EP3443146B1 - Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition - Google Patents

Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition Download PDF

Info

Publication number
EP3443146B1
EP3443146B1 EP17725581.7A EP17725581A EP3443146B1 EP 3443146 B1 EP3443146 B1 EP 3443146B1 EP 17725581 A EP17725581 A EP 17725581A EP 3443146 B1 EP3443146 B1 EP 3443146B1
Authority
EP
European Patent Office
Prior art keywords
metal
salt preparation
gold
metal salt
electroplating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17725581.7A
Other languages
German (de)
English (en)
Other versions
EP3443146A1 (fr
Inventor
Rayko Ehnert
Prof. Dr. Frank KÖSTER
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.)
Saxonia Edelmetalle GmbH
Original Assignee
Saxonia Edelmetalle GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saxonia Edelmetalle GmbH filed Critical Saxonia Edelmetalle GmbH
Publication of EP3443146A1 publication Critical patent/EP3443146A1/fr
Application granted granted Critical
Publication of EP3443146B1 publication Critical patent/EP3443146B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/13—Organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating

Definitions

  • the present invention relates to a method for production of a metal salt preparation, not comprising cyanide and halogen ions, the metal salt preparation comprising at least one metal alkylsulfonate and thiourea and the use for surface coating by electroplating or electroless plating of a metal or metal alloy.
  • coatings with noble metals are produced by electroplating or electroless plating from noble metal cyanide complexes.
  • the alkaline, acidic or neutral plating solutions comprise as source of a noble metal for example potassium dicyanoaurate, potassium tetracyanoaurate or alkaline sulfites.
  • US 2003/0194485 A1 discloses aqueous gold-silver alloy plating solutions for electroless plating including organic acids having at least one sulfonic acid group, a complexing agent, selected from cyanides; a thio-compound, a water soluble gold compound, a water soluble silver compound and a sequestering agent and being prepared through mixing of the single components, eg. Ag(I) or Au(I) salts.
  • JP 2003041378 A describes gold plating solutions containing cyanides, halogen ions and a special aromatic compound for electroless plating and a method for the preparation based on mixing a single component with an Au(I) salt.
  • WO 2014/054429 A1 or US 2015/0137356 A1 disclose a non-cyan metal plating bath comprising alkaline gold sulfites or ammonium gold sulfites and a conductive salt including sulfite and sulfate.
  • the main disadvantage of the disclosed plating solution is the poor stability.
  • EP 0 611 840 A1 discloses a cyanide-free electroplating solution for depositing monovalent copper, silver, gold and other metals complexed by a thiosulfate ion, and a stabilizer of an organic sulfinate compound in an amount sufficient to stabilize the thiosulfate ion when the solution is operated at an acidic pH of less than 7.
  • the main disadvantage of the disclosed plating solution is the limitation of the current density and the formation of toxic sulphur dioxide at the presence of sulfites.
  • JP 3365866 B2 discloses a non-cyan noble metal plating bath comprising a water-soluble noble metal salt and a nonionic surfactant.
  • the acidic noble metal plating bath comprises an alkane sulfonic acid or the like with a noble metal selected from gold or silver.
  • Nonionic surfactants are preferred Pururafakku LF401 (manufactured by BASF), TetronicTR-702 (manufactured by Asahi Denka Kogyo Co., Ltd.), Nymeen L-207 (manufactured by NOF Corporation) orLiponox NC- 100 (manufactured by Lion Corporation).
  • US 6,251,249 B1 discloses iodide-free formulations comprising organosulfur compounds and/or carboxylic acids and a source of a soluble precious metal ion; and procedures for the deposition of precious metals onto solid substrates.
  • the source of a soluble precious metal ion is selected from precious metal alkanesulfonate, precious metal alkanesulfonamide or precious metal alkanesulfonimide, preferred silver methanesulfonate, silver methanesulfonamide or silver dimethanesulfonimide.
