EP0410497A1 - Process for the passivate rinsing of phosphate coatings - Google Patents

Process for the passivate rinsing of phosphate coatings Download PDF

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Publication number
EP0410497A1
EP0410497A1 EP90201689A EP90201689A EP0410497A1 EP 0410497 A1 EP0410497 A1 EP 0410497A1 EP 90201689 A EP90201689 A EP 90201689A EP 90201689 A EP90201689 A EP 90201689A EP 0410497 A1 EP0410497 A1 EP 0410497A1
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EP
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Prior art keywords
rinsing
aqueous solutions
rinsed
passivating
metal surfaces
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EP90201689A
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German (de)
French (fr)
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EP0410497B1 (en
Inventor
Dieter Hauffe
Thomas Kolberg
Gerhard Müller
Horst Dr. Gehmecker
Werner Dr. Rausch
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Chemetall GmbH
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Metallgesellschaft AG
Continentale Parker SA
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the invention relates to a method for the passivative rinsing of phosphate layers on metals, in particular steel, galvanized steel, alloy galvanized steel and aluminum, before painting or applying adhesives by means of chromium-free aqueous solutions.
  • the process of phosphating is widely used industrially to prepare metal surfaces for subsequent painting.
  • the phosphate layers generated with this cause u. a. better adhesion of the paint films to the metal, increase the corrosion resistance and inhibit the penetration of paint from damage points in the paint film when exposed to corrosion.
  • the protective properties of the phosphate layers are further improved if they are subjected to an aqueous passivating rinse.
  • the passivating rinsing agents based on hexavalent and / or trivalent chromium offer good application properties.
  • the toxicity of the tri- and especially the hexavalent chromium compounds is disadvantageous.
  • US-A-4376000 describes a chrome-free rinse aid based on polyvinylphenol. However, this must be used in a comparatively high concentration, which causes an undesirable wastewater pollution, in particular due to the high oxygen requirement required for the breakdown.
  • soluble zirconium compounds for the aftertreatment of conversion layers.
  • the rinsing agents contain alkali and ammonium as cations. The presence of alkaline earth metal cations is expressly warned. They are used at a pH of 3 to 8.5. However, these rinsing agents do not reach the quality level of the chrome-containing agents.
  • US-A-3895970 describes acidic, aqueous rinsing agents for phosphate layers based on simple or complex fluorides and names chromium zirconium fluoride and zirconium fluoride from the group of zirconium compounds. With the exception of chrome zirconium fluoride, the products mentioned in this patent only meet moderate requirements. Chromium zirconium fluoride, however, has the disadvantage of toxicity already mentioned above.
  • the object of the invention is to provide a method for passivating rinsing of phosphate layers on metals before painting or applying adhesives, which does not have the disadvantages of the known methods and is characterized by higher corrosion protection and very good paint and adhesive adhesion and the Does not pollute the environment or only to a very small extent.
  • 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 phosphated metal surfaces are rinsed with aqueous solutions which contain aluminum fluorozirconate with a molar ratio of Al: Zr: F of (0.15 to 0.67) : 1: (5 to 7) included, the total concentration of Al + Zr + F being 0.1 to 2.0 g / l and the pH being adjusted to 3 to 5.
  • the phosphated metal surfaces are rinsed with aqueous solutions whose total concentration of Al + Zr + F is 0.2 to 0.8 g / l.
  • the method according to the invention is suitable for all types of phosphate layers which can be produced on metals, in particular steel, galvanized and alloy-galvanized steel, aluminized steel, zinc, zinc alloys, aluminum and aluminum alloys.
  • metals in particular steel, galvanized and alloy-galvanized steel, aluminized steel, zinc, zinc alloys, aluminum and aluminum alloys.
  • These include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc iron phosphate, zinc manganese phosphate, zinc calcium phosphate and other layer types with two or more divalent cations.
  • the metal surfaces are expediently rinsed with water before z. B. treated by dipping, spraying, flooding or rolling in accordance with the inventive method.
  • the rinsing agents used in the process according to the invention can be chemically classified into the group of weakly acidic aluminum fluorozirconates.
  • Their manufacture can e.g. B. done so that metallic zirconium or zirconium carbonate is first dissolved in aqueous hydrofluoric acid, complex fluorozirconic acid being formed. Then metallic aluminum or aluminum hydroxide is introduced and dissolved.
  • the rinsing agents can also be prepared in other ways.
  • the phosphated metal surfaces are rinsed with aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l.
  • aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l.
  • the anions can be introduced via the corresponding acids or salts.
  • the pH of the rinse solutions is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
  • the application of the passivating rinse on the phosphated metal surfaces can be done in dipping, flooding, spraying and wetting, e.g. B. done by roller application. Treatment times are between about 1 sec to 2 min.
  • the application temperature can range from room temperature to about 80 ° C. Temperatures between 20 and 50 ° C are usually preferred. Demineralized or low-salt water is preferably used for the preparation of the rinse baths. Water with a high salt content is less suitable for bathing.
  • a further advantageous embodiment of the invention provides that the phosphated metal surfaces are rinsed with deionized water.
  • the method according to the invention is used to prepare the phosphated metal surfaces before painting or applying adhesives. It increases the adhesion of the organic films to the metallic substrate, improves the resistance of the organic films to blistering when exposed to corrosion, and inhibits corrosion penetration from damage points in the film.
  • the method has proven to be particularly advantageous in connection with cathodic electrocoating materials, powder coatings, low-solvent high-solid coatings and with coatings in which water is the main solvent.
  • the phosphating solution had the following composition: 0.7 g / l Zn 0.04 g / l FeIII 1.0 g / l Mn 13 g / l P2O5 1.0 g / l Ni 2.1 g / l NO3 2.9 g / l Na 0.3 g / l F 0.15 g / l NH4 0.07 g / l NO2
  • Fine-crystalline, uniformly covering phosphate layers with a basis weight of 2.5 to 3 g / m 2 were produced on the three metal substrates.
  • the sheets were then rinsed with water and then rinsed passively.
  • the passivating rinsing was carried out by spraying at 30 ° C and 1 min treatment time.
  • the final treatment was a rinse with deionized water.
  • a cathodic electrodeposition primer, a filler and a topcoat were used to paint the sheets. Each layer of paint was baked separately. The total layer thickness was approx. 90 ⁇ m.
  • the rinse aid used in the process according to the invention was prepared by diluting 1.6 g of an aqueous concentrate with 0.855% Al + 8.62% Zr + 10.7% F using deionized water. The pH was then brought to 3.5-4.0 with ammonia. The rinse aid then had the following composition: 0.014 g / l Al + 0.14 g / l Zr + 0.17 g / l F + 0.026 g / l NH3.
  • the individual sample sheets were tested according to the salt spray test according to DIN 50021 SS (1008 h), the filiform test according to ASTM D 2803 (1008 h) and the General Motors Test Method TM 54-26 with 20 cycles (GM-Scab-Test).
  • the paint infiltration was measured in mm.

