Black stone-decorated component and its manufacturing method

Abstract

To provide a method for manufacturing a component for a watch or jewellery, which is coated in black, decorated by stones, and especially set with stones.SOLUTION: A component for an internal part or a movement of a timer or jewellery is provided. The component includes a substrate 2 partially coated with a black layer 3, and is decorated with at least one stone 4. The black layer includes a carbon nanotube or aluminum oxide. The substrate is not provided with the black layer in at least portions facing the stones. A method for manufacturing the component for a timer or jewellery is also provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to components intended for the internal parts or movements of timepieces or jewelry. The invention further relates to a method for manufacturing said component. [Background technology]

[0002] The "color" of black can be achieved either by the inherent color of the mass of material or by adding pigments or dyes to the material. Also, the "color" of black occurs only on the surface. Color can be achieved by many methods, typically by oxidation / sulfidation / carbonization of the metal substrate. by oxidation or by depositing oxides / sulfides / carbides on the substrate. Thus, carbon is a well-known element for darkening surfaces. A perfectly absorbing blackbody-like material with an optical absorption coefficient of up to 99.96% in the visible and near-infrared ranges. This black material can be obtained by forming it into elongated shapes in the form of nanotubes. is so perfect that it can obscure the three-dimensional shape of an object when viewed from the front.

[0003] The use of black coatings in the timekeeping industry is well known. P3327517 is a watch whose first substrate, facing the crystal, is a black nanotube layer. A dial is covered with a second substrate on the opposite side of the crystal, which is fixed to the first substrate. The first substrate has a window intended to form an index. The second substrate has a light-emitting property at least in an area facing the opening. a coating, whereby, in the first substrate, between the black layer and the illuminated index Creates contrast in the image.

[0004] In this way, contrast can be achieved by superimposing two substrates containing different coatings. This superposition allows both coatings to be selectively deposited on the same surface. This allows for the deposition of nanotubes without the need for excessive manipulation of the particularly fragile nanotube layers. Nevertheless, this overlap requires the production of two substrates. This increases the manufacturing costs.

[0005] Swiss patent CH711141 states that the decoration, i.e., the index, is made of carbon fiber. The present invention discloses a method for manufacturing a dial that is attached to a black coating. This allows the dial to be manufactured separately and then simply added to the dial. However, this manufacturing technique means that the black color underneath the decoration affects the aesthetics and / or appearance of the decoration. is not suitable for certain types of decorations that can adversely affect the shine.

[0006] In particular, this manufacturing technique is not well suited to decorations made of stones, especially diamonds. It is difficult to set stones on a dial covered with a black layer. The design completely surrounds the stone, creating the desired contrast, while remaining discontinuous at the stone's location. The manufacturing process requires careful consideration of the thickness of the stone, otherwise the brilliance of the stone will be diminished. Special care must be taken not to damage the carbon nanotube layer. The tube layer is so brittle that it is nearly impossible to touch it without damaging the surface. Damaging the surface will create a contrast to the original color of the carbon nanotubes. This can result in small shiny spots or holes that can cause damage. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention relates to a black coated, stone decorated, and especially stone set, The present invention aims to provide a method for manufacturing a component for a timepiece or a piece of jewelry. The method was developed so that the black layer was interrupted at the stone location, but the black coating was not damaged. Ta. [Means for solving the problem]

[0008] Therefore, the manufacturing method according to the present invention does not merely involve coating, decoration, In this case, it does not involve adding stones. The decoration is made directly on the substrate from which the black layer has been selectively removed, thereby leaving a black layer underneath the decoration. Maintain a surface free of color layers.

[0009] In particular, the present invention relates to an internal component or movement of a timepiece or piece of jewelry. The method for manufacturing a component is intended, said component comprising at least one The black layer comprises a substrate partially coated with a black layer, the black layer comprising carbon nanotubes or aluminum oxide. The aluminum-containing coated substrate is placed on a bed of the substrate. The substrate is decorated with at least one stone, and the substrate has at least one stone on the surface of the bed. and the black layer is absent, the method includes step a) of providing the substrate, followed by: In any order, step b) depositing the black layer on the substrate; c) forming a bed and d) placing and fixing the stones within the bed. and step e), the method further comprising: Step d) is then carried out to selectively remove the black layer already deposited on the substrate.

