EP3480338B1 - Dépôt autocatalytique d'alliage de nickel-phosphore et électrolyte correspondant - Google Patents

Dépôt autocatalytique d'alliage de nickel-phosphore et électrolyte correspondant Download PDF

Info

Publication number
EP3480338B1
EP3480338B1 EP18201278.1A EP18201278A EP3480338B1 EP 3480338 B1 EP3480338 B1 EP 3480338B1 EP 18201278 A EP18201278 A EP 18201278A EP 3480338 B1 EP3480338 B1 EP 3480338B1
Authority
EP
European Patent Office
Prior art keywords
group
electrolyte
hydrogen atom
nickel
salts
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
EP18201278.1A
Other languages
German (de)
English (en)
Other versions
EP3480338A1 (fr
Inventor
André Egli
Mathias Schnippering
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.)
RIAG Oberflachentechnik AG
Original Assignee
RIAG Oberflachentechnik AG
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 RIAG Oberflachentechnik AG filed Critical RIAG Oberflachentechnik AG
Priority to PL18201278T priority Critical patent/PL3480338T3/pl
Publication of EP3480338A1 publication Critical patent/EP3480338A1/fr
Application granted granted Critical
Publication of EP3480338B1 publication Critical patent/EP3480338B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel

Definitions

  • the present invention relates to a chemical, i. H. externally electroless process for generating a nickel alloy by electroless metal deposition in an aqueous electrolyte and a corresponding electrolyte.
  • Electroless nickel Phosphorus is used as protection against corrosion and wear. d. Usually deposited on metallic materials in the form of a nickel coating. In contrast to galvanic nickel processes, no electronic current is used for the deposition.
  • nickel alloys are nickel-phosphorus alloys that are used in particular in functional areas of application.
  • the layer properties can be controlled via the phosphorus deposited in the layer. A distinction is made between a high (10-14% by weight), medium (9-12% by weight) and low (3-7% by weight) phosphorus content.
  • a method for producing a lead-free nickel alloy in which a metallic substrate is immersed in an aqueous electrolyte containing nickel cations, hypophosphite ions, bismuth ions in a concentration of bismuth of at most 0.3 ppm and antimony ions in a concentration of antimony of at least 10 Contains ppm.
  • An electrolyte for the production of lead-free nickel layers generated externally without current is from the U.S. 2,884,344 known. According to the method described there, at least two cations are added to the electrolyte, selected from the group of antimony, arsenic and bismuth.
  • the electrolyte contains a metal salt, with at least one salt consisting of metal acetate, metal formate, metal oxalate, metal propionate, metal citrate and metal ascorbate, particularly preferably metal acetate, so that pore-free and crack-free coatings with constant layer properties and high phosphorus contents can be produced at an increased deposition rate.
  • the resulting layers have significantly improved corrosion resistance and hardness due to the co-deposited phosphorus.
  • nickel alloys with a particularly high phosphorus content are desired.
  • the object of the invention is therefore to provide a method for producing a nickel alloy generated externally in a currentless manner which brings about a particularly high rate of incorporation or co-deposition of phosphorus. Another task is to provide a suitable electrolyte.
  • nickel-phosphorus alloys can be produced which have a phosphorus content of greater than 10% by weight based on all components of the alloy.
  • a high deposition rate is preferably achieved that a phosphorus content of more than 11% by weight based on all components of the alloy is achieved.
  • the pyrones of the formula I can therefore be, inter alia, ethyl maltol, kojic acid or dehydroacetic acid (DHA).
  • DHA dehydroacetic acid
  • R1 represents a hydroxyl group
  • R2 represents an ethyl group
  • R3 and R4 represent a hydrogen atom in a pyrone of the formula I.
  • ethyl maltol as an additive is particularly preferred and particularly good results are obtained with this pyrone with regard to the phosphorus content achieved. This enables phosphorus alloy proportions of over 11% by weight to be achieved.
  • the electrolyte additionally contains ascorbic acid, iso- ascorbic acid or their salts, in addition to a high rate of phosphorus incorporation, the deposition of phosphorus can also be accelerated without the aid of sulfur-containing compounds or other semimetals such as selenium and Tellurium.
