EP2208809B9 - Zusammensetzung zur Beschichtung eines metallischen Substrates - Google Patents

Zusammensetzung zur Beschichtung eines metallischen Substrates Download PDF

Info

Publication number
EP2208809B9
EP2208809B9 EP20100159057 EP10159057A EP2208809B9 EP 2208809 B9 EP2208809 B9 EP 2208809B9 EP 20100159057 EP20100159057 EP 20100159057 EP 10159057 A EP10159057 A EP 10159057A EP 2208809 B9 EP2208809 B9 EP 2208809B9
Authority
EP
European Patent Office
Prior art keywords
weight
coating composition
film
composition according
dry coating
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.)
Expired - Lifetime
Application number
EP20100159057
Other languages
English (en)
French (fr)
Other versions
EP2208809A1 (de
EP2208809B1 (de
Inventor
Jean-Marie Poulet
Alain Chesneau
Georges Leger
Denis Begue
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.)
NOF Metal Coatings Europe
Original Assignee
NOF Metal Coatings Europe
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27772234&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2208809(B9) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by NOF Metal Coatings Europe filed Critical NOF Metal Coatings Europe
Publication of EP2208809A1 publication Critical patent/EP2208809A1/de
Application granted granted Critical
Publication of EP2208809B1 publication Critical patent/EP2208809B1/de
Publication of EP2208809B9 publication Critical patent/EP2208809B9/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a metal substrate coating composition based on an aqueous solution of lithium silicate.
  • the present invention also relates to methods of applying this composition to said metal substrate and to the various uses of this coating composition.
  • the coating composition is intended to be applied to a steel substrate having a free outer surface consisting of a metal layer of zinc or zinc-based alloy.
  • said metal layer may have been deposited on said steel substrate electrolytically or by hot dipping.
  • the metal surface treatment is subject to multiple constraints of a technical, economic and environmental nature.
  • Sheet metal coils are produced by steelmakers using very fast processes, with line speeds ranging from a few m / min up to 250 m / min.
  • the surface treatment technologies must accommodate these line speed constraints.
  • Technical difficulties can then arise if one wishes to maintain a good chemical reactivity between the substrate and the treatment products, but also in terms of film formation, if one wishes to obtain a good tension and a good homogeneity of the deposits. of movie.
  • Anti-corrosion treatment technologies usually use chromium-based products (hexavalent or trivalent) that are applied in one or more layers. However, these products are harmful to the environment and need to be replaced by non-environmental treatment products.
  • on-line operating constraints also require products that are on the one hand mono-component (that is to say that do not require the preparation of a mixture of several products prior to industrial implementation) and which are, on the other hand, stable over time (that is to say, with a lifespan of more than 3 weeks to accommodate the productions made by campaign).
  • the present invention relates to a composition that meets the requirements and constraints mentioned above.
  • the coating composition is intended to be applied to a metal substrate.
  • the wet film thus obtained is then dried and gives rise to a dry coating film.
  • the coating composition preferably contains 5 to 30% by weight of lithium siticate (s), more preferably 5 to 20% by weight of lithium silicate (s), even more preferentially 8 to 15% by weight of silicate (s). ) of lithium.
  • this coating composition may be prepared in the form of a concentrate in which the percentage of lithium silicate (s) may be up to about 40% by weight, or in the form of a powder in which the percentage of silicate (s) lithium can reach up to about 80% by weight.
  • the present invention also relates to the dry coating film obtainable from the application method (described below) of the coating composition on a metal substrate.
  • This dry film of coating is characterized in that it comprises at least 40% by weight of dry matter lithium sillcate (s), preferably between 60% and 99.9% by weight relative to the total weight of dry film coating.
  • tensioning agent means an additive whose function is to lower and control the liquid surface energy of the composition (or surface tension).
  • Surface energy is the energy required to bring the molecules of the liquid interior of the composition to its surface. The lower the surface energy of the composition, the greater the wettability of the surface of the metal substrate. Wettability is the ability for said substrate to receive a liquid allowing it to spread over the largest possible area.
  • the surface energy of the composition is preferably adjusted to obtain good wettability of the surface to be coated under high line speed conditions before the product is frozen upon entering the drying zone.
  • the coating composition contains between 0.01 and 1% by weight of a tensioning agent, preferably about 0.1% by weight of a tensioning agent.
  • the tensioning agent may be added separately or on the occasion of the incorporation of another component containing such an agent, for example a dispersion or an emulsion of a polymer.
  • voltage agent may be mentioned copolymers of polypropylene glycol and polyéthytèneglycol (such as Pluronic ® PE 3100 manufactured by BASF), silicone resins (such as ® BYK348, manufactured by BYK ), acetylenic glycols (such as Dyno1604 ® manufactured by Air Products), anionic and nonionic mixtures (such as Dapro W95 HS ® , marketed by Elementis), quaternary ammoniums (such as Cycloquart ® , manufactured by Clariant ), modified polyethoxylated alcohols (such as Triton ® DF16, manufactured by Union Carbide), and compatible mixtures thereof.
  • copolymers of polypropylene glycol and polyéthytèneglycol such as Pluronic ® PE 3100 manufactured by BASF
  • silicone resins such as ® BYK348, manufactured by BYK
  • acetylenic glycols such as Dyno1604 ® manufactured by Air Products
  • the tensioning agent can be added to the composition according to the present invention in the form of an aqueous solution, a dispersion or an emulsion in water, with or without a co-solvent.
