EP3428314B1 - Composition et procédé de passivation de composants galvanisés - Google Patents

Composition et procédé de passivation de composants galvanisés Download PDF

Info

Publication number
EP3428314B1
EP3428314B1 EP17181407.2A EP17181407A EP3428314B1 EP 3428314 B1 EP3428314 B1 EP 3428314B1 EP 17181407 A EP17181407 A EP 17181407A EP 3428314 B1 EP3428314 B1 EP 3428314B1
Authority
EP
European Patent Office
Prior art keywords
composition
passivation
galvanized
compound
zinc
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.)
Active
Application number
EP17181407.2A
Other languages
German (de)
English (en)
Other versions
EP3428314A1 (fr
Inventor
Carolina Battaglia
Hanna SMOLL
Marcel Roth
Reiner Wark
Ingo KLÜPPEL
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.)
Ewald Doerken AG
Original Assignee
Ewald Doerken AG
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
Application filed by Ewald Doerken AG filed Critical Ewald Doerken AG
Priority to EP17181407.2A priority Critical patent/EP3428314B1/fr
Priority to ES17181407T priority patent/ES2765816T3/es
Priority to DK17181407.2T priority patent/DK3428314T3/da
Publication of EP3428314A1 publication Critical patent/EP3428314A1/fr
Application granted granted Critical
Publication of EP3428314B1 publication Critical patent/EP3428314B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—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
    • C23C22/42—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 phosphates
    • 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
    • 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
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to the technical field of passivation of metallic surfaces, in particular of galvanized surfaces.
  • the present invention relates to a composition for the passivation of galvanized or zinc-containing surfaces provided with surfaces.
  • the present invention relates to a process for passivation, in particular black passivation of galvanized substrates.
  • Corrosion phenomena on metals are observed in all fields of technology and are of great importance, since the durability or service life of machines, vehicles, industrial plants or even buildings often depends crucially on the corrosion properties of the metals used. Corrosion means that metal parts have to be replaced or repaired, which entails an expenditure of time, material and costs.
  • corrosion is the physico-chemical interaction between a metal and its environment, which leads to a change in the properties of the metal and which significantly affects the functions of the metal, the environment or the technical system of which they form part. can lead.
  • the corrosion of metals is usually electrochemical processes, namely the oxidation of metals by oxygen, optionally in the presence of aqueous electrolyte solution.
  • This so-called cathodic corrosion protection can be achieved on the one hand by applying an external voltage, but it is also possible, the metal to be protected in electrical contact with a less noble metal, d. H. a metal with lower standard electrochemical potential.
  • a less noble metal is the anode compared to the nobler metal and is oxidized, it represents the so-called sacrificial anode, while the nobler metal is the cathode at which it is reduced.
  • a special form of cathodic corrosion protection is the coating of components to be protected with a less noble metal.
  • the galvanizing which is used in particular for the protection of steel components or steel sheets.
  • hot-dip galvanizing In galvanizing usually steel, especially steel sheet, coated by immersion in baths of molten zinc in the context of so-called hot-dip galvanizing with elemental zinc, which hot-dip galvanized steel sheets - also called HDGS (Hot Dip Galvanized Steel) - are obtained.
  • the hot-dip galvanizing is particularly suitable for galvanizing steel sheets or piece goods, but quite high layer thicknesses of up to 200 microns are obtained, so that the process for highly detailed and finely divided workpieces is only partially suitable.
  • zinc flake coatings so-called zinc flake primers in which platelet-shaped zinc particles are dispersed in a binder matrix. Due to the binder matrix, the zinc of the zinc particles is significantly better protected against corrosion compared to coatings with elemental zinc or zinc alloys, so that components coated with zinc flake coatings often have significantly longer lifetimes in comparison to other cathodic corrosion protection systems. Due to the significantly higher costs, however, zinc flake coatings are often used only for small parts or special components to which special requirements are made. In particular, zinc flake transitions are often used as corrosion protection for connecting parts or threads due to the small layer thickness, high mechanical strength and low tolerance.
  • the hot-dip galvanizing and electrogalvanizing currently represent the usual method for improving the corrosion protection of steel sheets or bulk goods.
  • the galvanizing with elemental zinc or zinc alloys as carried out in the context of hot-dip galvanizing or galvanizing, however, has the disadvantage that zinc or zinc alloys are rapidly corroded under oxidative conditions, on the one hand deteriorates the visual appearance of the coatings by the formation of zinc oxide, the so-called white rust and on the other hand, the durability of the cathodic corrosion protection layer, for example under adverse climatic conditions, such as the marine climate, clearly is lowered.
  • the formation of zinc oxide impairs the adhesion of other decorative or functional coatings applied to the zinc layer.
  • the galvanized components are usually subjected to a conversion treatment or passivation, whereby the formation of a conversion or passivation layer causes the oxidation susceptibility and thus the corrosion of the elemental zinc or of the zinc alloy is significantly reduced.
  • the chromating has proven in which the galvanized components are immersed in an acid solution of chromium (VI) -containing compounds. As a result, a chromate layer is deposited on the zinc surface, which passivates the surface and significantly reduces the corrosion susceptibility of the zinc. Due to the harmful effect of chromium (VI) compounds, chromating is now preferably carried out only with chromium (III) compounds, which, however, does not generally lead to comparable results, but requires a further coating of the conversion layer with, for example, organic polymers. to slow down or suppress the formation of white rust sufficiently.
  • the coating applied to the galvanic zinc layer is colored or dark, in particular black, colored. This is especially true when a metallic shiny zinc layer is optically not desired.
  • black coated components or workpieces are used.
  • the dark coated and galvanized components are easily damaged during installation, so that minor flaking of the outer coating, in particular the paint layer, the result.
  • the components with small paint defects are not defective in the technical sense, but fully functional, but the blemishes in the optics are often not accepted by the customer, especially in very high-quality cars.
  • the replacement of components with slightly damaged paint spots causes a significant loss of time and is associated with higher costs.
  • black passivations were developed especially for zinc coatings, in particular galvanic zinc coatings, in which minor defects of the final coating are not noticeable.
  • the concerns EP 2 341 164 a chromium-free surface treatment method capable of treating a surface of a metallic element having a surface of zinc or a zinc alloy so as to provide a good blackening and rust-inhibiting capability, and an aqueous solution for a chemical conversion coating used in the Treatment method can be applied.
  • the aqueous solution contains no trivalent or hexavalent chromium and per liter of composition 5 to 20 g of phosphate ions, 0.1 to 3 g of divalent iron ions, 1 to 3 g of nitrate ions and 1 to 10 g of divalent manganese ions.
  • the aqueous solution has a pH of 1 to 3.
  • a black coating of Fe 3 O 4 is formed by immersing the metallic element in the aqueous solution, whereupon a conversion coating film of ceria is formed, followed by forming a silicon-containing coating film.
  • the DE 103 05 450 A1 describes a composition, a process and a substance use for carrying out and activating a black passivation of zinc alloys based on a chromium (III) ion-containing reaction solution.
  • the activators are phosphoric acid esters, in particular alkyl phosphates, such as, for example, isopropyl esters.
  • the concerns CN 103 397 320 B a cathodic electrophoresis pretreatment fluid used on the surface of a hot-dip galvanized plate of an automobile and belonging to the technical field of surface treatment of hot-dip galvanized plates.
  • the treatment liquor consists of: 10 to 20% of an organic silane, 5 to 10% of a phosphate-containing component and deionized water, wherein the phosphate-containing component of 0.8 to 1 g / l manganese nitrate, 0.8 to 1.2 g / l of zinc oxide , 5 to 15 g / L of phosphoric acid, 0.8 to 1 g / L of nickel nitrate and 0.8 to 1.5 g / L of iron (II) phosphate, and the organic silane is an (epoxy / propoxy) -propyltrimethoxysilane.
  • the treatment liquid is adjusted to a pH of 3 to 4 with phosphoric acid, stirred for 30 minutes and allowed to stand for 1 hour and then
  • a first, acidic passivation and a second, alkaline passivation comprising a silane-modified and / or siloxane-modified silicate, with which improved Corrosion protection is achieved, as well as an aqueous, acidic composition for passivation and a passivated substrate and a device for applying the passivation.
