EP3175303B1 - Timepiece component with a surface comprising silk fibroin - Google Patents

Timepiece component with a surface comprising silk fibroin Download PDF

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Publication number
EP3175303B1
EP3175303B1 EP15738111.2A EP15738111A EP3175303B1 EP 3175303 B1 EP3175303 B1 EP 3175303B1 EP 15738111 A EP15738111 A EP 15738111A EP 3175303 B1 EP3175303 B1 EP 3175303B1
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EP
European Patent Office
Prior art keywords
fibroin
component according
component
watchmaking
friction
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EP15738111.2A
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German (de)
French (fr)
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EP3175303A1 (en
Inventor
Xavier LANDREAU
Xavier RIOU
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Cartier International AG
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Cartier International AG
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Publication of EP3175303A1 publication Critical patent/EP3175303A1/en
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    • 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
    • G04B1/00—Driving mechanisms
    • G04B1/10—Driving mechanisms with mainspring
    • G04B1/14—Mainsprings; Bridles therefor
    • G04B1/145—Composition and manufacture of the springs
    • G04B13/026—
    • 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
    • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
    • G04B31/06—Manufacture or mounting processes

Definitions

  • the present invention relates to a component of a watch movement undergoing friction and requiring good tribological properties.
  • the present invention is directed to a bearing, a cog, an exhaust, or a watch motor spring.
  • Lubrication is generally obtained by the application of oils or greases, generally based on hydrocarbons, fluorocarbons or silicones. This solution is not however free from disadvantages.
  • Silk is a well-known natural fiber produced by the larvae of the butterfly Bombyx mori, which has traditionally been used in the form of yarns and fabrics for thousands of years.
  • Fibroin is a highly insoluble protein that is predominantly (up to 90%) composed of the amino acids glycine, alanine, and serine, and has an extremely high fibrous structure and mechanical strength.
  • fibroin is also other natural fibers produced by insects or arachnids which, while much less used, also contain fibroin and are known by their mechanical qualities.
  • the present invention relates to a watch component with fibroin from any natural or artificial source.
  • Embodiments of the invention may include, but are not limited to, fibroin obtained from cocoons of Bombyx mori or other lepidopteran larvae, spiders, bacteria, yeasts, molds, cell cultures. In the context of the invention, fibroin can be obtained from genetically modified organisms.
  • fibroin The unique properties of fibroin have been the subject of much attention, particularly in the medical industry.
  • WO2014011644 for example, provides methods for the production of pure fibroin, and its use as a biocompatible material and in drugs.
  • WO2013163407 For example, it describes the production of fibroin microspheres with a low coefficient of dry friction, however, for a medical application: the treatment of joint pain.
  • WO2012145594 proposes, for example, shaping by molding to produce implantable devices capable of integrating with living tissues.
  • the patent application JP11042106 describes a painting comprising silk particles.
  • the paint is applied to the surface of a watch so that the surface is pleasant to the touch.
  • An object of the present invention is to provide components that can be used in a watch movement without the limitations of the known components, in particular in relation to lubrication and tribological properties.
  • the present invention as defined in claim 1, relates to a component for a watch movement and having a surface undergoing friction at least a portion of which surface is formed of a material comprising fibroin.
  • the fibroin may be applied as a thin layer to the surface of the component, or the component itself may comprise a composite material incorporating fibroin into a suitable matrix. Moreover, the invention also relates to components integrally made of fibroin.
  • fibroin in the context of the invention can be used in pure form, or in combination with functional additives allowing the improvement of its performance, for example plasticizers, adhesives, lubricants, the latter comprising for example mineral oils, glycerol, lipids, solid lubricants or any other suitable lubricating substance, pigments, and so on.
  • functional additives for example plasticizers, adhesives, lubricants, the latter comprising for example mineral oils, glycerol, lipids, solid lubricants or any other suitable lubricating substance, pigments, and so on.
  • the invention can be applied to all components of the watch that are moving or that are subject to friction.
  • the wheels and in particular the working surfaces of the gears; the stones or simple bearings and the axes of mobiles which are housed there; the exhaust members comprising the teeth of the escape wheel, the pallets, the fork and the stinger of the anchor, the ankle and the balance plate; the mainspring and the barrel. This list and however far from exhaustive.
  • the exhaust system 1 comprises in particular an escape wheel 3, comprising an escape wheel secured to an exhaust pinion, pivotally mounted on an axle 30, an anchor 2 pivotally mounted on an anchor rod 23, and a plate 4 driven on a balance shaft 40.
  • the plate 4 comprises a small plate 41 provided with a notch 42 and a large plate 43 provided with an ankle (not shown in FIG. figure 1 ).
  • the anchor 2 comprises arms 21 comprising lifts 22 cooperating with teeth 31 of the escape wheel 3.
  • the rod 20 comprises a dart 24 and a fork 25.
  • the dart 24 is intended to cooperate with the small plate 41 to prevent accidental movements of the fork 25.
  • the fork 25 is preferably mounted directly above the dart 24 and comprises two horns 26 intended to come into contact with the large plate pin 43 so, following the rotation of the pin, to cause the anchor 2 pivoting about its rod 23 in a back and forth motion.
  • the exhaust systems are difficult to develop because they are the compromise between the lowest possible inertia and the best possible tribological properties, in particular, the lifts 22 and the fork 25. Thus, it is difficult to avoid the collars between the plateau pin and the horns 26 of the fork 25 while preserving minimal inertia and even insensitivity to magnetic fields.
  • the mobiles are coated at least partially with a layer comprising fibroin in order to favorably modify their tribology.
  • the layer comprising the fibroin may be a solid layer, for example deposited by evaporation of aqueous solutions of fibroin, or a liquid or colloidal layer, in which fibroin particles are suspended in a liquid matrix or gel.
