EP3092531B1 - Verfahren zur befestigung eines uhrenglases an einem uhrengehäuse - Google Patents

Verfahren zur befestigung eines uhrenglases an einem uhrengehäuse Download PDF

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Publication number
EP3092531B1
EP3092531B1 EP15700185.0A EP15700185A EP3092531B1 EP 3092531 B1 EP3092531 B1 EP 3092531B1 EP 15700185 A EP15700185 A EP 15700185A EP 3092531 B1 EP3092531 B1 EP 3092531B1
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EP
European Patent Office
Prior art keywords
glass
watch case
layer
electrode
contact
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Application number
EP15700185.0A
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English (en)
French (fr)
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EP3092531A2 (de
Inventor
Sébastien BRUN
Sandrine GUERIN DELETANG
Herbert Keppner
Sophie FARINE
Eric Guyot
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Cartier International AG
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Cartier International AG
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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
    • G04B39/00—Watch crystals; Fastening or sealing of crystals; Clock glasses
    • G04B39/02—Sealing crystals or glasses
    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/06—Devices for shaping or setting watch glasses

Definitions

  • the present invention relates to a method for attaching an upper and/or lower crystal to a watch case, more precisely to a bezel or to a bezel middle part of a watch case.
  • the present invention aims to provide a method for attaching a crystal to a watch case without using a gasket or glue while ensuring a tight and resistant attachment.
  • the subject of the present invention is a method for attaching a crystal to a watch case which is distinguished by the characteristics listed in claim 1.
  • the specificity and the object of the present invention is to produce a gas-tight and liquid-tight assembly without welding, without solder and without organic compound (glue).
  • Several preparations of the surfaces are necessary and illustrated in the appended drawing which illustrates schematically and by way of example, the successive steps of an execution of the method of fixing a crystal on a watch case according to the invention.
  • the present method makes it possible to fix a watch crystal which can typically be made of mineral glass, sapphire or other transparent or translucent ceramics with or without anti-reflective coating on part or all of the surface, to a bezel or carrure bezel of a watch case by the anodic bonding technique.
  • the zone of the watch case on which the crystal is fixed is typically made of stainless steel, platinum or gold, or comprises the various alloys associated with these materials.
  • the aforementioned materials can be coated with rhodium or any other material used for the manufacture of watch cases or jewelry or jewelry products.
  • the anodic bonding process is used in the general field of microtechnology, more particularly in the biomedical, aerospace and electronics sectors, where connections are made between materials compatible from the point of view of thermal expansion coefficients close to the anodic assembly technology.
  • anode assemblies is mainly used for thin and flat films and layers, in particular such as metal, glass and silicon wafers.
  • the assembly proposed by the present invention is carried out by means of intermediate layers, this with the aim of consolidating the bond, increasing the speed of diffusion and allowing assembly for a greater range of materials. and more massive parts, subjected to high stresses and having to resist shocks.
  • This fixing method is applied to mechanical components subjected to high mechanical stresses, in particular between a watch crystal on a steel, gold or platinum watch case in particular.
  • the method for attaching a watch crystal to a watch case according to the invention consists in producing a permanent and sealed anode assembly between the case and the crystal by the use of surface treatment on the areas of the crystal and/ or the box coming into contact allowing the migration of ions and electrons.
  • An electrode is connected to the crystal and a counter-electrode is connected to the watch case and then a voltage of between 1kV and 15kV is applied to improve the intimate contact between the partners and to bring kinetic energy assisted by the electric field to the charged particles For allow them to diffuse and create new ionic or covalent metallic bonds.
  • the crystal and/or the watch case Prior to their placement, are provided in the areas coming into contact with a semiconductor or insulating element promoting migration, such as glass or silicon.
  • a semiconductor or insulating element promoting migration such as glass or silicon.
  • the process is carried out at low temperature ensuring that none of the materials in the system, watch case, glass or intervening layers, leave their solid phase.
  • the electrodes are adapted to the geometry of the contact surface.
  • the geometry of the electrode is considered in three dimensions, the part in contact with the sapphire is without edges and without tip, typically of curved shape.
  • a surface functionalization by ion implantation makes it possible to improve the phenomena of diffusion by the contribution of element in the matrix and by the disturbance of the crystal lattice or of the stoichiometry.
  • a surface functionalization by UV exposure makes it possible to improve the phenomena of diffusion by the disturbance of the crystal lattice or of the stoichiometry resulting from the supply of energy in the matrix.
  • a surface treatment allowing a structural modification of the substrates typically comprising heat, activation plasma, etching plasma or sonochemical treatments can be used to facilitate the diffusion phenomena.
  • the assembly described is carried out by anodic bonding only, no element is fused, even partially. This differentiates the assembly obtained in a significant way from assemblies obtained by laser or ultrasonic welding.
  • the assembly described makes it possible to produce metal-to-metal, metal-to-non-metal and non-metal-to-non-metal connections.
  • the intermediate semiconductor element can be attached by a separate piece or deposited by physical or chemical means (PVD, PE-CVD, Sol-gel, electroplating).
  • the thin intermediate layers considered have a non-constant stoichiometry.
  • the degree of nitriding or carburizing oxidation varies with layer thickness.
  • the thin layer of the bezel may also contain its natural or forced passivation layer.
  • a masking layer is deposited on the glass in order to mask the contact zone.
  • This layer may consist of metallic elements and alloys of at least one of the following elements: Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au and Ag.
