EP0355525A1 - Process for producing coatings on zinc - Google Patents

Process for producing coatings on zinc Download PDF

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Publication number
EP0355525A1
EP0355525A1 EP89114427A EP89114427A EP0355525A1 EP 0355525 A1 EP0355525 A1 EP 0355525A1 EP 89114427 A EP89114427 A EP 89114427A EP 89114427 A EP89114427 A EP 89114427A EP 0355525 A1 EP0355525 A1 EP 0355525A1
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Prior art keywords
nickel
coatings
zinc
ions
produced
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German (de)
French (fr)
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EP0355525B1 (en
Inventor
Kazuhiko Nihon Parkerizing Co. Ltd. Mori
Toshi Nihon Parkerizing Co. Ltd. Miyawaki
Ishii Hitoshi
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a method for producing coatings from nickel or nickel compounds on surfaces of zinc or zinc alloys by means of aqueous alkaline solutions containing nickel compounds, and to the use thereof for preparing the surfaces for phosphating.
  • the treatment liquids predominantly contain organic chelating agents as complexing agents for metals.
  • organic chelating agents due to inadequate deposition of metal or metal compounds, it is difficult to obtain coatings with a sufficiently high corrosion resistance. If the treatment is carried out at a high pH for a longer period of time so that a sufficiently high metal deposition takes place, problems arise in so far as not only the adhesion of the coatings to the metal surface is low, but also a possibly subsequently applied lacquer film is of poor quality.
  • the object of the invention is to provide a method which does not have the disadvantages of the abovementioned methods and which, when treating surfaces made of zinc or zinc alloys, leads to coatings which have a sufficiently high layer weight and satisfactory adhesion to the metal surface.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the coatings are produced by means of a solution which contains at least 20 ppm of nickel2 mol ions and at least 6 times the molar amount of NH3 per mol of nickel and has a pH value less than 11.
  • the coatings of nickel or nickel compounds produced by the process according to the invention have a sufficiently high layer weight so that dissolution of zinc from the metal surface is largely suppressed in the case of subsequent treatments.
  • the concentration of nickel2+ ions in the treatment liquid is below 20 ppm, a sufficient layer weight of the coating is not reached.
  • the stoichiometric ratio of NH3 to nickel2+ ions is less than 6, similar results are observed as in the case of a too low Ni2 Konzentration concentration. If the concentration of Ni2+ ions and NH3 exceeds 100 g / l or 300 g / l, problems arise when using the method insofar as crystallization of nickel compounds and evaporation of ammonia cannot be avoided and therefore changes in the composition of the treatment liquid occur.
  • the coatings are produced by means of a solution which contains 5 to 50 g / l of Ni2+ ions and 10 to 100 g / l of NH3.
  • the coatings are applied by means of a solution whose temperature is in the range from room temperature to 50 ° C.
  • the treatment solution is preferably applied by dipping or spraying. A generation of the coatings by electrolytic means is not excluded.
  • the process according to the invention is particularly advantageously applicable to the pretreatment of the surfaces of zinc or zinc alloys for the subsequent phosphating.
  • the phosphate coatings formed are of high quality with regard to adhesive strength and corrosion resistance.
  • painting, in particular electro-dipping can follow.
  • the inventive method is particularly suitable for the production of black workpieces.
  • Tables 1 and 2 below contain the treatment conditions for carrying out Examples 1 to 9 and Comparative Examples 1 to 4.
  • the treatment liquid was applied in each case by immersion.
  • the treatment temperature was 40 ° C, except for Comparative Example 3, in which the temperature of the treatment liquid was 25 ° C.
  • Nickel2+ ions were added to the treatment liquid in the form of nickel sulfate in the event that the pH was adjusted with sulfuric acid or as nickel chloride when the pH was adjusted with hydrochloric acid.
  • Ammonia was introduced in the form of a 28% by weight aqueous solution. If necessary, ammonium sulfate or ammonium chloride was also added.
  • Table 1 Treatment conditions example Substrate Main components pH adjustment pH Duration of treatment Phosphating 1 EG (1) Ni2+ 10 g / l H2SO4 9.5 20 sec. Yes NH3 50 g / l 2nd GI (1) Ni2+ 20 g / l - 10.0 30 sec.
  • the test results show that the method according to the invention markedly improves the resistance of the treated sheets with regard to paint detachment. This is based on the excellent phosphatability of the nickel and / or nickel compound coatings produced and on the adhesion of the lacquer applied subsequently.
  • the advantage of the invention lies in particular in the fact that the excellent results are obtained with a comparatively simple treatment liquid, which is also chemically, i.e. can be achieved without the use of electricity. In particular, this ensures simple monitoring of the treatment liquid.
  • the process is also associated with low costs.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

