Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
• • A—HUMAN NECESSITIES
  • A44—HABERDASHERY; JEWELLERY
  • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
  • A44C17/00—Gems or the like
  • A44C17/02—Settings for holding gems or the like, e.g. for ornaments or decorations
• • 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
  • G04B19/00—Indicating the time by visual means
  • G04B19/06—Dials
  • G04B19/12—Selection of materials for dials or graduations markings
• • 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
  • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
  • G04B45/0007—Light-, colour-, line-, or spot-effects caused by parts or pictures moved by the clockwork
• • 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
  • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
  • G04B45/0015—Light-, colour-, line- or spot-effects caused by or on stationary parts
• • G—PHYSICS
  • G04—HOROLOGY
  • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
  • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
  • G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams

Definitions

• the invention relates to a component intended for the interior trim or the movement of a timepiece or piece of jewelry. It also relates to the manufacturing process of said component.
• the black “color” can be obtained in the mass of a material by its intrinsic color or via the addition of pigments or dyes within the material.
• the black “color” may also be present only on the surface.
• This surface coloring can be obtained in different ways, generally by oxidation/sulfidation/carburization of a metal substrate or by depositing an oxide/sulfide/carbide on a substrate.
• Carbon is therefore a well-known element for blackening a surface.
• Document EP 3 327 517 discloses a dial with a first substrate coated with a black layer of nanotubes facing the watch glass and with a second substrate fixed to the first substrate on the surface opposite the glass.
• the first substrate is perforated in order to produce openings acting as windows intended to form indexes.
• the second substrate includes a luminescent coating at least in the zones opposite the openings so as to create a contrast at the level of the first substrate between the black layer and the illuminated indexes.
• the contrast is obtained via the superposition of two substrates having distinct coatings.
• This superposition makes it possible to avoid selectively depositing one and the other coating on the same surface and to manipulate the layer of nanotubes, which is particularly fragile, more than necessary.
• This superposition nevertheless has the drawback of requiring the manufacture of two substrates, which increases the production costs.
• this manufacturing technique is not very suitable for a decoration formed of stones, in particular of diamonds.
• the difficulty lies in the crimping of the stones on the dial coated with a black layer.
• the latter must be discontinuous at the level of the stones under penalty of degrading the brilliance of the stones, while perfectly coating the stones to obtain the expected contrast.
• Particular attention must be paid to the manufacturing process so as not to damage the layer of carbon nanotubes.
• the layer can be so friable that it is almost impossible to touch it without degrading the surface, showing shiny veils or even holes contrasting with the original color of the carbon nanotubes.
• the object of the present invention is to provide a method for manufacturing a watch or jewelry component coated in black and decorated with stones, and more particularly set with stones. This process is developed so as not to damage the black coating while having a discontinuous black layer at the level of the stones.
• the manufacturing process according to the invention cannot thus be content with adding a decoration, in this case stones, to the coating as according to the prior art.
• the decoration formed from the stones is manufactured directly on the substrate with the black layer selectively removed so as to maintain a surface free of black below the decoration.
• the invention relates to a process for manufacturing a component intended for the interior trim or the movement of a timepiece or piece of jewelry, said component comprising a substrate coated at least partially with a layer black comprising carbon nanotubes or aluminum oxide, the coated substrate being decorated with at least one stone seated in a housing formed in the substrate, the latter being at least devoid of the black layer on the surface of the housing, said method comprising:
• step e) of positioning and fixing the stone within the housing, said method comprising an additional step d) of selective removal of the black layer previously deposited on the substrate so that at least the surface of the housing is devoid of the black layer.
• step b) is replaced by a step b′) of depositing a layer of a precursor comprising carbon nanotubes.
• the additional step d) is then replaced by an additional step d) of selective removal of the layer of precursor so that at least the surface of the housing is devoid of the layer of precursor.
• This method further comprises a step f) which consists in carrying out a chemical or laser attack on the layer of precursor in order to reveal the black layer of carbon nanotubes.
• Step d) or d') of selective removal can be carried out mechanically, for example using a crimping tool, or preferably by laser ablation.
• Selective removal can also be carried out indirectly during the step of machining the housing or even during a step of growing a support for the stone on the substrate via, for example, an additive manufacturing operation and more. precisely additive manufacturing by inkjet.
• the present invention also relates to the interior trim or movement component for a timepiece or piece of jewelery comprising a substrate partially coated with a black layer and decorated with at least one stone seated in a housing provided in or on the substrate, said black layer comprising carbon nanotubes or an aluminum oxide, said substrate being at least devoid of the black layer on the portion facing the stone or, in other words, on the surface of the housing.
