EP2014793A2 - Anti-corrosion treatment for conversion coatings - Google Patents

Anti-corrosion treatment for conversion coatings Download PDF

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Publication number
EP2014793A2
EP2014793A2 EP07011720A EP07011720A EP2014793A2 EP 2014793 A2 EP2014793 A2 EP 2014793A2 EP 07011720 A EP07011720 A EP 07011720A EP 07011720 A EP07011720 A EP 07011720A EP 2014793 A2 EP2014793 A2 EP 2014793A2
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EP
European Patent Office
Prior art keywords
acids
treatment solution
acid
chromium
iii
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP07011720A
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German (de)
French (fr)
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EP2014793B1 (en
EP2014793A3 (en
Inventor
Björn Dingwerth
Andreas Noack
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to EP07011720.5A priority Critical patent/EP2014793B1/en
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to ES07011720.5T priority patent/ES2444406T3/en
Priority to KR1020097027482A priority patent/KR20100038325A/en
Priority to PCT/EP2008/004793 priority patent/WO2008151829A1/en
Priority to JP2010511544A priority patent/JP5266317B2/en
Priority to CN200880017265A priority patent/CN101720364A/en
Priority to US12/664,002 priority patent/US8435360B2/en
Publication of EP2014793A2 publication Critical patent/EP2014793A2/en
Publication of EP2014793A3 publication Critical patent/EP2014793A3/en
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a conversion layer.
  • the coating of the metallic workpiece to be protected with a coating of another metal is a widely used and established method in the art.
  • the coating metal can behave in the corrosive medium either electrochemically nobler or less noble than the material base metal. If the coating metal behaves less noble, it acts in the corrosive medium compared to the base metal as a sacrificial anode (cathodic corrosion protection).
  • this protective function associated with the formation of corrosion products of the coating metal is thus desired, the corrosion products of the coating often lead to undesirable decorative and often also to functional impairments of the workpiece.
  • cathodically protective base coating metals such as, for example, Zinc or aluminum and their alloys often used so-called conversion coatings.
  • conversion coatings These are reaction products of the non-noble coating metal which are insoluble in aqueous media over a wide pH range with the treatment solution. Examples of these so-called conversion layers are so-called phosphating and chromating.
  • the layer to be protected is immersed in an acidic solution containing phosphate ions (see, for example, US Pat WO 00/47799 ).
  • the acidic medium leads to the partial dissolution of zinc from the coating.
  • the liberated Zn 2+ cations form a sparingly soluble zinc phosphate layer on the surface with the phosphate ions of the treatment solution. Since zinc phosphate layers themselves form only a comparatively bad corrosion protection, but an excellent primer for For this applied paints and paints, their main application is in the function of a primer for coatings and paints.
  • chromium (VI) ions see EP 0 553 164 A1 .
  • chromium (VI) is reduced to chromium (III), which in the surface film which is more alkaline by the evolution of hydrogen, inter alia as chromium (III) hydroxide or as sparingly soluble ⁇ -oxo or ⁇ -hydroxo bridged chromium (III) Complex is deposited.
  • chromium (III) hydroxide inter alia as chromium (III) hydroxide or as sparingly soluble ⁇ -oxo or ⁇ -hydroxo bridged chromium (III) Complex is deposited.
  • sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well protects against corrosion attack by electrolytes conversion coating on the zinc surface.
  • chromium (VI) compounds are acutely toxic and highly carcinogenic, requiring replacement of the methods associated with these compounds.
  • a disadvantage of this additional process step using polymer dispersions is the occurrence of drainage drops in the coating of workpieces produced on the frame and / or the bonding of coated bulk material;
  • problems such as dimensional accuracy of threads and the like are associated with the layer thickness of these organic sealants. If such sealings have a high degree of corrosion protection, the adhesion to the coated substrate is generally very good. This also means a very good adhesion to machine parts of the coating equipment, what their Cleaning difficult. Goods with coating defects, which should again go through the entire coating process, also has to be stripped of costs again, which usually requires an additional process step.
  • the object of the invention is to provide processes for increasing the corrosion protection of metallic, in particular zinc-containing, surfaces provided with conversion layers.
  • the aim is to preserve or improve the decorative and functional properties of the surfaces.
  • the above-mentioned problems in the use of chromium (VI) -containing compounds or post-treatments with polymer dispersions should be avoided.
  • the invention provides a method for producing a corrosion-protective coating layer, wherein a surface to be treated is contacted with an aqueous treatment solution containing chromium (III) ions and at least one phosphate compound, wherein the ratio of molar concentration (ie the concentration in mol / l) of chromium (III) ions to the molar concentration of the at least one phosphate compound (calculated based on orthophosphate) ([chromium (III) ions]: [phosphate compound]) between 1: 1.5 and 1: 3 lies.
  • Phosphate compounds are derived from phosphorus in the oxidation state + V derived oxo compounds and their esters with organic radicals having up to 12 carbon atoms and the salts of mono- and diesters.
  • Suitable phosphate compounds are in particular alkyl phosphates with alkyl groups having up to 12 carbon atoms.
  • Suitable phosphate compounds are ortho-phosphoric acid (H 3 PO 4 ) and its salts, polyphosphoric acid and its salts, meta-phosphoric acid and its salts, Phosphoric acid methyl esters (mono-, di- and triesters), phosphoric acid ethyl esters (mono-, di- and triesters), phosphoric acid n- propyl esters (mono-, di- and triesters), phosphoric acid isopropyl ester (mono-, di- and triesters), phosphoric acid n -butyl ester (mono-, di- and triester), phosphoric acid 2-butyl ester (mono-, di- and triester), phosphoric acid tert-butyl ester (mono-, di- and triester), the salts of the monosubstituted and diesters and di- phosphorus pentoxide and mixtures of these compounds.
  • the term "salts" includes not only the salts of
  • the treatment solution preferably contains between 0.2 g / l and 20 g / l of chromium (III) ions, more preferably between 0.5 g / l and 15 g / l of chromium (III) ions and more preferably between 1 g / 1 and 10 g / l of chromium (III) ions.
  • the ratio of the molar concentration of chromium (III) ions to the molar concentration of the at least one phosphate compound (calculated on the basis of orthophosphate) is between 1: 1.5 and 1: 3, preferably between 1: 1.7 and 1: 2.5.
  • Chromium (III) may be added to the treating solution either in the form of inorganic chromium (III) salts, e.g. basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, chromium (III) nitrate, potassium chromium (III) sulfate or chromium (III) salts organic Acids such as Chromium (III) methanesulfonate, chromium (III) citrate may be added or produced by reduction of suitable chromium (VI) compounds in the presence of suitable reducing agents. Suitable chromium (VI) compounds are e.g.
  • Chromium (VI) oxide Chromium (VI) oxide, chromates, such as potassium or sodium chromate, dichromates, e.g. Potassium or sodium dichromate.
  • Suitable reducing agents for in situ generation of chromium (III) ions are e.g. Sulfites, e.g. Sodium sulfite, sulfur dioxide, phosphites, e.g. Sodium hypophosphite, phosphorous acid, hydrogen peroxide, methanol.
  • the treatment solution preferably has a pH between pH 2.5 and pH 7, preferably between pH 3 and pH 6, and particularly preferably between pH 3.5 and pH 5.
  • the treatment solution may additionally (optionally) contain one or more complexing agents.
  • Suitable complexing agents are, in particular, organic chelate ligands.
  • suitable complexing agents are polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids.
  • suitable carboxylic acids are citric, tartaric, malic, lactic, gluconic, glucuronic, ascorbic, isocitric, gallic, glycolic, 3-hydroxypropionic, 4-hydroxybutyric, salicylic, nicotinic, alanine, glycine, asparagine, aspartic, cysteine, glutamic, glutamine , Lysine.
  • Suitable hydroxyphosphonic acids are, for example, Dequest 2010 TM (from Solutia Inc.); suitable as aminophosphonic acids, for example Dequest 2000 TM (from Solutia Inc.).
  • the treatment solution will contain at least one metal or metalloid, e.g. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P.
  • metal or metalloid e.g. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P.
  • These elements may be added in the form of their salts or in the form of complex anions or the corresponding acids of these anions such as hexafluoroboric acid, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid or their salts.
  • zinc which may be added in the form of zinc (II) salts, for example zinc sulfate, zinc chloride, zinc phosphate, zinc oxide or zinc hydroxide.
  • the treatment solution is added between 0.5 g / l and 25 g / l, more preferably between 1 g / l and 15 g / l Zn 2+ .
  • the list of zinc compounds merely gives examples of compounds suitable according to the invention, but does not limit the amount of suitable zinc compounds to the substances mentioned.
  • the treatment solution may additionally (optionally) contain one or more water-soluble or water-dispersible polymers selected from the group consisting of polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols to improve the film formation on the surface to be treated and to increase the hydrophobicity of the surface.
  • polyethylene glycols polyvinylpyrrolidones
  • polyvinyl alcohols polyvinyl alcohols
  • the concentration of the at least one polymer is preferably in the range between 50 mg / l and 20 g / l.
  • the layer properties of the deposited corrosion protection layer are significantly improved.
  • the treatment solution may additionally (optionally) contain one or more wetting agents.
  • one or more wetting agents may additionally (optionally) contain one or more wetting agents.
  • fluoroaliphatic polymeric esters such as Fluorad FC-4432 TM (from 3M).
  • the surfaces treated according to the invention are metallic, preferably zinc-containing, surfaces provided with a chromium (III) -containing conversion layer.
  • a layer is deposited on the treated surface comprising chromium, phosphate (s) and optionally a metal, e.g. Zinc, and optionally one or more polymeric components.
  • the inventive method leads to untreated, that is freshly deposited, not provided with a conversion layer zinc or zinc alloy surfaces not significantly contributing to the corrosion protection layers.
  • the contacting of the treatment solution with the surface to be treated can be carried out in the inventive method according to known methods, in particular by immersion.
  • the temperature of the treatment solution is preferably between 10 ° C and 90 ° C, more preferably between 20 ° C and 80 ° C, more preferably between 40 ° C and 60 ° C.
  • the duration of the contacting is preferably between 0.5 s and 180 s, more preferably between 5 s and 60 s, most preferably between 10 s and 30 s.
  • the treatment solution can be prepared prior to carrying out the method according to the invention by dilution of a correspondingly higher concentrated concentrate solution.
  • the objects treated according to the invention are no longer rinsed after being brought into contact, but dried.
  • a treatment solution according to the invention was prepared which contained the following constituents: 7 g / l Cr 3+ from chromium (III) hydroxide 28 g / l PO 4 3- from ortho-phosphoric acid 9 g / l Zn 2+ from zinc oxide 18 g / l citric acid
  • the pH of the solution was adjusted to pH 3.9 with 20% sodium hydroxide solution.
  • test parts made of steel were coated in a weakly acidic process (Protolux 3000 TM from Atotech GmbH) with an 8-10 ⁇ m thick zinc coating and rinsed with demineralized water.
  • a treatment solution according to the invention having the same composition as in Example 1 was prepared; the pH of the solution was adjusted to pH 3.9 with 20% sodium hydroxide solution.
  • the test part used was a galvanized steel part, which was treated with a black passivation solution containing essentially Cr 3+ , NO 3 - , F - , and Fe 2+ (Tridur Zn H1 TM from Atotech GmbH) with a black Conversion layer has been provided.
  • the sample part thus treated was rinsed after the black passivation and immersed without intermediate drying step for 20 s in the inventive, heated to 60 ° C treatment solution.
  • the part was then dried without rinsing at 60-80 ° C for 5 minutes in a convection oven.
  • the part thus treated had a black, slightly iridescent surface. There were clearly visible trace traces.
  • the neutral salt spray test according to DIN 50021 SS showed no white corrosion for up to 48 h.
  • Example 3 to 6 were carried out as Example 2 except that the composition of the treatment solution was varied as shown in Table 1. (In addition, the drying time in Examples 4 to 6 was 15 minutes each.) The appearance of the surface of the obtained sample parts and the corrosion properties are also shown in Table 1 (together with the data of Example 2). ⁇ b> Table 1.

