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EP0149720B1 - Process for after passivating phosphated metal surfaces using titanium and/or manganese and/or cobalt and/or nickel and/or copper cations containing solutions - Google Patents

Process for after passivating phosphated metal surfaces using titanium and/or manganese and/or cobalt and/or nickel and/or copper cations containing solutions Download PDF

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Publication number
EP0149720B1
EP0149720B1 EP84111060A EP84111060A EP0149720B1 EP 0149720 B1 EP0149720 B1 EP 0149720B1 EP 84111060 A EP84111060 A EP 84111060A EP 84111060 A EP84111060 A EP 84111060A EP 0149720 B1 EP0149720 B1 EP 0149720B1
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Prior art keywords
solutions
ethanate
cations
metal surfaces
nickel
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EP84111060A
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German (de)
French (fr)
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EP0149720A3 (en
EP0149720A2 (en
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Reinhard Opitz
Kurt Hosemann
Heinz Portz
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Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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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

Definitions

  • the invention relates to a method for the 'post-passivation of phosphated metal surfaces.
  • Such phosphate layers not only improve the corrosion protection of the metal surfaces, but also increase the adhesion for paints to be applied to the surface. In certain cases, they can also help to improve the properties of metal sheets during cold forming and when using deep-drawing processes.
  • the phosphate layer on the metal surfaces is not completely closed. Rather, there are more or less large “pores” that have to be closed in the course of a so-called “post-passivation” in order not to leave a point of attack for corrosive influences on the metal surfaces.
  • concentration of fluoride ions in these solutions is 0.01 to 25 g / l.
  • solutions disclosed in the abovementioned application contain anions which have a highly corrosive effect on system parts (for example Cl - , So 4 2- ) and / or are known to disrupt the passivation process (for example F - ).
  • Manganese (II) ethanate and cobalt (II) ethanate the content of Mn (II) cations and Co (II) cations in the solutions in each case being 0.05 to 1 g / l.
  • Nickel (II) ethanate and copper (II) ethanate the content of Ni (II) cations in the solutions 0.1 to 1 g / I and the content of Cu (II) cations in the same 0.03 is up to 1 g / l.
  • the pH of the application solutions is in the acidic to neutral range, i.e. in the range of 3.0 to 7.0.
  • the solutions are preferably adjusted, for example using ethanoic acid (acetic acid) or phosphoric acid on the one hand or sodium hydroxide solution on the other hand, in such a way that they have a pH between 4.0 and 5.0.
  • the solutions containing titanium and / or manganese and / or cobalt and / or nickel and / or copper salts used according to the inventive method can be used in the temperature range from 20 to 120 ° C., but are preferably used in the temperature range from 30 to 50 ° C worked. Treatment times of approximately 1 minute are sufficient to achieve excellent post-passivation of the phosphated metal surfaces even at these temperatures.
  • the process according to the invention is carried out in such a way that cleaned phosphated metal surfaces are first rinsed with water and then, according to the present process, with an acidic, titanium (IV) - and / or manganese (II) - and / or cobalt (II) - and / or solution containing nickel (II) and / or copper (II) salts in the temperature range of preferably 30 to 50 ° C., which can be obtained by adding solid or liquid concentrates containing the corresponding salts in a suitable amount dissolves in water in a manner known per se.
  • the treatment time is usually 1 minute.
  • the post-passivated metal surfaces are rinsed with deionized water and then dried with compressed air.
  • the metal surfaces post-passivated in accordance with the method according to the invention are outstandingly suitable for subsequent coating with paints, lacquers, varnishes and the like.
  • the post-passivated metal surfaces in this way offer an outstandingly suitable reason for cathodic electrocoat materials.
  • the phosphated and post-passivated metal surfaces are also suitable for other post-treatment processes.
  • Steel parts were sprayed with an alkaline cleaning solution for 2 min at 50 ° C. and then rinsed with water. They were then phosphated with a zinc phosphate solution for 2 minutes in a spray at 50 ° C. and then rinsed with water.
  • the steel parts were then post-passivated with the post-passivation solution containing 0.3 g of copper (II) ethanate hydrate per liter at 35 ° C. for 1 min in spraying. It was then rinsed with deionized water and dried with compressed air.
  • the post-passivation solution containing 0.3 g of copper (II) ethanate hydrate per liter at 35 ° C. for 1 min in spraying. It was then rinsed with deionized water and dried with compressed air.
  • the dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes.
  • the dry film thickness of the paint was 18 ⁇ m.
  • the parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.
  • Ni (CH 3 COO) 2 .4H 2 0 was made into a 0.7 g to prepare a post-passivation solution.
  • 1- 1 containing solution dissolved in water, corresponding to 0.17 g Ni per liter of solution.
  • Steel parts were immersed for 10 minutes at 80 ° C with an alkaline cleaning solution and then rinsed with water. The parts were then dipped in a zinc phosphate solution at 50 ° C. for 3 minutes and rinsed again.
  • the solution containing 0.7 g of nickel (II) ethanate tetrahydrate per liter at 35 ° C. was used for the post-passivation, the treatment time being 1 min in immersion.
  • the post-passivated parts were rinsed with deionized water and dried with compressed air.
  • an electro-dip coating was applied cathodically, which was dried by heating to 185 ° C. for 20 minutes.
  • the dry film thickness of the lacquer was 18 ⁇ m.
  • the painted parts were then provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 hours.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.
  • Ni (CH 3 COO) 2 .4H 2 0 and C U (CH 3 -COO) 2 .H 2 0 were dissolved in water to give a solution containing 0.5 g ⁇ I -1 nickel (II) ethanate tetrahydrate and 0.1 g - I -1 copper (II) ethanate hydrate contained. This corresponds to a content of 0.12 g Ni and 0.03 g Cu per liter of solution.
  • the parts were treated with the solution containing nickel and copper ions prepared as described above for 1 min at 40 ° C. in an immersion, then rinsed with deionized water and dried with compressed air.
  • the parts passivated in this way were then coated with a cathodic electrocoating material and dried for 20 minutes by heating to 185.degree.
  • the dry film thickness of the lacquer was 18 pm.
  • the parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.2 to 0.4 mm.
  • Example 1 To prepare the rinse solutions, the cations listed in Table 1 were dissolved individually in water (Examples 4 to 9) or in combination (Examples 10 to 14) to give solutions containing 0.1 gl -1 of total cation (s).
  • the salts used were the ethanates (acetates) or (in the case of Ti (IV) the 2,4-pentanedionate (titanylacetylacetonate).
  • the steel parts were then post-passivated with the post-passivation solutions containing the cations in the amount listed in Table I, rinsed with demineralized water and dried with compressed air.
  • the dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes.
  • the dry film thickness of the paint was 18 ⁇ m.
  • the parts were provided with individual cuts and subjected to the alternating climate test according to VW standard P 12 10 30 days.

