EP1678345B1 - Coloured conversion layers devoid of chrome formed on metal surfaces - Google Patents

Coloured conversion layers devoid of chrome formed on metal surfaces Download PDF

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Publication number
EP1678345B1
EP1678345B1 EP04790238.2A EP04790238A EP1678345B1 EP 1678345 B1 EP1678345 B1 EP 1678345B1 EP 04790238 A EP04790238 A EP 04790238A EP 1678345 B1 EP1678345 B1 EP 1678345B1
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Prior art keywords
ions
treatment solution
aqueous treatment
metal
persulfate
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EP04790238.2A
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German (de)
French (fr)
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EP1678345A1 (en
Inventor
Pavel Gentschev
Matthias Schweinsberg
Marco Bastian
Ulrich JÜPTNER
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/73—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 characterised by the process

Definitions

  • the invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys. It describes chromium-free conversion processes for such metal surfaces, i. H. chemical treatment processes which result in the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated.
  • the chromium-free coating is colored, so that it can be determined by simple visual inspection whether a sufficient conversion layer has been formed.
  • the object of this conversion layer is to reduce the tendency of the metal surface to corrode and to produce good adhesion between the metal surface and an organic coating such as a lacquer or an adhesive applied to the conversion layer.
  • WO 94/25640 a method of producing blue colored conversion coatings on zinc / aluminum alloys.
  • the metal surfaces are brought into contact with a treatment solution which has a pH of between 3.5 and 6 and contains 0.2 to 3.0% by weight of molybdenum and a fluoride content of 0.1 to 2.0% by weight. % having.
  • Molybdenum can be used as molybdate, as phosphomolybdic acid, as molybdenum chloride and the like.
  • Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoro acids such as fluorotitanic acid or fluorozirconic acid.
  • the treatment solution contains heterooxoanions of molybdenum, tungsten or vanadium with one of the heteroions phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel.
  • the treatment solution contains an organic film former, which can be selected for example from acrylates.
  • the heterooxo anions such as, for example, anions of heteropolyacids, can be formed directly in the treatment solution by adding thereto the starting materials, for example molybdate ions and phosphoric acid.
  • the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similar etchant.
  • the doctrine of WO 00/26437 goes the way to colorize the conversion layer by an organic dye (Alizerinfarbstoff).
  • the conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
  • a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
  • an amino-substituted poly-4-hydroxy-styrene polyvinylphenol
  • colored layers on aluminum can be obtained by chemical oxidation with aromatic nitro compounds.
  • the different positional isomers of nitrobenzoic acid can be used for this purpose.
  • the chemical oxidation of aluminum surfaces with persulfate ions is reported in DE-A-741 337 described.
  • the aim is to produce crystal-clear and colorless layers on aluminum and its alloys.
  • such layers are obtained by allowing ammonia to act on the carefully cleaned light metal in a hot, aqueous solution which also contains an addition of alkali persulfate, suitably 1%.
  • the cleaning can be done for example by immersion in concentrated nitric acid.
  • the treatment with the ammoniacal persulfate solution takes place at temperatures of at least 70 ° C.
  • the duration is about 15 to 60 minutes. It is reported that at temperatures below 70 ° C also receives protective layers, but are less transparent and often yellowish. In the context of the disclosure of said document such yellowish layers are apparently undesirable, since one does not want to paint the treated parts, but to retain their metallic appearance.
  • the inventors of the present invention have found that reduced (light gold to golden) layers on surfaces of suitable metals obtained at reduced temperature and reduced treatment time, on the one hand chromium-free and on the other hand excellent adhesion to a subsequently applied coating based organic polymers, for example a paint or an adhesive.
  • the object of the present invention is now to maintain the effectiveness of such treatment methods of surfaces of zinc, aluminum, magnesium or their alloys for a prolonged period of time.
  • the present invention relates, in a first aspect, to a process for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys by contacting the surfaces with a chromium-free aqueous treatment solution containing a total of 3 to 35 g / l of persulfate ions and / or or peroxodisulfate ions, in addition from about 1 to about 50 g / l sulfate ions and not more than 10 g / l ammonia or ammonium ions, has a pH in the range of 10 to 12 and a temperature in the range of 30 to 70 ° C, wherein the surfaces for a period in the range of 0.5 to 5 minutes with the Contact treatment solution.
  • the treatment solution may contain 8 to 35 g / L of persulfate ions.
  • the persulfate and / or peroxodisulfate ions are preferably introduced into the treatment solution as alkali metal salts, in particular as sodium or potassium salt.
  • the sulfate ions are introduced, for example, in the form of sodium or potassium salts.
  • the excess of sulfate ions means that to maintain the required alkaline pH in the course of the process according to the invention less sodium hydroxide must be added than without this excess. This saves on chemicals costs.
  • the required alkaline pH is preferably adjusted by an alkali metal hydroxide solution, in particular by sodium hydroxide solution and / or potassium hydroxide solution.
  • the aqueous treatment solution does not contain more than 1 g / L of ammonia or ammonium ions.
  • the treatment solution in the process of the invention has a temperature in the range of 30 to 70 ° C.
  • the treatment time is in the range of 0.5 to 5 minutes. At lower treatment times, sufficient layers are no longer formed. Although treatment times of more than 5 minutes lead to strongly colored layers, the paint adhesion on these layers deteriorates.
  • the surfaces are first cleaned prior to the chemical oxidation step. This can be done for example by brief pickling in cold, concentrated nitric acid. Or the surfaces are rubbed with a chamois leather.
  • an alkaline cleaning solution if desired with water, preferably with deionized water Water, rinsed and then in an acidic solution, for example in nitric acid, dekapiert.
  • the metal surfaces are prepared so that they assume a uniform light golden to golden coloration on the one hand in the process step of chemical oxidation and on the other hand have good adhesion properties to a subsequent coating based on organic polymers.
  • sulfate ions for example in the form of sodium or potassium salts, brings about the same technical effect as described in the process according to the invention for producing colored layers and thus solves the problem underlying the invention.
  • the metal surfaces are rinsed with water, preferably with demineralized water.
  • the metal surfaces are dried after rinsing with water or not. If the coating with organic polymers, for example, in such a way that immersing the metal surfaces in an aqueous coating dispersion, a drying after rinsing is not required. However, if the organic polymer-based coating is, for example, an adhesive or a powder coating, it is preferable to dry the metal surfaces prior to this step.
  • the invention relates to a method according to one or more of claims 1 to 5, characterized in that the metal surfaces, after it has been brought into contact with the aqueous treatment solution, rinsed and coated with a coating based on organic polymers.
  • these metal strips, metal sheets or metal parts on the colored conversion layer which results from the treatment with the persulfate and / or peroxodisulfate-containing solution, carry a coating based on organic polymers, for example one or more paint layers or an adhesive layer.
  • the metal parts according to the invention can be connected to other metal parts.
  • the painted test panels were subjected to a cross-hatch cooking test to test the paint adhesion.
  • corrosion test salt spray test according to DIN 50021 SS was carried out and the paint infiltration at the Ritz was measured according to DIN 53167. The results are included in Table 1.
  • Table 1 Treatment parameters and treatment results Experiment No.