  • a disadvantage of the conventional systems for black passivation is that they usually do not work without highly toxic metals such as nickel and cobalt, or that the adhesion-promoting properties of the dark passivation layers obtained are so poor that further coatings must be applied as adhesion promoters the final decorative coating adheres firmly enough.
  • galvanized components in the manufacturing process only galvanized and then provided, for example, with a cathodic dip coating, so that a temporarily applied conversion coating must not change the electrical properties of the component, in particular the galvanized surface, not serious and in particular not uneven.
  • the disclosure WO 2008/151829 A1 a method for producing a corrosion-protective black coating layer with an aqueous treatment solution containing chromium (III) ions and at least one phosphate compound, wherein the ratio of the molar concentration of chromium (III) ions to the molar concentration of the phosphate compound, calculated as orthophosphate, is between 1: 1.5 and 1: 3.
  • the process is intended in particular to improve the corrosion protection of zinc-containing conversion coatings while preserving or improving the decorative and functional properties of the surfaces.
  • the DE 101 62 756 A1 relates to a composition and a method for chromium (VI) -free black passivation of zinc alloys, wherein an aqueous acid solution with chromium (III) ions and phosphate ions is used.
  • a nickel-containing chromate layer is produced, including, in particular, nickel-containing zinc alloys having at least 10 to 12% nickel content.
  • a further object of the present invention is to provide a composition and a method for passivation of galvanized surfaces, in particular of galvanized components, which subsequently provide a trouble-free and uniform coating of the passivated zinc surfaces by means of galvanic methods, in particular by means of cathodic dip coating, enable.
  • the present invention proposes a composition according to claim 1; Further advantageous embodiments of this aspect of the invention are the subject of the relevant subclaims.
  • compositions conversion coatings in particular passivations, which not only have a black color, but significantly improve the corrosion resistance of the galvanized surfaces and, moreover, are excellent adhesion promoters for subsequent coatings.
  • susceptibility to corrosion of zinc coatings in particular the formation of white rust on substrates, can be significantly reduced.
  • composition according to the invention and the conversion or passivation layers produced with it enable a problem-free subsequent coating of the passivated zinc surface by electrocoating, in particular by cathodic dip coating (KTL), in particular compared to conventional conversion coatings significantly improved and uniform over the entire coated surface electrical conductivities can be achieved.
  • KTL cathodic dip coating
  • passivation is to be understood in particular as the reduction of the reactivity of metals, in particular of metallic surfaces, such as, for example, zinc or zinc-containing coatings.
  • an iron compound is understood in particular to mean a chemical compound which contains the element iron (Fe).
  • the composition is free of cobalt, nickel and / or chromium (VI) compounds.
  • VI chromium
  • the iron compound is usually a salt.
  • salts in particular soluble salts
  • liquid compositions in particular compositions in the form of aqueous solutions, a particularly rapid and complete conversion to the desired target compounds and thus a rapid passivation is possible.
  • the salt is a purely inorganic salt.
  • the salt is a nitrate, a chloride, a bromide, an iodide, a chlorate, a phosphite, a hypophosphite, a phosphonate, a bisphosphonate, a phosphate, a pyrophosphate, a carbonate or a sulfate, preferably a nitrate.
  • the salt is a nitrate, a phosphite, a hypophosphite, a phosphonate, a bisphosphonate, a phosphate, a pyrophosphate, a carbonate or a sulfate, whereby the use of nitrates, in particular of iron ( III) nitrate, is preferred.
  • the composition preferably contains the iron compound in amounts of 0.03 to 1.5% by weight, preferably 0.1 to 1% by weight, preferably 0.15 to 0.5% by weight, particularly preferably 0, 2 to 0.3 wt .-%, based on the composition.
  • the phosphorus-containing compound is generally selected from hypophosphites, phosphites, phosphates and phosphonates and mixtures thereof and free acids, in particular hypophosphites, phosphites, phosphates, pyrophosphates, phosphonates, bisphosphonates and mixtures thereof and free acids.
  • the phosphorus-containing compound is a phosphonate or contains a phosphonate
  • the phosphonate is usually selected from the group of the primary and secondary alkyl phosphonates, in particular the primary alkyl phosphonates.
  • the phosphorus-containing compound is a phosphate
  • the phosphate is selected from monophosphates, diphosphates and / or polyphosphates or their free acids.
  • the phosphorus-containing compound a monophosphate, in particular phosphoric acid, preferably orthophosphoric acid.
  • the composition contains the phosphorus-containing compound in amounts of 0.01 to 0.7 wt .-%, preferably 0.05 to 0.5 wt .-%, preferably 0.10 to 0.20 wt .-%, particularly preferably 0.12 to 0.15 wt .-%, based on the composition contains.
  • contents of phosphorus-containing compound in the abovementioned ranges iron phosphate or iron-phosphate-containing compounds, such as mixed zinc iron phosphates, for example, can be rapidly deposited on the galvanized surface in the course of a conversion treatment using acidic compositions.
  • the further transition metal compound is generally present in the form of a salt, an oxide or an acid.
  • the metals of the further transition metal compound in the form of cations, in particular complex cations or cationic complexes, anions, in particular complex anions or anionic complexes, oxides or free acids.
  • the transition metals often as a cation, in particular, cationic complexes or complex cations can be used.
  • a complex cation is, for example, vanadyl (VO 2+ ), which is preferably used in the context of the present invention in the form of its sulfate.
  • the salt is a nitrate, a chloride, a bromide, an iodide, a chlorate, a phosphate, a carbonate or a sulfate, in particular a nitrate, a phosphate, a carbonate or a sulfate.
  • halogen-free inorganic compounds are also preferred with respect to the further transition metal compound.
  • the salt is a nitrate, a phosphate, a carbonate or a sulfate, preferably a nitrate or a sulfate.
  • the transition metal of the further transition metal compound is in the form of an anion, in particular a complex anion or an anionic complex, in particular a complex anion.
  • complex anions are permanganate as well as tungstates and molybdate.
  • the transition metal of the further transition metal compound in the form of an oxide such as vanadium oxide (V 2 O 5 ), or an acid such as tungstic acid (HWO 4 ), is present.
  • the further transition metal compound is selected from compounds of transition metals from the group of scandium, yttrium, lanthanides, the fifth (5th) group of the Periodic Table of the Elements, the sixth (6th) group of the Periodic Table the elements and mixtures thereof, preferably mixtures thereof.
  • the groups of the Periodic Table of the Elements are numbered consecutively from group 1, the alkali metals, to group 18, the noble gases, in the context of the present invention according to IUPAC recommendation.
  • the further transition metal compound is selected from compounds of metals of the group of lanthanides, vanadium, niobium, chromium, in particular chromium (III), molybdenum, tungsten and mixtures thereof, in particular lanthanides, vanadium , Chromium and their mixtures.
  • the further transition metal is particularly preferably selected from cerium, vanadium, chromium and mixtures thereof, in particular mixtures thereof.
  • a mixture of Compounds of cerium, vanadium and chromium, in particular chromium (III) used.
  • the amount of other transition metal compounds having the composition within the scope of the present invention may also vary widely. Particularly good results are obtained when the composition comprises the further transition metal compound in amounts of 0.004 to 0.25% by weight, preferably 0.007 to 0.15% by weight, preferably 0.01 to 0.1% by weight, especially preferably 0.04 to 0.05 wt .-%, based on the composition contains. In the context of the present invention, it is therefore possible to obtain excellent improvements with regard to the corrosion resistance of the galvanized surfaces even with particularly low concentrations of transition metal compounds.
  • the composition comprises at least one compound of an element from the group of scandium, yttrium and lanthanides.
  • the further transition metal compound is selected from elements from the group of scandium, yttrium, lanthanides, the fifth period of the periodic table of the elements, the sixth period of the periodic table of the elements and mixtures thereof, in particular mixtures different transition metals are preferred.
  • particularly good results are obtained when at least one compound of an element from the group of scandium, yttrium, and lanthanides is included in the composition.