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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)

Description

Die Erfindung betrifft ein Verfahren zur' Nachpassivierung von phosphatierten Metalloberflächen.The invention relates to a method for the 'post-passivation of phosphated metal surfaces.

Der Schutz metallischer Oberflächen, insbesondere der Schutz von Eisen- und Stahloberflächen durch phosphathaltige Überzüge ist seit langer Zeit bekannt. Dabei werden die sog. «nichtschichtbildende Phosphatierung", d.h. die Verwendung von Alkali- und/oder Ammoniumorthophosphatlösungen zur Erzeugung von Eisenphosphatschichten, in denen das Eisenion aus der zu überziehenden metallischen Oberfläche stammt, und die sog. «schichtbildende Phosphatierung» unterschieden, bei der auf Metalloberflächen unter Verwendung von Zinkphosphatschichten bzw. Zink-Calciumphosphat-Schichten gebildet werden.The protection of metallic surfaces, in particular the protection of iron and steel surfaces by phosphate-containing coatings, has been known for a long time. A distinction is made between the so-called "non-layer-forming phosphating " , ie the use of alkali and / or ammonium orthophosphate solutions for producing iron phosphate layers in which the iron ion comes from the metallic surface to be coated, and the so-called "layer-forming phosphating" Metal surfaces are formed using zinc phosphate layers or zinc calcium phosphate layers.

Derartige Phosphatschichten verbessern nicht nur den Korrosionsschutz der Metalloberflächen, sondern erhöhen auch die Haftung für auf die Oberfläche zu applizierende Lacke. Zudem können sie in bestimmten Fällen dazu beitragen, die Eigenschaften von Metallblechen bei der Kaltumformung und bei der Anwendung von Tiefziehverfahren zu verbessern.Such phosphate layers not only improve the corrosion protection of the metal surfaces, but also increase the adhesion for paints to be applied to the surface. In certain cases, they can also help to improve the properties of metal sheets during cold forming and when using deep-drawing processes.

In Abhängigkeit von der Zusammensetzung der für die Phosphatierung verwendeten Lösung, dem für das Phosphatierverfahren verwendeten Beschleuniger, dem Verfahren der Aufbringung der Phosphatierlösung auf die Metalloberflächen und/ oder auch weiteren Verfahrensparametern ist die Phosphatschicht auf den Metalloberflächen nicht vollständig geschlossen. Es verbleiben vielmehr mehr oder weniger grosse «Poren», die im Zuge einer sog. «Nachpassivierung» geschlossen werden müssen, um korrodierenden Einflüssen auf die Metalloberflächen keinen Angriffspunkt zu lassen.Depending on the composition of the solution used for the phosphating, the accelerator used for the phosphating process, the method of applying the phosphating solution to the metal surfaces and / or also other process parameters, the phosphate layer on the metal surfaces is not completely closed. Rather, there are more or less large “pores” that have to be closed in the course of a so-called “post-passivation” in order not to leave a point of attack for corrosive influences on the metal surfaces.

Es ist seit langer Zeit bekannt, für diese Zwecke Chromsalze enthaltende Lösungen zu verwenden. Insbesondere wird die Korrosionsbeständigkeit der durch Phosphatierung erzeugten Überzüge durch eine Nachbehandlung der Oberflächen mit Lösungen, die Chrom(VI) enthalten, erheblich verbessert.It has long been known to use solutions containing chromium salts for these purposes. In particular, the corrosion resistance of the coatings produced by phosphating is considerably improved by post-treatment of the surfaces with solutions containing chromium (VI).

