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EP4075205B1 - Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder - Google Patents

Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder Download PDF

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Publication number
EP4075205B1
EP4075205B1 EP21168779.3A EP21168779A EP4075205B1 EP 4075205 B1 EP4075205 B1 EP 4075205B1 EP 21168779 A EP21168779 A EP 21168779A EP 4075205 B1 EP4075205 B1 EP 4075205B1
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EP
European Patent Office
Prior art keywords
thin layer
phosphorus
intermediate layer
nickel
layer
Prior art date
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Active
Application number
EP21168779.3A
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English (en)
French (fr)
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EP4075205A1 (de
Inventor
Serge Nicoud
Sébastien RODER
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.)
ETA SA Manufacture Horlogere Suisse
Original Assignee
ETA SA Manufacture Horlogere Suisse
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Filing date
Publication date
Application filed by ETA SA Manufacture Horlogere Suisse filed Critical ETA SA Manufacture Horlogere Suisse
Priority to EP21168779.3A priority Critical patent/EP4075205B1/de
Priority to JP2022031472A priority patent/JP7378523B2/ja
Priority to US17/692,303 priority patent/US12147200B2/en
Priority to CN202210413895.6A priority patent/CN115220325A/zh
Priority to KR1020220047071A priority patent/KR102749073B1/ko
Publication of EP4075205A1 publication Critical patent/EP4075205A1/de
Application granted granted Critical
Publication of EP4075205B1 publication Critical patent/EP4075205B1/de
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Classifications

    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B15/00—Escapements
    • G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/20—Compensation of mechanisms for stabilising frequency
    • G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
    • G04B17/227—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature composition and manufacture of the material used
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/20—Compensation of mechanisms for stabilising frequency
    • G04B17/26—Compensation of mechanisms for stabilising frequency for the effect of variations of the impulses
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
    • G04B31/08—Lubrication
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B43/00—Protecting clockworks by shields or other means against external influences, e.g. magnetic fields
    • G04B43/007—Antimagnetic alloys