  • a deposition rate of generally more than 12 ⁇ m, more particularly more than 16 ⁇ m and ideally more than 20 ⁇ m per hour can be achieved.
  • ascorbic acid or iso- ascorbic acid or their salts in no way leads to a loss of stability.
  • ascorbic acid stabilizes the system, as is to be expected from a bidentate ligand.
  • ascorbic acids accelerate the deposition in a similar way to what is known from sulfur compounds.
  • the known sulfur compounds can be used.
  • the two types of acceleration are not mutually exclusive and can be added, ie in addition to ascorbic acid, sulfur-containing compounds of a known type can also be used. It is therefore possible to accelerate medium-phosphorous processes to up to 40 ⁇ m per hour and high-phosphorous processes to over 20 ⁇ m per hour.
  • the electrolyte additionally contains a monohydroxy carboxylic acid or its salts, a further improvement in the phosphorus content can be achieved while maintaining the deposition rate.
  • the pyrones of the formula I are contained in an amount between 5 ppm and the solubility limit, preferably between 0.1 g / L and 25 g / L, particularly preferably between 0.5 g / L and 20 g / L .
  • the process is carried out at a temperature of the electrolyte of at least 85 ° C., preferably at least 92 ° C., a significant increase in the deposition rate can be achieved. This increase does not take place continuously, but in stages. This means that there are three discrete temperature ranges: (i) below 85 ° C there is practically no deposition, analogous to the known processes, (ii) between 86 and 91 ° C it is 50 to 70% faster than traditional processes Deposition takes place and (iii) from 92 ° C. the deposition rate is at least doubled.
  • representatives (e.g. ethyl maltol, kojic acid, DHA) of the mentioned class of substances have pK values between 5 and 10, which makes it possible to increase the pH value of the coating solution to above 5 without reducing the concentration of free nickel ions would be increased in aqueous solution.
  • This increase in the pH value favors the reducing properties of the hypophosphite, which more than doubles the rate of separation together with the ascorbic acid, without impairing the phosphorus incorporation.
  • a particularly high separation speed is achieved when the pH value is increased to above 5 and when ascorbic acid is used at the same time.
  • the invention accordingly also relates to an aqueous electrolyte for the production of nickel-phosphorus alloys containing at least nickel cations, hypophosphite ions, stabilizers, complexing agents and reducing agents, characterized in that the electrolyte additionally contains pyrons of the formula I or their salts (which release the corresponding compound in the aqueous medium), where R1 is a hydrogen atom or a hydroxyl group, R2 is a methyl group, an ethyl group or a hydroxymethyl group, R3 is a hydrogen atom or a hydroxyl group and R4 is a hydrogen atom, a hydroxyl group or a methyl ketone group.
  • aqueous solution consisting of 5 g / L Ni 2+ cations, used as nickel sulfate, 40 g / L sodium hypophosphite monohydrate, 35 g / L iso-ascorbic acid, 45 g / L lactic acid, 35 g / L ethyl maltol, 2 g / L sodium saccharin and 1 ppm Pb 2+ cations, used as lead acetate, were heated to 93 ° C. at a pH of 4.5 (adjusted with sodium carbonate).
  • a stainless steel / steel plate with a total surface area of 1 dm 2 which was previously cleaned for 15 minutes in a commercially available hot degreasing system with ultrasound and then activated for 4 minutes in a 10 percent hydrochloric acid solution, was coated for one hour.
  • the weight of the platelet was weighed, the layer was etched off with half-concentrated nitric acid, the weight was again determined and the nickel and phosphorus content in the etching solution by ICP-OES (inductively coupled plasma atomic emission spectroscopy; instrument from Agilent Technologies (720 Series)) DIN ISO 4527 determined.
  • ICP-OES inductively coupled plasma atomic emission spectroscopy
  • the layer had a P alloy content of 11.2% by weight (based on all components of the alloy).
  • a stainless steel / steel plate was coated there in accordance with the above information and then examined.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemically Coating (AREA)

Claims (10)

