EP2449149A1 - Anti-corrosive treatment for surfaces made of zinc and zinc alloys - Google Patents

Anti-corrosive treatment for surfaces made of zinc and zinc alloys

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Publication number
EP2449149A1
EP2449149A1 EP10728680A EP10728680A EP2449149A1 EP 2449149 A1 EP2449149 A1 EP 2449149A1 EP 10728680 A EP10728680 A EP 10728680A EP 10728680 A EP10728680 A EP 10728680A EP 2449149 A1 EP2449149 A1 EP 2449149A1
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EP
European Patent Office
Prior art keywords
acid
treatment solution
acids
chromium
group
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Application number
EP10728680A
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German (de)
French (fr)
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EP2449149B1 (en
Inventor
Udo Hofmann
Hermann Donsbach
Jörg UNGER
Volker Krenzel
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • 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 surface of zinc or zinc alloys.
  • 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.
  • 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 sparingly soluble ⁇ -oxo or ⁇ -hydroxoxide.
  • bridged chromium (III) -Konnplex is deposited.
  • sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well before the corrosion attack by electrolyte ⁇ protective 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 is the occurrence of drainage drops in the coating of workpieces made on the frame and / or the bonding of coated bulk material; In addition, problems such as dimensional accuracy of threads and the like, which are associated with the layer thickness of these seals arise.
  • Document EP 0 479 289 A1 describes a chromating process in which the substrates are immersed in a treatment solution which contains, in addition to chromium (VI) and chromium (III) ions, hydrofluoric acid and phosphoric acid, a silane coupling agent.
  • the patent EP 0 922 785 B1 describes a treatment solution and a process for the production of protective layers on metals, in which the surface to be protected with a treatment solution, the chromium (III) ions, an oxidizing agent and an oxyacid or an oxyacid salt of phosphorus or a corresponding anhydride contains.
  • This treating solution may further contain a monomeric silane coupling agent.
  • the document EP 1 051 539 B1 describes a treatment solution for increasing the corrosion protection of substrates, which in addition to chromium (VI) and chromium (III) ions also contains phosphoric acid, hydrofluoric acid, colloidal silicon dioxide and a monomeric epoxy-functionalized silane.
  • WO 2008/14166 A1 describes a treatment solution for the production of anticorrosive coatings.
  • This treatment solution contains, in addition to zinc ions, phosphoric acid or acidic phosphates, organic or inorganic anions which one of the elements boron, silicon, titanium or zirconium, trivalent chromium ions and an inorganic or organic peroxide as an oxidizing agent.
  • the document WO 97/15700 A1 describes a treatment solution for the production of corrosion protection layers.
  • the treatment solution contains hydrolyzed silanes and phosphoric acid and is free of chromium ions and chromium containing compounds.
  • the invention has for its object to provide methods for increasing the corrosion protection of metallic, especially zinc-containing and zinc-containing, provided with a conversion layer, surfaces.
  • 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 and hydrofluoric acid or post-treatments for sealing should be avoided.
  • the process usually carried out in two separate stages, is to apply a passivation step containing chromium (III) ions followed by a one-step process in which the functionality of a chromium (III) ion-containing passivation layer and a seal are combined.
  • a further aspect of the invention is that it is possible to dispense with the rinsing steps which are normally required in the two-stage processes known from the prior art between the application of the passivation containing chromium (III) ions and the sealing. This significantly reduces the amount of heavy metal contaminated wastewater. Furthermore, the handling of silanes and other metal alkoxides should be made controllable by separately prepared under suitable reaction conditions organosols of sufficient stability and film-forming properties and then only with the remaining components of the treatment solution (chromium (III) ion, phosphate source and other optional components) be mixed.
  • the invention provides a process 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, the ratio of the molar concentration (ie the concentration in mol / l) of chromium (III) ions to the molar concentration of the at least one phosphate compound (based on orthophosphate) ([chromium (III) ions]: [phosphate compound]) is preferably between 1: 1.5 and 1: 3. Furthermore, this treatment solution contains a separately prepared by hydrolysis and condensation organosol, which by reaction
  • One or more alkoxides of the formula (2) contains Me (OR 2 J n (2) wherein Me is Ti, Zr, Hf, Al, Si and n are the oxidation state of Me and R 2 is selected from substituted or unsubstituted hydrocarbon groups containing from 1 to 8 carbon atoms, the aqueous treatment solution being free from inorganic and organic compounds Is peroxides.
  • 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 ester (mono-, di- and thester), phosphoric acid ethyl ester (mono-, di- and thester ), Phosphoric acid n-propyl esters (mono-, di- and triesters), isopropyl phosphates (mono-, di- and triesters), phosphoric acid n-butyl esters (mono-, di- and triesters), phosphoric acid 2-butyl ester (Mono -, di- and triesters), phosphoric acid / t-butyl ester (mono-, di- and triesters), the salts of said mono- and diesters and c // - phosphorus pentoxide and mixtures of these compounds.
  • the term "salts" includes not only the salts of completely depro
  • the treatment solution preferably contains between 0.2 g / l and 20 g / l chromium (III) ions, more preferably between 0.5 g / l and 15 g / l chromium (III) ions and more preferably between 1 g / l and 10 g / l chromium (III) ions.
  • the ratio of the molar concentration of chromium (III) ions to the molar concentration of the at least one phosphate compound (based on orthophosphate) is between 1: 1.5 and 1: 3, preferably between 1: 1.7 and 1: 2.5.
  • Chromium (III) ions may be added to the treatment solution either in the form of inorganic chromium (III) salts such as 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 of organic acids such as chromium (III) methanesulfonate, chromium (III) citrate are added or produced by reduction of suitable chromium (VI) compounds in the presence of suitable reducing agents.
  • inorganic chromium (III) salts such as basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride , Chromium (III) nitrate, potassium chromium
  • Suitable chromium (VI) compounds include chromium (VI) oxide, chromates such as potassium or sodium chromate, dichromates such as potassium or sodium dichromate.
  • Suitable reducing agents for the in situ generation of chromium (III) ions are, for example, sulfites such as sodium sulfite, sulfur dioxide, phosphites such as Nathumhypophosphit, phosphorous acid, hydrogen peroxide, methanol, hydroxycarboxylic acids and hydroxydicarboxylic acids such as gluconic acid, citric acid and malic acid.
  • the treatment solution preferably has a pH between pH 2 and pH 7, more preferably between pH 2.5 and pH 6, and most preferably between pH 2.5 and pH 3.
  • the above-mentioned organosol can be obtained by per se known hydrolysis and condensation of the at least one alkoxysilane of the formula (1).
  • Particularly preferred among the above alkoxysilanes of the formula (1) is at least one in which at least one R has a group which can undergo a polyaddition (including polymerization) or polycondensation reaction.
  • This grouping capable of polyaddition or polycondensation reaction is preferably an epoxy group or carbon-carbon multiple bonds, with a (meth) acrylate group being a particularly preferred example of the latter groupings.
  • Particularly preferred alkoxysilanes according to formula (1) are those in which x is 2 or 3 and in particular 3 and a radical R is co-glycidyloxy-C 2 6 -alkyl or ⁇ - (meth) acryloxy-C 2 - 6 -alkyl stands.
  • alkoxysilanes are 3-glycidoxypropyltri (m) ethoxysilane, 3,4-epoxybutyltri (m) ethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltri (m) ethoxysilane, 3- (meth) acryloxypropylth (m) ethoxysilane and 2- (Meth) acryloxyethyltri (m) ethoxysilane, 3-glycidoxypropyldimethyl (m) ethoxysilane, 3-glycidoxypropylmethyldi (m) ethoxysilane, 3- (meth) acryloxypropylmethyldi (m) ethoxysilane and 2- (meth) acryloxyethylmethyl-di (m) ethoxysilane.
  • alkoxysilanes of the formula (1) which can preferably be used in combination with alkoxysilanes having the above groupings capable of polyaddition or polycondensation reaction are, for example, hexadecyltri (m) ethoxysilane, cyclohexyltri (m) ethoxysilane, cyclopentyltri (m) ethoxysilane, ethylth (m) ethoxysilane, phenylethyltri (m) ethoxysilane, phenylth (m) ethoxysilane, n-propyltri (m) ethoxysilane, cyclohexyl (m) ethyldimethoxysilane, dimethyldi (m) ethoxysilane, diisopropyldi (m) ethoxysilane and phenylmethyldi (m) ethoxysilane.