  • the organosulfur compound is selected from alkyl mercaptan, aryl mercaptan, heterocyclic mercaptan, dialkyl sulfide, diaryl sulfide, aryl alkyl sulfide, organic disulfide, organic polysulfide, organic xanthate, organic thiocyanate, or thiourea and the carboxylic acid is selected from alkanecarboxylic acid, aromatic carboxylic acid, ⁇ -amino acid, amino acid, dicarboxylic acid or polycarboxylic acid.
  • the substrate for electroplating are selected from brass, bronze, silver, gold, palladium, copper, copper alloys, nickel, nickel alloys, iron, iron alloys, tin, tin alloys, zinc, zinc alloys, aluminum or organic based plastics.
  • Precious metals are selected from silver, gold, platinum, palladium, iridium, rhodium, osmium and ruthenium, preferred silver, palladium and gold.
  • the main disadvantage of this formulation is the use of gold (III) complexes produced from tetrachloroaurate (III) complexes which comprise chloride ions.
  • DE 10 2009 024 396 A1 discloses cyan-free, neutral or alkaline, aqueous electrolytes for the electroplating of gold or gold alloys comprising an anionic gold thiolate complex. Furthermore, DE 10 2009 024 396 A1 describes the addition of complexing agents, brighteners, surfactants and/or conducting salts.
  • DE 10 2103 215 476 B3 discloses cyan-free, acidic and aqueous electrolytes for the electroplating of silver-palladium alloys comprising a silver compound, a palladium compound, a tellurium or selenium compound, urea and/or at least one amino acids, and a sulfonic acid. Furthermore, DE 10 2103 215 476 B3 discloses a method for electroplating.
  • CN 105316718 A discloses an electroplating liquid with a good dispersion capacity and covering capacity and an electroplating method for cyanide-free gold electroplating with sulfite.
  • the electroplating liquid comprises gold chloride, a sulfite as coordination agent and an alkali metal mercaptopropionic sulfonate as auxiliary coordination agent.
  • US 2016/0230287 A1 discloses a reductive electroless gold plating solution, comprising a water-soluble gold compound, citric acid or a citrate salt, ethylenediamintetratacetic acid (EDTA) or an ethylenediamine tetraacetate salt, hexamethylenetetramine, and a chain polyamine having an alkyl group having 3 or more carbon atoms and 3 or more amino groups; and a method for electroless gold plating using the plating solution.
  • EDTA ethylenediamintetratacetic acid
  • EDTA ethylenediamine tetraacetate salt
  • hexamethylenetetramine hexamethylenetetramine
  • a chain polyamine having an alkyl group having 3 or more carbon atoms and 3 or more amino groups
  • Disadvantages of the disclosed plating solutions and methods for electroplating is the use of toxic substances or persistent substances. Thus, problems occur in the degradation of the plating solution after electroplating.
  • DE 199 28 047 A1 discloses low-pollutant to pollutant-free and thus, environmentally compatible, aqueous solutions for electroplating of noble metals and noble metal alloys.
  • the plating solutions comprise a gold and/or silver complex with amino acid derivatives and/or at least one water soluble sulfonic acid and/or at least one water soluble nitro compound.
  • the plating solution comprise gold (III).
  • the main disadvantage of the use of gold (III) comprising plating solutions is the considerably higher current demand in comparison to gold (I).
  • the object of the present invention is to provide an alternative to cyanide based metal plating solutions and to provide metal plating solutions which are biological degradable after metal plating.
  • the object has been solved by a method for production of a metal salt preparation, not comprising cyanide and halogen ions, by membrane electrolysis comprising the steps
  • the metal is selected from gold (Au), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) or indium (In). More preferred the metal is gold (Au).
  • the membrane is a cation-exchange membrane or an anion-exchange membrane, more preferred the membrane is a cation-exchange membrane, preferable with a sulfonated tetrafluoroethylene based fluoropolymer-copolymer (like NafionTM).
