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EP1402083B1 - Corrosion protection method for metal surfaces - Google Patents

Corrosion protection method for metal surfaces Download PDF

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Publication number
EP1402083B1
EP1402083B1 EP02780906A EP02780906A EP1402083B1 EP 1402083 B1 EP1402083 B1 EP 1402083B1 EP 02780906 A EP02780906 A EP 02780906A EP 02780906 A EP02780906 A EP 02780906A EP 1402083 B1 EP1402083 B1 EP 1402083B1
Authority
EP
European Patent Office
Prior art keywords
treatment
acid
vinylpyrrolidone
homo
copolymer
Prior art date
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.)
Expired - Lifetime
Application number
EP02780906A
Other languages
German (de)
French (fr)
Other versions
EP1402083A1 (en
Inventor
Heike Quellhorst
Alina Monica Koch
Patrick Droniou
Marian Pawlik
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Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication of EP1402083A1 publication Critical patent/EP1402083A1/en
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 fluorides or complex fluorides
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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 is in the field of corrosion protection treatment of Metal surfaces.
  • the aim of the invention is to be on the bare Metal surface to deposit a corrosion-protective layer. It is a special feature of the invention is that no toxic heavy metals such as chromium or nickel have to.
  • DE-C-19 33 013 discloses treatment baths having a pH above 3.5, in addition to complex fluorides of boron, titanium or zirconium in amounts of 0.1 to 15 g / l, based on the metals, in addition 0.5 to 30 g / l of oxidizing agent, in particular Natriummetanitrobenzolsulfonat included.
  • DE-C-24 33 704 describes treatment baths for increasing the paint adhesion and the permanent corrosion protection on, inter alia, aluminum which calculates 0.1 to 5 g / l of polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l of ammonium fluorozirconate as ZrO 2 , may contain.
  • the pH values of these baths can vary over a wide range. The best results are generally obtained when the pH is 6-8.
  • a molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10.
  • DE-A-27 15 292 discloses treatment baths for chromium-free pretreatment of aluminum cans comprising at least 10 ppm of titanium and / or zirconium, between 10 and 1000 ppm of phosphate and a sufficient amount of fluoride to form complex fluorides of the existing titanium and / or zirconium, at least however, contain 13 ppm, and have pHs between 1.5 and 4.
  • WO 92/07973 teaches a chromium- free treatment process for aluminum containing, as essential components in acidic aqueous solution, from 0.01 to about 18% by weight of H 2 ZrF 6 and from 0.01 to about 10% by weight of a 3- (NC 1 4- alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer.
  • Optional components are 0.05 to 10% by weight of dispersed SiO 2 , 0.06 to 0.6% by weight of a solubilizer for the polymer and surfactant.
  • the non-prepublished German patent application DE 100 05 113 is based on recognizing that homo- or copolymers of vinylpyrrolidone a have excellent corrosion protection.
  • This invention provides a method of anticorrosive treatment of a Metal surface, characterized in that the metal surface with a homo- or copolymer of vinylpyrrolidone is brought into contact.
  • the metal surface may be first be subjected to a conversion treatment according to the prior art, for example, a zinc or iron phosphating, a Conversion treatment with fluoric acids of metals, for example of titanium, Zirconium or hafnium or even boron or silicon, or a treatment with a solution or suspension of an organic polymer containing no Contains vinylpyrrolidone units. Examples of such polymers are given in the introductory part cited literature mentioned.
  • An alternative embodiment of the cited invention is that the Metal surface with a homo- or copolymer of vinyl pyrrolidone in contact while undergoing a conversion treatment.
  • a homo- or copolymer in the treatment solution present with the on the metal surface a conversion layer is generated.
  • the processing solution for producing the conversion layer may For example, phosphoric acid or their anions.
  • divalent cations such as zinc and / or Manganese may be present.
  • a particular example of such a treatment solution for producing a conversion layer is a zinc phosphating solution, on the metal surface a crystalline layer of zinc-containing Metal phosphates produced.
  • the treatment solution can also Phosphoric acid and / or their anions, but not divalent metals contain.
  • An example of this is a Eisenphosphatierates on a Metal surface, in particular a ferrous surface, an im essential non-crystalline layer of metal phosphates and / or metal oxides generated.
  • the presence of homopolymers or copolymers of vinylpyrrolidone in Such a treatment solution improves the corrosion protection by the conversion layer is achieved. This also applies if the treatment solution except homopolymers or copolymers of vinylpyrrolidone as the conversion layer forming agent Component fluoro acids and / or complex fluorides of metals and Semi-metals such as boron, silicon, titanium, zirconium and / or hafnium contains.
  • the ready-to-use contains Solution for the treatment of metal surfaces preferably between 0.05 and 200 g / l of a homo- or copolymer of vinylpyrrolidone.
  • the present Invention has set itself the task of the subject of DE 100 05 113 terms Improve the efficiency of chemical use.
  • WO-A-97/45568 relates to a process for phosphating metal surfaces Steel, galvanized or alloy galvanized steel, aluminum and / or aluminum-magnesium alloys.
  • the phosphating solutions used in this case contain in addition Zinc ions, phosphate ions, manganese ions and one or more accelerators further from 0.001 to 0.5 g / l of one or more polymers selected from polyethers, polycarboxylates, polymeric phosphonic acids, polymeric phosphinocarboxylic acids and nitrogen-containing organic polymers.
  • Preferred polymers are amino group-containing Poly (vinylphenol) derivatives and homo or copolymer compounds of vinylpyrrolidone.
  • DE-A-36 27 249 discloses a method for producing conversion layers Surfaces of titanium or titanium alloys described.
  • watery Used solutions containing fluoride ions e.g. introduced as silicofluoric acid, one or more metal ions from the group Mg, Ca, Mn, Fe, Co, Ni, Zn or Mo and chelating agents, water-soluble high molecular weight Containing organic compounds and surfactant, wherein the pH in the range of 1.5 to 4.5.
  • the high molecular weight organic compound is in particular polyvinyl alcohol, Gelatin and / or polyvinylpyrrolidone in question.
  • the method is particular suitable for the preparation of titanium workpieces for cold forming.
  • agents according to the invention contain copolymers of vinylpyrrolidone,
  • terpolymers mixtures of homo- and two-component Copolymers, homopolymers and terpolymers or two-component copolymers and terpolymers are used.
  • the ready-to-use agent can be prepared by diluting a concentrate be received, the subject of the unpublished German Patent Application DE 100 05 113 is.
  • the concentrates in split at least two components, each containing selected components of the ready-to-use corrosion inhibitor.
  • a component of the concentrate at least predominantly contains the inorganic constituents of the agent, while at least one other component of the concentrate, the organic polymers contains.
  • the two components of the concentrate can then be different Have pH values, whereby the storage stability of the concentrate components can be increased.
  • the individual components of the concentrate with Water diluted so far that the active ingredients in the desired Concentration range available. It may be necessary to adjust the pH by adding an acid or an alkali to the desired range adjust.
  • Preferred concentration ranges for the active ingredients a) and b) in the Application solution are: In case of the fluoro acids one such amount that Zr, Ti, Hf and / or Si based on these elements in a Concentration in the range between 20 and 1000 mg / l, in particular 50 to 400 mg / l are present.
  • the concentration of polymers or copolymers of Vinyl pyrrolidone in the use solution is preferably in the range of 20 to 45 mg / l.
  • Suitable homopolymers or copolymers of vinylpyrrolidone are, for example, the polymers or polymers listed in Table 1 of the monomers mentioned there.
  • the agent is free from Nickel and chrome. This means that these metals or their compounds the Means should not be added intentionally. However, it can not be ruled out that from the container material or from the surfaces to be treated such as For example, steel alloys ions of nickel and / or chromium in less Concentration in the agent (the treatment solution) get. However, in the Practice expects that the concentrations of nickel and / or chromium in the ready-to-use treatment solution not higher than about 10 ppm.
  • the ready-to-use agent preferably has a pH in the range of 1 to 6 and especially in the range of 2 to 5.5.
  • Farther can acid-soluble compounds of Zr, Ti, Hf or Si and hydrofluoric acid or soluble fluorides are added separately, as this results in the fluoroanions form the said elements.
  • the metal surfaces are selected from surfaces of steel, galvanized steel (electrolytic or hot-dip galvanized), alloy-galvanized steel, aluminum or magnesium.
  • the metals aluminum and magnesium are generally not pure Shape, but as alloys with other elements such as Lithium, zinc, copper, silicon, magnesium (in the case of aluminum alloys) or aluminum (in the case of magnesium alloys).
  • that is Process for the treatment of surfaces of such metals designed in the Vehicle construction, in the household appliance industry, in architecture or Furnishing area can be used.
  • Treatment process then becomes a corrosion-protective coating generated at the same time the liability of a possibly later to be applied improved organic coating such as a varnish.
  • the metal surfaces for example, by spraying or immersing with the treatment solution in Be brought in contact.
  • the Treatment solution after a period of exposure, for example, in the field between 30 seconds and 5 minutes, is rinsed with water.
  • the treatment solution with the metal surface in the so-called No-rinse procedure can be brought into contact.
  • the Treatment solution either sprayed on the metal surface or by Transfer application rollers to the surface. After that takes place after a Duration of exposure, for example in the range of 2 to 20 seconds can, without further intermediate rinsing a drying of the treatment solution. This can be done for example in a heated oven.
  • the treatment solution preferably a pH in the range of 1 to 6, depending on the substrate and type of application and duration of action tighter pH ranges may be preferred can.
  • the pH is blanked for treatment
  • Metal surfaces preferably in the range of 2 to 6, in the treatment of Aluminum surfaces in particular in the range of 2 to 4; at treatment of steel, zinc or galvanized steel in particular in the range of 3 to 5 one.
  • the temperature of the Treatment solution in the execution of the method according to the invention can generally between the freezing point and the boiling point of the Treatment solution lie, for practical reasons, temperatures in the Range of room temperature or above are preferred.
  • the treatment solution has a temperature in the range of 15 to 60 ° C and in particular from 20 to 45 ° C.
  • the treatment method according to the invention represents a partial step in one otherwise usual sequence of procedural steps in the area concerned
  • the metal surfaces to be treated become common before the treatment according to the invention with a customary cleaning solution cleaned.
  • the cleaning step can be omitted if the treatment to be treated Metal surfaces immediately before the treatment according to the invention coated, for example galvanized were.
  • the metal surfaces usually with an organic coating, such as a paint Mistake.
  • a particularly preferred when using the method according to the invention consists in that the metal surface with an aqueous Solution of an acid before it is used to create a conversion layer, so during a conversion treatment, with the above contact means described.
  • the upstream process step, the Metal surface before the conversion treatment with an aqueous solution of a Acid treatment is also referred to in the art as "acid stain" or "Passivation”.
  • Process sequence for this acids can be used, which are commonly used for acid pickling or Beizpassivitation be used. An example of this is Phosphoric acid.
  • HDG hot dip galvanized steel
  • EC electrolytically galvanized steel
  • AC120 aluminum
  • CRS cold rolled steel
  • Example 2 Process sequence as above but without steps 3 and 4.
  • Galvanized substrates Lacquer adhesion to salt water storage aluminum Copper-accelerated salt spray test CASS DIN 50021, 10 days stolen Salt spray test SS DIN 50021, 21 days
  • Example 3 Conversion method with subsequent powder coating (galvanized steels) with copolymer mixtures

