EP0015020B2 - Process for the surface treatment of metals and its use for the treatment of aluminium surfaces - Google Patents

Process for the surface treatment of metals and its use for the treatment of aluminium surfaces Download PDF

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Publication number
EP0015020B2
EP0015020B2 EP80200096A EP80200096A EP0015020B2 EP 0015020 B2 EP0015020 B2 EP 0015020B2 EP 80200096 A EP80200096 A EP 80200096A EP 80200096 A EP80200096 A EP 80200096A EP 0015020 B2 EP0015020 B2 EP 0015020B2
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European Patent Office
Prior art keywords
liquid
wetted
process according
metal
metal surface
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EP80200096A
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German (de)
French (fr)
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EP0015020A1 (en
EP0015020B1 (en
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Dieter Dr. Oppen
Karl Lampatzer
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/40—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/40—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the invention relates to a process for the preparation of metal surfaces for subsequent coating with organic coatings by applying a phosphate coating by wetting with an aqueous phosphating liquid containing at least 2-valent cations and then drying the liquid film without intermediate rinsing and its application to the treatment of aluminum surfaces .
  • the so-called three-step process is becoming increasingly important.
  • the metal surface is cleaned to free it of oil, dirt and corrosion products.
  • the second stage is a rinse with water, whereby chemical residues from the first stage are removed from the metal surface.
  • the metal surface is wetted with an aqueous chemical reaction solution and the liquid film is dried.
  • DE-B-1 769 582 describes a method in which an aqueous solution which contains hexavalent chromium, trivalent chromium, alkali ions and silicon dioxide in certain proportions is dried on the metal.
  • the coatings formed are e.g. B. as electrical insulation, as corrosion protection and as a primer for paints and the like.
  • DE-A-25 06 349 discloses means, solution and method for applying phosphate layers on metal surfaces which aim to produce iron phosphate layers.
  • the known aqueous phosphating solutions contain monosodium phosphate or monoammonium phosphate, and the fact that the phosphating solution mentioned as the main constituent of monosodium orthophosphate in addition to small amounts of manganese (11) oxalate, boric acid, benzenesulfonate, ammonium molybdate, tartaric acid, phosphoric acid, surfactant and contains urea.
  • the phosphate layer is formed by immersion or spraying at approx. 40 to 70 ° C, i.e. in constant contact with excess solution.
  • the object of the invention is to provide a method which avoids the known, in particular the aforementioned disadvantages, and yet can be carried out simply and without additional effort.
  • 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 metal surface is wetted with a phosphating liquid in which the cationic component of the metal phosphate is replaced by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, Nickel, cobalt and / or manganese is formed, which has a pH of 1.5 to 3.0, is chromium-free and contains soluble molybdate, tungstate, vanadate, niobate and / or tantalate ions in addition to metal phosphate.
  • a phosphating liquid in which the cationic component of the metal phosphate is replaced by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, Nickel, cobalt and / or manganese is formed, which has a pH of 1.5 to 3.0, is chromium-free and contains soluble molybdate, tungstate, vanadate, niobate and / or tantalate
  • the wetting of the metal surface can e.g. B. by dipping and then draining, pouring and spinning, brushing, spraying with compressed air, air-less and also electrostatically, spraying, rolling with structured and smooth rollers in the same direction and in counter-rotation.
  • the phosphating liquid to be used according to the method according to the invention can be modified by additionally adding simple or complex-bound fluoride ions, such as fluotitanate, fluozirconate, fluostannate, fluoborate and / or fluosilicate. This results in an increased improvement in the anchoring as a result of a corresponding pickling attack on the metal surface.
  • simple or complex-bound fluoride ions such as fluotitanate, fluozirconate, fluostannate, fluoborate and / or fluosilicate.
