EP2826569A1 - Procédé de passivation de tôle noire en forme de bande - Google Patents

Procédé de passivation de tôle noire en forme de bande Download PDF

Info

Publication number
EP2826569A1
EP2826569A1 EP20140175621 EP14175621A EP2826569A1 EP 2826569 A1 EP2826569 A1 EP 2826569A1 EP 20140175621 EP20140175621 EP 20140175621 EP 14175621 A EP14175621 A EP 14175621A EP 2826569 A1 EP2826569 A1 EP 2826569A1
Authority
EP
European Patent Office
Prior art keywords
black plate
black
treatment solution
chromium
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20140175621
Other languages
German (de)
English (en)
Other versions
EP2826569B1 (fr
Inventor
Reiner Dr. Sauer
Andrea Dr. Marmann
Helmut Dr. Oberhoffer
Tatjana KASDORF
Gerhard Menzel
Dirk Dr. Matusch
Rainer Götz
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.)
ThyssenKrupp Rasselstein GmbH
Original Assignee
ThyssenKrupp Rasselstein GmbH
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 ThyssenKrupp Rasselstein GmbH filed Critical ThyssenKrupp Rasselstein GmbH
Priority to RS20170926A priority Critical patent/RS56351B1/sr
Publication of EP2826569A1 publication Critical patent/EP2826569A1/fr
Application granted granted Critical
Publication of EP2826569B1 publication Critical patent/EP2826569B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • C23C22/182Orthophosphates containing manganese cations containing also zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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
    • C23C22/74Chemical 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 for obtaining burned-in conversion coatings
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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
    • C23C22/76Applying the liquid by spraying
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • C23C22/80Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/82After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/34Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal

Definitions

  • the invention relates to a method for the passivation of strip-shaped black sheet, wherein in an initial step by an electrochemical treatment of the black plate an inert layer is formed on the black plate surface and in a further step, an aqueous chromium-free treatment solution on at least one surface of the black plate to form a protective against corrosion Conversion layer is applied, which also forms an adhesive layer for paints and organic coating materials.
  • Passivation is understood here to mean the targeted generation of a protective layer (here: conversion layer) on the black sheet, which prevents or at least greatly slows the corrosion of the black sheet.
  • the invention further relates to the use of black plates treated according to the invention as packaging steel.
  • the metallic surface is provided with a coating of another, usually less noble, metal (such as zinc and chromium). So it is e.g. known steel sheets with zinc or chromium or with tin (which, however, is nobler compared to steel) to coat.
  • metal such as zinc and chromium
  • tin which, however, is nobler compared to steel
  • Tinplate very extensively tinned Feinstbleche
  • Tinplates are characterized by a very good corrosion resistance and a good forming behavior and their weldability and are therefore very well suited for the production of packaging, such. Beverage cans.
  • Conversion layers are non-metallic, usually inorganic, very thin layers on a metal surface, which are generally produced by chemical reaction of an aqueous treatment solution with the metallic substrate. Conversion coatings ensure a very effective corrosion protection, in particular with fine metal sheets, a good primer for coatings and plastics and they reduce surface friction and abrasion.
  • Chromium-containing conversion layers have proven to be very effective corrosion protection.
  • chromating the metallic surface is treated with an acidic solution containing chromium (VI) ions, whereby chromium (VI) is reduced to chromium (III). The treatment forms a chromium-containing conversion layer which protects against corrosion on the metal surface.
  • chromium (VI) compounds are acutely toxic and carcinogenic.
  • the passivation of metal surfaces containing chromium (VI) -containing substances has already been banned in the EU.
  • chromium-free conversion layers have been developed in the prior art. So are, for example, from the WO 97/40208-A and the EP 2532769 A1 Method for producing chromium-free conversion layers on zinc or aluminum surfaces known.
  • treatment solutions for the production of chromium-free conversion layers are described which contain oxo cations and halogen complex ions, which lead to colorless and slightly iridescent conversion layers.
  • Tinplate has excellent properties as a food packaging material and has been manufactured and processed for many decades for this purpose.
  • tin which is the anticorrosion coating on tinplate
  • electrolytically plated chromium plated steel sheets are known as Tin Free Steel (TFS) or Electrolytic Chromium Coated Steel (ECCS) .
  • TFS Tin Free Steel
  • ECCS Electrolytic Chromium Coated Steel
  • these tin-free steel sheets are distinguished by a good adhesion to paints or organic protective coatings (for example of PP or PET), but on the other hand have considerable advantages in carrying out the coating process because of the toxic and health-endangering properties of the chromium-VI-containing materials used for coating Disadvantages.
  • the object of the present invention is therefore to provide a chromium-free packaging steel, which is suitable as a substitute for tin-free steel sheet (TFS or ECCS) and as a replacement for tinplate and in particular both in terms of Corrosion resistance as well as with respect to the adhesion for paints or organic coatings should be comparable to tinplate or tin-free steel sheet.
  • TFS tin-free steel sheet
  • ECCS tin-free steel sheet
  • an uncoated black plate is used in strip form and the surface rendered inert in a first step by an electrochemical treatment, then rinsed with water or other rinsing liquid and finally coated in a further step with a corrosion stable conversion coating by applying to at least one surface of the black sheet an aqueous chromium free treatment solution.
  • the steel may, for example, be a ferritic steel or else a multiphase steel which has a plurality of structural constituents, in particular ferrite, martensite, bainite and / or retained austenite.
  • Such multiphase steels are characterized by a high strength of more than 500 MPa with simultaneously good elongation at break of more than 10%.
  • the grades of the steel sheet defined in DIN EN 10202: 2001: "Cold-rolled packaging sheet products (electrolytically tinned and chromium-plated)" are preferably observed.
  • this standard defines the analysis and mechanical characteristics of the steel.
  • the grades are in particular between TS230 (soft hood furnace grade, yield strength 230 MPa) to TH620 (DO, 620MPa).
  • the black plate in strip form is moved at a belt speed of preferably more than 200 m / min and up to 750 m / min.
  • a step of forming an inert layer on the surface of the black sheet by an electrochemical treatment is first cleaned in a possibly required pretreatment step and in particular degreased, then rinsed, pickled and rinsed again.
  • the cold-rolled and recrystallization-annealed black sheet is usually tempered after recrystallization annealing, for example, when wet-rolling with a water-oil suspension or dry-soaking the blackplate surfaces by oil, iron abrasion, soaps and others Contaminants are contaminated. This contamination is eliminated by the (optional) pretreatment step.
  • the black plate is passed into a cleaning tank with an alkaline sodium or potassium hydroxide solution.
  • concentration of the alkaline degreasing agent is preferably between 20 and 100 g / l at bath temperatures of 20-70 ° C.
  • a degreasing of the black plate is expediently carried out in two steps, wherein in a first step a dipping method and in the second step an electrolytic method with current densities of 2 to 30 A / dm 2 is performed. After degreasing, each band side of the black plate is rinsed, for example, by a triple cascade rinsing with 10-30 m 3 / h of water.
  • Removal of oxide residues may, if necessary, be accomplished by passing the blackplate tape into further cleansing tanks having a salt or sulfuric acid pickle at a concentration of, for example, 10 to 120 g / l in two consecutive dives, followed by a dive with a dive.
  • the temperatures of the pickling solution and the rinsing water are typically between 20 and 60 ° C.
  • a homogeneous, dense, inert steel surface is produced by electrochemical treatment by passing the black metal strip through an electrolyte.
  • the electrolyte is preferably alkaline.
  • the electrochemical, preferably alkaline treatment of the black plate is used for inerting and for equalizing the surface properties of the steel strip before applying the conversion coating.
  • the black plate belt is passed through the belt speed through an electrolytic bath while being connected as an anode at a preferred current densities of 2-30 A / dm 2 .
  • the electrolyte is, for example, a sodium hydroxide solution having a preferred NaOH concentration of 20-100 g / l, and more particularly a sodium hydroxide bath containing a 3% NaOH solution.
  • a soda solution in particular a 5% sodium carbonate solution (Na 2 CO 3 ), may also be used as the electrolyte.
  • the bath temperatures of the electrolysis bath are suitably maintained between 20 and 80 ° C.
  • the black plate is rinsed with water.
  • the rinsing can be done by immersing the tape in a water tank or by spraying with water. Preference is given to using demineralized (DI), deionized water, osmosis water or distilled water at temperatures of 20-60 ° C. However, untreated drinking water or other rinsing liquids can also be used. After rinsing, the black plate is dried.