Abstract

Formation of a corrosion inhibiting coating involves contacting the surface to be treated with an aqueous solution (I) containing (a) trivalent chromium ions and (b) phosphate compound(s), at a weight ratio of (a) to (b) (calculated as orthophosphate) of 1:1.5-3.

Description

Gebiet der ErfindungField of the invention

Die Erfindung betrifft den Korrosionsschutz von metallischen Werkstoffen, insbesondere von solchen, die mit einer Konversionsschicht versehen sind.The invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a conversion layer.

Hintergrund der ErfindungBackground of the invention

Zum Schutz metallischer Werkstoffoberflächen vor korrosiven Umwelteinflüssen stehen im Stand der Technik unterschiedliche Methoden zur Verfügung. Die Beschichtung des zu schützenden metallischen Werkstücks mit einem Überzug aus einem anderen Metall ist dabei eine in der Technik weit verbreitete und etablierte Methode. Das Beschichtungsmetall kann sich im korrodierenden Medium dabei entweder elektrochemisch edler oder unedler als das Werkstoffgrundmetall verhalten. Verhält sich das Beschichtungsmetall unedeler, so fungiert es im korrodierenden Medium gegenüber dem Basismetall als Opferanode (kathodischer Korrosionsschutz). Diese mit der Bildung von Korrosionsprodukten des Überzugmetalls verbundene Schutzfunktion ist damit zwar erwünscht, die Korrosionsprodukte des Überzugs führen aber oft zu unerwünschten dekorativen und nicht selten auch zu funktionellen Beeinträchtigungen des Werkstücks. Um die Korrosion des Überzugmetalls zu reduzieren bzw. möglichst lange zu verhindern, werden speziell auf kathodisch schützenden unedlen Überzugsmetallen wie z.B. Zink oder Aluminium sowie deren Legierungen oft so genannte Konversionsschichten eingesetzt. Hierbei handelt es sich um in wässrigen Medien in einem weiten pH-Bereich unlösliche Reaktionsprodukte des unedlen Beschichtungsmetalls mit der Behandlungslösung. Beispiele für diese so genannten Konversionsschichten sind so genannte Phosphatierungen und Chromatierungen.To protect metallic material surfaces from corrosive environmental influences, different methods are available in the prior art. The coating of the metallic workpiece to be protected with a coating of another metal is a widely used and established method in the art. The coating metal can behave in the corrosive medium either electrochemically nobler or less noble than the material base metal. If the coating metal behaves less noble, it acts in the corrosive medium compared to the base metal as a sacrificial anode (cathodic corrosion protection). Although this protective function associated with the formation of corrosion products of the coating metal is thus desired, the corrosion products of the coating often lead to undesirable decorative and often also to functional impairments of the workpiece. In order to reduce or prevent the corrosion of the coating metal as far as possible, special attention is given to cathodically protective base coating metals, such as, for example, Zinc or aluminum and their alloys often used so-called conversion coatings. These are reaction products of the non-noble coating metal which are insoluble in aqueous media over a wide pH range with the treatment solution. Examples of these so-called conversion layers are so-called phosphating and chromating.

