in that it contains 3-mercapto-1,2,4-triazole and/or thiourea as levelling agent.
    24. A bath according to claim 22 or 23, characterised in that it contains the sulfur compound in an amount of from 0.01 to 0.50 g/l.
    25. A process for electrodeposition of zinc coatings or zinc alloy coatings, characterised in that the bath used is a bath according to claims 1 to 24.
    26. A process according to claim 25, characterised in that the bath is operated at a current density of from 0.01 to 10 A/dm2.
    27. A process according to claim 25 or 26, characterised in that the bath is operated at temperatures of from 15 to 45°C.
    28. A process according to any one of claims 25 to 27, characterised in that coatings are deposited on a conductive substrate using a drum plating process.
    29. A process according to any one of claims 25 to 27, characterised in that the coatings are deposited on a conductive substrate using a rack plating process.
    30. A process according to any one of claims 25 to 29, characterised in that a zinc coating is deposited.
    31. A process according to any one of claims 25 to 29, characterised in that a zinc alloy coating is deposited.
    32. A process according to claim 31, characterised in that a coating of a zinc alloy with one or more metals from the group cobalt, nickel, manganese or iron is deposited.
    EP99936607A 1998-09-02 1999-07-26 Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings Expired - Lifetime EP1114206B1 (en)

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    DE19840019A DE19840019C1 (en) 1998-09-02 1998-09-02 Aqueous alkaline cyanide-free bath for the electrodeposition of zinc or zinc alloy coatings and method
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