  • At least one alkoxide according to formula (2) is then combined with the hydrolyzate of the at least one alkoxysilane of formula (1).
  • the alkoxides according to formula (2) are very reactive, so that in the absence of a complexing agent, the components according to formulas (1) and (2) would hydrolyze and condense very rapidly on contact with water. According to the invention, however, it is not necessary to use the reactive alkoxides directly in complexed form. Rather, it is possible to add the complexing agent or compounds shortly after the start of the reaction of the components according to formulas (1) and (2).
  • alkoxides of the formula (2) are aluminum sec-butoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, zirconium isopropoxide, zirconium propoxide,
  • complexing agents are ethanolamines and alkyl phosphates, such as tri-, diethanolamine and butyl phosphate.
  • examples of such complexed alkoxides according to formula (2) are titanium acetylacetonates, titanium bisacetoacetates, thethanolamine titanates, triethanolamine zirconates and zirconium diethyl citrates.
  • the complexing agent in particular a chelate compound, causes some complexation of the metal cation, so that the hydrolysis and condensation rate of the components according to formulas (1) and (2) is reduced.
  • the organosol comprising an water-compatible or water-miscible solvent having a boiling point of at least 150 0 C.
  • an water-compatible or water-miscible solvent having a boiling point of at least 150 0 C.
  • diethylene glycol, triethylene glycol, butyl diglycol, propylene glycols, butylene glycols, and polyethylene glycols can be used for this purpose.
  • the object of the high-boiling solvents is that improved resistance of the organosols can be achieved in exchange for the liberated during hydrolysis low molecular weight alcohol.
  • the organosol is characterized in that the weight ratio of the component according to formula (1) to the component according to formula (2) in the range 1 to 1 to 1 to 100, particularly preferably in the range 1 to 1 to 1 to 25 lies. Since the components according to formula (2) also serve as crosslinking agents for the alkoxysilanes according to formula (1), they should be present in the organosols at least in equimolar amounts relative to the component of formula (1).
  • the organosol is the treatment solution according to the invention based on an active ingredient content of 25% in the organosol in an amount of 1 g / l to 50 g / l, preferably 3 g / l to 20 g / l and most preferably 5 g / l to 15 g / l added.
  • the treatment solution may additionally (optionally) contain one or more further complexing agents.
  • Suitable further complexing agents are, in particular, organic chelate ligands.
  • suitable further complexing agents are polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids,
  • Aminocarboxylic acids or hydroxyphosphonic acids are citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, Glucuronic acid, ascorbic acid, isocitric acid, gallic acid, glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, salicylic acid, nicotinic acid, alanine, glycine, asparagine, aspartic acid, cysteine, glutamic acid, 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.
  • metal or metalloid e.g. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si.
  • 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 are only 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 treatment solution may additionally (optionally) contain one or more wetting agents.
  • a more uniform layer structure and a better drainage behavior is achieved, especially on complex parts or on heavier wettable surfaces.
  • fluoroaliphatic polymeric esters such as Fluorad FC-4432 TM (from 3M).
  • the treatment solution may additionally (optionally) contain one or more lubricants.
  • Suitable lubricants are, for example, polyether-modified siloxanes,
  • Polyether wax emulsions ethoxylated alcohols, PTFE, PVDF, ethylene copolymers, paraffin emulsions, polypropylene wax emulsions, M0S 2 and dispersions thereof, WS 2 and emulsions thereof, polyethylene glycols, polypropylene, Fischer-Tropsch hard waxes, micronized and synthetic hard waxes, graphite, metal soaps and polyurea.
  • Particularly preferred lubricants are PTFE, micronized hard waxes and polyether wax emulsions.
  • the optional lubricants are added in an amount of 0.1 g / l to 300 g / l, preferably 1 g / l to 30 g / l of the treatment solution according to the invention.
  • the surfaces treated according to the invention are metallic, preferably zinc-containing, and zinc-containing surfaces which are optionally provided with a conversion layer containing chromium (III).
  • a layer is deposited on the treated surface, the chromium (III) ions, phosphate (s), a silicon / metal-organic network and optionally further metal ions, such as. Zinc ions, and optionally one or more polymeric components.
  • 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 0 C and 90 0 C, more preferably between 20 0 C and 80 0 C, more preferably between 25 0 C and 50 0 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 contacting, but are dried directly.
  • the process according to the invention leads to increased corrosion protection in the case of articles which have a zinc-containing surface.
  • the method of the invention may also be used.
  • the process according to the invention after application of a so-called conversion layer is applied to fully metallic zinc and zinc alloy surfaces.
  • Conversion layers can be deposited from treatment solutions containing, for example, chromium (III) ions and an oxidizing agent.
  • the method of the present invention is applied to full metal zinc and zinc alloy surfaces after oxidative activation.
  • This oxidative activation is, for example, immersing the galvanized substrate in an aqueous solution containing an oxidizing agent.
  • Suitable oxidizing agents for this purpose are nitrates and nitric acid, peroxides such as hydrogen peroxide, persulfates and perborates.
  • zinc flake coatings the process according to the invention is applied directly after application and curing of the zinc flake coating.
  • Sample parts made of steel were first coated in a weakly acidic electroplating process (Unizinc ACZ 570 from Atotech GmbH) with an 8-10 ⁇ m thick zinc coating and rinsed with demineralized water.
  • a weakly acidic electroplating process Unizinc ACZ 570 from Atotech GmbH
  • sample parts were provided with a chromium (III) ion and nitrate-containing conversion layer (EcoTri® HC2 from Atotech Deutschland GmbH) and dried.
  • a chromium (III) ion and nitrate-containing conversion layer (EcoTri® HC2 from Atotech Deutschland GmbH)
  • treatment solution A a treatment solution with a pH of 3.9 was applied, which contained the following constituents:
  • the corrosion resistance formation of red corrosion according to EN ISO 9227 was tested with a neutral salt spray test. The formation of red corrosion was observed after 864 h.
  • Sample parts made of steel were coated in a weakly acidic galvanic process (Unizinc ACZ 570 from Atotech GmbH) with an 8-10 ⁇ m thick zinc coating and rinsed with demineralized water.
  • a weakly acidic galvanic process Unizinc ACZ 570 from Atotech GmbH
  • sample parts were provided with a chromium (III) ion and nitrate-containing conversion layer (EcoTri®HC2 from Atotech Deutschland GmbH) and dried.
  • a chromium (III) ion and nitrate-containing conversion layer (EcoTri®HC2 from Atotech Deutschland GmbH)
  • an organosol having an active substance content of 25% (in% by weight) prepared from tetraethoxysilane as alkoxysilane according to formula (1) and 3-glycidyloxypropylthethoxysilane as metal alkoxide according to formula (2).
  • the corrosion resistance formation of red corrosion according to EN ISO 9227 was tested with a neutral salt spray test. The formation of red corrosion was observed after 1500 hours.
  • Sample parts made of steel were coated with a zinc flake-containing treatment solution (Zintek® 800 WD 1 from Atotech Deutschland GmbH) with a 10 ⁇ m thick zinc flake-containing overlay.
  • a zinc flake-containing treatment solution Zintek® 800 WD 1 from Atotech GmbH
  • Example 1 Example 1 according to the invention was applied and the sample parts coated in this way were dried.
  • the corrosion resistance formation of red corrosion according to EN ISO 9227
  • the formation of red corrosion was observed after 3500 hours.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

The invention relates to a method for producing an anti-corrosive cover layer, a surface to be treated being brought into contact with an aqueous treatment solution containing chromium(III) ions and at least one phosphate compound and an organosol. The method improves the anti-corrosion protection of metal, in particular zinc-containing, surfaces and zinc-containing surfaces provided with conversion layers. This produces or improves the decorative and functional properties of the surfaces. In addition, it avoids the known problems arising with the use of chromium(VI)-containing compounds or multi-stage processes in which a chromium ion-containing passivation layer and a seal are applied consecutively.

Description

Korrosionsschutzbehandlung für Oberflächen aus Zink und Zinklegierungen  Anti-corrosion treatment for zinc and zinc alloy surfaces
Gebiet der Erfindung Field of the invention
Die Erfindung betrifft den Korrosionsschutz von metallischen Werkstoffen, insbesondere von solchen, die mit einer Oberfläche aus Zink oder Zinklegierungen versehen sind. The invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a surface of zinc or zinc alloys.