Im Falle von Phosphatierungen wird die zu schützende Schicht in eine saure, Phosphationen enthaltende Lösung getaucht (siehe z.B. WO 00/47799 ). Das saure Medium führt zur partiellen Auflösung von Zink aus der Beschichtung. Die freigesetzten Zn2+-Kationen bilden mit den Phosphationen der Behandlungslösung eine schwerlösliche Zinkphosphatschicht auf der Oberfläche. Da Zinkphosphatschichten selbst nur einen vergleichsweise schlechten Korrosionsschutz ausbilden, aber ein ausgezeichneter Haftgrund für hierauf aufgebrachte Lacke und Farben sind, liegt ihr Anwendungsschwerpunkt in der Funktion als Grundierung für Lackierungen und Anstriche.In the case of phosphating, the layer to be protected is immersed in an acidic solution containing phosphate ions (see, for example, US Pat WO 00/47799 ). The acidic medium leads to the partial dissolution of zinc from the coating. The liberated Zn 2+ cations form a sparingly soluble zinc phosphate layer on the surface with the phosphate ions of the treatment solution. Since zinc phosphate layers themselves form only a comparatively bad corrosion protection, but an excellent primer for For this applied paints and paints, their main application is in the function of a primer for coatings and paints.

Im Falle von Chromatierungen wird die zu behandelnde Oberfläche in eine saure, Chrom(VI)-lonen enthaltende Lösung getaucht (siehe EP 0 553 164 A1 ). Handelt es sich beispielsweise um eine Zink-Oberfläche, so löst sich ein Teil des Zinks auf. Unter den hierbei herrschenden reduzierenden Bedingungen wird Chrom(VI) zu Chrom(III) reduziert, das in dem durch die Wasserstoffentwicklung alkalischeren Oberflächenfilm u.a. als Chrom(III)-hydroxid bzw. als schwerlöslicher µ-Oxo- oder µ-Hydroxoverbrückter Chrom(III)-Komplex abgeschieden wird. Parallel wird schwerlösliches Zinkchromat(VI) gebildet. Insgesamt entsteht ein dicht geschlossener, sehr gut vor dem Korrosionsangriff durch Elektrolyte schützender Konversions-Überzug auf der Zinkoberfläche.In the case of chromating, the surface to be treated is immersed in an acidic solution containing chromium (VI) ions (see EP 0 553 164 A1 ). For example, if it is a zinc surface, some of the zinc will dissolve. Under the reducing conditions prevailing here, chromium (VI) is reduced to chromium (III), which in the surface film which is more alkaline by the evolution of hydrogen, inter alia as chromium (III) hydroxide or as sparingly soluble μ-oxo or μ-hydroxo bridged chromium (III) Complex is deposited. In parallel, sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well protects against corrosion attack by electrolytes conversion coating on the zinc surface.

Chrom(VI)-Verbindungen sind jedoch akut toxisch und stark karzinogen, so dass ein Ersatz der mit diesen Verbindungen einhergehenden Verfahren notwendig ist.However, chromium (VI) compounds are acutely toxic and highly carcinogenic, requiring replacement of the methods associated with these compounds.

Als Ersatz für Chromatierungsverfahren mit sechswertigen Chromverbindungen haben sich mittlerweile eine Vielzahl von Verfahren etabliert, die unterschiedliche Komplexe dreiwertiger Chromverbindungen verwenden (siehe DE 196 38 176 A1 ). Da der damit erzielte Korrosionsschutz in der Regel dem der mit sechswertigem Chrom arbeitenden Verfahren unterlegen ist, wird oftmals zusätzlich eine organische Versiegelung, die meist aus wässrigen Polymerdispersionen abgeschieden wird, auf der Oberfläche des Werkstücks aufgebracht. Insbesondere bei Verwendung so genannter Schwarzpassivierungen, also Verfahren, die mit Hilfe von dreiwertigen Chromverbindungen auf zinkhaltigen Oberflächen schwarze Schichten ausbilden, ist eine Nachbehandlung dieser ersten Konversionsschicht zur Steigerung von deren Korrosionsschutz im Stand der Technik (siehe WO 02/07902 A2 ) unerlässlich. Nachteilig an diesem zusätzlichen Verfahrensschritt unter Anwendung von Polymerdispersionen ist das Auftreten von Ablauftropfen bei Beschichtung von am Gestell gefertigten Werkstücken und / oder das Verkleben von beschichtetem Schüttgut; außerdem ergeben sich Probleme wie Maßhaltigkeit von Gewinden u.dgl., die mit der Schichtdicke dieser organischen Versiegelungen einhergehen. Weisen derartige Versiegelungen einen hohen Korrosionsschutz auf, ist in der Regel die Haftung zum beschichteten Untergrund sehr gut. Dies bedeutet auch eine sehr gute Haftung zu Maschinenteilen der Beschichtungsanlagen, was deren Reinigung erschwert. Ware mit Beschichtungsfehlern, die erneut den gesamten Beschichtungsprozess durchlaufen soll, muss zudem aufwendig wieder entschichtet werden, wofür meist ein zusätzlicher Verfahrensschritt erforderlich ist.As a substitute for chromating processes with hexavalent chromium compounds, a multitude of processes have now been established that use different complexes of trivalent chromium compounds (see DE 196 38 176 A1 ). Since the corrosion protection thus achieved is usually inferior to that of the process using hexavalent chromium, an organic seal, which is usually deposited from aqueous polymer dispersions, is often additionally applied to the surface of the workpiece. In particular, when using so-called black passivations, ie processes which form black layers on zinc-containing surfaces with the aid of trivalent chromium compounds, a post-treatment of this first conversion layer to increase its corrosion protection in the prior art (see WO 02/07902 A2 ) essential. A disadvantage of this additional process step using polymer dispersions is the occurrence of drainage drops in the coating of workpieces produced on the frame and / or the bonding of coated bulk material; In addition, problems such as dimensional accuracy of threads and the like are associated with the layer thickness of these organic sealants. If such sealings have a high degree of corrosion protection, the adhesion to the coated substrate is generally very good. This also means a very good adhesion to machine parts of the coating equipment, what their Cleaning difficult. Goods with coating defects, which should again go through the entire coating process, also has to be stripped of costs again, which usually requires an additional process step.

Darüber hinaus erschweren Oberflächen, die durch Behandlung mit den bekannten Polymerdispersionen erhalten werden und deren Zustand im wesentlichen durch die Charakteristika des dispergierten Polymers bestimmt werden, die Einstellung von Reibbeiwerten µges. > 0,25 (DIN 946).In addition, surfaces obtained by treatment with the known polymer dispersions, the state of which is determined essentially by the characteristics of the dispersed polymer, make it difficult to adjust friction coefficients μ ges . > 0.25 (DIN 946).

