EP2937450B1 - Galvanisches bad oder mischung zur verwendung in einem galvanischen bad zur abscheidung einer glanznickelschicht sowie verfahren zur herstellung eines artikels mit einer glanznickelschicht - Google Patents

Galvanisches bad oder mischung zur verwendung in einem galvanischen bad zur abscheidung einer glanznickelschicht sowie verfahren zur herstellung eines artikels mit einer glanznickelschicht Download PDF

Info

Publication number
EP2937450B1
EP2937450B1 EP15164491.1A EP15164491A EP2937450B1 EP 2937450 B1 EP2937450 B1 EP 2937450B1 EP 15164491 A EP15164491 A EP 15164491A EP 2937450 B1 EP2937450 B1 EP 2937450B1
Authority
EP
European Patent Office
Prior art keywords
oder
galvanic bath
und
mol
mixture
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.)
Revoked
Application number
EP15164491.1A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2937450A1 (de
Inventor
Jörg Cordes
Gerd Schöngen
Reiner Dickbreder
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.)
Kiesow Dr Brinkmann & Co KG GmbH
Original Assignee
Kiesow Dr Brinkmann & Co KG GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52997919&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2937450(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kiesow Dr Brinkmann & Co KG GmbH filed Critical Kiesow Dr Brinkmann & Co KG GmbH
Priority to PL15164491T priority Critical patent/PL2937450T3/pl
Priority to SI201530067A priority patent/SI2937450T1/sl
Publication of EP2937450A1 publication Critical patent/EP2937450A1/de
Application granted granted Critical
Publication of EP2937450B1 publication Critical patent/EP2937450B1/de
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/16—Acetylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds

Definitions

  • the present invention relates to a galvanic bath for depositing a bright nickel layer, a corresponding mixture for use in a galvanic bath for depositing a bright nickel layer, a corresponding method for producing an article with a bright nickel layer by depositing nickel on a corresponding workpiece, the use of a galvanic according to the invention Bath or a mixture according to the invention for the deposition or production of a bright nickel layer and an article comprising a bright nickel layer according to the invention.
  • Galvanic baths and processes for the electrodeposition of a bright nickel coating are known from the prior art.
  • the international patent application with the publication number WO 91/16474 A1 shows an acidic bright nickel bath containing as essential components nickel sulfate, nickel chloride, boric acid, 2-ethylhexylsulfate sodium salt as wetting agent, saccharin, formaldehyde and a betaine.
  • German patent application with the publication number DE 196 10 361 A1 discloses a bath and method for the electrodeposition of semi-bright nickel.
  • one or more cyclic N-allyl or N-vinylammonium compounds, in particular pyridinium compounds, are used as the brightener.
  • the patent in turn, refers to a number of prior art publications concerning the electrodeposition of semi-bright nickel.
  • various chemical compounds are mentioned, which can be used in the galvanic bath.
  • At least one to two, possibly also more nickel salts such as, for example, nickel sulfate, nickel chloride, nickel fluoride and others, and at least one inorganic acid, such as, for example, sulfuric acid or boric acid, are always present in the baths.
  • nickel salts such as, for example, nickel sulfate, nickel chloride, nickel fluoride and others
  • inorganic acid such as, for example, sulfuric acid or boric acid
  • German patent with the publication number describes DE 10 2008 056 470 B3 a method of inspecting a metal layer either alone on a substrate or forming part of a multilayer metal layer system, and a method of analytically controlling a deposition electrolyte for depositing such a metal layer.
  • the metal layer is an electrodeposited nickel layer.
  • nickel layers as corrosion-protective coatings on parts made of different materials, such as copper, brass or steel or plastic, where The nickel layers are deposited in different quality and in a specific order, namely, for example, as a semi-gloss nickel layer, shiny nickel layer, optionally. with a particularly sulfur-rich intermediate layer, and again as a semi-bright nickel layer, which is optionally deposited together with particles.
  • the basic composition of a nickel deposition electrolyte is according to the publication DE 10 2008 056 470 B3 typically a so-called Watts nickel bath containing nickel, chloride, sulfate ions and boric acid, for example in the following composition: 60 g / l NiCl 2 .6H 2 O, 270 g / l NiSO 4 .6H 2 O, 45 g / l H 3 BO 3 .
  • the pH of the deposition electrolyte is generally 2.5-6.0, preferably 3-4.5 and especially about 4.0.
  • the deposition is carried out at a temperature of 40-70 ° C, preferably 50-60 ° C and especially about 55 ° C.
  • the respective layers are electrodeposited from deposition electrolytes having different compositions, particularly with respect to the additives.
  • the semi-glossy base layer on the substrate material typically contains salicylic acid, ethyne derivatives such as hexynediol or butynediol, propargyl alcohol derivatives, formaldehyde and / or chloral hydrate, or mixtures of these compounds as additives.
  • the optionally deposited sulfur-rich glossy or matt intermediate layer typically contains saccharin, sulfonic acids and / or ethyne derivatives as additives.
  • the shiny nickel layer typically contains sulfur-containing compounds as additives, for example toluenesulfonic acid or propargylsulfonates, and additionally saccharin instead of salicylic acid or mixtures of these compounds.
  • the upper semigloss nickel layer typically contains saccharin or a saccharin salt, chloral hydrate and / or formaldehyde or else mixtures of these compounds as additives and optionally additionally particles, for example of SiO 2 , Al 2 O 3 .
  • the deposition electrolytes may contain other additives, such as brighteners and wetting agents.
  • CH 514683 refers to a "process and bath for electrolytic nickel plating" (title).
  • the bright nickel layers are less noble than the underlying semi-bright nickel layer due to the chemical incorporation of sulfur-containing organic components.
  • the sulfur-containing organic component saccharin is usually used as part of the bright nickel layer.
  • the migration of nickel as a commonly used in the electroplating metal from the base material protective coating is in view of the fact that nickel is considered as one of the most common trigger of contact allergies (nickel dermatitis), a health hazard to the consumer.
  • this knowledge is taken into account in Germany by the Second Ordinance to Amend the Drinking Water Ordinance (TrinkwV 2001), which came into force on 14 December 2012. Accordingly, in so-called stagnation samples of the respective alloy or coating to be examined, a maximum of 10 ⁇ g of nickel may be released into one liter of drinking water. Coatings previously used, regardless of whether duplex or triplex coatings, usually do not meet the requirements of the new drinking water ordinance.
  • the galvanic bath or the corresponding mixture to be specified should enable the deposition of a bright nickel layer which also has certain typical properties of a semi-bright nickel layer. These properties include, in particular, a columnar layer structure which was hitherto known only in semi-bright nickel layers and which can be determined by measuring a significant potential difference between the semi-bright nickel layer and the bright nickel layer. An effective corrosion protection would thus already be given by a layer system of such a bright nickel layer and a final chromium layer.
  • the galvanic bath according to the invention or the mixture according to the invention comprises benzoic acid sulfimide (saccharin, E954, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide, CAS Number: 81-07-2) and / or Benzoeklaresulfimidanionen as a sulfur source, which means that a bright nickel layer produced using a galvanic bath according to the invention or a mixture according to the invention is electrochemically less noble than a semi-bright nickel layer disclosed in the prior art.
