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EP4075205B1 - Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same - Google Patents

Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same 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
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
EP21168779.3A
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German (de)
French (fr)
Other versions
EP4075205A1 (en
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
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 ETA SA Manufacture Horlogere Suisse filed Critical ETA SA Manufacture Horlogere Suisse
Priority to EP21168779.3A priority Critical patent/EP4075205B1/en
Priority to JP2022031472A priority patent/JP7378523B2/en
Priority to US17/692,303 priority patent/US12147200B2/en
Priority to CN202210413895.6A priority patent/CN115220325A/en
Priority to KR1020220047071A priority patent/KR102749073B1/en
Publication of EP4075205A1 publication Critical patent/EP4075205A1/en
Application granted granted Critical
Publication of EP4075205B1 publication Critical patent/EP4075205B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (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)

Description

Domaine technique de l'inventionTechnical field of the invention

L'invention appartient au domaine des composants de micromécanique, et plus précisément celui des mobiles d'horlogerie, notamment des mécanismes d'échappement comportant au moins une roue d'échappement et au moins une ancre, dont au moins l'un d'eux est à caractère amagnétique.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.

L'invention concerne en particulier un procédé de fabrication d'un composant de micromécanique, notamment d'un mobile d'horlogerie.The invention relates in particular to a method of manufacturing a micromechanical component, in particular a watch mobile.

Arrière-plan technologiqueTechnological background

Les mécanismes d'échappement d'horlogerie à ancre de l'état de la technique comprennent généralement des roues d'échappement réalisées en acier nickelé. Ces roues d'échappement sont sensibles aux champs magnétiques.State-of-the-art anchor escapement mechanisms generally include escapement wheels made of nickel-plated steel. These escapement wheels are sensitive to magnetic fields.

Pour résoudre les inconvénients résultants de cette sensibilité aux champs magnétiques, des roues d'échappement ont été développées avec des matériaux ayant un comportement amagnétique, comme le nickel-phosphore (NiP12) mis en oeuvre notamment par procédé dit « LIGA » (de l'allemand « Röntgenlithographie, Galvanoformung, Abformung » signifiant en langue française « lithographie, galvanisation, formage »).To resolve the drawbacks resulting from this sensitivity 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").

Toutefois l'emploi de tels matériaux peut se révéler sensible dans certaines conditions climatiques, dans la mesure où ils sont susceptibles d'entraîner une dégradation des performances, notamment en termes de régularité d'amplitude, d'arrêts, ou encore de vieillissement.However, the use of such materials may prove sensitive in certain climatic conditions, to the extent that they are likely to lead to a deterioration in performance, particularly in terms of amplitude regularity, stops, or even aging.

Cette dégradation des performances est d'autant plus importante quand deux composants antagonistes coopérant l'un avec l'autre de sorte à produire un couple de frottement sont réalisés dans des matériaux LIGA similaires.This performance degradation is all the more significant when two antagonistic components cooperate with each other in such a way as to producing friction torque are made of similar LIGA materials.

En particulier, il est capital de prévenir toute pollution de l'ancre, notamment de la fourchette d'ancre, et d'assurer la présence de lubrifiant sur les surfaces de contact de la roue d'échappement et de l'ancre, en particulier, le contact entre la levée en rubis de l'ancre et la dent de la roue d'échappement, afin de limiter le vieillissement de la roue d'échappement et de l'ancre.In particular, it is essential to prevent any pollution of the anchor, in particular the anchor fork, and to ensure the presence of lubricant on the contact surfaces of the escape wheel and the anchor, in particular, the contact between the ruby lift of the anchor and the tooth of the escape wheel, in order to limit the aging of the escape wheel and the anchor.

Le problème principal est la perte d'effet épilame sur la planche de la roue d'échappement, qui provoque un étalement de l'huile et une perte de lubrification au contact entre la dent de la roue et la levée en rubis.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.

La stabilité de la lubrification au contact entre les levées de l'ancre et la roue d'échappement doit permettre de garantir la constance de l'amplitude.The stability of the lubrication in contact between the levers of the anchor and the escape wheel must ensure the constancy of the amplitude.

Le document CH698230 traite du problème des frottements des pièces en mouvement dans un mouvement horloger, mais n'aborde pas notamment les problématiques liées au magnétisme ou de la sensibilité des matériaux dans certaines conditions climatiques.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.