Beschreibung der ErfindungDescription of the invention

Der Erfindung liegt die Aufgabe zugrunde, Verfahren zur Steigerung des Korrosionsschutzes metallischer, insbesondere zinkhaltiger, mit Konversionsschichten versehener Oberflächen bereitzustellen. Dabei sollen die dekorativen und funktionellen Eigenschaften der Oberflächen erhalten oder verbessert werden. Außerdem sollen die oben genannten Probleme beim Einsatz von Chrom(VI)-haltigen Verbindungen oder von Nachbehandlungen mit Polymerdispersionen vermieden werden.The object of the invention is to provide processes for increasing the corrosion protection of metallic, in particular zinc-containing, surfaces provided with conversion layers. The aim is to preserve or improve the decorative and functional properties of the surfaces. In addition, the above-mentioned problems in the use of chromium (VI) -containing compounds or post-treatments with polymer dispersions should be avoided.

Zur Lösung dieser Aufgabe stellt die Erfindung ein Verfahren zur Erzeugung einer korrosionsschützenden Überzugsschicht bereit, wobei eine zu behandelnde Oberfläche mit einer wässrigen Behandlungslösung in Kontakt gebracht wird, die Chrom(III)-Ionen und mindestens eine Phosphatverbindung enthält, wobei das Verhältnis der Stoffmengenkonzentration (d.h. der Konzentration in mol/l) von Chrom(III)-lonen zur Stoffmengenkonzentration der mindestens einen Phosphatverbindung (bezogen auf Orthophosphat berechnet) ([Chrom(III)-lonen] : [Phosphatverbindung]) zwischen 1 : 1,5 und 1 : 3 liegt.To achieve this object, the invention provides a method for producing a corrosion-protective coating layer, wherein a surface to be treated is contacted with an aqueous treatment solution containing chromium (III) ions and at least one phosphate compound, wherein the ratio of molar concentration (ie the concentration in mol / l) of chromium (III) ions to the molar concentration of the at least one phosphate compound (calculated based on orthophosphate) ([chromium (III) ions]: [phosphate compound]) between 1: 1.5 and 1: 3 lies.

Phosphatverbindungen sind von Phosphor in der Oxidationsstufe +V abgeleitete Oxoverbindungen sowie deren Ester mit organischen Resten mit bis zu 12 Kohlenstoffatomen sowie die Salze der Mono- und Diester. Geeignete Phosphatverbindungen sind insbesondere Phosphorsäurealkylester mit Alkylgruppen mit bis zu 12 Kohlenstoffatomen.Phosphate compounds are derived from phosphorus in the oxidation state + V derived oxo compounds and their esters with organic radicals having up to 12 carbon atoms and the salts of mono- and diesters. Suitable phosphate compounds are in particular alkyl phosphates with alkyl groups having up to 12 carbon atoms.

Beispiele für geeignete Phosphatverbindungen sind ortho-Phosphorsäure (H3PO4) und ihre Salze, Polyphosphorsäure und ihre Salze, meta-Phosphorsäure und ihre Salze, Phosphorsäuremethylester (Mono-, Di- und Triester), Phosphorsäureethylester (Mono-, Di- und Triester), Phosphorsäure-n-propylester (Mono-, Di- und Triester), Phosphorsäureisopropylester (Mono-, Di- und Triester), Phosphorsäure-n-butylester (Mono-, Di- und Triester), Phosphorsäure-2-butylester (Mono-, Di- und Triester), Phosphorsäure-tert.-butylester (Mono-, Di- und Triester), die Salze der genannten Mono- und Diester sowie di-Phosphorpentoxid und Gemische dieser Verbindungen. Der Begriff "Salze" umfasst nicht nur die Salze der vollständig deprotonierten Säuren, sondern Salze in allen möglichen Protonierungsstufen, z.B. Hydrogenphosphate und Dihydrogenphosphate.Examples of suitable phosphate compounds are ortho-phosphoric acid (H 3 PO 4 ) and its salts, polyphosphoric acid and its salts, meta-phosphoric acid and its salts, Phosphoric acid methyl esters (mono-, di- and triesters), phosphoric acid ethyl esters (mono-, di- and triesters), phosphoric acid n- propyl esters (mono-, di- and triesters), phosphoric acid isopropyl ester (mono-, di- and triesters), phosphoric acid n -butyl ester (mono-, di- and triester), phosphoric acid 2-butyl ester (mono-, di- and triester), phosphoric acid tert-butyl ester (mono-, di- and triester), the salts of the monosubstituted and diesters and di- phosphorus pentoxide and mixtures of these compounds. The term "salts" includes not only the salts of completely deprotonated acids, but salts in all possible protonation stages, eg hydrogen phosphates and dihydrogen phosphates.

Die Behandlungslösung enthält bevorzugt zwischen 0,2 g/l und 20 g/l Chrom(III)-lonen, mehr bevorzugt zwischen 0,5 g/l und 15 g/l Chrom(III)-lonen und besonders bevorzugt zwischen 1 g/l und 10 g/l Chrom(III)-lonen.The treatment solution preferably contains between 0.2 g / l and 20 g / l of chromium (III) ions, more preferably between 0.5 g / l and 15 g / l of chromium (III) ions and more preferably between 1 g / 1 and 10 g / l of chromium (III) ions.

Das Verhältnis der Stoffmengenkonzentration von Chrom(III)-lonen zur Stoffmengenkonzentration der mindestens einen Phosphatverbindung (bezogen auf Orthophosphat berechnet) liegt zwischen 1 : 1,5 und 1 : 3, bevorzugt zwischen 1 : 1,7 und 1 : 2,5.The ratio of the molar concentration of chromium (III) ions to the molar concentration of the at least one phosphate compound (calculated on the basis of orthophosphate) is between 1: 1.5 and 1: 3, preferably between 1: 1.7 and 1: 2.5.

Chrom(III) kann der Behandlungslösung entweder in Form von anorganischen Chrom(III)-Salzen wie z.B. basisches Chrom(III)-sulfat, Chrom(III)-hydroxid, Chrom(III)-dihydrogenphosphat, Chrom(III)-chlorid, Chrom(III)-nitrat, Kaliumchrom(III)-sulfat oder Chrom(III)-Salzen organischer Säuren wie z.B. Chrom(III)-methansulfonat, Chrom(III)-citrat zugegeben werden oder durch Reduktion geeigneter Chrom(VI)-Verbindungen in Gegenwart geeigneter Reduktionsmittel erzeugt werden. Geeignete Chrom(VI)-Verbindungen sind z.B. Chrom(VI)-oxid, Chromate wie Kalium- oder Natriumchromat, Dichromate wie z.B. Kalium- oder Natriumdichromat. Geeignete Reduktionsmittel zur in situ Erzeugung von Chrom(III)-lonen sind z.B. Sulfite wie z.B. Natriumsulfit, Schwefeldioxid, Phosphite wie z.B. Natriumhypophosphit, phosphorige Säure, Wasserstoffperoxid, Methanol.Chromium (III) may be added to the treating solution either in the form of inorganic chromium (III) salts, e.g. basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, chromium (III) nitrate, potassium chromium (III) sulfate or chromium (III) salts organic Acids such as Chromium (III) methanesulfonate, chromium (III) citrate may be added or produced by reduction of suitable chromium (VI) compounds in the presence of suitable reducing agents. Suitable chromium (VI) compounds are e.g. Chromium (VI) oxide, chromates, such as potassium or sodium chromate, dichromates, e.g. Potassium or sodium dichromate. Suitable reducing agents for in situ generation of chromium (III) ions are e.g. Sulfites, e.g. Sodium sulfite, sulfur dioxide, phosphites, e.g. Sodium hypophosphite, phosphorous acid, hydrogen peroxide, methanol.