Bei einem Verfahren zur Erzeugung von haftfesten, gut phosphatierbaren Überzügen aus Nickel und/oder Nickelverbindungen auf Oberflächen von Zink oder Zinklegierungen arbeitet man mit einer Lösung, die mindestens 20 ppm Ni²<+>-Ionen und pro Mol Nickel mindestens die 6-fache molare Menge NH3 enthält und einen pH-Wert kleiner als 11 aufweist. Verzugsweise kommen Lösungen mit einem Gehalt von 5 bis 50 g/l Ni²<+>-Ionen und 10 bis 100g/l NH3, die bei einer Temperatur im Bereich von Raumtemperatur bis 50°C appliziert wurden, zum Einsatz.In a method for producing adherent, readily phosphatable coatings of nickel and / or nickel compounds on surfaces of zinc or zinc alloys, a solution is used which contains at least 20 ppm of Ni 2 <+> ions and at least 6 times the molar amount per mole of nickel Contains NH3 and has a pH value less than 11. Solutions with a content of 5 to 50 g / l Ni 2 <+> ions and 10 to 100 g / l NH 3, which were applied at a temperature in the range from room temperature to 50 ° C., are preferably used.

Description

Die Erfindung betrifft ein Verfahren zur Erzeugung von Überzügen aus Nickel oder Nickelverbindungen auf Oberflächen von Zink oder Zinklegierungen mittels Nickelverbindungen enthaltender wäßriger alkalischer Lösungen sowie dessen Anwendung zwecks Vorbereitung der Oberflächen für die Phosphatierung.The invention relates to a method for producing coatings from nickel or nickel compounds on surfaces of zinc or zinc alloys by means of aqueous alkaline solutions containing nickel compounds, and to the use thereof for preparing the surfaces for phosphating.

Es ist bekannt, daß der Korrosionswiderstand von Oberflächen aus Zink oder Zinklegierungen verbessert werden kann, wenn Überzüge von Nickel oder Nickelverbindungen auf diesen Oberflächen erzeugt werden. So ist es bekannt, Lösungen anzuwenden, die ein Metall aus der Gruppe Nickel, Kobalt, Chrom, Antimon, Titan oder Mangan sowie einen Chelatbildner, wie Glyzin, enthalten (Japanische Patentpublikation Sho 57-45 833 (1982) ). Weiterhin ist es bekannt, mit Überzugsmitteln, die Silber, Magnesium, Kadmium, Aluminium, Zinn, Titan, Antimon, Molybdän, Chrom, Cer, Wolfram, Mangan, Kobalt, Eisen-III oder Eisen-II und Nickel sowie einen Komplexbildner in einer Menge, die ausreicht, das Metallion in gelöstem Zustand zu halten, zu arbeiten (Japanische Patentpublikation Sho 43-12 974 (1968) ). Im letztgenannten Fall soll der pH-Wert der Behandlungsflüssigkeit höher als 11 sein.It is known that the corrosion resistance of surfaces made of zinc or zinc alloys can be improved if coatings of nickel or nickel compounds are produced on these surfaces. It is known to use solutions which contain a metal from the group consisting of nickel, cobalt, chromium, antimony, titanium or manganese and a chelating agent such as glycine (Japanese patent publication Sho 57-45 833 (1982)). Furthermore, it is known to use coating agents containing silver, magnesium, cadmium, aluminum, tin, titanium, antimony, molybdenum, chromium, cerium, tungsten, manganese, cobalt, iron-III or iron-II and nickel as well as a complexing agent in an amount sufficient to keep the metal ion in a dissolved state to work (Japanese Patent Publication Sho 43-12 974 (1968)). In the latter case, the pH of the treatment liquid should be higher than 11.