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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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

An agent and process for the corrosion protection treatment of a metal surface are provided. The metal surface is contacted with a homo- or copolymer of vinylpyrrolidone, the application solution containing a) 0.02 to 20 g/l phosphoric acid and/or at least one fluoric acid of one or more elements selected from Zr, Ti, Hf and Si or anions thereof, as well as b) 10 to 49.9 g/l of a homo- or copolymer of vinylpyrrolidone.

Description

Die Erfindung liegt auf dem Gebiet der Korrosionsschutzbehandlung von Metalloberflächen. Das Ziel der Erfindung besteht darin, auf der blanken Metalloberfläche eine korrosionsschützende Schicht abzuscheiden. Dabei liegt ein besonderes Merkmal der Erfindung darin, daß keine toxischen Schwermetalle wie beispielsweise Chrom oder Nickel verwendet werden müssen.The invention is in the field of corrosion protection treatment of Metal surfaces. The aim of the invention is to be on the bare Metal surface to deposit a corrosion-protective layer. It is a special feature of the invention is that no toxic heavy metals such as chromium or nickel have to.

Für die Abscheidung korrosionsschützender Schichten auf blanken Metalloberflächen bzw. die Nachspülung bereits beschichteter Metalloberflächen zur Erhöhung des Korrosionsschutzes besteht ein umfangreicher Stand der Technik. Im folgenden sind einige Beispiele für Dokumente aufgeführt, die insbesondere die chromfreie Behandlung von Aluminiumoberflächen zum Gegenstand haben. Der hierbei gebrauchte Begriff "Konversionsbehandlung" sagt aus, daß Komponenten der Behandlungslösung mit der Metalloberfläche chemisch reagieren, wodurch eine Korrosionsschutzschicht entsteht, in die sowohl Komponenten der Behandlungslösung als auch Metallatome aus der Metalloberfläche eingebaut sind.For the deposition of anticorrosion coatings on bare surfaces Metal surfaces or the rinsing of already coated metal surfaces To increase the corrosion protection is an extensive state of Technology. The following are some examples of documents listed in particular the chromium-free treatment of aluminum surfaces for Have the subject. The term used here "conversion treatment" says from that components of the treatment solution with the metal surface react chemically, creating a corrosion protection layer in both Components of the treatment solution as well as metal atoms from the Metal surface are installed.

Die chromfreie Konversionsbehandlung von Aluminiumoberflächen mit Fluoriden von Bor, Silicium, Titan oder Zirkonium allein oder in Verbindung mit organischen Polymeren ist zur Erzielung eines permanenten Korrosionsschutzes und zur Erzeugung einer Grundlage für eine anschließende Lackierung prinzipiell bekannt:The chrome-free conversion treatment of aluminum surfaces with fluorides of boron, silicon, titanium or zirconium alone or in combination with organic Polymer is to achieve a permanent corrosion protection and to Generating a basis for a subsequent painting known in principle:

Die US-A-5 129 967 offenbart Behandlungsbäder für eine No-Rinse-Behandlung (dort als "dried in place conversion coating" bezeichnet) von Aluminium, enthaltend

  • a) 10 bis 16 g/l Polyacrylsäure oder deren Homopolymere,
  • b) 12 bis 19 g/l Hexafluorozirkonsäure,
  • c) 0,17 bis 0,3 g/l Fluorwasserstoffsäure und
  • d) bis zu 0,6 g/l Hexafluorotitansäure.
    • US-A-5 129 967 discloses treatment baths for no-rinse treatment (referred to therein as "dried in place conversion coating") of aluminum containing
  • a) 10 to 16 g / l of polyacrylic acid or its homopolymers,
  • b) 12 to 19 g / l hexafluorozirconic acid,
  • c) 0.17 to 0.3 g / l hydrofluoric acid and
  • d) up to 0.6 g / l hexafluorotitanic acid.

    • EP-B-8 942 offenbart Behandlungslösungen, vorzugsweise für Aluminiumdosen, enthaltend

  • a) 0,5 bis 10 g/l Polyacrylsäure oder eines Esters davon und
  • b) 0,2 bis 8 g /l an mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, wobei der pH-Wert der Lösung unterhalb von 3;5 liegt,
    • sowie ein wäßriges Konzentrat zum Wiederauffrischen der Behandlungslösung enthaltend
  • a) 25 bis 100 g/l Polyacrylsäure oder eines Esters davon,
  • b) 25 bis 100 g/l von mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, und
  • c) eine Quelle freier Fluoridionen, die 17 bis 120 g/l freies Fluorid liefert.
    •  EP-B-8 942 discloses treatment solutions preferably containing aluminum cans
  • a) 0.5 to 10 g / l of polyacrylic acid or an ester thereof and
  • b) 0.2 to 8 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , the pH of the solution being below 3; 5,
    • and an aqueous concentrate for replenishing the treatment solution
  • a) 25 to 100 g / l of polyacrylic acid or an ester thereof,
  • b) 25 to 100 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , and
  • c) a source of free fluoride ion that provides 17 to 120 g / L free fluoride.