Ein wesentlicher Nachteil der Verwendung von Chromsalze enthaltenden Lösungen besteht darin, dass derartige Lösungen hochtoxisch sind. Ausserdem wird verstärkt eine unerwünschte Blasenbildung bei der nachfolgenden Applikation von Lacken oder anderen Überzugsmaterialien beobachtet.A major disadvantage of using solutions containing chromium salts is that such solutions are highly toxic. In addition, undesirable blistering is increasingly observed in the subsequent application of paints or other coating materials.

Deswegen wurden zahlreiche weitere Möglichkeiten zur Nachpassivierung phosphatierter Metalloberflächen vorgeschlagen, wie zum Beispiel die Verwendung von Zirkoniumsalzen (NL-A-71 16 498), Cersalzen (DE-A 23 34 342), polymeren Aluminiumsalzen (DE-A-23 25 974) oder auch Oligo- oder Polyphosphorsäureestern des Inosits in Verbindung mit einem wasserlöslichen Alkali-oder Erdalkalimetallsalz dieser Ester (DE-A-24 03 022).For this reason, numerous other possibilities for the post-passivation of phosphated metal surfaces have been proposed, such as, for example, the use of zirconium salts (NL-A-71 16 498), cerium salts (DE-A 23 34 342), polymeric aluminum salts (DE-A-23 25 974) or also oligo- or polyphosphoric acid esters of inosite in combination with a water-soluble alkali or alkaline earth metal salt of these esters (DE-A-24 03 022).

Gegenstand der DE-A-2428065 (=FR-A-22 32 615) ist gleichfalls ein Verfahren zum Nachpassivieren von Phosphatüberzügen, auf Metalloberflächen, wobei wässrige saure Lösungen Verwendung finden, die einen oder mehrere der folgenden Bestandteile enthalten: Calciumfluorid, Zinkfluorid, Aluminiumfluorid, Titanfluorid, Zirkoniumfluorid, Chromfluorid, Chromzirkoniumfluorid, Nickelfluorid, Ammoniumfluorid, Fluorwasserstoffsäure oder Fluorborsäure. Die Konzentration an Fluoridionen in diesen Lösungen beträgt 0,01 bis 25 g/I.The subject of DE-A-2428065 (= FR-A-22 32 615) is also a method for re-passivating phosphate coatings on metal surfaces, using aqueous acidic solutions containing one or more of the following components: calcium fluoride, zinc fluoride, aluminum fluoride , Titanium fluoride, zirconium fluoride, chromium fluoride, chromium zirconium fluoride, nickel fluoride, ammonium fluoride, hydrofluoric acid or fluoroboric acid. The concentration of fluoride ions in these solutions is 0.01 to 25 g / l.

In Chemical Abstracts, Band 99 (1983), Seite 242, Referat 99: 199 009 g, wird ein Nachpassivierungs-Mittel für phosphatierte Metalloberflächen beschrieben, welches aus einer wässrigen Lösung besteht, die unter anderem Salze von Nickel, Cobalt oder Mangan enthält. Aus der entsprechenden JP-A-58 130 282 ist ersichtlich, dass es sich bei den Anionen dieser Salze um Chlorid beziehungsweise Sulfat handelt.Chemical Abstracts, Volume 99 (1983), page 242, Unit 99: 199 009 g, describes a post-passivation agent for phosphated metal surfaces, which consists of an aqueous solution which contains, inter alia, salts of nickel, cobalt or manganese. From the corresponding JP-A-58 130 282 it can be seen that the anions of these salts are chloride or sulfate.

Die FR-A-23 39 683 (= DE-A-27 01 321) beschreibt ein Verfahren zur Nachbehandlung von Phosphatierungsschichten mit wässrigen Lösungen, welche Titanionen und ausserdem eine oder mehrere Komponenten aus der Gruppe Phosphorsäure, Phytinsäure, Tannin und Wasserstoffperoxid enthalten. Als Anionen für die Titankationen kommer hierbei Fluorid, Oxalat oder Sulfat in Frage. Zu den Sulfat-Anionen wird hier gesagt, dass sie den Korrosionswiderstand ungünstig beeinflussen; daher sei es besser, das Sulfat aus solchen Lösungen zu entfernen.FR-A-23 39 683 (= DE-A-27 01 321) describes a process for the aftertreatment of phosphating layers with aqueous solutions which contain titanium ions and also one or more components from the group consisting of phosphoric acid, phytic acid, tannin and hydrogen peroxide. Fluoride, oxalate or sulfate are possible anions for the titanium cations. The sulfate anions are said to have an adverse effect on corrosion resistance; therefore it is better to remove the sulfate from such solutions.