  • the fibroin layer comprises additives to improve the tribological characteristics, for example lubricants, glycerol, plasticizers, adhesives, pigments, or substances whose purpose is to inhibit the degradation of fibroin.
  • additives to improve the tribological characteristics for example lubricants, glycerol, plasticizers, adhesives, pigments, or substances whose purpose is to inhibit the degradation of fibroin.
  • the fibroin may be a functional component of a composite material, in a solid matrix composed for example by a resin.
  • the composite material may have a fibroin matrix and also reinforcements made of fibroin material of another form.
  • the fibroin when in the form of dispersed particles, in a solid, liquid or gel matrix, they may be microspheres, needles, fibers, or grains or particles of any shape.
  • the watch component of the invention can be made from a monolithic solid block comprising fibroin as the main or secondary ingredient.
  • a monolithic solid block comprising fibroin as the main or secondary ingredient.
  • Such a block can be made for example by fusing powders of fibroin material under high temperatures and pressures.
  • the component of the invention may also alternatively be covered by a tissue or entanglement of fibroin fibers, optionally with additives.
  • the entire surface of the component may be coated with the fibroin-containing layer.
  • the anchor 2 may be coated only at the fork 25 and the lifts 22. In this configuration, the fork 25 and the lifts 22 have a low wear and a low coefficient of friction in association with the ankle.
  • the escape wheel 3 may be coated at the teeth 31.
  • the plate 4 may be coated with the fibroin-containing layer only at the level of the large plateau pin 43.
  • the substrate on which the layer is deposited can be made according to the techniques and materials commonly used in watchmaking, for example steel, brass, nickel silver, gold, titanium. If, on the other hand, fibroin is used as a solid block, or as a functional component (reinforcement and / or matrix) of a composite material, the component of the invention will be entirely made of this material, or will comprise a part made of a material containing fibroin.
  • the component whose surface contains fibroin is used for the manufacture of fixed watch components that are subject to friction.
  • Such components may include the watch frame, for example, the deck and / or the decks, serving as a support for other movable members (not shown in FIG. figure 2 ) of the watch.
  • the figure 2 represents a bridge 50 of a watch.
  • the component 50 may be made of steel, brass, nickel silver, titanium, or any other suitable material.
  • the component 50 may be coated at least partially with a layer comprising fibroin in order to modify the tribology and / or the friction resistance characteristics.
  • the layer may coat the portion supporting the mobile, in particular the portion 52 of the component where the pivot of the mobile comes to hunt.
  • the wall of the hole 51 forming a bearing may be coated with the layer comprising fibroin thereby decreasing the coefficient of friction on the wall of the holes and improving the friction torque between the bearing and the shaft of the mobile which can itself even be coated with fibroin. In this way, it is possible to pass ruby pad (or stone) in which are normally mounted pivots.
  • the hole 51 forming a bearing is in a part made of a material containing fibroin, fixed on the bridge 50.
  • An advantage of the component 50 according to the invention is to allow the production of plates and bridges having very small thicknesses. It therefore becomes possible to manufacture thinner watch cases. Another advantage is to be able to realize the component (frame, plate and / or bridge) in one piece with great precision while avoiding the disadvantages induced by mounting steps (stonework). The flatness and precision of the component are improved despite its small thickness.
  • One embodiment of the invention relates to the use, in a component for a watch movement, of a material comprising fibroin.
  • the method for producing components in solid, coated or composite form comprises two steps: a first step of adjusting the experimental conditions for bringing the raw material to flow or to be projected to form an object; this first step involves the development of a suitable protein solution.
  • a second step is to adjust the conditions of the raw material either to bring the raw material to a gel state, or to bring it near the sol-gel transition point.
  • the process uses one or more solvents which may be for example aqueous solvents, fluorinated, ionic liquids or strong acids for example.
  • solvents may be for example aqueous solvents, fluorinated, ionic liquids or strong acids for example.
  • some of the fibroin may remain insoluble and within the solution. This solid material is preferably removed from the solution, for example by centrifugation or pressure filtration.
  • additives may be added. These additives may be, for example, color pigments, anti-wear inserts, polymers, fats or oils, powders, surfactants, etc.
  • additives may be, for example, color pigments, anti-wear inserts, polymers, fats or oils, powders, surfactants, etc.
  • this shaping can take the form of capsules, spheres, fibers, foams, gelled monolithic massifs, or combinations of the above.
  • the formatting of the various architectures described above can be carried out by many processes such as molding, spinning, electrospinning, projection or precipitation (non-exhaustive), or in the form of a monolith by molding.
  • the material developed can advantageously replace liquid lubricants traditionally used in watch movements.
  • Tests carried out on the material of the invention have revealed a dynamic coefficient of friction as low as 0.03 for contact pressures of 50 MPa when in contact with steel under conditions of relative speed of the order mm / s. This low coefficient is maintained for large friction distances (> 1km). All other conditions being equal, this coefficient of friction is lower than that measured for a diamond / diamond contact.
  • the low density of the material (about 1.2 g / cm3) compared to that of steel (about 7 g / cm3) makes it possible to increase the transmission efficiency (by reducing the moments of particularly inertia) and therefore the overall power reserve of the watch movement.
  • the density and the mechanical properties of the components are close to those of the plastic components of the PEEK type.
  • the tribological properties particularly in terms of coefficient of friction and wear, are much higher.
  • the developed components successfully validate the tests of resistance to chemicals and climatic watchmaking, including synthetic sweat tests, salt spray or tropical climate.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)