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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)
  • Paints Or Removers (AREA)

Abstract

A method for producing coloured layers on zinc, aluminium, magnesium or alloy surfaces. The surfaces are brought into contact with an aqueous treatment solution which is devoid of chrome, said solution containing, in total, 3-35 g/l persulfate ions and/or peroxodisulfate ions and not more than 10 g/l ammonia or ammonium ions, it has a pH value in the region of between 10-12 and a temperature in the range of between 30-80 ° C. The surfaces are brought into contact with the treatment solution for a period in the region of 0.5-5 minutes and optionally, they are covered with a coating based on organic polymers. The invention further relates to metal parts treated according to said method.

Description

Die Erfindung liegt auf dem Gebiet der chemischen Oberflächenbehandlung von Zink oder verzinktem Stahl, Aluminium, Magnesium oder deren Legierungen. Sie beschreibt chromfreie Konversionsverfahren für solche Metalloberflächen, d. h. chemische Behandlungsverfahren, die zur Bildung einer Oberflächenschicht führen, in die sowohl Kationen der behandelten Metalloberfläche als auch Ionen aus der Behandlungslösung eingebaut werden. Die chromfreie Beschichtung ist farbig, damit durch einfache visuelle Kontrolle festgestellt werden kann, ob eine ausreichende Konversionsschicht gebildet wurde. Aufgabe dieser Konversionsschicht ist es, die Korrosionsneigung der Metalloberfläche zu verringern und eine gute Haftung zwischen der Metalloberfläche und einer auf die Konversionsschicht aufgebrachten organischen Beschichtung wie beispielsweise einem Lack oder einem Klebstoff herzustellen.The invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys. It describes chromium-free conversion processes for such metal surfaces, i. H. chemical treatment processes which result in the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated. The chromium-free coating is colored, so that it can be determined by simple visual inspection whether a sufficient conversion layer has been formed. The object of this conversion layer is to reduce the tendency of the metal surface to corrode and to produce good adhesion between the metal surface and an organic coating such as a lacquer or an adhesive applied to the conversion layer.

