EP1863952A2 - Composition et procede de preparation de revetements de protection sur des substrats metalliques - Google Patents

Composition et procede de preparation de revetements de protection sur des substrats metalliques

Info

Publication number
EP1863952A2
EP1863952A2 EP05851727A EP05851727A EP1863952A2 EP 1863952 A2 EP1863952 A2 EP 1863952A2 EP 05851727 A EP05851727 A EP 05851727A EP 05851727 A EP05851727 A EP 05851727A EP 1863952 A2 EP1863952 A2 EP 1863952A2
Authority
EP
European Patent Office
Prior art keywords
compound
carboxylic
composition
grams
inhibitor
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
EP05851727A
Other languages
German (de)
English (en)
Other versions
EP1863952B1 (fr
EP1863952A4 (fr
Inventor
Craig A. Matzdorf
William C. Nickerson, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Department of Navy
Original Assignee
US Department of Navy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/058,715 external-priority patent/US20100032060A1/en
Priority claimed from US11/076,106 external-priority patent/US20060180247A1/en
Priority claimed from US11/116,165 external-priority patent/US7811391B2/en
Priority claimed from US11/116,166 external-priority patent/US20060240191A1/en
Application filed by US Department of Navy filed Critical US Department of Navy
Publication of EP1863952A2 publication Critical patent/EP1863952A2/fr
Publication of EP1863952A4 publication Critical patent/EP1863952A4/fr
Application granted granted Critical
Publication of EP1863952B1 publication Critical patent/EP1863952B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—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 characterised by the process
    • C23C22/77—Controlling or regulating of the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • This invention relates to compositions and to a process for using said compositions for preparing protective coatings on various metal substrates.
  • the process comprises treating the metal substrates with effective amounts of an acidic aqueous solution containing at least one trivalent chromium compound, at least one fluorozirconate, at least one carboxylic compound and/or polyhydroxy compound, at least one corrosion inhibitor, and optionally effective amounts of fluorometallic compounds such as fluorotitanates, fluorotantalates, fluoroborates, fluorosilicates, divalent zinc compounds, surfactants, wetting agents and/or thickeners.
  • fluorometallic compounds such as fluorotitanates, fluorotantalates, fluoroborates, fluorosilicates, divalent zinc compounds, surfactants, wetting agents and/or thickeners.
  • this invention relates to stable acidic aqueous solutions and the process for treating various metal substrates including pre-coated metal substrates such as anodized aluminum to improve the metal substrates adhesion bonding and corrosion-resistant properties.
  • the process comprises treating the metal substrates with a stable acidic aqueous solution containing effective amounts of at least one water-soluble trivalent chromium salt, at least one water soluble hexafluorozirconate, at least one water soluble poly or mono-carboxylic compound and/or polyhydroxy compound, and at least one water soluble anti-pitting or corrosion inhibitor.
  • compounds that can be added to improve the color and stability of the acidic solutions in small but effective amounts include at least one water soluble hexa or tetra-fluorometallic compounds, divalent zinc salts, and effective amounts of water soluble thickeners and/or water soluble surfactants.
  • This invention comprises a range of aqueous solutions or compositions of specific chemicals and to the processes for depositing coatings derived from these chemicals onto a variety of metallic substrates including pre-existing metal coated substrates.
  • the compositions or solutions are particularly useful for coating aluminum and aluminum alloy i.e.
  • aluminum conversion coatings to enhance corrosion protection and paint adhesion for sealing anodic coatings to enhance corrosion protection; for treatment of titanium or titanium alloys for enhanced paint adhesion; for treatment of magnesium alloys for enhanced paint adhesion and corrosion protection; for coating steel for enhanced paint adhesion and rust inhibition; and for post-treatment of phosphate coatings, zinc, zinc-nickel, tin-zinc, and cadmium sacrificial coatings on iron alloys and other metal substrates e.g. steel for enhanced paint adhesion and corrosion protection.
