EP2402484A1 - Method of creating a protective coating on flat products made of titanium zinc - Google Patents

Method of creating a protective coating on flat products made of titanium zinc Download PDF

Info

Publication number
EP2402484A1
EP2402484A1 EP11005194A EP11005194A EP2402484A1 EP 2402484 A1 EP2402484 A1 EP 2402484A1 EP 11005194 A EP11005194 A EP 11005194A EP 11005194 A EP11005194 A EP 11005194A EP 2402484 A1 EP2402484 A1 EP 2402484A1
Authority
EP
European Patent Office
Prior art keywords
titanium
copper
protective layer
treatment
zinc alloy
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
EP11005194A
Other languages
German (de)
French (fr)
Other versions
EP2402484B1 (en
Inventor
Ralf Prof. Dr.-Ing Feser
Marianne Dr. Schönnenbeck
Andreas Friedrich
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.)
Rheinzink GmbH and Co KG
Original Assignee
Rheinzink GmbH and Co KG
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=44587594&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2402484(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rheinzink GmbH and Co KG filed Critical Rheinzink GmbH and Co KG
Publication of EP2402484A1 publication Critical patent/EP2402484A1/en
Application granted granted Critical
Publication of EP2402484B1 publication Critical patent/EP2402484B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants

Definitions

  • the invention relates to a method for producing a protective layer in gray tinting on rolled flat products made of a titanium-zinc alloy and the semifinished product produced therefrom.
  • a process for the preparation of uniform hue protective coatings on flat zinc products has been made DE 196 36 370 known.
  • the flat products are pickled in a pickling bath with mixed acid containing sulfuric acid and nitric acid and, after rinsing, passivated by applying chromate-containing polymers to form a protective layer.
  • the aforementioned method requires, in addition to the treatment with strong acids, the aftertreatment with chromate-containing polymers, which encounters environmental protection concerns.
  • Zinc oxalate coatings on zinc layers with relatively low concentration oxalate solutions are used in the EP 1 252 367 B4 described, wherein the Oxalationsaten Cu 2+ ions are attached.
  • the result of the treatment of the zinc surface is a "lubrication pre-coating" (prelubrification). A certain shade of zinc oxalate coatings is not sought.
  • the object of the invention is to provide a method using a coating solution "can be provided with the titanium zinc sheets and other products and products produced therefrom with a homogeneous, textured gray protective layer, which works without the use of chromate polymers and in which the resulting product no
  • different shades of gray should be producible with the components of the same overall composition of the coating solution.
  • the correspondingly treated titanium-zinc alloy flat products show a protective layer of uniform gray hue, in which the natural microstructure of the surface becomes visible as a texture after the treatment.
  • the alloy can remain unchanged, only the composition of the treatment solution is varied within the limits listed above.
  • oxalic acid HOOC-COOH
  • malonic acid HOOC- (CH 2 ) -COOH
  • the color is slightly lighter.
  • the acids can be used mixed. By appropriate mixing ratios of oxalic acid and malonic acid then different shades of color can be produced.
  • Copper compounds which form Cu + or Cu 2+ ions in the coating solution are preferably copper (I) oxides or copper (II) oxides and copper nitrate. Copper sulfate can be used as another copper salt at the expense of color deviations.
  • a rolled strip consisting of a zinc alloy in accordance with the European standard EN 988 is degreased by rinsing with an alkaline degreasing solution at a temperature of approx. 60 ° C and a rinsing pressure of approx. 2.5 bar and then with a water spray jet at a temperature of about 65 ° C and a pressure of about 2.5 bar hosed. To assist the rinse and surface roughening, the strip is brushed in the final rinse step.
  • the strip is treated in a treatment bath at room temperature with an aqueous treatment solution with a proportionate 35 g / l phosphoric acid, 40 g / l oxalic acid, 3 g / l ammonium nitrate and 0.5 g / l copper oxide, wherein the residence time of the respective band section in the bath 60 seconds.
  • the pH of the treatment solution is at pH 2.5.
  • the treatment is carried out at a bath temperature of about 40 ° C. The result is a gray color of the surface.
  • the color of the deposited color protective layer is essentially dependent on the pH of the solution and the component ratios. Uniform shades between light gray and dark gray can be produced for the same alloy composition of the substrate.
  • the emerging from the treatment bath band is rinsed with water.
  • the tape thus obtained shows a similar resistance to white discoloration due to white rust formation in the condensation climate humidity change test as untreated titanium-zinc alloy flat products. Electrochemical investigations confirm the corrosion protection effect of the protective layer obtained. Kelvin probe measurements show that the protective layer inhibits zinc dissolution.
  • an existing from a zinc alloy according to the European standard EN 988 tape was treated according to Example 1, wherein instead of oxalic acid, the same molar mass of malonic acid was used.
  • the ratio of the molecular weights is about 65 to 83, ie per 1 of water about 51 g of malonic acid were used.
  • As Cu 2+ -forming salt 3.0 g / l copper nitrate [Cu (NO 3 ) 2 ] was added.
  • the resulting ribbon showed the same properties as described above, with the color being slightly lighter than the oxalic acid treated ribbon.
  • a band consisting of a zinc alloy according to the European standard EN 988 was treated according to Example 1, using a mixture of 15 g / l oxalic acid and 20 g / l malonic acid.
  • the resulting ribbon showed the same properties as described above, with the color assuming an intermediate tone between the staining according to Examples 1 and 2.
  • the invention further relates to a flat rolled semi-finished product of a titanium-zinc alloy with a gray-tinted protective layer produced by means of one of the appended method claims.
  • the thickness of the protective layer is preferably between 0.1 and 10 microns.
  • a finished part for example a downpipe or roof share made of a titanium-zinc alloy according to the European standard EN 988, is prepared according to the invention from a flat product treated in an aqueous treatment solution of the type mentioned above and in the examples and thereby with a protective layer uniformly gray, but variably adjustable color tint is provided.
  • the flat product thus obtained exhibits the natural surface structure and has a comparable sensitivity to whitening by the formation of white rust as naturally patinated titanium-zinc alloy flat products, so that it is suitable for many uses, even in a free atmosphere.