Résumé de l'inventionSummary of the invention

L'invention se propose de résoudre le problème technique de la tenue du lubrifiant horloger habituel, et plus particulièrement de garantir un effet épilame, dans toutes conditions climatiques, sur des composants en LIGA NiP12, ou similaire, non ferromagnétique, en particulier sur des ancres et des roues d'échappement à ancre suisse.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.

À cet effet, l'invention concerne un procédé de fabrication d'un mobile d'horlogerie, comprenant les étapes successives de :

  • dépôt d'une première couche mince avec un premier matériau comportant au moins du nickel, selon une forme géométrique dont la périphérie définit le contour de la géométrie du mobile d'horlogerie,
  • dépôt d'une couche intermédiaire, avec un second matériau comportant au moins du nickel et du phosphore, de sorte à recouvrir une face de la première couche mince et de sorte à présenter une forme géométrique dont la périphérie correspond à celle de la forme géométrique de la première couche mince,
  • dépôt d'une seconde couche mince avec le premier matériau, de sorte à recouvrir une face de la couche intermédiaire et de sorte à présenter une forme géométrique dont la périphérie correspond à celle de la forme géométrique de la première couche mince.
To this end, the invention relates to a method of manufacturing a timepiece mobile, comprising the successive steps of:
  • depositing a first thin layer with a first material comprising at least nickel, according to a geometric shape whose periphery defines the outline of the geometry of the watch mobile,
  • deposition of an intermediate layer, with a second material comprising at least nickel and phosphorus, so as to cover one face of the first thin layer and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer,
  • depositing a second thin layer with the first material, so as to cover one face of the intermediate layer and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer.

La première et la seconde couche mince sont plus pauvres en phosphore que la couche intermédiaire, ou sont dépourvues de phosphore.The first and second thin layers are poorer in phosphorus than the intermediate layer, or are devoid of phosphorus.

Dans des modes particuliers de mise en oeuvre, l'invention peut comporter en outre l'une ou plusieurs des caractéristiques suivantes, prises isolément ou selon toutes les combinaisons techniquement possibles.In particular embodiments, the invention may further comprise one or more of the following features, taken individually or in any technically possible combination.

Dans des modes particuliers de mise en oeuvre, la couche intermédiaire est superposée à la première couche mince et la seconde couche mince est superposée à la couche intermédiaire, respectivement au niveau d'au moins une face d'interface contiguë à au moins une face de frottement du mobile d'horlogerie destinée à être au contact d'un autre composant d'horlogerie.In particular embodiments, 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.

Dans des modes particuliers de mise en oeuvre, les étapes de dépôt de la première couche mince, de la couche intermédiaire et de la seconde couche mince sont mises en oeuvre par LIGA.In particular embodiments, the steps of deposition of the first thin layer, the intermediate layer and the second thin layer are implemented by LIGA.

Dans des modes particuliers de mise en oeuvre, le second matériau est constitué uniquement de nickel et de phosphore.In particular embodiments, the second material consists solely of nickel and phosphorus.

Dans des modes particuliers de mise en oeuvre, le second matériau présente une proportion en masse de phosphore comprise entre 1% et 15%.In particular embodiments, the second material has a mass proportion of phosphorus of between 1% and 15%.

Dans des modes particuliers de mise en oeuvre, le second matériau est réalisé en NiP12.In particular embodiments, the second material is made of NiP12.

Dans des modes particuliers de mise en oeuvre, le premier matériau comportant uniquement du nickel pur, ou bien uniquement du nickel et du phosphore.In particular embodiments, the first material comprises only pure nickel, or only nickel and phosphorus.

Dans des modes particuliers de mise en oeuvre, le premier matériau comprend une proportion en masse de phosphore inférieure ou égale à 9%.In particular embodiments, the first material comprises a mass proportion of phosphorus less than or equal to 9%.

Dans des modes particuliers de mise en oeuvre, le premier matériau comprend une proportion en masse de phosphore comprise entre 6% et 9 %.In particular embodiments, the first material comprises a mass proportion of phosphorus of between 6% and 9%.

Dans des modes particuliers de mise en oeuvre, le premier matériau comprend une proportion en masse de phosphore comprise entre 1% et 6 %.In particular embodiments, the first material comprises a mass proportion of phosphorus of between 1% and 6%.