  • a reduction equivalent here means the amount of reducing agent that is able to increase the valency of the introduced molybdate, tungstate, vanadate, niobate and / or tantalate ions by one valence level, e.g. from Mo VI to Mo V. It must be taken into account here that individual reducing agents within a molecule can have several groups capable of reduction.
  • a further preferred embodiment of the invention consists in using phosphating liquids which additionally contain finely tailed silica and / or dispersible, film-forming organic polymers, such as polyacrylate.
  • organic polymers such as polyacrylate.
  • pyrogenic silica obtained from silicon tetrachloride or silica precipitated in an aqueous medium from alkali silicates have proven to be the source of the finely divided silica. What is important here is the small grain size of the silica, since it ensures a uniform, stable suspension in the aqueous, acidic reaction liquid.
  • the organic polymers which can be used are those which are customary in paint production.
  • the addition of the abovementioned substances serves in particular to thicken the phosphating liquid and thus represents one of the possibilities for regulating the thickness of the liquid film to be applied.
  • the addition of organic polymers has an advantageous effect on the adhesion in individual applications dependent on the subsequent treatment.
  • Further preferred refinements of the method according to the invention consist in wetting the metal surface with a phosphating liquid in which the molar ratio of metal phosphate (calculated as Me “ + (H 2 P0 4 ) n ) to molybdate, tungstate, niobate, tantalate and / or vanadate ion (calculated as MoO 3 , W0 3 , Nb 2 0 5 , Ta 2 0 5 , V 2 0 5 ) in the range of 1: (0.4 to 0.01) and / or in which the molar ratio from metal phosphate (calculated as Me "+ (H 2 P0 4 ) n ) to silica (calculated as Si0 2 ) to fluoride (calculated as (Me n + F n + 2 ) 2- ) in the range of 1: (0.2 to 5.0). (0.04 to 2.0) and / or in which the weight ratio of metal phosphate (calculated as Me " + (H 2
  • the liquids used according to the invention preferably contain the components in an amount such that they have an evaporation residue of 5 to 150 g / l.
  • a liquid film amount between 2.5 and 25 ml / m 2 workpiece surface is preferably used.
  • Particularly good application results are achieved if the film of the phosphating liquid is dimensioned such that a layer weight of 0.03 to 0.6 g / m 2 is obtained after drying.
  • the drying after the wetting of the metal surface can already take place at room temperature. However, better results are achieved at higher temperatures, preferably temperatures between 50 and 100 ° C.
  • the metallic workpieces can be in various forms, e.g. as a shaped body, tube, rod, wire, but preferably as sheet metal or tape, are used.
  • the method according to the invention is suitable for a large number of metals and metal alloys.
  • a special application is in the treatment of metal surfaces made of iron, zinc or alloys thereof.
  • the method according to the invention is of outstanding importance for the coating of surfaces made of aluminum or aluminum alloys.
  • the layers obtained are non-toxic, have high corrosion protection and good adhesion and adhesion-promoting properties, and that the treatment liquid is stable, ie. H. does not experience a change in composition due to reaction or precipitation of components.
  • the process has no wastewater problems.
  • the subsequent treatment following the process according to the invention consists in particular in the application of lacquers, adhesives or plastics, which can be carried out in the manner customary for this.
  • the contents of the individual treatment liquids of active substances as well as the amount of liquid applied per square meter in ml, the evaporation residue of the treatment liquid in g / l and the layer weight obtained in mg / m 2 surface are summarized in a table.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Vorbereitung von Metalloverflächen zur anschließenden Beschichtung mit organischen Überzügen durch Aufbringen einer Phosphatüberzuges mittels Benetzen mit einer mindestens 2-wertige Kationen enthaltenden wäßrigen Phosphatierungs-Flüssigkeit und an-schließendes Auftrocknen des Flüssigkeitsfilmes ohne Zwischenspülung sowie dessen Anwendung auf die Behandlung von Aluminiumoberflächen.The invention relates to a process for the preparation of metal surfaces for subsequent coating with organic coatings by applying a phosphate coating by wetting with an aqueous phosphating liquid containing at least 2-valent cations and then drying the liquid film without intermediate rinsing and its application to the treatment of aluminum surfaces .