  • watch case also includes the other components of the casing such as the back and the middle.
  • a watch case is considered to be all the components enabling the movement to be enclosed in a watertight manner.
  • the crystal considered consists of at least one of the following elements: aluminum oxide such as sapphire, spinel, spinel AION, aluminum oxynitride, yttria, YAG (Yttrium Aluminum Garnet) and Nd :YAG or silicon oxide such as mineral glass or pyrex.
  • aluminum oxide such as sapphire, spinel, spinel AION, aluminum oxynitride, yttria, YAG (Yttrium Aluminum Garnet) and Nd :YAG or silicon oxide such as mineral glass or pyrex.
  • the temperature of the partners, watchcase and crystal, during the bonding process is below 380°C, and preferably below 250°C.
  • the temperature may vary during assembly, for example from 120°C to 250°C.
  • the rate of extension of the anode link is for example greater than 1 mm 2 /minute.
  • the surface roughness of the bezel is obtained by mechanical machining or fine stamping with the addition of chemical electropolishing.
  • step No. 2 ie polishing the upper face of the bezel, can be omitted.
  • bezel can be replaced by a middle bezel or any other part of the watch case on which the crystal must be fixed.
  • An alternative consists of using an added glass material between the crystal and the caseband coated according to the figure 1 .
  • the intermediate layer is deposited on the upper face of the bezel by the physical or chemical technology mentioned above and the composition of the matrix of this intermediate layer typically consists of TixOy, Si x O y , Si x N y , Al x O y or mixtures of oxides containing light metal atoms / ions such as Li, Na, K, Ca, Be, or halogens favoring ion migration.
  • the addition of a thin metallic layer is possible before the deposition of the intermediate layer in order to better guarantee the shine and the visual metallic aspect under the transparent glass. This can by its choice increase the adhesion between the intermediate layer, the transition between the materials can even be done gradually.
  • the anode assembly is carried out under a voltage of less than 15 kV.
  • the anode assembly will take place at a temperature below 250°C.
  • the determination of the nature of the intermediate layer or layers requires the qualification of the materials to be assembled, typically its physico-chemical composition, the mechanical properties, the surface condition, in order to optimize the characteristics of the deposit which will serve as the first intermediate layer. This is qualified by the following factors: adhesion with the raw materials, types of defects and gaps allowing the diffusion of ions and migration, electronegativity of the ions contained within the intermediate layer(s), concentration of ions and gaps, orientation of these same gaps.
  • the layer or layers can contain alkaline, alkaline-earth and halogenated materials because of their ease of migration and the size of their atoms.
  • the intermediate layer(s) will define the quality of the bond, its mechanical properties and sealing, but also its aesthetic properties. To understand the importance of this or these intermediate layers and to differentiate an assembly according to the present invention from conventional welding or brazing techniques where there is no question of the use of an electric field, it is a question of understanding the specific atomic transfers during the anode assembly process.
  • any charged particle placed under the influence of a uniform electric field moves at a speed proportional to this field, the proportionality factor being called the electric mobility of the particle.
  • This migration will take place from the anode towards the cathode for the positively charged particles, in the opposite direction for the negatively charged particles.
  • a potential difference is observed between the partners, which generates a plating between the partners induced under the effect of electrostatic forces. If this plating is insufficient, the application of a mechanical load to force contact between the partners is considered.
  • the electric field increases the diffusion process, assembly speeds are reduced on the order of minutes, encouraging increased throughput and better reproducibility.
  • Transport phenomena Properties relating to electric currents and displacements of charge carriers under the influence of applied forces are called transport phenomena.
  • transport phenomena mobility, whether for example vacancies, impurities, charge carriers (the materials are differentiated by the Debye length of the majority carriers and their behavior is described in particular by the continuity equation ) as well as diffusion (based on Fick's laws) are the key mechanisms of anodic assembly.
  • the parameters that most influence the mobility of the charge carriers are the temperature and the volume number of impurities.
  • the defects can be distinguished impurities and gaps.
  • the choice of the intermediate layer or layers strongly depends on the "properties" of the charge carriers.
  • the chemical composition of the layer(s) is naturally important since the transport phenomena depend on the characteristics of the atomic bonds.
  • the bonds created during the anodic assembly process are mostly covalent type bonds. These strong bonds are established by the pooling of a pair of electrons from each of the charge carriers.
  • PVD deposition method is preferred, but an intermediate layer (mono or multilayer) can be deposited by another physical or chemical deposition process.
  • the temperature and the voltage applied as well as the contact time are closely linked and complementary since they control the electrostatic force necessary for the chemical reaction between the parts to be assembled.
  • the voltage will not go beyond 15 kV, and the temperature will not exceed 250°C.
  • the gap between the parts to be assembled has a significant effect on the magnitude of the electrostatic force, which implies that the quality of the bond formed by anodic assembly also depends on the surface condition.
  • electrochemical polishing is used.
  • the deposit of a layer mimicking the material of the bezel is deposited on the ice before the deposition of the functional layer. Such a deposit is selective, masking the assembly zone, with an aesthetic function.
  • This selectivity is obtained by masking technique, typically by lithography, stamping, selective etching or by adhesion promotion.
  • optical rendering color surface appearance
  • the optical rendering, color surface appearance is obtained by adapting the layers, in particular by their thickness, their composition and their pre-treatments.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (13)