Definitions

  • the invention belongs to the field of micromechanical components, and more precisely that of watch mobiles, in particular escapement mechanisms comprising at least one escape wheel and at least one anchor, at least one of which is non-magnetic.
  • the invention relates in particular to a method of manufacturing a micromechanical component, in particular a watch mobile.
  • State-of-the-art anchor escapement mechanisms generally include escapement wheels made of nickel-plated steel. These escapement wheels are sensitive to magnetic fields.
  • escapement wheels have been developed with materials having amagnetic behavior, such as nickel-phosphorus (NiP12) implemented in particular by the so-called “LIGA” process (from the German “Röntgenlithographie, Galvanoformung, Abformung” meaning in French “lithography, galvanization, forming”).
  • NiP12 nickel-phosphorus
  • the main problem is the loss of epilame effect on the escape wheel board, which causes oil spreading and loss of lubrication at the contact between the wheel tooth and the ruby lift.
  • the stability of the lubrication in contact between the levers of the anchor and the escape wheel must ensure the constancy of the amplitude.
  • the document CH698230 deals with the problem of friction between moving parts in a watch movement, but does not address issues related to magnetism or the sensitivity of materials in certain climatic conditions.
  • the invention aims to solve the technical problem of the resistance of the usual watch lubricant, and more particularly to guarantee an epilame effect, in all climatic conditions, on components made of LIGA NiP12, or similar, non-ferromagnetic, in particular on anchors and Swiss anchor escapement wheels.
  • the first and second thin layers are poorer in phosphorus than the intermediate layer, or are devoid of phosphorus.
  • the invention may further comprise one or more of the following features, taken individually or in any technically possible combination.
  • the intermediate layer is superimposed on the first thin layer and the second thin layer is superimposed on the intermediate layer, respectively at the level of at least one interface face contiguous to at least one friction face of the watch mobile intended to be in contact with another watch component.
  • the steps of deposition of the first thin layer, the intermediate layer and the second thin layer are implemented by LIGA.
  • the second material consists solely of nickel and phosphorus.
  • the second material has a mass proportion of phosphorus of between 1% and 15%.
  • the second material is made of NiP12.
  • the first material comprises only pure nickel, or only nickel and phosphorus.
  • the first material comprises a mass proportion of phosphorus less than or equal to 9%.
  • the first material comprises a mass proportion of phosphorus of between 6% and 9%.
  • the first material comprises a mass proportion of phosphorus of between 1% and 6%.
  • the first material comprises a mass proportion of phosphorus of between 0% and 1%.
  • the first material comprises boron
  • Boron allows the first and second layers to exhibit better tribological and hardness properties.
  • the first material consists solely of nickel and boron.
  • the first material has a thickness of between 0.2 micrometers and 10 micrometers.
  • a heat treatment is applied to an assembly formed by the first thin layer, the intermediate layer and the second thin layer, at a temperature between 100°C and 500°C, for 1 to 8 hours.
  • the method is applied to the manufacture of an escapement wheel which is an escape wheel or an anchor.
  • the first thin layer, the intermediate layer and the second thin layer are deposited so that the formed timepiece mobile comprises, in the sense and in the direction of deposition growth of said layers, a phosphorus concentration gradient defined by a progressive growth through the first thin layer, a stable state through the intermediate layer and a decrease through the second thin layer.
  • the present invention relates to a timepiece mobile manufactured by implementing the method described above, and comprising an intermediate layer interposed between a first thin layer and a second thin layer, said thin layers being made of a first material comprising at least nickel, the intermediate layer being made of a second material comprising at least nickel and phosphorus, the first and second thin layers being poorer in phosphorus than the intermediate layer, or being devoid of phosphorus.
  • the timepiece mobile constitutes an escape wheel or an anchor.
  • the present invention relates in particular to a method of manufacturing a timepiece mobile 10, the steps of which are represented by the flowchart of the figure 2 .
  • the thickness of said second thin layer 13 is substantially equal to the thickness of the first thin layer 11, as shown by the clockwork mobile schematically represented in the figure 1 , the sum of said thicknesses being several times less than that of the intermediate layer 12.
  • the periphery of the geometric shape of the first thin layer 11 defines the contour of the geometry of an escape wheel or an anchor, so that the timepiece mobile 10 obtained by implementing the method according to the present invention is an escape wheel or an anchor, or even the pallets of an anchor.
  • the first and second thin layers 11 and 13 and the intermediate layer 12 are deposited using a LIGA process, in a predefined deposition growth direction, perpendicular to a plane in which the geometric shape of the first thin layer 11 extends.