Description

Domaine techniqueTechnical area

La présente invention concerne un composant d'un mouvement horloger subissant des frottements et nécessitant de bonnes propriétés tribologiques. En particulier, mais pas exclusivement, la présente invention s'adresse à un palier, un rouage, un échappement, ou un ressort moteur de montre.The present invention relates to a component of a watch movement undergoing friction and requiring good tribological properties. In particular, but not exclusively, the present invention is directed to a bearing, a cog, an exhaust, or a watch motor spring.

Etat de la techniqueState of the art

Dans le domaine de la microtechnique, qui sera par la suite plus particulièrement illustré par le domaine horloger, on sait lubrifier des composants qui présentent des surfaces subissant des frottements. La lubrification est généralement obtenue par l'application d'huiles ou graisses, en général à base d'hydrocarbures, fluorocarbures ou silicones. Cette solution n'est pas toutefois exempte d'inconvénients.In the field of microtechnology, which will subsequently be more particularly illustrated by the watchmaking field, it is known to lubricate components which have surfaces undergoing friction. Lubrication is generally obtained by the application of oils or greases, generally based on hydrocarbons, fluorocarbons or silicones. This solution is not however free from disadvantages.

Les huiles et les graisses en particulier subissent une dégradation de leur pouvoir lubrifiant dans le temps, en raison d'altérations chimiques et contaminations, en sorte que tout mouvement lubrifié par ces moyens doit être périodiquement démonté, nettoyé et nouvellement lubrifié.Oils and fats in particular undergo degradation of their lubricity over time, due to chemical alterations and contaminations, so that any movement lubricated by these means must be periodically disassembled, cleaned and newly lubricated.

Dans le domaine de la microtechnique et notamment dans celui de l'horlogerie, il y a un besoin de matériaux structurels pouvant remplacer l'acier, le maillechort ou les métaux normalement utilisés tout en présentant une plus faible densité. Un tel matériau permettrait notamment d'améliorer le rendement énergétique des organes mécaniques, notamment des échappements et mouvements horlogers.In the field of microtechnology and especially in the field of watchmaking, there is a need for structural materials that can replace steel, nickel silver or metals normally used while having a lower density. Such a material would in particular improve the energy efficiency of mechanical devices, including escapements and watch movements.

On connait des mouvements de montre qu'emploient à cette fin des éléments réalisés en polymères techniques, par exemple le PEEK (polyétheréthercétone). Ces réalisations, toutefois, n'atteignent pas la durabilité et la fiabilité des composants métalliques traditionnels.Known watch movements are used for this purpose of elements made of technical polymers, for example the PEEK (Polyetheretherketone). These achievements, however, do not achieve the durability and reliability of traditional metal components.

La soie est une fibre naturelle bien connue produite par les larves du papillon Bombyx mori, qui est utilisée traditionnellement en forme de fils et tissus depuis des milliers d'années.Silk is a well-known natural fiber produced by the larvae of the butterfly Bombyx mori, which has traditionally been used in the form of yarns and fabrics for thousands of years.

Les propriétés mécaniques de la soie sont dues à une protéine nommée fibroïne qui forme le centre du fil. La fibroïne est une protéine hautement insoluble qui est composé en majorité (jusqu'à 90%) par les acides aminés: glycine, alanine, et sérine, et présente une structure fibreuse et une résistance mécanique extrêmement élevées. Ils existent aussi d'autres fibres naturelles produites par des insectes ou des arachnides qui, tout en étant beaucoup moins utilisés, contiennent également de la fibroïne et sont connues par leur qualités mécaniques. La présente invention porte sur un composant de montre avec de la fibroïne provenant de n'importe quelle source naturelle ou artificielle. Des modes de réalisation de l'invention peuvent utiliser notamment, mais pas exclusivement, de la fibroïne obtenue des cocons du Bombyx mori ou d'autres larves de lépidoptères, d'araignées, de bactéries, levures, moisissures, de cultures cellulaires. Dans le cadre de l'invention, la fibroïne peut être obtenue d'organismes modifiés génétiquement.The mechanical properties of silk are due to a protein called fibroin which forms the center of the thread. Fibroin is a highly insoluble protein that is predominantly (up to 90%) composed of the amino acids glycine, alanine, and serine, and has an extremely high fibrous structure and mechanical strength. There are also other natural fibers produced by insects or arachnids which, while much less used, also contain fibroin and are known by their mechanical qualities. The present invention relates to a watch component with fibroin from any natural or artificial source. Embodiments of the invention may include, but are not limited to, fibroin obtained from cocoons of Bombyx mori or other lepidopteran larvae, spiders, bacteria, yeasts, molds, cell cultures. In the context of the invention, fibroin can be obtained from genetically modified organisms.