[0010] In another embodiment of the method applicable when the black layer comprises carbon nanotubes, Step b) is followed by step b') of depositing a precursor layer containing carbon nanotubes. Therefore, the additional step d) is at least The precursor layer is then selectively removed so that it is free of the precursor layer. The method further comprises removing the precursor layer to expose the black carbon nanotube layer. and performing a step f) of chemically or laser etching on the substrate.

[0011] The selective removal step d) or d') can be carried out mechanically, for example by using a setting tool. Alternatively, selective laser ablation may be used. The removal may occur during the bed formation step or during additive manufacturing operations, particularly inkjet additive manufacturing. Indirectly during the step of growing a stone support on a substrate, using a method such as It is also possible.

[0012] The present invention further relates to an internal part or movement of a timepiece or a component of a piece of jewelry. The component includes a substrate partially coated with a black layer, and at least one The stone is placed on the substrate or a bed located on the substrate, and The black layer contains carbon nanotubes or aluminum oxide, and the substrate contains at least In both cases, the black layer is absent on the portion facing the stone, i.e., the surface of the bed.

[0013] In the case of diamond decoration on carbon nanotube coating, the present invention provides two diamonds on the surface. A component of a timepiece or jewellery containing two allotropes of carbon, It is very black thanks to carbon nanotubes, while the other allotrope is black thanks to diamond. It is possible to produce a product that is very white and has a very striking contrast and shine. This is what we propose.

[0014] Other features and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings. can be understood. [Brief explanation of the drawings]

[0015] [Figure 1] 1 shows a top view of a timepiece with a coated and stone-decorated dial according to the method of the invention, showing the stones together with the setting elements in an enlarged view. [Figure 2] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; [Figure 3] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; [Figure 4] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; [Figure 5] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; [Figure 6] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; [Figure 7] 1 is a schematic diagram of an embodiment of a method according to the invention, carrying out several sequential steps; DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention relates to components intended for the internal parts or movements of timepieces or jewelry. This component refers to the dial, hands, indexes, applicators, and vibration The weight, plate, bridge, etc. can be selected from the group consisting of: This is not an exhaustive list. According to the present invention, this component includes at least The present invention further provides a method for manufacturing a semiconductor device comprising: and an assembly comprising two of said components.

[0017] As shown in FIG. 1, a portable device formed by a substrate 2 coated with a black layer 3 is The present invention will be described in relation to the case where the present invention is applied to the dial 1 of a watch. The substrate may be steel, titanium, aluminum, titanium or aluminum alloys, brass or other copper alloys. The substrate can be made of a metal material such as ceramics, ... The substrate 2 may also be made of metal, sapphire, composite material or polymer material. One or more stones 4 are arranged within the black layer 3 and are decorated, preferably set. These stones4 may be precious stones such as diamonds, semi-precious stones, or zirconia. According to the present invention, at least one of the following can be provided on the substrate: In the opposite area, there is no black layer. The black layer is flush with the stone table. The substrate may also be decorated to form an alignment of multiple stones. The substrate includes a black layer between these alignments.

[0018] The substrate 2 has a bed 5 shown in FIG. 2, which is made up of stones 4, in particular of stones 4. The pavilion 4a serves as a seat for the stone 4, which is preferably The setting element 6 is fixed within the seat by setting. The setting element 6 is a setting claw arranged within the bed, a component of the base material Particles forming minute or baguettes and in the bed for invisible setting According to the present invention, the settings can be displayed to the user. To prevent this, the setting element is preferably coated with a black layer. Visually, the lacing blends in with the black background of the dial and becomes less noticeable. The stones can be attached within the seat with adhesive that does not deteriorate the shine of the stone. This does not prevent such things.