Hintergrund der Erfindung Background 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 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(lll) reduziert, das in dem durch die Wasserstoffentwicklung alkalischeren Oberflächenfilm u.a. als Chrom(lll)-hydroxid bzw. als schwerlöslicher μ-Oxo- oder μ-Hydroxo- verbrückter Chrom(lll)-Konnplex abgeschieden wird. Parallel wird schwerlösliches Zinkchromat(VI) gebildet. Insgesamt entsteht ein dicht geschlossener, sehr gut vor dem Korrosionsangriff durch Elektrolyt^ 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 sparingly soluble μ-oxo or μ-hydroxoxide. bridged chromium (III) -Konnplex is deposited. In parallel, sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well before the corrosion attack by electrolyte ^ protective 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 Versiegelung auf der Oberfläche des Werkstücks aufgebracht. Solche Versiegelungen können auf Basis z. B. anorganischer Silikate, organofunktioneller Silane, organischer Polymere und hybriden Systemen, die sowohl organische als auch anorganische Bestandteile als Filmbildner aufweisen, ausgeführt werden. Nachteilig an diesem zusätzlichen Verfahrensschritt 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 und dergleichen, die mit der Schichtdicke dieser Versiegelungen einhergehen. As a substitute for chromating processes with hexavalent chromium compounds, a large number of processes have now been established which 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, a seal is often additionally applied to the surface of the workpiece. Such seals may be based on z. As inorganic silicates, organofunctional silanes, organic polymers and hybrid systems that have both organic and inorganic components as film formers, are performed. A disadvantage of this additional process step is the occurrence of drainage drops in the coating of workpieces made on the frame and / or the bonding of coated bulk material; In addition, problems such as dimensional accuracy of threads and the like, which are associated with the layer thickness of these seals arise.
Ansätze, die Korrosionsschutzeigenschaften von Beschichtungen aus Chrom-haltigen Passivierungen und sich anschließenden Versieglungen in einer einzigen Schicht zu kombinieren sind im Stand der Technik beschrieben: Approaches to combine the anticorrosion properties of coatings of chromium-containing passivations and subsequent sealings in a single layer are described in the prior art:
Die Schrift EP 0 479 289 A1 beschreibt ein Chromatierungsverfahren, bei dem die Substrate in eine Behandlungslösung getaucht werden, die neben Chrom(VI)- und Chrom(lll)-Ionen, Flusssäure und Phosphorsäure ein Silan-Kopplungsmittel enthalten. Document EP 0 479 289 A1 describes a chromating process in which the substrates are immersed in a treatment solution which contains, in addition to chromium (VI) and chromium (III) ions, hydrofluoric acid and phosphoric acid, a silane coupling agent.
Das Patent EP 0 922 785 B1 beschreibt eine Behandlungslösung und ein Verfahren zur Herstellung von Schutzschichten auf Metallen, bei dem die zu schützende Oberfläche mit einer Behandlungslösung, die Chrom(lll)-Ionen, ein Oxidationsmittel und eine Oxysäure oder ein Oxysäuresalz des Phosphors oder ein entsprechendes Anhydrid enthält. Diese Behandlungslösung kann ferner ein monomeres Silan-Kopplungsmittel enthalten. The patent EP 0 922 785 B1 describes a treatment solution and a process for the production of protective layers on metals, in which the surface to be protected with a treatment solution, the chromium (III) ions, an oxidizing agent and an oxyacid or an oxyacid salt of phosphorus or a corresponding anhydride contains. This treating solution may further contain a monomeric silane coupling agent.
In der Schrift EP 1 051 539 B1 wird eine Behandlungslösung zur Erhöhung des Korrosionsschutzes von Substraten beschrieben, die neben Chrom(VI)- und Chrom(lll)- lonen weiterhin Phosphorsäure, Flusssäure, kolloidales Siliciumdioxid und ein monomeres Epoxy-funktionalisiertes Silan enthält. The document EP 1 051 539 B1 describes a treatment solution for increasing the corrosion protection of substrates, which in addition to chromium (VI) and chromium (III) ions also contains phosphoric acid, hydrofluoric acid, colloidal silicon dioxide and a monomeric epoxy-functionalized silane.
Die Schrift WO 2008/14166 A1 beschreibt eine Behandlungslösung zur Erzeugung von Korrosionsschutzschichten. Diese Behandlungslösung enthält neben Zink Ionen, Phosphorsäure oder sauren Phosphaten, organische oder anorganische Anionen die eines der Elemente Bor, Silizium, Titan oder Zirconium, trivalente Chrom Ionen und ein anorganisches oder organisches Peroxid als Oxidationsmittel. The document WO 2008/14166 A1 describes a treatment solution for the production of anticorrosive coatings. This treatment solution contains, in addition to zinc ions, phosphoric acid or acidic phosphates, organic or inorganic anions which one of the elements boron, silicon, titanium or zirconium, trivalent chromium ions and an inorganic or organic peroxide as an oxidizing agent.
Die Schrift WO 97/15700 A1 beschreibt eine Behandlungslösung zur Erzeugung von Korrosionsschutzschichten. Die Behandlungslösung enthält hydrolysierte Silane und Phosphorsäure und ist frei von Chrom Ionen und Chrom enthaltenden Verbindungen. The document WO 97/15700 A1 describes a treatment solution for the production of corrosion protection layers. The treatment solution contains hydrolyzed silanes and phosphoric acid and is free of chromium ions and chromium containing compounds.
Die im Stand der Technik beschriebenen Behandlungslösungen weisen die folgenden Nachteile auf: entweder enthalten sie toxische Substanzen, wie Chrom(VI)-lonen und Flusssäure oder monomere Silane. Eine gut kontrollierbare Hydrolyse und Kondensation von monomeren Silanen ist in derartigen Matrizes nicht durchführbar und führt daher zu schwankenden Eigenschaften der resultierenden Beschichtungen. The treatment solutions described in the prior art have the following disadvantages: they either contain toxic substances such as chromium (VI) ions and hydrofluoric acid or monomeric silanes. A well controllable hydrolysis and condensation of monomeric silanes is not feasible in such matrices and therefore leads to fluctuating properties of the resulting coatings.
Beschreibung der Erfindung Description of the invention
Der Erfindung liegt die Aufgabe zugrunde, Verfahren zur Steigerung des Korrosionsschutzes metallischer, insbesondere zinkhaltiger und zinkhaltiger, mit einer Konversionsschicht versehenen, 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 und Flusssäure oder von Nachbehandlungen zur Versiegelung vermieden werden. Weiterhin soll der üblicherweise in zwei separaten Stufen durchgeführte Prozess der Aufbringung eines Chrom(lll)-lonen-haltigen Passivierungsschritts gefolgt von einer Versieglung durch einen einstufigen Prozess ersetzt werden, in dem die Funktionalität einer Chrom(lll)-lonen-haltigen Passivierungsschicht und einer Versieglung vereint sind. Ein weiterer Aspekt der Erfindung besteht darin, dass auf die üblicherweise bei den aus dem Stand der Technik bekannten zweistufigen Verfahren notwendigen Spülschritte zwischen Aufbringung der Chrom(lll)-Ionen enthaltenden Passivierung und der Versiegelung verzichtet werden kann. Dadurch wird die Menge von mit Schwermetall belasteten Abwässern deutlich reduziert. Weiterhin soll die Handhabung von Silanen und anderen Metallalkoxiden kontrollierbar gemacht werden, indem separat unter dafür geeigneten Reaktionsbedingungen Organosole ausreichender Stabilität und Filmbildender Eigenschaften hergestellt und dann erst mit den restlichen Komponenten der Behandlungslösung (Chrom(lll)-Ionen, Phosphatquelle und weitere, optionale Komponenten) vermischt werden. The invention has for its object to provide methods for increasing the corrosion protection of metallic, especially zinc-containing and zinc-containing, provided with a conversion layer, surfaces. 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 and hydrofluoric acid or post-treatments for sealing should be avoided. Furthermore, the process, usually carried out in two separate stages, is to apply a passivation step containing chromium (III) ions followed by a one-step process in which the functionality of a chromium (III) ion-containing passivation layer and a seal are combined. A further aspect of the invention is that it is possible to dispense with the rinsing steps which are normally required in the two-stage processes known from the prior art between the application of the passivation containing chromium (III) ions and the sealing. This significantly reduces the amount of heavy metal contaminated wastewater. Furthermore, the handling of silanes and other metal alkoxides should be made controllable by separately prepared under suitable reaction conditions organosols of sufficient stability and film-forming properties and then only with the remaining components of the treatment solution (chromium (III) ion, phosphate source and other optional components) be mixed.
