Timepiece component with functional layer

Abstract

The invention relates to a timepiece component (1) formed of a substrate (10) that is at least partially covered by a coating (20) comprising at least one functional layer (20A) which is deposited by the MLD method and made of an organic material in order to improve the durability of said coating (20).

Description

WATCHMAKING COMPONENT WITH FUNCTIONAL LAYER TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to a method of depositing a functional layer on the body of a watch component blank and to the watch component thus obtained comprising the functional layer. TECHNICAL BACKGROUND OF THE INVENTION

[0002] In watchmaking, components are often metallized for aesthetic purposes. For example, many watch dials have a silver finish achieved by electroplating a layer of pure silver onto a substrate, or, in some cases, by using a solid silver piece. Each metallic component can be protected, for instance, by an alumina coating applied using an ALD (Atomic Layer Deposition) method. This alumina layer covers the metallic part, protecting it and potentially altering its color through interference.

[0003] However, these ALD-deposited coatings have drawbacks. They do not provide sufficient adhesion of the alumina to the metallic layer to meet the requirements of aging tests such as the "tape test," which poses a quality risk incompatible with force transmission applications. Furthermore, the adhesion of the ALD coating is also problematic with topcoats such as decorative lacquers that add depth to the color. Finally, ALD coatings are relatively rigid and brittle, making them unsuitable for watch components subjected to deformation (tension, compression, bending, etc.). Therefore, these ALD-deposited coatings cannot guarantee long-term protection.

[0004] As an example, as stated in document WO 2014 / 006229, the maximum thickness of an ALD coating on a watch balance spring must generally be limited in order to minimize the risk of cracking of the coating due to residual stresses created at the substrate-coating interface during deposition. SUMMARY OF THE INVENTION

[0005] The invention aims to provide a new watch component and a manufacturing process for this new watch component, featuring a coating with good adhesion to a wide variety of materials (positive "Scotch tape test"), flexibility capable of maintaining effective encapsulation even on a watch component subjected to deformation, and the ability to provide new functionalities while maintaining a thin-layer deposit with nanometer precision for applications including optical and decorative applications.

[0006] To this end, in a first embodiment, the invention relates to a watch component formed of a substrate which is at least partially covered by a coating, characterized in that said coating comprises at least one functional layer, deposited by MLD method, based on an organic material in order to improve the durability of said coating.

[0007] In a second embodiment, the invention relates to a watch component formed of a substrate which is at least partially covered by a coating, characterized in that said coating comprises at least one hybrid layer, deposited by hybrid MLD / ALD method, based on an organic material and an inorganic material in order to improve the durability of said coating.

[0008] The presence of cracks and leaks in a deposit can be measured by the water vapor transmission rate (sometimes abbreviated "WVTR"). The higher this rate, the more faults, breaks, or porosity the deposit has, allowing water vapor to infiltrate. The water vapor transmission rate of an alumina deposit, measured by the ALD method, is between 10 and 10 minutes. 3 and 10' 4 grrr 2 I 1 whereas a deposition of said at least one functional layer by MLD method or hybrid MLD / ALD method according to the invention made it possible to obtain a water vapor transmission rate of between 10' 5 at 10' 6 g m' 2 I 1 It is therefore understood that the watch component according to the invention for a static application already provides a clear improvement in terms of sealing.

[0009] The advantage of the watch component according to the invention is even more pronounced for applications involving deformation, such as a spring, balance spring, jumper, ratchet, or lever. Indeed, after deformation (bending, torsion, etc.), the alumina layer deposited by the ALD method being very rigid, the water vapor transmission rate increases significantly between 10 minutes. 2 and 10' 3 g m' 2 I 1 Advantageously, in such a situation, the deposition of an organic layer by the MLD method or of a hybrid layer by the hybrid MLD / ALD method according to the invention made it possible to maintain a substantially stable water vapor transmission rate, i.e. between 10' 5 at 10' 6 g nr 2 I 1 This demonstrates the advantage of the coating according to the invention, which remains more stable and more watertight even under mechanical stress.

[0010] Thus, advantageously according to the invention, the flexibility of the coating prevents the accumulation of internal stresses even in cumulative deposits of great thickness, typically greater than 100 nm, which guarantees high durability. Indeed, the risks of delamination (positive "tape test") and breakage, particularly due to internal stresses accumulated in the coating, are limited or even eliminated. The invention applies the coating to a watch component subjected to deformation, such as a spring, balance spring, jumper, ratchet, or lever. Due to the gaseous nature of the precursors used in the MLD or hybrid MLD / ALD method, advantageously according to the invention, the coating will be homogeneous and potentially cover the entire external surface of the substrate, including blind recesses. It is therefore understood that the coating according to the invention provides, in particular, effective protection against tarnishing of substrate materials such as silver, or more generally offers an effective mechanical and chemical barrier.