  • the compound of the group of scandium, yttrium, the lanthanides may be present in combination with elements of the fifth and sixth group of the Periodic Table of the Elements or may also be used as the sole transition metal compound, wherein a combination with elements of the fifth and sixth groups of the Periodic Table of the Elements is preferred.
  • the element from the group of scandium, yttrium and lanthanides is selected from the group of lanthanum, cerium, neodymium, praseodymium, europium, erbium and mixtures thereof, in particular lanthanum, cerium, neodymium and mixtures thereof.
  • the element from the group of scandium, yttrium and the lanthanides it is most preferred for the element from the group of scandium, yttrium and the lanthanides to be cerium.
  • passivation layers can be obtained which not only have excellent properties with regard to the corrosion resistance of the zinc surfaces, but also have excellent adhesion promoter properties.
  • the composition comprises a compound of an element from the group of scandium, yttrium and the lanthanides or their mixtures
  • the composition comprises the compound of an element from the group of scandium, yttrium, lanthanides in amounts of 0, 0001 to 0.05 wt .-%, in particular 0.0005 to 0.025 wt .-%, preferably 0.001 to 0.015 wt .-%, preferably 0.002 to 0.01 wt .-%, particularly preferably 0.004 to 0.007 wt .-% , based on the composition contains.
  • composition contains the compound of an element from the group of scandium, yttrium, the lanthanides or mixtures thereof in amounts of 0.005 wt .-%, based on the composition. Even if the composition comprises further transition metal compounds, in particular from the fifth and sixth group of the Periodic Table of the Elements, particularly good results are obtained if the composition comprises the element from the group of scandium, yttrium and lanthanides or mixtures thereof in the abovementioned Has quantities.
  • the composition additionally contains at least one reducing agent.
  • a reducing agent it is possible, without wishing to be bound by this theory, to deposit on the galvanized surface conversion or passivation layers of iron phosphate or zinc iron phosphate which contains small amounts of metallic iron, whereby the corrosion resistance of the zinc coating becomes clear is increased.
  • composition in the context of the present invention contains a reducing agent
  • the reducing agent is selected from the group of ascorbic acid, ascorbic acid derivatives, in particular ascorbic acid esters, hydrazine, sulfites and mixtures thereof, preferably ascorbic acid, ascorbic acid esters and mixtures thereof. Particularly good results are obtained in the context of the present invention, when L-ascorbic acid is used as the reducing agent.
  • the composition contains the reducing agent in amounts of 0.01 to 2 wt .-%, in particular 0.02 to 1 wt .-%, preferably 0.05 to 0.75 wt .-%, preferably 0.10 to 0, 50 wt .-%, particularly preferably 0.15 to 0.25 wt .-%, based on the composition.
  • the composition has a pH of less than 4. It has also proven useful if the composition has a pH of less than 3, preferably less than 2.
  • the composition has a pH in the range of 0 to 4, in particular 0.5 to 3, preferably 1 to 3, preferably 1.3 to 1.8.
  • the pH is adjusted in particular by at least one organic acid or inorganic acid, preferably at least one inorganic acid.
  • the inorganic acid is preferably selected from the group of sulfuric acid, phosphoric acid, nitric acid or mixtures thereof.
  • the pH is adjusted via phosphoric acid, wherein the phosphoric acid according to this preferred embodiment also forms the phosphorus-containing compound or a portion of the phosphorus-containing compound.
  • the composition comprises a solvent or dispersion medium.
  • composition comprises a solvent or dispersing agent
  • the composition of the solvent or dispersing agent in amounts of 94 to 99.9 wt .-%, in particular 97 to 99.9 wt .-%, preferably 99 to 99.8 wt .-%, preferably 99.2 to 99.7 wt .-%, particularly preferably 99.4 to 99.6 wt .-%, based on the composition , contains.
  • it is thus preferable to use highly dilute compositions which, however, even at a low exposure time to the galvanized substrate, lead to excellent conversion coatings or passivating coatings.
  • the solvent or dispersant may be selected in the context of the present invention from organic solvents and water and mixtures thereof.
  • the solvent or dispersant is or contains an organic solvent, it has proven useful if the organic solvent is selected from the group of alcohols, ketones, esters and mixtures thereof.
  • the organic solvent is selected from the group of methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, ethyl acetate and mixtures thereof.
  • the solvent or dispersant is water.
  • water has the advantage that it is available in large quantities in a cost-effective manner and, moreover, it is of no concern either from environmental aspects or from the point of view of occupational safety.
  • water is not flammable, so that can be dispensed with when using purely aqueous solutions to increased fire safety precautions.
  • the composition according to the invention when the composition according to the invention is in the form of a concentrate, the composition usually has a pH of 0 to 3, in particular 0.2 to 2, preferably 0.5 to 1.5, preferably 0.9 to 1.3 ,
  • composition in the form of a concentrate a compound of a metal from the group of scandium, yttrium, lanthanides or mixtures thereof in amounts of 0.01 to 0.1 wt .-%, in particular 0.03 to 0.08 wt .-%, preferably 0.04 to 0.06 wt .-%, based on the composition contains.
  • the concentrated composition is usually diluted before use, especially with a solvent or dispersing agent.
  • the concentrated composition in particular 1 part by weight of the concentrated composition, is provided with 1 to 99, in particular 2 to 50, preferably 3 to 40, in particular 4 to 20, preferably 5 to 15, parts by weight of solvent or dispersion medium in order to set the desired dilution ,
  • Particularly good results are obtained in the context of the present invention when the concentrate, in particular 1 part by weight of the concentrate, is diluted with 9 parts by weight of solvent or dispersant.
  • the substrate is for a duration of 0.1 to 300 seconds, in particular 0.5 to 200 seconds, preferably 1 to 120 seconds, preferably 10 to 100 seconds, particularly preferably 30 to 80 seconds , most preferably 50 to 70 seconds, is treated with the composition.
  • Such short treatment times are sufficient to produce a conversion or passivation layer in sufficient thickness, which is why the inventive method is also suitable for large-scale industrial processes.
  • the treatment of the substrate with the composition can be done in any suitable way. However, it has proven useful if the substrate is treated by dipping, spraying, knife coating or rolling, preferably dipping, with the composition.
  • the substrate contains or consists of metallic iron or its alloys.
  • the substrate comprises steel or consists of steel, in particular consists of steel.
  • the substrate is preferably a steel sheet or a steel strip.
  • the substrate is coated with zinc or zinc alloys, preferably zinc.
  • the substrate is hot-dip galvanized and / or galvanized, preferably galvanized.
  • conversion or passivation treatments are necessary and useful, since the coating in the context of hot-dip galvanizing or electrogalvanizing consists of elemental zinc or zinc alloys, which is not further protected from environmental influences.
  • Galvanized zinc coatings with layer thicknesses in the range of 10 to 40 ⁇ m are significantly thinner than coatings which are obtained by hot-dip galvanizing and have a layer thickness of up to 200 ⁇ m. Due to the small layer thickness, it is important in the case of galvanically galvanized substrates to protect the comparatively thin zinc coating or zinc-containing coating from corrosion by means of a conversion or passivation layer. In addition, in particular galvanized galvanized substrates are often subjected to a further coating, in particular an electrocoating, with a decorative lacquer whose adhesion to the substrate would be deteriorated by white rust formation.
  • the galvanized substrate is lightened before treatment with the composition, in particular by treatment with a whitening agent.
  • a whitening agent is used in the context of the present invention, it has proven useful to use nitric acid as whitening reagent, preferably 1% nitric acid.
  • the substrate is treated by dipping, spraying or rolling, preferably dipping, with the whitening reagent.
  • the duration of the treatment with the whitening agent it has proven useful for the substrate to last for a period of 0.5 to 200 seconds, in particular 1 to 100 seconds, preferably 5 to 80 seconds, preferably 10 to 60 seconds preferably 20 to 40 seconds, is treated with the whitening agent.
  • a cleaning, in particular degreasing, of the galvanized substrate can be carried out, in particular, whenever the galvanizing is temporally and / or spatially separated from the passivation.
  • the galvanized substrate is preferably subjected to any cleaning step or process, but only rinsed, especially with demineralized water.
  • the galvanized substrate is rinsed several times.
  • the galvanizing, in particular the galvanizing, and the subsequent passivation are carried out in a continuous process or process.
  • the substrate to be galvanized in particular a steel sheet, first degreased, especially degreased alkaline hot, preferably for a period of about 15 minutes.
  • the substrate is preferably rinsed with water and then optionally stained with hydrochloric acid. Preferably followed by further rinsing with demineralized water.