    • DE-C-19 33 013 offenbart Behandlungsbäder mit einem pH-Wert oberhalb 3,5, die neben komplexen Fluoriden des Bors, Titans oder Zirkoniums in Mengen von 0,1 bis 15 g/l, bezogen auf die Metalle, zusätzlich 0,5 bis 30 g/l Oxidationsmittel, insbesondere Natriummetanitrobenzolsulfonat enthalten. DE-C-19 33 013 discloses treatment baths having a pH above 3.5, in addition to complex fluorides of boron, titanium or zirconium in amounts of 0.1 to 15 g / l, based on the metals, in addition 0.5 to 30 g / l of oxidizing agent, in particular Natriummetanitrobenzolsulfonat included.

    DE-C-24 33 704 beschreibt Behandlungsbäder zur Erhöhung der Lackhaftung und des permanenten Korrosionsschutzes auf u.a. Aluminium, die 0,1 bis 5 g/l Polyacrylsäure oder deren Salze oder Ester sowie 0,1 bis 3,5 g/l Ammoniumfluorozirkonat, berechnet als ZrO2, enthalten können. Die pH-Werte dieser Bäder können über einen weiten Bereich schwanken. Die besten Ergebnisse werden im allgemeinen erhalten, wenn der pH bei 6 - 8 liegt. DE-C-24 33 704 describes treatment baths for increasing the paint adhesion and the permanent corrosion protection on, inter alia, aluminum which calculates 0.1 to 5 g / l of polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l of ammonium fluorozirconate as ZrO 2 , may contain. The pH values of these baths can vary over a wide range. The best results are generally obtained when the pH is 6-8.

    US-A-4 992 116 beschreibt Behandlungsbäder für die Konversionsbehandlung von Aluminium mit pH-Werten zwischen etwa 2,5 und 5, die mindestens drei Komponenten enthalten:

  • a) Phosphationen im Konzentrationsbereich zwischen 1,1x10-5 bis 5,3x10-3 mol/l entsprechend 1 bis 500 mg/l,
  • b) 1,1x10-5 bis 1,3x10-3 mol/l einer Fluorosäure eines Elements der Gruppe Zr, Ti, Hf und Si (entsprechend je nach Element 1,6 bis 380 mg/l) und
  • c) 0,26 bis 20 g/l einer Polyphenolverbindung, erhältlich durch Umsetzung von Poly(vinylphenol) mit Aldehyden und organischen Aminen.
    • US-A-4 992 116 describes treatment baths for the conversion treatment of aluminum with pH values between about 2.5 and 5, containing at least three components:
  • a) phosphate ions in the concentration range between 1.1 × 10 -5 to 5.3 × 10 -3 mol / l corresponding to 1 to 500 mg / l,
  • b) 1.1x10 -5 to 1.3x10 -3 mol / l of a fluoro acid of an element of the group Zr, Ti, Hf and Si (corresponding to 1.6 to 380 mg / l depending on the element) and
  • c) 0.26 to 20 g / l of a polyphenol compound obtainable by reaction of poly (vinylphenol) with aldehydes and organic amines.

    • Dabei ist ein Molverhältnis zwischen der Fluorosäure und Phosphat von etwa 2,5 : 1 bis etwa 1 : 10 einzuhalten.In this case, a molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10.

    DE-A-27 15 292 offenbart Behandlungsbäder für die chromfreie Vorbehandlung von Aluminiumdosen, die mindestens 10 ppm Titan und/oder Zirkon, zwischen 10 und 1000 ppm Phosphat und eine zur Bildung komplexer Fluoride des vorhandenen Titans und/oder Zirkons ausreichenden Menge Flourid, mindestens jedoch 13 ppm, enthalten und pH-Werte zwischen 1,5 und 4 aufweisen. DE-A-27 15 292 discloses treatment baths for chromium-free pretreatment of aluminum cans comprising at least 10 ppm of titanium and / or zirconium, between 10 and 1000 ppm of phosphate and a sufficient amount of fluoride to form complex fluorides of the existing titanium and / or zirconium, at least however, contain 13 ppm, and have pHs between 1.5 and 4.

    WO 92/07973 lehrt ein chromfreies Behandlungsverfahren für Aluminium, das als wesentliche Komponenten in saurer wäßriger Lösung 0,01 bis etwa 18 Gew.-% H2ZrF6 und 0,01 bis etwa 10 Gew.-% eines 3-(N-C1-4alkyl-N-2-hydroxyethylaminomethyl)-4hydroxystyrol-Polymers verwendet. Fakultative Komponenten sind 0,05 bis 10 Gew.-% dispergiertes SiO2, 0,06 bis 0,6 Gew.-% eines Lösevermittlers für das Polymer sowie Tensid. WO 92/07973 teaches a chromium- free treatment process for aluminum containing, as essential components in acidic aqueous solution, from 0.01 to about 18% by weight of H 2 ZrF 6 and from 0.01 to about 10% by weight of a 3- (NC 1 4- alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer. Optional components are 0.05 to 10% by weight of dispersed SiO 2 , 0.06 to 0.6% by weight of a solubilizer for the polymer and surfactant.

    Trotz dieses hier nur in Auszügen wiedergegebenen umfangreichen Stands der Technik besteht immer noch ein Bedarf nach verbesserten Mitteln und Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen. Despite this only in excerpts reproduced extensive state of the There is still a need for improved technology and methods for anti-corrosion treatment of metal surfaces.

    Die nicht vorveröffentlichte deutsche Patentanmeldung DE 100 05 113 basiert auf der Erkenntnis, daß Homo- oder Copolymere von Vinylpyrrolidon eine hervorragende Korrosionsschutzwirkung aufweisen. In einem ersten Aspekt betrifft diese Erfindung ein Verfahren zur Korrosionsschutzbehandlung einer Metalloberfläche, das dadurch gekennzeichnet ist, daß die Metalloberfläche mit einem Homo- oder Copolymer von Vinylpyrrolidon in Kontakt gebracht wird. Dabei kann in einer ersten Ausführungsform der Erfindung die Metalloberfläche zunächst einer Konversionsbehandlung nach dem Stand der Technik unterzogen werden, beispielsweise einer Zink- oder Eisenphosphatierung, einer Konversionsbehandlung mit Fluorosäuren von Metallen, beispielsweise von Titan, Zirkon oder Hafnium oder auch von Bor oder Silicium, oder einer Behandlung mit einer Lösung oder Suspension eines organischen Polymers, das keine Vinylpyrrolidoneinheiten enthält. Beispiele solcher Polymere sind in der einleitend zitierten Literatur erwähnt.The non-prepublished German patent application DE 100 05 113 is based on recognizing that homo- or copolymers of vinylpyrrolidone a have excellent corrosion protection. In a first aspect concerns This invention provides a method of anticorrosive treatment of a Metal surface, characterized in that the metal surface with a homo- or copolymer of vinylpyrrolidone is brought into contact. there For example, in a first embodiment of the invention, the metal surface may be first be subjected to a conversion treatment according to the prior art, for example, a zinc or iron phosphating, a Conversion treatment with fluoric acids of metals, for example of titanium, Zirconium or hafnium or even boron or silicon, or a treatment with a solution or suspension of an organic polymer containing no Contains vinylpyrrolidone units. Examples of such polymers are given in the introductory part cited literature mentioned.

