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EP1678344B1 - 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 Download PDF

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Publication number
EP1678344B1
EP1678344B1 EP20040790483 EP04790483A EP1678344B1 EP 1678344 B1 EP1678344 B1 EP 1678344B1 EP 20040790483 EP20040790483 EP 20040790483 EP 04790483 A EP04790483 A EP 04790483A EP 1678344 B1 EP1678344 B1 EP 1678344B1
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EP
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Prior art keywords
crosslinker
water
process according
alloys
weight
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EP20040790483
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German (de)
English (en)
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EP1678344A1 (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

    • 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
    • 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
    • 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 invention further relates to a passivation layer on a metallic surface of Zn, Zn alloys, Al or Al alloys obtainable by the process, metallic surfaces comprising such a passivation layer and a preparation for passivation.
  • maleic anhydride units are hydrolyzed directly at the beginning, in parallel or following the polymerization to maleic acid units, preferably with a base such as triethanolamine.
  • the type and concentration of the acid in the preparation (Z) is determined by the skilled person according to 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 more preferably 0.1 g / l to 5 g / l has proven.
  • the number average molecular weight M n of the crosslinker is from 112 to about 5000 g / mol, preferably from 150 to 2500 g / mol and more preferably from 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 C atoms.
  • a linking group X comprising at least 2 C atoms.
  • oxirane and thirane groups it is naturally possible to link only in the 2 or 3 position of the three-membered ring.
  • azirane groups the 1-position is also an option. This is also the preferred position.
  • Oxirane or azirane crosslinkers are preferred.
  • the linking group X may be a straight-chain, branched or cyclic aliphatic, aromatic or araliphatic group, which may also have additional heteroatoms or substituents.
  • the linking group is preferably a straight-chain or branched aliphatic group in which non-adjacent carbon atoms may also be replaced by O atoms.
  • m is a natural number from 2 to 6.
  • R 2 is H and / or a methyl group.
  • a cross-linker molecule comprises only the same radicals R 2 in the crosslinking groups, and most preferably, R 2 is a hydrogen atom.
  • the radical R 1 O m - is an m-valent, aliphatic alkoxy radical.
  • the remainder has at least m O atoms to which m radicals of the general formula (Ia) are connected.
  • the azirane groups are thus linked via linking groups with the radical R 1 O m -.
  • the aliphatic alkoxy radicals R 1 O m - may have further O atoms or other heteroatoms such as, for example, N in the radical R 1 . They are derived from the corresponding aliphatic alcohols R 1 (OH) m , where m ' ⁇ m.
  • the alcohols can also be reacted with ethylene oxide, propylene oxide or butylene oxide to di- or higher functional polyetherols. Preferably, only ethoxylated products are used.
  • the alcohols can also be oligomers or polymers of suitable molecular weight which comprise vinyl alcohol units, for example polyvinyl alcohol or polyvinyl alcohol copolymers.
  • Preferred for carrying out this invention are glycol, butanediol, glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, and their polyetherols based on ethylene oxide, particularly preferred is trimethylolpropane.
  • crosslinkers of the general formula (I) it is possible first to react an m'-valent alcohol of the general formula R 1 (OH) m 'with (meth) acrylic acid or a suitable (meth) acrylic acid derivative to give a (meth) acrylic acid ester. Not all OH groups of the alcohol have to be reacted as long as at least 2 are reacted.
  • (meth) acrylic acid anhydride is suitable for carrying out this reaction.
  • the resulting ester is reacted in a second reaction step with azirane or 2-methylazirane, wherein the azirane is added by means of a Michael addition to the double bond of the (meth) acrylic acid unit.
  • R 1 O m - has the meaning given above.