  • Hexavalent chromium is highly toxic and a known carcinogen. As a result, the solutions used to deposit these coatings and the coatings per se are toxic.
  • the hexavalent chromium films or coatings do, however, yield outstanding paint adhesion, good corrosion resistance, low electrical resistance and can be easily applied by immersion, spray or wipe-on techniques.
  • OSH local occupational, safety, and health
  • hexavalent chromium coatings are becoming more expensive as regulations tighten and costs become prohibitive with future PEL restrictions imposed by the EPA and OSHA.
  • certain processes like spraying chromate solutions are forbidden at some facilities due to OSH risk, forcing the use of less than optimum alternative solutions.
  • hexavalent chromate coatings are technically outstanding, but from a life-cycle cost, environmental, and OSH perspective, alternatives are highly desirable. Accordingly, research is underway to develop alternative processes for metal finishing that are technically equivalent or superior to hexavalent chromate coatings without the environmental and health drawbacks. Many of these alternatives, regardless of composition and methods of application, have a tendency to precipitate solid material from solution especially after heavy usage.
  • This precipitation can, over time, weaken the effectiveness of the coating solution as the active compounds precipitate as insoluble solids. Additionally, the solid precipitations have the potential to clog filters, lines, and pumps for both the immersion and spray applications. Therefore, better compositions are needed to stabilize the acidic solutions for storage and process applications that will not interfere with the deposition process or the subsequent performance of the deposited coating.
  • This invention relates to compositions and processes for preparing corrosion- resistant coatings on various metallic substrates including pre-coated metal substrates such as phosphate coatings or anodized coatings which comprises treating the metal substrates with an acidic aqueous solution comprising trivalent chromium HI compounds, fluorozirconates, corrosion or pitting inhibitors, e.g. triazoles, and stabilizing compounds.
  • an acidic aqueous solution comprising trivalent chromium HI compounds, fluorozirconates, corrosion or pitting inhibitors, e.g. triazoles, and stabilizing compounds.
  • one or more fluorometallic compounds, surfactants, thickeners, and divalent zinc compounds can be added to the acidic solutions.
  • This invention can be utilized to improve the adhesion of various other coatings such as paint to the metal surface and to prevent pitting and corrosion of the metal surface such as aluminum, steel, galvanized surfaces and the like.
  • the acidic solutions of this invention also contains effective amounts of at least one water-soluble, corrosion-inhibiting or anti- pitting compound together with stabilizing agents consisting of polyhydroxy compounds and/or water-soluble carboxylic compounds containing one or more carboxylic functional groups having the general formula R-COO- wherein R is hydrogen or a lower molecular weight organic radical or functional group.
  • the solution stabilizers i.e. the carboxylic compounds can be used in the form of their acids or salts, hi some cases the salts of the carboxylic stabilizers perform better than their acids.
  • organic acids such as formic, acetic, glycolic, propionic, citric and other short-chain or low molecular weight carboxylic acids that naturally buffer in the mildly acidic pH range can be utilized as the solution stabilizers.
  • the advantage of adding the polyhydroxy or carboxylic stabilizers to the acidic solution is the improved shelf-life and working stability of the solutions.
  • the acidic solutions with the addition of the stabilizing agents had substantially no precipitation after more than twenty-four months of shelf-life evaluation and without any degradation of the as-deposited coating performance.
  • Fig's 1-6 show the improved performance of an aluminum alloy coated with the triazole-containing solutions of this invention in comparison to the same coatings without the corrosion-inhibiting triazoles. It is therefore an object of this invention to provide a stable acidic aqueous solution comprising trivalent chromium compounds, fluorozirconates, polyhydroxy compounds or carboxylic compounds and an effective amount of an inhibitor for coating metal substrates including pre-coated substrates to improve the adhesion and corrosion- resistance properties of the metal.