In den vorgenannten Fällen enthalten die Behandlungsflüssigkeiten überwiegend organische Chelatbildner als Komplexbildner für Metalle. Hierbei ist es infolge einer unzulänglichen Abscheidung von Metall oder Metallverbindungen schwierig, Überzüge mit einem hinreichend hohen Korrosionswiderstand zu erhalten. Sofern die Behandlung bei einem hohen pH-Wert für eine längere Zeitdauer vorgenommen wird, damit eine hinreichend hohe Metallabscheidung erfolgt, treten Probleme insofern auf, als nicht nur die Haftung der Überzüge auf der Metalloberfläche gering ist, sondern auch ein eventuell nachträglich aufgebrachter Lackfilm von geringer Qualität ist.In the aforementioned cases, the treatment liquids predominantly contain organic chelating agents as complexing agents for metals. Here, due to inadequate deposition of metal or metal compounds, it is difficult to obtain coatings with a sufficiently high corrosion resistance. If the treatment is carried out at a high pH for a longer period of time so that a sufficiently high metal deposition takes place, problems arise in so far as not only the adhesion of the coatings to the metal surface is low, but also a possibly subsequently applied lacquer film is of poor quality.

Darüber hinaus schafft die Entwicklung von Ammoniakgasen Probleme am Arbeitsplatz bzw. macht apparativ aufwendige Vorrichtung erforderlich.In addition, the development of ammonia gases creates problems in the workplace or requires expensive equipment.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der vorgenannten Verfahren nicht aufweist, und bei der Behandlung von Oberflächen aus Zink oder Zinklegierungen zu Überzügen führt, die ein ausreichend hohes Schichtgewicht und eine zufriedenstellende Haftung auf der Metalloberfläche aufweist.The object of the invention is to provide a method which does not have the disadvantages of the abovementioned methods and which, when treating surfaces made of zinc or zinc alloys, leads to coatings which have a sufficiently high layer weight and satisfactory adhesion to the metal surface.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Überzüge mittels einer Lösung erzeugt, die mindestens 20 ppm Nickel²⁺-Ionen und pro Mol Nickel mindestens die 6-fache molare Menge NH₃ enthält und einen pH-Wert kleiner als 11 aufweist.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the coatings are produced by means of a solution which contains at least 20 ppm of nickel² mol ions and at least 6 times the molar amount of NH₃ per mol of nickel and has a pH value less than 11.

Zwar ist es aus der bereits oben genannten Japanischen Patentpublikation Sho 43-12 974 (1968) bekannt, mit wäßrigen Behandlungsflüssigkeiten zu arbeiten, die einen Nickel/Ammonium-Komplex enthalten, jedoch arbeiten diese Behandlungsflüssigkeiten bei einem pH-Wert oberhalb 11, so daß die bereits genannten Nachteile auftreten.Although it is known from the above-mentioned Japanese patent publication Sho 43-12 974 (1968) to work with aqueous treatment liquids which contain a nickel / ammonium complex, these treatment liquids work at a pH above 11, so that the disadvantages already mentioned occur.

Die nach dem erfindungsgemäßen Verfahren erzeugten Überzüge aus Nickel oder Nickelverbindungen weisen ein ausreichend hohes Schichtgewicht aus, so daß eine Auflösung von Zink aus der Metalloberfläche bei evtl. Folgebehandlungen weitgehend unterdrückt wird.The coatings of nickel or nickel compounds produced by the process according to the invention have a sufficiently high layer weight so that dissolution of zinc from the metal surface is largely suppressed in the case of subsequent treatments.