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(lll)-Ionen und mindestens eine Phosphatverbindung enthält, wobei das Verhältnis der Stoffmengenkonzentration (d.h. der Konzentration in mol/l) von Chrom(lll)-Ionen zur Stoffmengenkonzentration der mindestens einen Phosphatverbindung (bezogen auf Orthophosphat) ([Chrom(lll)-Ionen] : [Phosphatverbindung]) bevorzugt zwischen 1 : 1.5 und 1 : 3 liegt. Weiterhin enthält diese Behandlungslösung ein separat durch Hydrolyse und Kondensation hergestelltes Organosol, welches durch Reaktion To achieve this object, the invention provides a process 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, the ratio of the molar concentration (ie the concentration in mol / l) of chromium (III) ions to the molar concentration of the at least one phosphate compound (based on orthophosphate) ([chromium (III) ions]: [phosphate compound]) is preferably between 1: 1.5 and 1: 3. Furthermore, this treatment solution contains a separately prepared by hydrolysis and condensation organosol, which by reaction
• eines oder mehrerer Alkoxysilane der Formel (1 ) R4-xSi(OR1)x (1 ) wobei die Reste R gleich oder verschieden voneinander, jeweils eine substituierte oder unsubstituierte Kohlenwasserstoffgruppe mit 1 bis 22 Kohlenwasserstoffatomen darstellen und x gleich 1 , 2 oder 3 ist und R1 für eine substituierte oder unsubstituierte Kohlenwasserstoffgruppe mit 1 bis 8 Kohlenwasserstoffatomen steht, und • one or more alkoxysilanes of formula (1) R 4-x Si (OR 1 ) x (1) wherein the radicals R are the same or different from each other, each represents a substituted or unsubstituted hydrocarbon group having 1 to 22 hydrocarbon atoms and x is 1, 2 or 3 and R 1 is a substituted or unsubstituted hydrocarbon group having from 1 to 8 carbon atoms, and
• eines oder mehrerer Alkoxide der Formel (2) enthält Me(OR2Jn (2) wobei Me für Ti, Zr, Hf, AI, Si und n für die Oxidationsstufe von Me stehen und R2 ausgewählt wird aus substituierten oder unsubstituierten Kohlenwasserstoffgruppen, die 1 bis 8 Kohlenstoffatome enthalten, erhalten wird, wobei die wässrige Behandlungslösung frei von anorganischen und organischen Peroxiden ist. One or more alkoxides of the formula (2) contains Me (OR 2 J n (2) wherein Me is Ti, Zr, Hf, Al, Si and n are the oxidation state of Me and R 2 is selected from substituted or unsubstituted hydrocarbon groups containing from 1 to 8 carbon atoms, the aqueous treatment solution being free from inorganic and organic compounds Is peroxides.
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 Thester), Phosphorsäureethylester (Mono-, Di- und Thester), 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-te/t-butylester (Mono-, Di- und Triester), die Salze der genannten Mono- und Diester sowie c//-Phosphorpentoxid und Gemische dieser Verbindungen. Der Begriff „Salze" umfasst nicht nur die Salze der vollständig deprotonierten Säuren, sondern Salze in allen möglichen Proton ierungsstufen, 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 ester (mono-, di- and thester), phosphoric acid ethyl ester (mono-, di- and thester ), Phosphoric acid n-propyl esters (mono-, di- and triesters), isopropyl phosphates (mono-, di- and triesters), phosphoric acid n-butyl esters (mono-, di- and triesters), phosphoric acid 2-butyl ester (Mono -, di- and triesters), phosphoric acid / t-butyl ester (mono-, di- and triesters), the salts of said mono- and diesters and c // - phosphorus pentoxide and mixtures of these compounds. The term "salts" includes not only the salts of completely deprotonated acids, but salts in all possible proton ierungsstufen, eg hydrogen phosphates and dihydrogen phosphates.
Die Behandlungslösung enthält bevorzugt zwischen 0.2 g/l und 20 g/l Chrom(lll)-Ionen, mehr bevorzugt zwischen 0.5 g/l und 15 g/l Chrom(lll)-Ionen und besonders bevorzugt zwischen 1 g/l und 10 g/l Chrom(lll)-Ionen. The treatment solution preferably contains between 0.2 g / l and 20 g / l chromium (III) ions, more preferably between 0.5 g / l and 15 g / l chromium (III) ions and more preferably between 1 g / l and 10 g / l chromium (III) ions.
Das Verhältnis der Stoffmengen konzentration von Chrom(lll)-Ionen zur Stoffmengen konzentration der mindestens einen Phosphatverbindung (bezogen auf Orthophosphat) 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 (based on orthophosphate) is between 1: 1.5 and 1: 3, preferably between 1: 1.7 and 1: 2.5.
Chrom(lll)-Ionen können der Behandlungslösung entweder in Form von anorganischen Chrom(lll)-Salzen wie z.B. basisches Chrom(lll)-sulfat, Chrom(lll)-hydroxid, Chrom(lll)- dihydrogenphosphat, Chrom(lll)-chlorid, Chrom(lll)-nitrat, Kaliumchrom(lll)-sulfat oder Chrom(lll)-Salzen organischer Säuren wie z.B. Chrom(lll)-methansulfonat, Chrom(lll)- 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(lll)-Ionen sind z.B. Sulfite wie z.B. Natriumsulfit, Schwefeldioxid, Phosphite wie z.B. Nathumhypophosphit, phosphorige Säure, Wasserstoffperoxid, Methanol, Hydroxycarbonsäuren und Hydroxydicarbonsäuren wie z.B. Gluconsäure, Zitronensäure und Äpfelsäure. Chromium (III) ions may be added to the treatment solution either in the form of inorganic chromium (III) salts such as 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 of organic acids such as chromium (III) methanesulfonate, chromium (III) citrate are added or produced by reduction of suitable chromium (VI) compounds in the presence of suitable reducing agents. Suitable chromium (VI) compounds include chromium (VI) oxide, chromates such as potassium or sodium chromate, dichromates such as potassium or sodium dichromate. Suitable reducing agents for the in situ generation of chromium (III) ions are, for example, sulfites such as sodium sulfite, sulfur dioxide, phosphites such as Nathumhypophosphit, phosphorous acid, hydrogen peroxide, methanol, hydroxycarboxylic acids and hydroxydicarboxylic acids such as gluconic acid, citric acid and malic acid.
Die Behandlungslösung besitzt bevorzugt einen pH-Wert zwischen pH 2 und pH 7, besonders bevorzugt zwischen pH 2.5 und pH 6 und ganz besonders bevorzugt zwischen pH 2.5 und pH 3. The treatment solution preferably has a pH between pH 2 and pH 7, more preferably between pH 2.5 and pH 6, and most preferably between pH 2.5 and pH 3.