  • Fig. 1 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a conversion coating derived from the composition of Example 1 without the triazole inhibitor.
  • Fig. 2 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a conversion coating derived from the composition of Example 1 with the benzotriazole inhibitor.
  • Fig. 3 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a conversion coating derived from the composition of Example 2 without the triazole inhibitor.
  • Fig. 4 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a conversion coating derived from the composition of Example 2 with the benzotriazole inhibitor.
  • Fig. 5 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a conversion coating derived from the composition of Example 3 without the triazole inhibitor.
  • Fig 6 shows the corrosion performance of the aluminum alloy (2024-T3) panel with a coating derived from the composition of Example 3 with the benzotriazole inhibitor.
  • This invention relates to stable acidic aqueous solutions and to the process of using said aqueous solutions having a pH ranging from about 1.0 to 5.5, and preferably from about 2.5 to 4.5 or 3.4 to 4.0 for preparing zirconium-chromium coatings e.g. a conversion coating on metal substrates including, for example, pre-coated substrates such aass anodized aluminum or phosphate coated substrates to improve the adhesion bonding and corrosion-resistance properties of the metal.
  • Phosphate coatings known in the art include, for example, coatings of zinc phosphate, iron phosphate, manganese phosphates and mixed calcium-zinc phosphate coatings.
  • the process comprises using the acidic aqueous solution at temperatures ranging up to about 120 0 F or higher e.g. up to about 200 0 F.
  • the solutions comprise from about 0.01 to 100 grams and preferably from about 0.01 to 22 or 5.0 to 7.0 grams per liter of the acidic solution of at least one water soluble trivalent chromium compound e.g. chromium sulfate, about 0.01 to 24 grams and preferably about 1.0 to 12 or 1.0 to 6.0 grams per liter of the solution of at least one fluorozirconate e.g.
  • an effective amount sufficient to inhibit corrosion ranging, for example, from about 0.001 to 4.0 grams per liter and preferably about 0.25 to 2.0 grams or 0.25 to 1.0 gram per liter of a water-soluble corrosion inhibitor or anti-pitting compound such as benzotriazole, and from about 0.001 to 2.0 grams and preferably from 0.001 to 1.0 or 0.01 to 1.0 mole per liter of the solution of at least one water-soluble stabilizing agent or compound selected from the group consisting of carboxylic compounds, polyhydroxy compounds and mixtures of these stabilizing compounds in any ratio. If needed, each of the compounds of this invention can be used up to their solubility limits in the acidic aqueous solutions depending on the metal surface being treated.
  • the metal surfaces treated in accordance with the present invention may be any metal substrate including, for example, iron, zinc, magnesium, steel surfaces including galvanized steel, aluminum and aluminum alloys. Any metal surface, including metal surfaces containing a protective or pre-existing metal coating may be treated with the compositions of the present invention.
  • the coatings are applied after cleaning and deoxidizing or pickling the metal substrate e.g. aluminum substrate via conventional mechanical or chemical techniques.
  • the acidic solution of this invention is applied at about room temperature to the metal substrate via immersion, spray or wipe-on techniques similar to the process used for other metal treatments. Solution dwell time ranges from about 1.0 to 60 minutes or longer. With this solution, the 1.0 to 40 or 1.0 to 10 minute dwell time yields an optimum film for color change, paint adhesion, and corrosion resistance.
  • the 1.0 to 10 minute dwell time yields appreciable color change to the coating depending primarily on the chemical composition of the aqueous solution.
  • the remaining solution is subsequently rinsed from the metal substrate with tap or deionized water.
  • the addition of a thickener to the solution aids in optimum film formation during spray and wipe-on applications by slowing down solution evaporation. This mitigates the formation of powdery deposits that degrade paint adhesion.