  • the water used in the coating composition according to the present invention is first subjected to a deionization process such that the conductivity of this water is approximately less than 20 ⁇ S / cm.
  • the pH of the coating composition will be an alkaline pH of between 11 and 13, more preferably between 11 and 12.
  • the coating composition may further contain a polymer whose function is to lower the glass transition temperature of the dry coating film.
  • the presence of said polymer imparts elasticity and flexibility properties to the dry film of coating thus obtained. Said polymer then makes it possible to reduce or eliminate the appearance of cracks in the dry coating film, during a subsequent mechanical deformation of the metal substrate.
  • acrylic polymers or copolymers such as Polysol M-19 ® (manufactured by SHOWA Highpolymer Co. Ltd.) or Rhodopas D-20 40 ® (manufactured by Rhodia), polyurethanes, alkyds, epoxy esters, as well as their compatible mixtures.
  • said polymer can be added to the composition according to the present invention in the form of a dispersion or an emulsion in water or of an aqueous solution, in a proportion which advantageously allows to reach up to 60 % by weight of the dry coating film.
  • said polymer can at the same time provide the composition with the previously mentioned tensioning agent.
  • the coating composition contains an additive for increasing the hydrophobicity of the dry film coating, in a proportion that achieves up to 50% by weight of the dry film coating, preferably up to 25% by weight dry film coating.
  • This additive is a silane, preferably chosen from di- or trimethoxysilanes, or functionalized di- or triethoxysilanes, and mixtures thereof.
  • the organic functionality can be vinyl, amine or oxyrane (epoxy) type.
  • the silane is chosen from epoxy-functional silanes such as beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 4- (trimethoxysilyl) 1,2-butane-epoxide or gamma-glycidoxypropyltrimethoxysilane.
  • the silane may also act as a binder, a stabilizer for the coating composition, and may increase the corrosion resistance of the dry coating film.
  • silanes can be used independently or in combination in prehydrolysed form or not.
  • silane may also be associated addition of titanate or zirconate to enhance the crosslinking of the binder system depending on the characteristics required of the coating.
  • the increase in the hydrophobicity of the dry film coating can be observed visually, especially during cyclic corrosion tests (DIN 50017KTW), by the formation of droplets of condensed water vapor (from the electrolyte) less spread only in the case of a coating whose binder is only composed of silicate.
  • the introduction of the silane into the coating composition leads to the decrease of the permeability and / or porosity of the dry film coating to the electrolyte, thereby conferring its hydrophobicity.
  • the hydrophobicity of the dry coating film obtained by introducing the silane into the coating composition allows a lower dry film thickness to be applied for the same corrosion resistance result.
  • the coating composition may furthermore contain an additive making it possible to reduce the free surface alkalinity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight. dry film coating.
  • This additive is preferably a cerium (Ce) salt, a Lanthanum salt (La), a molybdenum salt (Mo), molybdic acid, paratoluene sulphonic acid, and their salts, or a polyol such as glycerol, as well as their mixtures.
  • the coating composition may furthermore contain an additive making it possible to increase the anticorrosion properties of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight of the film dry coating.
  • This additive is preferably a mineral binder such as a titanate or a zirconate, and mixtures thereof.
  • the coating composition may further contain a lubricating agent.
  • a lubricating agent such as polytetrafluoroethylene, polyethylene, polyethylene glycol or natural organic polymers such as carnauba wax or paraffins, and mixtures thereof.
  • the lubricant is added to the coating composition in a proportion which advantageously makes it possible to attain up to 15% by weight of the dry coating film, preferably between 1.5 and 15% by weight of the dry coating film, more preferably between 3 and 15% by weight of the dry coating film, more preferably between 5 and 15% by weight of the dry coating film.
  • the lubricant may require a stabilizer to avoid phase separation in the coating composition.
  • organophilic clays natural or synthetic
  • silica derivatives cellulose derivatives
  • xanthan gum or associative thickeners of polyurethane or acrylic type, and mixtures thereof.
  • the stabilizer is added to the coating composition according to the present invention in a proportion which achieves between about 0.1 and 5% by weight of the dry coating film.
  • the coating composition may additionally be added with an antifoam agent chosen in a manner compatible with the other constituents of the coating composition and the optimal amount of which is determined according to the conventional experiments of routines known to those skilled in the art.
  • said composition may be substantially free of organic solvent.
  • organic solvents have been found, in practice, to be incompatible with sodium and / or potassium and / or lithium silicates, the main constituents of the coating composition.
  • the present invention also relates to a method of coating a metal substrate which comprises applying the previously described coating composition to the surface of said substrate.
  • the application of the coating composition described above is carried out during an operation which consists in depositing a wet film of said composition, of suitable low thickness, followed by a drying operation of said composition.
  • metal substrate thus coated, giving rise to a dry coating film of said substrate.
  • the wet film thickness of the coating composition deposited on the metal substrate is between 0.3 and 39 ⁇ m, preferably between 0.3 and 30 ⁇ m and the wet film is applied at a rate of 0.6 at 40 g / m 2 , preferably from 0.6 to 24 g / m 2 .
  • the method which is the subject of the present invention can be carried out online, after the metal coating step of zinc or zinc-based alloy of the steel substrate, or on a recovery line such as on a pre-lacquering line (" coil-coating ").