Landscapes

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

Abstract

Producing a protective layer with a gray tint on rolled flat products made of titanium-zinc alloy or its derived products comprises treating the product with an acidic aqueous coating solution, where the treatment solution, which is prepared in 1000 cm 3>of water, comprises (in g) phosphoric acid (20-50), saturated oxalic acid and/or malonic acid (20-50), ammonium nitrate (2-5), copper containing compounds (0.1-5), which form cuprous or cupric ions in the treatment solution. An independent claim is also included for flat-rolled semi-finished products of titanium-zinc alloy with the protective layer with a gray tint, produced by the above mentioned method.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer Schutzschicht in grauer Farbtönung auf gewalzten Flacherzeugnissen aus einer Titan-Zink-Legierung sowie das daraus hergestellte Halbzeug.The invention relates to a method for producing a protective layer in gray tinting on rolled flat products made of a titanium-zinc alloy and the semifinished product produced therefrom.

Ein Verfahren zur Herstellung von Schutzschichten einheitlicher Farbtönung auf Zink-Flacherzeugnissen ist aus DE 196 36 370 bekannt. Die Flacherzeugnisse werden in einem Beizbad mit Schwefelsäure und Salpetersäure enthaltender Mischsäure gebeizt und nach dem Spülen durch Auftragen chromathaltiger Polymeren unter Bildung einer Schutzschicht passiviert. Das vorgenannte Verfahren erfordert neben der Behandlung mit starken Säuren die Nachbehandlung mit chromathaltigen Polymeren, was auf umweltschutzrechtliche Bedenken stößt.A process for the preparation of uniform hue protective coatings on flat zinc products has been made DE 196 36 370 known. The flat products are pickled in a pickling bath with mixed acid containing sulfuric acid and nitric acid and, after rinsing, passivated by applying chromate-containing polymers to form a protective layer. The aforementioned method requires, in addition to the treatment with strong acids, the aftertreatment with chromate-containing polymers, which encounters environmental protection concerns.

Bekannt ist weiterhin ein Verfahren zur Erzeugung texturiert-grauer Schichten durch Beizen der Zinkband-Oberfläche in einer Mischsäure, bestehend aus Salpetersäure und Schwefelsäure ( DE 2757592 ). Durch dieses Verfahren wird jedoch die Oberfläche in einer Form verändert, dass sie nachträglich durch Aufbringen einer Schutzschicht passiviert werden muss, damit sich keine unerwünschte Weißfärbung durch Bildung von Weißrost entwickelt. Darüber hinaus ist nur ein einziger Grauton einstellbar, zur Erzeugung anderer Grautöne muss die Legierungszusammensetzung der Titan-Zink- Legierung verändert werden.Also known is a process for producing textured gray layers by pickling the zinc strip surface in a mixed acid consisting of nitric acid and sulfuric acid ( DE 2757592 ). By this method, however, the surface is changed in a form that it must be subsequently passivated by applying a protective layer so that no unwanted whitening develops by the formation of white rust. In addition, only a single shade of gray is adjustable, to create other shades of gray, the alloy composition of the titanium-zinc alloy must be changed.

