EP4022398B1 - Method for gluing clock components - Google Patents

Method for gluing clock components Download PDF

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Publication number
EP4022398B1
EP4022398B1 EP20735065.3A EP20735065A EP4022398B1 EP 4022398 B1 EP4022398 B1 EP 4022398B1 EP 20735065 A EP20735065 A EP 20735065A EP 4022398 B1 EP4022398 B1 EP 4022398B1
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EP
European Patent Office
Prior art keywords
components
timepiece
primer composition
adhesive
component
Prior art date
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Application number
EP20735065.3A
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German (de)
French (fr)
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EP4022398A1 (en
Inventor
Sylvain Huot-Marchand
M. Marco VERARDO
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ETA SA Manufacture Horlogere Suisse
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ETA SA Manufacture Horlogere Suisse
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Publication of EP4022398A1 publication Critical patent/EP4022398A1/en
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Classifications

    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B15/00Escapements
    • G04B15/14Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B13/00Gearwork
    • G04B13/02Wheels; Pinions; Spindles; Pivots
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B17/00Mechanisms for stabilising frequency
    • G04B17/04Oscillators acting by spring tension
    • G04B17/06Oscillators with hairsprings, e.g. balance
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B19/00Indicating the time by visual means
    • G04B19/06Dials
    • G04B19/10Ornamental shape of the graduations or the surface of the dial; Attachment of the graduations to the dial
    • G04B19/103Ornamental shape of the graduations or the surface of the dial; Attachment of the graduations to the dial attached or inlaid numbers
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B19/00Indicating the time by visual means
    • G04B19/06Dials
    • G04B19/12Selection of materials for dials or graduations markings
    • GPHYSICS
    • G04HOROLOGY
    • G04DAPPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0017Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of gearworks
    • GPHYSICS
    • G04HOROLOGY
    • G04DAPPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0028Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the escape mechanism
    • G04D3/003Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the escape mechanism for levers
    • GPHYSICS
    • G04HOROLOGY
    • G04DAPPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0035Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism
    • GPHYSICS
    • G04HOROLOGY
    • G04DAPPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0043Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the time-indicating mechanisms
    • G04D3/0048Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the time-indicating mechanisms for dials
    • GPHYSICS
    • G04HOROLOGY
    • G04DAPPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0043Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the time-indicating mechanisms
    • G04D3/0051Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the time-indicating mechanisms for time markers