  • the first and second thin layers 11 and 13 and the intermediate layer 12 are configured to have non-magnetic properties.
  • first material and the second material are not necessarily non-magnetic; in this case, it is the low thickness of each layer which gives the part its non-magnetic character.
  • the first and second thin layers 11 and 13 may be made of nickel by galvanic means.
  • they may be made of a nickel alloy by galvanic means, for example, Ni-Fe, or Ni-W, or the like.
  • the deposition of the first and second thin layers 11 and 13 can be carried out chemically, according to a chemical nickel application process, for example pure nickel, a nickel-phosphorus low in phosphorus, for example NiP6-9, with 6% to 9% by mass of phosphorus, with a proportion by mass of phosphorus of between 0% and 1% or between 1% and 6%, or even a nickel-boron (NiB).
  • a chemical nickel application process for example pure nickel, a nickel-phosphorus low in phosphorus, for example NiP6-9, with 6% to 9% by mass of phosphorus, with a proportion by mass of phosphorus of between 0% and 1% or between 1% and 6%, or even a nickel-boron (NiB).
  • the first and second thin layers 11 and 13 are advantageously poorer in phosphorus than the intermediate layer 12, or are devoid of phosphorus.
  • the invention makes it possible to increase the stability of the epilame in normal climatic conditions, to increase the grip of the epilame, and therefore the resistance of any normal watchmaking lubricant.
  • the present invention makes it possible to greatly improve the performance of the movements.
  • the first thin layer 11 and the second thin layer 13 each have a thickness of less than 10 micrometers, and particularly between 0.2 micrometers and 5 micrometers, and preferably between 0.2 micrometers and 2 micrometers.
  • the intermediate layer 12 is at least 100 micrometers.
  • the intermediate layer 12 is made of nickel-phosphorus of formulation NiPx, with x between 1% and 15% by mass, or more particularly with x between 10% and 15% by mass, this latter range making it possible to guarantee the non-magnetic nature of the coating.
  • the intermediate layer 12 is made of NiP12.
  • the intermediate layer 12 may consist solely of nickel and phosphorus. Furthermore, it may be produced by galvanic or chemical means.
  • the heat treatment may consist of subjecting an assembly formed by the first thin layer 11, the intermediate layer 12, and the second thin layer 13, to a temperature between 100°C and 500°C, for 1 to 8 hours.
  • a chemical treatment to the surface of the first thin layer 11 and to the surface of the intermediate layer 12 to modify its surface state characteristics so as to facilitate the adhesion of the following layer, i.e. the intermediate layer 12 or the second thin layer 13.
  • This chemical treatment can in particular be carried out by galvanic means.
  • the method according to the invention is implemented by LIGA.
  • the invention makes it possible to guarantee normal aging conditions for the clockwork mobile 10, a constant amplitude, and the absence of stopping.
  • the intermediate layer 12 is superimposed on the first thin layer 11 and the second thin layer 13 is superimposed on the intermediate layer 12, respectively at the level of at least one face called “interface face” 14, contiguous to at least one contact face called “friction face” 15 of the watch mobile 10 intended to be in contact with another watch mobile or component.
  • the friction face(s) 15 may also constitute the guide surfaces of the clockwork mobile 10 for its pivoting or for its guidance according to a single degree of freedom.
  • the friction face(s) 15 correspond to the cross section of the first and second thin layers 11 and 13 and of the intermediate layer 12.
  • the timepiece mobile 10 comprises several friction faces 15.
  • the friction faces 15 are advantageously made up mainly of the second material to the extent that the sum of the thicknesses of the first and second thin layers 11 and 13 is relatively small compared to the thickness of the intermediate layer 12, for example by a factor of at most one tenth.
  • This feature is advantageous since the friction is carried out on a surface consisting mainly of nickel-phosphorus, which has good tribological properties.
  • the first and second thin layers 11 and 13 also have faces opposite each other constituting end faces 16 of the timepiece mobile 10.
  • Another advantage of the method according to the present invention lies in the fact of obtaining a single-piece timepiece mobile, which, compared to possible manufacturing methods of the prior art, makes it possible to avoid a step of depositing a coating.
  • the first thin layer 11, the intermediate layer 12 and the second thin layer 13 are deposited so that the timepiece mobile 10 formed comprises, in the sense and direction of growth of deposition of said layers, a phosphorus concentration gradient defined for example by a progressive growth through the first thin layer 11, a stable state through the intermediate layer 12 and a progressive decrease through the second thin layer 13.
  • the concentration gradient includes the phosphorus concentration values mentioned above in this description.
  • the phosphorus concentration may vary from a zero value in the end face 16 of the first thin layer 11 to a maximum of 12% by mass within the intermediate layer 12, then decrease so as to reach a zero value in the end face 16 of the second thin layer 13.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Gears, Cams (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)