Abstract

In a process for the passivating rinsing of phosphate layers on metals on which a coating or an adhesive is subsequently to be applied, aqueous solutions which contain aluminium fluorozirconate possessing a molar ratio of Al : Zr : F of (0.15 to 0.67) : 1 : (5 to 7) and have a total concentration of Al + Zr + F of 0.1 to 2.0 g/l, preferably 0.2 to 0.8, g/l and a pH of 3 to 5 are used. The rinsing solutions may additionally contain at least one of the anions benzoate, caprylate, ethylhexanoate and salicylate in a total concentration of 0.05 to 0.5 g/l and may preferably be adjusted to the required pH with cations of volatile bases, such as ammonium, ethanolammonium and di- and triethanolammonium. Subsequent coating is advantageously carried out using a cathodic electrocoating finish, a powder coating or a high-solid coating having a low solvent content.

Description

Die Erfindung betrifft ein Verfahren zur passivierenden Nachspülung von Phosphat­schichten auf Metallen, insbesondere Stahl, verzinktem Stahl, legierungsverzinktem Stahl und Aluminium, vor der Lackierung bzw. dem Auftrag von Klebern mittels chromfreier wässriger Lösungen.The invention relates to a method for the passivative rinsing of phosphate layers on metals, in particular steel, galvanized steel, alloy galvanized steel and aluminum, before painting or applying adhesives by means of chromium-free aqueous solutions.

Das Verfahren der Phosphatierung wird in großem Umfang industriell zur Vorberei­tung von Metalloberflächen für eine anschließende Lackierung eingesetzt. Die damit erzeugten Phosphatschichten bewirken u. a. eine bessere Haftung der Lackfilme auf dem Metall, erhöhen die Korrosionsbeständigkeit und hemmen die von Beschädigungsstellen im Lackfilm bei Korrosionsbeanspruchung ausgehende Lackunterwanderung. Die Schutzeigenschaften der Phosphatschichten werden weiter verbessert, wenn sie einer wässrigen passivierenden Nachspülung unterzogen werden.The process of phosphating is widely used industrially to prepare metal surfaces for subsequent painting. The phosphate layers generated with this cause u. a. better adhesion of the paint films to the metal, increase the corrosion resistance and inhibit the penetration of paint from damage points in the paint film when exposed to corrosion. The protective properties of the phosphate layers are further improved if they are subjected to an aqueous passivating rinse.

Gute anwendungstechnische Eigenschaften bieten die passivierenden Nachspül­mittel auf Basis von sechs- und/oder dreiwertigem Chrom. Nachteilig ist jedoch die Toxizität der drei- und insbesondere der sechswertigen Chromverbindungen.The passivating rinsing agents based on hexavalent and / or trivalent chromium offer good application properties. However, the toxicity of the tri- and especially the hexavalent chromium compounds is disadvantageous.