In Chemical Abstracts, Band 97 (1982), Seite 307, Referat 97: 220 959 n (entsprechend SU-A-914 652), wird ein Verfahren zur Verbesserung der Abriebbeständigkeit sowie der elektrischen Leitfähigkeit von Gussteilen, die mit porösen Phosphatschichten bedeckt sind, beschrieben. Hierzu werden die Phosphatschichten mit wässrigen Lösungen von Salzen des Silbers, Kupfers, Bleis oder Wismuts nachbehandelt. Geeignete Anionen für diese Salze sind Formiate und/oder Oxalate. Anschliessend werden die so behandelten Schichten erhitzt, wobei die anzuwendenden Temperaturen so hoch liegen, dass sich die Salze zersetzen.Chemical Abstracts, Volume 97 (1982), page 307, Section 97: 220 959 n (corresponding to SU-A-914 652) describes a method for improving the abrasion resistance and the electrical conductivity of cast parts which are covered with porous phosphate layers, described. For this purpose, the phosphate layers are aftertreated with aqueous solutions of salts of silver, copper, lead or bismuth. Suitable anions for these salts are formates and / or oxalates. The layers treated in this way are then heated, the temperatures to be used being so high that the salts decompose.

Abgesehen davon, dass Fluoride in für die Nachpassivierung geeigneten Lösungen nur in Ausnahmefällen verwendet werden, da F--Ionen, wie auch Sulfat-lonen, nach allgemeiner Auffassung eher korrosionsfördernd wirken, könnten sich derartige Verfahren in der Anwendung nicht durchsetzen. Vielmehr konnten die steigenden Anforderungen an Korrosionsschutz bisher nur durch versiegelnde Nachspülung mit chromathaltigen wässrigen Lösungen erfüllt werden (vgl. W. Rausch, Die Phosphatierung von Metallen, E. Leuze Verlag, Saulgau (1974)).In addition to the fact that fluorides are only used in exceptional cases in solutions suitable for post-passivation, since F ions, like sulfate ions, are generally believed to have a corrosive effect, such processes could not be used in practice. Rather, the increasing requirements for corrosion protection could previously only be met by sealing rinsing with chromate-containing aqueous solutions (cf. W. Rausch, Die Phosphatierung von Metallen, E. Leuze Verlag, Saulgau (1974)).

Ein weiteres Verfahren zur Behandlung metallischer phosphatierter Oberflächen wird durch die EP-A-0 085 626 offenbart. Nach dem Schritt des Phosphatierens und vor einer Applikation von Überzugsmaterialien werden gemäss der genannten Anmeldung metallische Oberflächen mit Titan(III)-Kationen enthaltenden wässrigen Lösungen behandelt, die einen sauren pH-Wert aufweisen. Das für die Nachpassivierungslösung benötigte Titan(III)-Kation muss dabei in einem vorgelagerten Reaktionsschritt aus Titan(IV) durch Reduktion hergestellt werden, was eine dem eigentlichen Nachpassivierungsschritt vorgelagerte Reduktionsreaktion mit entsprechend aufwendigen Produktionsanlagen erfordert. Ausserdem enthalten die in der genannten Anmeldung offenbarten Lösungen Anionen, die stark korrosiv auf Anlagenteilen wirken (z.B. Cl-, So4 2-) und/oder bekanntermassen den Passiviervorgang stören (z. B. F-).Another method for treating metallic phosphated surfaces is disclosed by EP-A-0 085 626. After the step of phosphating and before application of coating materials, metallic surfaces are added according to the application mentioned Treated aqueous solutions containing titanium (III) cations, which have an acidic pH. The titanium (III) cation required for the post-passivation solution has to be produced in a preceding reaction step from titanium (IV) by reduction, which requires a reduction reaction upstream of the actual post-passivation step with correspondingly complex production facilities. In addition, the solutions disclosed in the abovementioned application contain anions which have a highly corrosive effect on system parts (for example Cl - , So 4 2- ) and / or are known to disrupt the passivation process (for example F - ).

Der Ersatz chromhaltiger Lösungen, die fast ausschliesslich für die Nachpassivierung phosphatierter Metalloberflächen verwendet werden, durch nicht-toxische, keine Blasenbildung hervorrufende Lösungen ist aus den oben genannten Gründen dringend erwünscht. Die Entwicklung eines allgemein und im industriellen Massstab anwendbaren Verfahrens für die effiziente Nachpassivierung phosphatierter Metalloberflächen ist jedoch eine bisher ungelöste Aufgabe.The replacement of chromium-containing solutions, which are used almost exclusively for the post-passivation of phosphated metal surfaces, by non-toxic solutions which do not cause blistering is urgently desired for the reasons mentioned above. However, the development of a process which can be used in general and on an industrial scale for the efficient re-passivation of phosphated metal surfaces is a task which has not yet been solved.

Gegenstand der vorliegenden Erfindung ist nun ein Verfahren zur Nachpassivierung von phosphatierten Metalloberflächen aus Eisen, Stahl, verzinktem Stahl oder Aluminium mittels saurer bis neutraler wässriger Lösungen von Salzen mehrwertiger Metallionen, wobei man die phosphatierten Metalloberflächen zunächst mit Wasser spült, sodann mit wässrigen Lösungen behandelt, die einen pH-Wert im Bereich von 3 bis 7 sowie eine Temperatur im Bereich von 20 bis 120°C aufweisen und eines oder mehrere der nachfolgend angeführten Salze enthalten:

  • a) (2.4-Pentandionato)-titan (IV)-oxid (Titanylacetylacetonat),
  • b) Mangan (II)-ethanat (-acetat),
  • c) Cobalt (II)-ethanat (-acetat),
  • d) Nickel (II)-ethanat (-acetat),
  • e) Kupfer (II)-ethanat (-acetat),

wobei der Gehalt an Metall-Kationen in den Lösungen jeweils 0,01 bis 10 g/I beträgt und auch bei Vorliegen mehrerer der genannten Kationen den Wert von 10 g/I nicht übersteigt und wobei man anschliessend mit Wasser spült und gegebenenfalls trocknet.The present invention now relates to a method for the post-passivation of phosphated metal surfaces made of iron, steel, galvanized steel or aluminum by means of acidic to neutral aqueous solutions of salts of polyvalent metal ions, the phosphated metal surfaces first being rinsed with water and then treated with aqueous solutions which have a pH in the range from 3 to 7 and a temperature in the range from 20 to 120 ° C and contain one or more of the salts listed below:
  • a) (2,4-pentanedionato) titanium (IV) oxide (titanylacetylacetonate),
  • b) manganese (II) ethanate (acetate),
  • c) cobalt (II) ethanate (acetate),
  • d) nickel (II) ethanate (acetate),
  • e) copper (II) ethanate (acetate),

wherein the content of metal cations in the solutions is in each case from 0.01 to 10 g / I and does not exceed the value of 10 g / I even if several of the cations mentioned are present, and then rinsing with water and, if appropriate, drying.

Für das erfindungsgemässe Verfahren werden bevorzugt Lösungen eingesetzt, die eines oder mehrere der vorstehend unter a bis e angeführten Salze enthalten, wobei der Gehalt an Ti (IV)-, Mn (11)-, Co (II)- oder Ni (II)-Kationen in den Lösungen 0,1 bis 1 g/I und der Gehalt an Cu (II)-Kationen in denselben 0,03 bis 1 g/I beträgt.For the process according to the invention, preference is given to using solutions which contain one or more of the salts listed above under a to e, the content of Ti (IV) -, Mn (11) -, Co (II) - or Ni (II) - Cations in the solutions 0.1 to 1 g / I and the content of Cu (II) cations in the same is 0.03 to 1 g / I.

Im Sinne des erfindungsgemässen Verfahrens sind ferner die folgenden Ausführungsformen bevorzugt:In the sense of the method according to the invention, the following embodiments are also preferred:

A) Die Lösungen enthalten:A) The solutions contain:

Mangan (II)-ethanat und Cobalt (II)-ethanat, wobei der Gehalt an Mn(II)-Kationen und an Co(II)-Kationen in den Lösungen jeweils 0,05 bis 1 g/I beträgt.Manganese (II) ethanate and cobalt (II) ethanate, the content of Mn (II) cations and Co (II) cations in the solutions in each case being 0.05 to 1 g / l.

B) Die Lösungen enthalten:B) The solutions contain:

Nickel(II)-ethanat und Kupfer(II)-ethanat, wobei der Gehalt an Ni(II)-Kationen in den Lösungen 0,1 bis 1 g/I und der Gehalt an Cu(II)-Kationen in denselben 0,03 bis 1 g/I beträgt.Nickel (II) ethanate and copper (II) ethanate, the content of Ni (II) cations in the solutions 0.1 to 1 g / I and the content of Cu (II) cations in the same 0.03 is up to 1 g / l.

C) Die Lösungen enthalten:C) The solutions contain:

(2.4-Pentandionato)-titan (IV)-oxid und Cobalt (II)-ethanat und Nickel(II)-ethanat, wobei der Gehalt an Ti(IV)-, Co(II)- und Ni(II)-Kationen in den Lösungen jeweils 0,01 bis 1 g/I beträgt.(2,4-pentanedionato) titanium (IV) - oxide and cobalt (II) -ethanat and nickel (II) -ethanat, wherein the content of Ti (IV) -, Co (II) - and Ni (II) cations in the solutions each 0.01 to 1 g / l.

Der pH-Wert der Anwendungslösungen liegt im sauren bis neutralen Bereich, d.h. im Bereich von 3,0 bis 7,0. Vorzugsweise werden die Lösungen, beispielswe.ise unter Verwendung von Ethansäure (Essigsäure) oder Phosphorsäure einerseits oder Natronlauge andererseits so eingestellt, dass sie einen pH-Wert zwischen 4,0 und 5,0 aufweisen.The pH of the application solutions is in the acidic to neutral range, i.e. in the range of 3.0 to 7.0. The solutions are preferably adjusted, for example using ethanoic acid (acetic acid) or phosphoric acid on the one hand or sodium hydroxide solution on the other hand, in such a way that they have a pH between 4.0 and 5.0.

Die gemäss dem erfindungsgemässen Verfahren angewendeten Titan- und/oder Mangan- und/ oder Cobalt- und/oder Nickel- und/oder KupferSalze enthaltenden Lösungen sind im Temperaturbereich von 20 bis 120°C verwendbar, jedoch wird bevorzugt im Temperaturbereich von 30 bis 50 °C gearbeitet. Behandlungszeiten von ungefähr 1 Minute sind ausreichend, um selbst bei diesen Temperaturen eine hervorragende Nachpassivierung der phosphatierten Metalloberflächen zu erreichen.The solutions containing titanium and / or manganese and / or cobalt and / or nickel and / or copper salts used according to the inventive method can be used in the temperature range from 20 to 120 ° C., but are preferably used in the temperature range from 30 to 50 ° C worked. Treatment times of approximately 1 minute are sufficient to achieve excellent post-passivation of the phosphated metal surfaces even at these temperatures.