[0019] In another embodiment of the present invention, the black layer comprises carbon nanotubes. The nanotube layer contains at least 1% by weight of carbon nanotubes, preferably at least The carbon nanotube layer contains at least 10% by weight of carbon nanotubes. The varnish may contain at least 1% by weight, preferably at least 10% by weight. The higher the concentration, the darker the dark areas. This varnish can be applied by spraying or other methods. The carbon nanotube layer is made of carbon nanotubes aligned perpendicular to the plane of the substrate. At least 50% by weight, at least 60% by weight, at least 70% by weight, Preferably, the carbon dioxide contains at least 80% by weight, or at least 90% by weight, with the remainder being other forms of carbon. Preferably, the carbon nanotube layer is made of carbon nanotubes aligned perpendicular to the plane of the substrate. The nanotubes are 100% by weight. Such vertical alignment of the nanotubes is This produces a deeper black color than when the carbon nanotubes are randomly oriented, but However, there is a problem that the mechanical strength is lower than that of varnish. A protective layer can be deposited, but this reduces the light absorption coefficient. , varnishes, or thin layers of materials such as Al2O3, TiO2 or SiO2, or ALD (atomic layer deposition) A laminate of one or more of these materials deposited by layer deposition. Vertically aligned nanotubes can be grown by PVD (physical vapor deposition) and CVD (chemical vapor deposition). ), or deposited by vacuum methods such as laser ablation synthesis. The tube layer has a thickness of 1 to 100 μm.

[0020] In another alternative embodiment, the black layer is made of aluminum oxide Al, such as Al2O3. x O y and further containing non-ferrous metal oxides such as oxides of copper, zinc or manganese. This layer is made of Al x O y The content is at least 90%, preferably 100%. The aluminum content of the aluminum oxide is 45 to 65% by weight, preferably 45 to 50% by weight. This layer has a thickness of 1 to 50 μm, preferably 2 to 10 μm, more preferably 4 to 50 μm. This layer has a thickness of 7 μm. This layer can be formed by PVD, CVD or PECVD (plasma enhanced chemical vapor deposition). It can be deposited by evaporation.

[0021] The components according to the invention are shown in some implementations of the method, which are illustrated diagrammatically in FIGS. For the sake of clarity, FIGS. 2 to 7 show only the construction of a stone base. Only the substrate on which the bed is located is shown, not the setting elements. Any steps involved may involve mechanical preparation of setting elements such as particles, if necessary. This can involve:

[0022] The method for manufacturing this component includes steps b) through e) in order. Distinct, a) a step of providing a substrate 2; step b) depositing a black layer 3 on the substrate 2, or using carbon nanotubes; In an alternative embodiment, the precursor layer 7 containing carbon nanotubes is b') depositing the film on the substrate; - step c) forming a bed 5 in or on the substrate 2; - selectively removing the black layer 3 so that at least the surface of the bed 5 is free of the black layer 3 or the precursor layer 7; step d) selectively removing the precursor layer 7 already deposited on the substrate 2; Step d') and - placing and fixing, preferably setting, the stones 4 within the bed 5, step e ) and perform.

[0023] In the first embodiment shown in Figures 2 to 5, the method for manufacturing this component is , a step a) of providing a substrate 2 (FIGS. 2 to 5); - The bed, bed 5 (Fig. 3), or the top surface of stone 4, i.e., the table and crown of the ashlar. (FIGS. 4-5), all or part of the substrate 2, including the area intended to form (FIG. 2). b) depositing a black layer 3 on the - To form bed 5 (Fig. 2), bed 5 (Fig. 3), or the top surface of stone 4 (Figs. 4-5) and step d) of selectively removing the black layer 3 from the areas intended for it.

[0024] The method further comprises a step c) of forming a bed 5 on the substrate 2; Step e) of placing and fixing the stone 4. This fixing is called setting and bonding. This includes other fixation techniques such as

[0025] In an alternative embodiment shown in FIG. 2, the black layer 3 is applied to the substrate before forming the bed 5. The black layer 3 is then removed during the formation of the bed 5. Steps c) and d) are one and the same step. Finally, step e) is performed.

[0026] In an alternative embodiment shown in FIG. 3, after step c) of forming the bed 5: The black layer 3 is deposited on the substrate 2. The black layer 3 is then removed from the bed 5. can be done mechanically, in particular manually using a setting tool In a preferred embodiment, this selective removal is achieved by laser ablation, preferably Preferably, this is done using a pulsed laser such as a nanosecond, picosecond or femtosecond laser. Finally, perform step e).