In der US-A-4376000 wird ein chromfreies Nachspülmittel auf Basis von Polyvinyl­phenol beschrieben. Dieses muß aber in vergleichsweise hoher Konzentration angewendet werden, wodurch eine unerwünschte Abwasserbelastung, insbesondere durch den hohen zum Abbau erforderlichen Sauerstoffbedarf, hervorgerufen wird.US-A-4376000 describes a chrome-free rinse aid based on polyvinylphenol. However, this must be used in a comparatively high concentration, which causes an undesirable wastewater pollution, in particular due to the high oxygen requirement required for the breakdown.

Aus der US-A-3695942 ist es bekannt, lösliche Zirkonverbindungen zur Nachbe­handlung von Konversionsschichten einzusetzen. Die Nachspülmittel enthalten außer Zirkonium als Kationen Alkali und Ammonium. Vor der Anwesenheit von Erdalkalimetallkationen wird ausdrücklich gewarnt. Sie werden bei einem pH-Wert von 3 bis 8,5 eingesetzt. Diese Nachspülmittel erreichen jedoch nicht das Qualitätsniveau der chromhaltigen Mittel.From US-A-3695942 it is known to use soluble zirconium compounds for the aftertreatment of conversion layers. In addition to zirconium, the rinsing agents contain alkali and ammonium as cations. The presence of alkaline earth metal cations is expressly warned. They are used at a pH of 3 to 8.5. However, these rinsing agents do not reach the quality level of the chrome-containing agents.

Die US-A-3895970 beschreibt saure, wässrige Nachspülmittel für Phosphat­schichten auf Basis von einfachen oder komplexen Fluoriden und nennt aus der Gruppe der Zirkoniumverbindungen Chromzirkonfluorid und Zirkonfluorid. Mit Ausnahme des Chromzirkonfluorides genügen die in dieser Patentschrift genannten Produkte nur mittleren Ansprüchen. Chromzirkonfluorid hat jedoch den bereits oben genannten Nachteil der Toxizität.US-A-3895970 describes acidic, aqueous rinsing agents for phosphate layers based on simple or complex fluorides and names chromium zirconium fluoride and zirconium fluoride from the group of zirconium compounds. With the exception of chrome zirconium fluoride, the products mentioned in this patent only meet moderate requirements. Chromium zirconium fluoride, however, has the disadvantage of toxicity already mentioned above.

Aufgabe der Erfindung ist es, ein Verfahren zur passivierenden Nachspülung von Phosphatschichten auf Metallen vor der Lackierung bzw. dem Auftrag von Klebern bereitzustellen, das die Nachteile der bekannten Verfahren nicht aufweist und sich durch höheren Korrosionsschutz sowie durch sehr gute Lack- und Kleberhaftung auszeichnet und die Umwelt nicht bzw. nur in sehr geringem Ausmaße belastet.The object of the invention is to provide a method for passivating rinsing of phosphate layers on metals before painting or applying adhesives, which does not have the disadvantages of the known methods and is characterized by higher corrosion protection and very good paint and adhesive adhesion and the Does not pollute the environment or only to a very small extent.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die phosphatierten Metalloberflächen mit wässrigen Lösungen spült, die Aluminiumfluorozirkonat mit einem Molverhältnis von Al:Zr:F von (0,15 bis 0,67): 1: (5 bis 7) enthalten, wobei die Gesamt-Konzentration von Al + Zr + F 0,1 bis 2,0 g/l beträgt und der pH-Wert auf 3 bis 5 eingestellt ist.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 phosphated metal surfaces are rinsed with aqueous solutions which contain aluminum fluorozirconate with a molar ratio of Al: Zr: F of (0.15 to 0.67) : 1: (5 to 7) included, the total concentration of Al + Zr + F being 0.1 to 2.0 g / l and the pH being adjusted to 3 to 5.

Entsprechend einer bevorzugten Ausgestaltung der Erfindung spült man die phos­phatierten Metalloberflächen mit wässrigen Lösungen, deren Gesamtkonzentration von Al + Zr + F 0,2 bis 0,8 g/l beträgt.According to a preferred embodiment of the invention, the phosphated metal surfaces are rinsed with aqueous solutions whose total concentration of Al + Zr + F is 0.2 to 0.8 g / l.

Das erfindungsgemäße Verfahren eignet sich für alle Phosphatschichttypen, die auf Metallen, insbesondere Stahl, verzinktem und legierungsverzinktem Stahl, aluminiertem Stahl, Zink, Zinklegierungen, Aluminium und Aluminiumlegierungen erzeugt werden können. Hierzu zählen u. a. Zinkphosphat, Eisenphosphat, Mangan­phosphat, Calciumphosphat, Magnesiumphosphat , Nickelphosphat, Cobaltphosphat, Zinkeisenphosphat, Zinkmanganphosphat, Zinkcalciumphosphat und andere Schicht­typen mit zwei oder auch mehr zweiwertigen Kationen. Besonders eignet es sich für die Phosphatschichten, die mit Niedrigzink-Phosphatierverfahren mit und ohne Zusatz weiterer Kationen, wie Mn, Ni, Co, Mg, ausgebildet werden.The method according to the invention is suitable for all types of phosphate layers which can be produced on metals, in particular steel, galvanized and alloy-galvanized steel, aluminized steel, zinc, zinc alloys, aluminum and aluminum alloys. These include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc iron phosphate, zinc manganese phosphate, zinc calcium phosphate and other layer types with two or more divalent cations. It is particularly suitable for the phosphate layers which are formed using low-zinc phosphating processes with and without the addition of other cations, such as Mn, Ni, Co, Mg.