Die Behandlungslösung besitzt bevorzugt einen pH-Wert zwischen pH 2,5 und pH 7, bevorzugt zwischen pH 3 und pH 6 und besonders bevorzugt zwischen pH 3,5 und pH 5.The treatment solution preferably has a pH between pH 2.5 and pH 7, preferably between pH 3 and pH 6, and particularly preferably between pH 3.5 and pH 5.

Die Behandlungslösung kann zusätzlich (optional) einen oder mehrer Komplexbildner enthalten. Geeignete Komplexbildner sind insbesondere organische Chelatliganden.The treatment solution may additionally (optionally) contain one or more complexing agents. Suitable complexing agents are, in particular, organic chelate ligands.

Beispiele für geeignete Komplexbildner sind Polycarbonsäuren, Hydroxycarbonsäuren, Hydroxypolycarbonsäuren, Aminocarbonsäuren oder Hydroxyphosphonsäuren. Beispiele für geeignete Carbonsäuren sind Citronensäure, Weinsäure, Äpfelsäure, Milchsäure, Gluconsäure, Glucuronsäure, Ascorbinsäure, Isozitronensäure, Gallussäure, Glycolsäure, 3-Hydroxypropionsäure, 4-Hydroxybuttersäure, Salicylsäure, Nicotinsäure, Alanin, Glycin, Asparagin, Asparaginsäure, Cystein, Glutaminsäure, Glutamin, Lysin. Als Hydroxyphosphonsäuren eignet sich z.B. Dequest 2010™ (von Solutia Inc.); als Aminophosphonsäuren eignet sich z.B. Dequest 2000™ (von Solutia Inc.).Examples of suitable complexing agents are polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids. Examples of suitable carboxylic acids are citric, tartaric, malic, lactic, gluconic, glucuronic, ascorbic, isocitric, gallic, glycolic, 3-hydroxypropionic, 4-hydroxybutyric, salicylic, nicotinic, alanine, glycine, asparagine, aspartic, cysteine, glutamic, glutamine , Lysine. Suitable hydroxyphosphonic acids are, for example, Dequest 2010 ™ (from Solutia Inc.); suitable as aminophosphonic acids, for example Dequest 2000 ™ (from Solutia Inc.).

Im allgemeinen wird der Behandlungslösung zur Steigerung des Korrosionsschutzes mindestens ein Metall oder Metalloid wie z.B. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P zugesetzt. Diese Elemente können in Form ihrer Salze oder in Form komplexer Anionen oder der entsprechenden Säuren dieser Anionen wie Hexafluoroborsäure, Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkonsäure, Tetrafluoroborsäure oder Hexafluorophosphorsäure oder deren Salzen zugegeben werden.Generally, to enhance corrosion protection, the treatment solution will contain at least one metal or metalloid, e.g. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P. These elements may be added in the form of their salts or in the form of complex anions or the corresponding acids of these anions such as hexafluoroboric acid, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid or their salts.

Besonders bevorzugt wird Zink zugesetzt, das in Form von Zink(II)-salzen wie z.B. Zinksulfat, Zinkchlorid, Zinkphosphat, Zinkoxid oder Zinkhydroxid zugegeben werden kann. Bevorzugt werden der Behandlungslösung zwischen 0,5 g/l und 25 g/l, besonders bevorzugt zwischen 1 g/l und 15 g/l Zn2+ zugesetzt. Die Auflistung de Zinkverbindungen gibt lediglich Beispiele für erfindungsgemäß geeignete Verbindungen an, schränkt die Menge geeigneter Zinkverbindungen aber nicht auf die genannten Substanzen ein.Particular preference is given to adding zinc which may be added in the form of zinc (II) salts, for example zinc sulfate, zinc chloride, zinc phosphate, zinc oxide or zinc hydroxide. Preferably, the treatment solution is added between 0.5 g / l and 25 g / l, more preferably between 1 g / l and 15 g / l Zn 2+ . The list of zinc compounds merely gives examples of compounds suitable according to the invention, but does not limit the amount of suitable zinc compounds to the substances mentioned.

Die Behandlungslösung kann zur Verbesserung der Filmbildung auf der zu behandelnden Oberfläche und zur Steigerung der Hydrophobie der Oberfläche zusätzlich (optional) ein oder mehrere in Wasser lösliche oder in Wasser dispergierbare Polymere enthalten, die ausgewählt sind aus der Gruppe bestehend aus Polyethylenglykolen, Polyvinylpyrrolidonen, Polyvinylalkoholen, Polyitaconsäuren, Polyacrylaten und Copolymeren der jeweils zugrunde liegenden Monomere.The treatment solution may additionally (optionally) contain one or more water-soluble or water-dispersible polymers selected from the group consisting of polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols to improve the film formation on the surface to be treated and to increase the hydrophobicity of the surface. Polyitaconic acids, polyacrylates and copolymers of the respective underlying monomers.

Die Konzentration des mindestens einen Polymers liegt bevorzugt im Bereich zwischen 50 mg/l und 20 g/l.The concentration of the at least one polymer is preferably in the range between 50 mg / l and 20 g / l.

Durch die Zugabe der genannten Polymere zu der Behandlungslösung werden die Schichteigenschaften der abgeschiedenen Korrosionsschutzschicht signifikant verbessert.By adding the above-mentioned polymers to the treatment solution, the layer properties of the deposited corrosion protection layer are significantly improved.

Die Behandlungslösung kann zusätzlich (optional) ein oder mehrere Netzmittel enthalten. Dadurch wird insbesondere auf komplexen Teilen oder auf schwerer benetzbaren Oberflächen ein gleichmäßigerer Schichtaufbau und ein besseres Ablaufverhalten erzielt. Besonders vorteilhaft ist insbesondere die Verwendung fluoroaliphatischer polymerer Ester wie z.B. Fluorad FC-4432™ (von 3M).The treatment solution may additionally (optionally) contain one or more wetting agents. As a result, a more uniform layer structure and a better drainage behavior is achieved, especially on complex parts or on heavier wettable surfaces. Especially advantageous is the use of fluoroaliphatic polymeric esters such as Fluorad FC-4432 ™ (from 3M).

Die erfindungsgemäß behandelten Oberflächen sind metallische, bevorzugt zinkhaltige, mit einer Chrom(III)-haltigen Konversionsschicht versehene Oberflächen.The surfaces treated according to the invention are metallic, preferably zinc-containing, surfaces provided with a chromium (III) -containing conversion layer.