Für die chemische Oberflächenbehandlung von Metallen, beispielsweise als Vorbereitung für den Auftrag von Lacken, Klebern und Kunststoffen, gewinnen die sogenannten Dreistufen-Verfahren zunehmend an Bedeutung. In der ersten Stufe wird die Metalloberfläche gereinigt, um sie von Öl, Schmutz und Korrosionsprodukten zu befreien. Die zweite Stufe stellt eine Spülung mit Waaser dar, wobei Chemikalienreste aus der ersten Stufe von der Metalloberfläche entfernt werden. In der driften Stufe schliesslich wird die Metalloberfläche mit einer wässrigen chemischen Reaktionslösung benetzt und der Flüssigkeitsfilm aufgetrocknet.For the chemical surface treatment of metals, for example as preparation for the application of paints, adhesives and plastics, the so-called three-step process is becoming increasingly important. In the first stage, the metal surface is cleaned to free it of oil, dirt and corrosion products. The second stage is a rinse with water, whereby chemical residues from the first stage are removed from the metal surface. Finally, in the drift stage, the metal surface is wetted with an aqueous chemical reaction solution and the liquid film is dried.

Durch das vorstehend geschilderte Verfahren wird auf dem Metall ein dünner, nichtmetallischer Überzug gebildet, der bei entsprechend gewählter Zusammensetzung der Behandlungsflüssigkeit und Reaktionsbedingung die Oberflächenqualität entscheidend verbessern kann. So können sich z. B. Überzüge aus Lacken, Klebern und Kunststoffen durch eine wesentlich grössere Haftung und einen beachtlich erhöhten Korrosionsschutz auszeichnen, wenn aie auf derartig vorbehandeltem Metall aufgebracht werden.The process described above forms a thin, non-metallic coating on the metal, which can decisively improve the surface quality if the composition of the treatment liquid and the reaction conditions are selected accordingly. So z. B. coatings from paints, adhesives and plastics are characterized by a much greater adhesion and a considerably increased corrosion protection, if aie are applied to such pretreated metal.

In der DE-B-1 769 582 ist beispielsweise ein Verfahren beschrieben, bei dem eine wässrige Lösung, die 6wertiges Chrom, 3wertiges Chrom, Alkaliionen und Siliciumdioxid in bestimmten Mengenverhältnissen enthält, auf dem Metall aufgetrocknet wird. Die gebildeten Überzüge sind z. B. als elektrische Isolation, als Korrosionsschutz und als Haftgrund für Lacke und dergleichen gut geeignet.For example, DE-B-1 769 582 describes a method in which an aqueous solution which contains hexavalent chromium, trivalent chromium, alkali ions and silicon dioxide in certain proportions is dried on the metal. The coatings formed are e.g. B. as electrical insulation, as corrosion protection and as a primer for paints and the like.

Aus der US-A-2 030 601 ist ein anderes Verfahren bekannt, bei dem auf Eisenoberflächen hochkonzentrierte wässrige Lösungen mit 10 bis 20 Gew.-% Phosphorsäure, 10 bis 15 Gew.-% Natriumdichromat, gegebenenfalls unter Zusatz von Kieselsäure, aufgebürstet und anschliessend aufgetrocknet werden. Diese Behandlung dient zum Schutz gegen Rostbildung.Another process is known from US Pat. No. 2,030,601, in which aqueous solutions with 10 to 20% by weight phosphoric acid, 10 to 15% by weight sodium dichromate, optionally with the addition of silica, are highly brushed on iron surfaces and then brushed on be dried out. This treatment serves to protect against rust formation.

Weiterhin ist es bekannt, Überzüge auf Metalloberflächen mit Hilfe von Überzugsmitteln herzustellen, die eine Verbindung des 6wertigen Chroms und einen polymeren organischen Stoff enthalten (sogenannte Primer) und anschliessend aufgetrocknet bzw. eingebrannt werden (AT-PS 197 164).Furthermore, it is known to produce coatings on metal surfaces with the aid of coating agents which contain a compound of hexavalent chromium and a polymeric organic substance (so-called primer) and are then dried or baked (AT-PS 197 164).

Allen vorgenannten Verfahren ist der Nachteil gemeinsam, dass infolge der Anwesenheit von 6wertigem Chrom besondere Vorsichtsmassnahmen bei der Applikation des Überzugsmittels und der Handhabung des beschichteten Metalles erforderlich sind und dass bei Verwendung derartig beschichteter Metalle als Behältermaterial für Lebensmittel und Getränke eine Beeinflussung des Behälterinhaltes nicht auszuschliessen ist. Sofern die Überzugsmittel organische Bestandteile aufweisen, ist ein weiterer Nachteil die geringe Standzeit (Topfzeit) der Behandlungsflüssigkeiten.All of the above-mentioned processes have the disadvantage that, due to the presence of hexavalent chromium, special precautionary measures are required when applying the coating agent and when handling the coated metal, and that the use of metals coated in this way as container material for food and beverages cannot affect the container contents . If the coating agents have organic components, a further disadvantage is the short service life (pot life) of the treatment liquids.