  • a pickling with strongly diluted hydrochloric acid is carried out before an acidic or alkaline galvanizing, which preferably takes place with a current density of 1.5 A / dm 2 .
  • an acidic or alkaline galvanizing which preferably takes place with a current density of 1.5 A / dm 2 .
  • the described first passivation layer in particular the dark or black colored passivation layer, preferably the black passivation, is applied to the substrate and the second passivation layer, which is obtainable from an aqueous passivating composition comprising at least one silane-modified silicate or a siloxane-modified silicate applied to the first passivation layer.
  • a second passivation layer based on modified silicates achieves a significantly improved corrosion protection of a substrate provided with the passivation system; on the other hand, the dark passivation layer, in particular the black passivation, which is located directly on the substrate, is further advanced against mechanical damage protected.
  • the dark passivation layer is therefore usually not destroyed in the case of superficial damage to the coating, so that the dark optics remain undisturbed.
  • the passivation system is outstandingly suitable for improving the corrosion protection of passivated substrates and allows good adhesion of topcoats, in particular lacquer coats. If the coating, in particular the lacquer layer, is a coating applied by electrodeposition coating, in particular cathodic dip coating, it is preferred if only the black passivation, i. H. the passivation layer described above, and not the particular multilayer passivation system. In contrast, the passivation system is outstandingly suitable for passivating galvanized substrates, which are subsequently coated by spraying, knife coating, rolling, rolling or dipping.
  • a silane-modified silicate or a siloxane-modified silicate here means a silicate, in particular a polysilicate, to which a silane or siloxane is bound by hydrolysis and condensation reaction.
  • the attachment of the silane or siloxane radical usually takes place via Si-O-Si units.
  • the composition for producing the second passivation layer has both compounds of silicates and silanes or siloxanes and optionally silicates and silanes or siloxanes.
  • the silanes or siloxanes are typically bound to the silicate (s) by the hydrolysis and condensation reactions as covalent side chains.
  • the silicate As far as the silicate is concerned, it may be selected from all suitable silicates. Usually, however, the silicate is selected from sodium, potassium, lithium and / or ammonium silicates, which are preferably in the form of aqueous solutions as so-called water glasses. Particularly preferred is the use of lithium silicate, in particular of lithium polysilicates, d. H. Lithium water glasses.
  • the aqueous composition for producing the second passivation layer comprises at least one silane or siloxane or their reaction products.
  • the addition of the silane or siloxane serves to increase the corrosion protection compared with the use of pure water glasses.
  • Various silane compounds can be used together in a mixture.
  • silane- or siloxane-modified silicate compounds used in the passivation composition it is advantageous to use an epoxy-functional, phenoxy-functional, vinyl-functional or amino-functional silane.
  • siloxanes, ie oligomers or polymers, of the siloxanes mentioned above and below it is also possible to use the siloxanes, ie oligomers or polymers, of the siloxanes mentioned above and below.
  • alkylalkoxysilanes preferably mono-, di- or trialkylalkoxysilanes, are individually or in mixture in combination with silicates suitable to build up a corrosion-protective coating and to protect the first passivation layer, ie the black passivation from damage.
  • silanes which have at least one Si-C bond, ie a bond between a silicon and a carbon atom.
  • Different silanes can be used together in a mixture.
  • Particularly suitable silanes are methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 Aminopropyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxys
  • Silane or siloxane and silicate are used in aqueous solution, preferably in the following proportions: Silane or siloxane can, based on the total amount of silicate used for the hydrolysis and / or condensation, in an amount of 1 wt .-% to 99 wt. -% are used.
  • Silane-modified or siloxane-modified silicate compounds containing only small amounts of silane or siloxane, z. B. up to 20 wt .-%, a significantly improved corrosion protection.
  • silane or siloxane and silicate are each advantageously used in a weight ratio of from 0.1: 1 to 2.5: 1, preferably from 0.4 to 1: 1.
  • the silane or siloxane can be used as a single compound or as a mixture of silanes or siloxanes, the same applies to the silicate, wherein the use of lithium silicate is preferred, both individually and in a silicate mixture.
  • the solids content of the silane-modified or siloxane-modified silicate passivation composition is usually between 1 and 70% by weight.
  • the solids content is advantageously between 1 and 50% by weight, particularly advantageously between 2 and 40% by weight.
  • the silane is preferably used as the monomer, but it is also possible to use an oligomer, ie, siloxane, or a mixture of silane and siloxane can be hydrolyzed and / or condensed in the presence of a silicate or a mixture of silicates.
  • silane-modified silicates by hydrolysis or condensation can also be carried out in such a way that organic oligomers or polymers are used which have silyl groups.
  • silicates in particular lithium polysilicate
  • an alkaline pH usually being in the range from pH 9 to pH 12.
  • the silane or siloxane is added and bound by hydrolysis and condensation reactions to the silicate.
  • the composition required for the second passivation layer is obtained by hydrolysis and condensation of silanes or siloxanes, preferably silanes, and silicate in alkaline solution and subsequent acidification.
  • silane- or siloxane-modified silicate solutions for passivation have improved properties when the solution has an acidic pH.
  • silicates especially water glasses, which are hydrolyzed or condensed in the alkaline with a silane or siloxane or mixtures thereof, are acidified to a pH of 7 or less, without causing the precipitation of silicates, especially water glass. This is particularly evident when using lithium silicate or lithium polysilicate and when using a mixture of waterglasses containing lithium silicate or lithium polysilicate.
  • the passivation composition which in the alkaline by hydrolysis and / or Condensation of the silane or siloxane produced silicate or siloxane-modified silicate compound contains in admixture with acid, can be used at pH values of pH 7 or lower, typically at acidic pHs of a maximum of pH 6 or up to pH 5 as an effective corrosion protection coating become.
  • Acidification preferably sets a pH value between 2 and 4, which can be reached and maintained without precipitation or flocculation of the silane- or siloxane-modified silicate compound.
  • the setting of a pH of 7 or less is preferably carried out by adding acid to the aqueous alkaline solution which contains completely or partially hydrolyzed or condensed silane- or siloxane-modified silicate compounds.
  • the pH can be adjusted with inorganic or organic acids or with a mixture of acids.
  • the pH after adding acid is preferably adjusted to a value between pH 2 and pH 5.
  • Acids are preferably used for acidification, which contain phosphorus, such as. As diphosphoric acid, phosphonic acids or di-phosphonic acids or a mixture of these acids. It is advantageous z. B.
  • inorganic acids such as nitric acid or sulfuric acid may be used, but also organic acids such as e.g. Acetic, acrylic, oxalic, citric, fumaric, benzoic, succinic, maleic, salicylic, aminosalicylic, nicotinic, formic, malic, tartaric, ascorbic, propionic, lactic, phthalic, acids.
  • the common hydrolysis and condensation of silicates and silanes or siloxanes in aqueous solution is preferably carried out at a pH equal to or greater than 9, the formation of the silane-modified or siloxane-modified silicates.
  • the hydrolysis may optionally be continued after the optional acidification to a pH equal to or less than 7.
  • the hydrolysis and condensation in the alkaline generally proceeds under the following conditions:
  • the hydrolysis and condensation takes place at room temperature, by slow addition, usually over several hours, up to a maximum of 12 hours, of the silane or siloxane, preferably of the silane, to the silicate and with constant stirring. After completion of the addition is advantageously still stirred for some time.
  • the reaction can take place over a period of 1 to 48 hours. Further stirring after completion of the hydrolysis or condensation is also carried out for at least 1 hour, but can, for. B. to improve the application properties and continue for up to 24 hours.
  • a silane- or siloxane-modified silicate in a first stage as described above in a second stage by further reaction with a tetraalkoxysilane, for.
  • tetramethoxysilane is further modified.
  • the further modification of the already silane or siloxane-modified silicate is carried out to z. B. to achieve one or more of the following effects:
  • the molecular weight is increased, the crosslinking density is increased and / or the reactivity is increased.
  • the subsequent hydrolysis with a tetraalkoxysilane takes place under the same conditions as described here in connection with the first stage of the silane modification or the siloxane modification.
