EP0015020A1 - 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
EP0015020A1
EP0015020A1 EP80200096A EP80200096A EP0015020A1 EP 0015020 A1 EP0015020 A1 EP 0015020A1 EP 80200096 A EP80200096 A EP 80200096A EP 80200096 A EP80200096 A EP 80200096A EP 0015020 A1 EP0015020 A1 EP 0015020A1
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Prior art keywords
wetted
liquid
metal
metal surface
phosphating
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German (de)
French (fr)
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EP0015020B2 (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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    • 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

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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)

Abstract

Bei einem Verfahren zur Vorbereitung von Metallorberflächen zur anschließenden Beschichtung mit organischen Überzügen, wie Lacken, Klebern und Kunststoffen, wird ein Phosphatüberzug aufgebracht, indem man die Metalloberflächen mit einer Phosphatierungsflüssigkeit, die mindestens 2-wertige Kationen enthält, benetzt und anschließend den Flüssigkeitsfilm auftrocknet. Damit Schichten erhalten werden, die nicht toxisch sind, sich aber dennoch durch guten Korrosionsschutz sowie gute Haft- und Haftvermittlungseigenschaften auszeichnen, werden Phospatierungsflüssigkeiten eingesetzt, die einen pH-Wert von 1.5 bis 3,0 besitzen, chromfrei sind und neben Metallphosphat lösliche Molybdat-, Wolframat-, Vanadat-, Niobat- und/oder Tantalat-Ionen enthalten. Weiterhin kann die Phosphatierungsflüssigkeit Fluorid, Reduktionsmittel, Kieselsäure, organisches Polymer enthalten. Das Behandlungsverfahren ist insbesondere für die Vorbehandlung von Aluminium, vorzugsweise in Blech- oder Bandform, bestimmt.In a process for preparing metal surfaces for subsequent coating with organic coatings, such as lacquers, adhesives and plastics, a phosphate coating is applied by wetting the metal surfaces with a phosphating liquid which contains at least 2-valent cations and then drying the liquid film. In order to obtain layers that are non-toxic, but still have good corrosion protection and good adhesion and adhesion-promoting properties, phosphating fluids are used that have a pH value of 1.5 to 3.0, are chromium-free and, in addition to metal phosphate, soluble molybdate, Contain tungstate, vanadate, niobate and / or tantalate ions. Furthermore, the phosphating liquid can contain fluoride, reducing agent, silica, organic polymer. The treatment process is particularly intended for the pretreatment of aluminum, preferably in sheet or strip form.

Description

Die Erfindung betrifft ein Verfahren zur Vorbereitung von Metalloberflächen zur anschließenden Beschichtung mit organischen Überzügen durch Aufbringen eines Phosphatüberzuges mittels Benetzen mit einer mindestens 2-wertige Kationen enthaltenden Phosphatierungs-Flüssigkeit und anschließendes Auftrocknen des Flüssigkeitsfilmes sowie dessen Anwendung auf die Behandlung von Aluminiumoberflächen.The invention relates to a method for preparing metal surfaces for subsequent coating with organic coatings by applying a phosphate coating by wetting with a phosphating liquid containing at least 2-valent cations and then drying the liquid film and applying it 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 Wasser dar, wobei Chemikalienreste aus der ersten Stufe von der Metalloberfläche entfernt werden. In der dritten 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. In Finally, in the third 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 sie 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. For example, Coatings made of lacquers, adhesives and plastics are characterized by a much greater adhesion and considerably increased protection against corrosion if they are applied to metal pretreated in this way.

In der DE-AS 17 69 582 ist beispielsweise ein Verfahren beschrieben, bei dem eine wäßrige Lösung, die sechswertiges Chrom, dreiwertiges 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.DE-AS 17 69 582 describes, for example, a process 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. well suited as electrical insulation, as corrosion protection and as a primer for paints and the like.

Aus der US-PS 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 dried will. This treatment serves to protect against rust formation.