Nach der Phosphatierung werden die Metalloberflächen zweckmäßigerweise mit Wasser gespült, ehe sie z. B. durch Tauchen, Spritzen, Fluten oder Aufwalzen entsprechend dem erfindungsgemäßen Verfahren nach behandelt werden.After the phosphating, the metal surfaces are expediently rinsed with water before z. B. treated by dipping, spraying, flooding or rolling in accordance with the inventive method.

Die im erfindungsgemäßen Verfahren zur Anwendung kommenden Nachspülmittel können chemisch in die Gruppe der schwach sauren Aluminiumfluorozirkonate eingestuft werden. Ihre Herstellung kann z. B. so erfolgen, daß zunächst metallisches Zirkonium oder Zirkoniumcarbonat in wässriger Flußsäure aufgelöst wird, wobei sich komplexe Fluorozirkonsäure bildet. Dann wird metallisches Aluminium oder Aluminiumhydroxid eingetragen und aufgelöst. Obgleich der be­schriebene Herstellweg bevorzugt wird, lassen sich die Nachspülmittel auch auf andere Weise zubereiten.The rinsing agents used in the process according to the invention can be chemically classified into the group of weakly acidic aluminum fluorozirconates. Their manufacture can e.g. B. done so that metallic zirconium or zirconium carbonate is first dissolved in aqueous hydrofluoric acid, complex fluorozirconic acid being formed. Then metallic aluminum or aluminum hydroxide is introduced and dissolved. Although the manufacturing route described is preferred, the rinsing agents can also be prepared in other ways.

Gemäß einer weiteren vorteilhaften Ausführungsform der Erfindung spült man die phosphatierten Metalloberflächen mit wässrigen Lösungen, die zusätzlich mindestens eines der Anionen Benzoat, Caprylat, Ethylhexoat, Salicylat in einer Gesamt-Konzentration von 0,05 bis 0,5 g/l enthalten. Hierdurch wird insbesondere eine weitere Steigerung des Blankkorrosionsschutzes bewirkt. Das Einbringen der Anionen kann über die entsprechenden Säuren bzw. die Salze erfolgen.According to a further advantageous embodiment of the invention, the phosphated metal surfaces are rinsed with aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l. This in particular brings about a further increase in the protection against bright corrosion. The anions can be introduced via the corresponding acids or salts.

Die Einstellung des pH-Wertes der Nachspüllösungen geschieht vorzugsweise mit Kationen flüchtiger Basen. Hierzu zählen insbesondere Ammonium, Ethanol­ammonium sowie Di- und Tri-Ethanolammonium.The pH of the rinse solutions is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.

Die Anwendung der passivierenden Nachspülung auf die phosphatierten Metallober­flächen kann im Tauchen, Fluten, Spritzen und Benetzen, z. B. durch Walzenauftrag erfolgen. Die Behandlungszeiten liegen zwischen etwa 1 sec bis 2 min. Die Anwendungstemperatur kann von Raumtemperatur bis etwa 80°C reichen. Üblicherweise werden Temperaturen zwischen 20 und 50°C bevorzugt. Für den Ansatz der Nachspülbäder wird vorzugsweise vollentsalztes bzw. salzarmes Wasser verwendet. Wässer mit hohem Salzgehalt sind zum Badansatz weniger geeignet.The application of the passivating rinse on the phosphated metal surfaces can be done in dipping, flooding, spraying and wetting, e.g. B. done by roller application. Treatment times are between about 1 sec to 2 min. The application temperature can range from room temperature to about 80 ° C. Temperatures between 20 and 50 ° C are usually preferred. Demineralized or low-salt water is preferably used for the preparation of the rinse baths. Water with a high salt content is less suitable for bathing.

Eine weitere vorteilhafte Ausführungsform der Erfindung sieht vor, die phos­phatierten Metalloberflächen mit vollentsalztem Wasser nachzuspülen.A further advantageous embodiment of the invention provides that the phosphated metal surfaces are rinsed with deionized water.

