EP1678344A1 - Procede essentiellement exempt de chrome destine a la passivation de surfaces metalliques en zn, alliages de zn, al ou alliages d'al - Google Patents

Procede essentiellement exempt de chrome destine a la passivation de surfaces metalliques en zn, alliages de zn, al ou alliages d'al

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Publication number
EP1678344A1
EP1678344A1 EP04790483A EP04790483A EP1678344A1 EP 1678344 A1 EP1678344 A1 EP 1678344A1 EP 04790483 A EP04790483 A EP 04790483A EP 04790483 A EP04790483 A EP 04790483A EP 1678344 A1 EP1678344 A1 EP 1678344A1
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EP
European Patent Office
Prior art keywords
water
preparation
alloys
acid
treatment
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.)
Granted
Application number
EP04790483A
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German (de)
English (en)
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EP1678344B1 (fr
Inventor
Frank Dietsche
Frank Klippel
Matthias KLÜGLEIN
Alexander Göthlich
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BASF SE
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BASF SE
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • the present invention relates to an essentially chromium-free process for passivating metallic surfaces made of Zn, Zn alloys, Al or Al alloys by treating the surface with an acidic, aqueous preparation which comprises at least one essentially uncrosslinked, water-soluble polymer or copolymer comprises at least 50% by weight of (meth) acrylic acid units, and also water or an aqueous solvent mixture containing at least 50% by weight of water, and by additionally treating the surface with at least one water-soluble crosslinking agent, the at least 2 crosslinking groups selected from the group of azirane , Oxirane or thiirane groups.
  • the invention further relates to passivation layers obtainable by means of the method and to a preparation suitable for this method.
  • the corrosion protection treatment of modern metallic materials is usually carried out in multi-stage processes, and the surface of treated metals has several different layers.
  • the corrosion protection treatment of aluminum surfaces and the surfaces of galvanized metals, in particular of galvanized or hot-dip galvanized iron or steel, is of particular technical and economic importance.
  • the protection against corrosion of the zinc is based on the fact that it is less noble than the metallic material itself and therefore initially corrodes itself.
  • the metallic material itself remains intact as long as it is continuously covered with zinc.
  • a thin oxide layer initially forms on the surface of Zn or Zn alloys, Al or Al alloys, which more or less slows down the corrosive attack on the underlying metal depending on the external conditions.
  • Passivation layers are comparatively thin and usually have a thickness of no more than 3 ⁇ m.
  • lacquer layers are generally applied to the passivation layer. It is usually a combination of several layers of paint, each serving different purposes. They serve, for example, to protect the passivation layer and the metal from corrosive gases and / or liquids, but also from mechanical damage, such as stone chips, and of course also for aesthetic purposes. Lacquer layers are usually significantly thicker than passivation layers. Typical thicknesses range from 5 ⁇ m to 400 ⁇ m.
  • crosslinkers with azirane, oxirane or thiirane groups in coating materials, lacquers or the like is known, for example from WO 01/30513, JP-A 2002/327096, JP-A 2003/027254 and JP-A 2002/326310. As shown above, however, painting or coating can be clearly distinguished from passivation.
  • the passivation can be used for permanent corrosion protection or only for temporary corrosion protection.
  • Temporary protection is used, for example, only for storing or transporting a metal sheet or other metallic workpiece and is removed again before final processing.
  • passivation layers on zinc or aluminum surfaces have usually been obtained by treating the workpiece to be protected with aqueous, acidic solutions of CrO 3 .
  • the mechanism of such passivation is complex.
  • metallic Zn or Al is released from the surface and precipitates again in the form of amorphous zinc chromium oxides or aluminum chromium oxides.
  • the layers can also contain foreign ions and / or other components from the treatment solution.
  • Cr (VI) is also incorporated into the passivation layer.
  • DE-A 195 16 765 discloses a chromium- and fluoride-free process for producing conversion layers on metallic surfaces made of Zn or Al.
  • the acidic solution used for the passivation comprises a water-soluble polymer, phosphoric acid and Al-chelate complexes.
  • the use of crosslinkers for passivation is not disclosed.
  • DE-A 197 54 108 discloses a chromium-free aqueous corrosion protection agent which contains hexafluoro anions of Ti (IV) and / or Zr (IV), vanadium ions. Cobalt ions and phosphoric acid. Various film-forming polymers can optionally also be added. The use of crosslinkers is not disclosed.