[0027] In an alternative embodiment shown in FIG. 4, the black layer 3 is applied to a substrate 2 already decorated with stones 4. The black layer 3 on the stone 4 may then be removed mechanically, but preferably by , and then remove it by laser ablation using a pulsed laser as in the previous case. This alternative embodiment of FIG. 4 is preferred because after the black layer has been selectively removed, 3 in which the substrate must be set after the selective removal step. This is because, unlike shapes, there is no need to process the surfaces.

[0028] In an alternative embodiment shown in FIG. 5, the substrate 2 is decorated with stones 4 according to step e). The method then further comprises an additional step f) of applying a mask 8 to the stone 4. The mask 8 can be a lacquer, an adhesive, a photosensitive film, etc. , for example, photolithography, stereolithography, digital printing, or adhesives In the case of a film, it can be deposited manually. Then, in step b), the black layer 3 is deposited on the substrate 2, including on the mask 8. Finally, in step d), the mask 8 The black layer 3 is selectively removed in the areas where there is a mask by laser ablation. Alternatively, the adhesive layer may be removed manually or mechanically, for example by using a special tool. (not shown), a mask can be placed within the bed prior to placing the stone. As in, before the stones are placed, a black layer is deposited and selectively removed.

[0029] In a second embodiment shown in FIG. 6, step b) is carried out on a substrate including on the surface of the bed 5. is replaced by step b') of depositing a precursor layer 7 on the substrate 2. Step b') comprises: A precursor layer is deposited and annealed to polymerize the precursor. The morphology is applied to the carbon nanotube-based black layer. The precursor is a mixture of polymer and carbon nanotube. The carbon nanotubes are contained in the polymer. The proportion of carbon nanotubes is 0.1 to 15% by weight. The polymer content is 85 to 99.9% by weight. polyethylene, polyimide, polypropylene, polystyrene, polyvinyl acetate and polymethacrylate Thermoplastics such as methyl acrylate, or thermoplastics such as polyepoxides and polyurethanes The curable material can be selected from the group consisting of polymers and carbon nanotubes. To improve this, the carbon nanotubes can be pre-functionalized. In the case of an imide matrix, carbon nanotubes can be oxidized in an acidic medium, e.g., nitric acid. It can be pre-functionalized by etching into a polyimide matrix. The precursor containing the mixture of distributed carbon nanotubes is deposited at 150-350 °C. Polymerization occurs at this temperature for 1 to 7 hours.

[0030] Then, a step d) of selectively removing the precursor layer 7 deposited in the bed 5 is carried out. This selective removal is preferably accomplished by laser ablation, but may be accomplished by any suitable method. This can also be done manually using a tool. After this, stones 4 are placed within the bed 5 of the substrate 2. Finally, in step f), the precursor layer 7 is subjected to chemical treatment. Chemical or laser etching is performed to remove the carbon nanotubes in the precursor layer. The black layer 3 is formed by exposing the surface of the polymer matrix. Depending on the case, an acidic medium (e.g., formic acid, acetic acid, sulfuric acid, nitric acid, hydrochloric acid or hydrofluoric acid) or a suitable This etching step can be carried out in a suitable solvent (e.g., m-cresol). The polymer matrix of the precursor layer is partially dissolved, roughening the surface and thus forming carbon The nanotubes are rich in nanostructures, exposing a fine structure suitable for trapping light. Laser etching using a laser (e.g., a femtosecond or picosecond laser) can also be used. It can be considered to create a surface microstructure such as

[0031] Alternatively (not shown), step b') can be performed before step c) of forming the bed. Thus, steps c) and d') are performed by forming a bed and extracting the precursor from the bed. Alternatively (not shown), the precursor layer can be selectively removed in a single concomitant step. , depositing the stone on the substrate, thus selectively removing the precursor on the stone. This can be done.

[0032] In a third embodiment shown in FIG. 7, the method further comprises: Addition of a material grown on a substrate 2 to form a support 11 intended to receive a stone 4 Thus, the method includes: a) a step of providing a substrate 2; - step b) depositing a black layer 3 on the substrate 2; - simultaneously with step d) of selectively removing the black layer 3, a material is deposited on the coated substrate 2; h) growing a silicon dioxide film to form a support 11; - placing and fixing the stones 4 within the bed 5 provided in the support 11 on the substrate 2; Step e) and step e) are carried out sequentially.