Das erfindungsgemäße Verfahren wird als Vorbereitung der phosphatierten Metall­oberflächen vor der Lackierung bzw. dem Auftrag von Klebern eingesetzt. Es erhöht die Haftung der organischen Filme auf dem metallischen Untergrund, verbessert die Beständigkeit der organischen Filme gegen Blasenbildung bei Korro­sionsbeanspruchung und hemmt die von Beschädigungsstellen im Film ausgehende Korrosionsunterwanderung. Besonders vorteilhaft hat sich das Verfahren in Verbin­dung mit kathodischen Elektrotauchlacken, Pulverlacken, lösemittelarmen High-­Solid-Lacken und mit Lacken, bei denen Wasser das wesentlichen Lösemittel ist, erwiesen.The method according to the invention is used to prepare the phosphated metal surfaces before painting or applying adhesives. It increases the adhesion of the organic films to the metallic substrate, improves the resistance of the organic films to blistering when exposed to corrosion, and inhibits corrosion penetration from damage points in the film. The method has proven to be particularly advantageous in connection with cathodic electrocoating materials, powder coatings, low-solvent high-solid coatings and with coatings in which water is the main solvent.

Das erfindungsgemäße Verfahren wird anhand des folgenden Beispieles näher und beispielsweise erläutert.The method according to the invention is explained in more detail and, for example, using the following example.

Beispielexample

Entfettete Bleche aus Stahl, elektrolytisch verzinktem Stahl und AlMgSi wurden mit einem manganmodifizierten Niedrigzink-Phosphatierverfahren 2 min bei 55°C im Spritzen behandelt. Die Phosphatierlösung hatte folgende Zusammensetzung:
0,7 g/l Zn    0,04 g/l FeIII
1,0 g/l Mn    13 g/l P₂O₅
1,0 g/l Ni    2,1 g/l NO₃
2,9 g/l Na    0,3 g/l F
0,15 g/l NH₄  0,07 g/l NO₂Degreased sheets of steel, electrolytically galvanized steel and AlMgSi were sprayed with a manganese-modified low-zinc phosphating process for 2 min at 55 ° C. The phosphating solution had the following composition:
0.7 g / l Zn 0.04 g / l FeIII
1.0 g / l Mn 13 g / l P₂O₅
1.0 g / l Ni 2.1 g / l NO₃
2.9 g / l Na 0.3 g / l F
0.15 g / l NH₄ 0.07 g / l NO₂

Auf den drei Metallsubstraten wurden feinkristalline, gleichmäßig deckende Phos­phatschichten mit einem Flächengewicht von 2,5 bis3 g/m² erzeugt. Die Bleche wurden anschließend mit Wasser gespült und danach passivierend nachgespült. Die passivierende Nachspülung erfolgte im Spritzen bei 30°C und 1 min Behandlungs­zeit. Als Schlußbehandlung diente ein Abbrausen mit vollentsalztem Wasser. Zur Lackierung der Bleche diente ein kathodischer Elektrotauchgrund, ein Füller und ein Decklack. Jede Lackschicht wurde gesondert eingebrannt. Die Gesamtlack­schichtdicke betrug ca. 90 µm.Fine-crystalline, uniformly covering phosphate layers with a basis weight of 2.5 to 3 g / m 2 were produced on the three metal substrates. The sheets were then rinsed with water and then rinsed passively. The passivating rinsing was carried out by spraying at 30 ° C and 1 min treatment time. The final treatment was a rinse with deionized water. A cathodic electrodeposition primer, a filler and a topcoat were used to paint the sheets. Each layer of paint was baked separately. The total layer thickness was approx. 90 µm.

Anschließend wurden die Bleche mit einer Stahlnadel bis zum Metalluntergrund angeritzt und verschiedenen Prüfungen ausgesetzt. Die Ergebnisse sind in den Tabellen 1 bis 3 zusammengefaßt.The sheets were then scribed to the metal surface with a steel needle and subjected to various tests. The results are summarized in Tables 1 to 3.

Das im erfindungsgemäßen Verfahren zum Einsatz kommende Nachspülmittel wurde durch Verdünnen von 1,6 g eines wässrigen Konzentrates mit 0,855 % Al + 8,62 % Zr + 10,7 % F unter Verwendung von vollentsalztem Wasser hergestellt. An­schließend wurde der pH-Wert durch Ammoniak auf 3,5 - 4,0 gebracht. Das Nachspülmittel wies dann folgende Zusammensetzung auf: 0,014 g/l Al + 0,14 g/l Zr + 0,17 g/l F + 0,026 g/l NH₃.The rinse aid used in the process according to the invention was prepared by diluting 1.6 g of an aqueous concentrate with 0.855% Al + 8.62% Zr + 10.7% F using deionized water. The pH was then brought to 3.5-4.0 with ammonia. The rinse aid then had the following composition: 0.014 g / l Al + 0.14 g / l Zr + 0.17 g / l F + 0.026 g / l NH₃.