[0011] Furthermore, the molecules of said at least one functional layer or of said at least one hybrid layer deposited at the nanoscale can also contribute to generating colors through interference phenomena. Finally, the molecules of said at least one functional layer or of said at least one hybrid layer can be selected with respect to the intended interface (substrate and / or layer deposited below and / or layer deposited above) to form covalent bonds, for example, with a silver-based layer (Ag, layer below), a varnish, or a lacquer (layer above) in order to advantageously improve the adhesion of the coating according to the invention.

[0012] The invention may also include one or more of the following optional features, taken alone or in combination.

[0013] Organic material is defined as being composed of at least one organic and / or organometallic molecule. Such an organic material may include a chain with at least two carbon atoms to provide flexibility to the coating. Naturally, the longer the chain, the more flexible it will be. Preferably, the organic material contains between 4 and 30 carbon atoms per chain, and even more preferably between 5 and 10 carbon atoms per chain.

[0014] Of course, each chain can contain at least one heteroatom such as sulfur (S), oxygen (O), or nitrogen (N). Furthermore, each chain can contain at least one aromatic and / or aliphatic ring. Finally, each chain can be saturated or unsaturated and / or have a linear or non-linear structure (for example, three, four, or five branches allowing for the addition of chemical functionalities).

[0015] The organic material or hybrid material preferentially has at least one functional site on at least one termination (preferably one at each end) in order to provide a function of adhesion and / or compatibility with a material above and / or below, and / or modification of surface tension and / or modification of surface chemistry.

[0016] According to one example, said at least one functional site may include a polyurea, a glycine, a glucose, an alkane, an alcohol, a carboxylic acid, an organosilane, An organosilicone or a perfluorinated compound is used to form a hydrophilic, hydrophobic, and / or lipophobic coating. This coating specialization can be used, for example, as an epilaminate or to enhance tribological properties.

[0017] The coating may also include at least one mechanical layer, deposited by the ALD method, based on an inorganic material in order to improve the mechanical strength and / or optical quality of said coating. It is understood that said at least one functional layer or said at least one hybrid layer will potentially deform to limit or even prevent any deterioration of said at least one mechanical layer while maintaining the encapsulation of the substrate (sealing, adhesion, etc.) and possibly improving the adhesion of said at least one mechanical layer to the substrate (if the deposit had been made directly onto it).

[0018] The coating may comprise several functional layers and / or several hybrid layers and / or several mechanical layers. Preferably, at least one functional or hybrid layer and at least one mechanical layer are deposited alternately. However, two mechanical layers (identical or not) and / or two successive functional or hybrid layers (identical or not) may be deposited. Depending on the intended applications, the thicknesses of each layer (mechanical or functional) may be selectively chosen.

[0019] Each mechanical layer can be ceramic-based, that is to say, based on a material (crystalline and / or amorphous) based on an oxide and / or carbide and / or sulfide and / or nitride.

[0020] The watch component can form a dial, a balance spring, a wheel, or a hand. Of course, other components such as a blank, an anchor, a lever, or a cam are also possible applications without departing from the scope of the invention.

[0021] Finally, the coating may have at least two layers, i.e. functional and / or hybrid and / or mechanical, to generate at least one color by interference effect in order to decorate the watch component according to a predetermined color.

[0022] The invention also relates to a timepiece comprising a watch movement, characterized in that it includes a watch component as described above. Typically, the watch component may form all or part of the casing of the timepiece or of the movement of the timepiece.

[0023] Furthermore, according to a first embodiment, the invention relates to a method for manufacturing a watch component comprising a substrate at least partially covered by a coating, characterized in that the process comprises the following steps: a. forming the substrate of the watch component; b. depositing, by an MLD method, at least one functional layer based on at least one precursor of an organic material on the substrate in order to improve the durability of said coating.

[0024] Finally, according to a second embodiment, the invention relates to a method for manufacturing a watch component comprising a substrate at least partially covered by a coating, characterized in that the method comprises the following steps: a. forming the substrate of the watch component; b. depositing, by a hybrid MLD / ALD method, at least one hybrid layer based on at least one precursor of an organic material and at least one precursor of an inorganic material on the substrate in order to improve the durability of said coating.

[0025] Step b advantageously according to the invention allows for deposits ranging, for example, from a few angstroms (0.1 nm) to 500 nm, i.e., of small or large thickness, and with remarkably reproducible thickness homogeneity. Due to the gaseous nature of the precursors used by the MLD method, advantageously according to the invention, said at least one functional or hybrid layer is deposited potentially over the entire external surface of the substrate, including in blind recesses of small cross-section and great depth. Step b makes the resulting coating more flexible and more watertight.

[0026] Step b advantageously allows, according to the invention, the deposition of layers of said at least one functional or hybrid layer of a wide variety of materials, thus enabling adhesion to a greater variety of materials for the deposition surface. The molecules of said at least one functional or hybrid layer can therefore be selected with respect to the intended interface (substrate and / or layer deposited below and / or layer deposited above) to form covalent bonds, for example, with a silver-based layer (Ag, layer below), a varnish, or a lacquer (layer above), in order to improve, advantageously according to the invention, the adhesion of the coating.

