EP1658392B1 - Couches de conversion colores sur des surfaces metalliques - Google Patents

Couches de conversion colores sur des surfaces metalliques Download PDF

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Publication number
EP1658392B1
EP1658392B1 EP04764202A EP04764202A EP1658392B1 EP 1658392 B1 EP1658392 B1 EP 1658392B1 EP 04764202 A EP04764202 A EP 04764202A EP 04764202 A EP04764202 A EP 04764202A EP 1658392 B1 EP1658392 B1 EP 1658392B1
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Prior art keywords
acid
concentration
diphosphonsäure
total
treatment solution
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German (de)
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EP1658392A1 (fr
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Ulrich JÜPTNER
Jörg BECKER
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys. It describes chromium-free conversion processes for such metal surfaces, i. H. chemical treatment processes which result in the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated.
  • the chromium-free coating is colored, so that it can be determined by simple visual inspection whether a sufficient conversion layer has been formed.
  • the object of this conversion layer is to reduce the tendency of the metal surface to corrode and to produce good adhesion between the metal surface and an organic coating such as a lacquer or an adhesive applied to the conversion layer.
  • WO 92/07973 teaches a chromium-free treatment process for aluminum containing, as essential components in acidic aqueous solution, from 0.01 to about 18% by weight of H 2 ZrF 6 and from 0.01 to about 10% by weight of a 3- (NC 1 4- alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer.
  • Optional components are 0.05-10% by weight of dispersed SiO 2 , 0.06-0.6% by weight of a solubilizer for the polymer, and surfactant.
  • Said polymer falls under the group of "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" described below and usable in the context of the present invention.
  • WO 94/28193 describes a process for the pretreatment of surfaces of aluminum or its alloys prior to a second, permanent corrosion-protective conversion treatment, wherein the surfaces in contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in admixture with one another in concentrations of the fluoro anions of in total between 100 and 4000, preferably 200 to 2000, mg / l and have a pH of between 0.3 and 3.5, preferably between 1 and 3.
  • the treatment solutions may additionally contain polymers of the polyacrylate type and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l.
  • Other potential components of the treatment baths are Polyhydroxycarboxylic acids or their anions, in particular gluconate ions, in concentrations up to 500 mg / l.
  • WO 95/04169 teaches the treatment of metal surfaces with a treatment solution containing at least the following components: fluorocomplexes of titanium, zirconium, hafnium, silicon, aluminum and boron, metal ions selected from cobalt, magnesium, manganese, zinc, nickel, tin, copper , Zirconium, iron and strontium, phosphates or phosphonates, as well as water-soluble or water-dispersible organic film formers.
  • WO 94/25640 discloses a method of producing blue colored conversion layers on zinc / aluminum alloys.
  • a treatment solution in contact which has a pH between 3.5 and 6 and which has 0.2 to 3.0 wt .-% molybdenum and a fluoride content of 0.1 to 2.0 wt .-%.
  • Molybdenum can be used as molybdate, as phosphomolybdic acid, as molybdenum chloride and the like.
  • Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoro acids such as fluorotitanic acid or fluorozirconic acid.
  • the treatment solution contains heterooxo anions of molybdenum, tungsten or vanadium with one of the heteroions. Phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel.
  • the treatment solution contains an organic film former, which can be selected for example from acrylates.
  • the heterooxo anions such as, for example, anions of heteropolyacids, can be formed directly in the treatment solution in which the starting materials for this are added, for example molybdate ions and phosphoric acid.
  • the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similar etchant.
  • WO 00/26437 The teaching of WO 00/26437 is the way to colorize the conversion layer by an organic dye (Alizerinfarbstoff).
  • the conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
  • a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
  • an amino-substituted poly-4-hydroxy-styrene polyvinylphenol
  • the metal surfaces may be surfaces of the metals mentioned or their alloys as such, but also surfaces of a substrate such as steel, which is coated with the metals or their alloys. Examples of the latter are electrolytically galvanized or hot dip galvanized steel, aluminized steel, or coated steel as Galvalume ® or Galfan ®, which carry a coating of zinc / aluminum alloys.
  • the treatment solution is free of chromium. Furthermore, it preferably also contains no other heavy metal ions than those listed as components a) and b). This reduces the demands on the treatment of wastewater.
  • the pH of the treatment solution should not be significantly lower than 1, since lower pH values lead to an increasingly stronger pickling attack on the metal surface.
  • the pH is not less than 2 and especially not less than 2.5.
  • the formation of the conversion layer is no longer to the desired extent.
  • the mentioned essential components a) to d) are all protolytes, that is to say molecules or ions which are capable of reacting with release or uptake of protons in the sense of an acid-base reaction.