Dans des modes particuliers de mise en oeuvre, le premier matériau comprend une proportion en masse de phosphore comprise entre 0% et 1 %.In particular embodiments, the first material comprises a mass proportion of phosphorus of between 0% and 1%.

Dans des modes particuliers de mise en oeuvre, le premier matériau comprend du bore.In particular embodiments, the first material comprises boron.

Le bore permet aux première et seconde couches de présenter de meilleures propriétés tribologique et de dureté.Boron allows the first and second layers to exhibit better tribological and hardness properties.

Dans des modes particuliers de mise en oeuvre, le premier matériau est constitué uniquement de nickel et de bore.In particular embodiments, the first material consists solely of nickel and boron.

Dans des modes particuliers de mise en oeuvre, le premier matériau présente une épaisseur comprise entre 0.2 micromètre et 10 micromètres.In particular embodiments, the first material has a thickness of between 0.2 micrometers and 10 micrometers.

Dans des modes particuliers de mise en oeuvre, un traitement thermique est appliqué à un ensemble formé par la première couche mince, la couche intermédiaire et la seconde couche mince, à une température comprise entre 100°C et 500°C, pendant 1 à 8 heures.In particular embodiments, 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.

Dans des modes particuliers de mise en oeuvre, le procédé est appliqué à la fabrication d'un mobile d'échappement qui est une roue d'échappement ou une ancre.In particular embodiments, the method is applied to the manufacture of an escapement wheel which is an escape wheel or an anchor.

Dans des modes particuliers de mise en oeuvre, la première couche mince, la couche intermédiaire et la seconde couche mince sont déposées de sorte que le mobile d'horlogerie formé comporte, dans le sens et dans la direction de croissance de dépôt desdites couches, un gradient de concentration de phosphore défini par une croissance progressive à travers la première couche mince, un état stable à travers la couche intermédiaire et une décroissance à travers la seconde couche mince.In particular embodiments, 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.

Selon un autre objet, la présente invention concerne un mobile d'horlogerie fabriqué par la mise en oeuvre du procédé décrit précédemment, et comprenant une couche intermédiaire interposée entre une première couche mince et une seconde couche mince, lesdites couches mince étant réalisées dans un premier matériau comportant au moins du nickel, la couche intermédiaire étant réalisée dans second matériau comportant au moins du nickel et du phosphore, la première et la seconde couche mince étant plus pauvres en phosphore que la couche intermédiaire, ou étant dépourvues de phosphore.According to another object, 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.

Dans des modes particuliers de réalisation, le mobile d'horlogerie constitue une roue d'échappement ou une ancre.In particular embodiments, the timepiece mobile constitutes an escape wheel or an anchor.

Brève description des figuresBrief description of the figures

D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée suivante donnée à titre d'exemple nullement limitatif, en référence aux dessins annexés dans lesquels :

  • la figure 1 représente schématiquement une vue de section d'un mobile d'horlogerie obtenu par la mise en oeuvre du procédé de fabrication d'un mobile d'horlogerie selon l'invention ;
  • la figure 2 représente un logigramme illustrant les étapes du procédé de fabrication d'un mobile d'horlogerie selon l'invention.
Other characteristics and advantages of the invention will appear on reading the following detailed description given by way of non-limiting example, with reference to the appended drawings in which:
  • there figure 1 schematically represents a section view of a timepiece mobile obtained by implementing the method of manufacturing a timepiece mobile according to the invention;
  • there figure 2 represents a flowchart illustrating the steps of the manufacturing process of a timepiece mobile according to the invention.

On note que les figures ne sont pas à l'échelle.Note that the figures are not to scale.

Description détaillée de l'inventionDetailed description of the invention

La présente invention concerne notamment un procédé de fabrication d'un mobile d'horlogerie 10 dont les étapes sont représentées par le logigramme de la figure 2.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 .