[0027] In addition, the molecules of said precursor can be selected from other precursors injected during the process (before and / or after) to form covalent bonds in order to improve, advantageously according to the invention, the adhesion of the coating, or to a function intended for the coating to modify the surface tension or the surface chemistry of the coating.

[0028] The invention may also include one or more of the following optional features, taken alone or in combination.

[0029] Said at least one precursor of said organic material may comprise a chain with at least two carbon atoms to provide flexibility to the coating. Naturally, the longer the chain, the more flexible it will be. Preferably, the organic material comprises between 4 and 30 carbon atoms per chain, and even more preferably between 50 and 10 carbon atoms per chain.

[0030] Of course, each chain can contain at least one heteroatom such as sulfur (S), oxygen (O), or nitrogen (N). Furthermore, each chain can contain at least one aromatic and / or aliphatic ring. Finally, each chain can be saturated or unsaturated and / or have a linear or non-linear structure (for example, three, four, or five branches allowing for the addition of chemical functionalities).

[0031] Said at least one precursor of said organic material may have at least one functional site on at least one termination. This termination thus allows interaction with the substrate or on the side opposite the substrate.

[0032] According to a first example, said at least one functional site may include an amine, a thiol, a hydroxyl, an epoxide, a carboxylic acid, an acrylate, a silane or an organosilane in order to improve the adhesion of the coating to the substrate or another layer on top.

[0033] According to a second example, said at least one functional site may comprise a polyurea, glycine, glucose, alkane, alcohol, carboxylic acid, organosilane, organosilicone or perfluorinated compound in order to form an external surface of the hydrophilic, hydrophobic and / or lipophobic coating.

[0034] Said precursor of said organic material may be based on 4-aminophenol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, hydroquinone, benzenedicarboxylic acid or ethylanoamine.

[0035] The process may further include the following step: c. depositing, by ALD method, at least one mechanical layer based on a precursor of an inorganic material in order to improve the mechanical strength and / or optical quality of said coating.

[0036] It is understood that the process can perform a step b followed by a step c, or vice versa. Since the ALD, MLD, and hybrid MLD / ALD methods are compatible, the substrate does not necessarily need to be moved to a different controlled chamber. The precursor injection and purging phases can therefore be carried out consecutively in the same chamber to implement at least one step b and at least one step c.

[0037] The said precursor of the said mechanical layer may be a precursor of a ceramic-based material, that is to say, based on a (crystalline and / or amorphous) material based on an oxide, carbide, sulfide or nitride.

[0038] The process may consist of several steps b and / or several steps c. Preferably, steps b and c are alternated. However, two successive steps b (identical or not) and / or two successive steps c (identical or not) may be carried out. Depending on the intended applications, the process parameters are adapted to selectively modify the thickness and material of each layer (mechanical, hybrid, or functional). BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Other features and advantages of the invention will become clear from the following description, which is given by way of example and not limitation, with reference to the accompanying drawings, in which: Figure 1 is a schematic view of an example of a timepiece according to the invention; Figure 2 is a perspective view of an example of a watch component according to the invention; Figure 3 is a diagram describing an example of phases of a step b of the process according to a second embodiment of the invention; Figure 4 is a schematic cross-sectional view of a component in deformation with a single mechanical layer; Figure 5 is a schematic cross-sectional view of an example of a watch component in deformation with a combination of functional (or hybrid) and mechanical layers according to the invention;Figure 6 is a view of examples of successive organic coatings obtained using successive steps b of the process according to a first embodiment of the invention in a repeated cycle; Figure 7 is a diagram describing another example of organic coating material obtained using the process according to the first embodiment of the invention in a supercycle; Figure 8 is a diagram describing the example of hybrid coating material of Figure 3; Figure 9 is a diagram describing another example of hybrid coating material obtained using the process according to the second embodiment of the invention in a supercycle; Figures 10 to 15 are schematic cross-sectional views of examples of watch components according to the invention. DETAILED DESCRIPTION OF AT LEAST ONE EMBODIMENT OF THE INVENTION

[0040] In the various figures, identical or similar elements bear the same references, possibly with an additional subscript. Therefore, a description of their structure and function is not systematically repeated.

[0041] Throughout this text, orientations refer to the orientations of the figures. In particular, the terms "upper," "lower," "left," "right," "above," "below," "forward," and "backward" are generally understood in relation to the direction in which the figures are represented. The term "horizontal" is therefore understood as a direction parallel to the main section of the watch movement's mainplate, and the term "vertical" is understood as a direction perpendicular to the horizontal direction and parallel to the thickness of the watch movement's mainplate.

[0042] In all that follows, orientation terms are understood with respect to the orthogonal coordinate system shown in Figure 1, in which we distinguish: a longitudinal axis X, horizontal extending from back to front; a transverse axis Y, horizontal extending from left to right; and a vertical axis Z, extending from bottom to top.