  1. Verfahren zur Befestigung eines Glases an einem Uhrengehäuse, das Folgendes umfasst:
    Anbringen, durch Flächenbehandlung, mindestens einer dünnen Zwischenschicht, welche die Migration der Ionen und/oder der Elektronen ermöglicht, auf einer Zone der Fläche des Glases, die dazu bestimmt ist, mit einer entsprechenden Zone des Uhrengehäuses in Kontakt zu gelangen, und/oder auf der entsprechenden Zone des Uhrengehäuses;
    Ansetzen dieser Zonen des Uhrengehäuses und des Glases gegeneinander;
    dadurch gekennzeichnet, dass auch die folgenden Schritte durchgeführt werden:
    Erhitzen der Uhrengehäuse-Glas-Anordnung auf eine Erhitzungstemperatur, die niedrig genug ist, um sicherzustellen, dass kein Material des Systems seine feste Phase verlässt;
    Verbinden des Glases mit einer Elektrode und des Uhrengehäuses mit einer Gegenelektrode; und
    Anlegen einer Spannung, welche die Diffusion der geladenen Partikel zwischen dem Glas und dem Uhrengehäuse beschleunigt und somit neue metallische, ionische oder kovalente Bindungen erzeugt, zwischen dieser Elektrode und dieser Gegenelektrode.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Spannung eine Gleichspannung von zwischen 1 kV und 15 kV ist.
  3. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Erhitzungstemperatur 250 °C nicht überschreitet und/oder dass sie zwischen 120 °C und 250 °C schwankt.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei vor dem Ansetzen der Zonen des Uhrengehäuses und des Glases gegeneinander eine Schicht aus einem Halbleiter- oder isolierenden Element angeordnet wird, das die Migration zwischen der Zone des Glases und der Zone des Uhrengehäuses begünstigt, wie Gläser, Silizium.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass das Halbleiter- oder isolierende Element durch ein getrenntes Teil angestückt oder physikalisch oder chemisch (PVD, PE-CVD, Sol-Gel, Galvanotechnik) abgeschieden wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mindestens eine Zwischenschicht eine Schicht umfasst, die auf dem Glas angebracht wird und eine chemische und strukturelle Entwicklung aufweist, wobei der Teil, der mit dem Glas in Kontakt ist, rein metallischer Beschaffenheit ist und je nach seinem Wachstum sein Oxidationsgrad sich allmählich entwickelt, um an der Fläche mit einem vollständigen TiO2-Oxidationszustand zu enden.
  7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass jede Elektrode eine Geometrie aufweist, die an die Fläche angepasst ist, mit der sie in Kontakt ist.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Geometrie der Elektrode, die mit dem Glas in Kontakt ist, gekrümmt und ohne Spitzen ist.
  9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mindestens eine Zwischenschicht eine nicht konstante Stöchiometrie aufweist, wobei der Oxidations-, Nitrierungs- oder Zementierungsgrad mit der Dicke der Schicht schwankt.
  10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mindestens eine Zwischenschicht eine dünne Schicht umfasst, die auf dem Gehäuse angebracht ist und eine natürliche oder erzwungene Passivierungsschicht enthält.
  11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mindestens eine Zwischenschicht eine Maskierungsschicht umfasst, die auf dem Glas abgeschieden wird, um seine Kontaktzone zu maskieren, wobei diese Schicht aus metallischen Elementen und Legierungen von mindestens einem der folgenden Elemente besteht: Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au und Ag.
  12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Glas aus mindestens einem der folgenden Elemente besteht: Aluminiumoxid wie Saphir, Spinell, Aluminiumoxynitrid-Spinell-ALON, Yttriumoxid, YAG (Yttrium-Aluminium-Granat) und Nd:YAG oder Siliziumoxid wie mineralisches Glas oder Pyrex.
  13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Flächenrauigkeit des Gehäuses durch eine mechanische Bearbeitung oder ein Feinstanzen mit einer zusätzlichen chemischen Elektropolierung erhalten wird.
EP15700185.0A 2014-01-07 2015-01-06 Verfahren zur befestigung eines uhrenglases an einem uhrengehäuse Active EP3092531B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH102014 2014-01-07
PCT/EP2015/050085 WO2015104252A2 (fr) 2014-01-07 2015-01-06 Procédé de fixation d'une glace sur une boîte de montre