  • the operation of depositing the wet film of the coating composition on the metal substrate can advantageously be carried out by spraying, spraying followed by a spinning operation, by soaking followed by spinning operation or by means of a coating system composed of at least one roller.
  • the spinning operation makes it possible to control the thickness of the wet film deposited on the metal substrate.
  • This spinning operation can be advantageously carried out using a set of spinning rolls.
  • the drying operation of the metal substrate coated with the wet film is carried out by heating the metal substrate or the wet film so as to bring the latter to a temperature of between room temperature and room temperature. ° C.
  • the heating operation can be performed directly by induction, or indirectly by convection or infrared. Convection heating generally requires a longer drying time than induction heating or infrared heating.
  • This drying operation is advantageously carried out by heating the metal substrate or the wet film so as to bring the latter preferably to a temperature of at least about 35 ° C for a period of at least 2 seconds if heating is used. convection and for a maximum of 10 seconds, preferably 5 seconds, more preferably 1 to 2 seconds, if using induction heating or infrared heating.
  • the drying operation is carried out in order to obtain a dry film thickness of coating of between 0.05 and 0.80 ⁇ m, preferably between 0.05 and 0.60 ⁇ m and so as to obtain a weight of layer of dry film coating between 0.1 g / m 2 and 1.3 g / m 2 , preferably between 0.2 g / m 2 and 1.2 g / m 2 , more preferably between 0.2 and 0.5 g / m 2 .
  • the wet film deposition and drying operations are carried out between zinc or zinc alloy metal coating operations of the steel substrate and final winding.
  • the present invention also relates to the various uses of the coating composition object of the present invention.
  • the coating composition can be used as a corrosion protection layer of metal sheets when it is applied to said sheets.
  • said composition can be used as an anti-corrosion protection layer for metal sheets to be temporarily stored.
  • a layer of dry coating film according to the present invention when it has been applied to a metal substrate and then dried at 240 ° C., completely resists said soak baths. degreasing.
  • said layer of dry coating film is partially solubilized by the degreasing baths and when it has been dried at 50 ° C., it is completely solubilized by the degreasing baths. .
  • the coating composition can be used as a lubricating layer when it further contains a lubricant and is applied to metal sheets for shaping, particularly for folding, bending and stamping said metal sheets.
  • the coating composition may be used as an anti-fingerprint agent.
  • metal sheets coated with the coating composition object of the present invention can be handled as is, without fingerprints remaining subsequently printed on said metal sheets.
  • the coating composition may be applied to metal substrate parts to be welded.
  • said substrates thus coated retain their weldability property and the welding operations can be done directly.
  • the coating composition may require the addition of conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
  • conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
  • Lubricated coating composition (B) % mass Sodium silicate 10.8 Polytetrafluoroethylene (PTFE) 0.7 Polyethylene (PE) 1.3 Acrylic polymer 1.1 Water 86.1 Composition of lubricated dry coating film (B) % mass Sodium silicate 78 Acrylic polymer 8 PTFE and PE 14
  • the test consists of subjecting the metal substrate sample to a friction over a length of about 50 mm (see FIG. figure 1 ).
  • the samples have a size of 50 mm x 200 mm and are processed on both sides.
  • a lateral force (F L ) is imposed on the sample and it is subjected to a constant speed pull of 20 mm / min.
  • the tensile force F T is measured after a friction distance of 50 mm.
  • the measurement temperature is 21 ⁇ 2 ° C.
  • the coating dry film layer weights deposited on the metal substrate samples are between 1 and 1.2 g / m 2 .
  • the reference sample is an electrogalvanised sheet (7.5 ⁇ m on each side) on which a layer of ANTICORRIT 4107 S ® oil (manufacturer FUCHS) has been applied at a height of 2.5 g / m 2 on each face .
  • This oil is widely used in the automotive industry as a lubricant for sheet metal for stamping.
  • the coefficients of friction of the dry film-coated samples of composition according to the present invention (B1) to (86) are lower than the coefficient of friction of the reference sample. This indicates that lubrication of the dry film-coated samples of the present invention (B1) to (B6) is better than that of the reference sample.
  • Sample hot-dip galvanized steel (10 ⁇ m) Sample of hot-dip galvanized steel (10 ⁇ m) coated with a dry coating film according to composition (A) with a coating weight of: 0.3 g / m 2 0.6 g / m 2 0.9g / m 2 1.2 g / m 2 Humidotherm test (duration 15 cycles) performed according to DIN 50017 White rust on 100% of the surface (after 5 cycles only) Change in appearance: White rust on 70% of the surface No appearance changes No appearance changes No appearance changes No appearance changes Salt spray test (48 hours duration) according to ISO 9227 White rust on 100% of the surface (after 24 hours only) White rust on 60% of the surface White rust on 20% of the surface White rust on less than 5% of the surface No appearance changes
  • Test DIN 50017KTW (20 cycles) Hot-dip galvanized steel substrate (10 ⁇ m) coated with a dry coating film according to composition (A) or (E) with a coating weight of: 0.2 g / m 2 0.5 g / m 2 0.65 g / m 2 Formulation (A) Change in appearance: white rust on 90% of the surface Change in appearance: white rust on 50% of the surface Very slight change in appearance: white rust on 15% of the surface Formulation (E) Very slight change in appearance: white rust on 20% of the surface No change in appearance No change in appearance No change in appearance No change in appearance No change in appearance
  • composition comprising the silane is more effective against corrosion than the silane-free composition.
  • introduction of silane thus makes it possible to reduce the weight of the layer while maintaining the same anticorrosion properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Liquid Crystal (AREA)