Für die Herstellung chromfreier Konversionsschichten auf den genannten Metalloberflächen existiert ein umfangreicher Stand der Technik, der beispielsweise in WO 94/28193 zitiert ist.For the production of chromium-free conversion layers on the metal surfaces mentioned, there is an extensive state of the art which can be found, for example, in US Pat WO 94/28193 is quoted.

Bei den dort zitierten Dokumenten ist es in vielen Fällen offensichtlich, daß die erzeugten Konversionsschichten farblos und durchscheinend sind, so daß die behandelten Metalloberflächen metallisch blank erscheinen. Aus der langjährigen Erfahrung mit der Chromatierung von Metalloberflächen ist es der Fachmann auf diesem Gebiet jedoch gewohnt, als Ergebnis der Konversionsbehandlung eine gefärbte Schicht zu erhalten. Er kann dann sofort visuell erkennen, ob die Behandlung den erwünschten Erfolg gebracht hat. Beim Erzeugen farbloser Schichten ist hierfür jedoch eine aufwendigere Oberflächenanalytik erforderlich, beispielsweise die Bestimmung des Ti-Gehalts der Oberfläche durch eine Röntgenfluoreszenzmessung. Daher besteht in der Praxis ein Bedarf nach Oberflächenbehandlungsverfahren, die nicht nur ähnlich gute Eigenschaften hinsichtlich Korrosionsschutz und Lackhaftung aufweisen wie die herkömmlichen Chromatierschichten, sondern die ähnlich wie Chromatierschichten für das menschliche Auge sichtbar sind.In the documents cited therein, it is evident in many cases that the conversion layers produced are colorless and translucent, so that the treated metal surfaces appear metallic bright. From the many years of experience with the chromating of metal surfaces, however, the person skilled in the art is accustomed to obtaining a colored layer as a result of the conversion treatment. He can then immediately visually recognize whether the treatment has brought the desired success. When producing colorless layers, however, a more complex surface analysis is required for this purpose, for example the determination of the Ti content of the surface by an X-ray fluorescence measurement. Therefore, there is a need in the art for surface treatment methods which not only have similar good corrosion protection and paint adhesion properties to conventional chromating layers, but are similar to chromating layers visible to the human eye.

Ansätze zur Lösung dieser Aufgabe sind im Stand der Technik vorhanden. Beispielsweise offenbart WO 94/25640 ein Verfahren zum Erzeugen blau gefärbter Konversionsschichten auf Zink/Aluminium-Legierungen. Hierbei bringt man die Metalloberflächen mit einer Behandlungslösung in Berührung, die einen pH-Wert zwischen 3,5 und 6 aufweist und die 0,2 bis 3,0 Gew.% Molybdän sowie einen Fluoridgehalt von 0,1 bis 2,0 Gew.-% aufweist. Molybdän kann als Molybdat, als Phosphomolybänsäure, als Molybdänchlorid und ähnliches eingesetzt werden. Fluorid kann in Form von Flußsäure, einfacher Fluoride, aber auch komplexer Fluorosäuren wie beispielsweise Fluorotitansäure oder Fluorozirkonsäure eingesetzt werden.Approaches to solve this problem are present in the prior art. For example disclosed WO 94/25640 a method of producing blue colored conversion coatings on zinc / aluminum alloys. Here, the metal surfaces are brought into contact with a treatment solution which has a pH of between 3.5 and 6 and contains 0.2 to 3.0% by weight of molybdenum and a fluoride content of 0.1 to 2.0% by weight. % having. Molybdenum can be used as molybdate, as phosphomolybdic acid, as molybdenum chloride and the like. Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoro acids such as fluorotitanic acid or fluorozirconic acid.

Ein ähnliches Behandlungsverfahren beschreibt WO 95/14117 , obwohl dort auf das optische Aussehen der Konversionsschichten nicht näher eingegangen wird. Nach diesem Dokument enthält die Behandlungslösung Heterooxoanionen von Molybdän, Wolfram oder Vanadium mit einem der Heteroionen Phosphor, Aluminium, Silizium, Mangan, Zirkon, Titan, Zinn, Cer oder Nickel. Außerdem enthält die Behandlungslösung einen organischen Filmbildner, der beispielsweise aus Acrylaten ausgewählt werden kann. Dabei können die Heterooxoanionen wie beispielsweise Anionen von Heteropolysäuren direkt in der Behandlungslösung gebildet werden, indem man dieser die Ausgangsprodukte hierfür zusetzt, beispielsweise Molybdationen und Phosphorsäure. Zusätzlich soll die Behandlungslösung vorzugsweise ein Ätzmittel für Aluminium, beispielsweise Fluorid, Tetrafluoroborat oder ähnlich wirkende Ätzmittel enthalten.A similar treatment method describes WO 95/14117 although there is no further detail on the visual appearance of the conversion layers. According to this document, the treatment solution contains heterooxoanions of molybdenum, tungsten or vanadium with one of the heteroions phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel. In addition, the treatment solution contains an organic film former, which can be selected for example from acrylates. The heterooxo anions, such as, for example, anions of heteropolyacids, can be formed directly in the treatment solution by adding thereto the starting materials, for example molybdate ions and phosphoric acid. In addition, the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similar etchant.