Durch das erfindungsgemäße Verfahren wird auf der behandelten Oberfläche eine Schicht abgeschieden, die Chrom, Phosphat(e), sowie optional ein Metall, wie z.B. Zink, und optional eine oder mehrere polymere Komponenten enthält. Das erfindungsgemäße Verfahren führt auf unbehandelten, dass heißt frisch abgeschiedenen, nicht mit einer Konversionsschicht versehenen Zink- bzw. Zinklegierungs-Oberflächen nicht zu signifikant zum Korrosionsschutz beitragenden Schichten.By the method according to the invention a layer is deposited on the treated surface comprising chromium, phosphate (s) and optionally a metal, e.g. Zinc, and optionally one or more polymeric components. The inventive method leads to untreated, that is freshly deposited, not provided with a conversion layer zinc or zinc alloy surfaces not significantly contributing to the corrosion protection layers.

Das Inkontaktbringen der Behandlungslösung mit der zu behandelnden Oberfläche kann bei dem erfindungsgemäßen Verfahren nach an sich bekannten Verfahren, insbesondere durch Eintauchen erfolgen.The contacting of the treatment solution with the surface to be treated can be carried out in the inventive method according to known methods, in particular by immersion.

Die Temperatur der Behandlungslösung liegt bevorzugt zwischen 10°C und 90 °C, mehr bevorzugt zwischen 20 °C und 80 °C, besonders bevorzugt zwischen 40 °C und 60 °C.The temperature of the treatment solution is preferably between 10 ° C and 90 ° C, more preferably between 20 ° C and 80 ° C, more preferably between 40 ° C and 60 ° C.

Die Dauer des Inkontaktbringens liegt bevorzugt zwischen 0,5 s und 180 s, mehr bevorzugt zwischen 5 s und 60 s, am meisten bevorzugt zwischen 10 s und 30 s.The duration of the contacting is preferably between 0.5 s and 180 s, more preferably between 5 s and 60 s, most preferably between 10 s and 30 s.

Die Behandlungslösung kann vor Durchführung des erfindungsgemäßen Verfahrens durch Verdünnen einer entsprechend höher konzentrierten Konzentratlösung hergestellt werden.The treatment solution can be prepared prior to carrying out the method according to the invention by dilution of a correspondingly higher concentrated concentrate solution.

Die erfindungsgemäß behandelten Gegenstände werden nach dem Inkontaktbringen nicht mehr gespült, sondern getrocknet.The objects treated according to the invention are no longer rinsed after being brought into contact, but dried.

BeispieleExamples

Nachfolgend wird die Erfindung anhand von Beispielen näher erläutert.The invention will be explained in more detail by way of examples.

Beispiel 1example 1

Es wurde eine erfindungsgemäße Behandlungslösung hergestellt, die folgende Bestandteile enthielt: 7 g/l Cr3+ aus Chrom(III)-hydroxid 28 g/l PO4 3- aus ortho-Phosphorsäure 9 g/l Zn2+ aus Zinkoxid 18 g/l Zitronensäure A treatment solution according to the invention was prepared which contained the following constituents: 7 g / l Cr 3+ from chromium (III) hydroxide 28 g / l PO 4 3- from ortho-phosphoric acid 9 g / l Zn 2+ from zinc oxide 18 g / l citric acid

Der pH-Wert der Lösung wurde mit 20 %iger Natronlauge auf pH 3,9 eingestellt.The pH of the solution was adjusted to pH 3.9 with 20% sodium hydroxide solution.

Insgesamt zwölf Probeteile aus Stahl wurden in einem schwach sauren Verfahren (Protolux 3000™ von Atotech Deutschland GmbH) mit einer 8 - 10 µm dicken Zink-Auflage beschichtet und mit demineralisiertem Wasser gespült.A total of twelve test parts made of steel were coated in a weakly acidic process (Protolux 3000 ™ from Atotech Deutschland GmbH) with an 8-10 μm thick zinc coating and rinsed with demineralized water.

Drei der Probeteile (Gruppe A; zum Vergleich) wurden nur bei 70 °C für 20 min im Umluftofen getrocknet.Three of the sample parts (group A, for comparison) were dried only at 70 ° C for 20 min in a convection oven.

Drei weitere Probeteile (Gruppe B; zum Vergleich) wurden ohne weitere Behandlung für 20 s in die erfindungsgemäße, auf 60 °C aufgeheizte Behandlungslösung getaucht. Die Teile wurden dann ohne sie zu spülen bei 70 °C für 20 min im Umluftofen getrocknet.Three further sample parts (group B, for comparison) were immersed without further treatment for 20 s in the inventive treatment solution heated to 60 ° C. The parts were then dried without rinsing at 70 ° C for 20 min in a convection oven.

Drei weitere Probeteile (Gruppe C; zum Vergleich) wurden mit einer dreiwertige Chromionen enthaltenden Lösung zur Blaupassivierung (Corrotriblue™ von Atotech Deutschland GmbH) behandelt, um eine chromhaltige Konversionsschicht auf der Oberfläche zu erzeugen, mit demineralisiertem Wasser gespült und bei 70 °C für 20 min im Umluftofen getrocknet.Three further sample parts (Group C, for comparison) were treated with a trivalent chromium ion-containing solution (Corrotriblue ™ from Atotech Deutschland GmbH) to produce a chromium-containing conversion layer on the surface, rinsed with demineralized water and quenched at 70 ° C for 20 min min dried in a convection oven.

Drei weitere Probeteile (Gruppe D; erfindungsgemäß) wurden mit einer dreiwertige Chromionen enthaltenden Lösung zur Blaupassivierung (Corrotriblue™ von Atotech Deutschland GmbH) behandelt, um eine chromhaltige Konversionsschicht auf der Oberfläche zu erzeugen, mit demineralisiertem Wasser gespült und für 20 s in die erfindungsgemäße, auf 60 °C aufgeheizte Behandlungslösung getaucht. Die Teile wurden dann ohne sie zu spülen bei 70 °C für 20 min im Umluftofen getrocknet.Three further sample parts (group D, according to the invention) were treated with a trivalent chromium ion-containing solution (Corrotriblue ™ from Atotech Deutschland GmbH) to produce a chromium-containing conversion layer on the surface, rinsed with demineralized water and placed in the 20 sec immersed according to the invention, heated to 60 ° C treatment solution. The parts were then dried without rinsing at 70 ° C for 20 min in a convection oven.

Die Probenteile der Gruppen A bis D (jeweils drei Teile) wurden anschließend im neutralen Salzsprühnebeltest nach DIN 50021 SS auf ihre Korrosionseigenschaften untersucht. Die Zeiten bis zum Auftreten einer Zinkkorrosion betrugen: Gruppe A: 3 h Gruppe B: 3 h Gruppe C: 24 h Gruppe D: 72 h The sample parts of groups A to D (in each case three parts) were then examined for their corrosion properties in the neutral salt spray test according to DIN 50021 SS. The times until the occurrence of zinc corrosion were: Group A: 3 h Group B: 3 h Group C: 24 hours Group D: 72 h

Beispiel 2Example 2

Es wurde eine erfindungsgemäße Behandlungslösung mit der gleichen Zusammensetzung wie in Beispiel 1 hergestellt; der pH-Wert der Lösung wurde mit 20 %iger Natronlauge auf pH 3,9 eingestellt.A treatment solution according to the invention having the same composition as in Example 1 was prepared; the pH of the solution was adjusted to pH 3.9 with 20% sodium hydroxide solution.