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EP3092531A2 EP3092531A2 (de) 2016-11-16
EP3092531B1 true EP3092531B1 (de) 2023-06-28

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EP (1) EP3092531B1 (de)
JP (1) JP6518264B2 (de)
CN (1) CN105960611B (de)
WO (1) WO2015104252A2 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006219A1 (fr) * 2015-07-06 2017-01-12 Cartier International Ag Procédé de fixation par assemblage anodique
CH711295B1 (fr) * 2015-07-06 2019-11-29 Cartier Int Ag Procédé de fixation par assemblage anodique.
JP6419391B2 (ja) * 2016-11-29 2018-11-07 京セラ株式会社 時計ケース
CN107065496B (zh) * 2017-04-15 2019-09-17 伯恩光学(惠州)有限公司 手表镜片
CH714459B1 (fr) * 2017-12-19 2024-06-14 Guenat Sa Montres Valgine Glace de montre.
CH716104A1 (fr) * 2019-04-18 2020-10-30 Sy&Se Sa Procédé d'amélioration de l'adhérence d'une couche sur un substrat.
CN110204223A (zh) * 2019-04-25 2019-09-06 厦门祐尼三的新材料科技有限公司 一种夹层玻璃及其制备方法
CN114953643A (zh) * 2022-06-15 2022-08-30 Oppo广东移动通信有限公司 终端及其壳体组件以及壳体组件的键合方法

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Publication number Priority date Publication date Assignee Title
CH649435GA3 (de) * 1981-05-22 1985-05-31
CH652270GA3 (de) * 1983-05-19 1985-11-15
CH678680GA3 (en) * 1990-02-20 1991-10-31 Watch glass mounting - has a deposited metal layer between decorative layer and solder to prevent visible effects of soldering
JPH08166469A (ja) * 1994-12-15 1996-06-25 Citizen Watch Co Ltd 時計用文字板およびその製造方法
US6823693B1 (en) * 1998-03-06 2004-11-30 Micron Technology, Inc. Anodic bonding
US20110151157A1 (en) * 2008-04-02 2011-06-23 Empa Eidgenossische Material-Profungs-Und Forschun Composite object and method for the production thereof
JP5529463B2 (ja) * 2009-08-25 2014-06-25 セイコーインスツル株式会社 パッケージの製造方法および圧電振動子の製造方法

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JP2017501425A (ja) 2017-01-12
EP3092531A2 (de) 2016-11-16
WO2015104252A2 (fr) 2015-07-16
CN105960611B (zh) 2019-11-05
JP6518264B2 (ja) 2019-05-22
CN105960611A (zh) 2016-09-21
WO2015104252A3 (fr) 2015-12-23

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