Weiterhin ist es bekannt, Überzüge auf Metalloberflächen mit Hilfe von Überzugsmitteln herzustellen, die eine Verbindung des sechswertigen Chroms und einen polymeren organischen Stoff enthalten (sogenannte Primer) und anschließend aufgetrocknet bzw. eingebrannt werden (AT-PS 197 164).It is also 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 6-wertigem 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 aforementioned 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 when using metals coated in this way as container material for food and beverages, there is no influence on the container contents is to be excluded. 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 6-wertiges 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-III-Ionen, Phosphationen und feinverteilte Kieselsäure, gegebenenfalls auch Acetat-, Maleinat-, Zink- und/oder Manganionen, enthält, zu benetzen und den Lösungsfilm aufzutrocknen (DE-OS 27 11 431). Obgleich dieses Verfahren gegenüber den vorgenannten erhebliche Vorteile aufweist, ist nachteilig, daß bei Verwendung der beschichteten Metalle als Behältermaterial eine gewisse Beeinflussung von Lebensmitteln und Getränken infolge des Chrom-III-Gehaltes der Schicht nicht gänzlich auszuschließen ist und daß die Behandlungsflüssigkeit durchBildung von schwerlöslichem Chromphosphat zur Instabilität neigt.In order to avoid the disadvantages associated with the use of treatment fluids containing hexavalent chromium, it is already known to clean the metal surface, in particular iron, zinc and aluminum, with an acidic aqueous solution which contains chromium III ions, phosphate ions and finely divided Contains silicic acid, optionally also acetate, maleinate, zinc and / or manganese ions, and to dry the solution film (DE-OS 27 11 431). Although this method has considerable advantages over the abovementioned, it is disadvantageous that when the coated metals are used as the container material, a certain influence on foods and beverages as a result of the chromium III content of the layer cannot be ruled out completely, and that the treatment liquid is formed by the formation of poorly soluble chromium phosphate Instability tends.

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 Phosphatierungs- flüssigkeit benetzt 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-Ionen enthält.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention is that the metal surface is wetted with a phosphating liquid which has a pH of 1.5 to 3.0, is chromium-free and, in addition to metal phosphate, soluble molybdate, tungstate, vanadate, niobate and / or tantalate Contains ions.

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. by dipping and then draining, pouring over and spinning off, brushing, spraying with compressed air, air-less and also electrostatically, spraying, rolling on with structured and smooth rollers in the same direction and in the opposite direction.

Die nach dem erfindungsgemäßen Verfahren einzusetzende Phosphatierungsflüssigkeit kann modifiziert werden, indem zusätzlich einfache oder komplexgebundene Fluoridionen, wie Fluotitanat, Fluozirkonat, Fluostannat, Fluoborat und/oder Fluosilikat zugegeben werden. Hierdurch wird eine erhöhte Verbesserung der Verankerung infolge eines entsprechenden Beiza-ngriffes auf die Metalloberfläche erzielt.The phosphating liquid to be used by 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 grip on the metal surface.

Vorzugsweise werden Metallphosphate eingesetzt, in denen die kationische Komponente des Metallphosphats durch Kalzium, Magnesium, Barium, Aluminium, Zink, Cadmium, Eisen, Nickel, Kobalt und/oder Mangan gebildet wird. Sie bilden in einfachster Weise festhaftende tertiäre Phosphate.Metal phosphates are preferably used in which the cationic component of the metal phosphate is formed by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese. They form adherent tertiary phosphates in the simplest way.

Als besonders vorteilhaft hat es sich erwiesen, der Phosphatierungsflüssigkeit reduzierende Substanzen, insbesondere aus der Gruppe Äldehyde, 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 derIt 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 means the amount of reducing agent that is capable of, the value of