Le procédé de fabrication comprend les étapes successives de :

  • dépôt 101 d'une première couche mince 11, ou d'un substrat, avec un premier matériau comportant au moins du nickel, selon une forme géométrique dont la périphérie définit le contour de la géométrie du mobile d'horlogerie 10, l'épaisseur de ladite première couche mince 11 étant inférieure à 5 micromètres,
  • dépôt 102 d'une couche intermédiaire 12, avec un second matériau comportant au moins du nickel et du phosphore, de sorte à recouvrir une face de la première couche mince 11, et de sorte à présenter une forme géométrique dont la périphérie correspond à celle de la forme géométrique de la première couche mince
  • dépôt 103 d'une seconde couche mince 13 avec le premier matériau, de sorte à recouvrir une face de la couche intermédiaire 12 et de sorte à présenter une forme géométrique dont la périphérie correspond à celle de la forme géométrique de la première couche mince 11.
The manufacturing process includes the successive stages of:
  • deposition 101 of a first thin layer 11, or of a substrate, with a first material comprising at least nickel, according to a geometric shape whose periphery defines the contour of the geometry of the timepiece mobile 10, the thickness of said first thin layer 11 being less than 5 micrometers,
  • deposit 102 of an intermediate layer 12, with a second material comprising at least nickel and phosphorus, so as to cover one face of the first thin layer 11, and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer
  • depositing 103 a second thin layer 13 with the first material, so as to cover one face of the intermediate layer 12 and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer 11.

L'épaisseur de ladite seconde couche mince 13 est sensiblement égale à l'épaisseur de la première couche mince 11, comme le montre le mobile d'horlogerie représenté schématiquement sur la figure 1, la somme desdites épaisseurs étant plusieurs fois inférieure à celle de la couche intermédiaire 12.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.

Préférentiellement, la périphérie de la forme géométrique de la première couche 11 mince définit le contour de la géométrie d'une roue d'échappement ou d'une ancre, de sorte que le mobile d'horlogerie 10 obtenu par la mise en oeuvre du procédé selon la présente invention soit une roue d'échappement ou une ancre, ou encore les palettes d'une ancre.Preferably, 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.

Préférentiellement, la première et la seconde couche mince 11 et 13 et la couche intermédiaire 12 sont déposées selon un procédé LIGA, selon une direction de croissance de dépôt prédéfinie, perpendiculaire à un plan dans lequel s'étend la forme géométrique de la première couche mince 11.Preferably, 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.

Préférentiellement, la première et la seconde couche mince 11 et 13 et la couche intermédiaire 12 sont configurées pour présenter des propriétés amagnétiques.Preferably, the first and second thin layers 11 and 13 and the intermediate layer 12 are configured to have non-magnetic properties.

Il y a lieu de noter que le premier matériau et le second matériau ne sont pas forcément amagnétiques, c'est dans ce cas, la faible épaisseur de chaque couche qui confère à la pièce son caractère amagnétique.It should be noted that the 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.

Dans un exemple de réalisation de l'invention, la première et la seconde couche mince 11 et 13 peuvent être réalisées en nickel par voie galvanique. Alternativement, elles peuvent être réalisées en un alliage de nickel par voie galvanique, par exemple, Ni-Fe, ou Ni-W, ou autre.In an exemplary embodiment of the invention, the first and second thin layers 11 and 13 may be made of nickel by galvanic means. Alternatively, they may be made of a nickel alloy by galvanic means, for example, Ni-Fe, or Ni-W, or the like.

En alternative, le dépôt de la première et de la seconde couche mince 11 et 13 peut être réalisé par voie chimique, selon un procédé d'application de nickel chimique, par exemple un nickel pur, un nickel-phosphore pauvre en phosphore, par exemple NiP6-9, avec de 6% à 9% en masse de phosphore, avec une proportion en masse de phosphore comprise entre 0% et 1% ou entre 1% et 6%, ou bien encore un nickel-bore (NiB).Alternatively, 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).

La première et la seconde couche mince 11 et 13 sont avantageusement plus pauvres en phosphore que la couche intermédiaire 12, ou sont dépourvues de phosphore.The first and second thin layers 11 and 13 are advantageously poorer in phosphorus than the intermediate layer 12, or are devoid of phosphorus.

Grâce à cette caractéristique, l'invention permet d'augmenter la stabilité de l'épilame en conditions climatiques usuelles, d'augmenter l'accroche de l'épilame, et donc la tenue de n'importe quel lubrifiant horloger usuel.Thanks to this characteristic, 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.