  • the addition of thickeners also aids in proper film formation during large area applications and mitigates the diluent effect of rinse water that remains on the substrate during processing from previous steps.
  • Water-soluble thickeners such as the cellulose compounds can be present in the acidic aqueous solution in amounts ranging from about 0.0 to 20 grams per liter and preferably 0.5 to 10 grams e.g., about 0.1 to 5.0 grams per liter of the aqueous solution.
  • an effective but small amount of at least one water-soluble surfactant or wetting agent can be added to the acidic solution in amounts ranging from about 0.0 to 20 grams and preferably from 0.5 to 10 grams e.g. 0.1 to 5.0 grams per liter of the acidic solution.
  • the surfactants can be selected from the group consisting of non-ionic, cationic and anionic surfactants.
  • the trivalent chromium is added to the solution as a water-soluble trivalent chromium compound, either as a liquid or solid and preferably as a trivalent chromium salt.
  • the chromium salt can be added conveniently to the solution in its water soluble form wherein the valence of the chromium is plus 3.
  • some of the preferred chromium compounds are incorporated in the solution in the form OfCr 2 (SO ⁇ , (NH 4 )Cr(SO 4 ) ⁇ Cr(NO) 3 -9H 2 O or KCr(SO 4 ) 2 and any mixtures of these compounds.
  • a preferred trivalent chromium salt concentration is within the range of about 5.0 to 7.0 grams per liter of the aqueous solution. It has been found that particularly good results are obtained from these processes when the trivalent chromium compound is present in solution in the preferred ranges.
  • the acidic solutions may contain at least one divalent zinc compound to provide color and also improve the corrosion protection of the metal when compared to other treatments or compositions that do not contain zinc.
  • the amount of the zinc compounds can be varied up to the solubility limits to adjust the color imparted to the coating, ranging from 0.0 to 100 grams to as little as about 0.001 grams per liter up to 10 grams per liter e.g. 0.5 to 2.0 grams of Zinc 2 +cation.
  • the divalent zinc can be supplied by any chemical compound e.g. salt that dissolves in water at the required concentration and is compatible with the other components in the acid solution.
  • Divalent zinc compounds that are water soluble at the required concentrations preferably include, for example, zinc acetate, zinc telluride, zinc tetrafluoroborate, zinc molybdate, zinc hexafluorosilicate, zinc sulfate and the like or any combination thereof in any ratio.
  • the treatment or coating of the metal substrates can be carried out at various temperatures including temperatures of the solution which ranges from ambient e.g. from about room temperature up to about 120 0 F or higher up to about 200 0 F. Room temperature is preferred, however, in that this eliminates the necessity for heating equipment.
  • the coating may be air dried by any of the methods known in the art including, for example, oven drying, forced-air drying, exposure to infra-red lamps, and the like.
  • compositions of Examples 1,2 and 3 were used to coat the aluminum alloy
  • the process comprises cleaning 3 inch by 5 inch by 0.030 inch (2024-T3) panels in Turco 425 at 140 0 F for 15 minutes. Rinse in warm tap water using cascading double backflow. Immediately, immerse coupons in Turco Smut Go for 5 minutes. Rinse in ambient temperature tap water using cascading double backflow. Immediately, immerse the panels in the compositions of Examples 1, 2 and 3 for five (5) minutes at 70-80°F. Rinse in ambient temperature tap water using cascading double backflow. Final rinse with deionized water. Let the panels air dry and stand overnight. Coatings are ready for testing or subsequent coating with an organic finish coating e.g. (MIL-PRF-23377) epoxy primer.
  • an organic finish coating e.g. (MIL-PRF-23377) epoxy primer.
  • Test panels were cleaned and coated by the process set forth in Example 7 then placed in neutral salt fog (ASTM B 117) at an incline of 6 degrees from vertical. After 3 weeks (21 days) in salt fog, the coating performance is shown in Figures 1-6. Control coatings were made from the compositions of Examples 1,2 and 3 without the addition of the triazole pitting inhibitors. It is evident from comparing Figures 1-6 (photos) that the addition of the pitting inhibitors resulted in a positive effect on the corrosion resistance of the coatings made from the different compositions.