  • the inventive galvanic bath or mixture according to the invention comprises one, two, more than two or all compounds selected from the group consisting of chloral hydrate, bromine hydrate, formic acid, formate, acetic acid, acetate, substituted or unsubstituted aliphatic aldehydes, particularly preferably chloral hydrate (Trichloraldehydhydrat , 2,2,2-trichloroacetaldehyde hydrate, 2,2,2-trichloro-1,1-ethanediol, CAS number: 302-17-0).
  • the present invention is based on the surprising finding that bright nickel layers, which are produced by means of a galvanic bath according to the invention or a mixture according to the invention, release significantly less nickel into the drinking water than conventional nickel protective layers.
  • the nickel ions originate from one, two or more than two nickel salts, such as nickel sulfate, nickel chloride, nickel fluoride, which are provided in anhydrous or differently hydrated form as constituents of the galvanic bath or mixture according to the invention.
  • a galvanic bath or a mixture according to the invention comprises one or more acids (component (b)), the term "acid” encompassing both the compound in dissociated and undissociated form at the respective pH.
  • the acid or the acids are used in particular for buffering the pH during the electrolysis process.
  • the constituents of the invention benzoic acid sulfinimide and / or Benzoeklaresulfinimidanionen (component (c)) and the optionally present (s) allylsulfonic acid and / or allylsulfonate (component (d)) are basic gloss (also primary brightener). Under glossing in particular the balance or the Leveling of unevenness in the base material understood, usually based on the use of low molecular weight organic surface-active compounds in a galvanically deposited layer.
  • leveling refers to the leveling of unevenness on a surface (ntik), as for example, after a previous polishing on the surface (ntik) remain (polishing strokes).
  • the polishing of a surface (n GmbH) represents a common processing step, which is carried out in particular in valves, particularly preferably in brass, zinc or zinc die-cast fittings, before electroplating.
  • Brighteners thus serve a uniform distribution of an applied by means of inventive galvanic bath or inventive mixture nickel layer in the entire current density range and the deposition of a ductile, stress-free nickel layer.
  • Particular preference is given here as or in component (c) benzoic acid sulfimide sodium salt (CAS number: 128-44-9) and / or as or in component (d) allylsulfonic acid sodium salt (sodium prop-2-ene-1 sulfonate, sodium allylsulfonate, prop-2-ene-1-sulfonic acid sodium salt, CAS number: 2495-39-8).
  • constituents of a galvanic bath according to the invention or a mixture according to the invention such as one or more acetylenically unsaturated compounds of the formula (I) (component (e)), one or more betaines of the formula (II) (component (f)) and one or more Wetting agents (component (g)) promote, inter alia, the gloss formation of a bright nickel layer applied to a base material by means of a galvanic bath according to the invention or by means of the inventive mixture.
  • Betaine of the formula (II) (component (f)) and acetylenically unsaturated compounds of the formula (I) (component (e)) are also referred to as brighteners (also secondary brighteners).
  • the wetting agents contained in a galvanic bath according to the invention or in a mixture according to the invention cause a lowering of the surface tension which promotes a rapid removal of hydrogen produced during the galvanization at the cathode.
  • Particularly preferred compounds of the formula (II) used are pyridiniumpropylsulfobetaine (PPS, 1- (3-sulfopropyl) pyridinium betaine, NDSB 201, 3- (1-pyridinium) -1-propanesulfonate, CAS number: 15471- 17-7) and 1- (2-hydroxy-3-sulfopropyl) pyridinium betaine (PPS-OH, CAS number: 3918-73-8). These compounds can be used singly or in combination with each other.
  • the preferred compounds of the formula (II) are preferably used with other components which are referred to above or below as being preferred.
  • salts of sulfosuccinic acid preferably sodium salts
  • the use of salts of sulfosuccinic acid (preferably sodium salts) as wetting agents in a galvanic bath according to the invention or in a mixture according to the invention is preferred in some cases.
  • the acid or acids used are particularly preferably selected from the group consisting of sulfuric acid, boric acid and hydrochloric acid.
  • a particularly preferred wetting agent is a C 13 -C 15 oxo alcohol ether sulfate (CAS number: 78330-30-0).
  • Also preferred as the wetting agent is sodium lauryl sulfate (sodium dodecyl sulfate, sodium dodecyl sulfate, sodium dodecyl sulfate, SLS, SDS, NLS, CAS number: 151-21-3). These compounds may be used singly or in combination, and are preferably used together with other components referred to above or below as being preferred.
  • Particularly preferred compounds of the formula (IV) are 2-ethylhexylsulfate sodium salt (CAS: 126-92-1) and sodium lauryl sulfate (see above). These compounds may be used singly or in combination, and are preferably used together with other components referred to above or below as being preferred.
  • compounds of the formula (V) which are selected from the group consisting of 2-butyne-1,4-diol ethoxylate (2,2 '- (but-2-yn-1,4-diylbis (oxy)) - (ethan-1-ol)), 2-butyne-1,4-diol propoxylate (4- (3-hydroxypropoxy) but-2-yn-1-ol), propargyl alcohol ethoxylate (2- (prop-2-yn-1) yloxy) ethan-1-ol), sodium propargylsulfonate (prop-2-yn-1-ylsulfite sodium salt, CAS number: 55947-46-1) and sodium vinylsulfonate (SVS, sodium ethylenesulfonate, vinylsulfonic acid sodium salt, ethylenesulfuric acid sodium salt, CAS- Number: 3039-83-6).
  • These compounds may be used singly or in combination, and are preferably used together with other components referred to above or
  • the individual constituents of a galvanic bath or a particularly preferred mixture according to the invention which are particularly preferred in practice are the galvanic bath or the mixture according to the invention after control analysis (for example by means of HPLC analysis) supplied on demand.