Zu Vergleichsversuchen dienten
eine CrVI-CrIII-haltige Nachspüllösung mit 0,2 g/l CrO₃ und 0,037 g/l CrIII (pH-­Wert 3,5-4,0)
eine Chromfluorozirkonatlösung mit
0,047 g/l CrIII, 0,083 g/l Zr und
0,121 g/l F (pH-Wert 3,5 - 4,0)
sowie eine Polyvinylphenollösung einer Konzentration von 0,6 g/l (pH-Wert 3,5-4,0)Served for comparison experiments
a CrVI-CrIII-containing rinse solution with 0.2 g / l CrO₃ and 0.037 g / l CrIII (pH 3.5-4.0)
a chromium fluorozirconate solution with
0.047 g / l CrIII, 0.083 g / l Zr and
0.121 g / l F (pH 3.5 - 4.0)
as well as a polyvinylphenol solution with a concentration of 0.6 g / l (pH 3.5-4.0)

Die Prüfungen der einzelnen Musterbleche erfolgte nach dem Salzsprühtest gemäß DIN 50021 SS (1008 h), dem Filiformtest gemäß ASTM D 2803 (1008 h) sowie nach General Motors Test Method TM 54-26 mit 20 Zyklen (GM-Scab-Test). Gemessen wurde die Lackunterwanderung in mm. Tabelle 1 Ergebnisse auf Stahl Nachspülmittel pH Lackunterwanderung (mm) in Salzsprühtest DIN 50021 SS (1008 h) Filiformtest ASTM D 2803 (1008 h) GM-Scab-Test (20 Zyclen) Cr(VI)-Cr(III) 3,5 - 4,0 0 - <1 0 3,5 Chromfluorozirkonat 0 - <1 0 - <1 3,5 Polyvinylphenol 0 - 1 <1 4,0 Aluminiumfluorozirkonat NH₃ auf pH → (Erfindung) 0 0 3,5 Tabelle 2 Ergebnisse auf verzinktem Stahl Nachspülmittel pH Lackunterwanderung (mm) im Salzsprühtest DIN 50021 SS (1008 h) Filiformtest ASTM D 2803 (1008 h) GM-Scab-Test (20 Zyclen) Cr(VI)-Cr(III) 3,5 - 4,0 8,5 0 <1 - 1 Chromfluorozirkonat 7,0 0 - <1 <1 - 1 Polyvinylphenol 6,5 0 - <1 1 Aluminiumfluorozirkonat NH₃ auf pH → (Erfindung) 5,5 0 <1 - 1 Tabelle 3 Ergebnisse auf AlMgSi Nachspülmittel pH Lackunterwanderung (mm) im Salzsprühtest DIN 50021 SS (1008 h) Filiformtest ASTM D 2803 (1008 h) GM-Scab-Test (20 Zyclen) Cr(VI)-Cr(III) 3,5 - 4,0 <1 0 0,5-1 Chromfluorozirkonat 0 0 1 Polyvinylphenol 0 - <1 0 1 Aluminiumfluorozirkonat NH₃ auf pH → (Erfindung) 0 0 0,5-1 The individual sample sheets were tested according to the salt spray test according to DIN 50021 SS (1008 h), the filiform test according to ASTM D 2803 (1008 h) and the General Motors Test Method TM 54-26 with 20 cycles (GM-Scab-Test). The paint infiltration was measured in mm. Table 1 Results on steel Rinse aid pH Paint infiltration (mm) in Salt spray test DIN 50021 SS (1008 h) Filiform test ASTM D 2803 (1008 h) GM Scab test (20 cycles) Cr (VI) -Cr (III) 3.5 - 4.0 0 - <1 0 3.5 Chromium fluorozirconate 0 - <1 0 - <1 3.5 Polyvinylphenol 0 - 1 <1 4.0 Aluminum fluorozirconate NH₃ at pH → (invention) 0 0 3.5 Results on galvanized steel Rinse aid pH Paint infiltration (mm) in Salt spray test DIN 50021 SS (1008 h) Filiform test ASTM D 2803 (1008 h) GM Scab test (20 cycles) Cr (VI) -Cr (III) 3.5 - 4.0 8.5 0 <1 - 1 Chromium fluorozirconate 7.0 0 - <1 <1 - 1 Polyvinylphenol 6.5 0 - <1 1 Aluminum fluorozirconate NH₃ at pH → (invention) 5.5 0 <1 - 1 Results on AlMgSi Rinse aid pH Paint infiltration (mm) in Salt spray test DIN 50021 SS (1008 h) Filiform test ASTM D 2803 (1008 h) GM Scab test (20 cycles) Cr (VI) -Cr (III) 3.5 - 4.0 <1 0 0.5-1 Chromium fluorozirconate 0 0 1 Polyvinylphenol 0 - <1 0 1 Aluminum fluorozirconate NH₃ at pH → (invention) 0 0 0.5-1

Ein Vergleich der Tabellenwerte zeigt, daß das erfindungsgemäße Verfahren in jedem Fall mindestens so gute Werte lieferte wie das beste der drei mitgeprüften Vergleiche.A comparison of the table values shows that the method according to the invention in any case gave at least as good values as the best of the three comparisons which were also tested.