  • Preferred radicals in the crosslinkers (II) are derived from glycerol, oligoglycerols, in particular di- or triglycerol, glycol or polyethylene glycols of the general formula HO- (CH 2 -CH 2 -O) n -H, where n is preferably from 2 to 25 stands.
  • crosslinkers of the formula (II) a polyhydric alcohol of the general formula R 1 (OH) m ' can be reacted with glycidyl chloride. Not all OH groups of the alcohol have to be reacted as long as at least 2 are reacted.
  • Crosslinkers of the formula (II) comprising various oxirane groups are commercially available, for example under the trade name Denacol® (Nagase Chemicals Ltd.).
  • the water-soluble crosslinkers used according to the invention can be dissolved in the preparation (Z) so that the treatment of the metallic surface with the crosslinker and the treatment with the preparation take place simultaneously.
  • crosslinker it is also possible to treat the surface with the crosslinker in a separate step before and / or after the treatment with the preparation.
  • the latter is particularly recommendable if the crosslinker is not completely inert in the chosen preparation and the selected passivation conditions, but reacts with the components of the preparation. Adverse reactions are also advantageously avoided by mixing the crosslinker only immediately before use in the preparation.
  • the ratio of the crosslinker to the polymer is determined by the person skilled in the art according to the desired properties. As a rule, a weight ratio of polymer to crosslinker 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 may optionally further comprise other components via said components.
  • the optionally present components may 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 act. If Cr is present, the quantities defined above should not be exceeded.
  • no Cr (VI) compounds are used, more preferably no chromium compounds at all. They may also be compounds of main group elements, such as Si and / or Al. The compounds can be used for example in the form of the respective aqua complexes.
  • ligands such as, for example, fluoride complexes of Ti (IV), Zr (IV) or Si (IV) or oxometalates such as MoO 4 2- or WO 4 2- .
  • complexes with typical chelating ligands such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA) or methylglycinediacetic acid (MGDA).
  • 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 crosslinker, for example by spraying, dipping or rolling. After a dipping process, you can drain the workpiece to remove excess treatment solution; in the case of metal sheets, metal foils or the like, however, excess treatment solution can also be squeezed off or doctored off, for example.
  • the treatment at least parts of the polymer used as well as other components of the preparation are chemisorbed by the surface of the metal, so that a firm bond between the surface and the component comes about. Treatment with the preparation is usually carried out at room temperature without that higher temperatures should be excluded in principle.
  • the crosslinking of the polymer by the crosslinker can also be carried out at room temperature.
  • the metal surface is heated after the treatment of the metal with the preparation and the crosslinker.
  • the treatment of the metal surface with the preparation and the crosslinker may be carried out batchwise or preferably continuously.
  • a continuous process is particularly suitable for treating strip metals.
  • the metal strip is driven by a pan or a spray device with the preparation and optionally a pan or spray device for the crosslinker and optionally by other pre- or post-treatment stations.
  • the duration of treatment will be determined by the skilled person according to the desired properties of the layer, the composition used for the treatment and the technical conditions. It can be significantly less than a second or several minutes. In the continuous process, it has proven particularly useful to contact the surface with the preparation for a period of 1 to 60 seconds.
  • crosslinker is added to the preparation or the metal surface treated with the crosslinker in a separate step is decided by the skilled person depending on the desired result and the conditions.
  • the use of a preparation which already contains the crosslinker is easier and cheaper to carry out, because a separate second process step is not required.
  • the treatment with the preparation and with the crosslinker in two (or three) separate process steps has the advantage that it provides more process-technological degrees of freedom that can be used for special effects.