In der Praxis wird das erfindungsgemässe Verfahren so durchgeführt, dass gereinigte phosphatierte Metalloberflächen zuerst mit Wasser gespült und anschliessend gemäss dem vorliegenden Verfahren mit einer sauren, Titan(IV)- und/ oder Mangan(II)- und/oder Cobalt(II)- und/oder Nickel(II)- und/oder Kupfer(II)-Salze enthaltenden Lösung im Temperaturbereich von bevorzugt 30 bis 50°C behandelt werden, die dadurch erhalten werden können, dass man die entsprechenden Salze in geeigneter Menge enthaltende feste oder flüssige Konzentrate in an sich bekannter Weise in Wasser löst. Für die Behandlung der Metalloberflächen sind Spritzverfahren, Tauchverfahren oder andere, dem Fachmann bekannte Verfahren der Auftragung für die Nachpassivierung, wie z. B. Spritztauchen oder Fluten, geeignet. Die Behandlungszeit beträgt im Regelfall 1 Minute. Die derart nachpassivierten Metalloberflächen werden mit vollentsalztem Wasser gespült und anschliessend mit Druckluft getrocknet.In practice, the process according to the invention is carried out in such a way that cleaned phosphated metal surfaces are first rinsed with water and then, according to the present process, with an acidic, titanium (IV) - and / or manganese (II) - and / or cobalt (II) - and / or solution containing nickel (II) and / or copper (II) salts in the temperature range of preferably 30 to 50 ° C., which can be obtained by adding solid or liquid concentrates containing the corresponding salts in a suitable amount dissolves in water in a manner known per se. For the treatment of the metal surfaces, spray processes, immersion processes or other processes of application for the post-passivation known to the person skilled in the art, such as e.g. B. splash dipping or flooding. The treatment time is usually 1 minute. The post-passivated metal surfaces are rinsed with deionized water and then dried with compressed air.

Die entsprechend dem erfindungsgemässen Verfahren nachpassivierten Metalloberflächen sind für eine anschliessende Beschichtung mit Anstrichen, Lacken, Firnissen und dergleichen hervorragend geeignet. Insbesondere bieten die derart nachpassivierten Metalloberflächen einen hervorragend geeigneten Grund für kathodische Elektrotauchlacke. Die phosphatierten und gemäss der Erfindung nachpassivierten Metalloberflächen sind jedoch auch für andere Nachbehandlungsverfahren geeignet.The metal surfaces post-passivated in accordance with the method according to the invention are outstandingly suitable for subsequent coating with paints, lacquers, varnishes and the like. In particular, the post-passivated metal surfaces in this way offer an outstandingly suitable reason for cathodic electrocoat materials. However, the phosphated and post-passivated metal surfaces are also suitable for other post-treatment processes.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.

Beispiel 1example 1

Zur Herstellung einer Nachpassivierungslösung wurde Cu(CH3COO)2 · H2O in Wasser zu einer 0,3 g - I-1 enthaltenden Lösung gelöst, entsprechend 0,1 g Cu pro Liter Lösung.To prepare a post-passivation solution, Cu (CH 3 COO) 2 · H 2 O was dissolved in water ner solution containing 0.3 g - I -1 , corresponding to 0.1 g Cu per liter of solution.

Stahlteile wurden mit einer alkalischen Reinigungslösung 2 min im Spritzen bei 50°C gereinigt und dann mit Wasser gespült. Anschliessend wurden sie mit einer Zinkphosphatlösung 2 min im Spritzen bei 50°C phosphatiert und danach mit Wasser gespült.Steel parts were sprayed with an alkaline cleaning solution for 2 min at 50 ° C. and then rinsed with water. They were then phosphated with a zinc phosphate solution for 2 minutes in a spray at 50 ° C. and then rinsed with water.

Die Stahlteile wurden anschliessend mit der 0,3 g Kupfer(II)ethanat-Hydrat pro Liter enthaltenden Nachpassivierungslösung bei 35°C 1 min im Spritzen nachpassiviert. Es wurde dann mit vollentsalztem Wasser gespült und mit Druckluft getrocknet.The steel parts were then post-passivated with the post-passivation solution containing 0.3 g of copper (II) ethanate hydrate per liter at 35 ° C. for 1 min in spraying. It was then rinsed with deionized water and dried with compressed air.

Die getrockneten Teile wurden mit einem kathodischen Elektrotauchlack beschichtet und 20 min bei 185°C getrocknet. Die Trockenfilmdicke des Anstriches betrug 18 µm.The dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes. The dry film thickness of the paint was 18 µm.

Die Teile wurden mit Einzelschnitten versehen und dem Salzsprühtest (DIN 50 021) für 480 h unterworfen. Die Auswertung nach DIN 53 167 ergab eine Unterwanderung von 0,4 bis 0,6 mm.The parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h. The evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.