  • these components will undergo such reactions with one another and with the solvent of water until the appropriate chemical equilibria are achieved.
  • pH values it is to be expected that all these protolytes are in a partially protolysed state, irrespective of whether they have been introduced into the treatment solution in the form of their acids or their salts.
  • the said pH values which are in the acid range, are introduced by introducing the hexafluorotitanate and / or hexafluorozirconic acids in the form of the free acids.
  • An additional acid to adjust the acidic pH is then not required.
  • the molybdate and / or tungsten ions are preferably used in the form of their salts, for example as sodium salts.
  • the chelating complexing agents and the copolymer of group d) can also be used in the form of free acids or in the form of ammonium or alkali metal salts. This is primarily a matter of commercial availability. Should the desired pH range not be reached automatically when the essential components are mixed with water, the pH value can be adjusted downwards by adding an acid such as nitric acid, for example, by adding an alkali such as sodium hydroxide solution.
  • the definition of the chelating complexing agent c) is to be understood as representing a different compound than the copolymer mentioned under d), although this might also have chelating properties. Rather, the chelating complexing agents c) should preferably be non-polymeric molecules.
  • the minimum concentration for component a) is preferably 30 mg / l and especially 100 mg / l, for component b) 50 mg / l, especially 100 mg / l, for component c) 5 mg / l, especially 15 mg / l and for component d) 0.2 mg / l, in particular 0.5 mg / l.
  • the mentioned preferred minimum concentrations of the individual components are independent of each other. Preferably, however, all 4 components are present at the same time in each case with the minimum concentrations mentioned.
  • Component a) is preferably present in a maximum concentration of 1000 mg / l, in particular 500 mg / l, component b) in a maximum concentration of 2000 mg / l , in particular of 1000 mg / l, the component c) in a maximum concentration of 1000 mg / l, preferably 300 mg / l and the component d) in a maximum concentration of 10 mg / l, in particular 5 mg / l.
  • a "partial ester” is understood to mean that only a part of the alcohol groups is esterified, the ester formation taking place with non-polymeric carboxylic acids.
  • the ester formation can be carried out with monobasic carboxylic acids having 1 to 4 carbon atoms.
  • the polymers or copolymers of group f) may be selected, for example, from homopolymers or copolymers of acrylic acid and / or methacrylic acid whose acid groups may be partially replaced by amide groups or esterified with alcohols, in particular with simple alcohols having 1 to 4 carbon atoms.
  • Specific examples are homopolymers or copolymers of or with methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxitriacrylate. These specific examples are known, for example, from WO 95/14117.
  • the polymers of group f) may further be selected from those containing maleic acid monomers. A specific example of this is a maleic acid-methyl vinyl ether copolymer.
  • the treatment solution contains both polymers of group e) and those of group f).
  • the polymer of group f) is a maleic acid-methyl vinyl ether copolymer.
  • Polymers of group e) generally contain free alcohol groups, those of group f) free carboxylic acid groups. Therefore, these two polymers can be used not only in admixture with each other but in a form in which ester formation has occurred at least partially between the alcohol groups of the polymer e) and the carboxylic acid groups of the polymer f). This is explained in more detail in WO 94/12570. The teaching described therein can also be used in the context of the present invention.
  • the treatment solution may contain polymers of group h).
  • polymers of group h Such polymers and their use in treatment solutions for the conversion treatment are described in more detail in DE-A-100 05 113 and DE-A-101 31 723.
  • the additional polymers can be selected from those of group i), amine-substituted polymers of 4-hydroxystyrene, which are also referred to as polymers of polyvinylphenol. Examples of this can be found in WO 00/26437 and in the literature cited therein, in particular US Pat. No. 5,281,282.
  • the additional polymers can be selected from those of group k), as described in more detail in US Pat. No. 5,356,490.
  • the chelating complexing agent c) is preferably non-polymeric and preferably selected from molecules having 2 or more phosphonic acid groups, especially from geminal diphosphonic acids, and phosphonocarboxylic acids and their respective anions. (As explained above, in the treatment solution and in the concentrate, depending on the pH, the corresponding acid-base balance will be established between the acid form and the salt form of the complexing agent, regardless of the form in which it has been introduced into the solution or concentrate .)
  • the copolymer d) is preferably selected from copolymers of vinylphosphonic acid and one or more unsaturated carboxylic acids selected from acrylic acid, methacrylic acid and maleic acid whose acid groups may be at least partially esterified with alcohols having 1 to 4 carbon atoms.
  • a specific example is a vinylphosphonic acid-acrylic acid copolymer, which is available under CAS no. 27936-88-5 is known.
  • the molecular weight is in the range of 30,000 to 90,000. This polymer is commercially available, for example, as a 20% aqueous solution having a total phosphorus content of 2.0 ⁇ 0.2% by weight.