  • a galvanic bath according to the invention or a mixture according to the invention in the presence of cations comprises the amount of counterions required for charge balancing.
  • a galvanic bath or a mixture according to the invention which does not comprise suspended silicon oxide particles and aluminum oxide particles.
  • a galvanic bath or a mixture according to the invention which does not comprise the suspended particles in the galvanic bath or in the mixture.
  • a galvanic bath according to the invention or a mixture according to the invention having a pH in the range from 2.8 to 5.2, preferably from 3.8 to 4.8.
  • individual components of a preferred electroplating bath according to the invention or of a preferred mixture according to the invention are particularly readily soluble in water.
  • the temperature of the galvanic bath or of the mixture in step (b) is preferably in the range from 40 to 70 ° C., preferably in the range of 50-60 ° C. At such temperatures, individual components of a preferred galvanic bath according to the invention or of a preferred mixture according to the invention are particularly readily soluble in water.
  • the bright nickel layer is preferably deposited on a copper, brass or zinc surface of the workpiece.
  • the electrolytic nickel deposition takes place in a steel container with an acid-resistant lining (for example PVC) which is sufficient for the particular purpose or in a plastic container.
  • an acid-resistant lining for example PVC
  • the above-defined (preferred) constituents of a galvanic bath or a mixture according to the invention are usually dissolved in demineralized water at a temperature of 50 ° C with stirring.
  • the anode material used is metallic nickel in the form of plates, squares or crowns or in any other suitable form.
  • the workpiece to be nickel plated is switched as a cathode, and the electrodes are usually connected via a rectifier with direct current provided.
  • the required amount of current is typically 2-8 amps per dm 2 (A / dm 2 ) of cathode area.
  • the deposition rate of nickel on the workpiece connected as a cathode is generally about 1 ⁇ m nickel / minute with a current amount of 5 A / dm 2 .
  • a cathode movement is often required (relative movement to the electrolyte).
  • a circulation of the galvanic bath according to the invention or of the mixture according to the invention by blowing compressed air can take place (air movement).
  • air movement During the current process, filtration of the galvanic bath or the mixture according to the invention is generally required.
  • the analytical control of the composition of a galvanic bath according to the invention or of a mixture according to the invention as part of the method likewise according to the invention is preferably carried out by means of titration in the case of the acid and chloride concentration, in the case of the brightener concentration by HPLC analysis, in the case of wetting agents by means of measurement the surface tension and in the case of nickel (ion) concentration by chemical analysis or AAS (Atomabsorptionsspektroskopie) performed.
  • AAS can also be used to determine the concentration possibly in the galvanic bath or the mixture of foreign metals present.
  • the present invention additionally relates to the use of a galvanic bath or a mixture according to the invention as described above for depositing or producing a bright nickel layer.
  • a galvanic bath or a mixture according to the invention as described above for depositing or producing a bright nickel layer.
  • the present invention also relates to the use of a galvanic bath or a mixture as described above for the deposition or production of a bright nickel coating on an element of a fitting for a water-bearing pipeline.
  • a galvanic bath or a mixture as described above for the deposition or production of a bright nickel coating on an element of a fitting for a water-bearing pipeline.
  • a nickel layer deposited by means of a galvanic bath or a mixture according to the invention e.g. On a workpiece, there is a reduced tendency to release nickel ions into an aqueous solution in contact with this nickel layer as compared to conventional bright nickel layers. This is confirmed by measuring the potential of the deposited nickel layers.
  • the relevant parameters for the corrosion process namely the layer thicknesses of the individual nickel layers and their potential differences with each other, can be measured in a single step.
  • the application of the STEP test method makes use of the fact that the electrical potential measured during dissolution against a reference electrode changes abruptly after detachment of a nickel layer. This occurs after the dissolution of the respective nickel layers, the measured dissolution potentials depending, inter alia, on the type of the respective nickel layer. This is the case with sulfur-containing and sulfur-free nickel layers. With two sulfur-containing nickel layers, however, hardly any potential jump is measurable.
  • the STEP test is a measuring method that destroys the nickel layer to be analyzed or the nickel layer system to be analyzed and is performed with a couloscope.
  • the potential changes measured and graphically represented by the electrolytic detachment of individual nickel layers from a nickel system show, in the event of an abrupt change, a point of inflection from one nickel layer to the next in such a layer system.
  • the endpoint of a STEP test measurement is the achievement of the base material, e.g. B. the copper layer.
  • nickel potentials are measured in a solution of nickel chloride hexahydrate, sodium chloride and boric acid. A sufficient potential between semi-bright nickel and bright nickel layer is given in measurements in the above-mentioned electrolyte from -120 mV.
  • Corrodkote solution 20 g / l of ammonium chloride, 3.3 g / l of ferric chloride and 0.7 g / l of copper (II) nitrate 3-hydrate in aqueous solution are used according to Brugger, Robert (1984), "The Galvanic Nickel Plating", 2nd ed. Saulgau (Eugen G. Leutze Verlag Vol. 12) p. 301 ,
  • the reference bath and bath according to the invention had the same composition except for the proportion of chloral hydrate.