Definitions

  • the present invention relates to the field of watchmaking and relates more particularly to a process for bonding watchmaking components aimed at forming a one-piece assembly of watchmaking components.
  • pallets are fixed to the anchor by gluing, typically by means of a shellac dissolved in an alcohol solvent.
  • Shellac is a natural thermofusible resin, that is to say that it is honeyed at temperatures above its melting temperature (Tf) and solid below its melting temperature (Tf) or its glass transition temperature ( Tg ).
  • Tf melting temperature
  • Tf melting temperature
  • Tg glass transition temperature
  • Shellac is secreted by the female cochineal in the forests of Southeast Asia. Lacquer composition is highly dependent on mealybug diet and harvest season. The substance collected is purified and processed, but the purity and composition obtained are never guaranteed. It is therefore very difficult, if not impossible, to guarantee the constant performance of this natural product over time.
  • the industrial processes are insufficiently robust to guarantee the cleanliness of the body of the anchor and therefore an always identical surface tension.
  • the paddles are fully or partially epilamed as required.
  • An epilame is a product that modifies in one way or another the surface tension of the support. It is generally in the form of an invisible hydrophobic and oleophobic molecular layer, and is deposited in order to prevent the spreading of a lubricant or its components.
  • the epilame hooks the lubricant so that it stays in place or it pushes it back to keep it in well-defined areas. Thanks to epilaming, the surface tension is supposed to be controlled. However, it is observed that during the epilaming process, component cleaning operations are regularly resorted to after potentially messy manufacturing steps.
  • watch components assembled by bonding is found at the level of the balance wheel and more specifically concerns the hairspring bonded to its peak.
  • the document FR 1 551 159 A describes a bonding process comprising the application of a bonding layer.
  • An objective of the present invention consists in proposing a preparation of a watch component for bonding.
  • One aspect of the invention relates to a process for bonding watchmaking components, comprising the application of an adhesive to a first and/or a second watchmaking component to be bonded one on the other and the deposition of a bonding layer (primer, adhesion primer) on at least one of the first and second components to be bonded by spraying a primer composition in/on a bonding zone located on a portion of one face of each of these first and second components.
  • the glue is thus applied so as to form a layer of glue.
  • This application of the glue, or else the deposition of this layer of glue is then followed by the solidification of the primer composition.
  • the bonding zone can be called a bonding zone.
  • the deposition of the bonding layer is carried out before the application of the adhesive if the bonding is applied to the same component(s) as the bonding layer and, if necessary, before bringing the first and second watch components into contact.
  • the invention proposes in particular to deposit the bonding layer by spraying. This can be done, for example, using Aerosol Jet technology (trademark of Optomec) or any other digital printing technology.
  • Aerosol Jet technology trademark of Optomec
  • These technologies now allow the deposition of fluid materials in a very precise manner both in terms of volume and location. They can be adapted to watch components, as indicated in the patent applications WO 2016/203063 And EP1172714 .
  • the present invention notably exploits the precision potential of this deposition technology to prepare watch components for bonding.
  • the fact of using a bonding layer deposited by digital printing makes it possible to provide the components with a precisely delimited bonding zone and having a surface tension adapted to the glue. This makes possible the use of more resistant epilames which are not, or only slightly, wettable by the glue which it is desired to use.
  • the spraying of the fluid primer composition is performed by a spraying nozzle movably mounted on a multi-axis robot arm to change its orientation with respect to the first and/or second component on which the bonding layer is to be formed.
  • the spraying of the primer composition can be carried out essentially vertically from top to bottom by a spray nozzle, the first and/or second component on which the bonding layer is to be formed being in this case movably mounted on a multi-axis robot arm to change its orientation relative to the spray nozzle.
  • This second possibility has the advantage that the jet can remain vertical, which could facilitate precise delimitation of the bonding layer.
  • the primer composition may comprise a material curable by radiation (ultraviolet and/or electron beam) and in this case the solidification of the layer of primer composition is carried out by exposure to radiation.
  • the primer composition can also comprise a thermosetting material, in which case the solidification of the layer of primer composition is carried out by heat treatment.
  • the primer composition can be in the form of an ink comprising the primer composition dissolved or suspended in a solvent.
  • the primer composition could also be in the form of a polymeric resin (with or without mineral fillers) comprising reactive diluents instead of volatile solvents.
  • At least one of the first and second timepiece components to be bonded one on the other is epilamé.
  • the bonding layer is formed on the epilamé watch component.
  • the glue could include shellac.
  • the glue could comprise an epoxy glue.
  • the tie layer preferably has a chemical and/or physical affinity both for shellac and for epilame. It is noted that the two horological components could be epilamé.
  • the list of components that could be bonded is not exhaustive.
  • the invention can be used to improve the bonding of watch components which are currently already fixed to each other by bonding (as in the case of the anchor and its pallets).
  • the invention could however be useful for allowing the bonding of watch components which are currently fixed by other means, (eg by clamping or riveting).
  • the bonding of these horological components would make it possible to avoid or at least reduce the deformation or the breakage of the plate due to riveting or hunting while guaranteeing the cohesion between the plate and its axis during the stresses which are applied to them.
  • the tie layer could be based on polymer(s), eg polyurethane, acrylates or even epoxies. It will be noted that for the noble metals, certain products containing thiols can be used. It is understood that the person skilled in the art will choose the composition of the primer according to the nature of the horological components, respectively of the glue. It is noted that in the case of a primer composition based on polymers, polymers which undergo (irreversible) crosslinking are preferred. On the other hand, as regards the glue, for the bonding of certain components, a thermosetting glue is preferable whereas in other cases, thermoplastic glue is used instead.
  • the various aspects of the invention make it possible to improve the bonding of watchmaking components, to reduce the impact of dirt, to use more resistant epilames and/or to facilitate the application of the glue in compliance with the drop quality criteria (position, quantity).
  • Another aspect of the invention relates to a timepiece comprising such a one-piece assembly of timepiece components.
  • the figure 1 And 2 schematically illustrate embodiments of a bonding method according to the invention.
  • the method according to the invention can be used to glue the pallets 12, 14 to the lever 16 of the escapement 10 of a mechanical watch.
  • the figures show a Swiss lever escapement 10. It includes an escape wheel 18, typically made of hardened and polished steel.
  • the anchor 16 connects the escape wheel to the balance wheel (the figures of which show the small plate 20, the large plate 22 and the axis 24) and can switch between two positions at the rhythm imposed by the balance and hairspring assembly. At each alternation, the escape wheel 18 gives an impulse to the lever 16, which transfers it to the balance wheel so as to maintain the oscillations of the latter.
  • Pallets 12, 14 are typically made of ruby, because of its hardness and low coefficient of friction, bonded to anchor 16 by means of a shellac-based glue.
  • the vanes 12, 14 are completely or partially epilamed as needed. Thanks to the invention, it is possible to use resistant epilames, since the bonding areas on the pallets 12, 14 can be prepared before the application of the shellac with the aid of a bonding layer, which adjusts the surface tension so as to allow the wetting of the surface by the shellac in a satisfactory manner.
  • the bond coat is formed by applying a primer composition by a direct digital printing process to the component.
  • the bonding layer can be deposited by spraying the primer composition in the form of ink 26.
  • the quantity of ink and the position of each droplet are precisely controlled by a control unit 28 (e.g. a microprocessor, a computer, etc.).
  • the control unit 28 notably regulates the position and orientation of the component relative to the ink spray nozzle.
  • the possibility of orienting and positioning the projection nozzle 30 relative to the print medium is schematically indicated at reference number 32.
  • the component being printed on could remain stationary during printing.
  • the projection of the primer composition is effected by a projection nozzle 30 movably mounted, eg on a multi-axis robot arm, to change its orientation with respect to the component, i.e., in the illustrated case, the pallet 12 or 14 or the anchor 16.
  • the projection nozzle 30 remains oriented vertically from top to bottom during printing, and the component is in this case movably mounted, e. e of projection 30.
  • the primer composition is solidified.
  • this solidification of the primer composition is carried out after the application of the adhesive to the first and/or the second timepiece component to be bonded one on the other. It will be noted that in these two alternatives, the deposition of the bonding layer can be carried out before the application of the glue if the glue is applied to the same component as the bonding layer. Such solidification of the primary composition participates in ensuring in particular strong adhesion of the timepiece components bonded together.
  • solidification is carried out depending on the properties of the primer composition, e.g. by UV radiation or by electron beam in the case of a radiation-curable material, by heat treatment in the case of a thermosetting material, by laser sintering (“laser sintering”), or simply by evaporation of the solvent. It will be noted that such evaporation can be natural or forced.
  • the hardening method could combine several of these possibilities, eg to accelerate the hardening.
  • a bond coat can also be applied to the anchor 16.
  • the composition of the bond coat can be the same as that applied to the paddles 12, 14, provided the adhesion to both types of components is strong enough.
  • different tie layers will be used on the anchor 16 and the pallets 12, 14. In this context, these pallets 12, 14 and the anchor 16 then form a one-piece assembly of watch components.
  • FIG. 1 schematically shows a mode in which the primer composition consists of a single fluid
  • the picture 2 illustrates the case where the primer composition is of the two-component type mixed in situ.
  • two reactive fluids 26a and 26b are combined on the watch component in the bonding zone.
  • Another aspect of the invention relates to a timepiece comprising such a one-piece assembly of timepiece components.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)

Description

Domaine TechniqueTechnical area

La présente invention a trait au domaine de l'horlogerie et concerne plus particulièrement un procédé de collage de composants horlogers visant à former un ensemble monobloc de composants horlogers.The present invention relates to the field of watchmaking and relates more particularly to a process for bonding watchmaking components aimed at forming a one-piece assembly of watchmaking components.