Die Lehre der WO 00/26437 geht den Weg, die Konversionsschicht durch einen organischen Farbstoff (Alizerinfarbstoff) einzufärben. Die Konversionsschicht selbst wird mit einer Behandlungslösung erzeugt, die komplexe Fluoride beispielsweise von Titan und Zirkon neben weiteren anorganischen Oxiden, Hydroxiden oder Carbonaten bzw. deren Reaktionsprodukten mit den Fluorosäuren enthält. Zusätzlich kann als organisches Polymer ein mit Aminogruppen substituiertes Poly-4-hydroxi-styrol (Polyvinylphenol) anwesend sein.The doctrine of WO 00/26437 goes the way to colorize the conversion layer by an organic dye (Alizerinfarbstoff). The conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids. In addition, as the organic polymer, an amino-substituted poly-4-hydroxy-styrene (polyvinylphenol) may be present.

Gemäß FR-A-2 461 764 lassen sich gefärbte Schichten auf Aluminium durch chemische Oxidation mit aromatischen Nitroverbindungen erhalten. Beispielsweise können hierfür die unterschiedlichen Stellungsisomere von Nitrobenzoesäure verwendet werden. Die chemische Oxidation von Aluminiumoberflächen mit Persulfationen wird in DE-A-741 337 beschrieben. Dabei wird jedoch angestrebt, glasklare und farblose Schichten auf Aluminium und seinen Legierungen zu erzeugen. Gemäß diesem Dokument erhält man derartige Schichten, indem man Ammoniak in einer heißen, wäßrigen Lösung, die außerdem einen Zusatz von Alkalipersulfat, zweckmäßig 1 %, enthält auf das sorgfältig gereinigte Leichtmetall einwirken läßt. Die Reinigung kann beispielsweise durch Eintauchen in konzentrierte Salpetersäure erfolgen. Die Behandlung mit der ammoniakalischen Persulfatlösung erfolgt bei Temperaturen von mindestens 70 °C. Die Zeitdauer beträgt etwa 15 bis 60 Minuten. Dabei wird mitgeteilt, daß man bei Temperaturen unterhalb von 70 °C ebenfalls Schutzschichten erhält, die aber weniger lichtdurchlässig und vielfach gelbstichig sind. Im Rahmen der Offenbarung des genannten Dokuments sind derartige gelbstichige Schichten offenbar unerwünscht, da man die behandelten Teile nicht lackieren, sondern deren metallisches Aussehen behalten will.According to FR-A-2 461 764 For example, colored layers on aluminum can be obtained by chemical oxidation with aromatic nitro compounds. For example, the different positional isomers of nitrobenzoic acid can be used for this purpose. The chemical oxidation of aluminum surfaces with persulfate ions is reported in DE-A-741 337 described. However, the aim is to produce crystal-clear and colorless layers on aluminum and its alloys. According to this document, such layers are obtained by allowing ammonia to act on the carefully cleaned light metal in a hot, aqueous solution which also contains an addition of alkali persulfate, suitably 1%. The cleaning can be done for example by immersion in concentrated nitric acid. The treatment with the ammoniacal persulfate solution takes place at temperatures of at least 70 ° C. The duration is about 15 to 60 minutes. It is reported that at temperatures below 70 ° C also receives protective layers, but are less transparent and often yellowish. In the context of the disclosure of said document such yellowish layers are apparently undesirable, since one does not want to paint the treated parts, but to retain their metallic appearance.

Im Gegensatz hierzu haben die Erfinder der vorliegenden Erfindung gefunden, daß man bei abgesenkter Temperatur und verkürzter Behandlungsdauer farbige (hellgold- bis goldfarbene) Schichten auf Oberflächen geeigneter Metalle erhält, die einerseits chromfrei sind und die andererseits eine hervorragende Haftung zu einer anschließend aufgebrachten Beschichtung auf Basis organischer Polymere, beispielsweise einem Lack oder einem Klebstoff, aufweisen.In contrast, the inventors of the present invention have found that reduced (light gold to golden) layers on surfaces of suitable metals obtained at reduced temperature and reduced treatment time, on the one hand chromium-free and on the other hand excellent adhesion to a subsequently applied coating based organic polymers, for example a paint or an adhesive.