Claims (23)

  1. Beschichtungszusammensetzung für Metallsubstrat, eine freie Außenschicht aufweisend, die von einer Zinkschicht oder einer Schicht einer Legierung auf Zinkbasis gebildet wird, dadurch gekennzeichnet, dass sie umfasst (Gew.-%):
    - Lithiumsilikat(e), eingebracht in Form wässriger Lösung    3% - 35%
    - Tensid    0,01% - 1%
    - ein Silan in einem Anteil, der erlaubt, bis zu 50 Gew.-% der trockenen Beschichtungsschicht zu erreichen,
    - Wasser    qsp 100%,
    wobei die Zusammensetzung einen pH zwischen 11 und 13 inklusive, in vorteilhafter Weise zwischen 11 und 12 hat.
  2. Beschichtungszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass sie umfasst (Gew.-%):
    - 5 bis 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, in noch bevorzugter Weise 8 bis 15 Gew.-% Lithiumsilikat(e) und/oder
    - zirka 0,1 Gew.-% eines Tensids.
  3. Beschichtungszusammensetzung nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das Lithiumsilikat in der Zusammensetzung in Form einer wässrigen Lithiumsilikatlösung verwendet wird mit folgender Gewichtszusammensetzung:
    - - SiO2    15% - 40%
    - - Li2O    1% - 10%
    - - Wasser    qsp 100%.
  4. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Tensid ausgewählt ist aus einem Polypropylenglykol- und Polyethylenglykolcopolymer, einem Harz auf Silikonbasis, einem Azetylenglykol, einem anionischen und nicht ionischen Gemisch, einem quaternären Ammonium, einem modifizierten Polyethoxylalkohol und einem ihrer kompatiblen Gemische.
  5. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie weiterhin ein Polymer umfasst, dessen Funktion in der Absenkung der Glasübergangstemperatur der trockenen Beschichtungsschicht besteht, insbesondere ein Acrylpolymer oder -copolymer, ein Polyurethan, ein Alkyd, einen Epoxyester oder eines ihrer kompatiblen Gemische, wobei das Polymer in vorteilhafter Weise zu der Zusammensetzung in Form einer Dispersion oder einer Emulsion in Wasser oder einer wässrigen Lösung hinzugefügt wird.
  6. Beschichtungszusammensetzung nach Anspruch 5, dadurch gekennzeichnet, dass das Polymer der Zusammensetzung in einem Anteil hinzugefügt wird, der es erlaubt, bis zu 60 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
  7. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie weiterhin einen Hilfsstoff umfasst, der erlaubt, die freie Oberflächenalkalinität der trockenen Beschichtungsschicht zu verringern, insbesondere ein Ceriumsalz, ein Lanthansalz, ein Molybdänsalz, Molybdänsäure, p-Toluolsulfonsäure oder ein Polyol sowie ihre Gemische, in einem Anteil, der erlaubt, bis zu 25 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
  8. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie weiterhin einen Hilfsstoff umfasst, der erlaubt, die korrosionshemmenden Eigenschaften der trockenen Beschichtungsschicht zu steigern, insbesondere ein Titanat oder ein Zirconat sowie ihre Gemische, in einem Anteil, der erlaubt, bis zu 25 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
  9. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie weiterhin ein Schmiermittel enthält, insbesondere Polytetrafluorethylen, Polyethylen, Polyethylenglycol, Carnaubawachs oder Paraffin sowie ihre Gemische, wobei das Schmiermittel zu der Beschichtungszusammensetzung in einem Anteil hinzugefügt wird, der erlaubt, bis zu 15 Gew.-% der trockenen Beschichtungsschicht, vorzugsweise zwischen 1,5 und 15 Gew.-% der trockenen Beschichtungsschicht, in noch bevorzugter Weise zwischen 3 und 15 Gew.-% der trockenen Beschichtungsschicht, in noch mehr bevorzugter Weise zwischen 5 und 15 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
  10. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie weiterhin ein Antischaummittel umfasst.
  11. Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 10, durch einen Oberflächenspannungswert zwischen 20 mN.m-1 und 50 mN.m-1 inklusive, vorzugsweise zwischen 22 mN.m-1 und 45 mN.m-1, in noch bevorzugter Weise zwischen 22 mN.m-1 und 40 mN.m-1 gekennzeichnet.
  12. Metallsubstrat, welches mit Hilfe einer Zusammensetzung nach einem der Ansprüche 1 bis 11 beschichtet wird.
  13. Auftragsverfahren auf Metallsubstrat, das eine freie Außenschicht aufweist, die von einer Metallschicht auf Zinkbasis oder auf Basis einer Legierung auf Zinkbasis gebildet wird, einer Zusammensetzung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es einen Arbeitsgang umfasst, der darin besteht, eine feuchte Schicht der Zusammensetzung in geeigneter geringer Stärke aufzubringen, gefolgt von einem Arbeitsgang der Trocknung des derart beschichteten Metallsubstrats, wodurch eine trockene Beschichtungsschicht des Substrats gebildet wird.