  • Alkylsulfonate according to the invention is an alkyl sulfonate or an alkali or alkaline earth salt thereof.
  • the alkylsulfonate is a C1- to C10-alkyl sulfonate.
  • alky sulfonate refers to a linear or cyclic alkylic organosulfonate.
  • C1- to C10-alkyl refers to alkyl groups with 1 to 10 carbon atoms.
  • the sulfonate is a methanesulfonate, ethanesulfonate, propanesulfonate or an alkali or alkaline earth salt thereof.
  • the concentration of the at least one alkylsulfonate solution is 0.1% (w/w) to 20% (w/w).
  • the alkylsulfonate solution is an aqueous solution.
  • Molar ratios of metal to thiourea lie between 10.000:1 to 1:10, preferred 100:1 to 1:5, more preferred 10:1 to 1:2.
  • the pH value of the at least one alkylsulfonate solution is in the range between pH 1 and pH 8, preferably between pH 3 and pH 8.
  • the anodic oxidation according to step c) is carried out with a current between 0.1 A and 500 A, preferred a current between 0.5 A and 50 A.
  • the anodic oxidation according to step c) is carried out with a voltage between 0.1 V and 10 V.
  • the at least one alkylsulfonate solution further comprises at least one further complexing agent, preferably selected from chelating agents or organosulfur compounds, more preferably selected from methylglycinediacetic acid or ethylenediamine-N,N'-disuccinic acid (EDDS) or an alkali or alkaline earth salt of these acids (e. g. TrilonTM M), methionine or cysteine.
  • complexing agent refers to a compound which forms complexes with metal ions.
  • chelating agent refers to a compound which forms chelates with metal ions.
  • chelates refers to complexes with the presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single metal ion.
  • the at least one chelating agent or organosulfur compound stabilizes the metal salt preparation.
  • the at least one further complexing agent is biodegradable.
  • biodegradable refers to compounds which break down under composting conditions, by bacteria, fungi or other biological means.
  • the method for production of a metal salt preparation comprises at least one further step selected from precipitation, flocculation, complexation, oxidation and/or reduction.
  • the method for production of a metal salt preparation further comprises a step after step c), wherein the further step is mixing at least two metal salt preparations.
  • the method for production of a metal salt preparation further comprises a step after step c), wherein the further step is solvation or dilution of the metal salt preparation in an aqueous, organic or ionic solution.
  • the present invention further comprises a metal salt preparation, not comprising cyanide and halogen ions, comprising at least one metal alkylsulfonate and thiourea, wherein the molar ratio of metal to thiourea is 10.000:1 to 1:10, preferred 100:1 to 1:5, more preferred 10:1 to 1:2, wherein the metal alkylsulfonate is selected from gold (Au), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) or indium (In) alkylsulfonates.
  • the at least one metal salt is a gold (Au) salt, more preferably a gold (I) (Au (I)) salt.
  • the at least one metal alkylsulfonate is preferably a C1- to C10-alkyl sulfonate.
  • the at least one metal alkylsulfonate is a methanesulfonate, ethanesulfonate, propanesulfonate or an alkali or alkaline earth salt thereof.
  • the metal salt preparation is an aqueous, organic or ionic solution with a concentration of the metal of 0.001 mol to 5 mol, preferably 0.01 mol to 0.5 mol.
  • the concentration of the metal alkylsulfonate in the preparation is 0.1% (w/w) to 20% (w/w).
  • the metal salt preparation is an aqueous solution with a pH value between pH 1 and pH 8, preferably between pH 3 and pH 8.
  • the metal salt preparation comprises at least one further complexing agent, preferably selected from chelating agents or organosulfur compounds, more preferably selected from methylglycinediacetic acid or ethylenediamine-N,N'-disuccinic acid (EDDS) or an alkali or alkaline earth salt of these acids (e. g. TrilonTM M), methionine or cysteine.