Claims (19)

  1. Verfahren zur Herstellung eines Drehteils für Uhrmacherei (10), die aufeinanderfolgenden Schritte umfassend, zum:
    - Abscheiden 101 einer ersten Dünnschicht (11) mit einem ersten Werkstoff, der mindestens Nickel beinhaltet, gemäß einer geometrischen Form, deren Umfang die Kontur der Geometrie des Drehteils für Uhrmacherei (10) definiert,
    - Abscheiden 102 einer Zwischenschicht (12), mit einem zweiten Werkstoff, der mindestens Nickel und Phosphor beinhaltet, um eine Seite der ersten Dünnschicht (11) zu bedecken und um eine geometrische Form aufzuweisen, deren Umfang jenem der geometrischen Form der ersten Dünnschicht (11) entspricht,
    - Abscheiden 103 einer zweiten Dünnschicht (13) mit dem ersten Werkstoff, um eine Seite der Zwischenschicht (12) zu bedecken und um eine geometrische Form aufzuweisen, deren Umfang jenem der geometrischen Form der ersten Dünnschicht (11) entspricht,
    - wobei die erste und die zweite Dünnschicht (11, 13) phosphorärmer als die Zwischenschicht (12) sind oder mit keinem Phosphor versehen sind.
  2. Verfahren nach Anspruch 1, wobei die Zwischenschicht (12) der ersten Dünnschicht (11) überlagert wird und die zweite Dünnschicht (13) der Zwischenschicht (12) überlagert wird, jeweils im Bereich von mindestens einer Schnittstellenseite (14), die an mindestens eine Reibseite (15) des Drehteils für Uhrmacherei (10) angrenzt, die dazu bestimmt ist, mit einer anderen Komponente für Uhrmacherei in Kontakt zu stehen.
  3. Verfahren nach Anspruch 2, wobei die Abscheideschritte 101, 102 und 103 der ersten Dünnschicht (11), der Zwischenschicht (12) und der zweiten Dünnschicht (13) durch LIGA durchgeführt werden.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der zweite Werkstoff nur aus Nickel und Phosphor besteht.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der zweite Werkstoff einen Massenanteil an Phosphor aufweist, der zwischen 1 % und 15 % liegt.
  6. Verfahren nach Anspruch 5, wobei der zweite Werkstoff aus NiP12 hergestellt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei der erste Werkstoff nur reines Nickel oder aber nur Nickel und Phosphor beinhaltet.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei der erste Werkstoff einen Massenanteil an Phosphor kleiner oder gleich 9 % umfasst.
  9. Verfahren nach Anspruch 8, wobei der erste Werkstoff einen Massenanteil an Phosphor umfasst, der zwischen 6 % und 9 % liegt.
  10. Verfahren nach Anspruch 8, wobei der erste Werkstoff einen Massenanteil an Phosphor umfasst, der zwischen 1 % und 6 % liegt.
  11. Verfahren nach Anspruch 8, wobei der erste Werkstoff einen Massenanteil an Phosphor umfasst, der zwischen 0 % und 1 % liegt.
  12. Verfahren nach einem der Ansprüche 1 bis 11, wobei der erste Werkstoff Bor umfasst.
  13. Verfahren nach Anspruch 12, wobei der erste Werkstoff nur aus Nickel und Bor besteht.
  14. Verfahren nach einem der Ansprüche 1 bis 13, wobei der erste Werkstoff eine Dicke aufweist, die zwischen 0,2 Mikrometern und 10 Mikrometern liegt.
  15. Verfahren nach einem der Ansprüche 1 bis 14, wobei eine Wärmebehandlung auf eine Einheit, die aus der ersten Dünnschicht (11), der Zwischenschicht (12) und der zweiten Dünnschicht (13) gebildet wird, bei einer Temperatur, die zwischen 100°C und 500°C liegt, 1 bis 8 Stunden lang angewendet wird.
  16. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass es auf die Herstellung eines Hemmungsdrehteils angewendet wird, der ein Hemmungsrad oder ein Anker ist.
  17. Verfahren nach einem der Ansprüche 1 bis 16, wobei die erste Dünnschicht (11), die Zwischenschicht (12) und die zweite Dünnschicht (13) abgeschieden werden, sodass der gebildete Drehteil für Uhrmacherei (10) in der Richtung und in der Richtung der Zunahme der Abscheidung der Schichten einen Gradienten der Phosphorkonzentration, der durch eine allmähliche Zunahme durch die erste Dünnschicht (11) hindurch definiert wird, einen stabilen Zustand durch die Zwischenschicht (12) und eine Abnahme durch die zweite Dünnschicht (13) hindurch beinhaltet.
  18. Drehteil für Uhrmacherei (10), der durch die Umsetzung eines Verfahrens nach einem der Ansprüche 1 bis 17 hergestellt wird, umfassend eine Zwischenschicht (12), die zwischen einer ersten Dünnschicht (11) und einer zweiten Dünnschicht (13) eingesetzt ist, wobei die Dünnschichten (11, 13) aus einem ersten Werkstoff hergestellt sind, der mindestens Nickel beinhaltet, die Zwischenschicht (12) aus einem zweiten Werkstoff hergestellt ist, der mindestens Nickel und Phosphor beinhaltet, wobei die erste und die zweite Dünnschicht (11, 13) phosphorärmer als die Zwischenschicht (12) sind oder mit keinem Phosphor versehen sind.
  19. Drehteil für Uhrmacherei (10) nach Anspruch 18, der ein Hemmungsrad oder einen Anker darstellt.
EP21168779.3A 2021-04-16 2021-04-16 Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder Active EP4075205B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21168779.3A EP4075205B1 (de) 2021-04-16 2021-04-16 Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder
JP2022031472A JP7378523B2 (ja) 2021-04-16 2022-03-02 時計可動体を製造するための方法および方法を実施することにより得られる時計可動体
US17/692,303 US12147200B2 (en) 2021-04-16 2022-03-11 Method for manufacturing a horological disc and horological disc obtained by its implementation
CN202210413895.6A CN115220325A (zh) 2021-04-16 2022-04-14 制造钟表运动件的方法和由实施该方法获得的钟表运动件
KR1020220047071A KR102749073B1 (ko) 2021-04-16 2022-04-15 시계 모빌을 제조하기 위한 방법 및 그 구현에 의해 획득된 시계 모빌