Les propriétés uniques de la fibroïne ont été l'objet de beaucoup d'attention, notamment dans l'industrie médicale. WO2014011644 , par exemple, propose des procédés permettant la production de fibroïne pure, et son utilisation comme matériau biocompatible et dans des médicaments. WO2013163407 décrit par exemple la production de microsphères de fibroïne à bas coefficient de frottement sec, ceci toutefois pour une application médicale : le traitement de la douleur articulaire. WO2012145594 propose par exemple la mise en forme par moulage pour réaliser des dispositifs implantables et capables de s'intégrer avec les tissus vivants.The unique properties of fibroin have been the subject of much attention, particularly in the medical industry. WO2014011644 for example, provides methods for the production of pure fibroin, and its use as a biocompatible material and in drugs. WO2013163407 For example, it describes the production of fibroin microspheres with a low coefficient of dry friction, however, for a medical application: the treatment of joint pain. WO2012145594 proposes, for example, shaping by molding to produce implantable devices capable of integrating with living tissues.

La demande de brevet JP11042106 décrit une peinture comprenant des particules de soie. La peinture est appliquée sur la surface d'une montre de sorte que la surface est agréable au toucher.The patent application JP11042106 describes a painting comprising silk particles. The paint is applied to the surface of a watch so that the surface is pleasant to the touch.

Bref résumé de l'inventionBrief summary of the invention

Un but de la présente invention est de proposer des composants utilisables dans un mouvement horloger exempt des limitations des composants connus, notamment en rapport avec la lubrification et les propriétés tribologiques.An object of the present invention is to provide components that can be used in a watch movement without the limitations of the known components, in particular in relation to lubrication and tribological properties.

La présente invention, telle que définie dans la revendication 1, concerne un composant pour un mouvement d'horlogerie et ayant une surface subissant des frottements dont au moins une partie de cette surface est formée d'un matériau comprenant de la fibroïne.The present invention, as defined in claim 1, relates to a component for a watch movement and having a surface undergoing friction at least a portion of which surface is formed of a material comprising fibroin.

La fibroïne peut être appliquée comme couche mince à la surface du composant, ou bien le composant lui-même peut comporter un matériau composite intégrant de la fibroïne en une matrice idoine. Par ailleurs, l'invention concerne aussi des composants intégralement réalisées en fibroïne.The fibroin may be applied as a thin layer to the surface of the component, or the component itself may comprise a composite material incorporating fibroin into a suitable matrix. Moreover, the invention also relates to components integrally made of fibroin.

Dans le cadre de l'invention la fibroïne peut être utilisée à l'état pur, ou bien en combinaison avec des additifs fonctionnels permettant l'amélioration de ses performances, par exemple des plastifiants, des adhésifs, des lubrifiants, ces derniers comportant par exemple des huiles minérales, du glycérol, des lipides, des lubrifiants solides ou toute autre substance lubrifiante appropriée, des pigments, et ainsi de suite.In the context of the invention fibroin can be used in pure form, or in combination with functional additives allowing the improvement of its performance, for example plasticizers, adhesives, lubricants, the latter comprising for example mineral oils, glycerol, lipids, solid lubricants or any other suitable lubricating substance, pigments, and so on.

Pour ce qui est des éléments réalisés, l'invention peut être appliquée à tous les composants de la montre qui sont en mouvement ou qui sont sujets à friction. On peut nommer à titre d'exemple les roues, et notamment les surfaces de travail des engrenages; les coussinets empierrés ou simples et les axes de mobiles qui y sont logés ; les organes d'échappement comprenant les dents de la roue d'échappement, les palettes, la fourchette et le dard de l'ancre, la cheville et le plateau du balancier ; le ressort moteur et le barillet. Cette liste et toutefois loin d'être exhaustive.As to the elements made, the invention can be applied to all components of the watch that are moving or that are subject to friction. By way of example, mention may be made of the wheels, and in particular the working surfaces of the gears; the stones or simple bearings and the axes of mobiles which are housed there; the exhaust members comprising the teeth of the escape wheel, the pallets, the fork and the stinger of the anchor, the ankle and the balance plate; the mainspring and the barrel. This list and however far from exhaustive.

Brève description des figuresBrief description of the figures

Des exemples de mise en oeuvre de l'invention sont indiqués dans la description illustrée par les figures annexées dans lesquelles :

  • la figure 1 illustrant un système d'échappement horloger selon un mode de réalisation; et
  • la figure 2 représentant un pont d'une montre, selon un mode de réalisation.
Examples of implementation of the invention are indicated in the description illustrated by the appended figures in which:
  • the figure 1 illustrating a watch exhaust system according to one embodiment; and
  • the figure 2 representing a bridge of a watch, according to one embodiment.

Exemple(s) de mode de réalisation de l'inventionExample (s) of embodiment of the invention

L'invention sera maintenant décrite avec référence aux composants pour mouvement d'horlogerie représentés sur les figures 1 et 2. Pour simplifier la description, cet exemple se réfère spécifiquement à un système d'échappement, mais il faut comprendre que l'invention n'est pas limitée à cette réalisation spécifique et englobe tout composant d'un mouvement horloger soumis à un frottement.The invention will now be described with reference to the components for a watch movement represented on the Figures 1 and 2 . To simplify the description, this example specifically refers to an exhaust system, but it should be understood that the invention is not limited to this specific embodiment and encompasses any component of a watch movement subjected to friction.