  • DE-A 199 23 084 discloses a chromium-free aqueous corrosion protection agent which contains hexafluoro anions of Ti (IV), Si (IV) and / or Zr (IV), an organophosphonic acid and a water-soluble or water-dispersible, film-forming organic polymer or Contains copolymer.
  • polymer binders include Acrylic acid and methacrylic acid disclosed.
  • urea derivatives, epoxy resins, (blocked) polyisocyanates or their oligomeric derivatives as crosslinkers is also disclosed.
  • epoxy resins based on bisphenol A or F units and epichlorohydrin are not water-soluble.
  • an (eth) acrylate dispersion is optionally used in combination with an epoxy resin.
  • dispersions are generally less suitable than homogeneous solutions because, on the one hand, the dispersing agents and surfactants present in dispersions can be disruptive and, furthermore, the low viscosity enables only very poor film thickness adjustment. Homogeneous systems are easier to handle because the viscosity can be adjusted simply by the content of the solvent.
  • the combination of a water-soluble polymer with more than 50% by weight of (meth) acrylic acid units with a water-soluble crosslinker is not disclosed in DE-A 199 23 084.
  • EP-A 787 830 discloses a chromium-free composition for the treatment of metallic surfaces which comprises an organic resin containing OH groups, phosphoric acid and at least one metal ion, for example Co, Cu, Fe, Mn, Sn or V.
  • the examples also disclose copolymers which have acrylic acid and / or methacrylic acid units. However, the amount of the (meth) acrylic acid units in the copolymers is in each case well below 50% by weight. In addition, acrylates are primarily used as comonomers.
  • the copolymers disclosed are not homogeneously water-soluble polymers. The document also optionally mentions the use of epoxy crosslinkers. The combination of a water-soluble polymer with however, more than 50% by weight of (meth) acrylic acid units with a water-soluble crosslinking agent is not disclosed.
  • JP-A 56-000279 discloses a Cr-free method for surface treatment, in which the surface of Zn or galvanized steel is treated with an aqueous solution of a polyamine and a metal salt of phytic acid. The use of crosslinkers is not disclosed.
  • a chromium-free process for passivation also has to meet a number of procedural requirements.
  • Passivation is technically carried out, for example, by immersing the workpieces to be passivated in a passivating solution.
  • Loose workpieces e.g. screws
  • Larger workpieces can also be mounted on a suitable frame and the frame can be immersed.
  • the contact time between the passivating solution and the workpiece can be determined comparatively freely by a person skilled in the art, and thus quite thick passivation layers can also be obtained.
  • the contact time can be in the range of minutes.
  • metal sheets are shaped using suitable techniques such as punching, drilling, folding, profiling and / or deep drawing. Larger components, such as automobile bodies, may be joined together by welding several individual parts.
  • the raw material for this is usually long metal strips, which are produced by rolling the metal and wound up into rolls (so-called “coils”) for storage and transport.
  • the galvanizing and passivation of such metal strips is carried out on an industrial scale in continuous plants.
  • the metal strip is first passed through a device for galvanizing, for example a trough with molten zinc, and then directly through another device for passivation, for example likewise a trough or a rinsing device.
  • a device for galvanizing for example a trough with molten zinc
  • another device for passivation for example likewise a trough or a rinsing device.
  • process steps are carried out continuously, for example cleaning or rinsing steps or also the application of a first lacquer layer to the passivation layer.
  • Typical speeds at which metal strips are moved through the continuous lines are 50 to 100 m / min. This means that the contact time between the metallic surface and the preparation used for passivation is only short. Usually only a few seconds are available for treatment.
  • a process that is suitable on an industrial scale must therefore have sufficient results with only short contact times.
  • the object of the invention was therefore to provide an improved, essentially Cr-free method for passivating metallic surfaces made of Zn, Zn alloys, Al or Al alloys, which offers improved corrosion protection compared to the prior art and in which For a satisfactory result, only short contact times between the metallic surface and the preparation used for passivation are required. In particular, the process should also be able to be carried out continuously.
  • (b) comprises water or an aqueous solvent mixture (B) containing at least 50% by weight of water,
  • the surface is further treated with at least one water-soluble crosslinking agent
  • the crosslinking agent comprising at least 2 crosslinking groups selected from the group of azirane, oxirane or thiirane groups which are linked to one another by means of a linking group (X) comprising at least 2 C atoms are connected, the number average molecular weight M ⁇ of the crosslinking agent is 112 to 5000 g / mol, and the treatment with the crosslinking agent is carried out before, after or simultaneously with the treatment with the preparation (Z).