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21168779.3A EP4075205B1 (de) 2021-04-16 2021-04-16 Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder

Publications (2)

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EP4075205A1 EP4075205A1 (de) 2022-10-19
EP4075205B1 true EP4075205B1 (de) 2024-12-11

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US (1) US12147200B2 (de)
EP (1) EP4075205B1 (de)
JP (1) JP7378523B2 (de)
KR (1) KR102749073B1 (de)
CN (1) CN115220325A (de)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH514873A (fr) * 1969-07-11 1971-07-15 Far Fab Assortiments Reunies Procédé de fabrication d'une ancre d'horlogerie
CH681370A5 (en) * 1992-02-25 1993-03-15 Estoppey Reber S A Solid lubricant coating prodn. for reducing friction between soft parts - by applying nickel@-phosphorus@ layer and gold@ layer and then heat treating
EP2082014B1 (de) 2006-11-02 2018-02-14 Rolex Sa Watch
EP1927648A1 (de) * 2006-12-01 2008-06-04 Rolex Sa Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame
JP5113687B2 (ja) 2008-02-25 2013-01-09 セイコーインスツル株式会社 摺動部品およびそれを用いた時計
EP2263971A1 (de) * 2009-06-09 2010-12-22 Nivarox-FAR S.A. Mikromechanisches Verbundbauteil und sein Herstellungsverfahren
CH707562B1 (fr) * 2013-02-13 2020-01-15 Nivarox Sa Procédé de fabrication d'une pièce de micromécanique monobloc comportant au moins deux niveaux distincts.
EP3171229A1 (de) 2015-11-19 2017-05-24 Nivarox-FAR S.A. Uhrwerkskomponente
EP3273306A1 (de) * 2016-07-19 2018-01-24 Nivarox-FAR S.A. Bauteil für uhrwerk
CH713970A1 (fr) * 2017-07-12 2019-01-15 Sa De La Manufacture Dhorlogerie Audemars Piguet & Cie Composant horloger en alliage binaire CuNi amagnétique.

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KR102749073B1 (ko) 2024-12-31
CN115220325A (zh) 2022-10-21
JP7378523B2 (ja) 2023-11-13
US12147200B2 (en) 2024-11-19
JP2022164565A (ja) 2022-10-27
US20220334539A1 (en) 2022-10-20
KR20220143605A (ko) 2022-10-25
EP4075205A1 (de) 2022-10-19

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