  14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die Schicht der Beschichtungszusammensetzung in Form einer feuchten Schicht einer Stärke zwischen 0,3 µm und 39 µm inklusive, vorzugsweise zwischen 0,3 und 30 µm inklusive aufgebracht wird.
  15. Verfahren nach einem der Ansprüche 13 und 14, dadurch gekennzeichnet, dass die Schicht der Beschichtungszusammensetzung in Form einer feuchten Schicht aufgebracht wird, die in einer Menge von 0,6 g/m2 bis 40 g/m2, vorzugsweise von 0,6 bis 24 g/m2 aufgetragen wird.
  16. Verfahren nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, dass der Arbeitsgang des Aufbringens der feuchten Schicht ausgeführt wird:
    - durch Zerstäuben; oder
    - durch Aufsprühen, gefolgt von einem Arbeitsgang des Abquetschens der aufgebrachten feuchten Schicht, um die Steuerung ihrer Stärke zu erlauben, wobei der Arbeitsgang des Abquetschens in vorteilhafter Weise mit Hilfe von einem Satz Abquetschwalzen durchgeführt wird; oder
    - durch Eintauchen, gefolgt von einem Arbeitsgang des Abquetschens, um die Stärke der aufgebrachten feuchten Schicht zu steuern, wobei der Arbeitsgang des Abquetschens in vorteilhafter Weise mit Hilfe von einem Satz Abquetschwalzen durchgeführt wird; oder
    - mittels eines Beschichtungssystems, das sich aus mindestens einer Walze zusammensetzt.
  17. Verfahren nach einem der Ansprüche 13 bis 16, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durch Erhitzen des Metallsubstrats oder der feuchten Schicht erfolgt in der Art, dass diese Letzteren auf eine Temperatur zwischen der Raumtemperatur und 240°C inklusive gebracht werden, der Arbeitsgang des Trocknens in vorteilhafter Weise durch Erhitzen des Metallsubstrats oder der feuchten Schicht erfolgt in der Art, dass diese Letzteren vorzugsweise auf eine Temperatur von mindestens zirka 35°C gebracht werden während einer Dauer von mindestens 2 Sekunden bei Verwendung einer Konvektionsheizung und während einer maximalen Dauer von 10 Sekunden, vorzugsweise von 5 Sekunden, in noch bevorzugter Weise von 1 bis 2 Sekunden bei Verwendung einer Induktions- oder Infrarotheizung.
  18. Verfahren nach einem der Ansprüche 13 bis 17, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durchgeführt wird, um eine Endstärke der trockenen Beschichtungsschicht zwischen 0,05 µm und 0,80 µm inklusive, vorzugsweise zwischen 0,05 und 0,60 µm zu erhalten.
  19. Verfahren nach einem der Ansprüche 13 bis 18, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durchgeführt wird, um ein Schichtgewicht der trockenen Beschichtungsschicht zwischen 0,1 g/m2 und 1,3 g/m2 inklusive, vorzugsweise zwischen 0,2 g/m2 und 1,2 g/m2, in noch bevorzugter Weise zwischen 0,2 und 0,5 g/m2 zu erhalten.
  20. Verfahren nach einem der Ansprüche 13 bis 19, dadurch gekennzeichnet, dass die Arbeitsgänge des Aufbringens der feuchten Schicht und des Trocknens zwischen den Arbeitsgängen der metallischen Beschichtung mit Zink oder einer Legierung auf Zinkbasis des Metallsubstrats und dem abschließenden Aufwickeln durchgeführt werden.
  21. Verfahren nach einem der Ansprüche 13 bis 20, dadurch gekennzeichnet, dass die trockene Beschichtungsschicht mindestens 40 Gew.-% Trockenmaterial Lithiumsilikat(e), vorzugsweise zwischen 60 Gew.-% und 99,9 Gew.-% im Verhältnis zum Gesamtgewicht der trockenen Beschichtungsschicht umfasst.
  22. Verwendung einer Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 11:
    - für den Rostschutz von Metallblechen;
    - als Mittel gegen Fingerabdrücke, wenn sie auf Metallbleche aufgetragen wird;
    - für das Beschichten von Metallsubstratteilen, die zum Schweißen bestimmt sind, was in vorteilhafter Weise ein direktes Schweißen der Metallsubstratteile erlaubt, sobald sie mit der Beschichtungszusammensetzung beschichtet sind.
  23. Verwendung einer Beschichtungszusammensetzung nach Anspruch 9 als Schmierschicht, wenn sie auf Metallbleche im Hinblick auf ihre Formung, insbesondere im Hinblick auf Biegen, Walzen und Pressen der Metallbleche, aufgetragen wird.
EP20100159057 2002-03-18 2003-03-18 Zusammensetzung zur Beschichtung eines metallischen Substrates Expired - Lifetime EP2208809B9 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0203353A FR2837218B1 (fr) 2002-03-18 2002-03-18 Composition de revetement de substrat metallique
EP20030727594 EP1485519B1 (de) 2002-03-18 2003-03-18 Zusammensetzung und verfahren zur beschichtung von metallsubstraten