Aus der US 4,509,992 ist ein Verfahren zur Herstellung von Konversionsschichten auf Aluminium bekannt. Diesem Dokument kann eine alkalische Lösung eines Komplexbildners enthaltend 2-30 g/l Natriumpersulfat entnommen werden. Die Oberflächen werden bei einer Temperatur von 25-45°C für 2-30 Minuten mit der Behandlungslösung kontaktiert. Es entstehen gefärbte Oberflächen, die überlackierbar sind.From the US 4,509,992 For example, a method for producing conversion layers on aluminum is known. This document can be taken from an alkaline solution of a complexing agent containing 2-30 g / l of sodium persulfate. The surfaces are contacted with the treatment solution at a temperature of 25-45 ° C for 2-30 minutes. The result is colored surfaces that are overpaintable.

Die Aufgabe der vorliegenden Erfindung besteht nunmehr darin, die Effektivität derartiger Behandlungsverfahren von Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen für einen längern Zeitraum aufrechtzuerhalten.The object of the present invention is now to maintain the effectiveness of such treatment methods of surfaces of zinc, aluminum, magnesium or their alloys for a prolonged period of time.

Die vorliegende Erfindung betrifft in einem ersten Aspekt ein Verfahren zum Erzeugen farbiger Schichten auf Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen, wobei man die Oberflächen mit einer chromfreien wässrigen Behandlungslösung in Kontakt bringt, die insgesamt 3 bis 35 g/l Persulfationen und/oder Peroxodisulfationen, zusätzlich etwa 1 bis etwa 50 g/l Sulfationen und nicht mehr als 10 g/l Ammoniak oder Ammoniumionen enthält, einen pH-Wert im Bereich von 10 bis 12 und eine Temperatur im Bereich von 30 bis 70 °C aufweist, wobei man die Oberflächen für eine Zeitdauer im Bereich von 0,5 bis 5 Minuten mit der Behandlungslösung in Kontakt bringt. Beispielsweise kann die Behandlungslösung 8 bis 35 g/l Persulfationen enthalten.The present invention relates, in a first aspect, to a process for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys by contacting the surfaces with a chromium-free aqueous treatment solution containing a total of 3 to 35 g / l of persulfate ions and / or or peroxodisulfate ions, in addition from about 1 to about 50 g / l sulfate ions and not more than 10 g / l ammonia or ammonium ions, has a pH in the range of 10 to 12 and a temperature in the range of 30 to 70 ° C, wherein the surfaces for a period in the range of 0.5 to 5 minutes with the Contact treatment solution. For example, the treatment solution may contain 8 to 35 g / L of persulfate ions.

Die Persulfat- und/oder Peroxodisulfationen werden vorzugsweise als Alkalimetallsalze, insbesondere als Natrium- oder Kaliumsalz in die Behandlungslösung eingebracht. Die Sulfationen werden beispielsweise in Form von Natrium- oder Kaliumsalzen eingebracht. Der Überschuß an Sulfationen führt dazu, dass zum Aufrechterhalten des erforderlichen alkalischen pH-Wertes im Verlauf des erfindungsgemäßen Verfahrens weniger Natronlauge zugegeben werden muss als ohne diesen Überschuss. Hierdurch werden Chemikalienkosten eingespart. Den erforderlichen alkalischen pH-Wert stellt man vorzugsweise durch eine Alkalilauge, insbesondere durch Natron- und/oder Kalilauge ein. Hierdurch werden Geruchsprobleme vermieden, die sonst beim Arbeiten mit heißen alkalischen Ammoniaklösungen auftreten, wie es offensichtlich bei dem Verfahren gemäß DE-A-741 337 der Fall sein muß. Vorzugsweise enthält die wässrige Behandlungslösung nicht mehr als 1 g/l Ammoniak oder Ammoniumionen.The persulfate and / or peroxodisulfate ions are preferably introduced into the treatment solution as alkali metal salts, in particular as sodium or potassium salt. The sulfate ions are introduced, for example, in the form of sodium or potassium salts. The excess of sulfate ions means that to maintain the required alkaline pH in the course of the process according to the invention less sodium hydroxide must be added than without this excess. This saves on chemicals costs. The required alkaline pH is preferably adjusted by an alkali metal hydroxide solution, in particular by sodium hydroxide solution and / or potassium hydroxide solution. This avoids odor problems that otherwise occur when working with hot alkaline ammonia solutions, as is apparent in the process according to DE-A-741 337 must be the case. Preferably, the aqueous treatment solution does not contain more than 1 g / L of ammonia or ammonium ions.