Das obengenannte Organosol kann durch an sich bekannte Hydrolyse und Kondensation des mindestens einen Alkoxysilans gemäß Formel (1 ) erhalten werden. Beispielsweise ist es möglich, ein Alkoxysilan gemäß Formel (1 ) mit einer wässrigen sauren Lösung zu versetzen, so dass ein klares Hydrolysat erhalten wird. Beispiele für Reste R1 in der Formel (1 ) sind lineare und verzweigte Alkyl-, Alkenyl-, Aryl-, Alkylaryl-, Arylalkyl-, Arylalkenyl-, Alkenylaryl-Reste (vorzugsweise mit jeweils 1 bis 22 und insbesondere 1 bis 16 Kohlenstoffatomen und cyclische Formen einschließend), die durch Sauerstoff-, Stickstoffatome oder die Gruppe NR2 (R2 = Wasserstoff oder Ci-H- Alkyl) unterbrochen sein können und einen oder mehrere Substituenten aus der Gruppe der Halogene, Amino-, Amid-, Carboxy-, Hydroxy-, Alkoxy-, Alkoxycarbonyl-, Acryloxy-, Methacryloxy- oder Epoxy- Gruppen tragen können. Besonders bevorzugt befindet sich unter den obigen Alkoxysilanen der Formel (1 ) mindestens eines, in welchem mindestens ein Rest R über eine Gruppierung verfügt, die eine Polyadditions- (einschließlich Polymerisations-) oder Polykondensationsreaktion eingehen kann. Bei dieser zur Polyadditions- oder Polykondensationsreaktion befähigten Gruppierung handelt es sich vorzugsweise um eine Epoxygruppe oder Kohlenstoff-Kohlenstoff- Mehrfachbindungen, wobei eine (Meth)acrylatgruppe ein besonders bevorzugtes Beispiel für die letztgenannten Gruppierungen ist. Besonders bevorzugte Alkoxysilane gemäß Formel (1 ) sind solche, in denen x gleich 2 oder 3 und insbesondere 3 ist und ein Rest R für co-Glycidyloxy-C2 6-Alkyl oder ω-(Meth)acryloxy-C2-6-Alkyl steht. Beispiele für derartige Alkoxysilane sind 3-Glycidoxypropyltri(m)ethoxysilan, 3,4- Epoxybutyltri(m)ethoxysilan und 2-(3,4-Epoxycyclohexyl)ethyltri(m)ethoxysilan, 3- (Meth)acryloxypropylth(m)ethoxysilan und 2-(Meth)acryloxyethyltri(m)ethoxysilan, 3- Glycidoxypropyldimethyl(m)ethoxysilan, 3-Glycidoxypropylmethyldi(m)ethoxysilan, 3- (Meth)acryloxypropylmethyldi(m)ethoxysilan und 2-(Meth)acryloxyethylmethyl- di(m)ethoxysilan. The above-mentioned organosol can be obtained by per se known hydrolysis and condensation of the at least one alkoxysilane of the formula (1). For example, it is possible to add an alkoxysilane according to formula (1) with an aqueous acidic solution so that a clear hydrolyzate is obtained. Examples of radicals R 1 in the formula (1) are linear and branched alkyl, alkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl radicals (preferably having in each case 1 to 22 and in particular 1 to 16 carbon atoms and including cyclic forms) which may be interrupted by oxygen, nitrogen atoms or the group NR 2 (R 2 = hydrogen or Ci-H-alkyl) and one or more substituents from the group of halogens, amino, amide, carboxy , Hydroxy, alkoxy, alkoxycarbonyl, acryloxy, methacryloxy or epoxy groups can carry. Particularly preferred among the above alkoxysilanes of the formula (1) is at least one in which at least one R has a group which can undergo a polyaddition (including polymerization) or polycondensation reaction. This grouping capable of polyaddition or polycondensation reaction is preferably an epoxy group or carbon-carbon multiple bonds, with a (meth) acrylate group being a particularly preferred example of the latter groupings. Particularly preferred alkoxysilanes according to formula (1) are those in which x is 2 or 3 and in particular 3 and a radical R is co-glycidyloxy-C 2 6 -alkyl or ω- (meth) acryloxy-C 2 - 6 -alkyl stands. Examples for such alkoxysilanes are 3-glycidoxypropyltri (m) ethoxysilane, 3,4-epoxybutyltri (m) ethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltri (m) ethoxysilane, 3- (meth) acryloxypropylth (m) ethoxysilane and 2- (Meth) acryloxyethyltri (m) ethoxysilane, 3-glycidoxypropyldimethyl (m) ethoxysilane, 3-glycidoxypropylmethyldi (m) ethoxysilane, 3- (meth) acryloxypropylmethyldi (m) ethoxysilane and 2- (meth) acryloxyethylmethyl-di (m) ethoxysilane.
Weitere Alkoxysilane gemäß Formel (1 ), die bevorzugt in Kombination mit Alkoxysilanen mit den obigen zur Polyadditions- bzw. Polykondensationsreaktion befähigten Gruppierungen eingesetzt werden können, sind beispielsweise Hexadecyltri(m)ethoxysilan, Cyclohexyltri(m)ethoxysilan, Cyclopentyltri(m)ethoxysilan, Ethylth(m)ethoxysilan, Phenylethyltri(m)ethoxysilan, Phenylth(m)ethoxysilan, n- Propyltri(m)ethoxysilan, Cyclohexyl(m)ethyldimethoxysilan, Dimethyldi(m)ethoxysilan, Diisopropyldi(m)ethoxysilan und Phenylmethyldi(m)ethoxysilan. Further alkoxysilanes of the formula (1) which can preferably be used in combination with alkoxysilanes having the above groupings capable of polyaddition or polycondensation reaction are, for example, hexadecyltri (m) ethoxysilane, cyclohexyltri (m) ethoxysilane, cyclopentyltri (m) ethoxysilane, ethylth (m) ethoxysilane, phenylethyltri (m) ethoxysilane, phenylth (m) ethoxysilane, n-propyltri (m) ethoxysilane, cyclohexyl (m) ethyldimethoxysilane, dimethyldi (m) ethoxysilane, diisopropyldi (m) ethoxysilane and phenylmethyldi (m) ethoxysilane.
Im Verlauf der Reaktion wird dann wenigstens ein Alkoxid gemäß Formel (2) mit dem Hydrolysat des mindestens einem Alkoxysilans der Formel (1 ) zusammengegeben. Die Alkoxide gemäß Formel (2) sind sehr reaktiv, so dass in Abwesenheit eines Komplexbildners die Komponenten gemäß Formeln (1 ) und (2) bei Kontakt mit Wasser sehr schnell hydrolysieren und kondensieren würden. Erfindungsgemäß ist es jedoch nicht erforderlich, die reaktionsfähigen Alkoxide direkt in komplexierter Form einzusetzen. Vielmehr ist es möglich, den oder die Komplexbildner kurz nach dem Start der Reaktion der Komponenten gemäß Formeln (1 ) und (2) hinzuzugeben. In the course of the reaction, at least one alkoxide according to formula (2) is then combined with the hydrolyzate of the at least one alkoxysilane of formula (1). The alkoxides according to formula (2) are very reactive, so that in the absence of a complexing agent, the components according to formulas (1) and (2) would hydrolyze and condense very rapidly on contact with water. According to the invention, however, it is not necessary to use the reactive alkoxides directly in complexed form. Rather, it is possible to add the complexing agent or compounds shortly after the start of the reaction of the components according to formulas (1) and (2).
Beispiele für Alkoxide gemäß Formel (2) sind Aluminium-sek.-butylat, Titanisopropoxid, Titanpropoxid, Titanbutoxid, Zirkoniumisopropoxid, Zirkoniumpropoxid,Examples of alkoxides of the formula (2) are aluminum sec-butoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, zirconium isopropoxide, zirconium propoxide,
Zirkoniumbutoxid, Zirkoniumethoxid, Tetraethoxysilan, Tetramethoxysilan, Tetrapropyloxysilan und Tetrabutyloxysilan. Bei den reaktionsfähigeren Alkoxiden gemäß Formel (2) mit Me = AI, Ti, Si, Zr und Hf, kann es sich jedoch empfehlen, diese direkt in komplexierter Form einzusetzen, wobei Beispiele für geeignete Komplexbildner gesättigte wie auch ungesättigte Carbonsäuren und 1 ,3-Dicarbonyl-Verbindungen, wie Essigsäure, Milchsäure, Methacrylsäure, Acetylaceton und Acetessigsäurethylester sind. Ebenfalls geeignet als Komplexbildner sind Ethanolamine sowie Alkylphosphate, wie Tri-, Diethanolamin und Butylphosphat. Beispiele für derartig komplexierte Alkoxide gemäß Formel (2) sind Titanacetylacetonate, Titanbisethylacetoacetate, Thethanolamintitanate, Triethanolaminzirconate und Zirconiumdiethylcitrate. Der Komplexbildner, insbesondere eine Chelat-Verbindung, bewirkt eine gewisse Komplexierung des Metallkations, so dass die Hydrolyse- und Kondensationsgeschwindigkeit der Komponenten gemäß Formeln (1 ) und (2) reduziert wird. Zirconium butoxide, zirconium ethoxide, tetraethoxysilane, tetramethoxysilane, tetrapropyloxysilane and tetrabutyloxysilane. In the case of the more reactive alkoxides of formula (2) where Me = Al, Ti, Si, Zr and Hf, it may be advisable to use them directly in complexed form, examples of suitable complexing agents being saturated and unsaturated carboxylic acids and Dicarbonyl compounds such as acetic acid, lactic acid, methacrylic acid, acetylacetone and ethyl acetoacetate are. Also suitable as complexing agents are ethanolamines and alkyl phosphates, such as tri-, diethanolamine and butyl phosphate. Examples of such complexed alkoxides according to formula (2) are titanium acetylacetonates, titanium bisacetoacetates, thethanolamine titanates, triethanolamine zirconates and zirconium diethyl citrates. The complexing agent, in particular a chelate compound, causes some complexation of the metal cation, so that the hydrolysis and condensation rate of the components according to formulas (1) and (2) is reduced.