    Eine alternative Ausführungsform der zitierten Erfindung besteht darin, daß die Metalloberfläche mit einem Homo- oder Copolymer von Vinylpyrrolidon in Kontakt gebracht wird, während sie einer Konversionsbehandlung unterzogen wird. In diesem Falle ist also ein Homo- oder Copolymer in der Behandlungslösung vorhanden, mit der auf der Metalloberfläche eine Konversionsschicht erzeugt wird. Die Behandlungslösung zum Erzeugen der Konversionsschicht kann beispielsweise Phosphorsäure oder deren Anionen enthalten. Weiterhin können in der Behandlungslösung zweiwertige Kationen wie beispielsweise Zink und/oder Mangan vorhanden sein. Ein besonderes Beispiel einer derartigen Behandlungslösung zum Erzeugen einer Konversionsschicht ist eine Zinkphosphatierlösung, die auf der Metalloberfläche eine kristalline Schicht von zinkhaltigen Metallphosphaten erzeugt. Die Behandlungslösung kann jedoch auch Phosphorsäure und/oder deren Anionen, jedoch keine zweiwertigen Metalle enthalten. Ein Beispiel hierfür ist eine Eisenphosphatierlösung, die auf einer Metalloberfläche, insbesondere einer eisenhaltigen Oberfläche, eine im wesentlichen nichtkristalline Schicht von Metallphosphaten und/oder Metalloxiden erzeugt. Die Anwesenheit von Homo- oder Copolymeren von Vinylpyrrolidon in einer derartigen Behandlungslösung verbessert den Korrosionsschutz, der durch die Konversionsschicht erzielt wird. Dies gilt auch, wenn die Behandlungslösung außer Homo- oder Copolymeren von Vinylpyrrolidon als Konversionsschichtbildende Komponente Fluorosäuren und/oder komplexe Fluoride von Metallen und Halbmetallen wie Bor, Silicium, Titan, Zirkon und/oder Hafnium enthält.An alternative embodiment of the cited invention is that the Metal surface with a homo- or copolymer of vinyl pyrrolidone in contact while undergoing a conversion treatment. In In this case, therefore, a homo- or copolymer in the treatment solution present, with the on the metal surface a conversion layer is generated. The processing solution for producing the conversion layer may For example, phosphoric acid or their anions. Furthermore, in the treatment solution divalent cations such as zinc and / or Manganese may be present. A particular example of such a treatment solution for producing a conversion layer is a zinc phosphating solution, on the metal surface a crystalline layer of zinc-containing Metal phosphates produced. However, the treatment solution can also Phosphoric acid and / or their anions, but not divalent metals contain. An example of this is a Eisenphosphatierlösung on a Metal surface, in particular a ferrous surface, an im essential non-crystalline layer of metal phosphates and / or metal oxides generated. The presence of homopolymers or copolymers of vinylpyrrolidone in Such a treatment solution improves the corrosion protection by the conversion layer is achieved. This also applies if the treatment solution except homopolymers or copolymers of vinylpyrrolidone as the conversion layer forming agent Component fluoro acids and / or complex fluorides of metals and Semi-metals such as boron, silicon, titanium, zirconium and / or hafnium contains.

    Gemäß der vorstehend zitierten DE 100 05 113 enthält die anwendungsfertige Lösung zur Behandlung von Metalloberflächen vorzugsweise zwischen 0,05 und 200 g/l eines Homo- oder Copolymers von Vinylpyrrolidon. Die vorliegende Erfindung stellt sich die Aufgabe, den Gegenstand der DE 100 05 113 hinsichtlich Effizienz des Chemikalieneinsatzes zu verbessern. According to the above-cited DE 100 05 113, the ready-to-use contains Solution for the treatment of metal surfaces preferably between 0.05 and 200 g / l of a homo- or copolymer of vinylpyrrolidone. The present Invention has set itself the task of the subject of DE 100 05 113 terms Improve the efficiency of chemical use.

    Die WO-A-97/45568 betrifft ein Verfahren zum Phosphatieren von Metalloberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium und/oder aus Aluminium-Magnesium-Legierungen. Die hierbei eingesetzten Phosphatierlösungen enthalten neben Zinkionen, Phosphationen, Manganionen und einem oder mehreren Beschleunigern ferner 0,001 bis 0,5 g/l eines oder mehrere Polymere ausgewählt aus Polyethern, Polycarboxylaten, polymeren Phosphonsäuren, polymeren Phosphinocarbonsäuren und stickstoffhaltigen organischen Polymeren. Bevorzugte Polymere sind aminogruppenhaltige Poly(vinylphenol)-Derivate und Homo- oder Copolymerverbindungen des Vinylpyrrolidons.WO-A-97/45568 relates to a process for phosphating metal surfaces Steel, galvanized or alloy galvanized steel, aluminum and / or aluminum-magnesium alloys. The phosphating solutions used in this case contain in addition Zinc ions, phosphate ions, manganese ions and one or more accelerators further from 0.001 to 0.5 g / l of one or more polymers selected from polyethers, polycarboxylates, polymeric phosphonic acids, polymeric phosphinocarboxylic acids and nitrogen-containing organic polymers. Preferred polymers are amino group-containing Poly (vinylphenol) derivatives and homo or copolymer compounds of vinylpyrrolidone.

    In der DE-A-36 27 249 wird ein Verfahren zur Erzeugung von Konversionsschichten auf Oberflächen von Titan oder Titanlegierungen beschrieben. Hierbei werden wässrige Lösungen eingesetzt, die Fluoridionen, z.B. eingebracht als Silikofluorwasserstoffsäure, ein oder mehrere Metallionen aus der Gruppe Mg, Ca, Mn, Fe, Co, Ni, Zn oder Mo sowie Chelatbildner, wasserlösliche hochmolekulare organische Verbindungen und Tensid enthalten, wobei der pH-Wert im Bereich von 1,5 bis 4,5 liegt. Als hochmolekulare organische Verbindung kommt insbesondere Polyvinylalkohol, Gelatine und/oder Polyvinylpyrrolidon in Frage. Das Verfahren ist insbesondere zur Vorbereitung von Titan-Werkstücken für die Kaltumformung geeignet.DE-A-36 27 249 discloses a method for producing conversion layers Surfaces of titanium or titanium alloys described. Here are watery Used solutions containing fluoride ions, e.g. introduced as silicofluoric acid, one or more metal ions from the group Mg, Ca, Mn, Fe, Co, Ni, Zn or Mo and chelating agents, water-soluble high molecular weight Containing organic compounds and surfactant, wherein the pH in the range of 1.5 to 4.5. The high molecular weight organic compound is in particular polyvinyl alcohol, Gelatin and / or polyvinylpyrrolidone in question. The method is particular suitable for the preparation of titanium workpieces for cold forming.

    Demgegenüber betrifft die vorliegende Erfindung ein Verfahren zur Behandlung von Metalloberflächen, ausgewählt aus Oberflächen von Stahl, verzinktem Stahl, legierungsverzinktem Stahl, Aluminium oder Magnesium oder Legierungen von Aluminium oder Magnesium, dadurch gekennzeichnet, daß man die Metalloberflächen, während sie einer Konversionsbehandlung unterzogen werden, mit einem Mittel in Kontakt bringt, das mindestens eine Fluorosäure eines oder mehrerer Elemente der Gruppe Zr, Ti, Hf und Si oder jeweils deren Anionen sowie ein Homo- oder Copolymer von Vinylpyrrolidon enthält, wobei dieses Mittel als gebrauchsfertige Anwendungslösung vorliegt, die keine Phosphatierlösung darstellt und die