Um die mit der Verwendung von 6wertiges Chrom enthaltenden Behandlungsflüssigkeiten verbundenen Nachteile zu vermeiden, ist es bereits bekannt, die gereinigte Metalloberfläche, insbesondere von Eisen, Zink und Aluminium, mit einer sauren wässrigen Lösung, die Chrom-111-lonen, Phosphationen und feinverteilte Kieselsäure, gegebenenfalls auch Acetat-, Maleinat-, Zink- und/oder Manganionen, enthält, zu benetzen und den Lösungsfilm aufzutrocknen (DE-OS 2711 431). Obgleich dieses Verfahren gegenüber den vorgenannten erhebliche Vorteile aufweist, ist nachteilig, dass bei Verwendung der beschichteten Metalle ala Behältermaterial eine gewisse Beeinflussung von Lebensmitteln und Getränken infolge des Chrom-III-Gehaltes der Schicht nicht ganzlich auszuschiiessen ist und daas die Behandlungsflüssigkeit durch Bildung von schwerlösslichem Chromphosphat zur instabiiität neigt.In order to avoid the disadvantages associated with the use of treatment fluids containing hexavalent chromium, it is already known to clean the cleaned metal surface, in particular iron, zinc and aluminum, with an acidic aqueous solution containing the chromium-111 ions, phosphate ions and finely divided silica. optionally also contains acetate, maleate, zinc and / or manganese ions to wet and dry the solution film (DE-OS 2711 431). Although this method has considerable advantages over the aforementioned, it is disadvantageous that when using the coated metals as container material, a certain influence on food and beverages due to the chromium III content of the layer cannot be completely ruled out, and that the treatment liquid is formed by the formation of poorly soluble chromium phosphate tends to be instable.

Schließlich sind aus der DE - A - 25 06 349 Mittel, Lösung und Verfahren zum Aufbringen von Phosphatschichten auf Metalloberflächen bekannt, die darauf zielen, Eisenphosphatschichten zu erzeugen. Im Einklang hiermit steht der Hinweis, daß die bekannten wäßrigen Phosphatierungslösungen Mononatriumphosphat oder Monoammoniumphosphat enthalten, und die Tatsache, daß die beispielsweise genannte Phosphatierungslösung als Hauptbestandteil Mononatriumorthophosphat neben geringen Mengen Mangan (11)-Oxalat, Borsäure, Benzolsulfonat, Ammoniummolybdat, Weinsäure, Phosphorsäure, Tensid und Harnstoff enthält.Finally, DE-A-25 06 349 discloses means, solution and method for applying phosphate layers on metal surfaces which aim to produce iron phosphate layers. In line with this is the indication that the known aqueous phosphating solutions contain monosodium phosphate or monoammonium phosphate, and the fact that the phosphating solution mentioned as the main constituent of monosodium orthophosphate in addition to small amounts of manganese (11) oxalate, boric acid, benzenesulfonate, ammonium molybdate, tartaric acid, phosphoric acid, surfactant and contains urea.

Bei diesem Verfahren erfolgt die Ausbildung der Phosphatschicht im Tauchen oder Spritzen bei ca. 40 bis 70° C, also in ständigem Kontakt mit überschüssiger Lösung.In this process, the phosphate layer is formed by immersion or spraying at approx. 40 to 70 ° C, i.e. in constant contact with excess solution.

Da bei derartigen Verfahren schon zur Entfernung der Alkalisalzreste eine Wasserspülung üblich ist, gehört es nicht in die vorstehend behandelte Verfahrenskategorie der sogenannten Dreistufen-Verfahren, bei denen die Metalloberfläche mit einer wäßrigen chemischen Reaktionslösung benetzt und der Flüssigkeitsfilm aufgetrocknet wird.Since a water rinse is already customary in such processes for removing the alkali salt residues, it does not belong to the process category of the so-called three-step processes, in which the metal surface is wetted with an aqueous chemical reaction solution and the liquid film is dried.

Aufgabe der Erfindung ist, ein Verfahren bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile vermeidet und dennoch einfach und ohne zusätzlichen Aufwand durchführbar ist.The object of the invention is to provide a method which avoids the known, in particular the aforementioned disadvantages, and yet can be carried out simply and without additional effort.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, in der die kationische Komponente des Metallphosphats durch Kalzium, Magnesium, Barium, Aluminium, Zink, Cadmium, Eisen, Nickel, Kobalt und/oder Mangan gebildet wird, die einen pH-Wert von 1,5 bis 3,0 aufweist, chromfrei ist und neben Metallphosphat lösliche Molybdat-, Wolframat-, Vanadat-, Niobat- und/oder Tantalat-lonen enthält.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 metal surface is wetted with a phosphating liquid in which the cationic component of the metal phosphate is replaced by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, Nickel, cobalt and / or manganese is formed, which has a pH of 1.5 to 3.0, is chromium-free and contains soluble molybdate, tungstate, vanadate, niobate and / or tantalate ions in addition to metal phosphate.

Kationen der vorgenannten Art bilden in einfachster Weise festhaftende tertiäre Phosphate.Cations of the aforementioned type form easily adhering tertiary phosphates.