Zur Herstellung von Schutzschichten und Unterlagen für einen Farbanstrich werden laut AT 143 280 Zink oder Zinklegierungen mit Oxalsäure, Malonsäure oder Weinsäure vorbehandelt, wobei die Säurelösung eine Grundlage für eine Farb- oder Lackschicht bildet, die dort fest anhaftet. Auf einen bestimmten Farbton der Grundschicht wird nicht geachtet.For the production of protective layers and documents for a paint application are loud AT 143 280 Zinc or zinc alloys pretreated with oxalic acid, malonic acid or tartaric acid, wherein the acid solution forms a basis for a paint or varnish layer, which adheres firmly there. On a certain hue of the base layer is not respected.

Zinkoxalatbeschichtungen auf Zinkschichten mit relativ gering konzentrierten Oxalationslösungen werden in der EP 1 252 367 B4 beschrieben, wobei den Oxalationslösungen Cu2+-Ionen beigefügt sind. Es ergibt sich bei der Behandlung der Zink-Oberfläche eine "Schmierungsvorbeschichtung" (prelubrification). Ein bestimmter Farbton der Zinkoxalatbeschichtungen wird nicht angestrebt.Zinc oxalate coatings on zinc layers with relatively low concentration oxalate solutions are used in the EP 1 252 367 B4 described, wherein the Oxalationslösungen Cu 2+ ions are attached. The result of the treatment of the zinc surface is a "lubrication pre-coating" (prelubrification). A certain shade of zinc oxalate coatings is not sought.

Der US 1 954 744 lässt sich ein Verfahren zur Behandlung von Metall-Oberflächen entnehmen, bei der eine Lösung aus Oxalsäure, einem Kupfersalz und einem anorganischen Nitrat verwendet wird. Als Kupfersalz wird speziell ein Kupfersulfat genannt. Nach der Behandlung mit der Lösung soll sich eine Oberfläche wie unpoliertes Chrom ergeben, die aber zu einer polierten Oberfläche, wie bei Chrom üblich, poliert werden kann. Es ergibt sich ein silbriger Glanz.Of the US 1 954 744 For example, there is disclosed a method of treating metal surfaces using a solution of oxalic acid, a copper salt and an inorganic nitrate. As copper salt is specifically called a copper sulfate. After treatment with the solution, a surface should appear as unpolished chrome, but which can be polished to a polished surface, as is common in chrome. The result is a silvery shine.

Für die Erfindung stellt sich die Aufgabe, ein Verfahren unter Verwendung einer Beschichtungslösung anzugeben " mit dem Titanzinkbleche und andere Flacherzeugnisse und daraus hergestellte Produkte mit einer homogenen, texturiertgrauen Schutzschicht versehen werden können, das ohne Verwendung von chromathaltigen Polymeren arbeitet und bei dem das resultierende Produkt keine Neigung zur Weißfärbung durch Bildung von Weißrost zeigt. Darüber hinaus sollen verschiedene Grautöne mit den Komponenten derselben summarischen Zusammensetzung der Beschichtungslösung herstellbar sein.The object of the invention is to provide a method using a coating solution "can be provided with the titanium zinc sheets and other products and products produced therefrom with a homogeneous, textured gray protective layer, which works without the use of chromate polymers and in which the resulting product no In addition, different shades of gray should be producible with the components of the same overall composition of the coating solution.

Diese Aufgabe wird dadurch gelöst, dass die Flacherzeugnisse in einem Bad mit einer Behandlungslösung behandelt werden, bei der zur Herstellung anteilig einer Menge von 1000 cm3 Wasser zugegeben wird:

  1. a. 20 bis 50g Phosphorsäure;
  2. b. 20 bis 50g gesättigte Oxalsäure, Malonsäure oder ein Gemisch dieser Säuren,
  3. c. 2 bis 5g Ammoniumnitrat;
  4. d. 0,1 bis 5,0g Kupfer, zugefügt in einer Verbindung, die in der Beschichtungslösung Cu+- oder Cu2+-Ionen bildet.
This object is achieved in that the flat products are treated in a bath with a treatment solution in which a proportion of 1000 cm 3 of water is added for the preparation:
  1. a. 20 to 50 g of phosphoric acid;
  2. b. 20 to 50 g of saturated oxalic acid, malonic acid or a mixture of these acids,
  3. c. 2 to 5 g ammonium nitrate;
  4. d. 0.1 to 5.0 g of copper added in a compound which forms Cu + or Cu 2+ ions in the coating solution.