  1. Procédé de production d'un alliage nickel-phosphore, procédé dans lequel un substrat métallique est immergé dans un électrolyte aqueux qui contient au moins des cations nickel, des ions hypophosphite, des stabilisants et des agents complexants, caractérisé en ce que l'électrolyte contient en outre des pyrones de la formule I
    Figure imgb0007
     ou leurs sels, R1 représentant un atome d'hydrogène ou un groupe hydroxyle,
    R2 représentant un groupe méthyle, un groupe éthyle ou un groupe hydroxyméthyle, R3 représentant un atome d'hydrogène ou un groupe hydroxyle et R4 représentant un atome d'hydrogène, un groupe hydroxyle ou un groupe méthylcétone.
  2. Procédé selon la revendication 1, caractérisé en ce que R1 représente un groupe hydroxyle, R2 représente un groupe éthyle et R3 et R4 représentent un atome d'hydrogène dans un pyrone de la formule I.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'électrolyte contient en outre de l'acide ascorbique, de l'acide iso-ascorbique et/ou leurs sels, de préférence dans une quantité comprise entre 0,5 g/L et 100 g/L.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'électrolyte contient en outre un acide mono-hydroxy-carboxylique ou ses sels.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que les pyrones de la formule I ou leurs sels sont contenus dans une quantité comprise entre 5 ppm et la limite de solubilité, de préférence entre 0,1 g/L et 25 g/L.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le procédé est mis en œuvre à une température de l'électrolyte d'au moins 85 °C, de préférence d'au moins 92 °C.
  7. Électrolyte aqueux destiné à la production d'alliages nickel-phosphore contenant au moins des cations nickel, des ions hypophosphite, des stabilisants et des agents complexants, caractérisé en ce que l'électrolyte contient en outre des pyrones de la formule I.
    Figure imgb0008
     ou leurs sels, R1 représentant un atome d'hydrogène ou un groupe hydroxyle,
    R2 représentant un groupe méthyle, un groupe éthyle ou un groupe hydroxyméthyle, R3 représentant un atome d'hydrogène ou un groupe hydroxyle et R4 représentant un atome d'hydrogène, un groupe hydroxyle ou un groupe méthylcétone.
  8. Électrolyte aqueux selon la revendication 7, caractérisé en ce que l'électrolyte contient en outre de l'acide ascorbique, de l'acide iso-ascorbique et/ou leurs sels, de préférence dans une quantité comprise entre 0,5 g/L et 100 g/L et/ou un acide mono-hydroxy-carboxylique ou ses sels.
  9. Électrolyte aqueux selon la revendication 7 ou 8, caractérisé en ce que l'électrolyte contient les pyrones de la formule I ou leurs sels dans une quantité comprise entre 5 ppm et la limite de solubilité, de préférence entre 0,1 g/L et 25 g/L.
  10. Électrolyte aqueux selon l'une des revendications 7 à 9, caractérisé en ce que l'électrolyte contient un pyrone de la formule I dans laquelle R1 représente un groupe hydroxyle, R2 représente un groupe éthyle et R3 et R4 représentent un atome d'hydrogène.
EP18201278.1A 2017-11-07 2018-10-18 Dépôt autocatalytique d'alliage de nickel-phosphore et électrolyte correspondant Active EP3480338B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL18201278T PL3480338T3 (pl) 2017-11-07 2018-10-18 Bezprądowe osadzanie stopu niklowo-fosforowego i odpowiedni elektrolit

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102017125954.6A DE102017125954A1 (de) 2017-11-07 2017-11-07 Außen stromloses Verfahren zur Erzeugung einer Nickellegierung und entsprechender Elektrolyt

Publications (2)

Publication Number Publication Date
EP3480338A1 EP3480338A1 (fr) 2019-05-08
EP3480338B1 true EP3480338B1 (fr) 2020-09-09

Family

ID=63914900

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18201278.1A Active EP3480338B1 (fr) 2017-11-07 2018-10-18 Dépôt autocatalytique d'alliage de nickel-phosphore et électrolyte correspondant

Country Status (4)

Country Link
US (1) US20190136382A1 (fr)
EP (1) EP3480338B1 (fr)
DE (1) DE102017125954A1 (fr)
PL (1) PL3480338T3 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884344A (en) 1957-10-07 1959-04-28 Reynolds Metals Co Nickel plating
US6706418B2 (en) * 2000-07-01 2004-03-16 Shipley Company L.L.C. Metal alloy compositions and plating methods related thereto
DE10052960C9 (de) 2000-10-25 2008-07-03 AHC-Oberflächentechnik GmbH & Co. OHG Bleifreie Nickellegierung
DE10246453A1 (de) * 2002-10-04 2004-04-15 Enthone Inc., West Haven Verfahren zur stromlosen Abscheidung von Nickel
CN102268658A (zh) * 2011-07-22 2011-12-07 深圳市精诚达电路有限公司 一种化学镀镍液及化学镀镍工艺

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
US20190136382A1 (en) 2019-05-09
PL3480338T3 (pl) 2021-02-08
EP3480338A1 (fr) 2019-05-08
DE102017125954A1 (de) 2019-05-09