  • the acidification is usually also at room temperature.
  • the completely or partially hydrolyzed and / or condensed silicate-silane or siloxane mixture, the acid or the acid mixture is added slowly with constant stirring; also the acidification can take 1 to 10 hours.
  • the pH is constantly monitored and the addition is stopped when the desired pH is reached. Even after the acidification is still advantageous for some time for 1 to 24 hours further stirred to improve the application properties.
  • alkaline silane-silicate or silane-silicate hydrolyzate up to 6 months, advantageously up to 3 months and only then acidify. It is thus possible to decouple the production of acidified, wholly or partially alkaline hydrolysed or condensed silane or siloxane-modified silicates in so far as the acidification can take place without loss of quality offset in time. It is also available after a storage period of 3 or 6 months and only then acidification a hydrolyzate or condensate with excellent corrosion protection properties obtained.
  • aqueous acidic compositions can be provided which are low in volatile organic compounds (low in VOCs) or which are free of volatile organic compounds (VOC-free).
  • the liberated by the hydrolysis alcohols can, for example, by ultramembrane filtration or reverse osmosis, but also by distillation, for. B. vacuum distillation can be removed.
  • Typical aqueous alkaline or acidified compositions for passivating metallic substrates contain at most 1% by weight of alcohol, preferably at most 0.3% by weight of alcohol.
  • the removal of the alcohol also promotes the hydrolysis or condensation reaction of the silane or of the silane with the silicate.
  • the passivation composition comprising a silane- or siloxane-modified silicate has one or more titanate and / or zirconate compounds.
  • the titanate and / or zirconate compound may be hydrolyzed or condensed with the silane or siloxane either in the presence of the silicate or previously in a reaction only between the silane and the titanate and / or zirconate compound. If the titanate and / or zirconate compound is completely or partially hydrolyzed or condensed in advance with the silane or siloxane, this can be achieved, for example, by B. take place as in the US 5,849,110 disclosed.
  • the titanate and / or zirconate compound is added in the presence of the silicate, this can be done either already in the alkaline hydrolysis or only after the acidification.
  • the titanate and / or zirconate compound is incorporated less into the silane- or siloxane-modified silicate skeleton, the later it is added; the incorporation is therefore the lowest if the titanate and / or zirconate compound is added only after the acidification of the silane- or siloxane-modified silicate compound, especially if the hydrolysis or condensation is usually largely completed at this time.
  • the titanate and / or zirconate is in the form of nanoparticles.
  • the formation of a covalent bond is also possible between the titanate and / or zirconate compound and the silicate possible, comparable to the covalent bond between the silane or siloxane and the silicate.
  • a covalent bond to silicate or siloxane groups bonded to the silicate is also possible.
  • the resulting polymer thus preferably has in side chains in simplified representation the structural elements "water glass Si-O-Ti-R" or “water glass Si-O-Zr-R", wherein the same letters have the same meaning as stated above and where Ti is titanium and Zr is zirconium.
  • titanates and zirconates are monoalkyltrialkoxytitanate, Dialkyldialkoxytitanate, Trialkylmonoalkoxytitanate and Tetraalkoxytitanate such.
  • the titanium compound, the zirconium compound or mixtures of titanium, zirconium or of titanate and zirconium compounds is preferably mixed with the silane or siloxane at room temperature.
  • this mixture typically: silane / siloxane, titanates, zirconates
  • this mixture in lithium polysilicate or another silicate or a mixture of silicates is incorporated dropwise with stirring, stirred for some time and then acidified.
  • the addition of the titanium or zirconium compound, typically titanate, zirconate, or the mixture of these additives, can be carried out after acidification at room temperature. This is also added dropwise with stirring and then stirred for a further 1 to 24 hours.
  • the preparation of the second Passivi mecanicszusammens with mixtures of silanes or siloxanes and titanates and / or zirconates, but also with Among other things, mixtures of silicates can serve to adjust the crosslinking density of the passivation layer which is produced on the metallic substrate.
  • the crosslinking density of the passivation layer and its strength, the z. B. can be influenced by the solids content of the passivation composition, influence the corrosion property of the deposited on the metallic substrate and dried passivation.
  • a higher crosslinked film can offer good corrosion protection even with a lower film thickness
  • composition comprising silane- and / or siloxane-modified silicates contains additives which, for. B. improve the storage stability, the processing properties or the anti-corrosive effect of the applied coating.
  • additives can be added both during the alkaline hydrolysis and during or after the optional acidification. Especially preferred is the addition of additives after acidification.
  • Typical additives are catalysts, wetting agents, corrosion inhibitors, stabilizers and defoamers. Individual additives are explained in more detail below in their effect in the composition:
  • metal-oxygen compounds of the metals strontium, molybdenum, vanadium, titanium, zirconium, manganese and / or tungsten in the aqueous acidic passivation composition are used as corrosion inhibitors.
  • salts or oxides of the abovementioned metals, vanadates, molybdate, titanates, zirconates, manganates, salts and oxides of strontium and their polycondensates in particular potassium orthovanadate, potassium metavanadate, sodium orthovanadate, sodium metavanadate , Sodium tungstate, sodium paratungstate, vanadyl sulfate and vanadium pentoxide, as well as sodium molybdate and potassium molybdate.
  • surface-active substances are used.
  • a phosphonic acid or a mixture of phosphonic acids is or are used as surface-active substances.
  • organic phosphonic acids for example (1-hydroxyethane-1,1-diyl) biphosphonic acid, 2-phosphonobutanel 1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, ethylenediamine tetramethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, Hydroxyethylaminodimethylen-phosphonic acid, 2-phosphonobutane-1,2,3-tricarboxylic acid, Bishexamethylentriaminpentamethylenphosphonklare or Diethylentriaminpentamethylenphosphonklare or mixtures thereof.
  • salts of phosphonic acid may prove advantageous.
  • These salts dissociate in the aqueous, acidic passivating composition so that the phosphonates are available as surfactants.
  • Phosphonic acids and their derivatives can also be advantageously used in conjunction with vanadium and tungsten compounds in acidic aqueous compositions.
  • the use of phosphonic acid or phosphonates has proved to be a surface-active substance.
  • the addition of phosphonates allows faster acidification or acidification with less acid.
  • a combination of phosphonates and phosphoric acid proves to be suitable for the preparation of passivation compositions having good corrosion properties.
  • composition according to the invention or the method according to the invention are also suitable for use in a coating system, in particular a dark-colored coating system comprising a passivation layer or a passivation system, each as described above, and at least one lacquer layer.
  • the above-described, in particular dark colored passivation layer not only improves the corrosion protection of the substrate, but also ensures improved adhesion of the paint layer applied by electrocoating and a uniform and uniformly thick paint layer. If the lacquer layer is applied to the substrate by means of electrodeposition coating, in particular cathodic dip coating, then it is preferred if only the dark-colored or black passivation layer described above is applied to the substrate and not the passivation system.
  • the passivation system is preferred because it allows a further markedly improved corrosion protection and protection of the black passivation layer from mechanical stress.
  • FIG. 1 a schematic representation of a coating system 1 obtainable with the composition according to the invention or the method according to the invention, which is applied to a galvanized metal substrate 2, in particular a galvanized steel sheet.
  • the coating system 1 has a passivation layer 3, which is applied directly to the galvanized substrate 2.
  • the passivation layer 3 is preferably in the form of a black passivation and protects the galvanized metallic substrate 2 against corrosion, in particular against white rust formation.
  • passivation layer 3 has excellent adhesion-promoting properties.
  • a cover layer 4 is applied, which is preferably applied to the passivation layer 3 in the form of a cathodic dip coating (KTL coating).
  • the galvanizing of the steel sheets and the optionally following black passivation or phosphating of the galvanized surfaces are carried out in a process sequence. Before galvanizing, the steel sheets are degreased and cleaned to allow good adhesion of the zinc coating to the steel sheets.
  • Both acidic and alkaline galvanic zinc plating are performed at current densities of 1.5 A / dm 2 .