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP03727594.8 Division 2003-03-18
EP20030727594 Division EP1485519B1 (de) 2002-03-18 2003-03-18 Zusammensetzung und verfahren zur beschichtung von metallsubstraten

Publications (3)

Publication Number Publication Date
EP2208809A1 EP2208809A1 (de) 2010-07-21
EP2208809B1 EP2208809B1 (de) 2013-06-12
EP2208809B9 true EP2208809B9 (de) 2014-11-12

Family

ID=27772234

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20100159057 Expired - Lifetime EP2208809B9 (de) 2002-03-18 2003-03-18 Zusammensetzung zur Beschichtung eines metallischen Substrates
EP20030727594 Expired - Lifetime EP1485519B1 (de) 2002-03-18 2003-03-18 Zusammensetzung und verfahren zur beschichtung von metallsubstraten

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP20030727594 Expired - Lifetime EP1485519B1 (de) 2002-03-18 2003-03-18 Zusammensetzung und verfahren zur beschichtung von metallsubstraten

Country Status (11)

Country Link
US (1) US7232479B2 (de)
EP (2) EP2208809B9 (de)
AT (1) ATE468424T1 (de)
AU (1) AU2003233381A1 (de)
BR (1) BR0308562A (de)
CA (1) CA2479060C (de)
DE (1) DE60332605D1 (de)
ES (2) ES2423317T3 (de)
FR (1) FR2837218B1 (de)
MX (1) MXPA04009082A (de)
WO (1) WO2003078683A2 (de)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2837218B1 (fr) * 2002-03-18 2005-02-18 Dacral Sa Composition de revetement de substrat metallique
US20060263613A1 (en) * 2005-05-20 2006-11-23 General Electric Company Temperature dependent transparent optical coatings for high temperature absorption
US8124113B2 (en) * 2005-09-06 2012-02-28 Hamilton Sundstrand Space Systems International, Inc. Hydrophilic coating
JP2009514694A (ja) * 2005-10-21 2009-04-09 アグフア−ゲヴエルト 改竄防止ｉｄ証書の作製方法
KR100858995B1 (ko) * 2007-11-23 2008-09-18 씨캠 주식회사 송전시설의 부식방지 및 전력손실을 방지하는 기능을 보유한 기능성도료 조성물
KR101168628B1 (ko) † 2008-01-24 2012-07-30 유껜 고교 가부시기가이샤 내식성 도포막을 갖는 부재, 그 제조 방법 및 그것을 제조하기 위한 도료 조성물
EP2154111A1 (de) * 2008-07-10 2010-02-17 Cognis IP Management GmbH Wasserlösliche Silikate und deren Verwendung
GB2466270A (en) 2008-12-19 2010-06-23 3M Innovative Properties Co Composition for providing stain release or stain repellency to stone substrates
CN201383872Y (zh) * 2009-01-19 2010-01-13 歌尔声学股份有限公司 电容式麦克风的隔离片
US8067486B1 (en) 2009-01-26 2011-11-29 The Sherwin-Williams Company Low VOC water-based epoxy coatings
EP2451880B1 (de) 2009-07-07 2014-04-16 Ak Steel Properties, Inc. Polymerbeschichtetes metallisches substrat und verfahren zu dessen herstellung
EP2633099B1 (de) * 2010-10-27 2019-07-03 Chemetall GmbH Wässerige zusammensetzung zur vorbehandlung einer metallischen oberfläche vor einer weiteren beschichtung oder zur behandlung jener oberfläche
DE102011111757A1 (de) * 2011-08-24 2013-02-28 Coventya Gmbh Versiegelungsmittel sowie dessen Verwendung und versiegeltes metallisches Substrat
ITFI20130039A1 (it) * 2013-03-01 2014-09-02 Colorobbia Italiana Spa Composizioni a base di vetro polimerico per coating vetroso.