Similar Documents

Publication Publication Date Title
EP1413646B1 (fr) Procédé de dépot sans courant de métaux
DE2522939C2 (de) Wäßriges Abscheidungsbad für die stromlose Abscheidung einer polymetallischen Nickellegierung
DE3210268C2 (de) Wäßriges alkalisches Bad zur stromlosen Abscheidung von Goldüberzügen
DE2049061B2 (de) Alkalisches wäßriges Bad und dessen Verwendung zur stromlosen Verkupferung
DE4119807C1 (en) Bath for electroless plating of e.g. nickel@, zinc@ - consisting of e.g. titanium halogenide(s), cyclo:pentadienyl-complex cpds. of titanium sulphate and hydroxide
EP3070188A2 (fr) Procede de revetement d'une broche inseree par compression et broche inseree par compression
DE3320308A1 (de) Waessriges bad zur stromlosen abscheidung von gold und ein verfahren zur stromlosen abscheidung von gold unter verwendung dieses bades
EP3480338B1 (fr) Dépôt autocatalytique d'alliage de nickel-phosphore et électrolyte correspondant
DE3029785A1 (de) Saures goldbad zur stromlosen abscheidung von gold
DE10052960C5 (de) Bleifreie Nickellegierung
EP2492371A1 (fr) Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
DE112019006704T5 (de) LÖSUNG ZUR STROMLOSEN ABSCHEIDUNG EINER Ni-Fe LEGIERUNG
EP0281804A2 (fr) Bain alcalin stabilisé de dépôt chimique d'or
DE2348362A1 (de) Verfahren zur beschichtung verschleissbeanspruchter bauteile
DE2057757C3 (de) Badlösung zum stromlosen Abscheiden von Metallen
DE3404270A1 (de) Waessriges alkalisches bad zur chemischen abscheidung von kupfer, nickel, kobalt und deren legierungen
EP0542771B1 (fr) Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation
DE2414650C3 (de) Stromlos arbeitendes wässriges Verkupferungsbad
EP0161343A1 (fr) Bain stabilisé pour le dépôt chimique de nickel phosphore, cobalt phosphore et d'alliage nickel-cobalt phosphore
DE2236493C3 (de) Verfahren zum galvanischen Abscheiden glänzender Goldüberzüge mit hohem Goldgehalt
DE2634232C2 (de) Verfahren zur stromlosen reduktiven Abscheidung von Nickel-Phosphor-Schichten, insbesondere für elektrische Widerstände
CH680449A5 (fr)
DE2807564C2 (de) Verfahren zur stromlosen Abscheidung einer Gold-Nickel-Legierung
EP1495157B1 (fr) Procede de placage de cuivre ou de bronze sur des objets et melanges liquides utilises a cet effet
DE2122455C3 (de) Wäßrige Lösung für die stromlose Ablagerung einer Nickel-Kupfer-Phosphor-Legierung mit höchstens 25 Gew.% Kupfer

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

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: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191106

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

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: 20200529

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: AT

Ref legal event code: REF

Ref document number: 1311662

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200915

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502018002385

Country of ref document: DE

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: CH

Ref legal event code: NV

Representative=s name: ALDO ROEMPLER PATENTANWALT, CH

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

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: 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: 20201210

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: 20200909

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: 20200909

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: 20201209

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: 20201209

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: 20200909

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: 20200909

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: 20200909

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: 20200909

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

Ref country code: CZ

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

Effective date: 20200909

Ref country code: RO

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

Effective date: 20200909

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: 20210111

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: 20200909

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: 20200909

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: 20200909

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: 20200909

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: 20210109

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502018002385

Country of ref document: DE

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

Ref country code: MC

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

Effective date: 20200909

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: 20200909

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

26N No opposition filed

Effective date: 20210610

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: 20200909

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: 20200909

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

Effective date: 20200909

Ref country code: IE

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

Effective date: 20201018

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: 20200909

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: 20200909

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: 20200909

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: 20200909

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

Effective date: 20221018

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: 20221018

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

Ref country code: NL

Payment date: 20231023

Year of fee payment: 6

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

Ref country code: LU

Payment date: 20231023

Year of fee payment: 6

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

Ref country code: FR

Payment date: 20231023

Year of fee payment: 6

Ref country code: DE

Payment date: 20231031

Year of fee payment: 6

Ref country code: CH

Payment date: 20231102

Year of fee payment: 6

Ref country code: AT

Payment date: 20231019

Year of fee payment: 6

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

Ref country code: PL

Payment date: 20231006

Year of fee payment: 6

Ref country code: BE

Payment date: 20231023

Year of fee payment: 6