  • the steel sheets are optionally passivated, either by black passivation obtainable according to the invention or by phosphating with Gardobond® 26SW42OC.
  • passivation compositions according to the invention with the components listed in Table 1 are prepared in the form of a concentrate.
  • compositions shown in Table 1 are diluted to 10% of the original concentration by adding 9 parts by weight of water. With these diluted passivation compositions, a part of the steel sheets is then black passivated.
  • Table 2 Process sequence of galvanizing and passivation step duration temperature No. description 1 Alkaline hot degreasing 15 minutes 65 ° C 2 do the washing up 30 sec RT 3 do the washing up 30 sec RT 4 Pickling HCl 10 sec RT 5 do the washing up 30 sec RT 6 do the washing up 30 sec RT 7 Electrolytic degreasing 4 min RT 8th do the washing up 30 sec RT 9 do the washing up 30 sec RT 10 Dappling with 30 sec RT 0.3% hydrochloric acid 11 acid galvanizing or 30 min 40 ° C (sour) alkaline galvanizing RT (alkaline) 12 do the washing up 30 sec RT 13 do the washing up 30 sec RT 14 Brightening with 30 sec RT 1% nitric acid 15 do the washing up 30 sec RT 16 Passivation / phosphating 60 sec RT 17 do the washing up 30 sec RT 18 do the washing up 30 sec RT 19 do the washing up 30 sec RT
  • the galvanized and optionally passivated steel sheets are then subjected to a cathodic dip coating with a black paint.
  • the layer thickness is about 11 microns.
  • the exact deposition conditions, in particular the deposition times and the applied voltages, and the Layer thicknesses are shown in Table 3. After completion of the deposition, the paints are baked at 175 ° C for 20 minutes.
  • Table 3 Separation parameters and layer thicknesses of dipcoats substratum Separation parameters / layer thickness alkaline galvanized (comparative) 31 ° C, 160 V, 30 s / 10 - 11 ⁇ m Zinc plated (comparison) 31 ° C, 160 V, 30 s / 10 - 12 ⁇ m alkaline galvanized + black passivated (required) 31 ° C, 160 V, 60 s / 10 - 11 ⁇ m acid-zinc plated + black passivated (required) 31 ° C, 160 V, 60 s / 10 - 11 ⁇ m alkaline galvanized + phosphated 1 (comparative) 31 ° C, 160 V, 60 s / 10 - 11 ⁇ m Zinc-plated + phosphated 1 (comparative) 31 ° C, 240 V, 60 s / 10 - 11 ⁇ m 1 : Gardobond® 26SW42OC
  • the steel plates provided with a cathodic dipplate coating are subsequently subjected to a stone impact test.
  • the results of the stone impact test are exemplary in the FIGS. 2 to 8 shown.
  • FIG. 2 a comparison between an inventive black passivated (left), an untreated (center) and a phosphated (right) sheet, which were previously each galvanized alkaline, with black KTL coating after stone impact test. It can be seen that in the case of the untreated, galvanized sheet, most of the flaking and shiny metallic areas are exposed by exposing the zinc layer.
  • the passivation and bonding agent layer in the form of a phosphating having alkaline galvanized sheet with KTL coating shows after stone impact test in comparison to the untreated sheet significantly lower flaking of the KTL coating, what the adhesion-promoting properties the phosphating is due.
  • the invention black passivated alkaline galvanized sheet (left) with KTL coating shows by stone chip test compared to the phosphating a significantly improved image again. In particular, both the numbers of Lackabplatzept or defects as well as the number of shiny metallic areas compared to the phosphated sheet again significantly reduced.
  • FIG. 3 a comparison between an inventively black passivated (left), an untreated (center) and a phosphated (right) steel sheet, which were each zinc-plated, with KTL coating after stone impact test.
  • the untreated galvanized steel sheet shows the greatest number of damages in the lacquer layer as well as in visible shiny metallic areas.
  • the passivated by phosphating steel shows significantly less flaking or defects of the paint layer and shiny metallic sites due to exposure of the zinc layer, which - as in the alkaline galvanized and phosphated sheet - is due to the adhesion-promoting effect of phosphating.
  • the sheet with the black passivated surface according to the invention shows by far the lowest number of shiny metallic areas. This is, as already explained above in connection with alkaline galvanizing, attributable on the one hand to the good adhesion-promoting properties of the passivation layer obtainable according to the invention and, on the other hand, to the dark coloration of the passivation layer obtainable according to the invention, which makes the flaking in the KTL coating clearly less noticeable.
  • FIG. 4 in 30x magnification a section of the in Fig. 2 illustrated alkaline galvanized, but otherwise untreated steel sheet after KTL coating and stone impact test. From the enlarged picture It becomes clear that any defect in the cathodic dipplate coating leads to shiny metallic spots in the surface, as the cathodic dipplate coating is applied directly to the galvanized surface.
  • Fig. 5 shows in 30x magnification a section of the already in Fig. 2 illustrated alkaline galvanized and phosphated steel sheets after KTL coating and stone impact test. It can be seen that due to the adhesion-promoting properties of the phosphating significantly less flaking and thus significantly less shiny metallic surfaces are visible on the surface in comparison to the untreated and alkaline galvanized steel sheet according to Fig. 4 ,
  • Fig. 6 shows in 30x magnification that already in Fig. 2 represented, according to the invention black passivated alkaline galvanized steel sheet after KTL coating and stone impact test.
  • Fig. 7 also shows in 30x magnification another section of the already in Fig. 2 represented according to the invention black passivated and alkaline galvanized steel sheet after KTL coating and stone impact test.
  • FIGS. 6 and 7 clearly shows that the black passivation obtainable according to the invention on the one hand the number of flaking, ie the paint defects, compared to a non-galvanized steel sheet, as in Fig. 4 shown, is significantly reduced and on the other hand, even when flaking the number of shiny metallic sites is significantly reduced or the individual areas in which the galvanization are exposed, are significantly reduced.
  • Fig. 8 Finally, a section of an alkaline-galvanized and inventively black passivated steel sheet after black KTL coating and stone impact test is shown in 100 times magnification. It turns out that part of the KTL coating has flaked off due to the rockfall and that the underlying passivation layer and the zinc layer are recognizable. It can be clearly seen that only a very small part of the area in which the KTL coating has flaked, shines metallic due to exposure of the zinc coating. The much larger part of the chipped area is covered by the black passivation, so that the damage of the cathodic dip-paint coating is much less noticeable.
  • the black passivation is applied to a steel sheet as described above under 1. using the composition 6 according to Table 1 for the black passivation.
  • Another passivation composition based on an aqueous solution of a silane-modified silicate is applied to the black passivation.
  • the aqueous passivation solution based on a silane-modified silicate used is shown in Table 4 as composition 15.
  • Table 4 Passivation solution with silane-modified silicate composition 15 component Wt .-% N- [3- (trimethoxysilyl) propyl] -ethylenediamine 20 vinyltrimethoxysilane 1 Lithium polysilicate (23%) 10 Phosphonic acid (15%) 1.5 water 67.5
  • lithium polysilicate is initially introduced in water, whereby a strongly basic pH is established.
  • the silanes are then added dropwise with stirring over a period of 3 hours and stirred after completion of the addition for a further 3 hours.
  • the alcohol released in the hydrolysis is removed by distillation, so that the hydrolyzate has an alcohol content of less than 0.3 wt .-%.
  • the phosphoric acid is added dropwise over a period of 3 hours until a pH of 3 is reached and stirred for a further 3 hours.
  • the passivation composition thus prepared is knife-coated at a layer thickness of 100 ⁇ m onto the black passivation and the passivation composition is dried at room temperature.
  • the passivated steel sheet is subjected to a salt spray test in accordance with DIN EN ISO 9227.
  • the results of the salt spray test are shown in Table 5 below.
  • Table 5 Comparison of the corrosion resistance of the multilayer passivation system obtainable according to the invention and a passivation layer obtainable according to the invention galvanizing black passivation Silane silicate passivation First WR 1 [h] First RR 2 [h] Composition no. Concentration [% by weight] Composition no.
  • the passivation system obtainable according to the invention has a significantly improved corrosion protection compared to the black passivation obtainable according to the invention.
  • the salt spray test in accordance with DIN EN ISO 9227 shows galvanized steel sheets treated with the black passivation according to the invention, first white rust after 2 to 4 hours, while on galvanized steel sheets treated with the passivation system obtainable according to the invention, first white rust only after 24 to 48 hours observed.
  • first red rust is formed on the substrates coated with the passivation system obtainable according to the invention only after more than twice the time in comparison to substrates which are coated exclusively with the black passivation obtainable according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (12)