  • the anti-pitting or corrosion inhibitors are water-soluble compounds selected from the group consisting of triazoles, benzimidazoles, benzazoles, benzoxazoles and mixtures of these inhibitors in any ratio.
  • the preferred corrosion inhibitors or anti-pitting compounds include the triazoles containing up to 12 carbon atoms, such as the alkyl and preferably the aryl triazoles.
  • the aryl triazoles contain from 6-10 carbon atoms, including compounds such as benzotriazole and tolyltriazole, and the alkyl triazoles containing up to six carbons such as methyl or ethyl triazole.
  • the triazoles such as benzotriazole are commercially available under the trade name COBRATEC.
  • the anti- pitting inhibitors are dissolved in the solutions in an effective amount sufficient to inhibit corrosion, and preferably in amounts ranging from about 0.001 to 4.0 grams per liter, and more preferably in amounts of 0.25 to 2.0 grams or from about 0.25 to 1.0 grams per liter.
  • Other useful triazoles include the water soluble hydroxybenzotriazole, such as hydroxy-4- alkylbenzotriazoles, hydroxy-6-benzotriazole, hydroxy-5-chlorobenzotriazole, hydroxy-6- carboxybenzotriazole, hydroxy-5-aIkylbenzotriazoles and the like.
  • the stabilizing carboxylic compounds added to the acidic aqueous solutions include water-soluble acids and/or carboxylic acid salts, including the water-soluble carboxylic acids and salts such as adipic, citric, acetic, citraconic, fumaric, glutaric, tartaric acids, or ethylenediamine tetraacetic acid provided the hydrocarbon chain on the carboxylic group does not contain a significant number of carbons which decrease the compounds degree of solubility. Combinations of two or more of the salts and/or acids can be used to obtain a specific pH.
  • the lower molecular acids and/or salts such as potassium formate or citrate can be used at concentrations of at least 0.001 to 2.0 moles or 0.001 to 1.0 mole per liter.
  • These compounds are good all-around stabilizers. Particularly good results were obtained from acidic solutions prepared by adding about 0.01 mole per liter of potassium formate after 4 days of the initial solution preparation. Good results are obtained if the stabilizing agents are carboxylic compounds containing both hydroxy and carboxylic groups including, for example, compounds such as citric acid, glycolic acid, lactic acid, gluconic acids, glutaric acid and their salts.
  • small but effective amount of polyhydroxy compounds also can be used as stabilizers in amounts ranging from about 0.001 to 2.0 and preferably from 0.01 to 2.0 moles or 0.01 to 1.0 mole per liter.
  • the compounds include the trihydric compounds e.g. glycerol and the dihydric ether alcohols e.g. glycol ethers including alkylene glycol ethers, such as Methylene glycol ether, propylene glycol ether, tripropyleneglycol ether, or diethyleneglycol ether.
  • glycols include some of the lower molecular weight compounds such as ethylene glycol, propylene glycol, butylene glycol, cyclohexanol, and the water-soluble poly (oxyalkylene glycols) e.g. the poly-(oxyethylene) or poly- (oxypropylene glycols), having lower molecular weights ranging up to about 1000 may be employed to promote stability and dispersibility of solids in the coating bath or acid solutions.
  • di- and trihydric aliphatic alcohols include the water soluble lower alkanols, such as the di- and tri-hydric alkanols containing up to twelve carbon atoms.
  • This class of di- and trihydric lower alkanols can include glycols containing up to ten carbon atoms in the alkylene group e.g. trimethylene glycol, and the polyglycols, such as diethylene glycol, Methylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other polyalkylene glycols wherein the alkylene radical contains up to eight carbon atoms and preferably from two to four carbon atoms.
  • trimethylene glycol e.g. trimethylene glycol
  • polyglycols such as diethylene glycol, Methylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other polyalkylene glycols wherein the alkylene radical contains up to eight carbon atoms and preferably from two to four carbon atoms.
  • the acidic aqueous solutions may contain small but effective amounts of from 0.0 to 24 grams e.g. 0.01 to 12 grams per liter of solution of at least one fluorometallic compound preferably including stabilizing compounds such as hexafluorotitanate, heptafluorotantalate, tetrafluoroborate and hexafluorosilicate.