Arrière-plan technologiqueTechnology background

Dans le domaine de l'horlogerie, certains composants horlogers peuvent être assemblés entre eux au moyen d'une colle (adhésif liquide au moment de son application).In the field of watchmaking, certain watchmaking components can be assembled together by means of an adhesive (liquid adhesive at the time of its application).

A titre d'exemple, dans un échappement à ancre d'une montre mécanique, des palettes (ou « levées, généralement en rubis) sont fixées sur l'ancre par collage, typiquement au moyen d'une gomme-laque dissoute dans un solvant alcool. La gomme-laque est une résine naturelle thermofusible, c'est-à-dire qu'elle est mielleuse à des températures supérieures à sa température de fusion (Tf) et solide en dessous de sa température de fusion (Tf) ou de sa température de transition vitreuse (Tg). Selon le processus de fabrication de l'ancre, il est possible que le résultat du collage ne soit pas en conformité avec les exigences, soit parce que la tenue mécanique de la palette est insuffisante, soit parce que l'esthétique de la goutte est en-dehors des spécifications. Dans les deux cas, la cause de la non-conformité est souvent un problème de tension de surface.By way of example, in a lever escapement of a mechanical watch, pallets (or “levers, generally in rubies) are fixed to the anchor by gluing, typically by means of a shellac dissolved in an alcohol solvent. Shellac is a natural thermofusible resin, that is to say that it is honeyed at temperatures above its melting temperature (Tf) and solid below its melting temperature (Tf) or its glass transition temperature ( Tg ). Depending on the anchor manufacturing process, it is possible that the bonding result does not comply with the requirements, either because the mechanical strength of the pallet is insufficient, or because the aesthetics of the drop is outside the specifications. In both cases, the cause of non-compliance is often a surface tension problem.

La gomme-laque est sécrétée par la femelle de la cochenille dans les forêts du sud-est asiatique. La composition de la laque dépend fortement du régime alimentaire des cochenilles et de la saison de récolte. La substance récoltée est purifiée et traitée mais la pureté et la composition obtenues ne sont jamais garanties. Il est donc très difficile si ce n'est impossible de de garantir dans la durée les performances constantes de ce produit naturel.Shellac is secreted by the female cochineal in the forests of Southeast Asia. Lacquer composition is highly dependent on mealybug diet and harvest season. The substance collected is purified and processed, but the purity and composition obtained are never guaranteed. It is therefore very difficult, if not impossible, to guarantee the constant performance of this natural product over time.

D'autre part, les processus industriels sont insuffisamment robustes pour garantir une propreté du corps de l'ancre et donc une tension de surface toujours identique. Il peut y avoir des pollutions diverses physiques ou chimiques, comme des particules, des adsorptions d'eau ou d'autres substances, qui toutes modifient la réaction de la surface lors du dépôt de la gomme-laque.On the other hand, the industrial processes are insufficiently robust to guarantee the cleanliness of the body of the anchor and therefore an always identical surface tension. There may be various physical or chemical pollutions, such as particles, adsorptions of water or other substances, which all modify the reaction of the surface during the deposition of the shellac.

Les palettes sont complètement ou partiellement épilamées selon les besoins. Un épilame est un produit qui modifie dans un sens ou dans un autre la tension superficielle du support. Il se présente généralement sous la forme d'une couche moléculaire invisible hydrophobe et oléophobe, et est déposée afin d'éviter l'étalement d'un lubrifiant ou de ses composants. L'épilame accroche le lubrifiant pour qu'il reste en place soit il le repousse pour le maintenir dans des zones bien déterminées. Grâce à l'épilamage, la tension de surface est censée être maîtrisée. On constate toutefois que durant le processus d'épilamage, il est régulièrement fait recours à des opérations de nettoyage de composants après des étapes de fabrication potentiellement salissantes. De tels nettoyages peuvent dégrader au moins partiellement l'effet épilame, ce qui occasionne des fluctuations dans les propriétés de surface au détriment du collage des palettes. À l'inverse, il est possible de recourir à des épilames résistants. Ceux-ci conduisent cependant à des tensions de surface incompatibles avec le mouillage de la surface par la gomme-laque. Dans ce cas, il est impossible de coller la palette puisque la gomme-laque aura tendance à fuir la surface épilamée.The paddles are fully or partially epilamed as required. An epilame is a product that modifies in one way or another the surface tension of the support. It is generally in the form of an invisible hydrophobic and oleophobic molecular layer, and is deposited in order to prevent the spreading of a lubricant or its components. The epilame hooks the lubricant so that it stays in place or it pushes it back to keep it in well-defined areas. Thanks to epilaming, the surface tension is supposed to be controlled. However, it is observed that during the epilaming process, component cleaning operations are regularly resorted to after potentially messy manufacturing steps. Such cleanings can at least partially degrade the epilame effect, which causes fluctuations in the surface properties to the detriment of the sticking of the pallets. Conversely, it is possible to use resistant epilames. However, these lead to surface tensions that are incompatible with the wetting of the surface by the shellac. In this case, it is impossible to glue the palette since the shellac will tend to leak from the epilame surface.

Un autre exemple de composants horlogers assemblés par collage se trouve au niveau du balancier et concerne plus précisément le spiral collé sur son piton.Another example of watch components assembled by bonding is found at the level of the balance wheel and more specifically concerns the hairspring bonded to its peak.