  • the potential of a nickel foil made using a reference bath was + 484 mV; the potential of a nickel foil made using a bath of the invention with 1 g / l chloral hydrate was +582 mV; the above note applies accordingly.
  • Application Examples 1 -7 preparing a plating solution by mixing water with selected ingredients (components); Concentration in mol / L:
  • the pH of the galvanic bath after mixing is between 3.8 and 4.8.
  • the above ingredients are incorporated in the above concentration in an aqueous solution.
  • the order of addition of the individual components in the aqueous solution is not critical here. All concentration data are based on the galvanic bath.
  • Examples 8 -14 preparing a plating solution by mixing water with selected ingredients (components); Concentration in mol / L:
  • the pH of the galvanic bath after mixing is between 3.8 and 4.8.
  • the above ingredients are incorporated in the above concentration in an aqueous solution.
  • the order of addition of the individual components in the aqueous solution is not critical here. All concentration data are based on the galvanic bath.
  • the non-salts selected components (components) of a galvanic bath according to the invention are added to this purified solution.
  • the galvanically coated copper tubes described above under (a), (b) and (c) (1x comparison, 2x according to the invention) were then immersed separately in city water.
  • the concentration of nickel / nickel ions in city water was measured after 72 hours of service life. Further measurements are carried out after a further 48 hours, 120 hours, 72 hours and 144 hours. In all cases, the water was renewed after the measurement;
  • the copper tubes to be tested were also rinsed ten times with 150 ml of city water each time before further use.
  • the measurement results were determined by ICP-OES spectrometer and are given in the following table. The numerical values refer in each case to the measured nickel ion concentration in ⁇ g / l.
  • chloral hydrate significantly reduces the tendency to release nickel / nickel ions into the surrounding medium (here: city water), especially with long contact times (2nd to 5th measurement).
  • the non-salts selected components (components) of a galvanic bath according to the invention are added to this purified solution.
  • M Components (components) of the specific galvanic bath according to the invention M Component: Connection: g / L [g / mol) minor a NiSO 4 .6H 2 O 280 262.84 1.0653 a NiCl 2 .6H 2 O 60 237.68 .2524 b B (OH) 3 40 61.83 .6469 c Benzolklaresulfimid sodium salt 2 205.16 0.0097 d Allyl sulfonic acid sodium salt 1 144.12 0.0069 f Pyridiniumpropylsulfobetain 0.1 201.24 0.00050 e 2-propyn-1-ol 0.02 56.06 0.000357 e Hex-3-yne-2,5-diol 0.01 114.14 0.000088 H chloral hydrate 1 165.39 0.0060 G Sodium lauryl ether sulfate 1 416.5 0.0024
  • the coating time ie the time required to deposit a bright nickel layer by means of the specific bath according to the invention, is about 15 minutes at a current density of 4 A / dm 2 .
  • Application and Comparative Example 16 Preparation of a specific article according to the invention (a bath fitting as an example of a water-bearing pipeline) with a bright nickel layer:
  • the constituents (components) of a specific galvanic bath to be used according to the invention for producing the article according to the invention (bath fitting with bright nickel coating) are listed in the following table "Application Example 16" and were dissolved in the stated concentration in demineralized water (preferred water temperature 55 ° C.): Table "Application Example 16" Component: Connection: g / L M [g / mol] minor a NiSO 4 .6H 2 O 280 262.84 1.0653 a NiCl 2 .6H 2 O 60 237.68 .2524 b B (OH) 3 40 61.83 .6469 c Benzolklasulfimid sodium salt 2 205.16 0.0097 f Pyridiniumpropylsulfobetain 0.15 201.24 0.00050 e
  • the constituents of a galvanic bath not prepared according to the invention for comparison purposes are identical to those in Table "Application Example 16" and were also dissolved in the indicated concentration in demineralized water (preferred water temperature 55 ° C), but the galvanic bath prepared for comparison purposes does not comprise chloral hydrate ,
  • the coating time ie the time for depositing a bright nickel layer by means of the specific bath according to the invention or by means of the galvanic bath not prepared according to the invention, was about 15 minutes at a current density of 4 A / dm 2 .
  • the values shown represent arithmetic mean values of four measurements each.
  • the coated bathroom fitting body according to the invention (as an example of an article according to the invention) released less nickel than the non-inventive coated bathroom fitting body.
  • the bath used according to the invention comprised chloral hydrate, whereby the tendency for the release of nickel / nickel ions in the surrounding medium (here: town water) was significantly reduced.
  • the results of the fourth and fifth week show that the nickel release stagnated and at the same time was significantly lower than the nickel release of the non-inventive coated brass fittings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Cosmetics (AREA)
EP15164491.1A 2014-04-25 2015-04-21 Galvanisches bad oder mischung zur verwendung in einem galvanischen bad zur abscheidung einer glanznickelschicht sowie verfahren zur herstellung eines artikels mit einer glanznickelschicht Revoked EP2937450B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL15164491T PL2937450T3 (pl) 2014-04-25 2015-04-21 Kąpiel galwaniczna lub mieszanina do zastosowania w kąpieli galwanicznej do osadzania warstwy niklu błyszczącego, jak też sposób wytwarzania produktu z warstwą niklu błyszczącego
SI201530067A SI2937450T1 (sl) 2014-04-25 2015-04-21 Galvanska kopel ali zmes za uporabo v galvanski kopeli za nanašanje plasti niklja z visokim leskom in postopek za izdelavo izdelka s plastjo niklja z visokim leskom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102014207778.8A DE102014207778B3 (de) 2014-04-25 2014-04-25 Verwendung einer Mischung zur Verwendung in einem galvanischen Bad oder eines galvanischen Bades zur Herstellung einer Glanznickelschicht sowie Verfahren zur Herstellung eines Artikels mit einer Glanznickelschicht