Beispiel 2Example 2

Zur Herstellung einer Nachpassivierungslösung wurde Ni(CH3COO)2 · 4H20 zu einer 0,7 g . 1-1 enthaltenden Lösung in Wasser gelöst, entsprechend 0,17 g Ni pro Liter Lösung. Stahlteile wurden im Tauchverfahren 10 min bei 80°C mit einer alkalischen Reinigungslösung gereinigt und dann mit Wasser gespült. Die Teile wurden anschliessend 3 min im Tauchverfahren mit einer Zinkphosphatlösung bei 50°C phosphatiert und wiederum gespült.Ni (CH 3 COO) 2 .4H 2 0 was made into a 0.7 g to prepare a post-passivation solution. 1- 1 containing solution dissolved in water, corresponding to 0.17 g Ni per liter of solution. Steel parts were immersed for 10 minutes at 80 ° C with an alkaline cleaning solution and then rinsed with water. The parts were then dipped in a zinc phosphate solution at 50 ° C. for 3 minutes and rinsed again.

Zur Nachpassivierung wurde die 0,7 g Nickel-(II)ethanat Tetrahydrat pro Liter enthaltende Lösung bei 35°C eingesetzt, die Behandlungszeit betrug dabei 1 min im Tauchen. Die nachpassivierten Teile wurden mit vollentsalztem Wasser gespült und mit Druckluft getrocknet.The solution containing 0.7 g of nickel (II) ethanate tetrahydrate per liter at 35 ° C. was used for the post-passivation, the treatment time being 1 min in immersion. The post-passivated parts were rinsed with deionized water and dried with compressed air.

Anschliessend wurde kathodisch ein Elektrotauchlack aufgetragen, der 20 min durch Erwärmen auf 185 °C getrocknet wurde. Die Trockenfilmdicke des Lackes betrug 18 µm.Subsequently, an electro-dip coating was applied cathodically, which was dried by heating to 185 ° C. for 20 minutes. The dry film thickness of the lacquer was 18 µm.

Die lackierten Teile wurden dann mit Einzelschnitten versehen und dem Salzsprühtest (DIN 50 021 ) für 480 Stunden unterworfen. Die Auswertung nach DIN 53 167 ergab eine Unterwanderung von 0,4 bis 0,6 mm.The painted parts were then provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 hours. The evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.

Beispiel 3Example 3

Zur Herstellung einer Nachpassivierungslösung wurden Ni(CH3COO)2 · 4H20 und CU(CH3-COO)2 · H20 in Wasser zu einer Lösung gelöst, die 0,5 g · I-1 Nickel(II)ethanat-Tetrahydrat und 0,1 g - I-1 Kupfer(II)ethanat-Hydrat enthielt. Dies entspricht einem Gehalt von 0,12 g Ni und 0,03 g Cu pro Liter Lösung.To prepare a post-passivation solution, Ni (CH 3 COO) 2 .4H 2 0 and C U (CH 3 -COO) 2 .H 2 0 were dissolved in water to give a solution containing 0.5 g · I -1 nickel (II) ethanate tetrahydrate and 0.1 g - I -1 copper (II) ethanate hydrate contained. This corresponds to a content of 0.12 g Ni and 0.03 g Cu per liter of solution.

Stahlteile wurden im Tauchverfahren 10 min bei 80°C mit einer alkalischen Reinigungslösung gereinigt und dann mit Wasser gespült. Die Teile wurden daraufhin 3 min im Tauchverfahren mit einer Zinkphosphatlösung bei 50°C phosphatiert und wiederum gespült.Steel parts were immersed for 10 minutes at 80 ° C with an alkaline cleaning solution and then rinsed with water. The parts were then dipped in a zinc phosphate solution at 50 ° C. for 3 minutes and rinsed again.

Zur Nachpassivierung wurden die Teile mit der wie oben beschrieben hergestellten Nickel- und Kupfer-Ionen enthaltenden Lösung 1 min bei 40°C im Tauchen behandelt, anschliessend mit vollentsalztem Wasser gespült und mit Druckluft getrocknet.For post-passivation, the parts were treated with the solution containing nickel and copper ions prepared as described above for 1 min at 40 ° C. in an immersion, then rinsed with deionized water and dried with compressed air.

Die derart nachpassivierten Teile wurden dann mit einem kathodischen Elektrotauchlack beschichtet und 20 min durch Erwärmen auf 185°C getrocknet. Die Trockenfilmdicke des Lackes betrug 18 pm.The parts passivated in this way were then coated with a cathodic electrocoating material and dried for 20 minutes by heating to 185.degree. The dry film thickness of the lacquer was 18 pm.

Die Teile wurden mit Einzelschnitten versehen und dem Salzsprühtest (DIN 50 021) für 480 h unterworfen. Die Auswertung nach DIN 53 167 ergab eine Unterwanderung von 0,2 bis 0,4 mm.The parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h. The evaluation according to DIN 53 167 showed an infiltration of 0.2 to 0.4 mm.

Beispiele 4-14Examples 4-14

Zur Herstellung der Nachspüllösungen wurden die in Tabelle 1 aufgeführten Kationen in Wasser einzeln (Beispiele 4 bis 9) oder in Kombination (Beispiele 10 bis 14) zu jeweils 0,1 gl-1 Gesamt- kation(en) enthaltenden Lösungen gelöst. Dabei wurden als Salze die Ethanate (Acetate) bzw. (im Falle von Ti(IV) das 2.4-Pentandionat (Titanylacetylacetonat) eingesetzt.To prepare the rinse solutions, the cations listed in Table 1 were dissolved individually in water (Examples 4 to 9) or in combination (Examples 10 to 14) to give solutions containing 0.1 gl -1 of total cation (s). The salts used were the ethanates (acetates) or (in the case of Ti (IV) the 2,4-pentanedionate (titanylacetylacetonate).