Le document FR 1 551 159 A décrit un procédé de collage comportant l'application d'une couche d'accrochage.The document FR 1 551 159 A describes a bonding process comprising the application of a bonding layer.

Un objectif de la présente invention consiste à proposer une préparation d'un composant horloger au collage.An objective of the present invention consists in proposing a preparation of a watch component for bonding.

Description générale de l'inventionGeneral description of the invention

Un aspect de l'invention concerne un procédé de collage de composants horlogers, comprenant l'application d'une colle sur un premier et/ou un second composant horloger à coller l'un sur l'autre et le dépôt d'une couche d'accrochage (apprêt, primaire d'adhésion) sur au moins un des premier et second composants à coller par projection d'une composition de primaire dans/sur une zone de liaison localisée sur une portion d'une face de chacun de ces premier et deuxième composants. La colle est ainsi appliquée de manière à former une couche de colle. Cette application de la colle, ou encore le dépôt de cette couche de colle, est ensuite suivie de la solidification de la composition de primaire. On notera que la zone de liaison peut être appelée zone de collage. Le dépôt de la couche d'accrochage est effectué avant l'application de la colle si la colle est appliquée sur le(s) même(s) composant(s) que la couche d'accrochage et, au besoin, avant de mettre en contact les premier et second composants horlogers.One aspect of the invention relates to a process for bonding watchmaking components, comprising the application of an adhesive to a first and/or a second watchmaking component to be bonded one on the other and the deposition of a bonding layer (primer, adhesion primer) on at least one of the first and second components to be bonded by spraying a primer composition in/on a bonding zone located on a portion of one face of each of these first and second components. The glue is thus applied so as to form a layer of glue. This application of the glue, or else the deposition of this layer of glue, is then followed by the solidification of the primer composition. It will be noted that the bonding zone can be called a bonding zone. The deposition of the bonding layer is carried out before the application of the adhesive if the bonding is applied to the same component(s) as the bonding layer and, if necessary, before bringing the first and second watch components into contact.

L'invention propose notamment de déposer la couche d'accrochage par projection. Celle-ci peut être effectuée, p.ex., au moyen de la technologie Aerosol Jet (marque de fabrique de la société Optomec) ou par toute autre technologie d'impression numérique. Ces technologies permettent aujourd'hui le dépôt de matériaux fluides de manière très précise tant en volume qu'en localisation. Elles peuvent être adaptées aux composants horlogers, comme l'indiquent les demandes de brevet WO 2016/203063 et EP1172714 . La présente invention exploite notamment le potentiel de précision de cette technologie de dépôt pour préparer des composant horlogers au collage. Le fait de recourir à une couche d'accrochage déposée par impression numérique permet de doter les composants d'une zone de collage précisément délimitée et présentant une tension de surface adaptée à la colle. Ceci rend possible l'utilisation d'épilames plus résistants qui ne sont pas ou seulement peu mouillables par la colle que l'on souhaite employer.The invention proposes in particular to deposit the bonding layer by spraying. This can be done, for example, using Aerosol Jet technology (trademark of Optomec) or any other digital printing technology. These technologies now allow the deposition of fluid materials in a very precise manner both in terms of volume and location. They can be adapted to watch components, as indicated in the patent applications WO 2016/203063 And EP1172714 . The present invention notably exploits the precision potential of this deposition technology to prepare watch components for bonding. The fact of using a bonding layer deposited by digital printing makes it possible to provide the components with a precisely delimited bonding zone and having a surface tension adapted to the glue. This makes possible the use of more resistant epilames which are not, or only slightly, wettable by the glue which it is desired to use.

De préférence, la projection de la composition de primaire fluide est effectuée par une buse de projection montée mobile sur un bras de robot multiaxes pour changer son orientation par rapport au premier et/ou second composants sur lequel la couche d'accrochage doit être formée. De manière alternative, la projection de la composition de primaire peut être effectuée essentiellement verticalement du haut vers le bas par une buse de projection, le premier et/ou second composants sur lequel la couche d'accrochage doit être formée étant dans ce cas monté mobile sur un bras de robot multiaxes pour changer son orientation par rapport à la buse de projection. Cette deuxième possibilité a l'avantage que le jet peut rester vertical, ce qui pourra faciliter une délimitation précise de la couche d'accrochage.Preferably, the spraying of the fluid primer composition is performed by a spraying nozzle movably mounted on a multi-axis robot arm to change its orientation with respect to the first and/or second component on which the bonding layer is to be formed. Alternatively, the spraying of the primer composition can be carried out essentially vertically from top to bottom by a spray nozzle, the first and/or second component on which the bonding layer is to be formed being in this case movably mounted on a multi-axis robot arm to change its orientation relative to the spray nozzle. This second possibility has the advantage that the jet can remain vertical, which could facilitate precise delimitation of the bonding layer.

La composition de primaire peut comprendre un matériau durcissable par rayonnement (ultraviolet et/ou faisceau d'électrons) et dans ce cas la solidification de la couche de composition de primaire est effectuée par exposition au rayonnement.The primer composition may comprise a material curable by radiation (ultraviolet and/or electron beam) and in this case the solidification of the layer of primer composition is carried out by exposure to radiation.

La composition de primaire peut également comprendre un matériau thermodurcissable auquel cas la solidification de la couche de composition de primaire est effectuée par traitement thermique.The primer composition can also comprise a thermosetting material, in which case the solidification of the layer of primer composition is carried out by heat treatment.

La composition de primaire peut se présenter sous forme d'une encre comprenant la composition de primaire dissoute ou suspendue dans un solvant. La composition de primaire pourrait également se présenter sous forme de résine polymérique (avec ou sans charges minérales) comprenant des diluants réactifs au lieu de solvants volatiles.The primer composition can be in the form of an ink comprising the primer composition dissolved or suspended in a solvent. The primer composition could also be in the form of a polymeric resin (with or without mineral fillers) comprising reactive diluents instead of volatile solvents.