  • a) 0,02 bis 20 g/l mindestens einer Fluorosäure eines oder mehrerer Elemente der Gruppe Zr, Ti, Hf und Si oder jeweils deren Anionen sowie
  • b) 10 bis 49,9 mg/l eines Homo- oder Copolymers von Vinylpyrrolidon enthält.
    • Je nach eingestelltem pH-Wert der Lösung liegen die genannten Fluorosäuren teilweise in Form ein- oder mehrfach negativ geladener Anionen vor. Das Verhältnis von Säureanionen zu undissozierter Säure hängt von der Protolysekonstante der jeweiligen Säure und von dem aktuell eingestellten pH-Wert ab. Diese Erscheinung ist allgemein als Säure-Base-Gleichgewicht bekannt. Außer den genannten essentiellen Komponenten enthalten die Mittel Wasser sowie erwünschtenfalls weitere Wirkoder Hilfsstoffe zum Einstellen des pH-Werts, zur Erhöhung der Korrosionsschutzwirkung, zum Verbessern der Applizierbarkeit und möglicherweise für weitere Zwecke.In contrast, the present invention relates to a method for the treatment of metal surfaces selected from surfaces of steel, galvanized steel, alloy galvanized steel, aluminum or magnesium or alloys of aluminum or magnesium, characterized in that the metal surfaces, while undergoing a conversion treatment with a means in contact, which contains at least one fluoro acid of one or more elements of the group Zr, Ti, Hf and Si or their anions and a homo- or copolymer of vinylpyrrolidone, this agent being present as a ready-to-use application solution, which is not a phosphating solution, and the
  • a) 0.02 to 20 g / l of at least one fluoro acid of one or more elements of the group Zr, Ti, Hf and Si or their anions and also
  • b) contains 10 to 49.9 mg / l of a homo- or copolymer of vinylpyrrolidone.
    • Depending on the adjusted pH of the solution, said fluoro acids are present in the form of mono- or poly-negatively charged anions. The ratio of acid anions to undissociated acid depends on the protolysis constant of the respective acid and on the currently set pH. This phenomenon is commonly known as acid-base equilibrium. In addition to the essential components mentioned, the compositions contain water and, if desired, further active ingredients or auxiliaries for adjusting the pH, for increasing the anticorrosion effect, for improving the applicability and possibly for further purposes.

    Sofern die erfindungsgemäßeinzüsetzenden Mittel Copolymere von Vinylpyrrolidon enthalten, können diese Copolymere außer Vinylpyrrolidon eines oder mehrere andere Monomere enthalten. Sie können also beispielsweise als Copolymere aus 2 Komponenten oder als Copolymere aus 3 Komponenten (= Terpolymere) vorliegen. Weiterhin können Mischungen von Homo- und zweikomponentigen Copolymeren, Homo- und Terpolymeren oder zweikomponentigen Copolymeren und Terpolymeren eingesetzt werden.If the agents according to the invention contain copolymers of vinylpyrrolidone, For example, these copolymers other than vinylpyrrolidone may have one or more others Contain monomers. So you can, for example, as copolymers of 2 Components or as copolymers of 3 components (= terpolymers) available. Furthermore, mixtures of homo- and two-component Copolymers, homopolymers and terpolymers or two-component copolymers and terpolymers are used.

    Das anwendungsfertige Mittel kann durch das Verdünnen eines Konzentrats erhalten werden, das Gegenstand der nicht vorveröffentlichten deutschen Patentanmeldung DE 100 05 113 ist. Je nach spezieller Zusammensetzung kann es sein, daß Konzentrate, die bereits alle Wirkstoffe enthalten, nicht hinreichend lange lagerstabil sind. In diesen Fällen ist es vorzuziehen, die Konzentrate in mindestens zwei Komponenten aufzuteilen, die jeweils ausgewählte Komponenten des anwendungsfertigen Korrosionsschutzmittels enthalten. Beispielsweise kann es empfehlenswert sein, daß eine Komponente des Konzentrats zumindest überwiegend die anorganischen Bestandteile des Mittels enthält, während zumindest eine andere Komponente des Konzentrats die organischen Polymeren enthält. Die beiden Komponenten des Konzentrats können dann unterschiedliche pH-Werte aufweisen, wodurch die Lagerstabilität der Konzentratkomponenten erhöht werden kann. Zum Herstellen bzw. zum Auffrischen des Mittels in seiner Anwendungsform werden die einzelnen Komponenten des Konzentrats mit Wasser so weit verdünnt, daß die Wirkstoffe im erwünschten Konzentrationsbereich vorliegen. Dabei kann es erforderlich werden, den pH-Wert durch Zugabe einer Säure bzw. einer Lauge auf den gewünschten Bereich einzustellen.The ready-to-use agent can be prepared by diluting a concentrate be received, the subject of the unpublished German Patent Application DE 100 05 113 is. Depending on the specific composition can It may be that concentrates that already contain all active ingredients are not sufficient long shelf life. In these cases, it is preferable to use the concentrates in split at least two components, each containing selected components of the ready-to-use corrosion inhibitor. For example, can It may be advisable that a component of the concentrate at least predominantly contains the inorganic constituents of the agent, while at least one other component of the concentrate, the organic polymers contains. The two components of the concentrate can then be different Have pH values, whereby the storage stability of the concentrate components can be increased. For making or for refreshing the agent in his Application form, the individual components of the concentrate with Water diluted so far that the active ingredients in the desired Concentration range available. It may be necessary to adjust the pH by adding an acid or an alkali to the desired range adjust.

    Bevorzugte Konzentrationsbereiche für die Wirkstoffe a) und b) in der Anwendungslösung sind: Im Falle der Fluorosäuren eine derartige Menge, daß Zr, Ti, Hf und/oder Si bezogen auf diese Elemente in einer Konzentration im Bereich zwischen 20 und 1 000 mg/l, insbesondere 50 bis 400 mg/l vorliegen. Die Konzentration der Polymere oder Copolymere von Vinylpyrrolidon in der Anwendungslösung liegt vorzugsweise im Bereich von 20 bis 45 mg/l.Preferred concentration ranges for the active ingredients a) and b) in the Application solution are: In case of the fluoro acids one such amount that Zr, Ti, Hf and / or Si based on these elements in a Concentration in the range between 20 and 1000 mg / l, in particular 50 to 400 mg / l are present. The concentration of polymers or copolymers of Vinyl pyrrolidone in the use solution is preferably in the range of 20 to 45 mg / l.

    Als Homo- oder Copolymere von Vinylpyrrolidon kommen beispielsweise die in Tabelle 1 aufgelisteten Polymere bzw. Polymere der dort angeführten Monomere in Betracht. Beispiele für Homo- oder Copolymere von Vinylpyrrolidon Bezeichnung Handelsname bzw. Hersteller Vinylpyrrolidon, Homopolymer LuviskolR, BASF / ISP Vinylpyrrolidon/Vinylacetat LuviskolR, BASF / ISP VinylpyrrolidonNinylcaprolactam LuvitecR, BASF VinylpyrrolidonNinylimidazol LuvitecR, BASF Vinylpyrrolidon/Vinylimidazoliummethylsulfat Luvitec, BASF Vinylpyrrolidon/Na-methacrylat LuvitecR, BASF Vinylpyrrolidon/Olefine ISPR, Antaron Vinylpyrrolidon/Dimethylaminoethylmethacrylat ISPR Vinylpyrrolidon/Dimethylaminopropylmethacrylamid ISPR, Styleze Vinylpyrrolidon/Dimethylaminoethylmethacrylat Ammoniumsalz ISPR, Gafquat Vinylpyrrolidon/Vinylcaprolactam/Dimethylaminoethylmethacrylat ISPR Vinylpyrrolidon/Methacrylamidopropyltrimethylammoniumchlorid ISPR, Gafquat VinylpyrrolidonNinylcaprolactam/Dimethylaminoethylmethacrylat ISPR, Advantage Vinylpyrrolidon/Styrol ISPR, Antara Suitable homopolymers or copolymers of vinylpyrrolidone are, for example, the polymers or polymers listed in Table 1 of the monomers mentioned there. Examples of homopolymers or copolymers of vinylpyrrolidone description Trade name or manufacturer Vinyl pyrrolidone, homopolymer Luviskol R , BASF / ISP Vinylpyrrolidone / vinyl acetate Luviskol R , BASF / ISP VinylpyrrolidonNinylcaprolactam Luvitec R , BASF VinylpyrrolidonNinylimidazol Luvitec R , BASF Vinylpyrrolidone / vinylimidazolium Luvitec, BASF Vinylpyrrolidone / Na methacrylate Luvitec R , BASF Vinylpyrrolidone / olefins ISP R , Antaron Vinylpyrrolidone / dimethylaminoethyl ISP R Vinylpyrrolidone / dimethylaminopropylmethacrylamide ISP R , Styleze Vinyl pyrrolidone / dimethylaminoethyl methacrylate ammonium salt ISP R , Gafquat Vinylpyrrolidone / vinyl caprolactam / dimethylaminoethyl ISP R Vinylpyrrolidone / methacrylamidopropyltrimethylammonium ISP R , Gafquat VinylpyrrolidonNinylcaprolactam / dimethylaminoethyl ISP R , Advantage Vinylpyrrolidone / styrene ISP R , Antara