  1. Composition de passivation, en particulier de passivation noire, de surfaces galvanisées ou pourvues de revêtements contenant du zinc comprenant
    (a) au moins un composé du fer en des quantités allant de 0,01 à 3 % en poids,
    (b) au moins un composé contenant du phosphore en des quantités allant de 0,01 à 2 % en poids et
    (c) au moins un autre composé de métal de transition en des quantités allant de 0,001 à 0,5 % en poids, chacune par rapport à la composition,
    la composition étant exempte de composés du cobalt, du nickel ou du chrome(VI),
    la composition ayant un pH inférieur à 4, et
    l'autre composé de métal de transition étant choisi parmi les composés de métaux de transition du groupe du scandium, de l'yttrium, des lanthanides, du cinquième (5ème). groupe du tableau périodique des éléments, du sixième (6ème) groupe du tableau périodique des éléments et leurs mélanges.
  2. Composition selon la revendication 1, caractérisée en ce que le composé du fer est un sel.
  3. Composition selon la revendication 2, caractérisée en ce que le sel est un sel purement inorganique.
  4. Composition selon la revendication 2 ou 3, caractérisée en ce que le sel est un nitrate, un chlorure, un bromure, un iodure, un chlorate, un phosphite, un hypophosphite, un phosphonate, un bisphosphonate, un phosphate, un pyrophosphate, un carbonate ou un sulfate.
  5. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition contient le composé du fer en des quantités allant de 0,03 à 1,5 % en poids, de préférence de 0,1 à 1 % en poids, préférentiellement de 0,15 à 0,5 % en poids, d'une manière particulièrement préférée de 0,2 à 0,3 % en poids, par rapport à la composition.
  6. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le composé contenant du phosphore est choisi parmi les hypophosphites, les phosphites, les phosphates et les phosphonates ainsi que leurs mélanges et leurs acides libres.
  7. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition contient le composé contenant du phosphore en des quantités allant de 0,01 à 0,7 % en poids, de préférence de 0,05 à 0,5 % en poids, préférentiellement de 0,10 à 0,2 % en poids, d'une manière particulièrement préférée de 0,12 à 0,15 % en poids, par rapport à la composition.
  8. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition contient l'autre composé de métal de transition en des quantités allant de 0,004 à 0,25 % en poids, de préférence de 0,007 à 0,15 % en poids, préférentiellement de 0,01 à 0,1 % en poids, d'une manière particulièrement préférée de 0,04 à 0,05 % en poids, par rapport à la composition.
  9. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'autre composé de métal de transition comprend au moins un composé d'un élément du groupe du scandium, de l'yttrium, des lanthanides ou leurs mélanges.
  10. Procédé de passivation noire de substrats galvanisés (2), caractérisé en ce qu'un substrat galvanisé est traité avec une composition comprenant
    (a) au moins un composé du fer,
    (b) au moins un composé contenant du phosphore et
    (c) au moins un autre composé de métal de transition
    la composition étant exempte de composés du cobalt, du nickel ou du chrome(VI),
    la composition ayant un pH inférieur à 4, et
    l'autre composé de métal de transition étant choisi parmi les composés de métaux de transition du groupe du scandium, de l'yttrium, des lanthanides, du cinquième (5ème). groupe du tableau périodique des éléments, du sixième (6ème) groupe du tableau périodique des éléments et leurs mélanges.
  11. Procédé selon la revendication 10, caractérisé en ce que le substrat (2) est traité avec la composition pendant une période de 0,1 à 300 secondes, en particulier de 0,5 à 200 secondes, de préférence de 1 à 120 secondes, préférentiellement de 10 à 100 secondes, d'une manière particulièrement préférée de 30 à 80 secondes, plus préférablement 50 à 70 secondes.
  12. Procédé selon la revendication 11, caractérisé en ce que le substrat (2) est traité avec la composition par trempage, pulvérisation, revêtement à la racle ou au rouleau, de préférence par trempage.
EP17181407.2A 2017-07-14 2017-07-14 Composition et procédé de passivation de composants galvanisés Active EP3428314B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17181407.2A EP3428314B1 (fr) 2017-07-14 2017-07-14 Composition et procédé de passivation de composants galvanisés
ES17181407T ES2765816T3 (es) 2017-07-14 2017-07-14 Composición y procedimiento para pasivar componentes cincados
DK17181407.2T DK3428314T3 (da) 2017-07-14 2017-07-14 Sammensætning og fremgangsmåde til passivering af forzinkede dele