eingebrachten Molybdat-, Wolframat-, Vanadat-, Niobat-und/oder Tantalat-Ionen um eine Wertigkeitsstufe, also z.Bo 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.introduced molybdate, tungstate, vanadate, niobate and / or tantalate ions by one valence level, e.g. from Mo VI to Mo V, to ver wrestle. 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 feinverteilte Kieselsäure und/oder dispergierbare, filrbildende 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, sauren Reaktionsflüssigkeit gewährleistet ist. Als organische Polymere können die in der Lackherstellung üblichen verwendet werden.Another preferred embodiment of the invention consists in using phosphating liquids which additionally contain finely divided 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 des aufzubringenden 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 Men+(H2PO4)n) zu Molybdat-, Wolframat-, Niobat-, Tantalat- und/oder Vanadat-Ion (gerechnet als Mo03, W03, V2O5, Nb2O5, Ta 2 0 5) im Bereich von 1 : (0,4 bis 0,01) und/oder in der das Molverhältnis von Metallphosphat (gerechnet als Men+(H2P04)n) zu Kieselsäure (gerechnet als Si02) zu Fluorid (gerech- net 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 Men+(H2P04)n) zu Polymer im Bereich von 1 : (0,1 bis 2,0) liegt.Further preferred embodiments of the method according to the invention consist of wetting the metal surface with a phosphating liquid in which the molar ratio of metal phosphate (calculated as Me n + (H 2 PO 4 ) n ) to molybdate, tungstate, niobate, tantalate and / or vanadate ion (calculated as Mo03, W0 3 , V 2 O 5 , Nb 2 O 5 , Ta 2 0 5 ) in the range from 1: (0.4 to 0.01) and / or in which the molar ratio of metal phosphate (calculated as Me n + (H 2 P0 4) n) to silica (calculated as Si0 2) to fluoride (gerech- ne t n as (Me + 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 n + (H 2 P0 4 ) n ) to polymer in the range from 1: (0.1 to 2.0 ) lies.

Die erfindungsgemäß verwendeten Flüssigkeiten enthalten die Komponenten vorzugsweise in einer solchen Menge, daß sie einen Abdampfrückstand von 5 bis 150 g/1 aufweisen. 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. The drying following the wetting of the metal surface can in principle 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 Anwendungsfäll 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 case of application, it is expedient to — the generally required cleaning with a sulfuric or phosphoric acid solution, which may also contain surfactants, in particular nonionic, and possibly fluoride ions, in the pH range from 1.0 to 2.5 to take. 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 nicht toxisch 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.The main advantages of the process 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, i.e. does not experience a change in composition due to reaction or precipitation of components. In addition, the process has no wastewater problems.

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 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

Figure imgb0001
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
Figure imgb0001
 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/1 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 / 1 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 wurden hierbei technologische Werte gefunden, die im Vergleich zum Einsatz von Lösungen auf Basis Cr-III/Si02 mindestens gleichwertige, zum Teil sogar bessere Ergebnisse der erfindungsgemäßen Arbeitsweise auswiesen.

Figure imgb0002
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 imgb0002

Claims (13)