  • a conversion layer is applied to at least one surface of the black plate by applying an aqueous chromium-free treatment solution to the surface of the black plate previously rendered inert in the electrochemical treatment.
  • the conversion coating is expediently applied in a no-rinse method, that is to say rinsing after generation of the conversion layer is omitted.
  • the aqueous chromium-free treatment solution which forms the conversion coating is applied, for example, to the surface of the black plate with a coating device which comprises a roller coater, a rotary sprayer or spray nozzles.
  • the surface of the black plate to which the conversion layer is to be applied should be as clean and dry as possible. Therefore, at least the surface of the black plate to be coated with the conversion layer is dried with a drying device, eg with an air knife.
  • This air knife is a laminar hot air flow on the Inflated surface of the moving belt, so that disturbing foreign particles blown off the steel belt surface and the steel belt surface is dried.
  • the rotary sprayer has a plurality of spray rotors juxtaposed transversely to the belt running direction to which the aqueous treatment solution is supplied and which are rotated by a drive to spray the aqueous treatment solution on the or each surface of the belt in the form of a fine spray jet due to centrifugal force Form wet film of the aqueous solution.
  • a drive to spray the aqueous treatment solution on the or each surface of the belt in the form of a fine spray jet due to centrifugal force Form wet film of the aqueous solution.
  • the smoothing rollers are expediently arranged with respect to the black plate surface (s) such that they exert only little pressure on the wet film of the aqueous treatment solution and squeeze no or at most a minimal portion of the applied treatment solution from the surface.
  • the amount of treatment solution sprayed with the rotary sprayer is adjusted accordingly so that there is no excess on the blackplate surface. This eliminates the otherwise necessary disposal or treatment of the excess portion of the treatment solution.
  • the dry coating of the treatment solution after drying is expediently between 1 and 50 mg / m 2 and is preferably in the range from 10 to 30 mg / m 2 .
  • the amount of the aqueous treatment solution fed to the spray rotors of the rotary sprayer per unit time is expediently adapted to the belt speed.
  • a constant circulation of the wet film in the range of 2 ml / m 2 to 8 ml / m 2 and preferably of about 5 ml / m 2 per band side can be set independently of the belt speed.
  • the belt After applying the wet film of the processing solution, the belt is passed through a belt dryer to dry the wet film. After drying, a dry coating of the conversion layer formed in this way from 2 mg / m 2 to 30 mg / m 2 remains on the surface of the black plate per side.
  • the desired dry run of the Conversion layer can be adjusted by the rotation sprayer per unit time supplied amount of treatment solution.
  • An advantage of this type of application is that only fresh treatment solution is used and that it can not be contaminated by iron separation by contact and recycling with the steel strip.
  • the process is very economical, since only the exact amount needed is applied and no excess is needed, so that excess treatment solution does not have to be collected. This can prevent that post-treated wastewater arise.
  • the application of the treatment solution can also Rolling coater by a roller application - also on a previously dried black plate surface - done. Roll coaters are preferably used in the lower speed range of the belt speed and in particular at speeds of less than 200 m / min.
  • the application can also be carried out by spraying the treatment solution or by immersing the tape in a bath with the treatment solution. In this case, since the treatment solution is applied in excess to the black plate, it is necessary to achieve a predetermined desired edition of the conversion layer, squeeze off the excess portion of the wet film, for example by means of squeezing rollers, which can be done "wet on wet". In this method, however, the solution is not applied the same constant regardless of the speed and the treatment solution can also be contaminated by iron and must then be renewed and disposed of after exceeding a contamination threshold.
  • the wet film of the treatment solution applied with the described application methods is finally dried to form a dry conversion layer.
  • This can be done, for example, by passing the black plate through a drying oven in which wet film is dried by means of hot air or IR radiation. The drying is preferably carried out at temperatures of 50-250 ° C.
  • the surface of the dry conversion layer with Dioctylsebacat (DOS), acetyltributylcitrate (ATBC), butyl stearate (BSO) or polyalkylene glycol, in particular polyethylene glycol (PEG, preferably having a molecular weight of 6000 g / mol), or combinations thereof oiled or post-treated.
  • DOS Dioctylsebacat
  • ATBC acetyltributylcitrate
  • BSO butyl stearate
  • polyalkylene glycol in particular polyethylene glycol (PEG, preferably having a molecular weight of 6000 g / mol
  • the treatment solution further contains at least one adhesion promoter for paints or organic coating materials, the adhesion promoter in particular containing constituents of maleic acid, isophthalic acid and cyclohexanedimethanol (CHDM) or combinations thereof.
  • adhesion promoters have been found to be compositions containing polyethylene terephthalate (PET) or polycyclohexylenedimethylene terephthalate (PCT), e.g. glycol-modified polyethylene terephthalate (PET-G containing less than about 30% CHDM) or PCTG (containing more than about 30% CHDM).
  • the requirements are 1 to 50 mg / m 2 for the respective substances.
  • BASF® EFKA ® 4560 modified polyacrylates BASF® - Ti, Zn, Mn phosphate Henkel ® Granodine ® 1456 Ti, Zr Henkel ® GTP 10861 Gardo ® TP Zn phosphates Ti Chemetall ® GB X4744A Gardobond ® (Chemetall ®) Mn, Ti, Zr Chemetall ® GB X4591 A1 Ti, Zr Chemetall ® GB X4744 Ti, Zr Chemetall ®
  • the process according to the invention can be carried out without major installation effort into an existing coating installation, e.g. be integrated into a coil coating plant for the production of ECCS (or TFS).
  • the belt speed in such belt coating systems is typically 80-600 m / min.
  • the inventive method has the advantages of a chromium-free and thus environmentally friendly and not harmful to health and cost-effective coating on conventional black plate, especially in the fine and Feinstblech thickness range.
  • by the selected application method (no-rinse method) for applying the conversion layer by eliminating the final rinse effective cost and energy savings can be achieved.
  • advantages are achieved by the combination of inorganic passivation and polymer-containing thin-film coating.
  • the black sheets treated by the process of the invention are eminently suitable for the production of packaging, in particular cans, and can therefore replace the tinplates and tin-free steel sheets (TFS or ECCS) conventionally used as packaging steel. These black sheets are comparable in their corrosion resistance with tinplate and have similarly good adhesion properties for paints and plastic coatings, for example of PP or PET, on as tin-free steel sheets (TFS or ECCS).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
EP14175621.3A 2013-07-16 2014-07-03 Procédé de passivation de tôle noire en forme de bande Active EP2826569B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
RS20170926A RS56351B1 (sr) 2013-07-16 2014-07-03 Postupak za pasiviranje crnog lima u obliku trake