Dans l'exemple illustré à la figure 1, on peut voir un système d'échappement 1 pour une pièce d'horlogerie. Le système d'échappement 1 comprend notamment un mobile d'échappement 3, comprenant une roue d'échappement solidaire d'un pignon d'échappement, monté pivotant sur un axe 30, une ancre 2 montée pivotante sur une tige d'ancre 23, et un plateau 4 chassé sur un axe de balancier 40. Le plateau 4 comprend un petit plateau 41 muni d'une encoche 42 et un grand plateau 43 muni d'une cheville (non représentée sur la figure 1). L'ancre 2 comporte des bras 21 comprenant des levées 22 coopérant avec des dents 31 de la roue d'échappement 3. A l'extrémité opposée aux bras 21, la baguette 20 comporte un dard 24 et une fourchette 25. Le dard 24 est destiné à coopérer avec le petit plateau 41 afin d'empêcher les déplacements accidentels de la fourchette 25. La fourchette 25 est préférentiellement montée à l'aplomb du dard 24 et comprend deux cornes 26 destinées à entrer en contact avec la cheville de grand plateau 43 afin, suivant la rotation de la cheville, d'entraîner l'ancre 2 en pivotement autour de sa tige 23 selon un mouvement de va-et-vient.In the example shown in figure 1 , we can see an exhaust system 1 for a timepiece. The exhaust system 1 comprises in particular an escape wheel 3, comprising an escape wheel secured to an exhaust pinion, pivotally mounted on an axle 30, an anchor 2 pivotally mounted on an anchor rod 23, and a plate 4 driven on a balance shaft 40. The plate 4 comprises a small plate 41 provided with a notch 42 and a large plate 43 provided with an ankle (not shown in FIG. figure 1 ). The anchor 2 comprises arms 21 comprising lifts 22 cooperating with teeth 31 of the escape wheel 3. At the end opposite the arms 21, the rod 20 comprises a dart 24 and a fork 25. The dart 24 is intended to cooperate with the small plate 41 to prevent accidental movements of the fork 25. The fork 25 is preferably mounted directly above the dart 24 and comprises two horns 26 intended to come into contact with the large plate pin 43 so, following the rotation of the pin, to cause the anchor 2 pivoting about its rod 23 in a back and forth motion.

Les systèmes d'échappement sont difficiles à mettre au point car ils sont le compromis entre une inertie la plus faible possible et les meilleures propriétés tribologiques possibles, en particulier, des levées 22 et de la fourchette 25. Ainsi, il est difficile d'éviter les collements entre la cheville de plateau et les cornes 26 de la fourchette 25 tout en préservant une inertie minimale et même une insensibilité aux champs magnétiques.The exhaust systems are difficult to develop because they are the compromise between the lowest possible inertia and the best possible tribological properties, in particular, the lifts 22 and the fork 25. Thus, it is difficult to avoid the collars between the plateau pin and the horns 26 of the fork 25 while preserving minimal inertia and even insensitivity to magnetic fields.

Selon un aspect de l'invention, les mobiles sont revêtus au moins partiellement d'une couche comprenant de la fibroïne afin de modifier favorablement leur tribologie. La couche comprenant la fibroïne peut être une couche solide, par exemple déposée par évaporation de solutions aqueuses de fibroïne, ou encore une couche liquide ou colloïdale, dans laquelle des particules de fibroïne sont en suspension dans une matrice liquide ou gel.According to one aspect of the invention, the mobiles are coated at least partially with a layer comprising fibroin in order to favorably modify their tribology. The layer comprising the fibroin may be a solid layer, for example deposited by evaporation of aqueous solutions of fibroin, or a liquid or colloidal layer, in which fibroin particles are suspended in a liquid matrix or gel.

Avantageusement, la couche de fibroïne comporte des additifs visant à améliorer les caractéristiques tribologiques, par exemple des lubrifiants, du glycérol, des plastifiants, des adhésifs, des pigments, ou des substances dont le but est d'inhiber la dégradation de la fibroïne.Advantageously, the fibroin layer comprises additives to improve the tribological characteristics, for example lubricants, glycerol, plasticizers, adhesives, pigments, or substances whose purpose is to inhibit the degradation of fibroin.

Selon un autre aspect de l'invention, la fibroïne peut être un composant fonctionnel d'un matériau composite, dans une matrice solide composée par exemple par une résine. Dans une variante de cet aspect, le matériau composite peut avoir une matrice en fibroïne et également des renforts en matériau fibroïne d'une autre forme.According to another aspect of the invention, the fibroin may be a functional component of a composite material, in a solid matrix composed for example by a resin. In a variant of this aspect, the composite material may have a fibroin matrix and also reinforcements made of fibroin material of another form.

Lorsque la fibroïne se présente sous forme de particules dispersées, en une matrice solide, liquide ou gel, elles peuvent être des micro-sphères, des aiguilles, des fibres, ou des grains ou particules de n'importe quelle forme.When the fibroin is in the form of dispersed particles, in a solid, liquid or gel matrix, they may be microspheres, needles, fibers, or grains or particles of any shape.

