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EP1678345A1 - Coloured conversion layers devoid of chrome formed on metal surfaces - Google Patents

Coloured conversion layers devoid of chrome formed on metal surfaces

Info

Publication number
EP1678345A1
EP1678345A1 EP04790238A EP04790238A EP1678345A1 EP 1678345 A1 EP1678345 A1 EP 1678345A1 EP 04790238 A EP04790238 A EP 04790238A EP 04790238 A EP04790238 A EP 04790238A EP 1678345 A1 EP1678345 A1 EP 1678345A1
Authority
EP
European Patent Office
Prior art keywords
ions
treatment solution
metal
range
aqueous treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04790238A
Other languages
German (de)
French (fr)
Other versions
EP1678345B1 (en
Inventor
Pavel Gentschev
Matthias Schweinsberg
Marco Bastian
Ulrich JÜPTNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Publication of EP1678345A1 publication Critical patent/EP1678345A1/en
Application granted granted Critical
Publication of EP1678345B1 publication Critical patent/EP1678345B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 chrome-free conversion processes for such metal surfaces, i. H. chemical treatment processes that lead to the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated.
  • the chrome-free coating is colored so that a simple visual check can be used to determine whether an adequate conversion layer has been formed.
  • the task 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 applied to the conversion layer, such as, for example, a varnish or an adhesive.
  • WO 94/25640 discloses a method for producing blue-colored conversion layers on zinc / aluminum alloys.
  • the metal surfaces are brought into contact with a treatment solution which has a pH between 3.5 and 6 and which contains 0.2 to 3.0% by weight of molybdenum and a fluoride content of 0.1 to 2.0%. -% having.
  • Molybdenum can be used as molybdate, as phosphomolybenic acid, as molybdenum chloride and the like.
  • Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoric acids such as fluorotitanic acid or fluorozirconic acid.
  • the treatment solution contains heterooxo anions of molybdenum, tungsten or vanadium with one of the hetero ions phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel.
  • the treatment solution also contains an organic film former, which can be selected, for example, from acrylates.
  • the heterooxo anions such as anions of heteropolyacids, can be formed directly in the treatment solution by adding the starting products for this, for example molybdenum ions and phosphoric acid.
  • the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similarly acting etchants.
  • WO 00/26437 goes the way of coloring the conversion layer using an organic dye (alizerin dye).
  • the conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to other inorganic oxides, hydroxides or carbonates or their reaction products with the fluoric acids.
  • a poly-4-hydroxystyrene (polyvinylphenol) substituted with amino groups can be present as the organic polymer.
  • 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.
  • the chemical oxidation of aluminum surfaces with persulfate ions is described in DE-A-741 337.
  • the aim is to produce crystal-clear and colorless layers on aluminum and its alloys. According to this document, such are obtained Layers by allowing ammonia in a hot, aqueous solution, which also contains an addition of alkali metal sulfate, advantageously 1%, to act on the carefully cleaned light metal. It can be cleaned, for example, by immersing it in concentrated nitric acid.
  • the treatment with the ammoniacal persulfate solution takes place at temperatures of at least 70 ° C.
  • the time period is approximately 15 to 60 minutes. It is reported that protective layers are also obtained at temperatures below 70 ° C, but are less translucent and often yellowish. In the context of the disclosure of the document mentioned, such yellow-tinted layers are obviously undesirable, since the treated parts are not to be painted but rather to retain their metallic appearance.
  • the inventors of the present invention found that colored (light gold to gold-colored) layers are obtained on surfaces of suitable metals at reduced temperature and shortened treatment time, which are chromium-free on the one hand and which have excellent adhesion to a subsequently applied coating on the other organic polymers, for example a lacquer or an adhesive.
  • the present invention relates to a method for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being brought into contact with a chromium-free aqueous treatment solution which contains a total of 3 to 35 g / l persulfate ions and / or contains peroxodisulfate ions and not more than 10 g / l ammonia or ammonium ions, has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C, the surfaces being in the range from 0 to 5 to 5 minutes in contact with the treatment solution.