  • chelating agents or organosulfur compounds more preferably selected from methylglycinediacetic acid or ethylenediamine-N,N'-disuccinic acid (EDDS) or an alkali or alkaline earth salt of these acids (e. g. TrilonTM M), methionine or cysteine.
  • the stability of an aqueous solution of the metal salt preparation is at least some month, preferred at least some years.
  • the metal salt preparation according to the invention does not comprise cyanide. Further advantageously, the metal salt preparation according to the invention does not comprise halogen ions and/or resistant complexing agents. As used herein, the term “resistant” refers to non-biodegradable compounds.
  • the metal salt preparation according to the invention further comprises carboxylic acids.
  • carboxylic acids refers to an organic compound with at least one carboxyl group and 1 to 20 carbon atoms.
  • the carboxylic acid is a complexing agent and adjusts the pH value.
  • carboxylic acids are selected from formic acid, acetic acid, succinic acid, citric acid or salts thereof.
  • salts of the carboxylic acids are selected from sodium acetate, sodium succinate or sodium citrate.
  • the metal salt preparation according to the invention further comprises an aldehyde, an alcohol, a ketone, an ether and/or an ester.
  • the aldehyde, alcohol, ketone, ether and/or ester are complexing agents and surfactants (surface active agent).
  • surface active substance refers to a compound, which lowers the surface tension (or interfacial tension) between two liquids or between a liquid and a solid.
  • the metal salt preparation according to the invention further comprises a surfactant.
  • the surfactant is selected from cationic, anionic, nonionic and betaine tensides, preferably the surfactant is sodium dodecyl sulfate (SDS).
  • the metal salt preparation according to the invention further comprises an amine, preferred a primary amine.
  • the amine is a complexing agent and a buffer.
  • the amine is selected from amino acids, ethylenediamine and ethylamine.
  • the metal salt preparation according to the invention is stable at temperatures between 0°C and 100°C.
  • the present invention further comprises a plating solution comprising the metal salt preparation according to the invention.
  • Another object of the invention is the use of a metal salt preparation according to the invention for surface coating by electroplating or electroless plating of a metal or metal alloy.
  • electroplating refers to a process that uses electric current to reduce dissolved metal cations so that they form a thin coherent metal coating on an electrode.
  • the surface coating with the metal salt preparation according to the invention is resistant to corrosion and oxidation in moist air.
  • the metal salt preparation according to the invention is biodegradable according to OECD criteria after surface coating of the metal (OECD 1992).
  • the present invention further comprises a method for electroplating of a metal or metal alloy comprising the steps
  • the anode is an inert or soluble anode, preferred a mixed oxide anode or a metal anode.
  • the anode is selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), gold (Au) or indium (In).
  • the solution of at least one metal salt preparation has a metal content of 0.001 mol to 0.25 mol, preferred 0.01 mol to 0.1 mol.
  • the method for electroplating of a metal or metal alloy is carried out at a pH value between pH 1 and pH 8, preferred at a pH value between pH 2 and pH 6.
  • the method for electroplating of a metal or metal alloy is carried out at a temperature between 0 °C and 100 °C.
  • the method for electroplating of a metal or metal alloy is carried out with a current density between 0,1 A/dm 2 and 20 A/dm 2 .
  • the method for electroplating is carried out by pulse-plating
  • the method for electroplating of a metal alloy is carried out with a solution of at least one metal salt preparation according to the invention further comprising at least one metal or other metals.
  • the at least one metal is selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt) or gold (Au).