Selon une autre variante, le composant horloger de l'invention peut être réalisé à partir d'un bloc massif monolithique comprenant de la fibroïne comme ingrédient principal ou secondaire. Un tel bloc peut être réalisé par exemple en fusant des poudres de matériau fibroïne sous des températures et pressions élevées.According to another variant, the watch component of the invention can be made from a monolithic solid block comprising fibroin as the main or secondary ingredient. Such a block can be made for example by fusing powders of fibroin material under high temperatures and pressures.

Le composant de l'invention peut aussi être recouvert, dans des variantes, par un tissu ou un enchevêtrement de fibres de fibroïne, optionnellement comportant des additifs.The component of the invention may also alternatively be covered by a tissue or entanglement of fibroin fibers, optionally with additives.

Dans un mode de réalisation possible, la totalité de la surface du composant peut être revêtue de la couche contenant de la fibroïne. Il peut cependant être envisagé de ne revêtir qu'une portion du mobile. Par exemple, l'ancre 2 peut être revêtue qu'au niveau de la fourchette 25 et des levées 22. Dans cette configuration, la fourchette 25 et des levées 22 présentent une faible usure et un faible coefficient de frottement en association avec la cheville. Dans un autre exemple, le mobile d'échappement 3 peut être revêtu au niveau des dents 31. Similairement, le plateau 4 peut n'être revêtu de la couche comprenant de la fibroïne qu'au niveau de la cheville de grand plateau 43.In one possible embodiment, the entire surface of the component may be coated with the fibroin-containing layer. However, it may be considered to cover only a portion of the mobile. For example, the anchor 2 may be coated only at the fork 25 and the lifts 22. In this configuration, the fork 25 and the lifts 22 have a low wear and a low coefficient of friction in association with the ankle. In another example, the escape wheel 3 may be coated at the teeth 31. Similarly, the plate 4 may be coated with the fibroin-containing layer only at the level of the large plateau pin 43.

Lorsque l'invention comporte une couche mince de fibroïne, le substrat sur lequel la couche est déposée peut être réalisé selon les techniques et les matériaux couramment employés en horlogerie, par exemple acier, laiton, maillechort, or, titane. Si en revanche la fibroïne est utilisé en bloc massif, ou comme composante fonctionnelle (renfort et/ou matrice) d'un matériau composite, le composant de l'invention sera entièrement réalisé par ce matériau, ou comportera une partie réalisée dans un matériau contenant de la fibroïne.When the invention comprises a thin layer of fibroin, the substrate on which the layer is deposited can be made according to the techniques and materials commonly used in watchmaking, for example steel, brass, nickel silver, gold, titanium. If, on the other hand, fibroin is used as a solid block, or as a functional component (reinforcement and / or matrix) of a composite material, the component of the invention will be entirely made of this material, or will comprise a part made of a material containing fibroin.

Dans un mode de réalisation, le composant dont la surface contient de la fibroïne est utilisé pour la fabrication de composants horlogers fixes mais subissant des frottements. De tels composants peuvent comprendre le bâti de la montre, par exemple, la platine et/ou les ponts, servant de support à d'autres organes mobiles (pas représenté dans la figure 2) de la montre. A titre illustratif, la figure 2 représente un pont 50 d'une montre. Le composant 50 peut être réalisé en acier, laiton, maillechort, titane, ou tout autre matériau approprié.In one embodiment, the component whose surface contains fibroin is used for the manufacture of fixed watch components that are subject to friction. Such components may include the watch frame, for example, the deck and / or the decks, serving as a support for other movable members (not shown in FIG. figure 2 ) of the watch. As an illustration, the figure 2 represents a bridge 50 of a watch. The component 50 may be made of steel, brass, nickel silver, titanium, or any other suitable material.

Encore selon l'invention, le composant 50 peut être revêtu au moins partiellement d'une couche comprenant de la fibroïne afin de modifier la tribologie et/ou les caractéristiques de résistance à la friction. Par exemple, la couche peut revêtir la portion supportant le mobile, notamment la portion 52 du composant où vient se chasser le pivot du mobile. Plus particulièrement, la paroi du trou 51 formant palier peut être revêtue de la couche comportant de la fibroïne diminuant ainsi le coefficient de frottement sur la paroi des trous et améliorant le couple de frottement entre le palier et l'arbre du mobile qui peut lui-même être revêtu de fibroïne. De la sorte, il est possible de passer de coussinet en rubis (ou pierre) dans lesquelles sont normalement montés les pivots.Still according to the invention, the component 50 may be coated at least partially with a layer comprising fibroin in order to modify the tribology and / or the friction resistance characteristics. For example, the layer may coat the portion supporting the mobile, in particular the portion 52 of the component where the pivot of the mobile comes to hunt. More particularly, the wall of the hole 51 forming a bearing may be coated with the layer comprising fibroin thereby decreasing the coefficient of friction on the wall of the holes and improving the friction torque between the bearing and the shaft of the mobile which can itself even be coated with fibroin. In this way, it is possible to pass ruby pad (or stone) in which are normally mounted pivots.

Selon une variante, le trou 51 formant palier est dans une pièce réalisé en un matériau contenant de la fibroïne, fixée sur le pont 50.According to a variant, the hole 51 forming a bearing is in a part made of a material containing fibroin, fixed on the bridge 50.