[0043] The term "horizontal" is defined in relation to the XY plane (direction parallel to the main section of the clock movement plate 3), the terms "vertical plane" are defined in relation to a horizontal component projected along the vertical axis Z (direction perpendicular to the horizontal direction and parallel to the thickness of the clock movement plate 3).

[0044] The term "based on" refers to a material or alloy comprising at least 50% by total mass or weight of a given element, such as 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% by total mass. Of course, in the case of a material or alloy comprising at least three elements, the expression "based on a first element" means a material or alloy consisting primarily, by total mass or weight, of that first element, which may in this case be less than 50% of the total mass. In what follows, unless otherwise indicated, all percentages (%) are expressed as percentages by total mass or weight.

[0045] By "horological component 2", we mean all types of timekeeping or measuring instruments such as clocks, small clocks, watches, etc...

[0046] By "watch movement 3", we mean all types of mechanisms capable of counting time whether they are powered by mechanical energy (e.g. a barrel) or electrical energy (e.g. a battery).

[0047] The term "thin deposit" refers to a thin layer of material deposited on a receiving (target) surface with a thickness of substantially between 1 nm and 100 nm, such as a layer 20A or 20B of the coating 20, for example, implemented by step b and / or c of the process according to the invention. The thin deposit may thus comprise a deposited material thickness of 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.

[0048] Conversely, a "thick deposit" refers to a single or cumulative layer (several deposits) with a thickness greater than 100 nm. A thick deposit can thus include a thickness of deposited material equal to 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm or 1000 nm.

[0049] By "good adhesion coating," we mean a coating that withstands the adhesion tests ("tape test") of NI HS 96-50 standards using a tape previously applied to the coating (such as, for example, with 3M 600 or 3M 845 products from 3M®). In effect, the adhesion is either good because the coating remains intact during the adhesion test, or poor because the coating is partially or completely delaminated (at least part of the coating remains on the tape) during the adhesion test.

[0050] The unit "sccm" is an English abbreviation for "Standard Cubic Centimeters per Minute." It is the most common unit for measuring the mass flow rate of a gas. This unit corresponds to the flow rate of the gas injected into the vacuum chamber in cm³ 3 min' 1 under standard temperature and pressure conditions.

[0051] The term "polymer" refers to all materials formed from at least one polymer chain, sometimes called a fiber, of varying lengths, which may be of natural or synthetic origin. In the context of this invention, the term polymer may therefore refer, for example, to acrylonitrile butadiene styrene (ABS), polyamide (PA), polycarbonate (PC), cycloolefin (CO), or polymethyl methacrylate (PMMA).

[0052] By "ceramic" we mean all materials in crystalline and / or amorphous form based on an oxide, carbide, sulfide or nitride, especially metallic such as aluminium oxide (alumina, Al2O3), silicon oxide (SiO2), silicon nitride (SiSn4), aluminium nitride (Ni) or silicon carbide (SiC).

[0053] The term "oxide" refers to all materials in crystalline and / or amorphous form based on a molecule (M x O y ) including the element oxygen (O), such as a metal oxide. An oxide can therefore include aluminum oxide (alumina, Al2O3), zinc oxide (ZnO), titanium oxide (TiCh), silicon oxide (SiC2), zirconium oxide (zirconia, ZrCh), tantalum oxide (F2O3), oxide of magnesium (MgO), indium tin oxide (sometimes abbreviated ITO in English, a combination of I^Ch and SnCh) and hafnium oxide (HfCh).

[0054] The term "ALD method," short for "Atomic Layer Deposition," refers to a deposition process using atomic layers. This allows for the deposition of a thin, uniform layer on a surface (its thinness preventing any surface from existing), typically within ±1 nm. Indeed, more than the small deposition thickness itself, it is the uniformity of the thickness of the deposited layer(s) that is particularly crucial for choosing the ALD method. As the ALD method is well-known, it will not be explained further below.

[0055] The term "MLD method," short for "Molecular Layer Deposition," refers to a manufacturing process using molecular layers based on a principle derived from atomic layer deposition. This method allows for the deposition of layers of organic materials, enabling adhesion to a wider variety of materials for the deposition surface compared to atomic layer deposition (which is limited to inorganic deposition such as metals or metalloids).

[0056] MLD deposition is performed under reduced pressure or even at ambient pressure (between 1 mbar and 1 bar) in a heated or unheated chamber (between 20 °C and 500 °C, preferably below 120 °C to avoid molecular degradation) using gaseous precursors. These gaseous precursors can be introduced using a carrier gas such as an inert gas (e.g., argon (Ar) or nitrogen (N2)) in alternating sequences so that they adsorb onto the receiving surface (the target of the MLD deposition).

[0057] More specifically, the MLD method involves successively exposing a receiving surface to different chemical precursors to obtain thin layers of organic compounds. It is based on self-saturated surface reactions that occur sequentially, allowing for controlled growth. Generally, an MLD cycle includes at least two precursor injections, separated by a purging step to remove the precursor and reaction products before the introduction of the next precursor. Advantageously, MLD technology allows for the deposition of layers on a receiving surface with a very high aspect ratio, as the reaction takes place on a monolayer of precursor gases adsorbed directly onto the receiving surface.