Die Benetzung der Metalloberfläche kann z. B. durch Tauchen und anschliessendes Abtropfenlassen, Übergiessen und Abschleudern, Bürsten, Spritzen mit Pressluft, air-less und auch elektrostatisch, Sprühen, Aufwalzen mit strukturierten und glatten Walzen im Gleichlauf und Gegenlauf erfolgen.The wetting of the metal surface can e.g. B. by dipping and then draining, pouring and spinning, brushing, spraying with compressed air, air-less and also electrostatically, spraying, rolling with structured and smooth rollers in the same direction and in counter-rotation.

Die nach dem erfindungsgemässen Verfahren einzusetzende Phosphatierungsflüssigkeit kann modifiziert werden, indem zusätziich einfache oder komplexgebundene Fluoridionen, wie Fluotitanat, Fluozirkonat, Fluostannat, Fluoborat und/ oder Fluosilikat zugegeben werden. Hierdurch wird eine erhöhte Verbesserung der Verankerung infolge eines entsprechenden Beizangriftes auf die Metalloberfläche erzielt.The phosphating liquid to be used according to the method according to the invention can be modified by additionally adding simple or complex-bound fluoride ions, such as fluotitanate, fluozirconate, fluostannate, fluoborate and / or fluosilicate. This results in an increased improvement in the anchoring as a result of a corresponding pickling attack on the metal surface.

Als besonders vorteilhaft hat es sich erwiesen, der Phosphatierungsflüssigkeit reduzierende Substanzen, insbesondere aus der Gruppe Aldehyde, Oxycarbonsäure, Hydrazin, Hydroxylamin und/oder Hypophosphit, zuzusetzen. Die Zusatzmenge sollte dabei vorzugsweise mindestens ein Reduktionsäquivalent betragen. Ein Reduktionsäquivalent bedeutet hierbei die Reduktionsmittelmenge, die in der Lage ist, die Wertigkeit der eingebrachten Molybdat-, Wolframat-, Vanadat-, Niobat- und/oder Tantalat-lonen um eine Wertigkeitsstufe, also z.B. von Mo VI zu Mo V, zu verringern. Hierbei ist zu berücksichtigen, dass einzelne Reduktionsmittel innerhalb eines Moleküls mehrere zur Reduktion befähigte Gruppen besitzen können.It has proven to be particularly advantageous to add substances reducing the phosphating liquid, in particular from the group of aldehydes, oxycarboxylic acid, hydrazine, hydroxylamine and / or hypophosphite. The amount added should preferably be at least one reduction equivalent. A reduction equivalent here means the amount of reducing agent that is able to increase the valency of the introduced molybdate, tungstate, vanadate, niobate and / or tantalate ions by one valence level, e.g. from Mo VI to Mo V. It must be taken into account here that individual reducing agents within a molecule can have several groups capable of reduction.

Eine weitere vorzugsweise Ausgestaltung der Erfindung besteht darin, Phosphatierungsflüssigkeiten einzusetzen, die zusätzlich feinvertailte Kieselsäure und/oder dispergierbare, filmbildende organische Polymere, wie Polyacrylat, enthalten. Als Quelle für die feinverteilte Kieselsäure haben sich beispielsweise pyrogen aus Siliciumtetrachlorid gewonnene Kieselsäure oder im wässrigen Medium aus Alkalisilikaten gefällte Kieselsäure bewährt. Wesentlich ist dabei die geringe Korngrösse der Kieselsäure, da durch sie eine gleichmässige, stabile Suspendierung in der wässrigen, sauran Reaktionsflüssigkait gewährleistet ist. Als organische Polymere können die in der Lackherstellung üblichen verwendet werden.A further preferred embodiment of the invention consists in using phosphating liquids which additionally contain finely tailed silica and / or dispersible, film-forming organic polymers, such as polyacrylate. For example, pyrogenic silica obtained from silicon tetrachloride or silica precipitated in an aqueous medium from alkali silicates have proven to be the source of the finely divided silica. What is important here is the small grain size of the silica, since it ensures a uniform, stable suspension in the aqueous, acidic reaction liquid. The organic polymers which can be used are those which are customary in paint production.

Der Zusatz der vorgenannten Stoffe dient insbesondere der Verdickung der Phosphatierungsflüssigkeit und stellt damit eine der Möglichkeiten zur Regelung der Dicke desaufzubringenden Flüssigkeitsfilmes dar. Der Zusatz organischer Polymere wirkt sich in einzelnen von der Folgebehandlung abhängigen Anwendungsfällen vorteilhaft auf die Haftvermittlung aus.The addition of the abovementioned substances serves in particular to thicken the phosphating liquid and thus represents one of the possibilities for regulating the thickness of the liquid film to be applied. The addition of organic polymers has an advantageous effect on the adhesion in individual applications dependent on the subsequent treatment.