Publications (2)

Publication Number Publication Date
EP2937450A1 EP2937450A1 (de) 2015-10-28
EP2937450B1 true EP2937450B1 (de) 2017-04-05

Family

ID=52997919

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15164491.1A Revoked EP2937450B1 (de) 2014-04-25 2015-04-21 Galvanisches bad oder mischung zur verwendung in einem galvanischen bad zur abscheidung einer glanznickelschicht sowie verfahren zur herstellung eines artikels mit einer glanznickelschicht

Country Status (7)

Country Link
EP (1) EP2937450B1 (enExample)
JP (1) JP6687331B2 (enExample)
DE (1) DE102014207778B3 (enExample)
HU (1) HUE035050T2 (enExample)
PL (1) PL2937450T3 (enExample)
PT (1) PT2937450T (enExample)
SI (1) SI2937450T1 (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021095909A1 (ko) * 2019-11-12 2021-05-20 주식회사 엘콤 니켈인 합금 도금을 위한 조성물

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105170922B (zh) * 2015-10-19 2017-12-01 重庆天春科技有限公司 一种具有单质镍过渡层的结晶器铜管
CN105200462A (zh) * 2015-10-19 2015-12-30 姜少群 一种结晶器铜管的单质镍过渡层电镀方法
CN106245070B (zh) * 2016-10-21 2019-03-05 湘潭大学 一种用于镁合金电镀镍的组合镀液及镁合金表面电镀镍的方法
JP7536452B2 (ja) * 2017-06-23 2024-08-20 アトテック ドイチェランド ゲーエムベーハー ウント コ カーゲー 基材上に装飾ニッケルコーティングを堆積させるためのニッケル電気メッキ浴
WO2019215287A1 (en) * 2018-05-09 2019-11-14 Atotech Deutschland Gmbh Nickel comprising layer array and a method for its manufacturing
JP6542437B1 (ja) * 2018-06-19 2019-07-10 奥野製薬工業株式会社 光沢ニッケルめっき方法及び光沢ニッケルめっき皮膜の制御方法。
JP7190280B2 (ja) * 2018-08-10 2022-12-15 株式会社Lixil 水道用器具
TWI734362B (zh) * 2019-01-31 2021-07-21 美商麥克達米德恩索龍股份有限公司 用於製造鎳互連之組成物及方法
JP7141780B1 (ja) 2022-05-19 2022-09-26 奥野製薬工業株式会社 めっき皮膜の製造方法。
CN115161722A (zh) * 2022-08-25 2022-10-11 环晟光伏(江苏)有限公司 镀镍液及其制备方法、太阳能电池的制备方法

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH514683A (de) 1966-08-25 1971-10-31 M & T Chemicals Inc Verfahren und Bad zum elektrolytischen Vernickeln
DE2450527A1 (de) 1974-10-24 1976-05-06 Henkel & Cie Gmbh Saures bad fuer die herstellung von halbglaenzenden nickelueberzuegen
US4148797A (en) 1977-07-15 1979-04-10 Cilag-Chemie A.G. (N-Substituted pyridyl)-alkyl sulfonic acid betaines as electroplating additives
US4421611A (en) 1982-09-30 1983-12-20 Mcgean-Rohco, Inc. Acetylenic compositions and nickel plating baths containing same
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US4820388A (en) 1987-07-09 1989-04-11 Raschig Ag Polyalkylene glycol naphthyl-3-sulfopropyl diether compounds and their salts, process for preparing same and electroplating baths containing same
EP0343559A1 (de) 1988-05-25 1989-11-29 Raschig AG Verwendung von 2-substituierten Ethansulfonverbindungen als galvanotechnische Hilfsstoffe
WO1991016474A1 (de) 1990-04-23 1991-10-31 Schering Aktiengesellschaft Saure nickelbäder, enthaltend 1-(2-sulfoethyl)-pyridiniumbetain
US5164069A (en) 1990-11-05 1992-11-17 Shipley Company Inc. Nickel electroplating solution and acetylenic compounds therefor
WO1993015241A1 (de) 1992-01-25 1993-08-05 Basf Aktiengesellschaft Verfahren zur herstellung vernickelter formteile
DE19610361A1 (de) 1996-03-15 1997-09-18 Basf Ag Bad und Verfahren für die galvanische Abscheidung von Halbglanznickel
EP1489201A2 (de) 2003-06-18 2004-12-22 Raschig GmbH Propansulfonierte und 2-Hydroxy-propansulfonierte Alkylaminalkoxylate, ihre Herstellung und Verwendung als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten
WO2010006800A1 (en) 2008-07-15 2010-01-21 Atotech Deutschland Gmbh Method for electrochemically depositing a metal on a substrate
DE102008056470B3 (de) 2008-11-05 2010-04-22 Atotech Deutschland Gmbh Verfahren zum Untersuchen einer Metallschicht und Verfahren zur analytischen Kontrolle eines zum Abscheiden der Metallschicht dienenden Abscheideelektrolyten
WO2010092622A1 (en) 2009-02-13 2010-08-19 Nissan Motor Co., Ltd. Chrome-plated part and manufacturing method of the same
EP2532771A2 (de) 2011-06-09 2012-12-12 Keuco GmbH & Co. KG Kupfer- oder bronzebeschichtete Armaturen
WO2014180595A1 (en) 2013-05-08 2014-11-13 Atotech Deutschland Gmbh Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy, method for electroplating and use of such a bath and compounds for the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898138A (en) * 1974-10-16 1975-08-05 Oxy Metal Industries Corp Method and bath for the electrodeposition of nickel
DE2825966A1 (de) * 1978-06-14 1980-01-03 Basf Ag Saures galvanisches nickelbad, das sulfobetaine als glanz- und einebnungsmittel enthaelt
JP2962598B2 (ja) * 1991-06-20 1999-10-12 荏原ユージライト株式会社 マイクロポーラスクロムめっき方法
JP2003138396A (ja) * 2001-08-24 2003-05-14 Toto Ltd ニッケルクロムめっき方法及びそのめっきを施した水道用器具
US7442286B2 (en) * 2004-02-26 2008-10-28 Atotech Deutschland Gmbh Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH514683A (de) 1966-08-25 1971-10-31 M & T Chemicals Inc Verfahren und Bad zum elektrolytischen Vernickeln
DE2450527A1 (de) 1974-10-24 1976-05-06 Henkel & Cie Gmbh Saures bad fuer die herstellung von halbglaenzenden nickelueberzuegen
US4148797A (en) 1977-07-15 1979-04-10 Cilag-Chemie A.G. (N-Substituted pyridyl)-alkyl sulfonic acid betaines as electroplating additives
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US4421611A (en) 1982-09-30 1983-12-20 Mcgean-Rohco, Inc. Acetylenic compositions and nickel plating baths containing same
US4820388A (en) 1987-07-09 1989-04-11 Raschig Ag Polyalkylene glycol naphthyl-3-sulfopropyl diether compounds and their salts, process for preparing same and electroplating baths containing same
EP0343559A1 (de) 1988-05-25 1989-11-29 Raschig AG Verwendung von 2-substituierten Ethansulfonverbindungen als galvanotechnische Hilfsstoffe
WO1991016474A1 (de) 1990-04-23 1991-10-31 Schering Aktiengesellschaft Saure nickelbäder, enthaltend 1-(2-sulfoethyl)-pyridiniumbetain
US5164069A (en) 1990-11-05 1992-11-17 Shipley Company Inc. Nickel electroplating solution and acetylenic compounds therefor
WO1993015241A1 (de) 1992-01-25 1993-08-05 Basf Aktiengesellschaft Verfahren zur herstellung vernickelter formteile
DE19610361A1 (de) 1996-03-15 1997-09-18 Basf Ag Bad und Verfahren für die galvanische Abscheidung von Halbglanznickel
WO1997035049A1 (de) 1996-03-15 1997-09-25 Basf Aktiengesellschaft Bad und verfahren für die galvanische abscheidung von halbglanznickel
EP1489201A2 (de) 2003-06-18 2004-12-22 Raschig GmbH Propansulfonierte und 2-Hydroxy-propansulfonierte Alkylaminalkoxylate, ihre Herstellung und Verwendung als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten
WO2010006800A1 (en) 2008-07-15 2010-01-21 Atotech Deutschland Gmbh Method for electrochemically depositing a metal on a substrate
DE102008056470B3 (de) 2008-11-05 2010-04-22 Atotech Deutschland Gmbh Verfahren zum Untersuchen einer Metallschicht und Verfahren zur analytischen Kontrolle eines zum Abscheiden der Metallschicht dienenden Abscheideelektrolyten
WO2010092622A1 (en) 2009-02-13 2010-08-19 Nissan Motor Co., Ltd. Chrome-plated part and manufacturing method of the same
EP2532771A2 (de) 2011-06-09 2012-12-12 Keuco GmbH & Co. KG Kupfer- oder bronzebeschichtete Armaturen
WO2014180595A1 (en) 2013-05-08 2014-11-13 Atotech Deutschland Gmbh Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy, method for electroplating and use of such a bath and compounds for the same