Selon l'invention, au moins un des premier et second composants horlogers à coller l'un sur l'autre est épilamé. La couche d'accrochage est formée sur le composant horloger épilamé.According to the invention, at least one of the first and second timepiece components to be bonded one on the other is epilamé. The bonding layer is formed on the epilamé watch component.

La colle pourrait comprendre de la gomme-laque. De manière alternative, la colle pourrait comprendre une colle époxy.The glue could include shellac. Alternatively, the glue could comprise an epoxy glue.

Il s'agit donc de coller l'un sur l'autre des composants horlogers dont au moins l'un est épilamé au moyen d'une colle comprenant de la gomme-laque. Dans ce cas, la couche d'accrochage possède de préférence une affinité chimique et/ou physique aussi bien pour la gomme-laque que pour l'épilame. On note que les deux composants horlogers pourraient être épilamés.It is therefore a question of gluing one on the other watch components, at least one of which is epilamed by means of an adhesive comprising shellac. In this case, the tie layer preferably has a chemical and/or physical affinity both for shellac and for epilame. It is noted that the two horological components could be epilamé.

On note que la colle pourrait être appliquée à l'aide de la même technologie que la couche d'accrochage. Plus précisément, la colle pourrait être appliquée par une buse de projection de colle, la buse de projection étant :

  • montée mobile sur un bras de robot multiaxes pour changer son orientation par rapport au premier et/ou second composants sur lequel la colle doit être appliquée ; ou
  • essentiellement verticalement du haut vers le bas, et le premier et/ou second composants sur lequel colle doit être appliquée étant monté mobile sur un bras de robot multiaxes pour changer son orientation par rapport à la buse de projection de colle.
It is noted that the glue could be applied using the same technology as the tie layer. More specifically, the glue could be applied by a glue projection nozzle, the projection nozzle being:
  • movably mounted on a multi-axis robot arm to change its orientation relative to the first and/or second component to which glue is to be applied; Or
  • substantially vertically from top to bottom, and the first and/or second component to which glue is to be applied being movably mounted on a multi-axis robot arm to change its orientation relative to the glue spray nozzle.

On remarquera que divers composants horlogers peuvent être collés ensemble grâce à la présente invention. Par exemple :

  • le premier composant horloger peut être une ancre d'échappement et le second composant horloger une palette d'ancre,
  • le premier composant horloger peut être un piton de balancier et le second composant horloger un ressort spiral de balancier,
  • le premier composant horloger peut être une planche de mobile et le second composant horloger un axe, p.ex. un axe en métal,
  • le premier composant horloger peut être un plot d'index et le second composant horloger un cadran.
It will be noted that various timepiece components can be glued together thanks to the present invention. For example :
  • the first horological component can be an escapement lever and the second horological component an lever pallet,
  • the first horological component may be a balance stud and the second horological component a balance hairspring,
  • the first horological component can be a mobile plate and the second horological component an axle, e.g. a metal axle,
  • the first timepiece component can be an index pad and the second timepiece component a dial.

La liste des composants qui pourraient être collés n'est pas exhaustive. L'invention peut servir à améliorer le collage de composants horlogers qui sont déjà actuellement fixés l'un sur l'autre par collage (comme dans le cas de l'ancre et de ses palettes). L'invention pourrait cependant être utile pour permettre le collage de composants horlogers qui sont actuellement fixés par d'autres moyens, (p.ex. par serrage ou rivetage). On pense notamment à une planche mobile de conception fragile (du fait de sa faible épaisseur et/ou du fait d'être réalisé en un matériau fragile comme, p.ex., le silicium) sur un axe en métal (p.ex. en acier). Le collage de ces composants horlogers permettrait d'éviter ou au moins de réduire la déformation ou la rupture de la planche due au rivetage ou à la chasse tout en garantissant la cohésion entre la planche et son axe lors des sollicitations qui leur sont appliquées.The list of components that could be bonded is not exhaustive. The invention can be used to improve the bonding of watch components which are currently already fixed to each other by bonding (as in the case of the anchor and its pallets). The invention could however be useful for allowing the bonding of watch components which are currently fixed by other means, (eg by clamping or riveting). One thinks in particular of a mobile board of fragile design (due to its small thickness and/or the fact of being made of a fragile material such as, for example, silicon) on a metal axis (for example steel). The bonding of these horological components would make it possible to avoid or at least reduce the deformation or the breakage of the plate due to riveting or hunting while guaranteeing the cohesion between the plate and its axis during the stresses which are applied to them.

La couche d'accrochage pourrait être à base de polymère(s), p.ex. de polyuréthane, des acrylates ou encore des époxydes. On notera que pour les métaux nobles, certains produits contenant des thiols peuvent être utilisés. Il est entendu que l'homme du métier choisira la composition de primaire en fonction de la nature des composants horlogers, respectivement de la colle. On note qu'en cas de composition de primaire sur base de polymères, les polymères qui subissent une réticulation (irréversible) sont préférés. Par contre, en ce qui concerne la colle, pour le collage de certains composants, une colle thermodurcissable est préférable alors que dans d'autres cas, on recourt plutôt à de la colle thermoplastique.The tie layer could be based on polymer(s), eg polyurethane, acrylates or even epoxies. It will be noted that for the noble metals, certain products containing thiols can be used. It is understood that the person skilled in the art will choose the composition of the primer according to the nature of the horological components, respectively of the glue. It is noted that in the case of a primer composition based on polymers, polymers which undergo (irreversible) crosslinking are preferred. On the other hand, as regards the glue, for the bonding of certain components, a thermosetting glue is preferable whereas in other cases, thermoplastic glue is used instead.