EP2971230B1 (de) * 2013-03-16 2021-11-10 PRC-Desoto International, Inc. Korrosionshemmende sol-gel-zusammensetzungen
JP7036508B2 (ja) 2016-03-18 2022-03-15 スリーエム イノベイティブ プロパティズ カンパニー 金属表面をコーティングするための双性イオン性ポリマー含有組成物、方法、及び物品
FR3096051B1 (fr) * 2019-05-17 2021-06-04 Nof Metal Coatings Europe Composition de revetement deshydratee, sous forme solide, son procede d’obtention et son procede de rehydratation

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565675A (en) * 1966-10-05 1971-02-23 Philadelphia Quartz Co Coatings from lithium silicate
US3884863A (en) * 1970-11-27 1975-05-20 Exxon Research Engineering Co Zinc enriched lithium silicate-latex coating composition
JPS5276236A (en) * 1975-12-22 1977-06-27 Toyo Kohan Co Ltd Process for treating steel sheet to be worked
US4169916A (en) 1975-12-22 1979-10-02 Toyo Kohan Co., Ltd. Steel sheets and method of treating steel sheets
DE3064550D1 (en) * 1979-01-22 1983-09-22 Ball Corp A solution for imparting tarnish resistance on aluminium surfaces and method for applying it
CS231073B1 (cs) * 1982-06-11 1984-09-17 Karel Barton Přípravek pro úpravu povrchu zinku, hliníku a slitin na jejich bázi před nanášením organických povlaků
JPH0639568B2 (ja) * 1985-04-24 1994-05-25 東レ・ダウコーニング・シリコーン株式会社 シリコ−ン水性エマルジヨン組成物の製造方法
JPS62127366A (ja) * 1985-11-26 1987-06-09 Kansai Paint Co Ltd 無機質亜鉛末塗料
JPS62235477A (ja) * 1986-04-03 1987-10-15 Showa Alum Corp アルミニウムの親水性皮膜形成剤
JPS6372887A (ja) * 1986-09-12 1988-04-02 Nisshin Steel Co Ltd 耐食性、耐加工性に優れた溶融めつき鋼板の製造方法
US5350791A (en) * 1992-07-02 1994-09-27 Henkel Corporation Hydrophilicizing treatment for metal objects
US5412011A (en) * 1993-10-15 1995-05-02 Betz Laboratories, Inc. Composition and process for coating metals
US5854190A (en) * 1997-01-16 1998-12-29 Dalco Industries, Ltd. Water-based flushing for paints and other coatings
JPH10130687A (ja) * 1996-10-30 1998-05-19 Kawasaki Steel Corp 熱間加工用潤滑剤組成物
US5908501A (en) * 1998-01-27 1999-06-01 Pucillo; Patric M. Composition and a method for preventing dustfall from material
DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen
WO2002085541A2 (en) * 2001-04-20 2002-10-31 Savin Roland R Silicate coating compositions
FR2837218B1 (fr) * 2002-03-18 2005-02-18 Dacral Sa Composition de revetement de substrat metallique

Also Published As

Publication number Publication date
WO2003078683A9 (fr) 2004-07-15
EP2208809A1 (de) 2010-07-21
CA2479060C (fr) 2011-05-24
FR2837218B1 (fr) 2005-02-18
EP1485519A2 (de) 2004-12-15
DE60332605D1 (de) 2010-07-01
AU2003233381A1 (en) 2003-09-29
WO2003078683A3 (fr) 2004-06-03
ATE468424T1 (de) 2010-06-15
US7232479B2 (en) 2007-06-19
AU2003233381A8 (en) 2003-09-29
BR0308562A (pt) 2005-01-04
EP2208809B1 (de) 2013-06-12
US20060086281A1 (en) 2006-04-27
WO2003078683A2 (fr) 2003-09-25
FR2837218A1 (fr) 2003-09-19
ES2423317T3 (es) 2013-09-19
EP1485519B1 (de) 2010-05-19
MXPA04009082A (es) 2004-12-06
ES2343244T3 (es) 2010-07-27
CA2479060A1 (fr) 2003-09-25