  • known water soluble surfactants can be added to the trivalent chromium solutions in amounts ranging from about 0 to 20 grams per liter and preferably about 5.0 to 10 grams or 1.0 to 5.0 grams per liter.
  • the surfactants are added to the aqueous solution to provide better wetting properties by lowering the surface tension thereby insuring complete coverage, and a more uniform film on the metal substrates.
  • the surfactants include at least one water soluble compound selected from the group consisting of non-ionic, anionic, and cationic surfactants.
  • Some of the better known water soluble surfactants include the monocarboxyl imidoazoline, alkylsulfate sodium salts (DUPONOL®), ethoxylated or propoxylated alkylphenol (IGEPAL®), alkylsulfonamides, alkaryl sulfonates, palmiticalkanol amides (CENTROL®), octylphenyl polyethoxy ethanol (TRITON®), sorbitan monopahnitate (SPAN®), dodecylphenyl polyethyleneglycol ether (TERGITROL®), alkyl pyrrolidones, polyalkoxylated fatty acid esters, alkylbenzene sulfonates and mixtures thereof.
  • DUPONOL® alkylsulfate sodium salts
  • IGEPAL® ethoxylated or propoxylated alkylphenol
  • alkylsulfonamides alkaryl sulfonates, palm
  • water soluble surfactants include, for example, the nonylphenol ethoxylates, and adducts of ethylene oxide with fatty amines; see the publication: “Surfactants and Detersive Systems", by John Wiley et al. in Kirk- Othmer's Encyclopedia of Chemical Technology, 3 rd Ed.
  • thickening agents can be added to retain the aqueous solution on the surface for sufficient contact time.
  • the thickeners employed are known inorganic and preferably the organic water soluble thickeners added to the trivalent chromium solutions in effective amounts e.g. at sufficient concentrations ranging from about 0 to 20 grams per liter and preferably 0.5 to 10 grams or 1.0 to 5.0 grams per liter of the acidic solution.
  • Specific examples of some preferred thickeners include the cellulose compounds, e.g. hydroxypropyl cellulose (Klucel), ethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, methyl cellulose and mixtures thereof.
  • water soluble inorganic thickeners include colloidal silica, clays such as bentonite, starches, gum arabic, tragacanth, agar and various combinations.
  • the solution can be applied via immersion, spray or wipe-on techniques.
  • the TCP solutions of this invention can be used at elevated temperatures ranging up to 120 0 F or higher e.g. up to 200 0 F and optimally applied via immersion to further improve the corrosion resistance of the coatings.
  • Solution dwell time ranges from about 1 to 60 minutes, and preferably 1.0 to 40 or 1.0 to 10 minutes at about 75 0 F or higher. After dwelling, the remaining solution is then thoroughly rinsed from the substrate with tap or deionized water. No additional chemical manipulations of the deposited films are necessary for excellent performance.
  • the aqueous solutions may be sprayed from a spray tank apparatus designed to replace immersion tanks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Cette invention concerne une solution aqueuse acide utilisée pour traiter des substrats métalliques pour améliorer la liaison adhésive et la protection contre la corrosion de la surface métallique, laquelle solution comprend des quantités efficaces de composés chrome trivalent hydrosolubles, des fluorozirconates, des quantités efficaces d'au moins un inhibiteur de corrosion tel que le benzotriazole, des composés fluorométalliques, des composés zinc, des agents épaississants, des tensioactifs et au moins environ 0,001 mole par litre de la solution acide d'un composé polyhydroxy et/ou carboxylique comme agent stabilisant pour la solution aqueuse.
EP05851727A 2005-02-15 2005-11-14 Composition et procede de preparation de revetements de protection sur des substrats metalliques Active EP1863952B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US11/058,715 US20100032060A1 (en) 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for magnesium alloys
US11/076,106 US20060180247A1 (en) 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for iron and iron alloys
US11/116,165 US7811391B2 (en) 2005-04-21 2005-04-21 Composition and process for preparing protective coatings on metal substrates
US11/116,166 US20060240191A1 (en) 2005-04-21 2005-04-21 Composition and process for preparing chromium-zirconium coatings on metal substrates
PCT/US2005/041587 WO2006088521A2 (fr) 2005-02-15 2005-11-14 Composition et procede de preparation de revetements de protection sur des substrats metalliques