[0058] The term "hybrid MLD / ALD method" refers to a manufacturing process that combines ALD and MLD methods, meaning it combines atomic and molecular layers. For example, it allows the successive deposition of metals (or metalloids) and organic materials (organic molecules and / or organometallic), meaning both organic and inorganic, allows for adhesion to a wider variety of materials for the deposited surface compared to atomic layer deposition (which is limited to inorganic deposits), as well as between successive deposits and even simpler functionalization of the final layer. Of course, the hybrid MLD / ALD method can form more than just two different material layers to create a "supercycle."

[0059] More specifically, the hybrid MLD / ALD method involves successively exposing a receiving surface to first chemical precursors to obtain thin layers of organic compounds and then to second chemical precursors to obtain thin layers of selected atoms, or vice versa. It is based on self-saturated surface reactions that occur sequentially, allowing for controlled growth. Generally, a cycle of the hybrid MLD / ALD method comprises at least two injections of two different precursors, separated by a purging step to remove the precursor and any excess reaction products before the introduction of the other precursor. Advantageously, the hybrid MLD / ALD method enables the deposition of layers onto a highly technical receiving surface.

[0060] Component 1 was developed for use in watchmaking. Thus, watch component 1 can form all or part of a watch case 1A (example shown in Figure 1), such as all or part of a dial or flange, a display such as a hand or disc, a case, a bracelet, a crystal, or a control such as a crown or pusher. Watch component 1 can also form all or part of a watch movement 3, such as all or part of an escapement such as a Swiss lever mechanism, a resonator such as a balance spring mechanism, a power source such as a mainspring barrel, an automatic winding system, or a battery, a gear train such as a wheel or toothed wheel 1B (example shown in Figure 2), a spring, a screw, a bridge, or a mainplate.

[0061] According to the invention, the watch component 1 is formed of a substrate 10 which is at least partially covered by a coating 20. As shown in Figure 4, it is known to deposit a thick layer C of alumina onto a substrate S using the ALD method. However, it has been observed that this layer C deposited by the ALD method has drawbacks. Thus, the adhesion of the alumina layer C to a metallic substrate S fails the "tape test," a phenomenon that is even more pronounced for precious metals such as silver or gold. Furthermore, such a layer is very rigid, making it extremely brittle to the point of being unsuitable for substrate S used in deformation (see Figure 4, breakage B of layer C). Such a layer C deposited by the ALD method does not ultimately guarantee durable protection of the substrate S over time.

[0062] Thus, advantageously, the coating 20 according to the invention comprises at least one functional layer 20A, deposited by MLD method, based on an organic material in order to improve the durability of the coating 20 according to a first embodiment visible in the example of Figure 10. Alternatively, the coating 20 according to the invention comprises at least one hybrid layer 20C, deposited by hybrid MLD / ALD method, based on an organic material and an inorganic material in order to improve the durability of the coating 20 according to a second embodiment visible in the example of Figure 11.

[0063] Advantageously according to the invention, said at least one functional layer 20A or hybrid layer 20C based on said organic material provides flexibility to the coating 20 which avoids the accumulation of internal stresses even in cumulative deposits of great thickness, i.e. typically greater than 100 nm, which guarantees high durability of the coating 20.

[0064] Indeed, the risks of delamination (positive "tape test") and breakage, particularly due to internal stresses accumulated in the coating, are limited or even eliminated by the invention, even on a watch component 1 used under deformation. Due to the gaseous nature of the precursors used by the MLD method or hybrid MLD / ALD method, advantageously according to the invention, the coating 20 will be homogeneous over potentially the entire external surface of the substrate 10, including in blind recesses that are difficult to access. It is therefore understood that the coating 20 according to the invention provides, in particular, effective protection against tarnishing of the substrate materials 10, such as silver, or more generally offers an effective mechanical and chemical barrier.

[0065] Furthermore, the molecules of said at least one functional 20A or hybrid 20C layer deposited at the nanoscale can also contribute to generating colors through interference phenomena. Finally, the molecules of said at least one functional 20A or hybrid 20C layer can be selected with respect to the intended interface (substrate 10 and / or 20A, 20B, 20C layer deposited before and / or 20A, 20B, 20C layer deposited on top) to form covalent bonds, for example, with a silver (Ag)-based layer, a varnish, or a lacquer in order to advantageously improve, according to the invention, the adhesion of the coating 20.

[0066] For example, for the adhesion of acrylic varnishes and lacquers to a 20B mechanical coating, the following molecules can be used: TRIAP (N-(3-trimethoxysilylpropyl) diethylenetriamine; CAS: 35141-30-1) MEA (2-aminoethanol; CAS 141-43-5) TMSAPMA (3-(trimethoxysilyl)propyl methacrylate; CAS: 2530-85-0) H EMA (hydroxyethylmethacrylate; CAS: 868-77-9) MPTS ((3-mercaptopropyl)trimethoxysilane; CAS: 4420-74-0) GLYMO (3-glycidyloxypropyl)trimethoxysilane; CAS: 2530-83-8) (3-acryloxypropyl)trimethoxysilane, 96% (CAS: 4369-14-6).