  • the at least one other metal is selected from nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), cadmium (Cd) or indium (In).
  • the present invention further comprises a method for electroless plating of a metal comprising the steps
  • the solution of a metal salt preparation has a metal contend of 0.001 mol to 0.25 mol, preferred 0.01 mol to 0.1 mol.
  • the method for electroless plating of a metal is carried out at a pH value between pH 1 and pH 8, preferred at a pH value between pH 2 and pH 6.
  • the method for electroless plating of a metal is carried out at a temperature between 0 °C and 100 °C, preferred at a temperature between 60 °C and 80 °C.
  • the thickness of the layer of the at least one metal is 10 nm to 100 ⁇ m, preferred 100 nm to 10 ⁇ m.
  • the layer of the at least one metal acts as soldering aid or anticorrosive coating.
  • Fig. 1 shows a schema of the electrolytic cell comprising an anode comprising a metal and a cathode, wherein the anodic region and the cathodic region are separated by a membrane.
  • the electrolytic cell of Fig. 1 was used.
  • the electrolytic cell comprises an anode comprising gold with a high surface, which is produced according to known procedures, in particular by the Wohlwill process (Gmelin 1974), and a cathode, wherein the anodic region and the cathodic region are separated by a membrane.
  • the electrolyte is an alkyl sulfonic acid and thiourea.
  • the electrolyte is an alkyl sulfonic acid.
  • the anodic oxidation is carried out with direct current of 0.5 A, 1 A or 10 A.
  • the membrane electrolysis is carried out at 25°C. Alternatively, the membrane electrolysis can be carried out at temperatures between 20°C and 80°C.
  • the Au (I) salt solution is received and filtrated.
  • the catholyte is mixed of 70% methane sulfonic acid and distilled water to a solution of 5% methane sulfonic acid.
  • the anolyte comprises an aqueous solution of methane sulfonic acid (5%) with 20 g/l thiourea.
  • Platinated titanium was used as cathode and the anode was pure gold from the Wohlwill process.
  • the membrane between cathode and anode was a cation selective membrane from DuPont (Nafion).
  • the anodic oxidation is carried out with direct current of 1.0 A for two hours. Afterwards the anolyte contained 13.9 g gold as gold (I).
  • the catholyte is mixed of 70% methane sulfonic acid and distilled water to a solution of 20% methane sulfonic acid.
  • the anolyte comprises an aqueous solution of methane sulfonic acid (20%) with 40 g/l thiourea.
  • Platinated titanium was used as cathode and the anode was pure gold from the Wohlwill process.
  • the membrane between cathode and anode was a cation selective membrane from DuPont (Nafion).
  • the anodic oxidation is carried out with direct current of 1.0 A for five hours. Afterwards the anolyte contained 33.1 g gold as gold (I).
  • the catholyte and anolyte are 100% methane sulfonic acid.
  • Platinated titanium was used as cathode and the anode was pure gold from the Wohlwill process.
  • the membrane between cathode and anode was a cation selective membrane from DuPont (Nafion).
  • the anodic oxidation is carried out with direct current of 0.5 A for four hours. Afterwards the anolyte contained 13.4 g gold as gold (I) and was diluted with distilled water with solved thiourea in a concentration of 20 g/l.
  • the Au(I) methanesulfonate solution of example 1 was used for electroplating a nickel plated messing plate in a regular Hull Cell.
  • the Au (I) plating solution comprised 2g/l Au (I), 5 g/l thiourea, 5 g/l sodium methanesulfonate and 5 ml of a 0,005 % solution of sodium dodecyl sulfate. After plating with 0,5 A/dm 2 for 5 min the cathodic nickel/messing plate was yellow by the gold plating.
  • the Au(I) methanesulfonate solution of example 2 was used for electroless plating a nickel plated printed circuit board in a regular beaker.
  • the Au (I) plating solution comprised 2g/l Au (I), 5 g/l thiourea, 2 g/l Trilon M and 5 ml 0,005 % solution of sodium dodecyl sulfate. After heating to 62 °C and plating for 5 min the printed circuit board was yellow by the gold plating.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)