[0033] The material depositing step h) may be performed by digital printing, electroforming, selective laser melting, or any other suitable method. By additive manufacturing, like other additive methods, the material can be metallic, ceramic or polymeric. During this step, the black layer 3 is automatically removed from the support 11. The part of the substrate 2 facing the stone 4 to be set is therefore selectively removed. There is no black layer 3.

[0034] The bed 5 can be created directly during the growth step h) or at a later stage. It can be formed before step e).

[0035] All embodiments feature setting elements that blend in unobtrusively with the dial background. However, the present invention provides a method for selectively removing the black layer from the bed. This does not exclude that removal also includes removal from setting elements.

[0036] Finally, the present invention further comprises a first component and a second component. Regarding the assembly, each of these components is connected to the internal parts of the timepiece or movement. According to the present invention, the first and second The component includes at least one portion coated with a black layer. One component can move relative to the second component, and the second component This first component is attached to face one or more stone components. For example, the first component is a needle coated with a black layer, A hand decorated with a stone set or cemented to the tip of the hand, with a second component The main component is the dial, which is covered with a black layer. [Explanation of symbols]

[0037] 1 Front panel 2 Base material 3 Black layer 4 stones 4a Pavilion 5 beds 6 Setting Elements 7. Precursor Layer 8. Mask 11 Support

Claims

1. 1. A method for manufacturing an internal component or movement of a timepiece or a component intended for a piece of jewelry, comprising the steps of: The component comprises a substrate (2) at least partially coated with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided on the substrate (2), The black layer (3) contains carbon nanotubes, The substrate (2) is free of the black layer (3) at least on the surface of the bed (5), The method comprises: Step a) of preparing the substrate (2) is carried out; Then, in no particular order: a step b') of depositing and annealing a precursor layer (7) comprising carbon nanotubes on the substrate (2); Step c) of forming the bed (5) in the substrate (2); and step e) placing and fixing the stones (4) within the bed (5) of the substrate (2), The method further comprises: an additional step d') of selectively removing said precursor layer (7) so that at least said face of said bed is free of said precursor layer (7); and step f) chemically or laser-etching the precursor layer (7) to form the black layer (3) on the substrate (2). A method characterized by:

2. Step a) of providing the substrate (2); Step c) of forming the bed (5) in the substrate (2); a step b') of depositing and annealing the precursor layer (7) comprising carbon nanotubes on the substrate (2), including on the surface of the bed (5); a step d') of selectively removing the precursor layer (7) deposited on the surface of the bed (5); step e) placing and fixing the stones (4) within the bed (5) of the substrate (2); and step f) chemically or laser-etching the precursor layer (7) to form the black layer (3) on the substrate (2).

2. The method of claim 1 .

3. Step a) of providing the substrate (2); a step b') of depositing and annealing a precursor layer (7) on said substrate (2); Step c) forming said bed (5) on said substrate (2), thereby selectively removing said precursor layer (7) from said bed (5); step e) placing and fixing the stones (4) within the bed (5) of the substrate (2); and step f) chemically or laser-etching the precursor layer (7) to form the black layer (3) on the substrate (2).

2. The method of claim 1 .

4. Step a) of providing the substrate (2); Step c) of forming the bed (5) in the substrate (2); step e) placing and fixing the stones (4) within the bed (5) of the substrate (2); a step b') of depositing and annealing a precursor layer (7) on the substrate (2), including on the side free of said stones (4); a step d') of selectively removing the precursor layer (7) deposited on the surface free of the stones (4); and step f) of chemically or laser-etching the precursor layer (7) to form the black layer (3) on the substrate (2).

2. The method of claim 1 .

5. The precursor layer (7) comprises a polymer and carbon nanotubes.

5. The method according to claim 1, wherein the method comprises:

6. The proportion of carbon nanotubes is 0.1 to 15% by weight, and the proportion of polymer is 85 to 99.9% by weight.

6. The method of claim 5.

7. The polymer is selected from the group consisting of polyamide, polybutene, polyethylene, polyimide, polypropylene, polystyrene, polyvinyl acetate, polymethyl methacrylate, polyepoxide and polyurethane.

6. The method of claim 5.

8. The precursor layer (7) has a thickness of 10 to 200 μm, or 100 to 200 μm.

2. The method of claim 1 .

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