Als Probeteil wurde ein verzinktes Stahlteil eingesetzt, das durch Behandeln mit einer Lösung zur Schwarzpassivierung, die im wesentlichen Cr3+, NO3 -, F-, und Fe2+ enthält (Tridur Zn H1™ von Atotech Deutschland GmbH), mit einer schwarzen Konversionsschicht versehen wurde. Das so behandelte Probeteil wurde nach dem Schwarzpassivieren gespült und ohne zwischengeschalteten Trocknungsschritt für 20 s in die erfindungsgemäße, auf 60 °C aufgeheizte Behandlungslösung getaucht. Das Teil wurde dann ohne es zu spülen bei 60 - 80 °C für 5 min im Umluftofen getrocknet.The test part used was a galvanized steel part, which was treated with a black passivation solution containing essentially Cr 3+ , NO 3 - , F - , and Fe 2+ (Tridur Zn H1 ™ from Atotech Deutschland GmbH) with a black Conversion layer has been provided. The sample part thus treated was rinsed after the black passivation and immersed without intermediate drying step for 20 s in the inventive, heated to 60 ° C treatment solution. The part was then dried without rinsing at 60-80 ° C for 5 minutes in a convection oven.

Das so behandelte Teil wies eine schwarze, leicht irisierende Oberfläche auf. Es waren deutlich Ablaufspuren erkennbar. Im neutralen Salzsprühnebeltest nach DIN 50021 SS zeigte sich bis zu 48 h keine Weißkorrosion.The part thus treated had a black, slightly iridescent surface. There were clearly visible trace traces. The neutral salt spray test according to DIN 50021 SS showed no white corrosion for up to 48 h.

Beispiele 3 bis 6Examples 3 to 6

Die Beispiele 3 bis 6 wurden wie Beispiel 2 durchgeführt, wobei jedoch die Zusammensetzung der Behandlungslösung wie in Tabelle 1 angegeben variiert wurde. (Außerdem betrug die Trocknungszeit bei den Beispielen 4 bis 6 jeweils 15 min.) Das Aussehen der Oberfläche der erhaltenen Probenteile und die Korrosionseigenschaften sind (zusammen mit den Daten zu Beispiel 2) ebenfalls in Tabelle 1 angegeben. Tabelle 1. Zusammensetzung der Behandlungslösung und Eigenschaften der erhaltenen Probenteile in den Beispielen 2 bis 6 Bsp.2 Bsp.3 Bsp.4 Bsp.5 Bsp.6 Cr3+ (g/l) 7 7 7 7 7 PO3 4- (g/l) 28 28 28 28 23 Zn2+ (g/l) 9 9 9 9 9 Zitronensäure (g/l) 18 18 18 18 18 Polyvinylpyrrolidon [1] (g/l) 1 ionisches Tensid [2] (ml/l) 1 Polyvinylalkohol [3] (g/l) 1 1 1 Fluorotensid [4] (g/l) 1 1 Isopropylphosphat [5] (g/l) 8,5 Aussehen schwarz, leicht irisierend, deutliche Ablaufspuren homogen schwarz, nicht irisierend homogen schwarz, nicht irisierend homogen, glänzend schwarz, nicht irisierend homogen, glänzend schwarz, nicht irisierend Korrosion 48 h 72 h 120 h 168 h 120 h [1] Als Polyvinylpyrrolidon wurde eingesetzt: Sokalan HP 59™ von BASF
[2] Als ionisches Tensid wurde eingesetzt: Lutensit TC-APS 35™ von BTC
[3] Als Polyvinylalkohol wurde eingesetzt: Mowiol 5-88™ von Kuraray Specialties Europe GmbH
[4] Als Fluorotensid wurde eingesetzt: Fluorad FC-4432™ von 3M
[5] Als Isopropylphosphat wurde eingesetzt: ein Gemisch der Mono- und Diester von Merck Examples 3 to 6 were carried out as Example 2 except that the composition of the treatment solution was varied as shown in Table 1. (In addition, the drying time in Examples 4 to 6 was 15 minutes each.) The appearance of the surface of the obtained sample parts and the corrosion properties are also shown in Table 1 (together with the data of Example 2). <b> Table 1. </ b> Composition of the treatment solution and properties of the obtained sample parts in Examples 2 to 6 Ex.2 EX3 EX4 Bsp.5 Bsp.6 Cr 3+ (g / l) 7 7 7 7 7 PO 3 4- (g / l) 28 28 28 28 23 Zn 2+ (g / l) 9 9 9 9 9 Citric acid (g / l) 18 18 18 18 18 Polyvinylpyrrolidone [1] (g / l) 1 ionic surfactant [2] (ml / l) 1 Polyvinyl alcohol [3] (g / l) 1 1 1 Fluoro-surfactant [4] (g / l) 1 1 Isopropyl phosphate [5] (g / l) 8.5 Appearance black, slightly iridescent, noticeable traces of wear homogeneous black, not iridescent homogeneous black, not iridescent homogeneous, shiny black, not iridescent homogeneous, shiny black, not iridescent corrosion 48 h 72 h 120 h 168 h 120 h [1] Polyvinylpyrrolidone used was: Sokalan HP 59 ™ from BASF
As ionic surfactant was used: Lutensit TC-APS 35 ™ from BTC
[3] The polyvinyl alcohol used was: Mowiol 5-88 ™ from Kuraray Specialties Europe GmbH
[4] Fluorotenside used was: Fluorad FC-4432 ™ from 3M
[5] The isopropyl phosphate used was: a mixture of the mono- and diesters from Merck

Unter "Aussehen" ist das Aussehen der Oberfläche des Probenteils nach der Behandlung mit der erfindungsgemäßen Behandlungslösung und dem Trocknen abgegeben.Under "Appearance", the appearance of the surface of the sample part after the treatment with the treatment solution of the invention and drying is given.

Unter "Korrosion" ist die Zeitdauer angegeben, bis zu der im neutralen Salzsprühnebeltest nach DIN 50021 SS keine Weißkorrosion (< 1 %) beobachtet wurde.The term "corrosion" indicates the time until which no white corrosion (<1%) was observed in the neutral salt spray test according to DIN 50021 SS.

Claims (20)