  • the preparation containing the crosslinker can not be heated to elevated temperatures for a relatively long time, since otherwise at least parts of the crosslinker are prematurely and undesirably mixed with the polymer, other constituents of the polymer Preparation or react with yourself. Such unwanted side reactions may degrade passivation layer properties and, in the worst case, even completely unusable results.
  • the treatment in this case must therefore usually take place essentially at room temperature.
  • the treatment with the crosslinker can be carried out at significantly higher temperatures, for example at 50 to 80 ° C., without fear of undesired reactions of the crosslinker.
  • the formation of the passivation layer can be accelerated and / or other properties of the passivation layer, such as, for example, its thickness, can be influenced.
  • the treatment with the crosslinker is then carried out in a separate step, for example with a solution of the crosslinker at room temperature. It can be done afterwards, but also before the treatment with the preparation.
  • the process according to the invention may optionally also comprise one or more pretreatment steps.
  • the metallic surface can be cleaned prior to passivation with the preparation used according to the invention, e.g. to remove fats or oils.
  • it can also be pickled prior to passivation to remove oxide scale, scale, temporary corrosion protection and the like.
  • the surface must also be optionally rinsed with water after and between such pretreatment steps in order to remove the residues of rinsing solutions or pickling solutions.
  • the thickness of the passivation layer is adjusted by the person skilled in the art according to 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 applied components as well as the exposure time. Furthermore, it can be influenced by process parameters, for example by doctoring or rolling to over-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, assuming 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 which specific density the layer actually has.
  • a further subject 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.
  • strip metal is made of steel, which comprises a coating of Zn or a Zn alloy, and on which a passivation layer according to the invention is applied.
  • the metallic surface with passivation layer can be overcoated in a manner known in principle with one or more color or effect paint layers.
  • Typical lacquers, their composition and typical layer sequences in the case of several lacquer coats are known in principle to the person skilled in the art.
  • test plates made of galvanized steel (20 microns one-sided zinc coating) were used
  • aqueous solutions of the polymer used in each case were homogenized and filled in a dipping bath.
  • the solutions also contained 0.1% by weight of HNO 3 or H 3 PO 4 .
  • the pre-cleaned sheets were immersed for 10 seconds and at Room temperature dried. Finally, the edges of the passivated sheets were taped to eliminate edge effects.
  • the sheets were passivated as described below.
  • the thickness of the passivation layer was determined by differential weighing before and after exposure of the composition used according to the invention to the metal surface and assuming that the layer has a specific gravity of 1 kg / l.
  • layer thickness is always understood to mean a size determined in this way, regardless of which specific density the layer actually has.
  • the layer thickness is 0.6 ⁇ m.
  • the residence time until assessment 8 in a 5% salt spray atmosphere at 30 ° C. is ⁇ 2 h in each case.
  • the total layer thickness (crosslinker + polymer together) is 2.2 ⁇ m.
  • Dwell time up to grade 8 in a 5% salt spray atmosphere at 30 ° C is 19 hours.
  • the layer thickness is 1.0 ⁇ m.
  • crosslinkers can greatly improve the corrosion resistance of zinc surfaces by chemically stabilizing the passivating polyacrylate layer by reactive crosslinkers.
  • highly reactive polyfunctional azirane or Oxiranvernetzer are suitable. Due to their reactivity, the azirane crosslinkers can be used at room temperature and are stronger in their action than the oxirane crosslinkers.
  • crosslinker alone gives no effect, and the polymer alone shows a significantly worse effect than the combination of crosslinker and polymer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Laminated Bodies (AREA)