  • the metallic surface is the surface of a strip metal and, further preferably, the passivation is carried out by means of a continuous process.
  • the invention further relates to a passivation layer on a metallic surface made of Zn, Zn alloys, Al or Al alloys, which is obtainable by the method, metallic surfaces comprising such a passivation layer and a preparation for passivation.
  • essentially chromium-free in the sense of this invention means that the actual passivating effect is brought about by the polymer used in combination with the crosslinking agent and, if appropriate, further components of the preparation.
  • minor Amounts of chromium compounds could be added to fine-tune the properties of the passivation layer, but the amount should not exceed 10% by weight, preferably 5% by weight and particularly preferably 2% by weight, based on the amount of polymer and crosslinker used together, and also a content of 2% by weight, preferably 1% by weight and particularly preferably 0.5% by weight, of chromium in relation to all constituents of the composition should not be exceeded.
  • Cr (III) compounds should preferably be used In any case, the Cr (VI) content should be kept so low that the Cr (VI) - Content on the passivated metal does not exceed 1 mg / m 2 .
  • the preparation used for the passivation preferably contains no Cr (VI) and particularly preferably no chromium compounds, and chromium compounds of any oxidation state are deliberately not used in any other process step either. But even in this case, small amounts of chromium can be introduced into the process indirectly and unintentionally per se. If zinc or aluminum alloys which comprise chromium as an alloy component or galvanized steel in which the iron is alloyed with chromium are used for the process according to the invention, it is always possible that small amounts of chromium are present in the metal to be treated can be solved by the preparation used for the process and accordingly can inadvertently get into the preparation itself.
  • the metallic surfaces that are passivated by the method according to the invention are surfaces made of Zn, Zn alloys, Al or Al alloys. It can be the surfaces of bodies or workpieces made entirely of the said metals or alloys. However, it can also be the surfaces of bodies coated with Zn, Zn alloys, Al or Al alloys, wherein the bodies can consist of other materials, for example of other metals, alloys, polymers or composite materials. In particular, it can be the surface of galvanized iron or steel. In a special embodiment of the method, it is the surface of a strip metal, in particular electrolytically galvanized or hot-galvanized steel.
  • Zn or Al alloys are known to the person skilled in the art. Depending on the desired application, the person skilled in the art selects the type and amount of alloy components. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical components of aluminum alloys include, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. It can also be an Al / Zn alloy in which Al and Zn are present in approximately the same amount , Steel coated with such alloys is commercially available.
  • the preparation (Z) used for passivation comprises at least one water-soluble, uncrosslinked polymer or copolymer (A) which comprises at least 50% by weight of (meth) acrylic acid units (a1).
  • the COOH groups can also be present in whole or in part as salts, for example as ammonium or Na salts.
  • water-soluble in the sense of this invention is intended to mean that the polymer or copolymers (A) used should be homogeneously water-soluble.
  • Aqueous dispersions of crosslinked polymer particles per se of water-insoluble polymers are not within the scope of this invention.
  • the (co) polymers used should preferably be completely miscible with water, even if this is not absolutely necessary in every case. However, they must at least be water-soluble to such an extent that passivation is possible using the method according to the invention. As a rule, the (co) polymers used should have a solubility of at least 50 g / l, preferably 100 g / l and particularly preferably at least 200 g / l.
  • the polymer or copolymer (A) can be pure polyacrylic acid or polymethacrylic acid.
  • (A) is preferably a copolymer which comprises 50 to 99% by weight of (meth) acrylic acid units (Aa) and additionally 1 to 50% by weight of at least one further ethylenically unsaturated comonomer which is different from (meth) acrylic acid ,
  • the copolymer preferably comprises 60 to 95% by weight, particularly preferably 65 to 90% by weight and very particularly preferably 70 to 85% by weight of (meth) acrylic acid units (Aa).
  • the comonomers must meet a number of requirements: they must be copolymerizable with (meth) acrylic acid and, if appropriate, other comonomers.
  • the copolymer (A) must also be water-soluble.
  • the at least one comonomer is in particular at least one comonomer (Ab) which differs from (meth) acrylic acid and which has an ethylenically unsaturated group and an acidic group.
  • comonomer (Ab) which differs from (meth) acrylic acid and which has an ethylenically unsaturated group and an acidic group.
  • These can also be carboxylate groups, but also other acidic groups such as phosphoric acid, phosphonic acid or sulfonic acid groups.