  • the treatment solution contains an additional polymer or copolymer of group f), which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
  • an additional polymer or copolymer of group f which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
  • an additional polymer or copolymer of group f which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
  • a polymer can also be used its ester with polyvinyl alcohol, which has been described above as a polymer of group g).
  • the invention relates to a process for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys, by spraying or dipping the surfaces with an aqueous treatment solution for a period of time ranging from 2 seconds to 10 minutes one or more of claims 1 to 4 or 6 to 8 in contact, which has a temperature in the range of 10 to 70 ° C.
  • the concentration of the individual active ingredients there is a relationship between the concentration of the individual active ingredients and the time: the shorter the treatment time, the more concentrated the treatment solution is preferably chosen.
  • Treatment times at the lower end of the specified interval for example in the range of 2 to about 10 seconds, can be used in the treatment of running metal bands.
  • treatment times in the range of 0.5 to 3 minutes are preferably selected.
  • the temperature of the treatment solution is preferably adjusted to at least 20 ° C. A maximum temperature of 60 ° C is usually sufficient.
  • the treatment step according to the invention is usually part of a treatment sequence, as is usual in a conversion treatment of the metal surfaces mentioned before a subsequent coating or bonding.
  • a treatment sequence usually begins with a cleaning / degreasing of the metal surfaces, for which example an alkaline cleaner can be used.
  • This is followed by one or more rinses with water.
  • an acidic treatment step to remove superficial oxides which are not removed during alkaline cleaning.
  • This step is also referred to as "deoxidizing" or "pickling” and is used particularly on surfaces of aluminum and its alloys.
  • the treatment step according to the invention is then followed by the treatment solution according to the invention. Thereafter, it can be rinsed again with water.
  • the method can also be carried out as a "no-rinse” method, ie rinsing with water after the treatment step according to the invention can also be dispensed with.
  • a yellowish-colored, corrosion-protected metal surface is obtained which exhibits good adhesion to a subsequently applied layer based on organic polymers, for example a lacquer or an adhesive.
  • This surface usually contains 1 to 70 mg of titanium and / or zirconium per m 2 , in particular 3 to 30 mg / m 2 .
  • the molybdenum and / or tungsten coating is usually between 2 and 500 mg / m 2 .
  • the present invention also includes metal strips, metal sheets or metal parts, which - as explained in more detail above - have surfaces of zinc, aluminum, magnesium or their alloys and wear on these surfaces colored layers that were produced by the method according to the invention.
  • the metal strips, metal sheets or metal parts may be coated with a layer based on organic polymers such as a paint or an adhesive.
  • the invention also includes metal strips, metal sheets or metal parts with said surfaces which have been treated by the method according to the invention and which have subsequently been coated with a lacquer or bonded to other components.
  • these metal strips, metal sheets or metal parts may have a powder coating.
  • the inventive method thus provides metal surfaces, which have a good corrosion protection and a good paint adhesion, as the expert knows it as a result of technically very advantageous, for environmental and health reasons, however, undesirable Chromierung.
  • the person skilled in the art immediately sees whether a sufficient conversion layer has formed during the treatment, as he is accustomed to from chromating.
  • the process according to the invention therefore has the technical advantage over the production of colorless conversion layers that the result of the treatment is immediately visually recognizable without the need for special surface analysis.
  • the sheets were rinsed with demineralized water and dried and then painted with a commercial polyester paint (facade quality, white, TGIC-free). This was followed by a paint adhesion test which was customary in practice. The test panels were cross-hatched, stored for 2 hours in boiling demineralized water and then for one hour at room temperature. Then an adhesive tape was glued over the crosshatch area and pulled off again. The proportion of paint removed from the sample sheet was assessed and characterized by cross-cut notes: Gt 0: no loss of paint, Gt 5: substantial loss of paint.
  • Treatment solutions, treatment parameters and treatment results (V: comparative solutions not according to the invention, B: examples according to the invention); Concentrations in mg / l in water; Duration of treatment: 1 minute; V1 to V3 and B1 to B8: treatment by spraying, B9: treatment by dipping.
  • V1 V2 V3 B1 B2 B3 B4 B5 B6 B7 B8 B9 a) hexafluorotitanic acid 160 160 160 160 160 160 160 160 160 160 b) Sodium molybdate dihydrate 400 400 200 300 400 200 300 400 200 300 200 c) 1-Hydroxyethane-1,1-diphosphonic acid, Na salt 60 30 45 60 30 45 60 30 45 30 d) vinylphosphonic acid-acrylic acid copolymer, CAS no.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Chemical Treatment Of Metals (AREA)
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Claims (10)