In überraschender Weise zeigen die entsprechend behandelten Flacherzeugnisse aus Titan-Zink-Legierung eine Schutzschicht einheitlicher grauer Farbtönung, bei der die natürliche Gefügestruktur der Oberfläche nach der Behandlung als Textur sichtbar wird. Die so abgeschiedene Schicht zeigt auch ohne weitere Passivierung keine größere Neigung zur Bildung von weißen Verfärbungen als die natürliche, unbehandelte Oberfläche von Flacherzeugnissen aus Titan-Zink-Legierung. Zur Erzeugung unterschiedlich heller Grautöne kann die Legierung unverändert bleiben, lediglich die Zusammensetzung der Behandlungslösung wird in oben aufgeführten Grenzen variiert.Surprisingly, the correspondingly treated titanium-zinc alloy flat products show a protective layer of uniform gray hue, in which the natural microstructure of the surface becomes visible as a texture after the treatment. The layer thus deposited, even without further passivation, shows no greater tendency to form white discoloration than the natural, untreated surface of titanium-zinc alloy flat products. To produce different shades of gray, the alloy can remain unchanged, only the composition of the treatment solution is varied within the limits listed above.

Für die Behandlungslösung wird bevorzugt Oxalsäure (HOOC-COOH) verwendet. Bei Verwendung von Malonsäure (HOOC-(CH2)-COOH) fällt die Farbe geringfügig heller aus. Auch können die Säuren gemischt verwendet werden. Durch entsprechende Mischungsverhältnisse von Oxalsäure und Malonsäure lassen sich dann unterschiedliche Farbschattierungen herstellen.For the treatment solution, oxalic acid (HOOC-COOH) is preferably used. When using malonic acid (HOOC- (CH 2 ) -COOH), the color is slightly lighter. Also, the acids can be used mixed. By appropriate mixing ratios of oxalic acid and malonic acid then different shades of color can be produced.

Weitere Parameter-Bereiche sind in den Unteransprüchen genannt.Other parameter ranges are mentioned in the subclaims.

Als Kupferverbindungen, die in der Beschichtungslösung Cu+- oder Cu2+-Ionen bilden, kommen vorzugsweise Kupfer(I)- oder Kupfer(II)oxide und Kupfernitrat infrage. Als weiteres Kupfersalz ist unter Inkaufnahme von Farbabweichungen Kupfersulfat einsetzbar.Copper compounds which form Cu + or Cu 2+ ions in the coating solution are preferably copper (I) oxides or copper (II) oxides and copper nitrate. Copper sulfate can be used as another copper salt at the expense of color deviations.

Das erfindungsgemäße Verfahren wird nachstehend durch Ausführungsbeispiele erläutert:The method according to the invention is explained below by means of exemplary embodiments:

Beispiel 1example 1

Ein aus einer Zinklegierung gemäß der europäischen Norm EN 988 bestehendes, gewalztes Band wird durch Spülen mit einer alkalischen Entfettungslösung bei einer Temperatur von ca. 60°C und einem Spüldruck von ca. 2,5 bar entfettet und anschließend mit einem Wassersprühstrahl mit einer Temperatur von ca. 65°C und einem Druck von ca. 2,5 bar abgespritzt. Zur Unterstützung des Spülvorgangs und zur Oberflächenaufrauung wird in der letzten Spülstufe das Band gebürstet.A rolled strip consisting of a zinc alloy in accordance with the European standard EN 988 is degreased by rinsing with an alkaline degreasing solution at a temperature of approx. 60 ° C and a rinsing pressure of approx. 2.5 bar and then with a water spray jet at a temperature of about 65 ° C and a pressure of about 2.5 bar hosed. To assist the rinse and surface roughening, the strip is brushed in the final rinse step.