Für den Fall, daß die Konzentrationen an Nickel²⁺-Ionen in der Benahdlungsflüssigkeit unterhalb von 20 ppm liegt, wird ein ausreichendes Schichtgewicht des Überzuges nicht erreicht. Auch für den Fall, daß das stöchiometrische Verhältnis von NH₃ zu Nickel²⁺-Ionen geringer als 6 ist, werden ähnliche Ergebnisse beobachtet wie im Falle einer zu geringen Ni²⁺-Konzentration. Sofern die Konzentration an Ni²⁺-Ionen und NH₃ 100 g/l bzw. 300 g/l übersteigt, treten bei der Anwendung des Verfahrens insofern Probleme auf, als eine Auskristallisation von Nickelverbindungen und eine Verdampfung von Ammoniak nicht zu vermeiden ist und daher Veränderungen in der Zusammensetzung der Behandlungsflüssigkeit auftreten.In the event that the concentration of nickel²⁺ ions in the treatment liquid is below 20 ppm, a sufficient layer weight of the coating is not reached. In the event that the stoichiometric ratio of NH₃ to nickel²⁺ ions is less than 6, similar results are observed as in the case of a too low Ni² Konzentration concentration. If the concentration of Ni²⁺ ions and NH₃ exceeds 100 g / l or 300 g / l, problems arise when using the method insofar as crystallization of nickel compounds and evaporation of ammonia cannot be avoided and therefore changes in the composition of the treatment liquid occur.

Entsprechend einer bevorzugten Ausgestaltung der Erfindung erzeugt man die Überzüge mittels einer Lösung, die 5 bis 50 g/l Ni²⁺-Ionen und 10 bis 100 g/l NH₃ enthält.According to a preferred embodiment of the invention, the coatings are produced by means of a solution which contains 5 to 50 g / l of Ni²⁺ ions and 10 to 100 g / l of NH₃.

Entsprechend einer weiteren vorteilhaften Ausgestaltung der Erfindung bringt man die Überzüge mittels einer Lösung, deren Temperatur im Bereich von Raumtemperatur bis 50°C liegt, auf.According to a further advantageous embodiment of the invention, the coatings are applied by means of a solution whose temperature is in the range from room temperature to 50 ° C.

Die Applikation der Behandlungslösung erfolgt vorzugsweise im Tauchen oder Spritzen. Eine Erzeugung der Überzüge auf elektrolytischem Wege ist nicht ausgeschlossen.The treatment solution is preferably applied by dipping or spraying. A generation of the coatings by electrolytic means is not excluded.

Das erfindungsgemäße Verfahren ist mit besonderem Vorteil auf die Vorbehandlung der Oberflächen von Zink oder Zinklegierungen für die anschließende Phosphatierung anwendbar. Infolge der hohen Haftfestigkeit des erzeugten Überzuges von Nickel und/oder Nickelverbindungen und des ausreichend hohen Schichtgewichtes sind die gebildeten Phosphatüberzüge hinsichtlich Haftfestigkeit und Korrosionswiderstand von hoher Qualität. Im Anschluß an die Phosphatierung kann sich eine Lackierung, insbesondere eine Elektrotauchlackierung, anschließen. Im Hinblick darauf, daß die erzeugten Überzüge je nach Beschaffenheit der Behandlungsflüssigkeit ein schwarzes Aussehen besitzen und darüber hinaus die Schwärzung durch anschließende Phosphatierung erhöht werden kann, eignet sich das erfindungsgemäße Verfahren insbesondere auch zur Herstellung von schwarzen Werkstücken.The process according to the invention is particularly advantageously applicable to the pretreatment of the surfaces of zinc or zinc alloys for the subsequent phosphating. As a result of the high adhesive strength of the coating of nickel and / or nickel compounds produced and the sufficiently high layer weight, the phosphate coatings formed are of high quality with regard to adhesive strength and corrosion resistance. After phosphating, painting, in particular electro-dipping, can follow. In view of the fact that the coatings produced have a black appearance depending on the nature of the treatment liquid and, in addition, the blackening by subsequent Phosphation can be increased, the inventive method is particularly suitable for the production of black workpieces.

Die Erfindung wird anhand der nachfolgenden Beispiele näher und beispielsweise erläutert.The invention is explained in more detail and, for example, using the examples below.

BeispieleExamples

Die nachfolgenden Tabellen 1 und 2 enthalten die Behandlungsbedingungen bei Durchführung der Beispiele 1 bis 9 bzw. der Vergleichsbeispiele 1 bis 4. Die Behandlungsflüssigkeit wurde jeweils durch Tauchen appliziert. Die Behandlungstemperatur betrug 40°C, ausgenommen bei Vergleichsbeispiel 3, bei dem die Temperatur der Behandlungsflüssigkeit 25°C war.Tables 1 and 2 below contain the treatment conditions for carrying out Examples 1 to 9 and Comparative Examples 1 to 4. The treatment liquid was applied in each case by immersion. The treatment temperature was 40 ° C, except for Comparative Example 3, in which the temperature of the treatment liquid was 25 ° C.