Gemäß DE-A-741 337 sind beim dort beschriebenen Arbeiten mit ammoniakalischen Lösungen Temperaturen von mindestens 70 °C und Behandlungszeiten im Bereich von etwa 15 bis etwa 60 Minuten erforderlich. Demgegenüber weist die Behandlungslösung im erfindungsgemäßen Verfahren eine Temperatur im Bereich von 30 bis 70 °C auf. Bei Temperaturen oberhalb von 70 °C werden zwar ebenfalls stark farbige Schichten erhalten, diese weisen aber eine verringerte Lackhaftung auf. Die Behandlungsdauer liegt im Bereich von 0,5 bis 5 Minuten. Bei geringeren Behandlungszeiten werden keine ausreichenden Schichten mehr gebildet. Behandlungszeiten oberhalb von 5 Minuten führen zwar zu stark farbigen Schichten, jedoch verschlechtert sich die Lackhaftung auf diesen Schichten.According to DE-A-741 337 In the described work with ammoniacal solutions temperatures of at least 70 ° C and treatment times in the range of about 15 to about 60 minutes are required. In contrast, the treatment solution in the process of the invention has a temperature in the range of 30 to 70 ° C. At temperatures above 70 ° C, although strongly colored layers are obtained, but these have a reduced paint adhesion. The treatment time is in the range of 0.5 to 5 minutes. At lower treatment times, sufficient layers are no longer formed. Although treatment times of more than 5 minutes lead to strongly colored layers, the paint adhesion on these layers deteriorates.

Gemäß DE-A-741 337 werden die Oberflächen vor dem chemischen Oxidationsschritt zunächst gereinigt. Dies kann beispielsweise durch kurzes Beizen in kalter, konzentrierter Salpetersäure erfolgen. Oder die Oberflächen werden mit einem Fensterleder abgerieben. Demgegenüber hat es sich beim Arbeiten gemäß dem erfindungsgemäßen Verfahren als günstig herausgestellt, wenn man die Metalloberflächen zunächst mit einer alkalischen Reinigungslösung reinigt, erwünschtenfalls mit Wasser, vorzugsweise mit vollentsalztem Wasser, spült und anschließend in einer sauren Lösung, beispielsweise in Salpetersäure, dekapiert. Hierdurch werden die Metalloberflächen so vorbereitet, daß sie beim Verfahrensschritt der chemischen Oxidation einerseits eine gleichmäßige hellgoldene bis goldene Färbung annehmen und andererseits gute Haftungseigenschaften zu einer nachfolgenden Beschichtung auf Basis organischer Polymere aufweisen.According to DE-A-741 337 For example, the surfaces are first cleaned prior to the chemical oxidation step. This can be done for example by brief pickling in cold, concentrated nitric acid. Or the surfaces are rubbed with a chamois leather. On the other hand, when working according to the method of the invention, it has proven to be advantageous to first clean the metal surfaces with an alkaline cleaning solution, if desired with water, preferably with deionized water Water, rinsed and then in an acidic solution, for example in nitric acid, dekapiert. As a result, the metal surfaces are prepared so that they assume a uniform light golden to golden coloration on the one hand in the process step of chemical oxidation and on the other hand have good adhesion properties to a subsequent coating based on organic polymers.

In einem Verfahren zum Behandeln von Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen, können die Oberflächen

  1. a) mit einer alkalischen Reinigungslösung gereinigt werden,
  2. b) danach mit einer sauren Lösung dekapierte werden
  3. c) danach mit einer chromfreien wässrigen Behandlungslösung, die insgesamt 3 bis 35 g/l Persulfationen und/oder Peroxodisulfationen enthält und einen pH-Wert im Bereich von 10 bis 12 und eine Temperatur im Bereich von 30 bis 70 °C aufweist, für eine Zeitdauer im Bereich von 0,5 bis 5 Minuten in Kontakt gebracht werden, wobei die Behandlungslösung zusätzlich etwa 1 bis etwa 50 g/l Sulfationen enthält.
In a process for treating surfaces of zinc, aluminum, magnesium or their alloys, the surfaces may
  1. a) be cleaned with an alkaline cleaning solution,
  2. b) are then decanted with an acidic solution
  3. c) thereafter with a chromium-free aqueous treatment solution containing a total of 3 to 35 g / l of persulfate ions and / or peroxodisulfate ions and having a pH in the range of 10 to 12 and a temperature in the range of 30 to 70 ° C, for a period of time in the range of 0.5 to 5 minutes, wherein the treatment solution additionally contains about 1 to about 50 g / L sulfate ions.

Der Zusatz von Sulfat-Ionen, beispielsweise in Form von Natrium- oder Kaliumsalzen, bringt denselben technischen Effekt wie im erfindungsgemäßen Verfahren zur Erzeugung farbiger Schichten beschrieben und löst damit die der Erfindung zugrunde liegende Aufgabe.The addition of sulfate ions, for example in the form of sodium or potassium salts, brings about the same technical effect as described in the process according to the invention for producing colored layers and thus solves the problem underlying the invention.