  • the treatment solution can contain 8 to 35 g / l 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 salts.
  • the required alkaline pH is preferably set by means of an alkali solution, in particular sodium hydroxide solution and / or potassium hydroxide solution. This avoids odor problems that otherwise occur when working with hot alkaline ammonia solutions, as is obviously the case with the method according to DE-A-741 337.
  • the aqueous treatment solution preferably contains no more than 1 g / l ammonia or ammonium ions. According to DE-A-741 337, temperatures of at least 70 ° C.
  • the treatment solution in the process according to the invention has a temperature in the range from 30 to 70 ° C. At temperatures above 70 ° C, strongly colored layers are also obtained, but these have a reduced paint adhesion.
  • the duration of treatment is in the range of 0.5 to 5 minutes. With shorter treatment times, sufficient layers are no longer formed. Treatment times above 5 minutes lead to strongly colored layers, but the paint adhesion on these layers deteriorates.
  • the surfaces are first cleaned before the chemical oxidation step. This can be done, for example, by briefly pickling in cold, concentrated nitric acid. Or the surfaces are rubbed with a chamois.
  • the metal surfaces are first cleaned with an alkaline cleaning solution, if necessary rinsed with water, preferably with demineralized water, and then decapitated in an acidic solution, for example in nitric acid.
  • the metal surfaces are prepared in such a way that, on the one hand, they assume a uniform light golden to golden color in the chemical oxidation process step and, on the other hand, have good adhesion properties to a subsequent coating based on organic polymers.
  • the invention relates to a method for treating surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being a) cleaned with an alkaline cleaning solution, b) then picked up with an acidic solution, c) then with one Chromium-free aqueous treatment solution which contains a total of 3 to 35 g / l persulfate ions and / or peroxodisulfate ions and has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C. for a period in the range from 0, 5 to 5 minutes in contact.
  • the metal surfaces are washed with water, preferably with deionized water rinsed. Depending on the type of subsequent coating with organic polymers, the metal surfaces are dried or not after rinsing with water. Does that happen
  • the coating based on organic polymers is, for example, an adhesive or a powder coating, it is preferable to use the
  • the treatment solution has no other metal ions apart from alkali metal and possibly alkaline earth metal ions, for example no zinc ions and in particular no heavy metal ions.
  • the aqueous treatment solution can additionally contain about 1 to about 50 g / l of sulfate ions, for example in the form of sodium or potassium salts.
  • the hydrolysis of the persulfate and / or peroxodisulfate ions is suppressed by an excess of sulfate ions without their effect on the production of a colored layer waning.
  • the content of persulfate and / or peroxodisulfate ions in the aqueous treatment solution must therefore be added less frequently or to a lesser extent, which leads to savings in chemical costs.
  • the invention relates to a method according to one or more of claims 1 to 7, characterized in that the metal surfaces are rinsed after being brought into contact with the aqueous treatment solution and coated with a coating based on organic polymers ,
  • These metal strips, metal sheets or metal parts can have a coating based on organic polymers, for example one or more layers of paint or an adhesive layer, on the colored conversion layer which results from the treatment with the solution containing persulfate and / or peroxodisulfate.
  • the metal parts produced according to the invention can be connected to other metal parts via this adhesive layer. Such metal strips, metal sheets or metal parts also belong to the scope of the present invention. embodiments
  • Sample sheets made of aluminum AI 99.5 (the alloys AlMgSH, AlMgSiMn and AlMgSiO, 5 lead to similar results) were subjected to the following treatment steps:
  • the lacquered test panels were subjected to a boiling test with a cross cut to test the lacquer adhesion.
  • the coated test panels were boiled in demineralized water for 2 hours and then stored at room temperature for 1 hour.
  • the cross-cut test was then carried out.