Die Nickel²⁺-Ionen wurden der Behandlungsflüssigkeit in Form von Nickelsulfat für den Fall zugegeben, daß die Einstellung des pH-Wertes mit Schwefelsäure erfolgte bzw. als Nickelchlorid bei Einstellung des pH-Wertes mit Salzsäure. Ammoniak wurde in Form einer 28 Gew.-%-igen wäßrigen Lösung eingebracht. Sofern erforderlich, wurde auch Ammoniumsulfat oder Ammoniumchlorid zugesetzt. Tabelle 1 Behandlungsbedingungen Beispiel Substrat Hauptkomponenten pH-Einstellung pH Behandlungsdauer Phosphatieren 1 EG (1) Ni²⁺ 10 g/l H₂SO₄ 9.5 20 sec. ja NH₃ 50 g/l 2 GI (1) Ni²⁺ 20 g/l - 10.0 30 sec. ja NH₃ 70 g/l 3 EG Ni²⁺ 10 g/l HCl 9.5 20 sec. ja NH₃ 50 g/l 4 - Ni²⁺ 2.0 g/l H₂SO₄ 9.0 30 sec. ja NH₃ 10 g/l 5 - Ni²⁺ 80 g/l - 8.0 10 sec. ja NH₃ 300 g/l 6 - Ni²⁺ 20 g/l - 8.0 10 sec. ja NH₃ 40 g/l 7 - Ni²⁺ 100 ppm - 9.0 60 sec. ja NH₃ 10 g/l 8 - Ni²⁺ 30 ppm - 9.0 60 sec. ja NH₃ 10 g/l 9 - Ni²⁺ 10 g/l - 9.5 20 sec. nein NH₃ 50 g/l EG: Elektrolytisch verzinkt (20 g/m²) GI: Schmelztauch-verzinkt (90 g/m²) Tabelle 2 Vergleichsbeispiele Substrat Hauptkomponenten pH-Einstellung pH Behandlungsdauer Phosphatieren 1 - Ni²⁺ 15 ppm - 9.0 60 sec. ja NH₃ 5.0 g/l 2 - Ni²⁺ 100 ppm - 2.0 20 sec. ja 3 - Ni²⁺ 0.76 g/l Natriumtripolyphosphat 5 g/l+NaOH 8.6 30 sec. (25°C) ja Glyzin 9.0 g/l 4 - Co²⁺ 2.0 g/l NaOH (30 g/l) 14.0 10 sec. nein Natriumgluconat 2.0 g/l Beispiel 3: Jap. Pat. Pub. Sho 57-45 833 Beispiel 4: Jap. Pat. Pub. Sho 43-12 974 The Nickel²⁺ ions were added to the treatment liquid in the form of nickel sulfate in the event that the pH was adjusted with sulfuric acid or as nickel chloride when the pH was adjusted with hydrochloric acid. Ammonia was introduced in the form of a 28% by weight aqueous solution. If necessary, ammonium sulfate or ammonium chloride was also added. Table 1 Treatment conditions example Substrate Main components pH adjustment pH Duration of treatment Phosphating 1 EG (1) Ni²⁺ 10 g / l H₂SO₄ 9.5 20 sec. Yes NH₃ 50 g / l 2nd GI (1) Ni²⁺ 20 g / l - 10.0 30 sec. Yes NH₃ 70 g / l 3rd EG Ni²⁺ 10 g / l HCl 9.5 20 sec. Yes NH₃ 50 g / l 4th - Ni²⁺ 2.0 g / l H₂SO₄ 9.0 30 sec. Yes NH₃ 10 g / l 5 - Ni²⁺ 80 g / l - 8.0 10 sec. Yes NH₃ 300 g / l 6 - Ni²⁺ 20 g / l - 8.0 10 sec. Yes NH₃ 40 g / l 7 - Ni²⁺ 100 ppm - 9.0 60 sec. Yes NH₃ 10 g / l 8th - Ni²⁺ 30 ppm - 9.0 60 sec. Yes NH₃ 10 g / l 9 - Ni²⁺ 10 g / l - 9.5 20 sec. No NH₃ 50 g / l Ground floor: electrolytically galvanized (20 g / m²) GI: hot-dip galvanized (90 g / m²) Comparative examples Substrate Main components pH adjustment pH Duration of treatment Phosphating 1 - Ni²⁺ 15 ppm - 9.0 60 sec. Yes NH₃ 5.0 g / l 2nd - Ni²⁺ 100 ppm - 2.0 20 sec. Yes 3rd - Ni²⁺ 0.76 g / l Sodium tripolyphosphate 5 g / l + NaOH 8.6 30 sec. (25 ° C) Yes Glycine 9.0 g / l 4th - Co²⁺ 2.0 g / l NaOH (30 g / l) 14.0 10 sec. No Sodium gluconate 2.0 g / l Example 3: Jap. Pat. Pub. Sho 57-45 833 Example 4: Jap. Pat. Pub. Sho 43-12 974