  1. Solution aqueuse de traitement pour la production de couches colorées sur des surfaces en zinc, aluminium, magnésium ou leurs alliages, qui présente un pH de 1 à 6 et qui contient
    a) au total 4 à 4 000 mg/l d'ions hexafluorotitanate et/ou hexafluorozirconate,
    b) au total 10 à 4 000 mg/l d'ions molybdate et/ou tungsténate, calculé sous forme dihydratée du sel sodique,
    c) au total 1 à 2 000 mg/l d'un ou de plusieurs complexants formant un chélate,
    d) 0,04 à 40 mg/l d'un copolymère d'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés.
  2. Solution aqueuse de traitement selon la revendication 1, caractérisée en ce que
    la concentration en ions hexafluorotitanate et/ou hexafluorozirconate a) est au total d'au moins 30 mg/l, de préférence d'au moins 100 mg/l et/ou
    la concentration en ions molybdate et/ou tungsténate, calculée sous forme dihydratée du sel sodique b) est au total d'au moins 50 mg/l, de préférence d'au moins 100 mg/l et/ou
    la concentration totale en l'un ou plusieurs complexants formant un chélate c) est au total d'au moins 5 mg/l, de préférence d'au moins 15 mg/l et/ou
    la concentration en copolymère de l'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés d) est d'au moins 0,2 mg/l, de préférence d'au moins 0,5 mg/l.
  3. Solution aqueuse de traitement selon l'une ou les deux revendications 1 et 2, caractérisée en ce que
    la concentration en ions hexafluorotitanate et/ou hexafluorozirconate a) est au total d'au plus 1 000 mg/l, de préférence d'au plus 500 mg/l et/ou
    la concentration en ions molybdate et/ou tungsténate, calculée sous forme dihydratée du sel sodique b) est au total d'au plus 2 000 mg/l, de préférence d'au plus 1 000 mg/l et/ou
    la concentration totale en l'un ou plusieurs complexants formant un chélate c) est au total d'au plus 1 000 mg/l, de préférence d'au plus 300 mg/l et/ou
    la concentration en copolymère de l'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés d) est d'au plus 10 mg/l, de préférence d'au plus 5 mg/l.
  4. Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 3, caractérisée en ce qu'elle contient en outre un ou plusieurs autres polymères qui ne font pas partie du groupe d) et qui sont choisis parmi :
    e) le poly(alcool vinylique) ou des esters partiels solubles ou dispersibles dans l'eau de celui-ci en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 20 mg/l et d'au plus de 1 000 mg/l, de préférence d'au plus 500 mg/l, de préférence d'au plus 200 mg/l,
    f) les polymères ou les copolymères d'acides monocarboxyliques ou dicarboxyliques insaturés ou leurs amides, en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,
    g) les esters des polymères des groupes e) et f) en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,
    h) 0,01 à 20 g/l d'un polymère ou d'un copolymère de la vinylpyrrolidone,
    i) les polymères substitués par amine du 4-hydroxystyrène en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,
    k) les polymères du diglycidyléther du bisphénol A en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l.
  5. Concentrat aqueux destiné à préparer ou à compléter une solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4, qui contient
    b) au total 2 à 200 g/l d'ions molybdate et/ou tungsténate, calculé sous forme dihydratée du sel sodique,
    c) au total 0,5 à 200 g/l d'un ou de plusieurs complexants formant un chélate,
    d) 0,02 à 5 g/l d'un copolymère d'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés.
  6. Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou concentrat selon la revendication 5, caractérisé en ce que le complexant formant un chélate c) est choisi parmi les molécules présentant 2 groupes acide phosphonique ou plus, de préférence parmi les acides diphosphoniques géminés et les acides phosphonocarboxyliques et à chaque fois leurs anions.
  7. Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou concentrat selon la revendication 5, caractérisé en ce que le copolymère d) est choisi parmi les copolymères de l'acide vinylphosphonique et d'un ou de plusieurs acides carboxyliques insaturés choisis parmi l'acide acrylique, méthacrylique et maléique.
  8. Solution aqueuse de traitement selon la revendication 4, caractérisée en ce qu'elle contient au moins un polymère ou copolymère f) qui est choisi parmi les copolymères de l'acide maléique-méthylvinyléther et parmi les polymères ou copolymères de l'acide acrylique et/ou méthacrylique, dont les groupes carboxyle sont au moins partiellement remplacés par des groupes amide ou leurs esters avec du poly(alcool vinylique) comme polymère g).
  9. Procédé pour la production de couches colorées sur des surfaces en zinc, aluminium, magnésium ou leurs alliages, les surfaces étant mises en contact pendant un laps de temps situé dans la plage de 2 secondes à 10 minutes dans un procédé de pulvérisation ou d'immersion avec une solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou 6 à 8, qui présente une température dans la plage de 10 à 70°C.
  10. Bandes métalliques, tôles métalliques ou pièces métalliques qui présentent des surfaces en zinc, aluminium, magnésium ou leurs alliages et qui portent sur ces surfaces des couches colorées qui ont été produites par un procédé selon la revendication 9.
EP04764202A 2003-08-26 2004-08-17 Couches de conversion colores sur des surfaces metalliques Not-in-force EP1658392B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10339165A DE10339165A1 (de) 2003-08-26 2003-08-26 Farbige Konversionsschichten auf Metalloberflächen
PCT/EP2004/009212 WO2005021834A1 (fr) 2003-08-26 2004-08-17 Couches de conversion colorées sur des surfaces métalliques