Stahlteile wurden gemäss Tabelle 2 mit alkalischen Reinigungslösungen im Spritzen oder Tauchen gereinigt und dann mit Wasser gespült. Anschliessend wurden sie mit einer Zinkphosphatlösung im Spritzen oder Tauchen phosphatiert und danach mit Wasser gespült.Steel parts were cleaned according to Table 2 with alkaline cleaning solutions by spraying or dipping and then rinsed with water. They were then phosphated with a zinc phosphate solution by spraying or dipping and then rinsed with water.

Die Stahlteile wurden anschliessend mit den die Kationen in der in Tabelle I genannten Menge enthaltenden Nachpassivierungslösungen nachpassiviert, mit vollentsalztem Wasser gespült und mit Druckluft getrocknet.The steel parts were then post-passivated with the post-passivation solutions containing the cations in the amount listed in Table I, rinsed with demineralized water and dried with compressed air.

Die getrockneten Teile wurden mit einem kathodischen Elektrotauchlack beschichtet und 20 min bei 185°C getrocknet. Die Trockenfilmdicke des Anstriches betrug 18 µm.The dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes. The dry film thickness of the paint was 18 µm.

Die Teile wurden mit Einzelschnitten versehen und dem Wechselklimatest nach VW-Norm P 12 10 30 Tage unterzogen.The parts were provided with individual cuts and subjected to the alternating climate test according to VW standard P 12 10 30 days.

Die Auswertung nach DIN 53167 ergab die in der Tabelle 1 angegebenen Werte.

Figure imgb0001
Figure imgb0002
Figure imgb0003
 The evaluation according to DIN 53167 gave the values given in Table 1.
Figure imgb0001
Figure imgb0002
Figure imgb0003

Claims (8)

1. A process for the after-passivation of phosphated metal surfaces of iron steel, galvanized steel or aluminium using acidic to neutral aqueous solutions of salts of polyvalent metal ions, the phosphated metal surfaces first being rinsed with water, then treated with aqueous solutions which have a pH value in the range from 3 to 7 and a temperature in the range from 20 to 120 °C and which contain one or more of the following salts:
a) (2,4-pentanedionato)-titanium(IV) oxide (titanyl acetyl acetonate),
b) manganese(III)-ethanate (-acetate),
c) cobalt(II)-ethanate (-acetate),
d) nickel(II)-ethanate (-acetate),
e) copper(II)-ethanate (-acetate),

the content of metal ions in the solutions being from 0.01 to 10 g/I in each case and not exceeding a value of 10 g/l, even where several of the cations mentioned are present, and then being rinsed with water and, optionally, dried.
2. A process as claimed in claim 1, characterized in that the solutions contain one or more of the salts mentioned under a to e, the content of Ti(IV), Mn(II), Co(II) or Ni(II) cations in the solutions being from 0.1 to 1 g/I and the content of Cu(II) cations being from 0.03 to 1 g/I.
3. A process as claimed in claim 1, characterized in that the solutions contain
b) manganese(II)-ethanate and
c) cobalt(II)-ethanate,
the content of Mn(II) cations and of Co(II) cations in the solutions being from 0.05 to 1 g/l in either case.
4. A process as claimed in claim 1, characterized in that the solutions contain
d) nickel(II)-ethanate and
e) copper(II)-ethanate,
the content of Ni(II) cations in the solutions being from 0.1 to 1 g/I and the content of Cu(II) cations being from 0.03 to 1 g/l.
5. A process as claimed in claim 1, characterized in that the solutions contain
a) (2,4-pentanedionato)-titanium(IV) oxide and
c) cobalt(II)-ethanate and
d) nickel(II)-ethanate,

the content of Ti(IV), Co(II) and Ni(II) cations in the solutions being from 0.01 to 1 g/I in each case.
6. A process as claimed in claims 1 to 5, characterized in that the solutions have a pH value in the range from 4 to 5.
7. A process as claimed in claims 1 to 6, characterized in that the solutions have a temperature in the range from 30 to 50 °C.
8. A process as claimed in claims 1 to 7, characterized in that the phosphated metal surfaces are treated with the solutions by spraying or immersion and are then rinsed with fully deionized or low-salt water and dried.
EP84111060A 1984-01-07 1984-09-17 Process for after passivating phosphated metal surfaces using titanium and/or manganese and/or cobalt and/or nickel and/or copper cations containing solutions Expired EP0149720B1 (en)

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DE19843400339 DE3400339A1 (en) 1984-01-07 1984-01-07 METHOD FOR REPASSIVATING PHOSPHATED METAL SURFACES USING SOLUTIONS CONTAINING NICKEL AND / OR COPPER CATIONS

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JPH0790614A (en) * 1993-09-22 1995-04-04 Elna Co Ltd Aluminum or aluminum alloys and their chemical conversion treatment
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