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17181407.2A EP3428314B1 (fr) 2017-07-14 2017-07-14 Composition et procédé de passivation de composants galvanisés

Publications (2)

Publication Number Publication Date
EP3428314A1 EP3428314A1 (fr) 2019-01-16
EP3428314B1 true EP3428314B1 (fr) 2019-11-13

Family

ID=59366246

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17181407.2A Active EP3428314B1 (fr) 2017-07-14 2017-07-14 Composition et procédé de passivation de composants galvanisés

Country Status (3)

Country Link
EP (1) EP3428314B1 (fr)
DK (1) DK3428314T3 (fr)
ES (1) ES2765816T3 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3771749A1 (fr) * 2019-07-29 2021-02-03 Ewald Dörken Ag Procédé de passivation de substrats métalliques

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5849110A (en) 1996-11-04 1998-12-15 The Boeing Company Sol coating of metals
DE10162756A1 (de) 2001-12-20 2003-07-10 Walter Hillebrand Gmbh & Co Schwarzpassivierungsverfahren
DE10305450A1 (de) * 2003-02-11 2004-08-26 Walter Hillebrand Gmbh & Co. Aktivatoren der Schwarzpassivierung
DE102004001945A1 (de) 2004-01-14 2005-08-11 Ina-Schaeffler Kg Schwarzpassivierung von Zink- oder Zinklegierungsoberflächen
EP2014793B1 (fr) 2007-06-14 2013-11-20 Atotech Deutschland GmbH Traitement anti-corrosion pour couches de conversion
KR20110054009A (ko) * 2008-09-17 2011-05-24 호덴 세이미츠 카코 켄쿄쇼 컴퍼니 리미티드 아연 또는 아연 합금 표면의 흑색화 화성 처리용 수용액과 그 처리용 수용액을 이용하는 흑색화 방청 피막 형성 방법
DE102010001686A1 (de) * 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
CN104704050B (zh) 2012-10-10 2016-10-12 东丽株式会社 聚乳酸树脂组合物、成型体及聚乳酸树脂组合物的制备方法
CN103397320B (zh) * 2013-08-20 2015-07-15 安徽工业大学 一种用于汽车热镀锌板表面阴极电泳前处理液
EP2907894B1 (fr) * 2014-02-13 2019-04-10 Ewald Dörken Ag Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt
EP3040445B1 (fr) 2014-12-30 2019-02-06 Ewald Dörken Ag Composition de passivation comprenant un composé de silicate modifié par un silane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAZUYUKI UMETSU ET AL: "Effect of ligands on the redox reaction of metal ions and the use of a ligand buffer for improving the end-point detection in the potentiometric titration of vanadium(V) with iron(II).", ANALYTICAL SCIENCES, vol. 7, no. 1, 1 January 1991 (1991-01-01), JP, pages 115 - 118, XP055593929, ISSN: 0910-6340, DOI: 10.2116/analsci.7.115 *

Also Published As

Publication number Publication date
ES2765816T3 (es) 2020-06-11
EP3428314A1 (fr) 2019-01-16
DK3428314T3 (da) 2020-02-17

Similar Documents

Publication Publication Date Title
EP2507408B1 (fr) Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer
EP2255025B1 (fr) Procédé d enduction de surfaces métalliques avec un agent de passivation
EP2014793B1 (fr) Traitement anti-corrosion pour couches de conversion
EP2449149B1 (fr) Traitement de protection anticorrosion pour des surfaces à base de zinc et d'alliages de zinc
EP2907894B1 (fr) Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt
EP2145031B1 (fr) Prétraitement de métallisation de surfaces de zinc
EP2817434B1 (fr) Prétraitement de surfaces en zinc avant une passivation
EP1816234B1 (fr) Procédé et composition aqueuse pour la passivation du zinc ou des alliages à base de zinc
EP3040445B1 (fr) Composition de passivation comprenant un composé de silicate modifié par un silane
DE102016205815A1 (de) Verfahren zur nickelfreien Phosphatierung von metallischen Oberflächen
EP1692325A1 (fr) Traitement de conversion en deux etapes
DE102013223048A1 (de) Verfahren zur Beschichtung von metallischen Oberflächen mit nanokristallinen Zinkoxidschichten, wässerige Zusammensetzungen hierfür und Verwendung der derart beschichteten Oberflächen
WO2017194187A1 (fr) Couches de conversion pour surfaces métalliques
EP2215285B1 (fr) Phosphatation au zirconium de pièces métalliques, en particulier en fer
EP3044348B1 (fr) Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion
EP3428314B1 (fr) Composition et procédé de passivation de composants galvanisés
EP3676419B1 (fr) Procédé amélioré de phosphatage sans nickel des surfaces métalliques
DE102008017523A1 (de) Optimierte Elektrotauchlackierung von zusammengefügten und teilweise vorphosphatierten Bauteilen
EP3918108B1 (fr) Composition alternative et procédé alternatif de phosphatation effective de surfaces métalliques
EP3097221B1 (fr) Procédé servant à recouvrir des surfaces métalliques, substrats recouverts de cette manière et utilisation associée
DE102013202286B3 (de) Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate
EP4283012A1 (fr) Procédé de nettoyage alcalin des bandes en acier allié zinc-magnésium
WO2023174611A1 (fr) Couche de passivation pour substrats contenant un métal
EP3771749A1 (fr) Procédé de passivation de substrats métalliques
DE102017011379A1 (de) Anti-Korrosionsbeschichtung für metallische Substrate

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190311

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/23 20060101ALI20190521BHEP

Ipc: C23C 22/22 20060101ALI20190521BHEP

Ipc: C23C 22/83 20060101ALI20190521BHEP

Ipc: C23C 22/10 20060101AFI20190521BHEP

Ipc: C23C 22/76 20060101ALN20190521BHEP

Ipc: C23C 22/42 20060101ALI20190521BHEP

Ipc: C23C 22/08 20060101ALI20190521BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/23 20060101ALI20190613BHEP

Ipc: C23C 22/10 20060101AFI20190613BHEP

Ipc: C23C 22/83 20060101ALI20190613BHEP

Ipc: C23C 22/08 20060101ALI20190613BHEP

Ipc: C23C 22/42 20060101ALI20190613BHEP

Ipc: C23C 22/76 20060101ALN20190613BHEP

Ipc: C23C 22/22 20060101ALI20190613BHEP

INTG Intention to grant announced

Effective date: 20190711

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1201734

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191115

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502017002841

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20200210

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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: GR

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: 20200214

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: 20191113

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: 20191113

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: 20200213

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: 20191113

Ref country code: NO

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: 20200213

Ref country code: FI

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: 20191113

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: 20200313

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

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

Ref country code: RS

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: 20191113

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: 20200313

Ref country code: HR

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: 20191113

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2765816

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200611

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

Ref country code: AL

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: 20191113

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

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: 20191113

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: 20191113

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: 20191113

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502017002841

Country of ref document: DE

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

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: 20191113

Ref country code: SM

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: 20191113

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: 20200814

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: 20191113

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: 20191113

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200731

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

Ref country code: CH

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

Effective date: 20200731

Ref country code: LI

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

Effective date: 20200731

Ref country code: LU

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

Effective date: 20200714

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

Ref country code: BE

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

Effective date: 20200731

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: 20200714

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

Ref country code: TR

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: 20191113

Ref country code: MT

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: 20191113

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: 20191113

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

Ref country code: MK

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: 20191113

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

Ref country code: NL

Payment date: 20230719

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1201734

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220714

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

Ref country code: AT

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

Effective date: 20220714

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

Ref country code: IT

Payment date: 20230724

Year of fee payment: 7

Ref country code: GB

Payment date: 20230721

Year of fee payment: 7

Ref country code: ES

Payment date: 20230926

Year of fee payment: 7

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

Ref country code: SE

Payment date: 20230719

Year of fee payment: 7

Ref country code: FR

Payment date: 20230726

Year of fee payment: 7

Ref country code: DK

Payment date: 20230721

Year of fee payment: 7

Ref country code: DE

Payment date: 20230725

Year of fee payment: 7