  • a corrosion test salt spray test according to DIN 50021 SS was carried out and the paint penetration at the scratch was measured according to DIN 53167. The results are shown in Table 1.
  • Table 1 Treatment parameters and treatment results

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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

The invention relates to a method which is used to produce 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

"Farbige chromfreie Konversionsschichten auf Metalloberflächen""Colored chrome-free conversion layers on metal surfaces"
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 chrome-free conversion processes for such metal surfaces, i. H. chemical treatment processes that lead to the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated. The chrome-free coating is colored so that a simple visual check can be used to determine whether an adequate conversion layer has been formed. The task 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 applied to the conversion layer, such as, for example, a varnish or an adhesive.
Für die Herstellung chromfreier Konversionsschichten auf den genannten Metalloberflächen existiert ein umfangreicher Stand der Technik, der beispielsweise in WO 94/28193 zitiert ist.There is extensive prior art for the production of chromium-free conversion layers on the metal surfaces mentioned, which is cited, for example, in WO 94/28193.
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 Chroma- tierschichten, sondern die ähnlich wie Chromatierschichten für das menschliche Auge sichtbar sind. 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.In the documents cited there, it is evident in many cases that the conversion layers produced are colorless and translucent, so that the treated metal surfaces appear shiny metallic. However, from the many years of experience with the chromating of metal surfaces, the person skilled in the art is used 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, this requires more complex surface analysis, for example the determination of the Ti content of the surface by means of an X-ray fluorescence measurement. There is therefore a need in practice for surface treatment processes which not only have good corrosion protection and paint adhesion properties like the conventional chromating layers, but which are visible to the human eye in a similar way to chromating layers. There are approaches to solving this problem in the prior art. For example, WO 94/25640 discloses a method for producing blue-colored conversion layers on zinc / aluminum alloys. The metal surfaces are brought into contact with a treatment solution which has a pH between 3.5 and 6 and which contains 0.2 to 3.0% by weight of molybdenum and a fluoride content of 0.1 to 2.0%. -% having. Molybdenum can be used as molybdate, as phosphomolybenic acid, as molybdenum chloride and the like. Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoric 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.WO 95/14117 describes a similar treatment method, although the optical appearance of the conversion layers is not dealt with in more detail there. According to this document, the treatment solution contains heterooxo anions of molybdenum, tungsten or vanadium with one of the hetero ions phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel. The treatment solution also contains an organic film former, which can be selected, for example, from acrylates. The heterooxo anions, such as anions of heteropolyacids, can be formed directly in the treatment solution by adding the starting products for this, for example molybdenum ions and phosphoric acid. In addition, the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similarly acting etchants.
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 PoIy-4-hydroxi-styrol (Polyvinylphenol) anwesend sein.The teaching of WO 00/26437 goes the way of coloring the conversion layer using an organic dye (alizerin dye). The conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to other inorganic oxides, hydroxides or carbonates or their reaction products with the fluoric acids. In addition, a poly-4-hydroxystyrene (polyvinylphenol) substituted with amino groups can be present as the organic polymer.
Gemäß FR-A-2461 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-2461 764, 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. The chemical oxidation of aluminum surfaces with persulfate ions is described in DE-A-741 337. However, the aim is to produce crystal-clear and colorless layers on aluminum and its alloys. According to this document, such are obtained Layers by allowing ammonia in a hot, aqueous solution, which also contains an addition of alkali metal sulfate, advantageously 1%, to act on the carefully cleaned light metal. It can be cleaned, for example, by immersing it in concentrated nitric acid. The treatment with the ammoniacal persulfate solution takes place at temperatures of at least 70 ° C. The time period is approximately 15 to 60 minutes. It is reported that protective layers are also obtained at temperatures below 70 ° C, but are less translucent and often yellowish. In the context of the disclosure of the document mentioned, such yellow-tinted layers are obviously undesirable, since the treated parts are not to be painted but rather 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 to this, the inventors of the present invention found that colored (light gold to gold-colored) layers are obtained on surfaces of suitable metals at reduced temperature and shortened treatment time, which are chromium-free on the one hand and which have excellent adhesion to a subsequently applied coating on the other organic polymers, for example a lacquer or an adhesive.