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE201310107506 DE102013107506A1 (de) 2013-07-16 2013-07-16 Verfahren zur Passivierung von bandförmigem Schwarzblech

Publications (2)

Publication Number Publication Date
EP2826569A1 true EP2826569A1 (fr) 2015-01-21
EP2826569B1 EP2826569B1 (fr) 2017-06-21

Family

ID=51205191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14175621.3A Active EP2826569B1 (fr) 2013-07-16 2014-07-03 Procédé de passivation de tôle noire en forme de bande

Country Status (10)

Country Link
US (1) US20150024222A1 (fr)
EP (1) EP2826569B1 (fr)
JP (1) JP2015028210A (fr)
CN (1) CN104294348B (fr)
BR (1) BR102014017368B1 (fr)
CA (1) CA2855673C (fr)
DE (1) DE102013107506A1 (fr)
ES (1) ES2634870T3 (fr)
RS (1) RS56351B1 (fr)
RU (1) RU2663232C2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3133187A1 (fr) * 2015-08-21 2017-02-22 ThyssenKrupp Rasselstein GmbH Procede de traitement thermique d'une tole noire revetue d'une couche de conversion
EP3434807A1 (fr) * 2017-07-28 2019-01-30 ThyssenKrupp Rasselstein GmbH Tôle d'acier pourvue d'une couche de conversion, procédé de fabrication d'un tôle d'acier revêtue de la couche de conversion et milieu de traitement destiné à l'application d'une couche de conversion sur un tôle d'acier
EP3719169A4 (fr) * 2017-11-28 2021-01-13 JFE Steel Corporation Tôle magnétique en acier à grains orientés et son procédé de production
WO2021116320A1 (fr) * 2019-12-11 2021-06-17 Salzgitter Flachstahl Gmbh Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105567920A (zh) * 2015-12-31 2016-05-11 芜湖市金宇石化设备有限公司 一种变速箱壳体热处理用热处理剂
CN105695698A (zh) * 2015-12-31 2016-06-22 芜湖市金宇石化设备有限公司 一种变速箱壳体热处理用热处理剂的制备方法
DE202020100524U1 (de) * 2020-01-31 2021-05-04 Thyssenkrupp Rasselstein Gmbh Verpackungsblecherzeugnis, insbesondere Weißblech oder elektrolytisch verchromtes Stahlblech
KR102204664B1 (ko) * 2020-12-15 2021-01-19 우리하이피 주식회사 릴투릴 금속판재 및 가공품의 나노부동태 처리방법 및 그에 따라서 제조된 금속판재 및 가공품