  • the comonomers can each have only identical or different acid groups. Of course, several different comonomers (Ab) with acidic groups can also be used.
  • Examples of particularly suitable comonomers (Ab) include maleic acid, fumaric acid and vinylphosphonic acid.
  • the copolymer (A) can further comprise one or more comonomers (Ac) which comprise an ethylenically unsaturated group but no acid group.
  • monomers include olefins such as ethylene, propylene or styrene, esters of vinyl alcohol and monocarboxylic acids, in particular such as vinyl acetate or vinyl propionate, and furthermore in particular (meth) acrylates with a wide variety of alcohol residues such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( meth) acrylate or 2-ethylhexyl (meth) acrylate. It can also be monomers containing OH groups, such as p-vinylphenol or in particular ethoxylated or propoxylated (meth) acrylic acid.
  • the comonomers (Ac) are used to fine-tune the properties. If present, their amount is determined depending on the desired properties of the polymers, for example their solubility. However, the amount should generally not exceed 30% by weight, preferably 20% by weight, particularly preferably 10% by weight and very particularly preferably 5% by weight.
  • the copolymers (A) can be prepared by procedures known to those skilled in the art.
  • the polymers and / or copolymers are preferably prepared by radical copolymerization of the components (Aa) mentioned and, if appropriate, (Ab) and / or (Ac).
  • Monomers with more than one ethylenically unsaturated group, which have a corresponding crosslinking action, can be used in special cases to fine-tune the properties. However, they should at most be used in very small amounts so that the polymer remains essentially uncrosslinked.
  • the amount of a crosslinking monomer should generally not exceed 1% by weight, preferably 0.5% by weight, and preferably none is used at all.
  • the polymers can also be prepared by not using the free acids in the case of the acidic monomers for the polymerization, but rather in the form of their salts, esters, anhydrides or other hydrolyzable derivatives. Free acid groups can then be obtained in a separate step by hydrolysis, optionally using suitable bases.
  • Maleic acid in particular is usually polymerized in the form of maleic anhydride and hydrolyzed only after the polymerization, or possibly even only in the preparation.
  • the average molecular weight of the (co) polymers used is not restricted in principle as long as the (co) polymers are still sufficiently soluble in water to a sufficient extent. It is determined by the person skilled in the art depending on the desired application.
  • the weight average M w of the polymers is 500 to 2,000,000 g / mol, preferably 1,000 to 1,000,000, particularly preferably 2,000 to 500,000 g / mol and very particularly preferably 3,000 to 3,000,000 g / mol.
  • the copolymer (A) is particularly preferably one composed of (meth) acrylic acid and maleic anhydride, in particular from 70 to 80% by weight of (meth) acrylic acid and 20 to 30% by weight maleic anhydride.
  • vinylphosphonic acid can furthermore preferably be used as a further comonomer in amounts of 1 to 30% by weight, preferably 1 to 20% by weight and particularly preferably 1 to 10% by weight.
  • a preferred copolymer can be composed, for example, of 70 to 80% by weight of (meth) acrylic acid, 15 to 25% by weight of maleic anhydride and 1 to 10% by weight of vinylphosphonic acid.
  • the maleic anhydride units are hydrolyzed to maleic acid units immediately at the beginning, in parallel or after the polymerization, preferably with a base such as triethanolamine.
  • the preparation (Z) used for the process according to the invention preferably comprises only water or an aqueous solvent mixture containing at least 50% by weight of water. If an aqueous mixture is used, the mixture preferably comprises at least 65% by weight, particularly preferably at least 80% by weight and very particularly preferably at least 95% by weight of water.
  • the information relates to the total amount of all solvents.
  • Other components of a mixture are water-miscible solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butylglycol or methoxypropanol.
  • the concentration of the polymers or copolymers (A) in the preparation is determined by the person skilled in the art depending on the desired application.
  • the thickness of the passivation layer depends on the process technology chosen, but also, for example, on the viscosity of the composition used for the passivation.
  • a concentration of 0.01 g / l to has proven itself 500 g / l, preferably 0.1 g / l to 200 g / l, and particularly preferably 0.5 g / l to 5 g / l.
  • the specified concentrations refer to the ready-to-use preparation. As a rule, it is possible to first produce a concentrate, which is only diluted to the desired concentration on site with water or other solvent mixtures.
  • the preparation (Z) used according to the invention is acidic. It generally has a pH of 1 to 6, with narrower pH ranges being chosen depending on the substrate and type of application and the duration of action of the preparation (Z) on the surface.