Claims (24)

  1. Procédé pratiquement exempt de chrome pour la passivation de surfaces métalliques à base de Zn, d'alliages de Zn, d'Al ou d'alliages d'Al, par traitement de la surface par une préparation aqueuse acide d'un polymère qui comprend des groupes COOH et/ou leurs sels, caractérisé en ce que la préparation (Z) utilisée pour le traitement comprend au moins
    (a) au moins un polymère ou copolymère (A) hydrosoluble, pratiquement non réticulé, qui comprend au moins 50 % en poids de motifs acide (méth)acrylique, ainsi que
    (b) de l'eau ou un mélange aqueux de solvants (B) contenant au moins 50 % en poids d'eau,
    et on traite en outre la surface par au moins un agent de réticulation hydrosoluble, l'agent de réticulation comprenant au moins 2 groupes réticulables, choisis dans l'ensemble des groupes azirane, oxiranne ou thiiranne, qui sont liés entre eux par au moins un groupe de liaison (X) comprenant au moins 2 atomes de carbone, la masse moléculaire moyenne en nombre Mn de l'agent de réticulation valant de 112 à 5 000 g/mole, la solubilité de l'agent de réticulation dans l'eau étant d'au moins 10 g/l, et on effectue le traitement par l'agent de réticulation avant, après ou en même temps que le traitement par la préparation (Z).
  2. Procédé selon la revendication 1, caractérisé en ce qu'on effectue simultanément le traitement par l'agent de réticulation et le traitement par la préparation (Z) et l'agent de réticulation est contenu dans la préparation (Z).
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que (2) comprend encore en plus un acide organique ou inorganique.
  4. Procédé selon la revendication 3, caractérisé en ce que l'acide consiste en H3PO4 et/ou HNO3.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'agent de réticulation consiste en un agent de réticulation comportant au moins deux groupes azirane, de formule générale (I)
    Figure imgb0012
     dans laquelle m représente un nombre entier naturel ≥ 2, R1Om- représente un radical alcoxy aliphatique m-valent et R2 représente H ou le groupe méthyle.
  6. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'agent de réticulation consiste en un agent de réticulation comportant au moins deux groupes oxiranne, de formule générale (II)
    Figure imgb0013
     dans laquelle m représente un nombre entier naturel ≥ 2 et R1Om- représente un radical alcoxy aliphatique m-valent.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce que m représente un nombre entier naturel allant de 2 à 6.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polymère (P) hydrosoluble est constitué d'acide (méth)acrylique.
  9. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polymère (P) hydrosoluble consiste en un copolymère qui, outre des motifs acide (méth)acrylique, comprend encore au moins un comonomère différent de l'acide (méth)acrylique, comportant des groupes acides.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le rapport pondéral du polymère à l'agent de réticulation va de 0,5:1 à 50:1.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le solvant est l'eau.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'après le traitement on chauffe ensuite la surface métallique.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le traitement s'effectue par des procédés de laminage, de pulvérisation ou de trempage.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la surface métallique consiste en la surface d'un métal en ruban.
  15. Procédé selon la revendication 14, caractérisé en ce que le métal en ruban est constitué d'acier zingué à chaud ou zingué par électrolyse.
  16. Procédé selon la revendication 14 ou 15,
    caractérisé en ce qu'on effectue le traitement au moyen d'un procédé continu.
  17. Procédé selon l'une quelconque des revendications 14 à 16, caractérisé en ce que la surface est mise en contact avec la préparation pendant une durée de 1 à 60 secondes.
  18. Couche de passivation sur une surface métallique à base de Zn, d'alliages de Zn, d'Al ou d'alliages d'Al, pouvant être obtenue par un procédé selon l'une quelconque des revendications 1 à 17.
  19. Couche de passivation selon la revendication 18, caractérisée en ce que son épaisseur vaut de 0,01 à 3 µm.
  20. Surface métallique comprenant une couche de passivation selon la revendication 18 ou 19.
  21. Surface métallique selon la revendication 20,
    caractérisée en ce que sur la couche de passivation encore une ou plusieurs couches de peinture se trouvent appliquées les unes sur les autres.
  22. Métal en ruban à base d'acier, comprenant un revêtement à base de Zn ou d'un alliage de Zn, qui comporte une surface selon la revendication 20 ou 21.
  23. Préparation acide, pratiquement exempte de chrome, pour la passivation de surfaces métalliques à base de Zn, d'alliages de Zn, d'Al ou d'alliages d'Al, comprenant au moins
    (a) au moins un polymère ou copolymère (A) hydrosoluble, pratiquement non réticulé, qui comprend au moins 50 % en poids de motifs acide (méth)acrylique,
    (b) de l'eau ou un mélange aqueux de solvants (B) contenant au moins 50 % en poids d'eau, ainsi que
    (c) au moins un agent de réticulation hydrosoluble de formule générale
    Figure imgb0014
    ou
    Figure imgb0015
     m représentant un nombre entier valant de 2 à 6 et R1Om- représentant un radical alcoxy aliphatique m-valent et R2 représente H ou le groupe méthyle et la masse moléculaire moyenne en nombre Mn de l'agent de réticulation valant de 112 à 5 000 g/mole, et la solubilité de l'agent de réticulation dans l'eau étant d'au moins 10 g/l.
  24. Préparation selon la revendication 23, caractérisée en ce que la préparation contient en outre H3PO4 et/ou HNO3.
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 Expired - Lifetime EP1678344B1 (fr)

Applications Claiming Priority (2)

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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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EP1678344B1 true EP1678344B1 (fr) 2010-04-07

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AT (1) ATE463592T1 (fr)
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CA (1) CA2542090A1 (fr)
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EP1678344A1 (fr) 2006-07-12
DE502004011004D1 (de) 2010-05-20
BRPI0415542A (pt) 2006-12-26
US8241745B2 (en) 2012-08-14
WO2005042801A1 (fr) 2005-05-12
JP2007510058A (ja) 2007-04-19
ATE463592T1 (de) 2010-04-15
CN1871374A (zh) 2006-11-29
US20070082193A1 (en) 2007-04-12
KR20070001879A (ko) 2007-01-04
CA2542090A1 (fr) 2005-05-12
CN100529181C (zh) 2009-08-19
ES2342940T3 (es) 2010-07-19
MXPA06003938A (es) 2006-06-27

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