Als weiteren, optionalen Bestandteil umfasst das Organosol ein wasserverträgliches oder mit Wasser mischbares Lösemittel mit einem Siedepunkt von wenigstens 150 0C. Beispielsweise können Diethylenglykol, Triethylenglykol, Butyldiglykol, Propylenglykole, Butylenglykole, und Polyethylenglykole hierfür verwendet werden. Die Aufgabe der hochsiedenden Lösungsmittel besteht darin, dass im Austausch gegen den bei der Hydrolyse frei werdenden niedermolekularen Alkohol eine verbesserte Beständigkeit der Organosole erreicht werden kann. As a further optional ingredient, the organosol comprising an water-compatible or water-miscible solvent having a boiling point of at least 150 0 C. For example, diethylene glycol, triethylene glycol, butyl diglycol, propylene glycols, butylene glycols, and polyethylene glycols can be used for this purpose. The object of the high-boiling solvents is that improved resistance of the organosols can be achieved in exchange for the liberated during hydrolysis low molecular weight alcohol.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das Organosol dadurch gekennzeichnet, dass das Gewichtsverhältnis der Komponente gemäß Formel (1 ) zu der Komponente gemäß Formel (2) im Bereich 1 zu 1 bis 1 zu 100, besonders bevorzugt im Bereich 1 zu 1 bis 1 zu 25 liegt. Da die Komponente gemäß Formel (2) auch als Vernetzungsmittel für die Alkoxysilane gemäß Formel (1 ) dienen, sollten diese wenigstens in äquimolaren Mengen bezogen auf die Komponente gemäß Formel (1 ) in den Organosolen anwesend sein. In a preferred embodiment of the present invention, the organosol is characterized in that the weight ratio of the component according to formula (1) to the component according to formula (2) in the range 1 to 1 to 1 to 100, particularly preferably in the range 1 to 1 to 1 to 25 lies. Since the components according to formula (2) also serve as crosslinking agents for the alkoxysilanes according to formula (1), they should be present in the organosols at least in equimolar amounts relative to the component of formula (1).
Das Organosol wird der erfindungsgemäßen Behandlungslösung bezogen auf einen Wirkstoffgehalt von 25 % im Organosol in einer Menge von 1 g/l bis 50 g/l, bevorzugt 3 g/l bis 20 g/l und am meisten bevorzugt 5 g/l bis 15 g/l zugegeben. The organosol is the treatment solution according to the invention based on an active ingredient content of 25% in the organosol in an amount of 1 g / l to 50 g / l, preferably 3 g / l to 20 g / l and most preferably 5 g / l to 15 g / l added.
Die Behandlungslösung kann zusätzlich (optional) einen oder mehrere weitere Komplexbildner enthalten. Geeignete weitere Komplexbildner sind insbesondere organische Chelatliganden. Beispiele für geeignete weitere Komplexbildner sind Polycarbonsäuren, Hydroxycarbonsäuren, Hydroxypolycarbonsäuren,The treatment solution may additionally (optionally) contain one or more further complexing agents. Suitable further complexing agents are, in particular, organic chelate ligands. Examples of suitable further complexing agents are polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids,
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.). Aminocarboxylic acids or hydroxyphosphonic acids. Examples of suitable carboxylic acids are citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, Glucuronic acid, ascorbic acid, isocitric acid, gallic acid, glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, salicylic acid, nicotinic acid, alanine, glycine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, lysine. Suitable hydroxyphosphonic acids are, for example, Dequest 2010 ™ (from Solutia, Inc.); suitable as aminophosphonic acids, for example Dequest 2000 ™ (from Solutia, Inc.).
Optional 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, AI, Si 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. Optionally, to enhance the 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. 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(ll)-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 der 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 are only 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. 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). By adding the above-mentioned polymers to the treatment solution, the layer properties of the deposited corrosion protection layer are significantly improved. 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 Behandlungslösung kann zusätzlich (optional) ein oder mehrere Schmiermittel enthalten. Dadurch können gezielt gewünschte Reibungswerte der mit dem erfindungsgemäßen Verfahren hergestellten Oberflächen eingestellt werden. Geeignete Schmiermittel sind beispielsweise Polyether-modifizierte Siloxane,The treatment solution may additionally (optionally) contain one or more lubricants. As a result, it is possible to set desired desired friction values of the surfaces produced by the method according to the invention. Suitable lubricants are, for example, polyether-modified siloxanes,
Polyetherwachsemulsionen, ethoxylierte Alkohole, PTFE, PVDF, Ethylencopolymere, Paraffinemulsionen, Polypropylenwachsemulsionen, M0S2 und Dispersionen hiervon, WS2 und Emulsionen hiervon, Polyethylenglycole, Polypropylen, Fischer-Tropsch Hartwachse, micronisierte und synthetische Hartwachse, Graphit, Metallseifen und Polyharnstoff. Besonders bevorzugte Schmiermittel sind PTFE, micronisierte Hartwachse und Polyetherwachsemulsionen. Polyether wax emulsions, ethoxylated alcohols, PTFE, PVDF, ethylene copolymers, paraffin emulsions, polypropylene wax emulsions, M0S 2 and dispersions thereof, WS 2 and emulsions thereof, polyethylene glycols, polypropylene, Fischer-Tropsch hard waxes, micronized and synthetic hard waxes, graphite, metal soaps and polyurea. Particularly preferred lubricants are PTFE, micronized hard waxes and polyether wax emulsions.
Die optionalen Schmiermittel werden in einer Menge von 0.1 g/l bis 300 g/l, bevorzugt 1 g/l bis 30 g/l der erfindungsgemäßen Behandlungslösung zugegeben. The optional lubricants are added in an amount of 0.1 g / l to 300 g / l, preferably 1 g / l to 30 g / l of the treatment solution according to the invention.
Die erfindungsgemäß behandelten Oberflächen sind metallische, bevorzugt zinkhaltige, und zinkhaltige Oberflächen, die optional mit einer Chrom(lll)-haltigen Konversionsschicht versehenen sind. The surfaces treated according to the invention are metallic, preferably zinc-containing, and zinc-containing surfaces which are optionally provided with a conversion layer containing chromium (III).
Durch das erfindungsgemäße Verfahren wird auf der behandelten Oberfläche eine Schicht abgeschieden, die Chrom(lll)-Ionen, Phosphat(e), ein Silicium-/Metall- organisches Netzwerk sowie optional weitere Metall-Ionen, wie z.B. Zink-Ionen, und optional eine oder mehrere polymere Komponenten enthält. By the method according to the invention a layer is deposited on the treated surface, the chromium (III) ions, phosphate (s), a silicon / metal-organic network and optionally further metal ions, such as. Zinc ions, and optionally one or more polymeric components.
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 0C und 90 0C, mehr bevorzugt zwischen 20 0C und 80 0C, besonders bevorzugt zwischen 25 0C und 50 0C. 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 temperature of the treatment solution is preferably between 10 0 C and 90 0 C, more preferably between 20 0 C and 80 0 C, more preferably between 25 0 C and 50 0 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.
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 direkt getrocknet. The objects treated according to the invention are no longer rinsed after contacting, but are dried directly.
Das erfindungsgemäße Verfahren führt bei Gegenständen, die eine zinkhaltige Oberfläche aufweisen zu einem erhöhten Korrosionsschutz. Im Falle von vollmetallischen Zink- und Zinklegierungs-Oberflächen, die durch Verfahren wie galvanische Abscheidung, Feuerverzinken, mechanische Abscheidung und Sherardizing erhalten werden, kann das erfindungsgemäße Verfahren ebenfalls angewendet werden. In einer weiteren Ausführungsform der Erfindung wird das erfindungsgemäße Verfahren nach Applikation einer sogenannten Konversionsschicht (siehe WO 02/07902 A2) auf vollmetallischen Zink- und Zinklegierungs-Oberflächen angewandt. Konversionschichten können aus Behandlungslösungen abgeschieden werden, die beispielsweise Chrom(lll)-Ionen und ein Oxidationsmittel enthalten. The process according to the invention leads to increased corrosion protection in the case of articles which have a zinc-containing surface. In the case of fully metallic zinc and zinc alloy surfaces obtained by methods such as electrodeposition, hot dip galvanizing, mechanical deposition and sherardizing, the method of the invention may also be used. In a further embodiment of the invention, the process according to the invention after application of a so-called conversion layer (see WO 02/07902 A2) is applied to fully metallic zinc and zinc alloy surfaces. Conversion layers can be deposited from treatment solutions containing, for example, chromium (III) ions and an oxidizing agent.