  • the pH value for the treatment of aluminum surfaces is preferably set to the range from 2 to 4 and, for the treatment of zinc or galvanized steel, preferably to the range from 2 to 5.
  • the pH of the preparation can be controlled on the one hand by the type and concentration of the polymers or copolymers containing COOH groups and is thus obtained automatically.
  • the preparation can optionally also comprise at least one inorganic or organic acid or mixtures thereof.
  • suitable acids include phosphoric, sulfuric or nitrogen-containing acids such as phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acids such as methanesulfonic acid, amidosulfonic acid, p-toluenesulfonic acid, m-nitrobenzenesulfonic acid and derivatives thereof, nitric acid, hydrofluoric acid, hydrochloric acid, boric acid, formic acid, Oxalic acid or acetic acid.
  • the acid is preferably selected from the group consisting of HNO 3 , H 2 SO 4 , H 3 P0 4 , formic acid or acetic acid. H 3 PO 4 and / or HN0 3 are particularly preferred. Mixtures of different acids can of course also be used.
  • the type and concentration of the acid in the preparation (Z) is determined by the person skilled in the art depending on the desired application and pH. In general, a concentration of 0.01 g / l to 30 g / l, preferably 0.05 g / l to 3 g / l, and particularly preferably 0.1 g / l to 5 g / l, has proven successful.
  • At least one water-soluble crosslinker is also used for the process, the crosslinker comprising at least 2 crosslinking groups selected from the group of azirane, oxirane or thiirane groups.
  • the crosslinkers used only have one type of crosslinking group, even if deviations from this rule should be possible in special cases.
  • the crosslinking agents used should preferably be completely miscible with water, even if this is not absolutely necessary in every case. However, they must at least be water-soluble to such an extent that passivation is possible using the method according to the invention.
  • the crosslinking agents used should have a solubility in water of at least 10 g / l, preferably 30 g / l and particularly preferably at least 60 g / l.
  • the number average molecular weight M n of the crosslinker is from 112 to about 50O0 j g / mol, preferably 150 to 2500 g / mol and particularly preferably 200 to 2000 g / mol.
  • the at least two crosslinking groups are connected to one another by means of a linking group X comprising at least 2 carbon atoms.
  • a linking group X comprising at least 2 carbon atoms.
  • the linking group X can be a straight-chain, branched or cyclic aliphatic, aromatic or araliphatic group, which can also have additional heteroatoms or substituents.
  • the linking group is preferably a straight-chain or branched aliphatic group in which non-adjacent carbon atoms can also be replaced by O atoms.
  • the crosslinkers comprise at least 2 crosslinking groups. There is no upper limit on the number of crosslinking groups. However, a number of 2 to 20, preferably 2 to 10 and particularly preferably 3 to 6, crosslinking groups has proven useful.
  • crosslinkers of the general formula (I) containing azirane groups have proven useful for carrying out the present invention.
  • m is a natural number ⁇ 2.
  • M is preferably a natural number from 2 to 6.
  • R 2 is H and / or a methyl group.
  • a crosslinker molecule preferably comprises only the same radicals R 2 on the crosslinking groups and particularly preferably R 2 is an H atom.
  • the radical R 1 O m - is an m-valent, aliphatic alkoxy radical.
  • the remainder has at least m O atoms, to the m residues of the general formula
  • the azirane groups are therefore each linked to the radical R 1 O m - via linking groups.
  • the aliphatic alkoxy radicals R 1 O m - can have further O atoms or other heteroatoms such as N in the radical R 1 . They are derived from the corresponding aliphatic alcohols R 1 (OH) m ', where m' ⁇ m.
  • suitable alcohols include glycol, propanediol, butahdiol, butenediol, butynediol, pentanediol, hexanediol, diglycol, triglycol, oligo- or polyethylene glycol, glycerin, polypropylene glycol, neopentyl glycol, polyglycerol, trimethylol methane, trimethylolethane, trimethylolpropane, trimethylolpropane 4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, bis (trimethylolpropane) or sugar, such as, for example, glucose or sorbitol.
  • the alcohols can also be reacted with ethylene oxide, propylene oxide or butylene oxide to give the di- or higher-functional polyetherols. Only ethoxylated products are preferably used.
  • the alcohols can also be oligomers or polymers of suitable molecular weight which comprise vinyl alcohol units, such as, for example, polyvinyl alcohol or polyvinyl alcohol copolymers.