Anschließend wird das Band in einem Behandlungsbad bei Raumtemperatur mit einer wässrigen Behandlungslösung mit anteilig 35 g/l Phosphorsäure, 40 g/l Oxalsäure, 3 g/l Ammoniumnitrat und 0,5 g/l Kupferoxid behandelt, wobei die Verweilzeit des jeweiligen Bandabschnittes im Bad 60 Sekunden beträgt. Der pH-Wert der Behandlungslösung liegt bei pH 2,5. Die Behandlung wird bei einer Badtemperatur von etwa 40°C durchgeführt. Es ergibt sich eine graue Farbtönung der Oberfläche.Subsequently, the strip is treated in a treatment bath at room temperature with an aqueous treatment solution with a proportionate 35 g / l phosphoric acid, 40 g / l oxalic acid, 3 g / l ammonium nitrate and 0.5 g / l copper oxide, wherein the residence time of the respective band section in the bath 60 seconds. The pH of the treatment solution is at pH 2.5. The treatment is carried out at a bath temperature of about 40 ° C. The result is a gray color of the surface.

Die vorgenannten Parameter können innerhalb der in den Ansprüchen 1 bis 6 genannten Grenzwerten variiert werden, um nach fachmännischer Erfahrung verschiedene Tönungsvarianten zu erhalten.The aforesaid parameters may be varied within the limits specified in claims 1 to 6 in order to obtain various tonal variations according to expert experience.

Die Farbe, die die abgeschiedene farbgebende Schutzschicht hat, ist im Wesentlichen abhängig vom pH-Wert der Lösung und den Komponentenverhältnissen. Es können einheitliche Farbtöne zwischen hellgrau und dunkelgrau bei derselben Legierungszusammensetzung des Substrates erzeugt werden.The color of the deposited color protective layer is essentially dependent on the pH of the solution and the component ratios. Uniform shades between light gray and dark gray can be produced for the same alloy composition of the substrate.

Das aus dem Behandlungsbad austretende Band wird mit Wasser gespült.The emerging from the treatment bath band is rinsed with water.

Das so erhaltene Band zeigt im Kondensklima-Feuchtewechseltest eine vergleichbare Beständigkeit gegen Weißverfärbung durch Weißrostbildung wie unbehandelte Flacherzeugnisse aus Titan-Zink-Legierung. Elektrochemische Untersuchungen bestätigen die Korrosionsschutzwirkung der erhaltenen Schutzschicht. Kelvinsondenmessungen zeigen, dass die Schutzschicht die Zinkauflösung hemmt.The tape thus obtained shows a similar resistance to white discoloration due to white rust formation in the condensation climate humidity change test as untreated titanium-zinc alloy flat products. Electrochemical investigations confirm the corrosion protection effect of the protective layer obtained. Kelvin probe measurements show that the protective layer inhibits zinc dissolution.

Beispiel 2Example 2

In einem weiteren Ausführungsbeispiel wurde ein aus einer Zinklegierung gemäß der europäischen Norm EN 988 bestehendes Band gemäß Beispiel 1 behandelt, wobei anstelle von Oxalsäure die gleiche Molmasse an Malonsäure verwendet wurde. Das Verhältnis der Molmassen beträgt rund 65 zu 83, d.h. pro 1 Wasser wurden ca. 51 g Malonsäure eingesetzt. Als Cu2+-bildendes Salz wurden 3,0 g/l Kupfernitrat [Cu(NO3)2] hinzugegeben. Das so entstandene Band zeigte die gleichen Eigenschaften wie oben geschildert, wobei die Farbe geringfügig heller ausfiel als das mit Oxalsäure behandelte Band.In a further embodiment, an existing from a zinc alloy according to the European standard EN 988 tape was treated according to Example 1, wherein instead of oxalic acid, the same molar mass of malonic acid was used. The ratio of the molecular weights is about 65 to 83, ie per 1 of water about 51 g of malonic acid were used. As Cu 2+ -forming salt, 3.0 g / l copper nitrate [Cu (NO 3 ) 2 ] was added. The resulting ribbon showed the same properties as described above, with the color being slightly lighter than the oxalic acid treated ribbon.

Beispiel 3Example 3

In einem weiteren Ausführungsbeispiel wurde ein aus einer Zinklegierung gemäß der europäischen Norm EN 988 bestehendes Band gemäß Beispiel 1 behandelt, wobei ein Gemisch aus 15 g/l Oxalsäure und 20 g/l Malonsäure verwendet wurde. Das so entstandene Band zeigte die gleichen Eigenschaften wie oben geschildert, wobei die Farbe einen Zwischenton zwischen der Färbung gemäß Beispielen 1 und 2 annahm.In a further embodiment, a band consisting of a zinc alloy according to the European standard EN 988 was treated according to Example 1, using a mixture of 15 g / l oxalic acid and 20 g / l malonic acid. The resulting ribbon showed the same properties as described above, with the color assuming an intermediate tone between the staining according to Examples 1 and 2.