In einer weiteren Ausführungsform wird das erfindungsgemäße Verfahren auf vollmetallischen Zink- und Zinklegierungs-Oberflächen nach einer oxidativen Aktivierung angewandt. Diese oxidative Aktivierung besteht zum Beispiel darin, das verzinkte Substrat in eine wässrige Lösung zu tauchen, die ein Oxidationsmittel enthält. Hierfür geeignete Oxidationsmittel sind Nitrate und Salpetersäure, Peroxide wie Wasserstoffperoxid, Persulfate und Perborate. Im Falle sogenannter Zinklamellenbeschichtungen wird das erfindungsgemäße Verfahren direkt nach Applikation und Aushärtung der Zinklamellenbeschichtung angewandt. In another embodiment, the method of the present invention is applied to full metal zinc and zinc alloy surfaces after oxidative activation. This oxidative activation is, for example, immersing the galvanized substrate in an aqueous solution containing an oxidizing agent. Suitable oxidizing agents for this purpose are nitrates and nitric acid, peroxides such as hydrogen peroxide, persulfates and perborates. In the case of so-called zinc flake coatings, the process according to the invention is applied directly after application and curing of the zinc flake coating.
Beispiele Examples
Nachfolgend wird die Erfindung anhand von Beispielen näher erläutert. Vergleichsbeispiel 1 The invention will be explained in more detail by way of examples. Comparative Example 1
Probeteile aus Stahl wurden zunächst in einem schwach sauren galvanischen Verfahren (Unizinc ACZ 570 von Atotech Deutschland GmbH) mit einer 8-10 μm dicken Zink-Auflage beschichtet und mit demineralisiertem Wasser gespült. Sample parts made of steel were first coated in a weakly acidic electroplating process (Unizinc ACZ 570 from Atotech Deutschland GmbH) with an 8-10 μm thick zinc coating and rinsed with demineralized water.
Anschließend wurden die Probenteile mit einer Chrom(lll)-Ionen- und Nitrat-haltigen Konversionsschicht (EcoTri® HC2 von Atotech Deutschland GmbH) versehen und getrocknet. Subsequently, the sample parts were provided with a chromium (III) ion and nitrate-containing conversion layer (EcoTri® HC2 from Atotech Deutschland GmbH) and dried.
Anschließend wurde eine Behandlungslösung (= Behandlungslösung A) mit einem pH-Wert von 3,9 appliziert, die folgende Bestandteile enthielt: Subsequently, a treatment solution (= treatment solution A) with a pH of 3.9 was applied, which contained the following constituents:
4.5 g/l Cr3+ aus Chrom(lll)-hydroxid 4.5 g / l Cr 3+ from chromium (III) hydroxide
18 g/l PO4 3" aus ortho-Phosphorsäure 18 g / l PO 4 3 " from ortho-phosphoric acid
5.5 g/l Zn2+ aus Zinkoxid 5.5 g / l Zn 2+ from zinc oxide
11 g/l Citronensäure  11 g / L citric acid
Danach wurden die so beschichteten Probeteile getrocknet Thereafter, the thus coated sample parts were dried
Die Korrosionsbeständigkeit (Bildung von Rotkorrosion nach EN ISO 9227) wurde mit einem neutralen Salzsprühtest überprüft. Die Bildung von Rotkorrosion wurde nach 864 h beobachtet. The corrosion resistance (formation of red corrosion according to EN ISO 9227) was tested with a neutral salt spray test. The formation of red corrosion was observed after 864 h.
Beispiel 1 example 1
Probeteile aus Stahl wurden in einem schwach sauren galvanischen Verfahren (Unizinc ACZ 570 von Atotech Deutschland GmbH) mit einer 8-10 μm dicken Zink-Auflage beschichtet und mit demineralisiertem Wasser gespült. Sample parts made of steel were coated in a weakly acidic galvanic process (Unizinc ACZ 570 from Atotech Deutschland GmbH) with an 8-10 μm thick zinc coating and rinsed with demineralized water.
Danach wurden die Probeteile mit einer Chrom(lll)-Ionen- und Nitrat-haltigen Konversionsschicht (EcoTri®HC2 von Atotech Deutschland GmbH) versehen und getrocknet. Thereafter, the sample parts were provided with a chromium (III) ion and nitrate-containing conversion layer (EcoTri®HC2 from Atotech Deutschland GmbH) and dried.
Anschließend wurde einer erfindungsgemäßen Behandlungslösung mit einem pH-Wert von 2.8 appliziert, die folgende Bestandteile enthielt: Subsequently, a treatment solution according to the invention with a pH value of 2.8 was applied, which contained the following constituents:
4.5 g/l Cr3+ aus Chrom(lll)-hydroxid 4.5 g / l Cr 3+ from chromium (III) hydroxide
18 g/l PO4 3" aus ortho-Phosphorsäure 18 g / l PO 4 3 " from ortho-phosphoric acid
5.5 g/l Zn2+ aus Zinkoxid 5.5 g / l Zn 2+ from zinc oxide
11 g/l Citronensäure  11 g / L citric acid
50 g/l eines Organosols mit einem Wirkstoffgehalt von 25 % (in Gew.-%), das aus Tetraethoxysilan als Alkoxysilan gemäß Formel (1 ) und 3- Glycidyloxypropylthethoxysilan als Metallalkoxid gemäß Formel (2) hergestellt wurde. 50 g / l of an organosol having an active substance content of 25% (in% by weight) prepared from tetraethoxysilane as alkoxysilane according to formula (1) and 3-glycidyloxypropylthethoxysilane as metal alkoxide according to formula (2).
Danach wurden die so beschichteten Probeteile getrocknet. Thereafter, the thus coated sample parts were dried.
Die Korrosionsbeständigkeit (Bildung von Rotkorrosion nach EN ISO 9227) wurde mit einem neutralen Salzsprühtest überprüft. Die Bildung von Rotkorrosion wurde nach 1500 h beobachtet. The corrosion resistance (formation of red corrosion according to EN ISO 9227) was tested with a neutral salt spray test. The formation of red corrosion was observed after 1500 hours.
Beispiel 2 Example 2
Probeteile aus Stahl wurden mit Hilfe einer Zinklamellen-enthaltenden Behandlungslösung (Zintek® 800 WD 1 von Atotech Deutschland GmbH) mit einer 10 μm dicken Zinklamellen-enthaltenden Auflage beschichtet. Sample parts made of steel were coated with a zinc flake-containing treatment solution (Zintek® 800 WD 1 from Atotech Deutschland GmbH) with a 10 μm thick zinc flake-containing overlay.
Anschließend wurde die erfindungsgemäße Behandlungslösung aus Beispiel 1 appliziert und die so beschichteten Probeteile getrocknet. Die Korrosionsbeständigkeit (Bildung von Rotkorrosion nach EN ISO 9227) wurde mit einem neutralen Salzsprühtest. Die Bildung von Rotkorrosion wurde nach 3500 h beobachtet. Subsequently, the treatment solution of Example 1 according to the invention was applied and the sample parts coated in this way were dried. The corrosion resistance (formation of red corrosion according to EN ISO 9227) was tested with a neutral salt spray test. The formation of red corrosion was observed after 3500 hours.

Claims

Patentansprüche claims
1. Verfahren zur Erzeugung einer korrosionsschützenden Überzugsschicht, wobei eine zu behandelnde Oberfläche mit einer wässrigen Behandlungslösung in Kontakt gebracht wird, die A process for producing a corrosion-protective coating layer, wherein a surface to be treated is brought into contact with an aqueous processing solution which
• Chrom(lll)-Ionen,  Chromium (III) ions,
• mindestens eine Phosphatverbindung und  • at least one phosphate compound and
• ein durch Hydrolyse und Kondensation hergestelltes Organosol enthält, welches durch Reaktion eines oder mehrerer Alkoxysilane der Formel (1 )  Contains an organosol prepared by hydrolysis and condensation, which is prepared by reaction of one or more alkoxysilanes of the formula (1)
R4-xSi(OR1)x (1 ) R 4-x Si (OR 1 ) x (1)
wobei die Reste R gleich oder verschieden voneinander, jeweils eine substituierte oder unsubstituierte Kohlenwasserstoffgruppe mit 1 bis 22 Kohlenwasserstoffatomen darstellen und x gleich 1 , 2 oder 3 ist und R1 für eine substituierte oder unsubstituierte Kohlenwasserstoffgruppe mit 1 bis 8 Kohlenwasserstoffatomen darstellen, und einem oder mehrerer Alkoxide der Formel (2) wherein the radicals R are the same or different from each other, each represents a substituted or unsubstituted hydrocarbon group having 1 to 22 hydrocarbon atoms and x is 1, 2 or 3 and R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 8 hydrocarbon atoms, and one or more Alkoxides of the formula (2)
Me(OR2Jn (2) wobei Me für Ti, Zr, Hf, AI, Si und n für die Oxidationsstufe von Me stehen und R2 ausgewählt wird aus substituierten oder unsubstituierten Kohlenwasserstoffgruppen, die 1 bis 8 Kohlenstoffatome enthalten, Me (OR 2 J n (2) where Me is Ti, Zr, Hf, Al, Si and n are the oxidation state of Me and R 2 is selected from substituted or unsubstituted hydrocarbon groups containing from 1 to 8 carbon atoms
wobei die wässrige Behandlungslösung frei von anorganischen und organischen Peroxiden ist.  wherein the aqueous treatment solution is free from inorganic and organic peroxides.