  • Glycol, butanediol, glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol and their polyethers based on ethylene oxide are particularly suitable for carrying out this invention, and trimethylolpropane is particularly preferred.
  • an m'-alcohol of the general formula R 1 (OH) m ' with (meth) acrylic acid or a suitable (meth) acrylic acid derivative can first be used to form a (meth) acrylic acid ester be implemented. Not all of the OH groups of the alcohol need to be reacted as long as at least 2 are reacted.
  • (Meth) acrylic anhydride is particularly suitable for carrying out this reaction. The ester obtained is reacted with azirane or 2-methyl azirane in a second reaction step, the azirane being added to the double bond of the (meth) acrylic acid unit by means of a Michael addition.
  • Aziran tendency comprehensive cross-linking agent of formula (I) are also commercially available, for example as Corial ® hardener (Messrs. BASF AG)
  • at least two crosslinkers of the general formula (II) containing oxirane groups are also commercially available, for example as Corial ® hardener (Messrs. BASF AG).
  • M is preferably a natural number from 2 to 6.
  • R 1 O m - has the meaning given above.
  • Preferred residues in the crosslinkers (II) derive from glycerol, oligoglycerols, in particular di- or triglycerol, glycol or polyethylene glycols of the general
  • crosslinkers of the formula (II) To prepare the crosslinkers of the formula (II), a polyalcohol of the general formula R 1 (OH) m . be reacted with glycidyl chloride. Not all of the OH groups of the alcohol need to be reacted as long as at least 2 are reacted.
  • Various oxirane comprehensive crosslinkers of formula (II) are commercially available, for example under the trademark Denacol ® (Fa. Nagase Chemicals Ltd.).
  • the water-soluble crosslinking agents used according to the invention can be dissolved in the preparation (Z), so that the treatment of the metallic surface with the crosslinking agent and the treatment with the preparation take place simultaneously.
  • crosslinking agent in a separate step before and / or after the treatment with the preparation.
  • the latter is particularly recommended if the crosslinking agent in the selected preparation and the selected passivation conditions is not completely inert, but rather reacts with the components of the preparation. Undesired reactions are also advantageously avoided by mixing the crosslinking agent into the preparation immediately before use.
  • the ratio of the crosslinker to the polymer is determined by the person skilled in the art depending on the desired properties. As a rule, a weight ratio of polymer to crosslinking agent of 0.05: 1 to 50: 1, preferably 0.1 to 20: 1 and particularly preferably 0.5: 1 to 10: 1 has proven useful.
  • the preparation can optionally comprise further components in addition to the components mentioned.
  • the optionally available components can be, for example, transition metal ions and compounds, for example Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Ti, Zr, Hf, Bi, Cr and / or the lanthanides. If Cr is present, the quantities defined at the beginning should not be exceeded. Preferably no Cr (VI) compounds are used, particularly preferably no chromium compounds at all. It can also be connections of main group members, such as Si and / or Al. The compounds can be used, for example, in the form of the respective aqua complexes.
  • ligands such as fluoride complexes of Ti (IV), Zr (IV) or Si (IV) or oxometalates such as MoO 4 2 " or WO 2" .
  • Complexes with typical chelating ligands such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA) or methylglycinediacetic acid (MGDA) can also be used.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HEDTA hydroxyethylethylenediaminetriacetic acid
  • NTA nitrilotriacetic acid
  • MGDA methylglycinediacetic acid
  • Other optional components include surface-active compounds, corrosion inhibitors or typical electroplating aids.
  • the surface of the metal is treated with the preparation (Z) and with the crosslinking agent, for example by spraying, dipping or rolling on.
  • the workpiece can be drained to remove excess treatment solution; In the case of sheets, metal foils or the like, however, excess treatment solution can also be squeezed or doctored off, for example.
  • excess treatment solution can also be squeezed or doctored off, for example.
  • the treatment with the preparation is generally carried out at room temperature, without any higher temperatures being excluded in principle.
  • the crosslinker is preferably also dissolved in water and applied to the metal surface by, for example, spraying, rolling or dipping before and / or after treatment with the preparation without crosslinker.
  • part of the crosslinker can also be contained in the preparation, while a second part of the crosslinker is applied in a separate step.
  • the treatment can be a so-called "no-rinse" process, in which the treatment solution is dried in a drying oven immediately after application without rinsing.
  • the polymer can also be crosslinked by the crosslinking agent at room temperature r.
  • the metal surface is preferably heated after the treatment of the metal with the preparation and the crosslinker.