Die Bewertung der Ergebnisse erfolgte anhand von Proben der gemäß Tabellen 1 und 2 behandelten Bleche, die jeweils mit einem kathodischen Elektrotauchlack (Elecron 9410) mit einer Filmdicke von 20 µm beschichtet waren. Die Bleche wurden mit einem Gitterschnitt versehen und für die Dauer von 1 000 Stunden dem Salzsprühtest ausgesetzt. Es wurde die maximale Blasenbildung auf einer Seite der Ritzstelle ermittelt. Die Testergebnisse sind in Tabelle 3 zusammengestellt. Tabelle 3 Test-Ergebnisse einseitige Blasenbildung ( mm ) Beispiele 1 2.0 2 0.5 3 2.0 4 3.5 5 2.5 6 3.5 7 5.5 8 6.0 9 3.5 Vergleichsbeispiele 1 7.5 2 7.0 3 6.5 4 9.5 EG unbehandelt 7.5 GI unbehandelt 2.0 Bemerkung: EG unbehandelt und GI unbehandelt bedeuten: Behandlung von elektrolytisch bzw. Schmelztauch-verzinkten Blechen durch Phosphatieren und Elektrotauchlackierung ohne vorherige Erzeugung eines Überzuges von Nickel und/oder Nickelverbindung. The results were evaluated on the basis of samples of the sheets treated according to Tables 1 and 2, each of which was coated with a cathodic electrocoating material (Elecron 9410) with a film thickness of 20 μm. The sheets were cross-cut and exposed to the salt spray test for 1,000 hours. The maximum blistering on one side of the scratch was determined. The test results are summarized in Table 3. Table 3 Test results one-sided blistering (mm) Examples 1 2.0 2nd 0.5 3rd 2.0 4th 3.5 5 2.5 6 3.5 7 5.5 8th 6.0 9 3.5 Comparative examples 1 7.5 2nd 7.0 3rd 6.5 4th 9.5 EG untreated 7.5 GI untreated 2.0 Remark: EG untreated and GI untreated mean: Treatment of electrolytically or hot-dip galvanized sheet metal by phosphating and electrodeposition without prior coating of nickel and / or nickel compound.

Die Versuchsergebnisse zeigen, daß das erfindungsgemäße Verfahren den Widerstand der behandelten Bleche hinsichtlich Lackablösung deutlich verbessert. Dies beruht auf einer hervorragenden Phosphatierbarkeit der erzeugten Nickel und/oder Nickelverbindung enthaltenden Überzüge und auf der Haftung des nachfolgend aufgebrachten Lackes. Der Vorzug der Erfindung liegt insbesondere darin, daß die hervorragenden Ergebnisse mit einer vergleichsweise einfach beschaffenen Behandlungsflüssigkeit, die zudem auf chemischem Wege, d.h. ohne Anwendung von Strom, appliziert werden kann, erzielt werden. Insbesondere hierdurch ist eine einfache Überwachung der Behandlungsflüssigkeit gewährleistet. Das Verfahren ist zudem mit geringen Kosten verbunden.The test results show that the method according to the invention markedly improves the resistance of the treated sheets with regard to paint detachment. This is based on the excellent phosphatability of the nickel and / or nickel compound coatings produced and on the adhesion of the lacquer applied subsequently. The advantage of the invention lies in particular in the fact that the excellent results are obtained with a comparatively simple treatment liquid, which is also chemically, i.e. can be achieved without the use of electricity. In particular, this ensures simple monitoring of the treatment liquid. The process is also associated with low costs.