2. Verfahren nach Anspruch 1 , wobei das Verhältnis der Stoffmengen konzentration von Chrom(lll)-Ionen zur Stoffmengen konzentration der mindestens einen Phosphatverbindung in der wässrigen Behandlungslösung (bezogen auf Orthophosphat) zwischen 1 : 1.5 und 1 : 3 liegt. 2. The method of claim 1, wherein the ratio of the molar concentration of chromium (III) ions to the molar concentration of the at least one phosphate compound in the aqueous treatment solution (based on orthophosphate) is between 1: 1.5 and 1: 3.
3. Verfahren nach einem der Ansprüche 1 und 2, wobei die mindestens eine Phosphatverbindung in der wässrigen Behandlungslösung 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. 3. The method according to any one of claims 1 and 2, wherein the at least one phosphate compound in the aqueous treatment solution 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 with organic radicals having up to 12 carbon atoms and mixtures of these compounds.
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei die Konzentration der Chrom(lll)-Ionen in der wässrigen Behandlungslösung im Bereich zwischen 0.2 g/l und 20 g/l liegt. 4. The method according to any one of claims 1 to 3, wherein the concentration of chromium (III) ions in the aqueous treatment solution in the range between 0.2 g / l and 20 g / l.
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das mindestens eine Alkoxysilan gemäß Formel (1 ) ausgewählt ist aus der Gruppe bestehend aus Thalkoxysilanen und Dialkoxysilanen und R1 für gleiche oder verschiedene über ein C-Atom an das Siliziumatom gebundene, gegebenenfalls verzweigte Kohlenwasserstoffgruppen steht, die durch Sauerstoff, Stickstoff oder die Gruppe NR2, mit R2 gleich Wasserstoff oder Ci bis Cβ-Alkyl unterbrochen sind und einen oder mehrere Substituenten, ausgewählt aus der Gruppe der Halogene und der gegebenenfalls Amino-, Amido-, Carboxy-, Acryloxy-, Methacryloxy- und Epoxy- Alkylgruppen tragen können. 5. The method according to any one of claims 1 to 4, wherein the at least one alkoxysilane according to formula (1) is selected from the group consisting of thalkoxysilanes and dialkoxysilanes and R 1 is the same or different bonded via a carbon atom to the silicon atom, optionally branched Hydrocarbon groups which are interrupted by oxygen, nitrogen or the group NR 2 , with R 2 is hydrogen or Ci to Cβ-alkyl and one or more substituents selected from the group of halogens and optionally amino, amido, carboxy , Acryloxy, methacryloxy and epoxy alkyl groups.
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das mindestens eine Alkoxysilan gemäß Formel (1 ) ausgewählt ist aus der Gruppe bestehend aus 3- Glycidoxypropyltrimethoxysilan, 3-Glycidoxypropyltriethoxysilan, 3,4-Epoxybutyl- trimethoxysilan, 3,4-Epoxybutyltriethoxysilan, 2-(3,4-Epoxycyclohexyl)ethyl- trimethoxysilan und 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilan. 6. The method according to any one of claims 1 to 5, wherein the at least one alkoxysilane according to formula (1) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3,4-epoxybutyl-trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei Me in mindestens einer Verbindung gemäß Formel (2) Silizium ist. 7. The method according to any one of claims 1 to 6, wherein Me in at least one compound according to formula (2) is silicon.
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei das Organosol ein mit Wasser mischbares Lösungsmittel mit einem Siedepunkt von wenigstens 150 0C enthält. 8. The method according to any one of claims 1 to 7, wherein the organosol contains a water-miscible solvent having a boiling point of at least 150 0 C.
9 Verfahren nach einem der Ansprüche 1 bis 8, wobei das Organosol zusätzlich einen oder mehrere Komplexbildner enthält, ausgewählt aus der Gruppe bestehend aus gesättigte und ungesättigte Carbonsäuren, 1 ,3-Dicarbonyl- Verbindungen, Ethanolamine, Alkylphosphate, Polycarbonsäuren,9. The method according to any one of claims 1 to 8, wherein the organosol additionally contains one or more complexing agents selected from the group consisting of saturated and unsaturated carboxylic acids, 1, 3-dicarbonyl compounds, ethanolamines, alkyl phosphates, polycarboxylic acids,
Hydroxycarbonsäuren, Hydroxypolycarbonsäuren, Aminocarbonsäuren oder Hydroxyphosphonsäuren und Aminophosphonsäuren. Hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids and aminophosphonic acids.
10. Verfahren nach einem der Ansprüche 1 bis 9, wobei die wässrige Behandlungslösung mindestens einen weiteren Komplexbildner enthält, der ausgewählt ist aus der Gruppe bestehend aus Essigsäure, Methacrylsäure, Acetylaceton, Acetessigsäureethylester, Triethanolamin, Diethanolamin, Butylphosphat, 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. 10. The method according to any one of claims 1 to 9, wherein the aqueous treatment solution contains at least one further complexing agent selected from the group consisting of acetic acid, methacrylic acid, acetylacetone, ethyl acetoacetate, triethanolamine, diethanolamine, butyl phosphate, citric acid, tartaric acid, malic acid, lactic acid , Gluconic, glucuronic, ascorbic, isocitric, gallic, glycolic, 3-hydroxypropionic, 4-hydroxybutyric, salicylic, nicotinic, alanine, glycine, asparagine, aspartic, cysteine, glutamic, glutamine and lysine.
11. Verfahren nach einem der Ansprüche 1 bis 10, wobei die Behandlungslösung zusätzlich ein oder mehrere in Wasser lösliche oder in Wasser dispergierbare Polymere enthält, ausgewählt aus der Gruppe bestehend aus Polyethylenglykolen, Polypropylenglykolen, Polyvinylpyrrolidonen, Polyvinylalkoholen, Polyitaconsäuren, Polyacrylaten und Copolymeren der jeweils zugrunde liegenden Monomere. 11. The method according to any one of claims 1 to 10, wherein the treatment solution additionally contains one or more water-soluble or water-dispersible polymers selected from the group consisting of polyethylene glycols, polypropylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, polyitaconic acids, polyacrylates and copolymers of each lying monomers.
12. Verfahren nach einem der Ansprüche 1 bis 11 , wobei die wässrige Behandlungslösung zusätzlich mindestens ein Schmiermittel enthält. 12. The method according to any one of claims 1 to 11, wherein the aqueous treatment solution additionally contains at least one lubricant.
13. Verfahren einem der Ansprüche 1 bis 12, wobei die wässrige Behandlungslösung zusätzlich ein oder mehrere Metalle oder Metalloide, ausgewählt aus der Gruppe bestehend aus Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, AI, Si und P enthält. 13. A process as claimed in any of claims 1 to 12, wherein the aqueous treatment solution additionally comprises one or more metals or metalloids selected from the group consisting of Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, AI, Si and P.
14. Verfahren nach Anspruch 13, 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. 14. The method of claim 13, wherein the metal or metalloid has been added to the treatment solution in the form of one of its salts or in the form of a complex anion or acids of these anions such as hexafluoroboric acid, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid or salts thereof ,
15. Verfahren nach einem der Ansprüche 1 bis 14, wobei der pH-Wert der wässrigen Behandlungslösung zwischen pH 1.5 und pH 9 liegt. 15. The method according to any one of claims 1 to 14, wherein the pH of the aqueous treatment solution is between pH 1.5 and pH 9.
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