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 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.In a first aspect, the present invention relates to a method for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being brought into contact with a chromium-free aqueous treatment solution which contains a total of 3 to 35 g / l persulfate ions and / or contains peroxodisulfate ions and not more than 10 g / l ammonia or ammonium ions, has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C, the surfaces being in the range from 0 to 5 to 5 minutes in contact with the treatment solution. For example, the treatment solution can contain 8 to 35 g / l persulfate ions.
Die Persulfat- und/oder Peroxodisulfationen werden vorzugsweise als Alkalimetallsalze, insbesondere als Natrium- oder Kaliumsalz in die Behandlungslösung eingebracht. 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. 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.The persulfate and / or peroxodisulfate ions are preferably introduced into the treatment solution as alkali metal salts, in particular as sodium or potassium salts. The required alkaline pH is preferably set by means of an alkali solution, in particular sodium hydroxide solution and / or potassium hydroxide solution. This avoids odor problems that otherwise occur when working with hot alkaline ammonia solutions, as is obviously the case with the method according to DE-A-741 337. The aqueous treatment solution preferably contains no more than 1 g / l ammonia or ammonium ions. According to DE-A-741 337, temperatures of at least 70 ° C. and treatment times in the range from about 15 to about 60 minutes are required when working with ammoniacal solutions. In contrast, the treatment solution in the process according to the invention has a temperature in the range from 30 to 70 ° C. At temperatures above 70 ° C, strongly colored layers are also obtained, but these have a reduced paint adhesion. The duration of treatment is in the range of 0.5 to 5 minutes. With shorter treatment times, sufficient layers are no longer formed. Treatment times above 5 minutes lead to strongly colored layers, but 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, the surfaces are first cleaned before the chemical oxidation step. This can be done, for example, by briefly pickling in cold, concentrated nitric acid. Or the surfaces are rubbed with a chamois. In contrast, when working in accordance with the method according to the invention, it has proven to be advantageous if the metal surfaces are first cleaned with an alkaline cleaning solution, if necessary rinsed with water, preferably with demineralized water, and then decapitated in an acidic solution, for example in nitric acid. As a result, the metal surfaces are prepared in such a way that, on the one hand, they assume a uniform light golden to golden color in the chemical oxidation process step and, on the other hand, have good adhesion properties to a subsequent coating based on organic polymers.
Demnach betrifft die Erfindung in einem zweiten Aspekt ein Verfahren zum Behandeln von Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen, wobei man die Oberflächen a) mit einer alkalischen Reinigungslösung reinigt, b) danach mit einer sauren Lösung dekapiert, 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 bringt.Accordingly, in a second aspect, the invention relates to a method for treating surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being a) cleaned with an alkaline cleaning solution, b) then picked up with an acidic solution, c) then with one Chromium-free aqueous treatment solution which contains a total of 3 to 35 g / l persulfate ions and / or peroxodisulfate ions and has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C. for a period in the range from 0, 5 to 5 minutes in contact.
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 dasAfter the treatment solution containing persulfate or peroxodisulfate has acted on, the metal surfaces are washed with water, preferably with deionized water rinsed. Depending on the type of subsequent coating with organic polymers, the metal surfaces are dried or not after rinsing with water. Does that happen
Beschichten mit organischen Polymeren beispielsweise in der Art, daß man dieCoating with organic polymers, for example, in such a way that the
Metalloberflächen in eine wäßrige Lackdispersion eintaucht, ist ein Trocknen nach demImmersing metal surfaces in an aqueous paint dispersion is drying after
Spülen nicht erforderlich. Stellt jedoch die Beschichtung auf Basis organischer Polymere beispielsweise einen Klebstoff oder einen Pulverlack dar, ist es vorzuziehen, dieNo need to rinse. However, if the coating based on organic polymers is, for example, an adhesive or a powder coating, it is preferable to use the
Metalloberflächen vor diesem Schritt zu trocknen.Dry metal surfaces before 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.For economic and ecological reasons it is preferred that the treatment solution has no other metal ions apart from alkali metal and possibly alkaline earth metal ions, for example no zinc ions and in particular no heavy metal ions.