Un avantage du composant 50 selon l'invention est de permettre de réaliser des platines et ponts ayant de très faibles épaisseurs. Il devient donc possible de fabriquer des boîtiers de montre plus fins. Un autre avantage est de pouvoir réaliser le composant (bâti, platine et/ou pont) en une seule pièce avec une grande précision tout en évitant les inconvénients induits par des étapes de montage (empierrage). La planéité et la précision du composant sont améliorées en dépit de sa faible épaisseur.An advantage of the component 50 according to the invention is to allow the production of plates and bridges having very small thicknesses. It therefore becomes possible to manufacture thinner watch cases. Another advantage is to be able to realize the component (frame, plate and / or bridge) in one piece with great precision while avoiding the disadvantages induced by mounting steps (stonework). The flatness and precision of the component are improved despite its small thickness.

Un mode de réalisation de l'invention concerne l'utilisation, dans un composant pour un mouvement d'horlogerie, d'un matériau comprenant de la fibroïne. Le procédé d'élaboration des composants sous forme massive, en revêtement ou en composite comprend deux étapes : une première étape consistant à ajuster les conditions expérimentales permettant d'amener la matière première à couler ou à être projetée pour former un objet; cette première étape fait notamment appel à l'élaboration d'une solution protéique idoine. Une deuxième étape consiste à ajuster les conditions de la matière première soit pour amener la matière première à un état de gel, soit pour l'amener à proximité du point de transition sol-gel.One embodiment of the invention relates to the use, in a component for a watch movement, of a material comprising fibroin. The method for producing components in solid, coated or composite form comprises two steps: a first step of adjusting the experimental conditions for bringing the raw material to flow or to be projected to form an object; this first step involves the development of a suitable protein solution. A second step is to adjust the conditions of the raw material either to bring the raw material to a gel state, or to bring it near the sol-gel transition point.

Afin de parvenir à la dissolution de la fibroïne de soie, le procédé fait appel à un ou plusieurs solvants qui peuvent être par exemple des solvants aqueux, fluorés, des liquides ioniques ou encore des acides forts par exemple. Cependant, une partie de la fibroïne peut rester insoluble et en suspension au sein de la solution. Cette matière solide est préférablement retirée de la solution, ceci par centrifugation ou par filtration-pression par exemple.In order to achieve dissolution of the silk fibroin, the process uses one or more solvents which may be for example aqueous solvents, fluorinated, ionic liquids or strong acids for example. However, some of the fibroin may remain insoluble and within the solution. This solid material is preferably removed from the solution, for example by centrifugation or pressure filtration.

Suite à l'étape de dissolution, des additifs peuvent être ajoutés. Ces additifs peuvent être par exemple des pigments de couleur, des inserts anti-usure, des polymères, des graisses ou des huiles, des poudres, des tensio-actifs etc... A ce stade, il est également possible de procéder au mélangeage d'une première solution avec une deuxième ou une multitude, ceci de manière à créer un composite ou afin de modifier les propriétés chimiques et physiques du matériau obtenu, afin de viser une morphologie particulière par exemple.Following the dissolution step, additives may be added. These additives may be, for example, color pigments, anti-wear inserts, polymers, fats or oils, powders, surfactants, etc. At this stage, it is also possible to proceed with the mixing of a first solution with a second or a multitude, so as to create a composite or to modify the chemical and physical properties of the material obtained, in order to target a particular morphology for example.

Après l'étape de dissolution de la fibroïne, vient la mise en forme du matériau. De manière non-exhaustive, cette mise en forme peut s'effectue sous forme de capsules, sphères, fibres, mousses, massifs monolithiques gélifiés, ou par combinaisons des précédents. La mise en forme des différentes architectures décrites précédemment peut s'effectuer par de nombreux procédés comme le moulage, le spinning, l'electrospinning, la projection ou encore la précipitation (non-exhaustif), ou en forme de monolithe par moulage.After the fibroin dissolution step, comes the shaping of the material. Non-exhaustively, this shaping can take the form of capsules, spheres, fibers, foams, gelled monolithic massifs, or combinations of the above. The formatting of the various architectures described above can be carried out by many processes such as molding, spinning, electrospinning, projection or precipitation (non-exhaustive), or in the form of a monolith by molding.

De par ses propriétés autolubrifiantes, le matériau développé peut se substituer avantageusement aux lubrifiants liquides traditionnellement utilisés dans les mouvements horlogers. Des tests effectués sur le matériau de l'invention ont mis en évidence un coefficient de frottement dynamique aussi faible que 0.03 pour des pressions de contact de 50 MPa lors d'un contact avec l'acier dans des conditions de vitesse relative de l'ordre du mm/s. Ce faible coefficient est conservé pour des distances de frottement importantes (>1km). Toutes conditions égales par ailleurs, ce coefficient de frottement est inférieur à celui mesuré pour un contact diamant/diamant.Because of its self-lubricating properties, the material developed can advantageously replace liquid lubricants traditionally used in watch movements. Tests carried out on the material of the invention have revealed a dynamic coefficient of friction as low as 0.03 for contact pressures of 50 MPa when in contact with steel under conditions of relative speed of the order mm / s. This low coefficient is maintained for large friction distances (> 1km). All other conditions being equal, this coefficient of friction is lower than that measured for a diamond / diamond contact.