Nach dem Einwirken der persulfat- oder peroxodisulfathaltigen Behandlungslösung werden die Metalloberflächen mit Wasser, vorzugsweise mit vollentsalztem Wasser gespült. Je nach Art der nachfolgenden Beschichtung mit organischen Polymeren werden die Metalloberflächen nach der Spülung mit Wasser getrocknet oder nicht. Erfolgt das Beschichten mit organischen Polymeren beispielsweise in der Art, daß man die Metalloberflächen in eine wäßrige Lackdispersion eintaucht, ist ein Trocknen nach dem Spülen nicht erforderlich. Stellt jedoch die Beschichtung auf Basis organischer Polymere beispielsweise einen Klebstoff oder einen Pulverlack dar, ist es vorzuziehen, die Metalloberflächen vor diesem Schritt zu trocknen.After the action of persulfate or peroxodisulfate treatment solution, the metal surfaces are rinsed with water, preferably with demineralized water. Depending on the type of subsequent coating with organic polymers, the metal surfaces are dried after rinsing with water or not. If the coating with organic polymers, for example, in such a way that immersing the metal surfaces in an aqueous coating dispersion, a drying after rinsing is not required. However, if the organic polymer-based coating is, for example, an adhesive or a powder coating, it is preferable to dry the metal surfaces prior to this step.

Aus ökonomischen und ökologischen Gründen ist es bevorzugt, daß die Behandlungslösung außer Alkalimetall- und ggf. Erdalkalimetallionen keine weiteren Metallionen aufweist, beispielsweise keine Zinkionen und insbesondere keine Schwermetallionen. Schließlich betrifft die Erfindung ein Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Metalloberflächen, nachdem man sie mit der wässrigen Behandlungslösung in Kontakt gebracht hat, spült und mit einer Beschichtung auf Basis organischer Polymere überzieht. Dabei können diese Metallbänder, Metallbleche oder Metallteile auf der farbigen Konversionsschicht, die durch die Behandlung mit der Persulfat- und/oder Peroxodisulfat-haltigen Lösung entsteht, eine Beschichtung auf Basis organischer Polymere tragen, beispielsweise eine oder mehrere Lackschichten oder eine Klebstoffschicht. Über diese Klebstoffschicht können die erfindungsgemäß hergestellten Metallteile mit anderen Metallteilen verbunden sein.For economic and ecological reasons, it is preferred that the treatment solution except alkali metal and possibly alkaline earth metal ions have no further metal ions, for example no zinc ions and in particular no heavy metal ions. Finally, the invention relates to a method according to one or more of claims 1 to 5, characterized in that the metal surfaces, after it has been brought into contact with the aqueous treatment solution, rinsed and coated with a coating based on organic polymers. In this case, these metal strips, metal sheets or metal parts on the colored conversion layer, which results from the treatment with the persulfate and / or peroxodisulfate-containing solution, carry a coating based on organic polymers, for example one or more paint layers or an adhesive layer. About this adhesive layer, the metal parts according to the invention can be connected to other metal parts.

Ausführungsbeispieleembodiments

Probebleche aus Aluminium Al 99.5 (die Legierungen AlMgSi1. AlMgSiMn und AlmgSi0,5 führen zu ähnlichen Ergebnissen) wurden folgenden Behandlungsschritten unterworfen:

  1. 1. Reinigung mit einem kommerziellen alkalischen Reiniger der Anmelderin: RidolineR C72, 2 %, 65 °C. 1 Minute
  2. 2. Spülen mit vollentsalztem Wasser
  3. 3. Deoxidieren mit einer kommerziellen Deoxidierlösung der Anmelderin: DeoxidizerR 4902, 10 g/l, 25 °C, 1,5 Minuten
  4. 4. Spülen mit vollentsalztem Wasser
  5. 5. chemische Oxidation mit Behandlungslösungen gemäß Tabelle 1
  6. 6. Spülen mit vollentsalztem Wasser
  7. 7. Trocknen
  8. 8. Lackieren mit einem Pulverlack (AL 93-7005, grau, Firma Herberts)
Aluminum alloy plates Al 99.5 (AlMgSi1, AlMgSiMn and AlmgSi0.5 alloys yield similar results) were subjected to the following treatment steps:
  1. 1. Cleaning with a commercial alkaline cleaner of the applicant: Ridoline R C72, 2%, 65 ° C. 1 minute
  2. 2. Rinse with demineralized water
  3. 3. Deoxidize with Applicant's Commercial Deoxidizer Solution: Deoxidizer R 4902, 10 g / L, 25 ° C, 1.5 minutes
  4. 4. Rinse with demineralized water
  5. 5. chemical oxidation with treatment solutions according to Table 1
  6. 6. Rinse with demineralized water
  7. 7. Dry
  8. 8. Painting with a powder coating (AL 93-7005, gray, company Herberts)