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Sulfobetaine", WIKIPEDIA, 5 June 2017 (2017-06-05), pages 1, XP055450245, Retrieved from the Internet <URL:https://de.wikipedia.org/wiki/Sulfobetaine> [retrieved on 20171130]
FALBE J. ET AL: "Römpp Chemie Lexikon 9", vol. 5, 1995, article "Definition von Sulfobetainen", pages: 4381, XP055450260
JADECHEM: "PPS Pyrldinlum propyl sulphobetatne", PRODUCT DETAIL, 2012, pages 1, XP055451965, Retrieved from the Internet <URL:http://www.jadechem-intl.com/product_detail_en/id/71.html>
JADECHEM: "PPS-OH liquid Pyridinium hydroxyl propyl sulphobetalne", PRODUCT DETAIL, 2012, XP055451972, Retrieved from the Internet <URL:http://www.jadechem-intl.com/product_detail_en/id/72.html>
M. SCHLESINGER ET AL.: "Modern Electroplating", 2010, JOHN WILEY & SONS INC., article ELECTRODEPOSITION OF NICKEL, pages: 79 - 113, XP055450247

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021095909A1 (ko) * 2019-11-12 2021-05-20 주식회사 엘콤 니켈인 합금 도금을 위한 조성물

Also Published As

Publication number Publication date
SI2937450T1 (sl) 2017-07-31
PT2937450T (pt) 2017-06-30
DE102014207778B3 (de) 2015-05-21
JP6687331B2 (ja) 2020-04-22
HUE035050T2 (en) 2018-05-02
JP2015212417A (ja) 2015-11-26
PL2937450T3 (pl) 2017-08-31
EP2937450A1 (de) 2015-10-28