Weitere bevorzugte Ausgestaltungen des erfindungsgemässen Verfahrens bestehen darin, die Metalloberfläche mit einer Phosphatierungsflüssigkeit zu benetzen, in der das Molverhältnis von Metallphosphat (gerechnet als Me"+ (H2P04)n) zu Molybdat-, Wolframat-, Niobat-, Tantalat- und/ oder Vanadat-Ion (gerechnet als MoO3, W03, Nb205, Ta205, V205) im Bereich von 1 :(0,4 bis 0,01) und/oder in der das Molverhältnis von Metallphosphat (gerechnet als Me"+ (H2P04)n) zu Kieselsäure (gerechnet als Si02) zu Fluorid (gerechnet als (Men+Fn+2)2-) im Bereich von 1:(0,2 bis 5,0).(0,04 bis 2,0) und/oder in der das Gewichtsverhältnis Metallphosphat (gerechnet als Me"+(H2PO4)") zu Polymer im Bereich von 1 :(0,1 bis 2,0) liegt.Further preferred refinements of the method according to the invention consist in wetting the metal surface with a phosphating liquid in which the molar ratio of metal phosphate (calculated as Me " + (H 2 P0 4 ) n ) to molybdate, tungstate, niobate, tantalate and / or vanadate ion (calculated as MoO 3 , W0 3 , Nb 2 0 5 , Ta 2 0 5 , V 2 0 5 ) in the range of 1: (0.4 to 0.01) and / or in which the molar ratio from metal phosphate (calculated as Me "+ (H 2 P0 4 ) n ) to silica (calculated as Si0 2 ) to fluoride (calculated as (Me n + F n + 2 ) 2- ) in the range of 1: (0.2 to 5.0). (0.04 to 2.0) and / or in which the weight ratio of metal phosphate (calculated as Me " + (H 2 PO 4 ) " ) to polymer in the range from 1: (0.1 to 2, 0) lies.

Die erfindungsgemäss verwendeten Flüssigkeiten eanthalten die Komponenten vorzugsweise in einer solchen Menge, dass sie einen Abdampfrückstand von 5 bis 150 g/I autweisen. Bei der Benetzung wird vorzugsweise mit einer Flüssigkeitsfilmmenge zwischen 2,5 und 25 ml/m2 Werkstückoberfläche gearbeitet. Besonders gute anwendungstechnische Ergebnisse werden erzielt, wenn der Film der Phosphatierungsflüssigkeit derart bemessen wird, dass nach dem Auftrocknen ein Schichtgewicht von 0,03 bis 0,6 g/m2 erhalten wird. Die sich an die Benetzung der Metalloberfläche anschliessende Auftrocknung kann im Prinzip bereits bei Raumtemperatur erfolgen. Bessere Ergebnisse werden allerdings bei höheren Temperaturen erreicht, wobei vorzugsweise Temperaturen zwischen 50 und 100°C gewählt werden.The liquids used according to the invention preferably contain the components in an amount such that they have an evaporation residue of 5 to 150 g / l. When wetting, a liquid film amount between 2.5 and 25 ml / m 2 workpiece surface is preferably used. Particularly good application results are achieved if the film of the phosphating liquid is dimensioned such that a layer weight of 0.03 to 0.6 g / m 2 is obtained after drying. In principle, the drying after the wetting of the metal surface can already take place at room temperature. However, better results are achieved at higher temperatures, preferably temperatures between 50 and 100 ° C.

Die metallischen Werkstücke können in unterschiedlichster Form, z.B. als Formkörper, Rohr, Stange, Draht, vorzugsweise aber als Blech oder Band, zum Einsatz kommen.The metallic workpieces can be in various forms, e.g. as a shaped body, tube, rod, wire, but preferably as sheet metal or tape, are used.