Ainsi, la présente invention permet d'améliorer grandement les performances des mouvements.Thus, the present invention makes it possible to greatly improve the performance of the movements.

En effet, il a été démontré par différents tests que ces effets sur l'épilame sont obtenus quand la quantité de phosphore en surface est réduite.In fact, it has been demonstrated by various tests that these effects on epilame are obtained when the quantity of phosphorus on the surface is reduced.

Dans un exemple de réalisation de l'invention, la première couche mince 11 et la seconde couche mince 13 présentent chacune une épaisseur inférieure à 10 micromètres, et particulièrement comprise entre 0.2 micromètre et 5 micromètres, et, préférentiellement comprise entre 0.2 micromètre et 2 micromètres.In an exemplary embodiment of the invention, 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.

Dans un exemple de réalisation de l'invention, la couche intermédiaire 12 est d'au moins 100 micromètres.In an exemplary embodiment of the invention, the intermediate layer 12 is at least 100 micrometers.

Dans un exemple particulier de réalisation de l'invention, la couche intermédiaire 12 est réalisée en nickel-phosphore de formulation NiPx, avec x compris entre 1 % et 15% en masse, ou plus particulièrement avec x compris entre 10% et 15% en masse, cette dernière plage permettant de garantir le caractère amagnétique du revêtement.In a particular embodiment of the invention, 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.

Préférentiellement, la couche intermédiaire 12 est réalisée en NiP12.Preferably, the intermediate layer 12 is made of NiP12.

La couche intermédiaire 12 peut être constituée uniquement de nickel et de phosphore. En outre, elle peut être réalisée par voie galvanique ou par voir chimique.The intermediate layer 12 may consist solely of nickel and phosphorus. Furthermore, it may be produced by galvanic or chemical means.

Il est possible d'appliquer un traitement thermique au mobile d'horlogerie 10 formé par l'ensemble des couches.It is possible to apply a heat treatment to the clockwork mobile 10 formed by all of the layers.

Plus particulièrement, le traitement thermique peut consister à soumettre un ensemble formé par la première couche mince 11, la couche intermédiaire 12, et la seconde couche mince 13, à une température comprise entre 100°C et 500°C, pendant 1 à 8 heures.More particularly, 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.

Alternativement ou additionnellement, il est envisageable d'appliquer un traitement chimique à la surface de la première couche mince 11 et à la surface de la couche intermédiaire 12 pour modifier ses caractéristiques d'état de surface de façon à faciliter l'accroche de la couche suivante, c'est-à-dire de la couche intermédiaire 12 ou de la seconde couche mince 13. Ce traitement chimique peut notamment être réalisé par voie galvanique.Alternatively or additionally, it is possible to apply 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.

Le procédé selon l'invention est mis en oeuvre par LIGA.The method according to the invention is implemented by LIGA.

L'invention permet de garantir des conditions de vieillissement normal du mobile d'horlogerie 10, une constance de l'amplitude, et l'absence d'arrêt.The invention makes it possible to guarantee normal aging conditions for the clockwork mobile 10, a constant amplitude, and the absence of stopping.

Comme le montre la figure 1, la couche intermédiaire 12 est superposée à la première couche mince 11 et la seconde couche mince 13 est superposée à la couche intermédiaire 12, respectivement au niveau d'au moins une face dite « face d'interface » 14, contiguë à au moins une face de contact dite « face de frottement » 15 du mobile d'horlogerie 10 destinée à être au contact d'un autre mobile ou composant d'horlogerie. La ou les faces de frottement 15 peuvent également constituer les surfaces de guidage du mobile d'horlogerie 10 pour son pivotement ou pour son guidage selon un degré de liberté unique.As shown in the figure 1 , 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.

Autrement dit, la ou les faces de frottement 15 correspond à la section droite des première et seconde couches minces 11 et 13 et de la couche intermédiaire 12. Préférentiellement, le mobile d'horlogerie 10 comporte plusieurs faces de frottement 15.In other words, 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. Preferably, the timepiece mobile 10 comprises several friction faces 15.

Ainsi, les faces de frottement 15 sont avantageusement constituées en majorité du second matériau dans la mesure ou la somme des épaisseurs de la première et de la seconde couche mince 11 et 13 est relativement faible par rapport à l'épaisseur de la couche intermédiaire 12, par exemple d'un facteur d'au maximum un dixième.Thus, 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.