Les divers aspects de l'invention permettent d'améliorer le collage de composants d'horlogerie, de réduire l'impact de salissures, d'utiliser des épilames plus résistants et/ou de faciliter l'application de la colle dans le respect des critères de qualité de la goutte (position, quantité).The various aspects of the invention make it possible to improve the bonding of watchmaking components, to reduce the impact of dirt, to use more resistant epilames and/or to facilitate the application of the glue in compliance with the drop quality criteria (position, quantity).

Un autre aspect de l'invention concerne sur un ensemble monobloc de composants horlogers comprenant des premier et deuxième composants susceptibles d'être reliés l'un à l'autre à partir d'un tel procédé de collage. Dans d'autres modes de réalisation :

  • L'ensemble monobloc comprend une partie de liaison reliant des zones de liaison des premier et deuxième composants ;
  • la partie de liaison est formée d'une couche de colle et d'une couche d'accrochage notamment une couche de composition de primaire ;
  • le premier composant horloger est une ancre d'échappement et le second composant horloger est une palette d'ancre ;
  • le premier composant horloger est un piton de balancier et le second composant horloger est un ressort spiral ;
  • le premier composant horloger est planche de mobile et le second composant horloger est un axe, et
  • le premier composant horloger est un plot d'index et le second composant horloger est un cadran.
Another aspect of the invention relates to a one-piece assembly of timepiece components comprising first and second components capable of being connected to one another using such a bonding process. In other embodiments:
  • The one-piece assembly comprises a connection part connecting connection areas of the first and second components;
  • the connecting part is formed of a layer of adhesive and of a bonding layer, in particular a layer of primer composition;
  • the first horological component is an escapement pallet and the second horological component is an pallet lever;
  • the first horological component is a balance stud and the second horological component is a spiral spring;
  • the first horological component is a moving board and the second horological component is an axle, and
  • the first timepiece component is an index stud and the second timepiece component is a dial.

Un autre aspect de l'invention concerne une pièce d'horlogerie comprenant un tel ensemble monobloc de composants horlogers.Another aspect of the invention relates to a timepiece comprising such a one-piece assembly of timepiece components.

Brève description des dessinsBrief description of the drawings

D'autres particularités et caractéristiques de l'invention ressortiront de la description détaillée de certains modes de réalisation avantageux présentés ci-dessous, à titre d'illustration, avec référence aux dessins annexés qui montrent :

  • Fig. 1 : le schéma d'un premier mode de réalisation d'un procédé de collage selon l'invention ;
  • Fig. 2: le schéma d'un deuxième mode de réalisation d'un procédé de collage selon l'invention.
Other particularities and characteristics of the invention will emerge from the detailed description of certain advantageous embodiments presented below, by way of illustration, with reference to the appended drawings which show:
  • Fig. 1 : the diagram of a first embodiment of a bonding method according to the invention;
  • Fig. 2 : the diagram of a second embodiment of a bonding method according to the invention.

Description détaillée de modes de réalisation de l'inventionDetailed Description of Embodiments of the Invention

Les figures 1 et 2 illustrent, de manière schématique, des modes de réalisation d'un procédé de collage selon l'invention. Comme discuté plus haut, le procédé selon l'invention peut être employé pour coller les palettes 12, 14 sur l'ancre 16 de l'échappement 10 d'une montre mécanique. Les figures montrent un échappement 10 à ancre suisse. Il comprend une roue d'échappement 18, typiquement en acier trempé et poli. L'ancre 16 relie la roue d'échappement au balancier (dont les figures montrent le petit plateau 20, le grand plateau 22 et l'axe 24) et peut basculer entre deux positions au rythme imposé par l'ensemble balancier et spiral. À chaque alternance, la roue d'échappement 18 donne une impulsion à l'ancre 16, qui la transfère au balancier de sorte à entretenir les oscillations de ce dernier. Les palettes 12, 14 sont typiquement réalisées en rubis, à cause de sa dureté et de son faible coefficient de frottement, collés sur l'ancre 16 au moyen d'une colle à base de gomme-laque.THE figure 1 And 2 schematically illustrate embodiments of a bonding method according to the invention. As discussed more above, the method according to the invention can be used to glue the pallets 12, 14 to the lever 16 of the escapement 10 of a mechanical watch. The figures show a Swiss lever escapement 10. It includes an escape wheel 18, typically made of hardened and polished steel. The anchor 16 connects the escape wheel to the balance wheel (the figures of which show the small plate 20, the large plate 22 and the axis 24) and can switch between two positions at the rhythm imposed by the balance and hairspring assembly. At each alternation, the escape wheel 18 gives an impulse to the lever 16, which transfers it to the balance wheel so as to maintain the oscillations of the latter. Pallets 12, 14 are typically made of ruby, because of its hardness and low coefficient of friction, bonded to anchor 16 by means of a shellac-based glue.

Les palettes 12, 14 sont complètement ou partiellement épilamées selon les besoins. Grâce à l'invention, il est possible de recourir à des épilames résistants, car les zones de collage sur les palettes 12, 14 peuvent être préparées avant l'application de la gomme-laque à l'aide d'une couche d'accrochage, qui ajuste la tension de surface de sorte à permettre de manière satisfaisante le mouillage de la surface par la gomme-laque. On forme la couche d'accrochage en appliquant une composition de primaire par un procédé d'impression numérique directe sur le composant. On peut notamment déposer la couche d'accrochage par projection de la composition de primaire sous forme d'encre 26. La quantité d'encre et la position de chaque gouttelette sont précisément contrôlées par une unité de commande 28 (p.ex. un microprocesseur, un ordinateur, etc.) L'unité de commande 28 règle notamment la position et l'orientation du composant par rapport à la buse de projection de l'encre. La possibilité d'orienter et de positionner la buse de projection 30 par rapport au support d'impression est schématiquement indiquée au numéro de référence 32.The vanes 12, 14 are completely or partially epilamed as needed. Thanks to the invention, it is possible to use resistant epilames, since the bonding areas on the pallets 12, 14 can be prepared before the application of the shellac with the aid of a bonding layer, which adjusts the surface tension so as to allow the wetting of the surface by the shellac in a satisfactory manner. The bond coat is formed by applying a primer composition by a direct digital printing process to the component. In particular, the bonding layer can be deposited by spraying the primer composition in the form of ink 26. The quantity of ink and the position of each droplet are precisely controlled by a control unit 28 (e.g. a microprocessor, a computer, etc.). The control unit 28 notably regulates the position and orientation of the component relative to the ink spray nozzle. The possibility of orienting and positioning the projection nozzle 30 relative to the print medium is schematically indicated at reference number 32.