Die lackierten Probebleche wurden zur Prüfung der Lackhaftung einem Kochtest mit Gitterschnitt unterworfen. Hierzu wurden die lackierten Prüfbleche 2 Stunden in vollentsalztem Wasser gekocht und anschließend 1 Stunde bei Raumtemperatur gelagert. Danach erfolgte die Gitterschnittprüfung. Ein Wert von GT = 0 gilt als bestanden, GT-Werte von > 0 gelten als nicht bestanden. Weiterhin wurde Korrosionstest (Salzsprühtest nach DIN 50021 SS) vorgenommen und die Lackunterwanderung am Ritz nach DIN 53167 gemessen. Die Ergebnisse sind in Tabelle 1 enthalten. Tabelle 1: Behandlungsparameter und Behandlungsergebnisse Versuch Nr. Behandlungslösung pH-Wert Temp (°C) Zeit (Minuten) Gitterschnitt Salzsprühtest 1 20 g/l Na2S2O8 in Wasser 10,2 (NaOH) 55 3 GT = 0, in Ordnung 21 Tage: 0,7 - 1,1 mm 42 Tage: 0,9- 1,5 mm 2 12,7 g/l Na2S2O8 in Wasser 10,2 (NaOH) 55 3 3 10 g/l Na2S2O8 in Wasser 10,2 (NaOH) 55 3 4 5 g/l Na2S2O8 in Wasser 10,2 (NaOH) 55 3 5 21 g/l Na2S2O8 und 10 g/l Na2SO4 in Wasser 10,5 (NaOH) 30 3 The painted test panels were subjected to a cross-hatch cooking test to test the paint adhesion. For this purpose, the coated test panels were boiled for 2 hours in demineralized water and then stored for 1 hour at room temperature. Thereafter, the cross-cut test was carried out. A value of GT = 0 is passed, GT values of> 0 are considered as failed. Furthermore, corrosion test (salt spray test according to DIN 50021 SS) was carried out and the paint infiltration at the Ritz was measured according to DIN 53167. The results are included in Table 1. Table 1: Treatment parameters and treatment results Experiment No. treatment solution PH value Temp (° C) Time (minutes) Crosshatch salt spray test 1 20 g / l Na 2 S 2 O 8 in water 10.2 (NaOH) 55 3 GT = 0, okay 21 days: 0.7 - 1.1 mm 42 days: 0.9-1.5 mm 2 12.7 g / l Na 2 S 2 O 8 in water 10.2 (NaOH) 55 3 3 10 g / l Na 2 S 2 O 8 in water 10.2 (NaOH) 55 3 4 5 g / l Na 2 S 2 O 8 in water 10.2 (NaOH) 55 3 5 21 g / l Na 2 S 2 O 8 and 10 g / l Na 2 SO 4 in water 10.5 (NaOH) 30 3

Unter allen Bedingungen wurden hellgold- bis goldfarbene Schichten erhalten.Under all conditions light gold to gold colored layers were obtained.

Claims (6)

  1. A method for producing coloured layers on surfaces of zinc, aluminium, magnesium or the alloys thereof, the surfaces being brought into contact with a chromium-free aqueous treatment solution which contains in total 3 to 35 g/l persulfate ions and/or peroxydisulfate ions and no more than 10 g/l ammonia or ammonium ions and has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70°C, the surfaces being brought into contact with treatment solution for a duration in the range from 0.5 to 5 minutes, characterised in that the aqueous treatment solution additionally contains 1 to 50 g/l sulfate ions.
  2. A method according to claim 1, characterised in that the treatment solution contains 8 to 35 g/l persulfate ions.
  3. A method according to one or both of the preceding claims, characterised in that the persulfate and/or peroxydisulfate ions were introduced as alkali metal salts and in that the pH of the aqueous treatment solution is adjusted with sodium and/or potassium hydroxide solution.
  4. A method according to one or more of claims 1 to 3, characterised in that the aqueous treatment solution contains no more than 1 g/l ammonia or ammonium ions.
  5. A method according to one or more of claims 1 to 4, characterised in that the aqueous treatment solution contains no further metal ions other than alkali metal and/or alkaline earth metal ions.
  6. A method according to one or more of claims 1 to 5, characterised in that, after having been brought into contact with the aqueous treatment solution, the metal surfaces are rinsed and coated with a coating based on organic polymers.
EP04790238.2A 2003-11-07 2004-10-09 Coloured conversion layers devoid of chrome formed on metal surfaces Not-in-force EP1678345B1 (en)

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EP1678345A1 (en) 2006-07-12
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US7828911B2 (en) 2010-11-09
US20060272748A1 (en) 2006-12-07

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