Claims (11)

  1. Préparation de sel métallique, ne comprenant pas d'ions cyanure et halogène, comprenant au moins un alkylsulfonate métallique et de la thiourée,
    dans laquelle le rapport molaire du métal à la thiourée est de 10 000:1 à 1:10,
    dans laquelle l'alkylsulfonate métallique est choisi parmi les alkylsulfonates d'or (Au), de platine (Pt), de palladium (Pd), de rhodium (Rh), d'iridium (Ir), de ruthénium (Ru) ou d'indium (In).
  2. Préparation de sel métallique selon la revendication 1, dans laquelle la préparation de sel métallique est une solution aqueuse, organique ou ionique avec une concentration du métal de 0,001 mol à 5 mol, de préférence de 0,01 mol à 0,5 mol.
  3. Préparation de sel métallique selon la revendication 1 ou 2, dans laquelle la valeur pH est comprise entre pH 1 et pH 8.
  4. Préparation de sel métallique de l'une des revendications 1 à 3 comprenant au moins un autre agent complexant, de préférence choisi parmi les agents chélatants ou les composés organosoufrés, de préférence encore choisis parmi l'acide méthylglycinediacétique ou l'acide disuccinique-N,N'-éthylènediamine (EDDS) ou un sel alcalin ou alcalino-terreux de ces acides, méthionine ou cystéine.
  5. Procédé de production d'une préparation de sel métallique selon l'une des revendications 1 à 4 par électrolyse à membrane comprenant les étapes consistant à
    a) Fournir une cellule électrolytique comprenant une anode (2) comprenant un métal et une cathode (1), dans lequel une région anodique et une région cathodique sont séparées par une membrane (3),
    b) Fournir au moins une solution d'alkylsulfonate dans la région anodique,
    c) Oxyder anodiquement le métal et former la préparation de sel métallique comprenant un sulfonate métallique en faisant passer un courant à travers la cellule électrolytique,
    dans lequel la thiourée est ajoutée dans la région anodique après l'étape b) ou après l'étape c),
    dans lequel la concentration de thiourée est de 0,005 g/l à 200 g/l,
    dans lequel le métal est choisi parmi l'or (Au), le platine (Pt), le palladium (Pd), le rhodium (Rh), l'iridium (Ir), le ruthénium (Ru) ou l'indium (In).
  6. Procédé selon la revendication 5, dans lequel la membrane (3) est une membrane échangeuse de cations ou une membrane échangeuse d'anions.
  7. Procédé selon la revendication 5 ou 6, dans lequel l'alkylsulfonate est un alkylsulfonate d'alkyle en C1 à C10.
  8. Procédé selon l'une des revendications 5 à 7, dans lequel la concentration de la solution d'au moins un alkylsulfonate est de 0,1 % (m/m) à 20 % (m/m).
  9. Utilisation d'une préparation de sel métallique selon l'une des revendications 1 à 4 pour le revêtement de surface par dépôt électrolytique ou par dépôt autocatalytique d'un métal ou d'un alliage métallique,
    dans lequel le métal est choisi parmi l'or (Au), le platine (Pt), le palladium (Pd), le rhodium (Rh), l'iridium (Ir), le ruthénium (Ru) ou l'indium (In).
  10. Procédé de dépôt électrolytique d'un métal ou d'un alliage métallique comprenant les étapes consistant à
    a) Fournir un bain de dépôt électrolytique comprenant une anode (2), une cathode (1) et une solution d'au moins une préparation de sel métallique selon l'une des revendications 1 à 4,
    b) Appliquer un courant au bain de dépôt électrolytique, l'au moins un métal se formant sur la cathode (1), et
    c) Retirer la cathode (1) du bain de dépôt électrolytique,
    l'au moins un métal étant choisi parmi l'or (Au), le platine (Pt), le palladium (Pd), le rhodium (Rh), l'iridium (Ir), le ruthénium (Ru) ou l'indium (In).
  11. Procédé de dépôt chimique d'un métal comprenant les étapes suivantes consistant à
    a) Fournir un bain de dépôt comprenant une solution d'une préparation de sel métallique selon l'une des revendications 1 à 4,
    b) Mettre en contact un substrat solide avec le bain de dépôt, le métal se formant sur le substrat solide, et
    c) Retirer le substrat solide du bain de dépôt,
    dans lequel le métal est choisi parmi l'or (Au), le platine (Pt), le palladium (Pd), le rhodium (Rh), l'iridium (Ir), le ruthénium (Ru) ou l'indium (In).
EP17725581.7A 2017-05-23 2017-05-23 Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition Active EP3443146B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2017/062434 WO2018215057A1 (fr) 2017-05-23 2017-05-23 Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition

Publications (2)

Publication Number Publication Date
EP3443146A1 EP3443146A1 (fr) 2019-02-20
EP3443146B1 true EP3443146B1 (fr) 2019-12-25

Family

ID=58772561

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17725581.7A Active EP3443146B1 (fr) 2017-05-23 2017-05-23 Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition

Country Status (7)

Country Link
US (1) US20200095693A1 (fr)
EP (1) EP3443146B1 (fr)
JP (1) JP2020521060A (fr)
KR (1) KR20200010340A (fr)
CN (1) CN110770371A (fr)
ES (1) ES2773771T3 (fr)
WO (1) WO2018215057A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113897603B (zh) * 2021-08-31 2023-09-05 信丰正天伟电子科技有限公司 一种耐腐蚀钯类化学镀液及其应用

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4663005A (en) * 1985-11-15 1987-05-05 Edson Gwynne I Electropolishing process
JPS6324089A (ja) * 1986-07-16 1988-02-01 Tanaka Kikinzoku Kogyo Kk 金の電解液
US5302278A (en) 1993-02-19 1994-04-12 Learonal, Inc. Cyanide-free plating solutions for monovalent metals
JP3365866B2 (ja) 1994-08-01 2003-01-14 荏原ユージライト株式会社 非シアン性貴金属めっき浴
US6251249B1 (en) 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process
DE19928047A1 (de) 1999-06-19 2000-12-21 Gerhard Hoffacker Schadstoffarme bis schadstoffreie wäßrige Systeme zur galvanischen Abscheidung von Edelmetallen und Edelmetall-Legierungen
JP3697181B2 (ja) * 2001-07-27 2005-09-21 日本高純度化学株式会社 無電解金メッキ液
KR100442519B1 (ko) * 2002-04-09 2004-07-30 삼성전기주식회사 모듈화 인쇄회로기판의 표면처리용 합금 도금액
JP2009191335A (ja) * 2008-02-15 2009-08-27 Ishihara Chem Co Ltd めっき液及び電子部品
DE102009024396A1 (de) 2009-06-09 2010-12-16 Coventya Spa Cyanid-freier Elektrolyt zur galvanischen Abscheidung von Gold oder dessen Legierungen
TWI426157B (zh) * 2011-05-18 2014-02-11 Uwin Nanotech Co Ltd 剝金組成物以及使用方法
JP5622678B2 (ja) * 2011-07-14 2014-11-12 石原ケミカル株式会社 イミダゾール環結合型オキシアルキレン化合物を含有するメッキ浴
DE102012004348B4 (de) * 2012-03-07 2014-01-09 Umicore Galvanotechnik Gmbh Verwendung von organischen Thioharnstoffverbindungen zur Erhöhung der galvanischen Abscheiderate von Gold und Goldlegierungen
KR20170001748A (ko) 2012-10-04 2017-01-04 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 비시안계 전해 금도금액
DE102013215476B3 (de) 2013-08-06 2015-01-08 Umicore Galvanotechnik Gmbh Elektrolyt zur elektrolytischen Abscheidung von Silber-Palladium-Legierungen und Verfahren zu deren Abscheidung
CN105316718A (zh) 2014-07-31 2016-02-10 无锡永发电镀有限公司 一种亚硫酸盐无氰镀金的电镀液及电镀方法
JP6017726B2 (ja) 2014-08-25 2016-11-02 小島化学薬品株式会社 還元型無電解金めっき液及び当該めっき液を用いた無電解金めっき方法
PL3159435T3 (pl) * 2015-10-21 2018-10-31 Umicore Galvanotechnik Gmbh Dodatek do elektrolitów do stopu srebro-palladowego