[0067] Finally, the watch component 1 according to the invention offers a significant improvement in terms of water resistance compared to a prior art alumina layer C. The presence of cracks (or breaks B) in a coating and a lack of water resistance can be measured by the water vapor transmission rate (sometimes abbreviated "WVTR"). The higher this rate, the more cracks, breaks B, or porosity the coating has, allowing water vapor to penetrate.

[0068] The water vapor transmission rate of an alumina C layer by the ALD method is between 10' 3 and 10' 4 g nr 2 -j' 1 whereas a deposition of said at least one functional 20A or hybrid 20C layer based on an organic material by MLD method or hybrid MLD / ALD method according to the invention made it possible to obtain a water vapor transmission rate of between 10' 5 at 10' 6 g m' 2 j 1 It is therefore understood that the watch component 1 according to the invention for a static application already provides a clear improvement in terms of sealing.

[0069] The advantage of watch component 1 according to the invention is even more pronounced for applications involving deformation, such as a spring, balance spring, jumper, ratchet, or lever. Indeed, after deformation (bending, torsion, compression, etc.), the alumina layer C deposited by the ALD method being very rigid, the water vapor transmission rate increases between 10' 2 and 10' 3 g m' 2 I 1 Advantageously, in such a situation, deposition of said at least one functional 20A or hybrid 20C layer based on an organic material by MLD method or hybrid MLD / ALD method according to the invention made it possible to maintain a substantially stable water vapor transmission rate, i.e. substantially between 10' 5 at 10' 6 g m' 2 I 1 This demonstrates the advantage of coating 20 according to the invention, which remains more stable and more watertight under mechanical stress.

[0070] The organic material of said at least one functional 20A or hybrid 20C layer shall be understood as being composed of at least one organic and / or organometallic molecule. Such an organic material may include a chain with at least two carbon atoms to provide flexibility to the coating 20. Naturally, the longer the chain, the more flexible it will be. Preferably, the organic material comprises between 4 and 30 carbon atoms per chain, and even more preferably between 5 and 100 carbon atoms per chain. Naturally, each Each chain may contain at least one heteroatom such as sulfur (S), oxygen (O), or nitrogen (N). Furthermore, each chain may contain at least one aromatic and / or aliphatic ring. Finally, each chain may be saturated or unsaturated and / or have a linear or non-linear structure (e.g., three, four, or five hips allowing for the addition of chemical functionalities).

[0071] The said hybrid material can, for example, be based on alucone (AC, as seen in figures 3 and 8), titanicone, zincone, hafnicone, mangancone, vanadicone.

[0072] The organic material of said at least one functional 20A or hybrid 20C layer may include at least one functional site on at least one termination in order to provide an adhesion and / or compatibility function with a material above and / or below, and / or surface tension modification and / or surface chemistry modification.

[0073] As an example, at least one functional site may contain a polyurea, glycine, glucose, alkane, alcohol, carboxylic acid, organosilane, organosilicone, or perfluorinated compound to form a hydrophilic, hydrophobic, and / or lipophobic coating. This coating specialization can, for example, be used as an epilaminate or to enhance tribological properties.

[0074] Advantageously, according to the invention, the coating 20 may further comprise at least one mechanical layer 20B, deposited by the ALD method, based on an inorganic material in order to improve the mechanical strength and / or optical quality of said coating. It is understood that said at least one functional layer 20A or hybrid layer 20C will deform to limit or even prevent any deterioration of said at least one mechanical layer 20B while maintaining the encapsulation of the substrate 10 (sealing, adhesion, etc.) and possibly improving the adhesion of said at least one mechanical layer 20B to the substrate 10, that is, as if said at least one mechanical layer 20B had been deposited directly onto the substrate 10.

[0075] The said at least one 20B mechanical layer may be ceramic-based, that is to say, based on a material (crystalline and / or amorphous) based on an oxide and / or carbide and / or sulfide and / or nitride such as aluminium oxide (alumina, Al2O3), silicon oxide (SiCh), silicon nitride (SiSn^), aluminium nitride (NiAn) or silicon carbide (SiC).

[0076] In the examples illustrated in Figures 5 and 12 to 15, the coating 20 comprises several functional 20A or hybrid 20C layers and / or several mechanical 20B layers. Preferably, said at least one functional 20A or hybrid 20C layer and said at least one mechanical 20B layer are deposited alternately. However, two mechanical 20B layers (identical or not) and / or two 20A layers Functional or hybrid 20C layers (identical or not) can be deposited one on top of the other. Depending on the intended applications, the thickness of each layer (mechanical 20B, hybrid 20C, or functional 20A) can be selectively chosen.