Claims (4)

1. Verfahren zur Erzeugung von Überzügen aus Nickel und/oder Nickelverbindungen auf Oberflächen von Zink oder Zinklegierungen mittels Nickelverbindungen enthaltender wäßriger alkalischer Lösung, dadurch gekennzeichnet, daß man die Überzüge mit einer Lösung erzeugt, die mindestens 20 ppm Ni²⁺-Ionen und pro Mol Nickel mindestens die 6-fache molare Menge NH₃ enthält und einen pH-Wert kleiner als 11 aufweist.1. A process for producing coatings of nickel and / or nickel compounds on surfaces of zinc or zinc alloys by means of aqueous alkaline solution containing nickel compounds, characterized in that the coatings are produced with a solution which contains at least 20 ppm Ni²⁺ ions and per mole of nickel Contains at least 6 times the molar amount of NH₃ and has a pH value less than 11. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Überzüge mittels einer Lösung erzeugt, die 5 bis 50 g/l Ni²⁺-Ionen und 10 bis 100 g/l NH₃ enthält.2. The method according to claim 1, characterized in that the coatings are produced by means of a solution which contains 5 to 50 g / l Ni²⁺ ions and 10 to 100 g / l NH₃. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Überzüge mittels einer Lösung, deren Temperatur im Bereich von Raumtemperatur bis 50°C liegt, erzeugt.3. The method according to claim 1 or 2, characterized in that the coatings are produced by means of a solution whose temperature is in the range from room temperature to 50 ° C. 4. Anwendung des Verfahrens nach Anspruch 1, 2 oder 3, zwecks Vorbehandlung der Oberflächen von Zink oder Zinklegierungen für die Phosphatierung.4. Application of the method according to claim 1, 2 or 3, for the pretreatment of the surfaces of zinc or zinc alloys for phosphating.
EP19890114427 1988-08-10 1989-08-04 Process for producing coatings on zinc Expired - Lifetime EP0355525B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP199370/88 1988-08-10
JP63199370A JPH0723543B2 (en) 1988-08-10 1988-08-10 Surface treatment liquid for zinc-based plating and surface treatment method

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EP0355525A1 true EP0355525A1 (en) 1990-02-28
EP0355525B1 EP0355525B1 (en) 1992-03-25

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JP (1) JPH0723543B2 (en)
DE (2) DE3925840A1 (en)
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GB (1) GB2221698B (en)

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WO1991011542A2 (en) * 1990-01-30 1991-08-08 Henkel Corporation Surface treatment method and composition for zinc coated steel sheet
EP1381522A1 (en) * 2000-08-22 2004-01-21 Osaka Prefectural Government Processing method of creating rainbow color, method of manufacturing article which presents rainbow-coloured reflective luster, and article which presents rainbow-coloured reflective luster

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Publication number Priority date Publication date Assignee Title
JP2000160316A (en) 1998-11-27 2000-06-13 Isuzu Motors Ltd Joined structure of panel material for automotive outer or inner board

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EP1381522A4 (en) * 2000-08-22 2009-09-23 Osaka Prefecture Processing method of creating rainbow color, method of manufacturing article which presents rainbow-coloured reflective luster, and article which presents rainbow-coloured reflective luster

Also Published As

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GB2221698B (en) 1993-02-24
JPH0723543B2 (en) 1995-03-15
JPH0250976A (en) 1990-02-20
US4985087A (en) 1991-01-15
ES2032634T3 (en) 1993-02-16
GB8918153D0 (en) 1989-09-20
DE58901024D1 (en) 1992-04-30
GB2221698A (en) 1990-02-14
EP0355525B1 (en) 1992-03-25
DE3925840A1 (en) 1990-02-15

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