Le composant sur lequel on imprime pourrait rester immobile pendant l'impression. Dans ce cas, la projection de la composition de primaire est effectuée par une buse de projection 30 montée mobile, p.ex. sur un bras de robot multiaxes pour changer son orientation par rapport au composant, c.-à-d., dans le cas illustré, la palette 12 ou 14 ou l'ancre 16. De préférence, la buse de projection 30 reste toutefois orientée verticalement du haut vers le bas pendant l'impression, et le composant est dans ce cas monté mobile, p.ex. sur un bras de robot multiaxes, pour changer son orientation par rapport à la buse de projection 30.The component being printed on could remain stationary during printing. In this case, the projection of the primer composition is effected by a projection nozzle 30 movably mounted, eg on a multi-axis robot arm, to change its orientation with respect to the component, i.e., in the illustrated case, the pallet 12 or 14 or the anchor 16. Preferably, however, the projection nozzle 30 remains oriented vertically from top to bottom during printing, and the component is in this case movably mounted, e. e of projection 30.

Dans une première alternative, après le dépôt sur la surface du composant la composition de primaire est solidifiée. Dans une deuxième alternative, cette solidification de la composition de primaire est réalisée après l'application de la colle sur le premier et/ou le second composant horloger à coller l'un sur l'autre. On notera que dans ces deux alternatives, le dépôt de la couche d'accrochage peut être effectué avant l'application de la colle si la colle est appliquée sur le même composant que la couche d'accrochage. Une telle solidification de la composition primaire participe à assurer notamment une forte adhésion des composants horlogers collés entre eux.In a first alternative, after deposition on the surface of the component, the primer composition is solidified. In a second alternative, this solidification of the primer composition is carried out after the application of the adhesive to the first and/or the second timepiece component to be bonded one on the other. It will be noted that in these two alternatives, the deposition of the bonding layer can be carried out before the application of the glue if the glue is applied to the same component as the bonding layer. Such solidification of the primary composition participates in ensuring in particular strong adhesion of the timepiece components bonded together.

Dans ces deux alternatives, la solidification est faite en fonction des propriétés de la composition de primaire, p.ex. par rayonnement UV ou par faisceau d'électrons en cas de matériau durcissable aux rayonnements, par traitement thermique en cas de matériau thermodurcissable, par frittage au laser (« laser sintering »), ou simplement par évaporation du solvant. On notera qu'une telle évaporation peut être naturelle ou forcée. La méthode de durcissement pourrait combiner plusieurs de ces possibilités, p.ex. pour accélérer le durcissement.In these two alternatives, solidification is carried out depending on the properties of the primer composition, e.g. by UV radiation or by electron beam in the case of a radiation-curable material, by heat treatment in the case of a thermosetting material, by laser sintering (“laser sintering”), or simply by evaporation of the solvent. It will be noted that such evaporation can be natural or forced. The hardening method could combine several of these possibilities, eg to accelerate the hardening.

Outre les palettes 12, 14, on peut également appliquer une couche d'accrochage sur l'ancre 16. La composition de la couche d'accrochage peut être la même que celle qui est appliquée sur les palettes 12, 14, à condition que l'adhésion sur les deux types de composants soit assez forte. Alternativement, on utilisera des couches d'accrochage différentes sur l'ancre 16 et les palettes 12, 14. Dans ce contexte, ces palettes 12, 14 et l'ancre 16 forment alors un ensemble monobloc de composants horlogers.In addition to the paddles 12, 14, a bond coat can also be applied to the anchor 16. The composition of the bond coat can be the same as that applied to the paddles 12, 14, provided the adhesion to both types of components is strong enough. Alternatively, different tie layers will be used on the anchor 16 and the pallets 12, 14. In this context, these pallets 12, 14 and the anchor 16 then form a one-piece assembly of watch components.

Alors que la figure 1 montre schématiquement un mode dans lequel la composition de primaire est constituée d'un fluide unique, la figure 2 illustre le cas où la composition de primaire est de type bi-composant mélangé in situ. Dans ce cas, deux fluides réactifs 26a et 26b sont réunis sur le composant horloger dans la zone de collage.While figure 1 schematically shows a mode in which the primer composition consists of a single fluid, the picture 2 illustrates the case where the primer composition is of the two-component type mixed in situ. In this case, two reactive fluids 26a and 26b are combined on the watch component in the bonding zone.

Un autre aspect de l'invention concerne un ensemble monobloc de composants horlogers comprenant des premier et deuxième composants susceptibles d'être reliés l'un à l'autre à partir d'un tel procédé. Un tel ensemble monobloc comprend une partie de liaison reliant des zones de liaison des premier et deuxième composants. Cette partie de liaison est formée d'une couche de colle et d'une couche d'accrochage notamment une couche de composition de primaire. Dans cet ensemble monobloc :

  • le premier composant horloger est une ancre d'échappement et le second composant horloger est une palette d'ancre ;
  • le premier composant horloger est un piton de balancier et le second composant horloger est un ressort spiral ;
  • le premier composant horloger est planche de mobile et le second composant horloger est un axe ;
  • le premier composant horloger est un plot d'index et le second composant horloger est un cadran.
Another aspect of the invention relates to a one-piece assembly of timepiece components comprising first and second components capable of being connected to one another using such a method. Such a one-piece assembly comprises a connection part connecting connection areas of the first and second components. This connecting part is formed of a layer of adhesive and of a bonding layer, in particular a layer of primer composition. In this one-piece set:
  • the first horological component is an escapement pallet and the second horological component is an pallet lever;
  • the first horological component is a balance stud and the second horological component is a spiral spring;
  • the first timepiece component is a mobile board and the second timepiece component is an axle;
  • the first timepiece component is an index stud and the second timepiece component is a dial.