Similar Documents

Publication Publication Date Title
EP2208809B9 (de) Zusammensetzung zur Beschichtung eines metallischen Substrates
AU2004215240B2 (en) Method for coating metallic surfaces with a silane-rich composition
EP2010612B1 (de) Verwendung eines nanostrukturierten materials als schutzbeschichtung für metalloberflächen
WO2007003828A2 (fr) Sol pour le revetement par voie sol-gel d'une surface et procede de revetement par voie sol-gel le mettant en œuvre
EP2450470A1 (de) Hydroxysulfat-Oberflächenbehandlung
EP3250726A1 (de) Verfahren zur herstellung eines beschichteten blechs, mit anwendung einer wässrigen lösung mit aminosäure, und zugehörige verwendung zur verbesserung der kompatibilität mit einem klebstoff
EP2766508B1 (de) Verfahren zur korrosionsschutzbehandlung fester metallsubstrate
EP1373597B1 (de) Verfahren zur behandlung von metalloberflächen durch carboxylierung
WO2013054066A1 (fr) Procédé de traitement anticorrosion d'un substrat métallique solide et substrat métallique susceptible d'être obtenu par un tel procédé
EP1963545B1 (de) Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches
EP3347140B1 (de) Verfahren zum aufbringen einer korrosionsbeständigen beschichtung auf ein metallteil, wässrige beschichtungszusammensetzung, korrosionsbeständige beschichtung für metallteile und beschichtetes metallteil
FR2796655A1 (fr) Procede et composition de traitement anti-corrosion d'un substrat metallique prealablement protege par une couche de revetement a base de zinc
EP0517586B1 (de) Verfahren zum Erzeugen einer Antikorrosionsbeschichtung auf Copolymerbasis auf einer Metalloberfläche
EP3414360B1 (de) Entwicklung einer sol-gel-korrosionsschutzbehandlung
FR3026412A1 (fr) Traitement de surface de substrats metalliques
EP0897969B1 (de) Verfahren zur Behandlung von Metallblech-Oberflächen zur Verbesserung der Verklebung, der Tiefziehverarbeitung und der Entfettung
WO2022023685A1 (fr) Composition et utilisation de cette composition pour la formation d'un revêtement de type sol-gel sur une surface métallique
FR2742160A1 (fr) Procede pour proteger contre la corrosion et/ou preparer a la mise en forme une piece metallique
FR2742159A1 (fr) Procede pour proteger contre la corrosion et/ou preparer a la mise en forme une piece metallique
FR2879219A1 (fr) Procede de traitement de surface d'une piece revetue d'une couche de zinc ou de zinc allie ainsi que piece obtenue par la mise en oeuvre de ce procede

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

AC Divisional application: reference to earlier application

Ref document number: 1485519

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

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

17P Request for examination filed

Effective date: 20110111

17Q First examination report despatched

Effective date: 20110706

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 1485519

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

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

Ref legal event code: REF

Ref document number: 616729

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: MICHELI AND CIE SA, CH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60344299

Country of ref document: DE

Effective date: 20130808

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2423317

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130919

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: 20130612

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: 20130612

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: 20130913

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: 20130612

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 616729

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130612

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130612

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: 20130912

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130612

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: 20130612

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: 20130612

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: 20131014

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

Ref country code: NL

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: 20130612

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: 20130612

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: 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: 20130612

26N No opposition filed

Effective date: 20140313

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60344299

Country of ref document: DE

Effective date: 20140313

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140318

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: IE

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

Effective date: 20140318

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

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: 20130612

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: 20130612

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: 20030318

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: 20130612

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

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

Ref country code: CZ

Payment date: 20180314

Year of fee payment: 16

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

Ref country code: BE

Payment date: 20180330

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20180531

Year of fee payment: 16

Ref country code: CH

Payment date: 20180417

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20180327

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20180417

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20190312

Year of fee payment: 17

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

Ref country code: DE

Payment date: 20190415

Year of fee payment: 17

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

Ref country code: CZ

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

Effective date: 20190318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190318

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

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

Ref country code: LI

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

Effective date: 20190331

Ref country code: GB

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

Effective date: 20190318

Ref country code: CH

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

Effective date: 20190331

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

Ref country code: IT

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

Effective date: 20190318

Ref country code: BE

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

Effective date: 20190331

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200727

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60344299

Country of ref document: DE

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

Ref country code: ES

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

Effective date: 20190319

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

Ref country code: DE

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

Effective date: 20201001

Ref country code: FR

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

Effective date: 20200331