    Aus Gründen des Arbeits- und Umweltschutzes verzichtet man vorzugsweise auf den Zusatz von Chrom- oder Nickelionen. Demgemäß besteht eine bevorzugte Ausführungsform der Erfindung darin, daß das Mittel frei ist von Nickel und Chrom. Dies bedeutet, daß diese Metalle bzw. ihre Verbindungen dem Mittel nicht absichtlich zugesetzt werden. Es ist jedoch nicht auszuschließen, daß aus dem Behältermaterial oder aus den zu behandelnden Oberflächen wie beispielsweise Stahllegierungen Ionen von Nickel und/oder Chrom in geringer Konzentration in das Mittel (die Behandlungslösung) gelangen. Jedoch wird in der Praxis erwartet, daß die Konzentrationen von Nickel und/oder Chrom in der anwendungsfertigen Behandlungslösung nicht höher als etwa 10 ppm sind.For reasons of labor and environmental protection one renounces preferably on the addition of chromium or nickel ions. Accordingly, there is a preferred embodiment of the invention in that the agent is free from Nickel and chrome. This means that these metals or their compounds the Means should not be added intentionally. However, it can not be ruled out that from the container material or from the surfaces to be treated such as For example, steel alloys ions of nickel and / or chromium in less Concentration in the agent (the treatment solution) get. However, in the Practice expects that the concentrations of nickel and / or chromium in the ready-to-use treatment solution not higher than about 10 ppm.

    Das anwendungsfertige Mittel weist vorzugsweise einen pH-Wert im Bereich von 1 bis 6 und insbesondere im Bereich von 2 bis 5,5 auf. Dies bedeutet, daß die Fluorosäuren der Elemente Zr, Ti, Hf oder Si je nach pH-Wert und Protolysekonstanten teilweise in Form der freien Säuren, teilweise jedoch in Form ihrer Säureanionen vorliegen. Daher ist es unerheblich, ob diese Fluorosäuren als solche oder in Form ihrer Salze eingesetzt werden. Weiterhin können säurelösliche Verbindungen von Zr, Ti, Hf oder Si sowie Flußsäure oder lösliche Fluoride getrennt zugegeben werden, da sich hieraus die Fluoroanionen der genannten Elemente bilden. Je nach Einsatzart muß der pH-Wert durch Zugabe von Säure wie beispielsweise die freien Fluorosäuren der genannten Elemente, jedoch beispielsweise auch Flußsäure, Schwefelsäure, Salpetersäure oder Phosphorsäure oder durch Zugabe einer Base wie beispielsweise Alkalimetallcarbonatlösung, Alkalimetallhydroxidlösung oder Ammoniak auf den erwünschten Bereich eingestellt werden.The ready-to-use agent preferably has a pH in the range of 1 to 6 and especially in the range of 2 to 5.5. This means that the fluoro acids of the elements Zr, Ti, Hf or Si depending on the pH and protolysis constants partly in the form of the free acids, but partly in Form their acid anions present. Therefore, it does not matter if this Fluoro acids can be used as such or in the form of their salts. Farther can acid-soluble compounds of Zr, Ti, Hf or Si and hydrofluoric acid or soluble fluorides are added separately, as this results in the fluoroanions form the said elements. Depending on the application of the pH must Addition of acid such as the free fluoro acids of said Elements, but for example hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid or by adding a base such as Alkali metal carbonate solution, alkali metal hydroxide solution or ammonia on the desired range can be adjusted.

    Wegen der besonders guten Korrosionsschutzwirkung von Homo- oder Copolymeren von Vinylpyrrolidon, die Caprolactamgruppen enthalten, enthält das Mittel in einer speziellen Ausführungsform Homo- oder Copolymere von Vinylpyrrolidon, die Caprolactamgruppen enthalten.Because of the particularly good corrosion protection effect of homo- or Copolymers of vinylpyrrolidone containing caprolactam groups contain the Means in a specific embodiment homo- or Copolymers of vinylpyrrolidone containing caprolactam groups.

    Die Metalloberflächen sind ausgewählt aus Oberflächen von Stahl, verzinktem Stahl (elektrolytisch oder schmelztauchverzinkt), legierungsverzinktem Stahl, Aluminium oder Magnesium. Dabei liegen die Metalle Aluminium und Magnesium in der Regel nicht in reiner Form, sondern als Legierungen mit anderen Elementen wie beispielsweise Lithium, Zink, Kupfer, Silicium, Magnesium (im Falle von Aluminiumlegierungen) oder Aluminium (im Falle von Magnesiumlegierungen) vor. Insbesondere ist das Verfahren zur Behandlung von Oberflächen solcher Metalle konzipiert, die im Fahrzeugbau, in der Haushaltsgeräteindustrie, im Architektur- oder Einrichtungsbereich verwendet werden.The metal surfaces are selected from surfaces of steel, galvanized steel (electrolytic or hot-dip galvanized), alloy-galvanized steel, aluminum or magnesium. The metals aluminum and magnesium are generally not pure Shape, but as alloys with other elements such as Lithium, zinc, copper, silicon, magnesium (in the case of aluminum alloys) or aluminum (in the case of magnesium alloys). In particular, that is Process for the treatment of surfaces of such metals designed in the Vehicle construction, in the household appliance industry, in architecture or Furnishing area can be used.

    Dabei werden solche Metalloberflächen behandelt, die noch keine Korrosionsschutzschicht aufweisen. Durch das erfindungsgemäße Behandlungsverfahren wird dann eine korrosionsschützende Beschichtung erzeugt, die gleichzeitig die Haftung eines ggf. später aufzubringenden organischen Überzugs wie beispielsweise eines Lacks verbessert.In this case, such metal surfaces are treated, which are not yet Have corrosion protection layer. By the invention Treatment process then becomes a corrosion-protective coating generated at the same time the liability of a possibly later to be applied improved organic coating such as a varnish.

    Bei dem erfindungsgemäßen Behandlungsverfahren können die Metalloberflächen beispielsweise durch Aufspritzen oder Eintauchen mit der Behandlungslösung in Kontakt gebracht werden. In diesem Falle sieht man vorzugsweise vor, daß die Behandlungslösung nach einer Einwirkungsdauer, die beispielsweise im Bereich zwischen 30 Sekunden und 5 Minuten liegen kann, mit Wasser abgespült wird. Alternativ kann die Behandlungslösung mit der Metalloberfläche im sogenannten No-Rinse-Verfahren in Kontakt gebracht werden. Hierbei wird die Behandlungslösung entweder auf die Metalloberfläche aufgesprüht oder durch Auftragswalzen auf die Oberfläche übertragen. Danach erfolgt nach einer Einwirkungsdauer, die beispielsweise im Bereich von 2 bis 20 Sekunden liegen kann, ohne weitere Zwischenspülung ein Eintrocknen der Behandlungslösung. Dies kann beispielsweise in einem beheizten Ofen erfolgen.In the treatment method according to the invention, the metal surfaces for example, by spraying or immersing with the treatment solution in Be brought in contact. In this case, it is preferably provided that the Treatment solution after a period of exposure, for example, in the field between 30 seconds and 5 minutes, is rinsed with water. Alternatively, the treatment solution with the metal surface in the so-called No-rinse procedure can be brought into contact. Here is the Treatment solution either sprayed on the metal surface or by Transfer application rollers to the surface. After that takes place after a Duration of exposure, for example in the range of 2 to 20 seconds can, without further intermediate rinsing a drying of the treatment solution. This can be done for example in a heated oven.