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5989776A (ja) * 1982-11-13 1984-05-24 Sumitomo Metal Ind Ltd 化成性にすぐれた冷延鋼板の製造方法
WO1997040208A1 (fr) 1996-04-19 1997-10-30 SurTec Produkte und Systeme für die Oberflächenbehandlung GmbH Couche de conversion exempte de chrome(vi) et son procede de production
EP1060032A2 (fr) * 1998-03-02 2000-12-20 Corus UK Limited Bande metallique laminee
DE10161383A1 (de) * 2000-10-11 2002-08-22 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate
WO2008119675A1 (fr) 2007-03-29 2008-10-09 Atotech Deutschland Gmbh Moyen de réalisation de couches de protection contre la corrosion sur des surfaces métalliques
EP2532769A1 (fr) 2011-06-10 2012-12-12 Amcor Flexibles Kreuzlingen Ltd. Procédé de production dune couche de conversion sur une surface dune bande d'aluminium ou d'alliage d'aluminium

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4416416A1 (de) * 1994-05-10 1995-11-16 Rasselstein Ag Beschichtete Stahlfolie für Verpackungen, insbesondere für den Lebensmittelbereich, und Verfahren zu deren Herstellung
FR2730942B1 (fr) * 1995-02-24 1997-05-16 Lorraine Laminage Procede d'elaboration d'une tole ou d'une bande en acier pour la realisation d'une boite et tole ou bande en acier obtenue par ce procede
DE19635560A1 (de) * 1996-09-02 1998-03-05 Basf Lacke & Farben Porenfreie Beschichtung von Metallbehältern
JP4054539B2 (ja) * 2001-03-07 2008-02-27 日本パーカライジング株式会社 傾斜型2層潤滑皮膜を有する塑性加工用金属材料の製造方法
JP4110750B2 (ja) * 2001-06-07 2008-07-02 Jfeスチール株式会社 耐食性と導電性に優れた有機被覆鋼板
KR100700436B1 (ko) * 2003-01-31 2007-03-28 제이에프이 스틸 가부시키가이샤 흑색아연계 도금 강판
JP2005272972A (ja) * 2004-03-26 2005-10-06 Nisshin Steel Co Ltd 光輝焼鈍処理ステンレス鋼板の塗装前処理方法および塗装用光輝焼鈍処理ステンレス鋼板
JP4487651B2 (ja) * 2004-06-22 2010-06-23 東洋製罐株式会社 表面処理金属材料及びその表面処理方法、並びに樹脂被覆金属材料、金属缶、金属蓋
US20060042726A1 (en) * 2004-09-02 2006-03-02 General Electric Company Non-chrome passivation of steel
DE102005045033B3 (de) * 2005-09-21 2007-01-18 Rasselstein Gmbh Verfahren zur Erniedrigung des Reibwerts der Oberfläche von mit einer Beschichtung überzogenen Metallbändern und Vorrichtung für das Aufbringen einer metallischen Beschichtung auf ein Stahlband
US8673091B2 (en) * 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
JP5215043B2 (ja) * 2008-06-02 2013-06-19 日本パーカライジング株式会社 金属の表面処理用処理液及び表面処理方法
JP5380033B2 (ja) * 2008-10-09 2014-01-08 Jfe建材株式会社 耐食性と塗料密着性に優れた塗装金属材
JP5775453B2 (ja) * 2009-07-02 2015-09-09 日本パーカライジング株式会社 クロムおよびフッ素フリー金属表面用化成処理液、金属表面処理方法および金属表面塗装方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5989776A (ja) * 1982-11-13 1984-05-24 Sumitomo Metal Ind Ltd 化成性にすぐれた冷延鋼板の製造方法
WO1997040208A1 (fr) 1996-04-19 1997-10-30 SurTec Produkte und Systeme für die Oberflächenbehandlung GmbH Couche de conversion exempte de chrome(vi) et son procede de production
EP1060032A2 (fr) * 1998-03-02 2000-12-20 Corus UK Limited Bande metallique laminee
DE10161383A1 (de) * 2000-10-11 2002-08-22 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate
WO2008119675A1 (fr) 2007-03-29 2008-10-09 Atotech Deutschland Gmbh Moyen de réalisation de couches de protection contre la corrosion sur des surfaces métalliques
EP2532769A1 (fr) 2011-06-10 2012-12-12 Amcor Flexibles Kreuzlingen Ltd. Procédé de production dune couche de conversion sur une surface dune bande d'aluminium ou d'alliage d'aluminium