Die wässrige Behandlungslösung kann zusätzlich etwa 1 bis etwa 50 g/l Sulfationen enthalten, beispielsweise in Form von Natrium- oder Kaliumsalzen. Durch einen Überschuß an Sulfationen wird die Hydrolyse der Persulfat- und/oder Peroxodisulfationen zurückgedrängt, ohne daß deren Wirkung zum Erzeugen einer farbigen Schicht nachlässt. Der Gehalt an Persulfat- und/oder Peroxodisulfationen in der wässrigen Behandlungslösung muß deshalb seltener oder in geringerem Umfang ergänzt werden, was zur Einsparung von Chemikalienkosten führt.The aqueous treatment solution can additionally contain about 1 to about 50 g / l of sulfate ions, for example in the form of sodium or potassium salts. The hydrolysis of the persulfate and / or peroxodisulfate ions is suppressed by an excess of sulfate ions without their effect on the production of a colored layer waning. The content of persulfate and / or peroxodisulfate ions in the aqueous treatment solution must therefore be added less frequently or to a lesser extent, which leads to savings in chemical costs.
Schließlich betrifft die Erfindung in einem dritten Aspekt ein Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, 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. Derartige Metallbänder, Metallbleche oder Metallteile gehören ebenfalls zum Umfang der vorliegenden Erfindung. AusführungsbeispieleFinally, in a third aspect, the invention relates to a method according to one or more of claims 1 to 7, characterized in that the metal surfaces are rinsed after being brought into contact with the aqueous treatment solution and coated with a coating based on organic polymers , These metal strips, metal sheets or metal parts can have a coating based on organic polymers, for example one or more layers of paint or an adhesive layer, on the colored conversion layer which results from the treatment with the solution containing persulfate and / or peroxodisulfate. The metal parts produced according to the invention can be connected to other metal parts via this adhesive layer. Such metal strips, metal sheets or metal parts also belong to the scope of the present invention. embodiments
Probebleche aus Aluminium AI 99.5 (die Legierungen AlMgSH , AlMgSiMn und AlMgSiO,5 führen zu ähnlichen Ergebnissen) wurden folgenden Behandlungsschritten unterworfen:Sample sheets made of aluminum AI 99.5 (the alloys AlMgSH, AlMgSiMn and AlMgSiO, 5 lead to similar results) were subjected to the following treatment steps:
1. Reinigung mit einem kommerziellen alkalischen Reiniger der Anmelderin: RidolineR C72, 2 %, 65 °C. 1 Minute1. Cleaning with a commercial alkaline cleaner from the applicant: Ridoline R C72, 2%, 65 ° C. 1 minute
2. Spülen mit vollentsalztem Wasser2. Rinse with deionized water
3. Deoxidieren mit einer kommerziellen Deoxidierlösung der Anmelderin: DeoxidizerR 4902, 10 g/l, 25 °C, 1 ,5 Minuten3. Deoxidizing with a commercial deoxidizing solution from the applicant: Deoxidizer R 4902, 10 g / l, 25 ° C., 1.5 minutes
4. Spülen mit vollentsalztem Wasser4. Rinse with deionized water
5. chemische Oxidation mit Behandlungslösungen gemäß Tabelle 15. chemical oxidation with treatment solutions according to Table 1
6. Spülen mit vollentsalztem Wasser6. Rinse with deionized water
7. Trocknen7. Drying
8. Lackieren mit einem Pulverlack (AL 93-7005, grau, Firma Herberts)8. Painting with a powder coating (AL 93-7005, gray, Herberts company)
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 BehandlungsergebnisseThe lacquered test panels were subjected to a boiling test with a cross cut to test the lacquer adhesion. For this purpose, the coated test panels were boiled in demineralized water for 2 hours and then stored at room temperature for 1 hour. The cross-cut test was then carried out. A value of GT = 0 is considered passed, GT values of> 0 are considered failed. In addition, a corrosion test (salt spray test according to DIN 50021 SS) was carried out and the paint penetration at the scratch was measured according to DIN 53167. The results are shown in Table 1. Table 1: Treatment parameters and treatment results
Unter allen Bedingungen wurden hellgold- bis goldfarbene Schichten erhalten. Light gold to gold colored layers were obtained under all conditions.