    Für das erfindungsgemäße Behandlungsverfahren weist die Behandlungslösung vorzugsweise einen pH-Wert im Bereich von 1 bis 6 auf, wobei je nach Substrat und Applikationsart sowie Einwirkungsdauer engere pH-Bereiche bevorzugt sein können. Beispielsweise stellt man den pH-Wert zur Behandlung blanker Metalloberflächen vorzugsweise auf den Bereich von 2 bis 6, bei Behandlung von Aluminiumoberflächen insbesondere auf den Bereich von 2 bis 4; bei Behandlung von Stahl, Zink oder verzinktem Stahl inbsbesondere auf den Bereich von 3 bis 5 ein. Die Temperatur der Behandlungslösung bei der Ausführung des erfindungsgemäßen Verfahrens kann allgemein zwischen dem Gefrierpunkt und dem Siedepunkt der Behandlungslösung liegen, wobei aus praktischen Gründen Temperaturen im Bereich der Raumtemperatur oder darüber bevorzugt sind. Beispielsweise kann die Behandlungslösung eine Temperatur im Bereich von 15 bis 60 °C und insbesondere von 20 bis 45 °C aufweisen.For the treatment method according to the invention, the treatment solution preferably a pH in the range of 1 to 6, depending on the substrate and type of application and duration of action tighter pH ranges may be preferred can. For example, the pH is blanked for treatment Metal surfaces preferably in the range of 2 to 6, in the treatment of Aluminum surfaces in particular in the range of 2 to 4; at treatment of steel, zinc or galvanized steel in particular in the range of 3 to 5 one. The temperature of the Treatment solution in the execution of the method according to the invention can generally between the freezing point and the boiling point of the Treatment solution lie, for practical reasons, temperatures in the Range of room temperature or above are preferred. For example, can the treatment solution has a temperature in the range of 15 to 60 ° C and in particular from 20 to 45 ° C.

    Das erfindungsgemäße Behandlungsverfahren stellt einen Teilschritt in einer ansonsten auf dem betroffenen Gebiet üblichen Abfolge von Verfahrensschritten dar. Beispielsweise werden die zu behandelnden Metalloberflächen üblicherweise vor der erfindungsgemäßen Behandlung mit einer üblichen Reinigungslösung gereinigt. Der Reinigungsschritt kann jedoch entfallen, wenn die zu behandelnden Metalloberflächen unmittelbar vor der erfindungsgemäßen Behandlung beschichtet, beispielsweise verzinkt wurden. Nach der erfindungsgemäßen Behandlungsstufe werden die Metalloberflächen üblicherweise mit einem organischen Überzug, beispielsweise einem Lack versehen. Die kann beispielsweise ein Pulverlack oder ein elektrolytisch, insbesondere kathodisch, abscheidbarer Tauchlack sein.The treatment method according to the invention represents a partial step in one otherwise usual sequence of procedural steps in the area concerned For example, the metal surfaces to be treated become common before the treatment according to the invention with a customary cleaning solution cleaned. However, the cleaning step can be omitted if the treatment to be treated Metal surfaces immediately before the treatment according to the invention coated, for example galvanized were. After Treatment stage according to the invention are the metal surfaces usually with an organic coating, such as a paint Mistake. For example, a powder coating or an electrolytic, in particular cathodic, depositable dip.

    Eine bei Anwendung des erfindungsgemäßen Verfahrens besonders bevorzugte Verfahrensfolge besteht darin, daß man die Metalloberfläche mit einer wäßrigen Lösung einer Säure behandelt, bevor man sie zum Erzeugen einer Konversionsschicht, also während einer Konversionsbehandlung, mit dem vorstehend beschriebenen Mittel in Kontakt bringt. Der vorgeschaltete Verfahrensschritt, die Metalloberfläche vor der Konversionsbehandlung mit einer wäßrigen Lösung einer Säure zu behandeln, wird in der Technik auch als "saure Beize" oder "Beizpassivierung" bezeichnet. Im Rahmen der erfindungsgemäßen Verfahrensfolge können hierfür Säuren eingesetzt werden, die üblicherweise zur sauren Beize bzw. Beizpassivierung verwendet werden. Ein Beispiel hierfür ist Phosphorsäure.A particularly preferred when using the method according to the invention Process sequence consists in that the metal surface with an aqueous Solution of an acid before it is used to create a conversion layer, so during a conversion treatment, with the above contact means described. The upstream process step, the Metal surface before the conversion treatment with an aqueous solution of a Acid treatment is also referred to in the art as "acid stain" or "Passivation". In the context of the invention Process sequence for this acids can be used, which are commonly used for acid pickling or Beizpassivierung be used. An example of this is Phosphoric acid.

    Anwendungsbeispiele: Anwendung als KonversionsbehandlungApplication examples: Application as conversion treatment

    Beispiel 1: Konversionsverfahren mit vorhergehender Beizpassivierung Example 1: Conversion method with previous pickling passivation Substrate: Schmelztauchverzinkter Stahl (HDG), elektrolytisch verzinkter Stahl (EG), Aluminium (AC120), kaltgewalzter Stahl (CRS)Substrates: hot dip galvanized steel (HDG), electrolytically galvanized steel (EC), aluminum (AC120), cold rolled steel (CRS) Prozessfolge (Spritzapplikation):Process sequence (spray application):

    1.1. Reinigung:Cleaning: RidolineR 1570, 3 %; 82 Sekunden, 55 °C RidosolR 1270, 0,3 % (kommerzielle Metallreiniger der Anmelderin)Ridoline R 1570, 3%; 82 seconds, 55 ° C Ridosol R 1270, 0.3% (commercial metal cleaner of the Applicant) 2.Second Spülekitchen sink vollentsalztes Wassercompletely desalinated water 3.Third Beizpassivierung:Beizpassivierung: Phosphorsäure, 0,23 %, 82 Sekunden Phosphoric acid, 0.23%, 82 seconds 4.4th Spülekitchen sink VE WasserVE water 5.5th Konversionsbehandlung: 108 Sekunden; 30 °C, mit einer wäßrigen Lösung enthaltendConversion treatment: 108 seconds; 30 ° C, containing with an aqueous solution H2ZrF6-Säure (45 %ig; 1,38 g/l)H 2 ZrF 6 acid (45%, 1.38 g / l) Vinylpyrrolidon/ Vinylcaprolactam-Polymer (37 mg/l Feststoff)Vinyl pyrrolidone / vinyl caprolactam polymer (37 mg / L solid) 6.6th Spülekitchen sink vollentsalztes Wassercompletely desalinated water 7.7th Trocknen:Dry: Pressluftcompressed air 8.8th. Lackieren: LackdickePainting: paint thickness bleifreier kathodischer Tauchlack (BASF CG 310), 20-23 µmLead-free cathodic dip coating (BASF CG 310), 20-23 μm

    Beispiel 2: Prozessfolge wie oben jedoch ohne die Schritte 3 und 4. Example 2 : Process sequence as above but without steps 3 and 4. Korrosionstest:Corrosion test:

    Verzinkte Substrate:Galvanized substrates: Lackhaftung nach SalzwasserlagerungLacquer adhesion to salt water storage Aluminiumaluminum Kupferbeschleunigter Salzsprühtest CASS DIN 50021, 10 TageCopper-accelerated salt spray test CASS DIN 50021, 10 days Stahlstole Salzsprühtest SS DIN 50021, 21 TageSalt spray test SS DIN 50021, 21 days