Verfahren zur Erzeugung einer korrosionsschützenden Überzugsschicht, wobei eine zu behandelnde Oberfläche mit einer wässrigen Behandlungslösung in Kontakt gebracht wird, die Chrom(III)-lonen und mindestens eine Phosphatverbindung enthält, wobei das Verhältnis der Stoffmengenkonzentration von Chrom(III)-lonen zur Stoffmengenkonzentration der mindestens einen Phosphatverbindung (bezogen auf Orthophosphat berechnet) zwischen 1 : 1,5 und 1 : 3 liegt.A method for producing a corrosion-protective coating layer, wherein a surface to be treated is contacted with an aqueous treatment solution containing chromium (III) ions and at least one phosphate compound, wherein the ratio of the molar concentration of chromium (III) ions to the molar concentration of at least a phosphate compound (calculated on the basis of orthophosphate) is between 1: 1.5 and 1: 3. Verfahren nach Anspruch 1, wobei die mindestens eine Phosphatverbindung ausgewählt ist aus der Gruppe bestehend aus ortho-Phosphorsäure, Polyphosphorsäuren, meta-Phosphorsäure, den Salzen dieser Säuren, den Estern dieser Säuren mit organischen Resten mit bis zu 12 Kohlenstoffatomen sowie Gemischen dieser Verbindungen.The method of claim 1, wherein the at least one phosphate compound is selected from the group consisting of ortho-phosphoric acid, polyphosphoric acids, meta-phosphoric acid, the salts of these acids, the esters of these acids having organic radicals having up to 12 carbon atoms and mixtures of these compounds. Verfahren nach Anspruch 1 oder 2, wobei die Konzentration der Chrom(III)-lonen im Bereich zwischen 0,2 g/l und 20 g/l liegt.The method of claim 1 or 2, wherein the concentration of the chromium (III) ions is in the range between 0.2 g / l and 20 g / l. Verfahren nach einem der Ansprüche 1 bis 3, wobei die Behandlungslösung zusätzlich ein oder mehrere in Wasser lösliche oder in Wasser dispergierbare Polymere enthält, ausgewählt aus der Gruppe bestehend aus Polyethylenglykolen, Polyvinylpyrrolidonen, Polyvinylalkoholen, Polyitaconsäuren, Polyacrylaten und Copolymeren der jeweils zugrunde liegenden Monomere.Method according to one of claims 1 to 3, wherein the treatment solution additionally contains one or more water-soluble or water-dispersible polymers selected from the group consisting of polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, polyitaconic acids, polyacrylates and copolymers of the respective underlying monomers. Verfahren nach einem der Ansprüche 1 bis 4, wobei die Behandlungslösung zusätzlich einen oder mehrere Komplexbildner enthält, ausgewählt aus der Gruppe bestehend aus Polycarbonsäuren, Hydroxycarbonsäuren, Hydroxypolycarbonsäuren, Aminocarbonsäuren oder Hydroxyphosphonsäuren und Aminophosphonsäuren.A process according to any one of claims 1 to 4, wherein the treating solution additionally contains one or more complexing agents selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids and aminophosphonic acids. Verfahren nach Anspruch 5, wobei der Komplexbildner ausgewählt ist aus der Gruppe bestehend aus Citronensäure, Weinsäure, Äpfelsäure, Milchsäure, Gluconsäure, Glucuronsäure, Ascorbinsäure, Isozitronensäure, Gallussäure, Glycolsäure, 3-Hydroxypropionsäure, 4-Hydroxybuttersäure, Salicylsäure, Nicotinsäure, Alanin, Glycin, Asparagin, Asparaginsäure, Cystein, Glutaminsäure, Glutamin und Lysin.The method of claim 5, wherein the complexing agent is selected from the group consisting of citric, tartaric, malic, lactic, gluconic, glucuronic, ascorbic, isocitric, gallic, glycolic, 3-hydroxypropionic, 4-hydroxybutyric, salicylic, nicotinic, alanine, glycine , Asparagine, aspartic acid, cysteine, glutamic acid, glutamine and lysine. Verfahren nach einem der Ansprüche 1 bis 6, wobei die Behandlungslösung zusätzlich ein oder mehrere Metalle oder Metalloide enthält.Method according to one of claims 1 to 6, wherein the treatment solution additionally contains one or more metals or metalloids. Verfahren nach Anspruch 7, wobei das Metall oder Metalloid ausgewählt ist aus der Gruppe bestehend aus Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, AI, Si und P.The method of claim 7, wherein the metal or metalloid is selected from the group consisting of Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si and P. Verfahren nach Anspruch 7, wobei das Metall Zink ist und die Konzentration des Zinks im Bereich zwischen 0,5 g/l und 25 g/l liegt.The method of claim 7, wherein the metal is zinc and the concentration of the zinc is in the range between 0.5 g / l and 25 g / l. Verfahren nach einem der Ansprüche 7 bis 9, wobei das Metall oder Metalloid in Form eines seiner Salze oder in Form eines komplexen Anions oder der entsprechenden Säuren dieser Anionen wie Hexafluoroborsäure, Hexafluorokieselsäure, Hexafluorotitansäure oder Hexafluorozirkonsäure, Tetrafluoroborsäure oder Hexafluorophosphorsäure oder deren Salzen zu der Behandlungslösung zugegeben worden ist.Method according to one of claims 7 to 9, wherein the metal or metalloid in the form of one of its salts or in the form of a complex anion or the corresponding acids of these anions such as hexafluoroboric acid, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid or salts thereof are added to the treatment solution has been. Verfahren nach einem der Ansprüche 1 bis 10, wobei der pH-Wert der Behandlungslösung zwischen pH 2,5 und pH 7 liegt.Method according to one of claims 1 to 10, wherein the pH of the treatment solution is between pH 2.5 and pH 7. Verfahren nach einem der Ansprüche 1 bis 10, wobei der pH-Wert der Behandlungslösung zwischen pH 3,5 und pH 5 liegt.Method according to one of claims 1 to 10, wherein the pH of the treatment solution is between pH 3.5 and pH 5. Verfahren nach einem der Ansprüche 1 bis 10, wobei der pH-Wert der Behandlungslösung zwischen pH 3,8 und pH 4,5 liegt.A method according to any one of claims 1 to 10, wherein the pH of the treatment solution is between pH 3.8 and pH 4.5. Verfahren nach einem der Ansprüche 1 bis 13, wobei die Temperatur der Behandlungslösung zwischen 10 °C und 90 °C liegt.Method according to one of claims 1 to 13, wherein the temperature of the treatment solution is between 10 ° C and 90 ° C. Verfahren nach einem der Ansprüche 1 bis 13, wobei die Temperatur der Behandlungslösung zwischen 20 °C und 80 °C liegt.A method according to any one of claims 1 to 13, wherein the temperature of the treating solution is between 20 ° C and 80 ° C. Verfahren nach einem der Ansprüche 1 bis 13, wobei die Temperatur der Behandlungslösung zwischen 40 °C und 60 °C liegt.A method according to any one of claims 1 to 13, wherein the temperature of the treating solution is between 40 ° C and 60 ° C. Verfahren nach den Ansprüchen 1 bis 16, wobei die Behandlungslösung durch Verdünnen einer entsprechend höher konzentrierten Konzentratlösung hergestellt worden ist.Process according to claims 1 to 16, wherein the treatment solution has been prepared by dilution of a correspondingly higher concentrated concentrate solution. Verfahren nach einem der Ansprüche 1 bis 17, wobei die Dauer des Inkontaktbringens zwischen 0,5 s und 180 s liegt.A method according to any one of claims 1 to 17, wherein the duration of the contacting is between 0.5 s and 180 s. Verfahren nach einem der Ansprüche 1 bis 17, wobei die Dauer des Inkontaktbringens zwischen 5 s und 60 s liegt.Method according to one of claims 1 to 17, wherein the duration of the contacting is between 5 s and 60 s. Verfahren nach einem der Ansprüche 1 bis 17, wobei die Dauer des Inkontaktbringens zwischen 10 s und 30 s liegt.The method of any one of claims 1 to 17, wherein the duration of the contacting is between 10 seconds and 30 seconds.
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CN200880017265A CN101720364A (en) 2007-06-14 2008-06-13 Anticorrosive treatment for conversion layers
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US8435360B2 (en) 2013-05-07
CN101720364A (en) 2010-06-02
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