Similar Documents

Publication Publication Date Title
EP2937450B1 (de) Galvanisches bad oder mischung zur verwendung in einem galvanischen bad zur abscheidung einer glanznickelschicht sowie verfahren zur herstellung eines artikels mit einer glanznickelschicht
DE3031501C2 (enExample)
EP2116634B1 (de) Modifizierter Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
DE69917620T2 (de) Ductilität verbessernde additive für nickel-wolframlegierungen
DE19741990C1 (de) Elektrolyt zur galvanischen Abscheidung von spannungsarmen, rißfesten Rutheniumschichten, Verfahren zur Herstellung und Verwendung
EP2103717A1 (de) Pyrophosphat-basiertes Bad zur Abscheidung von Zinn-Legierungsschichten
AT514818A1 (de) Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
DE3012168C2 (enExample)
DE3402554C2 (enExample)
AT523922B1 (de) Elektrolytbad für Palladium-Ruthenium-Beschichtungen
DE10327374B4 (de) Verwendung von propansulfonierten und 2-Hydroxy-propansulfonierten Alkylaminaloxylaten als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten und galvanische Bäder enthaltend diese
AT516876B1 (de) Abscheidung von dekorativen Palladium-Eisen-Legierungsbeschichtungen auf metallischen Substanzen
DE102005059367A1 (de) Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten
DE2333096C3 (de) Galvanisch aufgebrachter mehrschichtiger Metallüberzug und Verfahren zu seiner Herstellung
DE3108466C2 (de) Verwendung eines Acetylenalkohols in einem Bad zur galvanischen Abscheidung einer Palladium/Nickel-Legierung
DE3232735C2 (de) Verwendung einer als Glanzbildnerzusatz zu Nickelbädern bekannten Verbindung als Korrosionsschutzadditiv
DE3619386C2 (enExample)
DE2743847A1 (de) Verfahren zur galvanischen abscheidung von nickel und kobalt alleine oder als binaere oder ternaere legierungen
DE19610361A1 (de) Bad und Verfahren für die galvanische Abscheidung von Halbglanznickel
DE2439656C2 (de) Wäßriges saures Bad zur galvanischen Abscheidung einer Zinn-Nickel-Legierung
DE3139641A1 (de) &#34;galvanisches bad und verfahren zur abscheidung halbglaenzender duktiler und spannungsfreier nickelueberzuege&#34;
DE102013110263A1 (de) Galvanisches Bad
DE843785C (de) Verfahren zur Herstellung harter galvanischer Silberueberzuege
DE1496823C (de) Verfahren zum galvanischen Absehet den von korrosionsbeständigen, dreischich tigen Nickel oder Nickel Kobalt Legierungs überzügen auf Metallen
DE102013113129A1 (de) Verfahren zur galvanischen Abscheidung von Nickel und entsprechender Elektrolyt

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

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

17P Request for examination filed

Effective date: 20160301

RBV Designated contracting states (corrected)

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

17Q First examination report despatched

Effective date: 20160614

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20161109

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: 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: 881937

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170415

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 3

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: DE

Ref legal event code: R096

Ref document number: 502015000800

Country of ref document: DE

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 2937450

Country of ref document: PT

Date of ref document: 20170630

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20170620

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170405

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: 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: 20170405

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

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: 20170705

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: 20170405

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: 20170706

Ref country code: ES

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: 20170405

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: 20170405

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

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: 20170405

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: 20170405

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: 20170805

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: 20170405

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502015000800

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 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: 20170405

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: 20170405

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: 20170405

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: 20170405

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: 20170405

26 Opposition filed

Opponent name: ATOTECH DEUTSCHLAND GMBH

Effective date: 20180105

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

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: 20170405

Ref country code: LU

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

Effective date: 20170421

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

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: 20170421

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E035050

Country of ref document: HU

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: 20170430

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

Ref country code: FR

Payment date: 20170112

Year of fee payment: 10

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: PT

Payment date: 20180411

Year of fee payment: 4

Ref country code: FI

Payment date: 20180418

Year of fee payment: 4

Ref country code: DE

Payment date: 20180503

Year of fee payment: 4

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

Ref country code: BG

Payment date: 20180423

Year of fee payment: 4

Ref country code: IT

Payment date: 20180430

Year of fee payment: 4

Ref country code: SI

Payment date: 20180410

Year of fee payment: 4

Ref country code: RO

Payment date: 20180412

Year of fee payment: 4

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: 20170405

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

Ref country code: HU

Payment date: 20180410

Year of fee payment: 4

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: CH

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

Effective date: 20180430

Ref country code: LI

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

Effective date: 20180430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502015000800

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502015000800

Country of ref document: DE

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

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: 20170405

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502015000800

Country of ref document: DE

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

Ref country code: MK

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

Effective date: 20170405

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

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

Effective date: 20190421

REG Reference to a national code

Ref country code: FI

Ref legal event code: MGE

27W Patent revoked

Effective date: 20190711

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

Ref country code: GB

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

Effective date: 20190421

Ref country code: FI

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

Effective date: 20190421

Ref country code: RO

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

Effective date: 20190421

Ref country code: HU

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

Effective date: 20190422

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

Ref country code: SI

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

Effective date: 20190422

Ref country code: FR

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

Effective date: 20190430

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: 20170405

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 881937

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200421

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: 20170405

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: 20190710

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 NON-PAYMENT OF DUE FEES

Effective date: 20190421

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 NON-PAYMENT OF DUE FEES

Effective date: 20190421

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 NON-PAYMENT OF DUE FEES

Effective date: 20190421

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 NON-PAYMENT OF DUE FEES

Effective date: 20190421