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EP1658392A1 EP1658392A1 (fr) 2006-05-24
EP1658392B1 true EP1658392B1 (fr) 2007-03-14

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US (1) US8293029B2 (fr)
EP (1) EP1658392B1 (fr)
AT (1) ATE356895T1 (fr)
DE (2) DE10339165A1 (fr)
WO (1) WO2005021834A1 (fr)

Cited By (1)

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US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates

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DE102004022565A1 (de) * 2004-05-07 2005-12-22 Henkel Kgaa Farbige Konversionsschichten auf Metalloberflächen
US20070264511A1 (en) * 2006-05-09 2007-11-15 Roberto Ponzellini Method and composition for forming a coloured coating on a metallic surface
US20090242081A1 (en) * 2008-03-26 2009-10-01 Richard Bauer Aluminum Treatment Composition
SG11201501406SA (en) 2012-08-29 2015-03-30 Ppg Ind Ohio Inc Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
DE102012017438A1 (de) 2012-09-04 2014-03-06 Carl Freudenberg Kg Behandlungslösung und Verfahren zur Beschichtung von Metalloberflächen
DE102014220976A1 (de) * 2013-10-17 2015-04-23 Chemetall Gmbh Verfahren zur Vorbereitung von metallischen Formkörpern für die Kaltumformung
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WO2005021834A1 (fr) 2005-03-10
US20060173099A1 (en) 2006-08-03
ATE356895T1 (de) 2007-04-15
US8293029B2 (en) 2012-10-23
EP1658392A1 (fr) 2006-05-24
DE10339165A1 (de) 2005-03-24
DE502004003236D1 (de) 2007-04-26

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