Claims

Patentansprüche claims
1. 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 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.1. A process for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being brought into contact with a chromium-free aqueous treatment solution containing a total of 3 to 35 g / l persulfate ions and / or peroxodisulfate ions and not more than 10 g / l contains ammonia or ammonium ions, has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C., the surfaces being treated with the treatment solution for a period in the range from 0.5 to 5 minutes brings in contact.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Behandlungslösung 8 bis 35 g/l Persulfationen enthält.2. The method according to claim 1, characterized in that the treatment solution contains 8 to 35 g / l persulfate ions.
3. Verfahren zum Behandeln von Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen, wobei man die Oberflächen a) mit einer alkalischen Reinigungslösung reinigt, b) danach mit einer sauren Lösung dekapiert, 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 bringt.3. A method for treating surfaces of zinc, aluminum, magnesium or their alloys, the surfaces being a) cleaned with an alkaline cleaning solution, b) then picked up with an acidic solution, c) then with a chromium-free aqueous treatment solution, the total of 3 contains up to 35 g / l persulfate ions and / or peroxodisulfate ions and has a pH in the range from 10 to 12 and a temperature in the range from 30 to 70 ° C. for a period in the range from 0.5 to 5 minutes ,
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Persulfat- und/oder Peroxodisulfationen als Alkalimetallsalze eingebracht wurden und dass der pH-Wert der wässrigen Behandlungslösung mit Natron- und/oder Kalilauge eingestellt ist.4. The method according to one or more of claims 1 to 3, characterized in that the persulfate and / or peroxodisulfate ions have been introduced as alkali metal salts and that the pH of the aqueous treatment solution is adjusted with sodium hydroxide solution and / or potassium hydroxide solution.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die wässrige Behandlungslösung nicht mehr als 1 g/l Ammoniak oder Ammoniumionen enthält.5. The method according to one or more of claims 1 to 4, characterized in that the aqueous treatment solution contains no more than 1 g / l ammonia or ammonium ions.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die wässrige Behandlungslösung keine weiteren Metallionen als Alkalimetall- und/oder Erdalkalimetallionen enthält. 6. The method according to one or more of claims 1 to 5, characterized in that the aqueous treatment solution contains no further metal ions than alkali metal and / or alkaline earth metal ions.
7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die wässrige Behandlungslösung zusätzlich 1 bis 50 g/l Sulfationen enthält.7. The method according to one or more of claims 1 to 6, characterized in that the aqueous treatment solution additionally contains 1 to 50 g / l sulfate ions.
8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, 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.8. The method according to one or more of claims 1 to 7, characterized in that, after having brought the metal surfaces into contact with the aqueous treatment solution, the metal surfaces are rinsed and coated with a coating based on organic polymers.
9. Metallbänder, Metallbleche oder Metallteile, die Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen aufweisen und auf diesen Oberflächen Schichten tragen, die mit einem Verfahren nach einem oder mehreren der Ansprüche 1 bis 8 erzeugt wurden. 9. Metal strips, metal sheets or metal parts which have surfaces of zinc, aluminum, magnesium or their alloys and which have layers on these surfaces which have been produced by a method according to one or more of claims 1 to 8.
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