Die Erfindung bezieht sich überdies auf flach gewalztes Halbzeug aus einer Titan-Zink-Legierung mit einer Schutzschicht mit grauer Farbtönung, das mittels einem der beigefügten Verfahrensansprüche hergestellt ist. Die Dicke der Schutzschicht liegt vorzugsweise zwischen 0,1 und 10 µm.The invention further relates to a flat rolled semi-finished product of a titanium-zinc alloy with a gray-tinted protective layer produced by means of one of the appended method claims. The thickness of the protective layer is preferably between 0.1 and 10 microns.

Aus den gewalzten Flacherzeugnissen werden Fertigteile hergestellt, insbesondere für den Baubereich. Ein Fertigteil, beispielsweise ein Regenfallrohr oder eine Dachschar aus einer Titan-Zink-Legierung gemäß der europäischen Norm EN 988, wird gemäß Erfindung aus einem Flacherzeugnis hergestellt, das in einer wässrigen Behandlungslösung der eingangs und in den Beispielen genannten Art behandelt und dadurch mit einer Schutzschicht einheitlich grauer, aber variabel einstellbarer Farbtönung versehen ist. Das so erhaltene Flacherzeugnis zeigt die natürliche Oberflächenstruktur und hat eine vergleichbare Empfindlichkeit gegenüber Weißfärbung durch Bildung von Weißrost wie natürlich patinierte Flacherzeugnisse aus Titan-Zink- Legierung, so dass es sich für viele Verwendungsarten, auch in freier Atmosphäre eignet.Finished parts are produced from the rolled flat products, in particular for the construction sector. A finished part, for example a downpipe or roof share made of a titanium-zinc alloy according to the European standard EN 988, is prepared according to the invention from a flat product treated in an aqueous treatment solution of the type mentioned above and in the examples and thereby with a protective layer uniformly gray, but variably adjustable color tint is provided. The flat product thus obtained exhibits the natural surface structure and has a comparable sensitivity to whitening by the formation of white rust as naturally patinated titanium-zinc alloy flat products, so that it is suitable for many uses, even in a free atmosphere.

Claims (8)

Verfahren zur Herstellung einer Schutzschicht in grauer Farbtönung auf gewalzten Flacherzeugnissen aus einer Titan-Zink-Legierung und daraus hergestellten Körpern, wobei die Behandlung in einer sauren wässrigen Beschichtungslösung stattfindet, dadurch gekennzeichnet, dass zur Herstellung der Behandlungslösung anteilig einer Menge von 1000 cm3 Wasser zugegeben wird: a. 20 bis 50g Phosphorsäure ; b. 20 bis 50g gesättigte Oxalsäure, Malonsäure oder ein Gemisch dieser Säuren, c. 2 bis 5g Ammoniumnitrat ; d. 0,1 bis 5,0g Kupfer, zugefügt in einer Verbindung, die in der Beschichtungslösung Cu+- oder Cu2+-Ionen bildet. A process for producing a protective layer in gray color tone on rolled flat products consisting of a titanium-zinc alloy and articles produced therefrom, wherein the treatment takes place in an acidic aqueous coating solution, characterized in that proportionately an amount of 1000 cm 3 of water were added to prepare the treatment solution becomes: a. 20 to 50 g of phosphoric acid; b. 20 to 50 g of saturated oxalic acid, malonic acid or a mixture of these acids, c. 2 to 5 g ammonium nitrate; d. 0.1 to 5.0 g of copper added in a compound which forms Cu + or Cu 2+ ions in the coating solution. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Kupferverbindungen, die in der Beschichtungslösung Cu+- oder Cu2+-Ionen bilden, ein oder mehrere Kupfer(I)- oder Kupfer(II)oxide oder Kupfernitrat, beigefügt werden.A method according to claim 1, characterized in that as copper compounds which form Cu + - or Cu 2+ ions in the coating solution, one or more copper (I) - or copper (II) oxides or copper nitrate, are added. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Titan-Zink-Legierung eine Zusammensetzung gemäß der Europäischen Bauzinknorm EN 988 hat.A method according to claim 1, characterized in that the titanium-zinc alloy has a composition according to the European building zinc standard EN 988. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Behandlung bei einer Badtemperatur zwischen 20 und 55°C erfolgt.Method according to one of claims 1 to 3, characterized in that the treatment is carried out at a bath temperature between 20 and 55 ° C. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der pH-Wert der Behandlungslösung zwischen pH 1,0 und pH 4,0 liegt.Method according to one of claims 1 to 4, characterized in that the pH of the treatment solution is between pH 1.0 and pH 4.0. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Behandlungszeit zwischen 15 sec und 15 min beträgt.Method according to one of claims 1 to 5, characterized in that the treatment time is between 15 seconds and 15 minutes. Flach gewalztes Halbzeug aus einer Titan-Zink-Legierung mit einer Schutzschicht mit grauer Farbtönung, hergestellt mittels eines Verfahrens nach einem der Ansprüche 1 - 6.A flat rolled semi-finished product of a titanium-zinc alloy with a gray-tinted protective layer, produced by a method according to any one of claims 1-6. Halbzeug nach Anspruch 7, dadurch gekennzeichnet, dass die Dicke der Schutzschicht zwischen 0,1 und 10 µm beträgt.Semifinished product according to claim 7, characterized in that the thickness of the protective layer is between 0.1 and 10 microns.
EP20110005194 2010-06-30 2011-06-27 Method of creating a protective coating on flat products made of titanium zinc Not-in-force EP2402484B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE201010025707 DE102010025707A1 (en) 2010-06-30 2010-06-30 Process for the preparation of protective coatings on flat titanium zinc products