• the present invention proposes making a watchmaking or jewelery component with two allotropic forms of carbon on the surface, one very black for the carbon nanotubes and the other very white for the diamond allowing very marked contrasts of brilliance.
• Figure 1 is a plan view of a timepiece provided with a dial coated and decorated with stones according to the method of the invention. In enlargement, a stone with the crimping element is shown.
• FIGS 2 to 7 are schematic representations of different embodiments of the method according to the invention with the successive steps implemented.
• the invention relates to a component intended for the interior trim or the movement of a timepiece or piece of jewelry. It can be chosen from the non-exhaustive list comprising a dial, a hand, an index, an applique, an oscillating weight, a plate, a bridge, etc. According to the invention, this component is at least partially coated with a black layer. The invention also relates to a set of two of said components at least partially coated with the black layer.
• Said substrate can be made of a material metal such as steel, titanium, aluminum, a titanium or aluminum alloy, brass or any other copper alloy. It can also be made in a ceramic material, a cermet, in sapphire, in a composite or in a polymer.
• the substrate 2 is decorated, and preferably crimped, with one or more stones 4 distributed within the black layer 3. It may be precious stones such as diamonds, semi-precious stones or even synthetic stones such as zirconia, etc.
• the substrate is at least devoid of the black layer on the facing portions of the stones.
• the black layer can be present so as to be flush with the table of the stone. It is also possible to decorate the substrate with several rows of stones, the substrate having a black layer between the rows.
• the substrate 2 comprises a housing 5 shown diagrammatically in FIG. 2 serving as a seat for the stone 4 and more particularly for the cylinder head 4a of the stone.
• the fixing of the stone within the seat is preferably carried out by crimping using a crimping element 6 shown in the enlargement of Figure 1. It may be claws of a kitten placed in the housing, grains that are an integral part of the substrate, grooves in a housing for bead or invisible crimping, etc.
• the crimping element is preferably also coated with the black layer so as to produce a crimping which seems invisible to the eyes of the user. Visually, this blends into the black background of the dial.
• the present invention does not exclude the stone being glued within the seat with an adhesive that does not degrade the shine of the stone.
• the black layer comprises carbon nanotubes.
• the layer of carbon nanotubes comprises at least 1% by weight, preferably at least 10% by weight, of carbon nanotubes.
• Said layer can be a varnish comprising by weight at least 1%, preferably at least 10% by weight, of carbon nanotubes. The larger the proportion, the darker the hue. In this varnish, the carbon nanotubes are randomly dispersed.
• This varnish can be deposited, for example, by spraying.
• the layer comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90% by weight of carbon nanotubes aligned vertically with respect to the plane of the substrate, the rest being made up of other forms of carbon.
• the layer comprises 100% carbon nanotubes aligned vertically with respect to the plane of the substrate.
• the vertical alignment of the nanotubes makes it possible to obtain a deeper black compared to the random orientation of the carbon nanotubes in the varnish, but has the disadvantage of having less mechanical strength than the varnish.
• a protective layer can be deposited on the black layer with, however, the corollary of a reduction in the light absorption coefficient.
• This protective layer can be a varnish or a thin layer of a material, for example AhOa, TiC or SiC, or a stack of layers of one or more of these materials deposited by ALD (for Atomic Layer Deposition).
• the nanotubes having a vertical orientation are deposited by vacuum processes such as PVD (for Physical Vapor Deposition in English), CVD (for Chemical Vapor Deposition in English) or else synthesis by laser ablation.
• the layer of carbon nanotubes has a thickness between 1 and 100 ⁇ m.
• the black layer is a layer mainly comprising aluminum oxides AlxOy such as Al2C>3 with, in addition, non-ferrous metal oxides such as, for example, copper oxides, zinc or manganese.
• This layer comprises at least 90% ALOy, preferably 100% AlxOy.
• the aluminum oxide has an aluminum content of between 45% and 65% by mass and preferably between 45% and 50% by mass.
• This layer has a thickness of between 1 and 50 microns, preferably between 2 and 10 microns, and more preferably between 4 and 7 microns. It can be deposited by PVD or CVD or PECVD (for Plasma-Enhanced Chemical Vapor Deposition in English).
• Figures 2 to 7 illustrate only the substrate provided with a housing for the seat of the stone without representing the crimping element. Any step referring to the machining of the housing includes, where applicable, the mechanical preparation of the crimping element such as the grains.
• the component manufacturing process includes, in an unspecified order for steps b) to e):
• the component manufacturing process comprises:
• step a) of making the substrate 2 available (fig.2-5)
• the fixing covers crimping as well as other fixing techniques such as than gluing.
• the black layer 3 is deposited on the substrate 2 before the machining of the housing 5. Then, the black layer 3 is removed during the machining of the housing 5, i.e. that steps c) and d) are one and the same step. Finally, step e) is performed.
• the black layer 3 is deposited on the substrate 2 after step c) of machining the housing 5. Then, the black layer
• step e) is performed.
• the deposition of the black layer 3 is carried out on the substrate 2 already decorated with the stone 4. Then, the black layer 3 on the stone 4 is removed mechanically or preferentially by laser ablation with, as previously, a pulsed laser.