Das erfindungsgemässe Verfahren ist für eine Vielzahl von Metallen und Metallegierungen geeignet. Ein besonderer Anwendungsfall liegt in der Behandlung von Metalloberflächen aus Eisen, Zink bzw. Legierungen hiervon. Von herausragender Bedeutung ist jedoch das erfindungsgemässe Verfahren für die Beschichtung von Oberflächen aus Aluminium oder Aluminiumlegierungen. Beim letztgenannten Anwendungsfall ist es zweckmässig, die generell erforderliche Reinigung mit einer schwefel- oder phosphorsauren Lösung, die auch Tenside, insbesondere nichtionogener Art, und gegebenenfalls Fluoridionen enthalten kann, im pH-Bereich von 1,0 bis 2,5 vorzunehmen. Hierdurch wird eine besonders saubere, von Metalloxid, insbesondere Magnesiumoxid, freie Oberfläche erhalten, die sich auf die Haftung der anschliessend aufzubringenden Phosphatschicht positiv auswirkt.The method according to the invention is suitable for a large number of metals and metal alloys. A special application is in the treatment of metal surfaces made of iron, zinc or alloys thereof. However, the method according to the invention is of outstanding importance for the coating of surfaces made of aluminum or aluminum alloys. In the latter application, it is expedient to carry out the generally required cleaning with a sulfuric or phosphoric acid solution, which can also contain surfactants, in particular nonionic, and optionally fluoride ions, in the pH range from 1.0 to 2.5. This results in a particularly clean surface free of metal oxide, in particular magnesium oxide, which has a positive effect on the adhesion of the phosphate layer to be subsequently applied.

Die wesentlichsten Vorteile des erfindungsgemässen Verfahrens bestehen darin, dass die erhaltenen Schichten nichttoxisch sind, hohen Korrosionsschutz und gute Haft- und Haftvermittlungseigenschaften besitzen und dass die Behandlungsflüssigkeit stabil ist, d. h. nicht durch Reaktion oder Ausfällung von Bestandteilen eine Veränderung in der Zusammensetzung erfährt. Ausserdem weist das Verfahren keine Abwasserprobleme auf. Die an das erfindungsgemässe Verfahren sich anschliessende Folgebehandlung besteht insbesondere im Auftrag von Lacken, Klebern oder Kunststoffen, der in der hierfür üblichen Weise erfolgen kann.The most important advantages of the method according to the invention are that the layers obtained are non-toxic, have high corrosion protection and good adhesion and adhesion-promoting properties, and that the treatment liquid is stable, ie. H. does not experience a change in composition due to reaction or precipitation of components. In addition, the process has no wastewater problems. The subsequent treatment following the process according to the invention consists in particular in the application of lacquers, adhesives or plastics, which can be carried out in the manner customary for this.

Die Erfindung wird anhand der folgenden Beispiele näher erläutert.The invention is illustrated by the following examples.

In sämtlichen Beispielen wurde Aluminiumband mittels einer Walzenbeschichtungsmaschine mit den nachfolgend näher beschriebenen Phosphatierungsflüssigkeiten benetzt. Die Auftrockentemperatur war jeweils 80° C. Vor der Walzenbeschichtung war das Aluminiumband in einer Lösung, enthaltend

  • 5 g/I Schwefeleäure (96%)
  • 0,5 g/I äthoxyliertes Alkylphenol
  • 0,05 g/I Flusssäure (100%).
  • die einen pH-Wert von 1,3 aufwies, gereinigt worden.
In all of the examples, aluminum strip was wetted with the phosphating liquids described in more detail below using a roll coating machine. The drying temperature was 80 ° C. in each case. Before the roll coating, the aluminum strip was in a solution containing
  • 5 g / l sulfuric acid (96%)
  • 0.5 g / l ethoxylated alkylphenol
  • 0.05 g / l hydrofluoric acid (100%).
  • which had a pH of 1.3, was cleaned.

Für acht Ausführungsbeispiele sind die Gehalte der einzelnen Behandlungsflüssigkeiten an wirksamen Substanzen sowie die pro Quadratmeter aufgebrachte Flüssigkeitsmenge in ml, der Abdampfrückstand der Behandlungsflüssigkeit in g/I und das erhaltene Schichtgewicht in mg/m2 Oberfläche tabellarisch zusammengestellt.For eight exemplary embodiments, the contents of the individual treatment liquids of active substances as well as the amount of liquid applied per square meter in ml, the evaporation residue of the treatment liquid in g / l and the layer weight obtained in mg / m 2 surface are summarized in a table.

Die so vorbehandelten Proben wurden mit einem Vinyl- und einem Epoxi-Phenolharz-Lack beschichtet und auf Haftung im Biegetest sowie auf Korrosionsbeständigkeit im Pasteurisiertest geprüft. Es wurde hierbei technologische Werte gefunden, die im Vergleich zum Einsatz von Lösungen auf Basis Cr-III/Si02 mindenstens gleichwertige, zum Teil sogar bessere Ergebnisse der erfindungsgemässen Arbeitsweise auswiesen.