Par comparaison à la lubrification humide utilisée conventionnellement dans le domaine horloger. L'utilisation de composants travaillant en lubrification sèche permet de réduire le temps nécessaire au nettoyage, vidange et huilage des mouvements tout en augmentant la durée de leur garantie.Compared to wet lubrication conventionally used in the watchmaking field. The use of dry lubrication components reduces the time required for cleaning, emptying and oiling movements while increasing the duration of their warranty.

En complément des propriétés tribologiques, la faible densité du matériau (environ 1,2 g/cm3) comparée à celle de l'acier (environ 7 g/cm3) permet d'augmenter le rendement de la transmission (en réduisant les moments d'inertie notamment) et donc la réserve de marche globale du mouvement horloger.In addition to the tribological properties, the low density of the material (about 1.2 g / cm3) compared to that of steel (about 7 g / cm3) makes it possible to increase the transmission efficiency (by reducing the moments of particularly inertia) and therefore the overall power reserve of the watch movement.

A titre comparatif, la densité et les propriétés mécaniques des composants, et notamment leur module d'Young (environ 12 GPa) et leur dureté (environ 30HV) sont proches de celles des composants plastiques de type PEEK. En revanche, les propriétés tribologiques, notamment en termes de coefficient de frottement et d'usure, sont très supérieures.By way of comparison, the density and the mechanical properties of the components, and in particular their Young's modulus (approximately 12 GPa) and their hardness (approximately 30HV) are close to those of the plastic components of the PEEK type. In contrast, the tribological properties, particularly in terms of coefficient of friction and wear, are much higher.

Les composants développés valident avec succès les tests de résistance aux agents chimiques et climatiques horlogers, notamment les tests de sueur synthétique, de brouillard salin ou encore de climat tropical.The developed components successfully validate the tests of resistance to chemicals and climatic watchmaking, including synthetic sweat tests, salt spray or tropical climate.

Numéros de référence employés sur les figuresReference numbers used in the figures

11
système d'échappementExhaust system
22
ancreanchor
2020
baguettebaguette
2121
brasarms
2222
levéelifting
2323
tige d'ancreanchor rod
2424
dardsting
2525
fourchettefork
2626
cornehorn
33
roue d'échappementescape wheel
3030
pignon d'échappementexhaust pinion
3131
dents de la roue d'échappementteeth of the escape wheel
3232
moyeuhub
44
plateautray
4040
axe de balancierbalance shaft
4141
petit plateausmall tray
4242
encochenick
4343
grand plateaubig plateau
5050
pontbridge
5151
trouhole
5252
portionportion

Claims (15)

  1. Component for a watchmaking movement having a surface being subjected to friction, and of which at least part of this surface is formed from a material containing fibroin.
  2. Component according to claim 1, wherein said surface being subjected to friction is one among: surface of a pivoting axis mounted on a support pad; bearing surface of a pad intended to receive a pivoting axis; impulsion surface of an escapement; surface of a pallet-stone; contact surface of a tooth; surface of a mainspring; internal surface of a barrel.
  3. Component according to claim 1 or 2, wherein said surface is at least partially covered by at least one layer of fibroin or by an assembly of fibres woven or tangled up with fibroin.
  4. Component according to claim 1 or 2, wherein said material is a composite material with particles and/or microspheres and/or granules and/or fibres of fibroin in a synthetic polymeric or metallic matrix.
  5. Component according to claim 1 or 2, wherein the fibroin is comprised in a solid matrix, in particular resin.
  6. Component according to claim 1 or 2, wherein the fibroin is in a gel form.
  7. Component according to claim 1 or 2, comprising an element of solid fibroin.
  8. Component according to claim 3, wherein the coating has a thickness between 2 and 100 µm.
  9. Component according to one of the claims 1 to 8, wherein the fibroin material comprises additives intended to improve the tribological characteristics.
  10. Component according to one of the claims 1 and 3 to 9 forming a fixed component of a watchmaking frame serving as a support to at least one mobile organ.
  11. Component according to one of the claims 1 and 3 to 9 forming a mobile organ intended to be mounted pivoting on an arbor supported by a fixed component of a watchmaking frame.
  12. Component according to one of claims 1 to 11 being entirely made of a material containing fibroin.
  13. Escapement system for a watchmaking movement, comprising a component according to claims 1 and 3 to 9, said component being one of the escapement organs and said surface being subjected to friction belongs to one among the teeth of the escapement wheel, the pallet-stones, the fork, the pallet dart, the pin, the balance plate, the mainspring and the barrel.
  14. Watchmaking movement comprising at least one component according to one of the claims 1 to 12.
  15. Timepiece comprising the movement according to claim 14.
EP15738111.2A 2014-08-01 2015-07-17 Timepiece component with a surface comprising silk fibroin Active EP3175303B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH11782014 2014-08-01
PCT/EP2015/066403 WO2016016019A1 (en) 2014-08-01 2015-07-17 Timepiece component with a surface comprising silk fibroin

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EP3175303A1 EP3175303A1 (en) 2017-06-07
EP3175303B1 true EP3175303B1 (en) 2019-01-02

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CN109375491B (en) * 2018-11-20 2020-10-13 苏州市信睦知识产权服务有限公司 Touch perception watch capable of distinguishing morning and afternoon by highlighting sun and moon patterns

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JP2017522572A (en) 2017-08-10
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WO2016016019A1 (en) 2016-02-04
EP3175303A1 (en) 2017-06-07
CN107077095A (en) 2017-08-18

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