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3133187A1 (fr) * 2015-08-21 2017-02-22 ThyssenKrupp Rasselstein GmbH Procede de traitement thermique d'une tole noire revetue d'une couche de conversion
DE102015113878A1 (de) * 2015-08-21 2017-02-23 Thyssenkrupp Ag Verfahren zur thermischen Behandlung eines mit einer Konversionsschicht beschichteten Schwarzblechs
RU2702667C2 (ru) * 2015-08-21 2019-10-09 ТиссенКрупп Рассельштайн ГмбХ Способ термообработки черной жести с конверсионным покрытием и способ изготовления защищенной от коррозии черной жести
DE102015113878B4 (de) 2015-08-21 2023-03-16 Thyssenkrupp Ag Verfahren zur thermischen Behandlung eines mit einer Konversionsschicht beschichteten Schwarzblechs
EP3434807A1 (fr) * 2017-07-28 2019-01-30 ThyssenKrupp Rasselstein GmbH Tôle d'acier pourvue d'une couche de conversion, procédé de fabrication d'un tôle d'acier revêtue de la couche de conversion et milieu de traitement destiné à l'application d'une couche de conversion sur un tôle d'acier
EP3719169A4 (fr) * 2017-11-28 2021-01-13 JFE Steel Corporation Tôle magnétique en acier à grains orientés et son procédé de production
US11473176B2 (en) 2017-11-28 2022-10-18 Jfe Steel Corporation Oriented electrical steel sheet and method for producing same
WO2021116320A1 (fr) * 2019-12-11 2021-06-17 Salzgitter Flachstahl Gmbh Tôle métallique comportant un revêtement promoteur d'adhérence en tant que produit semi-fini pour la fabrication de composants composites métal-thermoplastique, et procédé de production d'une tôle métallique de ce type

Also Published As

Publication number Publication date
EP2826569B1 (fr) 2017-06-21
ES2634870T3 (es) 2017-09-29
JP2015028210A (ja) 2015-02-12
CA2855673C (fr) 2016-09-27
RU2014128191A (ru) 2016-01-27
DE102013107506A1 (de) 2015-01-22
BR102014017368A2 (pt) 2015-10-06
BR102014017368B1 (pt) 2021-06-29
US20150024222A1 (en) 2015-01-22
CN104294348B (zh) 2017-12-12
RU2663232C2 (ru) 2018-08-02
RS56351B1 (sr) 2017-12-29
CA2855673A1 (fr) 2015-01-16
CN104294348A (zh) 2015-01-21