    Ergebnisse: Unterwanderung am Ritz (halbe Ritzbreite): U/2 in mm; Ergebnisse des Steinschlagtests für Lackhaftung (K-Wert, K = 1: beste Lackhaftung, K = 10: schlechteste Lackhaftung)) Beispiel CRS HDG EG AC120 U/2 mm K K U/2 mm Mit Schritt 3, 4 0,7 8 9 0,8 Ohne Schritt 3, 4 1,6 10 10 0,9 Results: infiltration at the scribe (half scribe width): U / 2 in mm; Results of the stone impact test for paint adhesion (K value, K = 1: best paint adhesion, K = 10: worst paint adhesion)) example CRS HDG EC AC120 U / 2 mm K K U / 2 mm With step 3, 4 0.7 8th 9 0.8 Without step 3, 4 1.6 10 10 0.9

    Beispiel 3: Konversionsverfahren mit anschließender Pulverlackierung (verzinkte Stähle) mit Copolymer-Mischungen Example 3: Conversion method with subsequent powder coating (galvanized steels) with copolymer mixtures Substrate: CRS, EG, HDGSubstrates: CRS, EG, HDG Prozessfolge (Tauchapplikation):Process sequence (immersion application):

    1.1. Reinigung:Cleaning: RidolineR 1570, 2 %; RidosolR 1237, 0,3 %; 5 Minuten; 55°C (kommerzielle Metallreiniger der Anmelderin)Ridoline R 1570, 2%; Ridosol R 1237, 0.3%; 5 minutes; 55 ° C (commercial metal cleaner of the applicant) 2.Second Spülekitchen sink vollentsalztes Wassercompletely desalinated water 3.Third Konversionsbehandlung:Conversion treatment: 180 Sekunden; 30 °C, mit einem der folgenden Badansätze180 seconds; 30 ° C, with one of the following baths H2ZrF6-Säure (45 %ig; 1,38 g/l)H 2 ZrF 6 acid (45%, 1.38 g / l) VinylpyrrolidonNinylcaprolactam-Copolymer (=Pa)+VinylpyrrolidoneNinylcaprolactam copolymer (= P a ) + Vinylpyrrolidon/Vinylimidazol-Copolymer (=Pb)Vinylpyrrolidone / vinylimidazole copolymer (= P b ) (37 mg/l Feststoffgehalt)(37 mg / l solids content) 4.4th Spülekitchen sink vollentsalztes Wassercompletely desalinated water 5.5th Trocknen:Dry: Pressluftcompressed air 6.6th Lackieren:Paint: Polyester PES 5807/RAL 5009 GL (TIGC-frei), Firma Herberts); ca. 60-80 µmPolyester PES 5807 / RAL 5009 GL (TIGC-free), Herberts); about 60-80 μm

    Korrosionstest:Corrosion test: Neutraler Salzsprühtest DIN 50021 SS, 21 TageNeutral salt spray test DIN 50021 SS, 21 days Ergebnisse: Lackunterwanderung am Ritz, halbe Ritzbreite; Lackhaftung gemäß GitterschnitttestResults: paint undercutting at the Ritz, half scratch width; Paint adhesion according to Cross-cut test

    Beispielexample Unterwanderunginfiltration Gitterschnitt (Skala 0 bis 5)Crosshatch (scale 0 to 5) CRSCRS 1,7 mm1.7 mm 00 EGEC 2,5 mm2.5 mm 00 HDGHDG 1,8 mm1.8 mm 00

    Die Polymerverhältnisse können zum Beispiel variiert werden zwischen Homound/oder Copolymeren Pa%=100%-Pb% mit Pa>0. The polymer ratios can be varied, for example, between homo- and / or copolymers P a % = 100% -P b % with P a > 0.

    Beispiel 4: Konversionsverfahren mit Copolymer-Mischungen (Pulverlackierung) Example 4 Conversion Method with Copolymer Blends (Powder Coating) Substrat: CRSSubstrate: CRS Prozessfolge (Tauchapplikation):Process sequence (immersion application):

    1.1. Reinigung:Cleaning: Ridoline 1570, 2 %; Ridosol 1237, 0,3 %; 5 Minuten, 55 °CRidoline 1570, 2%; Ridosol 1237, 0.3%; 5 minutes, 55 ° C 2.Second Spülekitchen sink Vollentsalztes WasserCompletely desalinated water 3.Third Konversionsbehandlungconversion treatment 180 s; 30 °C mit einem der Badansätze gemäß nachstehender Tabelle180 s; 30 ° C with one of the bath approaches according to the following table H2ZrF6-Säure (45 %ig; 1,38 g/l)H 2 ZrF 6 acid (45%, 1.38 g / l) + Vinylpyrrolidon/Vinylcaprolactam-Copolymer (=Pb)++ Vinylpyrrolidone / vinylcaprolactam copolymer (= P b ) + Vinylpyrrolidon/Vinylimidazol-Copolymer (=Pa)Vinylpyrrolidone / vinylimidazole copolymer (= P a ) (22 mg/l Feststoffgehalt)(22 mg / l solids content) 4.4th Spülekitchen sink Vollentsalztes WasserCompletely desalinated water 5.5th Trocknen:Dry: Pressluftcompressed air 6.6th Lackieren:Paint: Polyester PES 5807/RAL 5009 GL (TIGC-frei), Firma Herberts; ca. 60-80 µmPolyester PES 5807 / RAL 5009 GL (TIGC-free), Herberts; about 60-80 μm

    Korrosionstest:Corrosion test: Neutraler Salzsprühtest DIN 50021 SS, 21 TageNeutral salt spray test DIN 50021 SS, 21 days

    Polymerpolymer Unterwanderunginfiltration 100 % Pa 100% P a 3,9 mm3.9 mm 70 % Pa 70% P a 2,3 mm2.3 mm

    Claims (4)

    1. A process for treating metal surfaces selected from steel, galvanized steel, alloy-galvanized steel, aluminium or magnesium or alloys of aluminium or magnesium, characterized in that the metal surfaces are contacted during a conversion treatment with a preparation containing at least one fluoro acid of one or more elements from the group consisting of Zr, Ti, Hf and Si or anions thereof and a homo- or copolymer of vinyl pyrrolidone, the preparation being present as a ready-to-use application solution which is not a phosphating solution and which contains
      a) 0.02 to 20 g/l of at least one fluoro acid of one or more elements from the group consisting of Zr, Ti, Hf and Si or anions thereof and
      b) 10 to 49.9 mg/l of a homo- or copolymer of vinyl pyrrolidone.
    2. A process as claimed in claim 1, characterized in that the preparation is free from nickel and chromium.
    3. A process as claimed in one or both of claims 1 and 2, characterized in that the homo- or copolymer of vinyl pyrrolidone contains caprolactam groups.
    4. A process as claimed in one or more of claims 1 to 3, characterized in that the metal surface is subjected to acidic pickling before being contacted with the preparation claimed in one or more of claims 1 to 3.
    EP02780906A 2001-06-30 2002-06-21 Corrosion protection method for metal surfaces Expired - Lifetime EP1402083B1 (en)

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    DE10131723A DE10131723A1 (en) 2001-06-30 2001-06-30 Corrosion protection agents and corrosion protection processes for metal surfaces
    DE10131723 2001-06-30
    PCT/EP2002/006888 WO2003002781A1 (en) 2001-06-30 2002-06-21 Corrosion protection agent and corrosion protection method for metal surfaces

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    US20040151619A1 (en) 2004-08-05
    CA2453138A1 (en) 2003-01-09
    MXPA03011369A (en) 2004-07-01
    JP2004533542A (en) 2004-11-04
    DE50202924D1 (en) 2005-06-02
    KR20040043135A (en) 2004-05-22
    BR0210725A (en) 2004-07-20
    CN1527889A (en) 2004-09-08
    CZ20033572A3 (en) 2004-11-10
    DE10131723A1 (en) 2003-01-16
    EP1402083A1 (en) 2004-03-31
    ES2240824T3 (en) 2005-10-16

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