Cette caractéristique est avantageuse dans la mesure où le frottement est réalisé sur une surface constituée principalement en nickel-phosphore, qui présente de bonnes propriétés tribologique.This feature is advantageous since the friction is carried out on a surface consisting mainly of nickel-phosphorus, which has good tribological properties.

La première et la seconde couche mince 11 et 13 présentent également des faces opposées l'une à l'autre constituant des faces d'extrémités 16 du mobile d'horlogerie 10.The first and second thin layers 11 and 13 also have faces opposite each other constituting end faces 16 of the timepiece mobile 10.

Un autre avantage du procédé selon la présente invention réside dans le fait d'obtenir un mobile d'horlogerie monobloc, ce qui, comparativement à d'éventuels procédés de fabrication de l'art antérieur, permet de s'affranchir d'une étape de dépôt d'un revêtement.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.

Il a été décrit précédemment un exemple de réalisation de l'invention dans lequel la première couche mince 11, la couche intermédiaire 12 et la seconde couche mince 13 présentent chacune une concentration unique de phosphore.An exemplary embodiment of the invention has been described above in which the first thin layer 11, the intermediate layer 12 and the second thin layer 13 each have a unique concentration of phosphorus.

Toutefois, il peut être envisagé dans un autre exemple de réalisation de l'invention, que la première couche mince 11, la couche intermédiaire 12 et la seconde couche mince 13 sont déposées de sorte que le mobile d'horlogerie 10 formé comporte, dans le sens et la direction de croissance de dépôt desdites couches, un gradient de concentration de phosphore défini par exemple par une croissance progressive à travers la première couche mince 11, un état stable à travers la couche intermédiaire 12 et une décroissance progressive à travers la seconde couche mince 13.However, it may be envisaged in another exemplary embodiment of the invention that 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.

Le gradient de concentration comprend les valeurs de concentration de phosphore précitées dans la présente description.The concentration gradient includes the phosphorus concentration values mentioned above in this description.

À titre d'exemple, la concentration de phosphore peut évoluer d'une valeur nulle dans la face d'extrémité 16 de la première couche mince 11 jusqu'à un maximum de 12% en masse au sein de la couche intermédiaire 12, puis décroitre de sorte à atteindre une valeur nulle dans la face d'extrémité 16 de la seconde couche mince 13.For example, 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.

Claims (19)