Claims (9)

1. Verfahren zur passivierenden Nachspülung von Phosphatschichten auf Metallen, insbesondere Stahl, verzinktem Stahl, legierungsverzinktem Stahl und Alu­minium, vor der Lackierung bzw. dem Auftrag von Klebern mittels chromfreier wässriger Lösungen, dadurch gekennzeichnet, daß man die phosphatierten Metalloberflächen mit wässrigen Lösungen spült, die Aluminiumfluorozirkonat mit einem Molverhältnis von Al:Zr:F von (0,15 bis 0,67): 1: (5 bis 7) enthalten, wobei die Gesamt-Konzentration von Al + Zr + F 0,1 bis 2,0 g/l beträgt und der pH-Wert auf 3 bis 5 eingestellt ist.1. Process for the passivating rinsing of phosphate layers on metals, in particular steel, galvanized steel, alloy galvanized steel and aluminum, before painting or applying adhesives using chromium-free aqueous solutions, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which Contain aluminum fluorozirconate with a molar ratio of Al: Zr: F of (0.15 to 0.67): 1: (5 to 7), the total concentration of Al + Zr + F 0.1 to 2.0 g / l and the pH value is set to 3 to 5. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die phospha­tierten Metalloberflächen mit wässrigen Lösungen spült, deren Gesamtkonzen­tration von Al + Zr + F 0,2 bis 0,8 g/l beträgt.2. The method according to claim 1, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions whose total concentration of Al + Zr + F is 0.2 to 0.8 g / l. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die phosphatierten Metalloberflächen mit wässrigen Lösungen spült, die zusätzlich mindestens eines der Anionen Benzoat, Caprylat, Ethylhexoat, Salicylat in einer Gesamt-Konzentration 0,05 bis 0,5 g/l enthalten.3. The method according to claim 1 or 2, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which additionally at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l contain. 4. Verfahren nach den Ansprüchen 1, 2 oder 3, dadurch gekennzeichnet, daß man die phosphatierten Metalloberflächen mit wässrigen Lösungen spült, deren pH-­Wert mit Kationen flüchtiger Basen, vorzugsweise Ammonium, Ethanol­ammonium, Di- und Tri-Ethanolammonium, eingestellt ist.4. The method according to claims 1, 2 or 3, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions, the pH of which is adjusted with cations of volatile bases, preferably ammonium, ethanolammonium, di- and tri-ethanolammonium. 5. Verfahren nach den Ansprüchen 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man im Anschluß an die passivierende Nachspülung mit vollentsalztem Wasser nachspült.5. The method according to claims 1, 2, 3 or 4, characterized in that rinsing with demineralized water after the passivating rinsing. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekenn­zeichnet, daß man im Anschluß an die passivierende Nachspülung einen kathodischer Elektrotauchlack aufbringt.6. The method according to one or more of claims 1 to 5, characterized in that a cathodic electrocoat is applied following the passivating rinsing. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekenn­zeichnet, daß man im Anschluß an die passivierende Nachspülung einen Pulver­lack aufbringt.7. The method according to one or more of claims 1 to 5, characterized in that a powder coating is applied following the passivating rinsing. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekenn­zeichnet, daß man im Anschluß an die passivierende Nachspülung einen löse­mittelarmen High-Solid-Lack aufbringt.8. The method according to one or more of claims 1 to 5, characterized in that a low-solvent high-solid paint is applied following the passivating rinsing. 9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekenn­zeichnet, daß man im Anschluß an die passivierende Nachspülung einen Lack mit Wasser als wesentliches Lösemittel aufbringt.9. The method according to one or more of claims 1 to 5, characterized in that, after the passivating rinsing, a lacquer is applied with water as the essential solvent.
EP90201689A 1989-07-28 1990-06-26 Process for the passivate rinsing of phosphate coatings Expired - Lifetime EP0410497B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90201689T ATE81533T1 (en) 1989-07-28 1990-06-26 PROCESS FOR THE PASSIVATION RINSE OF PHOSPHATE COATINGS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3924984 1989-07-28
DE3924984A DE3924984A1 (en) 1989-07-28 1989-07-28 METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS

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EP0410497A1 true EP0410497A1 (en) 1991-01-30
EP0410497B1 EP0410497B1 (en) 1992-10-14

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EP (1) EP0410497B1 (en)
JP (1) JP2909517B2 (en)
AT (1) ATE81533T1 (en)
BR (1) BR9003594A (en)
CA (1) CA2018631C (en)
DD (1) DD298436A5 (en)
DE (2) DE3924984A1 (en)
ES (1) ES2035699T3 (en)
PL (1) PL164742B1 (en)
PT (1) PT94843B (en)
ZA (1) ZA905922B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459550A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Process for rinsing conversion coatings
EP0459549B1 (en) * 1990-05-29 1994-08-17 METALLGESELLSCHAFT Aktiengesellschaft Production of conversion coatings on zinc or zinc alloy surfaces
EP0486778B1 (en) * 1990-11-21 1996-01-03 Ppg Industries, Inc. Non-chrome final rinse for phosphated metal
US6090224A (en) * 1995-03-29 2000-07-18 Henkel Kommanditgesellschaft Auf Aktien Phosphating process with a copper-containing re-rinsing stage
WO2002066702A1 (en) 2001-02-16 2002-08-29 Henkel Kommanditgesellschaft Auf Atkien Process for treating multi-metal articles
US6447662B1 (en) 1998-08-01 2002-09-10 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing, rerinsing and cathodic electro-dipcoating
EP2405031A1 (en) * 2010-07-07 2012-01-11 Mattthias Koch Method for coating shaped bodies and coated shaped body
WO2017178619A1 (en) * 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Suppression of phosphate dragging resulting from the plant design in a dip coating process sequence
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11118271B2 (en) 2016-04-15 2021-09-14 Henkel Ag & Co. Kgaa Conveyor frame treatment for suppressing phosphate dragging resulting from the plant design in a dip coating process sequence