[0077] Furthermore, the watch component 1 may include an outer layer 30 and / or an inner layer 40 in addition to the coating 20. The outer layer 30 may be selected to form covalent bonds, for example, with a varnish or lacquer in order to advantageously improve the adhesion of the coating 20 according to the invention. The layer 30 may include a functional layer 30A, a mechanical layer 30B, or a hybrid layer 30C. The inner layer 40 may be selected to form covalent bonds, for example, with a silver (Ag)-based substrate 10 in order to advantageously improve the adhesion of the coating 20 according to the invention. The layer 40 may include a functional layer 40A, a mechanical layer 40B, or a hybrid layer 40C.

[0078] Thus, according to a first embodiment, the manufacturing process according to the invention comprises the following steps: a. forming the substrate 10 of the watch component 1; b. depositing, by an MLD method, at least one functional layer 20A based on at least one precursor of an organic material on the substrate 10 in order to improve the durability of said coating 20.

[0079] According to a second embodiment, the manufacturing process according to the invention comprises the following steps: a. forming the substrate 10 of the watch component 1; b. depositing, by a hybrid MLD / ALD method, at least one hybrid layer 20C based on at least one precursor of an organic material and at least one precursor of an inorganic material on the substrate 10 in order to improve the durability of said coating 20.

[0080] The step can be carried out from a usual manufacture of a watch component 1 such as a dial, a watch case, a balance spring or toothed wheel 1 B. Advantageously according to the invention, the substrate material 10 can thus be indifferently polymer-based such as a polyamide (PA), a polycarbonate (PC), a metal such as silver (Ag), nickel (Ni, NiZn, NiAu), niobium (NbZr, NbTi) or gold (Au), or a metalloid such as silicon (Si) or germanium (Ge).

[0081] Step b advantageously according to the invention allows the deposition of said at least one functional 20A or hybrid 20C layer with a thickness, for example, between a few angstroms (0.1 nm) and 500 nm, i.e., of small or large thickness, and with remarkably reproducible thickness homogeneity. This is achieved through the gaseous nature of the precursors used by the MLD method or hybrid method. MLD / ALD, advantageously according to the invention, said at least one functional layer 20A or hybrid layer 20C is deposited possibly over the entire external surface of the substrate 10, including in blind recesses of small cross-section and great depth. Step b makes the resulting coating 20 more flexible and more watertight.

[0082] Step b advantageously allows, according to the invention, the deposition of layers of said at least one functional layer 20A or hybrid layer 20C of a wide variety of materials, thus enabling adhesion to a greater variety of materials for the deposition surface (substrate 10, said at least one functional layer 20A, said at least one hybrid layer 20C, or said at least one mechanical layer 20B). Thus, the molecules of said at least one functional layer 20A or hybrid layer 20C can be selected with respect to the intended interface (substrate 10 and / or layer 20A, 20B, 20C deposited beforehand and / or layer 20A, 20B, 20C deposited on top) to form covalent bonds, for example, with a silver (Ag)-based substrate 10, a varnish, or a lacquer, in order to advantageously improve, according to the invention, the adhesion of the coating 20.

[0083] In addition, the molecules of said precursor can be selected from other precursors injected during the process (before and / or after) to form covalent bonds in order to improve, advantageously according to the invention, the adhesion of the coating 20 (inner layer 40), or to a function (outer layer 30) intended for the coating 20 to modify the surface tension or the surface chemistry of the coating 20.

[0084] In the example illustrated in Figure 6, forming a repeated cycle, a deposition by the MLD method can be carried out using the following sequence which can be repeated (with the same precursors or not) according to the desired thickness (for example from a few Angstroms to 500 nm) of the deposit (of course, if a repetition is carried out, there is no longer a need for an initialization phase): - initialization (figure 6-I): setting up the enclosure (pressure, temperature, purging with an inert gas, etc.) in order to have a controlled, non-reactive atmosphere with the products that will be used during the process; - First injection: Introduction of a first precursor in the form of an organic-type gas (for example, terephthalic acid (TPA, CeH^CChH^)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This first precursor will be absorbed onto the surface and adhere by forming bonds with residual groups (for example: amine or hydroxyl). - first purge (figure 6-II): Once the surface is saturated with the first precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - second injection: Introduction of the second precursor in gaseous form of organic type (for example paraphenylenediamine (PPDA, CeH^N^)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This second precursor will be absorbed onto the surface and adhere by forming bonds with the sites of the first precursor; - second purge (figure 6-III): Once the surface is saturated with the second precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s. - Third injection: Introduction of a third precursor in the form of an organic-type gas (e.g., terephthalic acid (TPA, CeH₂CChH₂)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This third precursor will be absorbed onto the surface and adhere by forming bonds with the sites of the second precursor. - third purge (figure 6-IV): Once the surface is saturated with the third precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - Fourth injection: Introduction of a fourth precursor in the form of an organic-type gas (e.g., paraphenylenediamine (PPDA, CeH^N^)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This fourth precursor will be absorbed onto the surface and adhere by forming bonds with the sites of the third precursor. - fourth purge (figure 6-V): Once the surface is saturated with the fourth precursor, the enclosure must be purged with an inert gas (e.g. argon (Ar) or nitrogen (N2)) for 1 to 360 s.