  • a temperature of 30 ° C. to 120 ° C., preferably 40 ° C. to 100 ° C. and particularly preferably 50 ° C. to 80 ° C. has proven useful.
  • the treatment of the metal surface with the preparation and the crosslinking agent can be carried out batchwise or preferably continuously.
  • a continuous process is particularly suitable for treating strip metals.
  • the metal strip is passed through a tub or a spray device with the preparation and optionally a tub or spray device for the crosslinker and optionally through further pre-treatment or post-treatment stations.
  • the duration of the treatment is determined by the person skilled in the art depending on the desired properties of the layer, the composition used for the treatment and the technical framework. It can be significantly less than a second or several minutes. In the continuous process, it has proven particularly useful to bring the surface into contact with the preparation for a period of 1 to 60 s.
  • treatment with the preparation and with the crosslinker in two (or three) separate process steps has the advantage that more procedural degrees of freedom are gained that can be used for special effects.
  • the preparation containing the crosslinking agent can, as a rule, at least not be heated to higher temperatures for a long time, because otherwise at least parts of the crosslinking agent prematurely and undesirably with the polymer, other constituents of the Preparation or reacting with yourself. Through such undesirable side reactions, properties of the passivation layer can deteriorate and, in the worst case, even completely useless results can be obtained. In this case, the treatment must therefore usually take place essentially at room temperature.
  • the treatment can be carried out with the crosslinking agent in a separate step, then the treatment can be carried out with the preparation at significantly higher temperatures, for example at 50 to 80 ° C without adverse reactions' of the crosslinking agent are to be feared.
  • the formation of the passivation layer can be accelerated and / or other properties of the passivation layer, such as its thickness, can be influenced.
  • the treatment with the crosslinker then takes place in a separate step, for example with a solution of the crosslinker at room temperature. It can be done afterwards, but also before treatment with the preparation.
  • the method according to the invention can optionally also comprise one or more pretreatment steps.
  • the metal surface can be cleaned with the preparation used according to the invention before passivation, e.g. to remove fats or oils. Furthermore, it can also be pickled before passivation in order to remove oxidic deposits, scale, temporary corrosion protection and the like. Furthermore, after and between such pretreatment steps, the surface may also have to be rinsed with water in order to remove the residues of rinsing solutions or pickling solutions.
  • a passivation layer on a metallic surface made of Zn, Zn alloys, Al or Al alloys can be obtained by means of the method according to the invention.
  • the composition of the passivation layer is not homogeneous, but the components seem to have concentration gradients.
  • the thickness of the passivation layer is adjusted by the person skilled in the art depending on the desired properties of the layer.
  • the thickness is 0.01 to 3 ⁇ m, preferably 0.1 to 2.5 ⁇ m, and particularly preferably 1 to 2 ⁇ m.
  • the thickness can be influenced, for example, by the type and amount of the components applied and the exposure time. Furthermore, it can be influenced by process engineering parameters, for example by doctoring or rolling off too much applied treatment solution.
  • the thickness of the layer is determined by differential weighing before and after the action of the composition used according to the invention on the metal surface, on the assumption that the layer has a specific density of 1 kg / l. In the following, the layer thickness is always determined in this way Understood in size, regardless of the specific density of the layer, these thin layers are sufficient to achieve excellent protection against corrosion, which ensures the dimensional accuracy of the passivated workpieces.
  • Another object of the present application is a metallic surface which comprises the passivation layer according to the invention.
  • the passivation layer is applied directly to the actual metal surface.
  • it is band metal made of steel, which comprises a coating made of Zn or a Zn alloy, and on which a passivation layer according to the invention is applied.
  • the metallic surface with a passivation layer can be overpainted in a manner known in principle with one or more coloring or effect-giving lacquer layers.
  • Typical lacquers, their composition and typical layer sequences in the case of several lacquer layers are known in principle to the person skilled in the art.
  • Test sheets made of galvanized steel (20 ⁇ m one-sided zinc coating) were used for the examples and comparative examples
  • Unpassivated steel sheets were immersed in a cleaning solution of 0.5% HCl and 0.1% of an alkylphenol ethoxylate with 10 ethylene oxide units for 10 s, immediately rinsed with water and then dried with nitrogen.
  • 5% aqueous solutions of the polymer used were homogenized and filled into an immersion bath.
  • the solutions also contained 0.1% by weight of HNO 3 or H PO.
  • the pre-cleaned sheets were immersed for 10 s and at Room temperature dried. Finally, the edges of the passivated sheets were taped to exclude edge effects.