Families Citing this family (4)

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DE19854091C2 (en) * 1998-11-24 2002-07-18 Audi Ag Process for the pre-treatment of bodies before painting
DE10010355A1 (en) * 2000-03-07 2001-09-13 Chemetall Gmbh Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution
KR20020051991A (en) * 2000-12-23 2002-07-02 이구택 Method of producing corrosion- resistance steel sheet coated with zirconium and silane coupling agent
MY162565A (en) * 2010-09-15 2017-06-30 Jfe Steel Corp Steel sheet for containers and manufacturing method for same

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FR2232615A1 (en) * 1973-06-11 1975-01-03 Pennwalt Corp
US3966502A (en) * 1972-08-17 1976-06-29 Amchem Products, Inc. Zirconium rinse for phosphate coated metal surfaces
EP0161667A1 (en) * 1984-05-18 1985-11-21 PARKER CHEMICAL COMPANY (a Delaware company) Process for the treatment of metal surfaces
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes

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FR2117256A5 (en) * 1970-12-02 1972-07-21 Amchem Prod
US3966502A (en) * 1972-08-17 1976-06-29 Amchem Products, Inc. Zirconium rinse for phosphate coated metal surfaces
FR2207199A1 (en) * 1972-11-20 1974-06-14 Pennwalt Corp
FR2232615A1 (en) * 1973-06-11 1975-01-03 Pennwalt Corp
EP0161667A1 (en) * 1984-05-18 1985-11-21 PARKER CHEMICAL COMPANY (a Delaware company) Process for the treatment of metal surfaces
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459549B1 (en) * 1990-05-29 1994-08-17 METALLGESELLSCHAFT Aktiengesellschaft Production of conversion coatings on zinc or zinc alloy surfaces
EP0459550A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Process for rinsing conversion coatings
EP0486778B1 (en) * 1990-11-21 1996-01-03 Ppg Industries, Inc. Non-chrome final rinse for phosphated metal
US6090224A (en) * 1995-03-29 2000-07-18 Henkel Kommanditgesellschaft Auf Aktien Phosphating process with a copper-containing re-rinsing stage
US6447662B1 (en) 1998-08-01 2002-09-10 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing, rerinsing and cathodic electro-dipcoating
EP1368507A1 (en) * 2001-02-16 2003-12-10 Henkel Kommanditgesellschaft auf Aktien Process for treating multi-metal articles
WO2002066702A1 (en) 2001-02-16 2002-08-29 Henkel Kommanditgesellschaft Auf Atkien Process for treating multi-metal articles
EP1368507A4 (en) * 2001-02-16 2009-11-25 Henkel Ag & Co Kgaa Process for treating multi-metal articles
EP2405031A1 (en) * 2010-07-07 2012-01-11 Mattthias Koch Method for coating shaped bodies and coated shaped body
WO2012003983A1 (en) * 2010-07-07 2012-01-12 Matthias Koch Method for coating moulded bodies and coated moulded body
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions
WO2017178619A1 (en) * 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Suppression of phosphate dragging resulting from the plant design in a dip coating process sequence
CN108779572A (en) * 2016-04-15 2018-11-09 汉高股份有限及两合公司 Inhibit the phosphate traction caused by plant design in dipping process sequence
US11118271B2 (en) 2016-04-15 2021-09-14 Henkel Ag & Co. Kgaa Conveyor frame treatment for suppressing phosphate dragging resulting from the plant design in a dip coating process sequence

Also Published As

Publication number Publication date
CA2018631A1 (en) 1991-01-28
PT94843A (en) 1991-04-18
PL286243A1 (en) 1991-04-22
PL164742B1 (en) 1994-10-31
JP2909517B2 (en) 1999-06-23
DE3924984A1 (en) 1991-01-31
CA2018631C (en) 1999-05-11
ZA905922B (en) 1992-03-25
EP0410497B1 (en) 1992-10-14
ATE81533T1 (en) 1992-10-15
DD298436A5 (en) 1992-02-20
DE59000357D1 (en) 1992-11-19
BR9003594A (en) 1991-08-27
PT94843B (en) 1997-03-31
ES2035699T3 (en) 1993-04-16
JPH0361385A (en) 1991-03-18

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