Publications (2)

Publication Number Publication Date
EP2402484A1 true EP2402484A1 (en) 2012-01-04
EP2402484B1 EP2402484B1 (en) 2012-10-24

Family

ID=44587594

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20110005194 Not-in-force EP2402484B1 (en) 2010-06-30 2011-06-27 Method of creating a protective coating on flat products made of titanium zinc

Country Status (3)

Country Link
EP (1) EP2402484B1 (en)
DE (1) DE102010025707A1 (en)
ES (1) ES2395005T3 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849866A (en) * 2014-02-14 2014-06-11 浙江工业大学 Grey protective layer for surface of titanium-zinc plate and preparation method
CN103849868A (en) * 2014-02-14 2014-06-11 浙江工业大学 Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid
CN114000132A (en) * 2021-10-28 2022-02-01 苏州市祥冠合金研究院有限公司 Zinc alloy surface gray protective layer and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954744A (en) 1932-06-07 1934-04-10 Delaney Chemical Company Method and solution for treating metal surfaces
US3767478A (en) * 1971-09-14 1973-10-23 Ball Corp Method for producing patina on a zinc surface and article so formed
DE2757592A1 (en) 1977-12-23 1979-07-05 Rheinisches Zinkwalzwerk Gmbh METHOD OF SURFACE TREATMENT OF MOLDED BODIES MADE OF ZINC OR ZINC ALLOYS
ATA143280A (en) 1980-03-17 1981-03-15 Eumig FILM STOCK INDICATOR
DE19636370A1 (en) 1996-09-09 1998-03-12 Rheinzink Gmbh Process for the production of protective layers on flat products made of titanium zinc
WO2001051682A1 (en) * 2000-01-13 2001-07-19 Usinor Method for oxalating the galvanized surface of sheet metal

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT143280B (en) * 1930-08-21 1935-10-25 Metal Finishing Res Corp Process for the production of protective layers on metal objects.
BE627337A (en) 1962-01-26
JP2668555B2 (en) * 1988-06-30 1997-10-27 日本ペイント株式会社 Chemical treatment agent and chemical treatment bath

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954744A (en) 1932-06-07 1934-04-10 Delaney Chemical Company Method and solution for treating metal surfaces
US3767478A (en) * 1971-09-14 1973-10-23 Ball Corp Method for producing patina on a zinc surface and article so formed
DE2757592A1 (en) 1977-12-23 1979-07-05 Rheinisches Zinkwalzwerk Gmbh METHOD OF SURFACE TREATMENT OF MOLDED BODIES MADE OF ZINC OR ZINC ALLOYS
ATA143280A (en) 1980-03-17 1981-03-15 Eumig FILM STOCK INDICATOR
DE19636370A1 (en) 1996-09-09 1998-03-12 Rheinzink Gmbh Process for the production of protective layers on flat products made of titanium zinc
WO2001051682A1 (en) * 2000-01-13 2001-07-19 Usinor Method for oxalating the galvanized surface of sheet metal
EP1252367B1 (en) 2000-01-13 2005-12-14 Usinor Method for oxalating the galvanized surface of sheet metal

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849866A (en) * 2014-02-14 2014-06-11 浙江工业大学 Grey protective layer for surface of titanium-zinc plate and preparation method
CN103849868A (en) * 2014-02-14 2014-06-11 浙江工业大学 Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid
CN114000132A (en) * 2021-10-28 2022-02-01 苏州市祥冠合金研究院有限公司 Zinc alloy surface gray protective layer and preparation method thereof