  • the sheets were passivated as described below.
  • the thickness of the passivation layer was determined by differential weighing before and after action of the composition used according to the invention on the metal surface and on the assumption that the layer has a specific density of 1 kg / l.
  • layer thickness is always understood to mean a size determined in this way, regardless of the specific density of the layer.
  • the corrosion-inhibiting effect was determined using a salt spray test in accordance with DIN 50021. Depending on the type of corrosion damage observed, the service life in the corrosion test is defined differently.
  • white spots generally form more than 1 mm in diameter (Zn or Al oxide, so-called white rust)
  • the service life is specified as the time after which the damage pattern has reached rating grade 8 in DIN EN ISO 10289 from April 2001, Appendix B, page 19.
  • the service life is specified as the time after which the damage pattern corresponds to rating grade 8 in DIN EN ISO 10289 of April 2001, Appendix A, page 9.
  • the sheet After 5 minutes drying / hardening at 80 ° C, the sheet shows no changes in color and metallic shine to the original sheet.
  • the layer thickness is 1.4 ⁇ m.
  • Residence time until evaluation 8 in a 5% salt spray atmosphere at 30 ° C. is 21 h.
  • the residence time until assessment 8 in a 5% salt spray atmosphere at 30 ° C. is in each case ⁇ 2 h.
  • the total layer thickness (crosslinker + polymer together) is 2.2 ⁇ m. Residence time until assessment 8 in a 5% salt spray atmosphere at 30 ° C is 19 h.
  • the layer thickness is 1.0 ⁇ m.
  • Residence time until evaluation 8 in a 5% salt spray atmosphere at 30 ° C. is ⁇ 2 h.
  • crosslinking agents can extremely improve the corrosion resistance of zinc surfaces by chemically stabilizing the passivating polyacrylate layer using reactive crosslinking agents.
  • Highly reactive polyfunctional azirane or oxirane crosslinkers are suitable for this. Due to their reactivity, the azirane crosslinkers can be used even at room temperature and are more effective than the oxirane crosslinkers.
  • crosslinker alone has no effect, and the polymer alone has a significantly poorer effect than the combination of crosslinker and polymer.

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Abstract

L'invention concerne un procédé essentiellement exempt de chrome destiné à la passivation de surfaces métalliques en Zn, alliages de Zn, Al ou alliages d'Al, par traitement de la surface au moyen d'une préparation acide aqueuse contenant au moins un polymère ou copolymère soluble dans l'eau, essentiellement non-réticulé, comportant au moins 50 % en poids d'unités d'acide (méth)acrylique, ainsi que de l'eau ou un mélange de solvants aqueux comportant au moins 50 % en poids d'eau, et traitement supplémentaire de la surface au moyen d'au moins un agent réticulant soluble dans l'eau comportant au moins 2 groupes réticulants choisis parmi des groupes azirane, oxirane ou thiirane. L'invention concerne également des couches de passivation pouvant être obtenues au moyen du procédé selon l'invention et une préparation adaptée au procédé selon l'invention.
EP20040790483 2003-10-23 2004-10-15 Procede essentiellement exempt de chrome destine a la passivation de surfaces metalliques en zn, alliages de zn, al ou alliages d'al Not-in-force EP1678344B1 (fr)

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DE2003149728 DE10349728A1 (de) 2003-10-23 2003-10-23 Im wesentlichen Chrom-freies Verfahren zum Passivieren von metallischen Oberflächen aus Zn, Zn-Legierungen, AI oder AI-Legierungen
PCT/EP2004/011641 WO2005042801A1 (fr) 2003-10-23 2004-10-15 Procede essentiellement exempt de chrome destine a la passivation de surfaces metalliques en zn, alliages de zn, al ou alliages d'al

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ATE463592T1 (de) 2010-04-15
ES2342940T3 (es) 2010-07-19
EP1678344B1 (fr) 2010-04-07
DE502004011004D1 (de) 2010-05-20
CN100529181C (zh) 2009-08-19
US8241745B2 (en) 2012-08-14
BRPI0415542A (pt) 2006-12-26
US20070082193A1 (en) 2007-04-12
JP2007510058A (ja) 2007-04-19
CN1871374A (zh) 2006-11-29
DE10349728A1 (de) 2005-05-25
WO2005042801A1 (fr) 2005-05-12
MXPA06003938A (es) 2006-06-27
KR20070001879A (ko) 2007-01-04
CA2542090A1 (fr) 2005-05-12

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