Un autre aspect de l'invention concerne une pièce d'horlogerie comprenant un tel ensemble monobloc de composants horlogers.Another aspect of the invention relates to a timepiece comprising such a one-piece assembly of timepiece components.

Alors que des modes de réalisation particuliers viennent d'être décrits en détail, l'homme du métier appréciera que diverses modifications et alternatives à ceux-là puissent être développées à la lumière de l'enseignement global apporté par la présente divulgation de l'invention. Par conséquent, les agencements et/ou procédés spécifiques décrits ci-dedans sont censés être donnés uniquement à titre d'illustration, sans intention de limiter la portée de l'invention, qui est déterminée par l'étendue des revendications rattachées.While particular embodiments have just been described in detail, those skilled in the art will appreciate that various modifications and alternatives thereto may be developed in light of the overall teaching provided by the present disclosure of the invention. Accordingly, the specific arrangements and/or methods described herein are intended to be given for illustrative purposes only, without the intention of limiting the scope of the invention, which is determined by the scope of the appended claims.

Claims (19)

  1. Method for bonding timepiece components, at least one whereof is coated with epilame, comprising:
    - applying an adhesive to a first and/or second timepiece component to be bonded to one another,
    - depositing an adhesion layer onto at least one of the first and second components to be bonded by spraying a primer composition in a localised joining area of the first or second component, and
    - solidifying the primer composition.
  2. Method according to the preceding claim, characterised in that said deposition of the adhesion layer is followed by the solidification of the primer composition.
  3. Method according to claim 1, characterised in that said application of the adhesive is followed by the solidification of the primer composition.
  4. Method according to any one of the preceding claims, characterised in that the adhesion layer is deposited prior to the application of the adhesive if the adhesive is applied to the same component as the adhesion layer.
  5. Method according to any one of the preceding claims, characterised in that the primer composition is sprayed using a spray nozzle mounted such that it can move on a multi-axis robotic arm in order to change the orientation thereof relative to the first and/or second components on which the adhesion layer is to be formed.
  6. Method according to claim 1, characterised in that the primer composition is sprayed substantially vertically from top to bottom using a spray nozzle, and wherein the first and/or second components on which the adhesion layer is to be formed is/are mounted such that it/they can move on a multi-axis robotic arm in order to change the orientation thereof relative to the spray nozzle.
  7. Method according to any one of the preceding claims, characterised in that the primer composition comprises a radiation-curable material and wherein the primer composition layer is solidified by exposure to the radiation.
  8. Method according to any one of the preceding claims, characterised in that the primer composition comprises a thermosetting material and wherein the primer composition layer is solidified by heat treatment.
  9. Method according to any one of the preceding claims, characterised in that the adhesion layer is deposited on the timepiece component coated with epilame.
  10. Method according to any one of the preceding claims, characterised in that the adhesive comprises shellac.
  11. Method according to the preceding claim, characterised in that the adhesive comprises shellac and wherein the adhesion layer has a chemical and/or physical affinity for both shellac and epilame.
  12. Method according to any one of the preceding claims, characterised in that the adhesive is applied by an adhesive spray nozzle, the spray nozzle being:
    i. mounted such that it can move on a multi-axis robotic arm in order to change the orientation thereof relative to the first and/or second components to which the adhesive must be applied; or
    ii. essentially vertically-oriented from top to bottom, and the first and/or second components to which adhesive must be applied being mounted such that it/they can move on a multi-axis robotic arm in order to change the orientation thereof relative to the adhesive spray nozzle.
  13. Method according to any one of the preceding claims, characterised in that the adhesion layer is polymer-based, for example polyurethane-based.
  14. Method according to any one of the preceding claims, characterised in that the primer composition consists of a single fluid or is a two-component composition mixed in situ.
  15. One-piece assembly of timepiece components comprising first and second components capable of being connected to one another using a bonding method according to any one of the preceding claims.
  16. One-piece assembly of timepiece components according to the preceding claim, characterised in that it comprises a joining part that connects the joining areas of the first and second components.
  17. One-piece assembly of timepiece components according to the preceding claim, characterised in that the joining part is formed by a layer of adhesive and an adhesion layer, in particular a primer composition layer.
  18. One-piece assembly of timepiece components according to any one of claims 15 to 17, characterised in that:
    - the first timepiece component is an escapement lever and the second timepiece component is a lever pallet-stone;
    - the first timepiece component is a balance stud and the second timepiece component is a balance spring;
    - the first timepiece component is a wheel plate and the second timepiece component is a staff;
    - the first timepiece component is an index block and the second timepiece component is a dial.
  19. Timepiece comprising a one-piece assembly of timepiece components according to any one of claims 15 to 18.
EP20735065.3A 2019-08-29 2020-06-09 Method for gluing clock components Active EP4022398B1 (en)

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EP19194407.3A EP3786721A1 (en) 2019-08-29 2019-08-29 Method for bonding clock components
PCT/EP2020/065984 WO2021037408A1 (en) 2019-08-29 2020-06-09 Method for bonding clock components

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EP3786721A1 (en) 2021-03-03
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JP7302091B2 (en) 2023-07-03
CN114341749A (en) 2022-04-12
US20220276610A1 (en) 2022-09-01
JP2022542842A (en) 2022-10-07
WO2021037408A1 (en) 2021-03-04

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