Publications (3)

Publication Number Publication Date
EP1863952A2 true EP1863952A2 (fr) 2007-12-12
EP1863952A4 EP1863952A4 (fr) 2010-01-13
EP1863952B1 EP1863952B1 (fr) 2013-03-06

Family

ID=36916893

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05851727A Active EP1863952B1 (fr) 2005-02-15 2005-11-14 Composition et procede de preparation de revetements de protection sur des substrats metalliques

Country Status (10)

Country Link
EP (1) EP1863952B1 (fr)
JP (1) JP5060964B2 (fr)
KR (1) KR20080000564A (fr)
AU (1) AU2005327548A1 (fr)
BR (1) BRPI0519981B1 (fr)
CA (1) CA2597630C (fr)
DK (1) DK1863952T3 (fr)
ES (1) ES2411429T3 (fr)
MX (1) MX2007009801A (fr)
WO (1) WO2006088521A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009132344A2 (fr) * 2008-04-25 2009-10-29 Henkel Ag & Co. Kgaa Trichrome passivant le traitement d’acier galvanisé
US8591670B2 (en) 2008-05-07 2013-11-26 Bulk Chemicals, Inc. Process and composition for treating metal surfaces using trivalent chromium compounds
DE102009028025A1 (de) 2009-07-27 2011-02-03 Henkel Ag & Co. Kgaa Mehrstufiges Verfahren zur Behandlung von Metalloberflächen vor einer Tauchlackierung
EP2711444A1 (fr) 2012-09-20 2014-03-26 Coventya SAS Solution aqueuse alcaline pour améliorer la résistance à la corrosion d'un revêtement de conversion Cr(III), procédé de production d'un tel revêtement et son utilisation
US10156016B2 (en) * 2013-03-15 2018-12-18 Henkel Ag & Co. Kgaa Trivalent chromium-containing composition for aluminum and aluminum alloys
CN107109659B (zh) * 2014-12-26 2020-05-05 迪普索股份公司 锌或锌合金基材用3价铬化成处理液和化成被膜
US10400338B2 (en) 2017-05-12 2019-09-03 Chemeon Surface Technology, Llc pH stable trivalent chromium coating solutions
EP3746580A1 (fr) * 2018-01-30 2020-12-09 PRC-Desoto International, Inc. Systèmes et procédés de traitement d'un substrat métallique
JP7118402B2 (ja) * 2018-04-26 2022-08-16 奥野製薬工業株式会社 アルミニウム合金の陽極酸化皮膜用封孔処理液、濃縮液及び封孔処理方法
JPWO2020170638A1 (fr) * 2019-02-21 2020-08-27
CA3233870A1 (fr) * 2021-10-27 2023-05-04 Prc-Desoto International, Inc. Compositions, systemes et procedes de traitement d'un substrat

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578122A (en) * 1984-11-14 1986-03-25 Omi International Corporation Non-peroxide trivalent chromium passivate composition and process
WO2003040431A2 (fr) * 2001-11-06 2003-05-15 The United States Of America As Represented By The Secretary Of The Navy Post-traitement pour substrats revetus de metal
WO2003040437A1 (fr) * 2001-11-06 2003-05-15 The United States Of America As Represented By The Secretary Of The Navy Post-traitement d'aluminium anodise
US20040054044A1 (en) * 2000-10-11 2004-03-18 Klaus Bittner Method for coating metallic surfaces with an aqueous composition, the aqueos composition and use of the coated substrates

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3521952A1 (de) * 1985-06-20 1987-01-02 Henkel Kgaa Waessrige zusammensetzungen fuer den hilite- und flux-prozess und ihre verwendung
DE3783173T2 (de) * 1986-07-23 1993-04-22 Fuji Photo Film Co Ltd Verfahren zur behandlung eines farbphotographischen silberhalogenidmaterials und farbentwickler.
JPH0225592A (ja) * 1988-07-14 1990-01-29 Fujitsu Ltd 陽極酸化皮膜の封孔処理方法
JPH07100873B2 (ja) * 1989-09-27 1995-11-01 日本パーカライジング株式会社 亜鉛系メッキ鋼板のクロメート塗布液
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
DE19615664A1 (de) * 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
EP0946786A1 (fr) * 1996-11-27 1999-10-06 Henkel Corporation Composition aqueuse et procede de preparation d'un substrat metallique destine a un formage a froid
JP3391252B2 (ja) * 1998-03-26 2003-03-31 日本軽金属株式会社 電着塗装アルミ材の製造方法
JP2002075767A (ja) * 2000-08-31 2002-03-15 Sumitomo Special Metals Co Ltd 耐食性被膜を有する希土類系永久磁石およびその製造方法
US6669764B1 (en) * 2000-10-31 2003-12-30 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
US6663700B1 (en) * 2000-10-31 2003-12-16 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
JP2002212746A (ja) * 2001-01-11 2002-07-31 Okuno Chem Ind Co Ltd 未貫通穴を有する被めっき物への無電解ニッケルめっき方法
CA2472069C (fr) * 2002-01-04 2010-03-09 University Of Dayton Pigments anticorrosion non toxiques a base de cobalt
JP3774415B2 (ja) * 2002-03-14 2006-05-17 ディップソール株式会社 亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成するための処理溶液及び亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成する方法。
JP2003306756A (ja) * 2002-04-18 2003-10-31 Jfe Steel Kk 溶融亜鉛めっき鋼板とその製造方法
JP2004083771A (ja) * 2002-08-28 2004-03-18 Nippon Hyomen Kagaku Kk 金属保護被膜形成用組成物
DE10310972A1 (de) * 2003-03-13 2004-09-23 Basf Ag Stickstoffhaltige Polymere für die Metalloberflächenbehandlung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578122A (en) * 1984-11-14 1986-03-25 Omi International Corporation Non-peroxide trivalent chromium passivate composition and process
US20040054044A1 (en) * 2000-10-11 2004-03-18 Klaus Bittner Method for coating metallic surfaces with an aqueous composition, the aqueos composition and use of the coated substrates
WO2003040431A2 (fr) * 2001-11-06 2003-05-15 The United States Of America As Represented By The Secretary Of The Navy Post-traitement pour substrats revetus de metal
WO2003040437A1 (fr) * 2001-11-06 2003-05-15 The United States Of America As Represented By The Secretary Of The Navy Post-traitement d'aluminium anodise