  1. Method for manufacturing a horological wheel set (10), which method comprises the successive steps of:
    - depositing 101 a first thin layer (11) using a first material comprising at least nickel, in a geometric shape whose periphery defines the contour of the geometry of the horological wheel set (10),
    - depositing 102 an intermediate layer (12) using a second material comprising at least nickel and phosphorus, so as to cover one face of the first thin layer (11) and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer (11),
    - depositing 103 a second thin layer (13) using the first material, so as to cover one face of the intermediate layer (12) and so as to have a geometric shape whose periphery corresponds to that of the geometric shape of the first thin layer (11),
    - the first and the second thin layer (11, 13) containing less phosphorus than the intermediate layer (12), or being phosphorus-free.
  2. Method according to claim 1, wherein the intermediate layer (12) is superimposed on the first thin layer (11) and wherein the second thin layer (13) is superimposed on the intermediate layer (12), respectively at at least one interface face (14) contiguous with at least one friction face (15) of the horological wheel set (10), which friction face is intended to be in contact with another timepiece component.
  3. Method according to claim 2, wherein the steps 101, 102 and 103 of depositing the first thin layer (11), the intermediate layer (12) and the second thin layer (13) are carried out by LIGA.
  4. Method according to one of claims 1 to 3, wherein the second material consists solely of nickel and phosphorus.
  5. Method according to one of claims 1 to 4, wherein the second material has a percentage by weight of phosphorus of between 1% and 15%.
  6. Method according to claim 5, wherein the second material is made of NiP12.
  7. Method according to one of claims 1 to 6, wherein the first material comprises only pure nickel, or only nickel and phosphorus.
  8. Method according to one of claims 1 to 7, wherein the first material comprises a percentage by weight of phosphorus of less than or equal to 9%.
  9. Method according to claim 8, wherein the first material comprises a percentage by weight of phosphorus of between 6% and 9%.
  10. Method according to claim 8, wherein the first material comprises a percentage by weight of phosphorus of between 1% and 6%.
  11. Method according to claim 8, wherein the first material comprises a percentage by weight of phosphorus of between 0% and 1%.
  12. Method according to one of claims 1 to 11, wherein the first material comprises boron.
  13. Method according to claim 12, wherein the first material consists solely of nickel and boron.
  14. Method according to one of claims 1 to 13, wherein the first material has a thickness of between 0.2 micrometres and 10 micrometres.
  15. Method according to one of claims 1 to 14, wherein a heat treatment is applied to an assembly formed by the first thin layer (11), the intermediate layer (12) and the second thin layer (13), at a temperature of between 100°C and 500°C, for 1 to 8 hours.
  16. Method according to one of claims 1 to 15, characterised in that it is applied to the manufacture of an escape wheel set which is an escape wheel or pallets.
  17. Method according to one of claims 1 to 16, wherein the first thin layer (11), the intermediate layer (12) and the second thin layer (13) are deposited such that the horological wheel set (10) formed has, in the direction and orientation of deposition growth of said layers, a phosphorus concentration gradient defined by progressive increase through the first thin layer (11), a steady state through the intermediate layer (12) and a decrease through the second thin layer (13).
  18. Horological wheel set (10) manufactured by carrying out a method according to one of claims 1 to 17, which wheel set comprises an intermediate layer (12) interposed between a first thin layer (11) and a second thin layer (13), said thin layers (11, 13) being made of a first material comprising at least nickel, the intermediate layer (12) being made of a second material comprising at least nickel and phosphorus, the first and second thin layers (11, 13) containing less phosphorus than the intermediate layer (12), or being phosphorus-free.
  19. Horological wheel set (10) according to claim 18, constituting an escape wheel or pallets.
EP21168779.3A 2021-04-16 2021-04-16 Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same Active EP4075205B1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21168779.3A EP4075205B1 (en) 2021-04-16 2021-04-16 Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same
JP2022031472A JP7378523B2 (en) 2021-04-16 2022-03-02 Method for manufacturing a timepiece movable body and timepiece movable body obtained by carrying out the method
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 (en) 2021-04-16 2022-04-14 Method for manufacturing a timepiece movement and timepiece movement obtained by implementing said method
KR1020220047071A KR102749073B1 (en) 2021-04-16 2022-04-15 Method for manufacturing a horological mobile and horological mobile obtained by its implementation

Applications Claiming Priority (1)

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EP21168779.3A EP4075205B1 (en) 2021-04-16 2021-04-16 Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same

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EP4075205B1 true EP4075205B1 (en) 2024-12-11

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EP (1) EP4075205B1 (en)
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CH1060769A4 (en) * 1969-07-11 1971-07-15
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
CH698230B1 (en) * 2006-11-02 2011-01-14 Rolex Sa Shows.
EP1927648A1 (en) * 2006-12-01 2008-06-04 Rolex Sa Ultra-thin water and oil repellent layer, manufacturing method and use in watchmaking as epilame
JP5113687B2 (en) * 2008-02-25 2013-01-09 セイコーインスツル株式会社 Sliding parts and watches using the same
EP2263971A1 (en) * 2009-06-09 2010-12-22 Nivarox-FAR S.A. Composite micromechanical part and method for manufacturing same
CH707562B1 (en) * 2013-02-13 2020-01-15 Nivarox Sa Method for manufacturing a one-piece micromechanical part comprising at least two distinct levels.
EP3171229A1 (en) 2015-11-19 2017-05-24 Nivarox-FAR S.A. Clock component
EP3273306B1 (en) * 2016-07-19 2025-08-27 Nivarox-FAR S.A. Part for clock movement
CH713970A1 (en) * 2017-07-12 2019-01-15 Sa De La Manufacture Dhorlogerie Audemars Piguet & Cie Watchmaking component in non-magnetic CuNi binary alloy.

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KR20220143605A (en) 2022-10-25
JP2022164565A (en) 2022-10-27
EP4075205A1 (en) 2022-10-19
JP7378523B2 (en) 2023-11-13
CN115220325A (en) 2022-10-21
US12147200B2 (en) 2024-11-19
US20220334539A1 (en) 2022-10-20

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