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3443146A1 (fr) 2019-02-20
CN110770371A (zh) 2020-02-07
US20200095693A1 (en) 2020-03-26
ES2773771T3 (es) 2020-07-14
JP2020521060A (ja) 2020-07-16
KR20200010340A (ko) 2020-01-30
WO2018215057A1 (fr) 2018-11-29

Similar Documents

Publication Publication Date Title
JP6370380B2 (ja) 銀−パラジウム合金の電着のための電解質、及びその析出方法
US20160024683A1 (en) Apparatus and method for electrolytic deposition of metal layers on workpieces
EP3159435B1 (fr) Supplement pour electrolyte d'alliage argent-palladium
JP2011520037A (ja) 改良された銅−錫電解液及び青銅層の析出方法
JP2004510053A (ja) 錫−銅合金層を析出させるための電解質及び方法
KR20110039460A (ko) 구리 층의 갈바닉 침착을 위한 시안화물-무함유 전해질 조성물
CA1291440C (fr) Electrodeposition de palladium et de ses alliages
CN102220610B (zh) 一种无氰型铜锡合金电镀液
EP3443146B1 (fr) Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition
JP7499235B2 (ja) 熱安定性銀合金コーティング
JPH10317183A (ja) 非シアンの電気金めっき浴
US4377450A (en) Palladium electroplating procedure
JP2016532004A (ja) 電気めっき浴
TWI846730B (zh) 熱穩定銀合金層
CN114108031B (zh) 一种环保无氰碱性镀铜细化剂及其制备方法
US20240150920A1 (en) Platinum Electrolyte
WO2022112379A1 (fr) Couche d'alliage de ruthénium et ses combinaisons de couches
JP2010150606A (ja) 電解再生式の無電解スズメッキ方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20181114

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190415

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: 20190604

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

DAV Request for validation of the european patent (deleted)
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

DAX Request for extension of the european patent (deleted)
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

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SAXONIA EDELMETALLE GMBH

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

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: 1217224

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017010165

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: VALIPAT S.A. C/O BOVARD SA NEUCHATEL, CH

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 40001456

Country of ref document: HK

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20191225

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20191225

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

Ref country code: FI

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

Effective date: 20191225

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: 20200326

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: 20191225

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: 20191225

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: 20200325

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: 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: 20191225

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: 20191225

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: 20191225

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2773771

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200714

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: 20191225

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: 20200520

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: 20191225

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: 20191225

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

Ref country code: DE

Payment date: 20200311

Year of fee payment: 4

Ref country code: NO

Payment date: 20200506

Year of fee payment: 4

Ref country code: CH

Payment date: 20200513

Year of fee payment: 4

Ref country code: FR

Payment date: 20200511

Year of fee payment: 4

Ref country code: RO

Payment date: 20200511

Year of fee payment: 4

Ref country code: ES

Payment date: 20200615

Year of fee payment: 4

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

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: 20200425

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: 20191225

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: 20191225

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

Ref country code: SE

Payment date: 20200514

Year of fee payment: 4

Ref country code: IT

Payment date: 20200531

Year of fee payment: 4

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017010165

Country of ref document: DE

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

Ref country code: DK

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

Effective date: 20191225

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: 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: 20191225

26N No opposition filed

Effective date: 20200928

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: 20191225

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

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: 20191225

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200531

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: 20200523

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: 20200523

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: 20200531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602017010165

Country of ref document: DE

REG Reference to a national code

Ref country code: NO

Ref legal event code: MMEP

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20210523

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 NON-PAYMENT OF DUE FEES

Effective date: 20210524

Ref country code: NO

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

Effective date: 20210531

Ref country code: RO

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

Effective date: 20210523

Ref country code: LI

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

Effective date: 20210531

Ref country code: CH

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

Effective date: 20210531

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1217224

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191225

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: 20210523

Ref country code: DE

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

Effective date: 20211201

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: 20191225

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: 20191225

Ref country code: FR

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

Effective date: 20210531

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: 20191225

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: 20191225

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220704

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: 20210524

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: 20200523

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1217224

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220523

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: 20220523