• This variant of Figure 4 is preferred because after the selective removal of the black layer, it is no longer necessary to handle the surface unlike the variant of Figure 3 where it is still necessary to crimp the substrate after removal selective.
• the substrate 2 is decorated with the stone
• the method includes an additional step f) of applying a mask 8 to the stone 4.
• the mask can be a lacquer, an adhesive, a photosensitive film, etc. It can be deposited by way of example by photolithography, stereolithography, digital printing or manually for an adhesive or film.
• the black layer 3 is deposited in step b) on substrate 2, including on mask 8.
• black layer 3 is selectively removed with mask 8 in step d).
• the mask can be removed by laser ablation or mechanically, for example manually with a dedicated tool. Alternatively (not shown), the mask could be positioned in the housing before positioning the stone. The deposit of the black layer and its selective removal are then carried out before the positioning of the stone.
• step b) is replaced by step b′) of depositing a layer of a precursor 7 on the substrate 2, including on the surface of the housing 5
• step b′) includes deposition of the layer of precursor and annealing to polymerize the precursor.
• This variant is applicable for a black layer based on carbon nanotubes.
• the precursor comprises a polymer and carbon nanotubes.
• the percentage by weight of carbon nanotubes is between 0.1 and 15% and the percentage by weight of polymer is between 85 and 99.9%.
• the polymer can be chosen from thermoplastics such as a polyamide, polybutene, polyethylene, polyimide, polypropylene, polystyrene, polyvinyl acetate and a polymethyl methacrylate or from thermosettings such as a polyepoxide and a polyurethane.
• thermoplastics such as a polyamide, polybutene, polyethylene, polyimide, polypropylene, polystyrene, polyvinyl acetate and a polymethyl methacrylate
• thermosettings such as a polyepoxide and a polyurethane.
• the latter can be functionalized beforehand.
• the carbon nanotubes can be functionalized beforehand by an attack in an acid medium, for example in nitric acid.
• the precursor comprising the mixture of carbon nanotubes distributed in the polyimide matrix is deposited and polymerized at a temperature of between 150 and 350° C. for a time of between 1 and 7 hours.
• this selective removal is carried out by laser ablation but it could also be done manually with an appropriate tool.
• step f) of the layer of precursor 7 is subjected to a chemical or laser attack which reveals the nanotubes of carbon from the precursor layer to form the black layer 3.
• the chemical attack can be carried out in an acid medium (e.g. formic acid, acetic acid, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid) or in an appropriate solvent (eg m-cresol) depending on the nature of the polymer matrix.
• This etching step has the effect of partially dissolving the polymer matrix of the precursor layer, creating surface roughness and thus revealing a microstructure rich in carbon nanotubes and conducive to light trapping.
• a laser attack with a pulsed laser eg femtosecond, picosecond is also possible to create such a surface microstructure.
• step b′) can be carried out before step c) of machining the housing, steps c) and d′) then being the same concomitant step of machining the housing and d selective removal of the precursor layer at the housing.
• the deposition of the layer of precursor can be carried out on the substrate set with the stone, the selective removal of the precursor then being carried out on the stone.
• the method comprises an additional step h) of growth of material on the substrate 2 coated with the black layer to form a support 11 intended to accommodate the stone 4. It thus comprises successively :
• step h) of growth of material on the coated substrate 2 to form the support 11 this step is concomitant with step d) of selective removal of the black layer 3, - A step e) of positioning and fixing the stone 4 within the housing 5 provided on the substrate 2 in the support 11.
• the material growth step is carried out by additive manufacturing such as digital printing, by electroforming, laser sintering or any other derived additive process.
• the material can be metallic, ceramic or polymeric.
• the black layer 3 will automatically be removed selectively at the level of the support 1 1 , which makes it possible to free the substrate 2 opposite the stone 4 to be crimped.
• the housing 5 can be made directly during step h) of growth or be machined later before step e).
• the present invention also covers an assembly comprising a first component and a second component each intended for the interior trim or the movement of a timepiece or piece of jewelry.
• the first and the second components comprise at least one portion coated with the black layer.
• the first component has a relative movement with respect to the second component and is mounted facing the latter.
• This first component is decorated with one or more stones.
• the first component is a hand coated with the black layer and decorated with a stone set or glued to the tip of the hand, and the second component is a dial coated with the black layer.

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• Chemical Kinetics & Catalysis (AREA)
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Citations (9)

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• 2020
  • 2020-08-11 EP EP20190566.8A patent/EP3954802A1/fr not_active Withdrawn
• 2021
  • 2021-07-23 CN CN202180056394.0A patent/CN116034178B/zh active Active
  • 2021-07-23 EP EP21746063.3A patent/EP4196621A1/fr active Pending
  • 2021-07-23 WO PCT/EP2021/070692 patent/WO2022033839A1/fr not_active Ceased
  • 2021-07-23 US US18/040,369 patent/US20230288875A1/en active Pending
  • 2021-07-23 JP JP2023507705A patent/JP7681094B2/ja active Active
• 2024
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• 2025
  • 2025-12-09 JP JP2025243587A patent/JP2026032293A/ja active Pending

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