Similar Documents

Publication Publication Date Title
EP2826569B1 (fr) Procédé de passivation de tôle noire en forme de bande
EP2145031B1 (fr) Prétraitement de métallisation de surfaces de zinc
EP0163325B1 (fr) Procédé et agent de revêtement pour le traitement de surfaces métalliques
EP2802688B1 (fr) Procédé de passivation de fer blanc
DE102016217507A1 (de) Vorbehandlung von Aluminiumoberflächen mit zirkon- und molybdänhaltigen Zusammensetzungen
EP2215285B1 (fr) Phosphatation au zirconium de pièces métalliques, en particulier en fer
DE2002599B2 (de) Verfahren zum aufbringen organischer lack- und farbueberzuege auf metallische oberflaechen
EP3133187B1 (fr) Procede de traitement thermique d'une tole noire revetue d'une couche de conversion
EP3434807A1 (fr) Tôle d'acier pourvue d'une couche de conversion, procédé de fabrication d'un tôle d'acier revêtue de la couche de conversion et milieu de traitement destiné à l'application d'une couche de conversion sur un tôle d'acier
EP3405600B1 (fr) Procédé de fabrication d'un produit en acier doté d'un revêtement de zinc et d'une couche active tribilogiquement appliquée sur celui-ci ainsi que produit en acier obtenu de maniere correspondante
EP0590594B1 (fr) Traitement de surfaces métalliques pour améliorer leur propriété adhésive et leurs propriétés anti-corrosion
DE102006035660B4 (de) Korrosionsschutzschicht mit verbesserten Eigenschaften und Verfahren zu ihrer Herstellung
DE202017104500U1 (de) Stahlblech mit einer Konversionsschicht und Behandlungsmittel zur Applizierung einer Konversionsschicht auf einem Stahlblech
DE2114333A1 (de) Beschichtetes Metall und Verfahren zum Beschichten von Metalloberflaechen
DE4333894C1 (de) Verfahren zur Harzvergütung einer Metalloberfläche
JP4143019B2 (ja) 無機有機複合処理亜鉛系めっき鋼板
WO2003052005A1 (fr) Produit servant a former un appret d'adherence sur des surfaces metalliques et procede de traitement
DE2904014A1 (de) Verzinktes stahlblech und aus diesem hergestellte dose
DE1303648B (de) Galvanisch plattiertes und lackiertes Stahlblech

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20140703

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

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

R17P Request for examination filed (corrected)

Effective date: 20150721

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

17Q First examination report despatched

Effective date: 20151026

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502014004301

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: B05D0007000000

Ipc: C23C0022780000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C23G 1/00 20060101ALI20170209BHEP

Ipc: C25D 11/34 20060101ALI20170209BHEP

Ipc: C23C 22/05 20060101ALI20170209BHEP

Ipc: C23C 22/78 20060101AFI20170209BHEP

Ipc: C23C 22/76 20060101ALI20170209BHEP

Ipc: C23C 22/34 20060101ALI20170209BHEP

Ipc: C23C 22/74 20060101ALI20170209BHEP

Ipc: C23C 22/73 20060101ALI20170209BHEP

Ipc: C23C 22/18 20060101ALI20170209BHEP

Ipc: C23C 22/83 20060101ALI20170209BHEP

INTG Intention to grant announced

Effective date: 20170308

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): 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: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

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: AT

Ref legal event code: REF

Ref document number: 903016

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014004301

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2634870

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170929

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

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: 20170621

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: 20170621

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: 20170921

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: 20170621

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: 20170922

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: 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: 20170921

Ref country code: SE

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: 20170621

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: 20170621

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

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: 20170621

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: 20170621

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: 20170621

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 25349

Country of ref document: SK

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

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: 20170621

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: 20171021

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: 20170621

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014004301

Country of ref document: DE

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: 20170621

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

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: 20170703

Ref country code: LI

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

Effective date: 20170731

Ref country code: DK

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: 20170621

Ref country code: CH

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

Effective date: 20170731

26N No opposition filed

Effective date: 20180322

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: 20170703

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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: 20170621

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

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: 20170621

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

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: 20140703

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

Ref country code: RS

Payment date: 20190620

Year of fee payment: 6

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: 20170621

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: 20170621

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

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: 20170621

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: 20170621

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 903016

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190703

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: 20190703

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 NON-PAYMENT OF DUE FEES

Effective date: 20200703

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

Ref country code: TR

Payment date: 20230622

Year of fee payment: 10

Ref country code: SK

Payment date: 20230620

Year of fee payment: 10

Ref country code: NL

Payment date: 20230720

Year of fee payment: 10

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

Ref country code: IT

Payment date: 20230731

Year of fee payment: 10

Ref country code: GB

Payment date: 20230724

Year of fee payment: 10

Ref country code: ES

Payment date: 20230821

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20230720

Year of fee payment: 10

Ref country code: DE

Payment date: 20230911

Year of fee payment: 10

Ref country code: BE

Payment date: 20230719

Year of fee payment: 10