1. Verfahren zur Vorbereitung von Metalloberflächen zur anschließenden Beschichtung mit organischen Überzügen durch Aufbringen eines Phosphatüberzuges mittels Benetzen mit einer mindestens 2-wertige Kationen enthaltenden Phosphatierungsflüssigkeit und anschließendes Auftrocknen des Flüssigkeitsfilms, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt 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-Ionen enthält.1. A process for preparing metal surfaces for subsequent coating with organic coatings by applying a phosphate coating by wetting with a phosphating liquid containing at least 2-valent cations and then drying the liquid film, characterized in that the metal surface is wetted with a phosphating liquid which has a pH Has a value 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. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, die zusätzlich einfache oder komplexgebundene Fluoridionen, wie Fluotitanat, Fluozirkonat, Fluostannat, Fluoborat und/oder Fluosilikat enthält.2. The method according to claim 1, characterized in that the metal surface is wetted with a phosphating liquid which additionally contains simple or complex-bound fluoride ions, such as fluotitanate, fluozirconate, fluostannate, fluoborate and / or fluosilicate. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, 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.3. The method according to claim 1 and 2, characterized in that the metal surface is wetted with a phosphating liquid in which the cationic component of the metal phosphate by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese is formed. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeich- net, daß die Metalloberfläche mit einer Phosphatierungs- flüssigkeit benetzt wird, die zusätzlich eine reduzierende Substanz, insbesondere aus der Gruppe Aldehyde, Oxycarbonsäuren, Hydrazin, Hydroxylamin und/oder Hypophosphit, vorzugsweise in Mengen mindestens eines Reduktionsäquivalents, enthält.4. The method of claim 1, 2 or 3, characterized ekennzeich- g net, that the metal surface is wetted with a phosphating liquid which additionally a reducing substance, especially from the group aldehydes, oxycarboxylic acids, hydrazine, hydroxylamine and / or hypophosphite, preferably in amounts of at least one reduction equivalent. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, die zusätzlich feinverteilte Kieselsäure enthält. 5 . Method according to one or more of claims 1 to 4, characterized in that the metal surface is wetted with a phosphating liquid which additionally contains finely divided silica. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, die zusätzlich ein dispergierbares, filmbildendes organisches Polymer, wie Polyacrylat, enthält.6. The method according to one or more of claims 1 to 5, characterized in that the metal surface is wetted with a phosphating liquid which additionally contains a dispersible, film-forming organic polymer, such as polyacrylate. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, in der das Molverhältnis von Metallphosphat (gerechnet als Men+(H2P04)n) zu Molybdat-, Wolframat-, Vanadat, Niobat-und/oder Tantalat-Ion (gerechnet als Mo03, W03, V205, Nb205, Ta205) im Bereich von 1 : (0,4 bis 0,01) liegt.7. The method according to one or more of claims 1 to 6, characterized in that the metal surface is wetted with a phosphating liquid in which the molar ratio of metal phosphate (calculated as Me n + (H 2 P0 4 ) n ) to molybdate, tungsten- , Vanadate, niobate and / or tantalate ion (calculated as Mo03, W0 3 , V205 , Nb205 , Ta 2 0 5 ) is in the range of 1: (0.4 to 0.01). 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, in der das Molverhältnis von Metallphosphat (gerechnet als Men+(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) liegt.8. The method according to one or more of claims 1 to 7, characterized in that the metal surface is wetted with a phosphating liquid in which the molar ratio of metal phosphate (calculated as Me n + (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). 9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Metalloberfläche mit einer Phosphatierungsflüssigkeit benetzt wird, in der das Gewichtsverhältnis Metallphosphat (gerechnet als Men+(H2P04)n) zu Polymer im Bereich von 1 : (0,1 bis 2,0) liegt.9. The method according to one or more of claims 1 to 8, characterized in that the metal surface is wetted with a phosphating liquid in which the weight ratio of metal phosphate (calculated as Me n + (H 2 P0 4 ) n ) to polymer in the range of 1: (0.1 to 2.0). 10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß der Film der Phosphatierungsflüssigkeit derart bemessen wird, daß nach dem Auftrocknen ein Schichtgewicht von 0,03 bis 0,6 g/m2 erhalten wird.10. The method according to one or more of claims 1 to 9, characterized in that 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. 11. Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Auftrocknung des Flüssigkeitsfilms bei Temperaturen zwischen 50 und 100°C erfolgt.11. The method according to one or more of claims 1 to 10, characterized in that the drying of the liquid film takes place at temperatures between 50 and 100 ° C. 12. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 11 auf die Vorbehandlung von Aluminium.12. Application of the method according to one or more of claims 1 to 11 to the pretreatment of aluminum. 13. Anwendung nach Anspruch 12 mit der Maßgabe, daß die Aluminiumoberfläche zuvor mit einer sauren wäßrigen Lösung gereinigt worden ist.13. Application according to claim 12 with the proviso that the aluminum surface has previously been 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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EP0015020B2 (en) 1986-02-05
GB2041987B (en) 1983-07-27
IT1149291B (en) 1986-12-03
JPS55131176A (en) 1980-10-11
JPS5931593B2 (en) 1984-08-02
DE3062096D1 (en) 1983-03-31
GB2041987A (en) 1980-09-17
DE2905535A1 (en) 1980-09-04
IT8019877A0 (en) 1980-02-13
US4264378A (en) 1981-04-28
EP0015020B1 (en) 1983-02-23
CA1133362A (en) 1982-10-12

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