Also Published As

Publication number Publication date
EP2402484B1 (en) 2012-10-24
ES2395005T3 (en) 2013-02-07
DE102010025707A1 (en) 2012-01-05

Similar Documents

Publication Publication Date Title
DE3031270C2 (en)
DE3432118C2 (en)
EP1816234B1 (en) Aqueous passivating coating composition for zinc or zinc alloys and method for using same
DE1219765B (en) Process for passivating metal surfaces
DE3234558C2 (en)
DE3151115C2 (en)
DE3650659T2 (en) Process for phosphating metal surfaces
EP0155742B1 (en) Process and coating composition for metallic surface treatment
EP2145980A1 (en) Coloured stainless steel surface and method for colouring stainless steel
EP0359296B1 (en) Phosphating process
DE4214954C2 (en) Process for the preparation of improved chromate conversion coatings on zinc surfaces and application of the process
EP0410497B1 (en) Process for the passivate rinsing of phosphate coatings
EP0492713A1 (en) Process for rinsing conversion coatings
EP2402484B1 (en) Method of creating a protective coating on flat products made of titanium zinc
DE69012374T2 (en) Phosphate coatings for metal surfaces.
DE2232067A1 (en) PHOSPHATING SOLUTIONS
DE2218899C2 (en) Aqueous, chromate-depositing composition and its use
DE3432141C2 (en)
DE19915058A1 (en) Composition and method for the anti-corrosion treatment of a non-ferrous metal
EP0264811A1 (en) Process for producing phosphate coatings
DE10156475A1 (en) Process for the production of dark protective layers on flat products made of titanium zinc
DE3300543A1 (en) AQUEOUS-ACID CHROMATING SOLUTION AND METHOD FOR PRODUCING COLORED CHROMATING COATINGS ON ELECTROCHEMICALLY DEPOSITED ZINC-NICKEL ALLOYS
EP1678345A1 (en) Coloured conversion layers devoid of chrome formed on metal surfaces
WO2014090752A1 (en) Aqueous agent and coating method for the anticorrosive treatment of metallic substrates
EP1713955B1 (en) Black passivation of zinc or zinc alloy surfaces

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20120209

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): 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: AT

Ref legal event code: REF

Ref document number: 581022

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502011000151

Country of ref document: DE

Effective date: 20121220

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2395005

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130207

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

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: 20121024

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: 20121024

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: 20121024

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: 20130224

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: 20130124

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: 20130225

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: 20130125

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: 20121024

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: 20121024

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: 20121024

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 20121024

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: 20121024

Ref country code: RS

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

Effective date: 20121024

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: 20121024

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: 20130124

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: 20121024

26 Opposition filed

Opponent name: UMICORE

Effective date: 20130724

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

Ref country code: RO

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

Effective date: 20121024

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502011000151

Country of ref document: DE

Effective date: 20130724

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: 20121024

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20121024

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: 20130627

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

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: 20121024

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: 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: 20121024

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502011000151

Country of ref document: DE

Representative=s name: BISCHOF & PARTNER RECHTSANWAELTE PARTNERSCHAFT, DE

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: 20140630

Ref country code: CH

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

Effective date: 20140630

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502011000151

Country of ref document: DE

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: 20121024

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: 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: 20121024

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: 20130627

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: 20110627

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: 20121024

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

Ref country code: ES

Payment date: 20150626

Year of fee payment: 5

Ref country code: GB

Payment date: 20150618

Year of fee payment: 5

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

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

Ref country code: NL

Payment date: 20150618

Year of fee payment: 5

Ref country code: BE

Payment date: 20150618

Year of fee payment: 5

Ref country code: IT

Payment date: 20150622

Year of fee payment: 5

Ref country code: FR

Payment date: 20150619

Year of fee payment: 5

27O Opposition rejected

Effective date: 20150516

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

Ref country code: BE

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

Effective date: 20160630

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20160701

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

Effective date: 20160627

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170228

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

Ref country code: FR

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

Effective date: 20160630

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 NON-PAYMENT OF DUE FEES

Effective date: 20160701

Ref country code: GB

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

Effective date: 20160627

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: 20160627

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 581022

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160627

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: 20160627

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: 20160628

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: 20121024

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181112

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

Ref country code: DE

Payment date: 20190318

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502011000151

Country of ref document: DE

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: 20210101