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006088521A2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions

Also Published As

Publication number Publication date
DK1863952T3 (da) 2013-03-25
BRPI0519981B1 (pt) 2016-03-08
WO2006088521A2 (fr) 2006-08-24
MX2007009801A (es) 2007-10-03
KR20080000564A (ko) 2008-01-02
JP2008537975A (ja) 2008-10-02
EP1863952B1 (fr) 2013-03-06
CA2597630C (fr) 2015-09-29
WO2006088521A3 (fr) 2007-10-18
EP1863952A4 (fr) 2010-01-13
JP5060964B2 (ja) 2012-10-31
AU2005327548A1 (en) 2006-08-24
CA2597630A1 (fr) 2006-08-24
ES2411429T3 (es) 2013-07-05
BRPI0519981A2 (pt) 2009-08-18

Similar Documents

Publication Publication Date Title
US7811391B2 (en) Composition and process for preparing protective coatings on metal substrates
EP1863952B1 (fr) Composition et procede de preparation de revetements de protection sur des substrats metalliques
EP1848841B1 (fr) Composition et procede permettant de preparer des revetements de chrome-zirconium sur des substrats metalliques
US20060240191A1 (en) Composition and process for preparing chromium-zirconium coatings on metal substrates
CN101410550B (zh) 用于在金属基底上制备保护性涂层的组合物和方法
EP1404894B1 (fr) Revetement anti-corrosion pour aluminium et alliages d'aluminium
US6521029B1 (en) Pretreatment for aluminum and aluminum alloys
KR101212335B1 (ko) 아연 또는 아연 합금 도금에 내식성 피막을 형성시키기 위한 표면 처리 수용액 및 처리 방법
US6527841B2 (en) Post-treatment for metal coated substrates
EP1433875A1 (fr) Agent de revêtement de conversion chimique et surfaces métalliques revêtues
US20070099022A1 (en) Non-chromium post-treatment for aluminum coated steel
WO2006088522A2 (fr) Procede permettant de preparer des revetements de conversion de chrome destines a des alliages de magnesium
WO2006088518A2 (fr) Procede permettant de preparer des revetements de conversion de chrome destines a du fer ou des alliages de fer
US20070095437A1 (en) Non-chromium conversion coatings for ferrous alloys
US20200325582A1 (en) Process and composition for treating metal surfaces using trivalent chromium compounds

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070815

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20091215

17Q First examination report despatched

Effective date: 20100415

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602005038495

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0022000000

Ipc: C23C0022340000

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/83 20060101ALI20120731BHEP

Ipc: C23C 22/34 20060101AFI20120731BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 599679

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130315

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602005038495

Country of ref document: DE

Effective date: 20130502

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2411429

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130705

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 599679

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130606

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20130400926

Country of ref document: GR

Effective date: 20130614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130706

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130708

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20131209

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005038495

Country of ref document: DE

Effective date: 20131209

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130306

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131114

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602005038495

Country of ref document: DE

Representative=s name: RIPPER, SIGRID, DIPL.-PHYS. DR.RER.NAT., DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131114

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20051114

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231127

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231123

Year of fee payment: 19

Ref country code: GR

Payment date: 20231128

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231201

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231109

Year of fee payment: 19

Ref country code: SE

Payment date: 20231124

Year of fee payment: 19

Ref country code: IT

Payment date: 20231129

Year of fee payment: 19

Ref country code: FR

Payment date: 20231127

Year of fee payment: 19

Ref country code: FI

Payment date: 20231128

Year of fee payment: 19

Ref country code: DK

Payment date: 20231122

Year of fee payment: 19

Ref country code: DE

Payment date: 20231121

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231127

Year of fee payment: 19