Figure imgb0001
The samples pretreated in this way were coated with a vinyl and an epoxy-phenolic resin lacquer and tested for adhesion in the bending test and for corrosion resistance in the pasteurization test. Technological values were found which, in comparison to the use of solutions based on Cr-III / Si0 2, gave at least equivalent, and in some cases even better, results of the procedure according to the invention.
Figure imgb0001

Claims (12)

1. Process for the preparation of metal surfaces for the subsquent application of organic catings by applying a phosphate coating by means of wetting with an aqueous phosphatizing liquid, containing metal cations of the valency ofat least two and subsequent drying in situ of the liquid film without intermediate rinsing, characterized in that the metal surface is wetted with a phosphatizing liquid, in which the cationic component of the metal phosphate is formed by calcium, magnesium, barium, aluminium, zink, cadium, iron, nickel, cobalt, and/or manganese, which possesses a pH-value of from 1.5 to 3.0, is free from chromium anf - appart from metal phosphate - contains soluble molybdate, tungstate, vanadate, niobate and tantalate ions.
2. Process according to claim 1, characterized in that the metal surface is wetted with a phosphatizing liquid, which additionally contains simple or complex-bound fluoride ions, such as fluotitanate, fluozirconate, fluostannate, fluoborate and/or fluosilicate.
3. Process according to claim 1, or 2, characterized in that the metal surface ia wetted with a phoaphatizing liquid, which additionally contains a reducing substance, especially from the group of aldehyds, oxycarboxylic acids, hydrazine, hydroxylamine and/or hypophosphite, preferably in a quantity of at least one reduction equivalent.
4. Process according to one or more of the claims 1 to 3, characterized in that the metal surface is wetted with a phosphatizing liquid, which additionally contains finely divided silica.
5. Process according to one or more of the claims 1 to 4, characterized in that the metal surface is wetted with a phosphatizing liquid, which additionally contains a dispersible film-forming organic polymer, such as polyacrylate.
6. Process according to one or more of the claims 1 to 5, characterized in that the metal surface is wetted with a phosphatizing liquid, in which the molecular ratio of metal phosphate (calculated as Me"+(H2P04)n) to molybdate, tungstate, vanadate, niobate and/or tantalate ions (calculated as MoO3, W03, V205, Nb205, Ta205) lies within the range of 1:(0.4 to 0.01). '
7. Process according to one or more of the claims 1 to 6, characterized in that the metal surface is wetted with a phosphatizing liquid, in which the molecular ratio of metal phosphate (calculated as Men+(H2P04)n) to silica (calculated as Si02) to fluoride (calculated as (Men+Fn+2)2-) lies in the range of 1:(0.2 to 6.0):(0.04 to 2.0).
8. Process according to one or more of the claims 1 to 7, characterized in that the metal surface is wetted with a phosphatizing liquid, in which the weight ratio of metal phosphate (calculated as Men+(H2PO4)n) to polymer lies in the range of 1 :(0.1 to 2.0).
9. Procoss according to one or more of the claims 1 to 8, characterized in that the film of the phosphatizing liquid is supplied in an amount such that after drying a coating weight of from 0.03 to 0.6 g/m2 is obtained.
10. Process according to one or more of the claims 1 to 9, characterized in that the drying of the liquid film is effected at temperatures of between 50 and 100°C.
11. Use of the process according to one or more of the claims 1 to 10 for the pretreatment of aluminum.
12. Use according to claim 11, wherein the aluminum surface is previously cleaned with an acidic aqueous solution.
EP80200096A 1979-02-14 1980-02-05 Process for the surface treatment of metals and its use for the treatment of aluminium surfaces Expired EP0015020B2 (en)

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DE2143957A1 (en) * 1971-09-02 1973-03-08 Metallgesellschaft Ag METHOD OF APPLYING A PHOSPHATUE COATING TO IRON AND STEEL
US4110127A (en) * 1974-01-23 1978-08-29 International Lead Zinc Research Organization, Inc. Procedure for depositing a protective precoating on surfaces of zinc-coated ferrous metal parts against corrosion in presence of water
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Also Published As

Publication number Publication date
GB2041987B (en) 1983-07-27
GB2041987A (en) 1980-09-17
IT8019877A0 (en) 1980-02-13
IT1149291B (en) 1986-12-03
US4264378A (en) 1981-04-28
DE3062096D1 (en) 1983-03-31
EP0015020A1 (en) 1980-09-03
CA1133362A (en) 1982-10-12
JPS5931593B2 (en) 1984-08-02
DE2905535A1 (en) 1980-09-04
JPS55131176A (en) 1980-10-11
EP0015020B1 (en) 1983-02-23

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