[0085] This first example in Figure 6 allows us to obtain a coating 20 by a purely organic functional layer 20A based on polyazomethine.

[0086] In the example illustrated in Figure 7 forming a supercycle, a deposition by the MLD method can be carried out using the following sequence which can be repeated (with the same precursors or not) according to the desired thickness (for example from a few Angstroms to 500 nm) of the deposit (of course, if a repetition is carried out, there is no longer a need for an initialization phase): - Initialization: setting up the enclosure (pressure, temperature, purging with an inert gas, etc.) in order to have a controlled, non-reactive atmosphere with the products that will be used during the process; - First injection: Introduction of a first precursor in the form of an organic-type gas (for example, pyromellitic dianhydride (PDMA, CeH2(C2O3)2)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This first precursor will be absorbed onto the surface and adhere by forming bonds with residual groups (for example: amine or hydroxyl). - first purge: Once the surface is saturated with the first precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - second injection: Introduction of the second precursor in gaseous form of organic type (for example 4,4'-diaminodiphenyl ether (DDE, C12H12N2O)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This second precursor will be absorbed onto the surface and adhere by forming bonds with the sites of the first precursor; - second purge: Once the surface is saturated with the second precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s. - Third injection: Introduction of a third precursor in the form of an organic-type gas (e.g., terephthaloyl chloride (TPC, C8H4CI2O2)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This third precursor will be absorbed onto the surface and adhere by forming bonds with the sites of the second precursor. - third purge: Once the surface is saturated with the third precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s;

[0087] This second example in Figure 7 allows obtaining a coating 20 by a purely organic functional layer 20A based on polyimide (PI) and polyamide (PA).

[0088] In the example illustrated in figures 3 and 8, a hybrid MLD / ALD deposition can be carried out using the following sequence which can be repeated (with the same precursors or not) depending on the desired thickness (for example from a few Angstroms to 500 nm) of the deposit (of course, if a repetition is carried out, there is no longer a need for an initialization phase): - Initialization: setting up the enclosure (pressure, temperature, purging with an inert gas, etc.) in order to have a controlled, non-reactive atmosphere with the products that will be used during the process; - First injection: Introduction of a first precursor in the form of a metallic-type gas (e.g., trimethylaluminium (TMA, Ah(CH3)6)) for 0.1 to 60 s (second) at flow rates ranging from 1 to 1000 sccm. This first precursor will be absorbed onto the surface and adhere by forming metallic bonds with residual groups (for example: amine or hydroxyl). - first purge: Once the surface is saturated with the first precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - second injection: Introduction of the second precursor in gaseous form of an organic type (for example ethylene glycol (EG, C2H6O)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This second precursor will be absorbed onto the surface and adhere by forming bonds with the metallic sites of the first precursor; - second purge: Once the surface is saturated with the second precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s.

[0089] This third example allows us to obtain a 20 coating based on alucone (AC-1) as seen in figures 3 and 8.

[0090] In the example illustrated in Figure 9 forming a supercycle, a hybrid MLD / ALD deposition can be carried out using the following sequence which can be repeated (with the same precursors or not) according to the desired thickness (for example from a few Angstroms to 500 nm) of the deposit (of course, if a repetition is carried out, there is no longer a need for an initialization phase): - Initialization: setting up the enclosure (pressure, temperature, purging with an inert gas, etc.) in order to have a controlled, non-reactive atmosphere with the products that will be used during the process; - First injection: Introduction of a first precursor in the form of a metallic gas (e.g., trimethylaluminium (TMA, Ah(CH3)6)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This first precursor will be absorbed onto the surface and adhere by forming metallic bonds with residual groups (e.g., amine or hydroxyl). - first purge: Once the surface is saturated with the first precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - second injection: Introduction of the second precursor in gaseous form of an organic type (for example ethanolamine (EA, C2H7NO)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This second precursor will be absorbed onto the surface and adhere by forming bonds with the metallic sites of the first precursor; - second purge: Once the surface is saturated with the second precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s. - third injection: Introduction of the second precursor in gaseous form of an organic type (for example maleic anhydrous (MA, C2H2(CO)2O)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This third precursor will be absorbed onto the surface and adhere by forming bonds with the second precursor; - third purge: Once the surface is saturated with the third precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s.

[0091] This fourth example allows obtaining a coating 20 based on alucone (AC-2) as seen in figure 9 with a longer chain than the third example (AC-1) of figures 3 and 8.

[0092] According to one variant, before the first injection, the receiving surface (substrate 10 and / or deposited layer 20A, 20B, 20C) can also be pre-treated with promoters capable of grafting between the receiving surface and the deposit by the MLD method or by a hybrid MLD / ALD method to confer better adhesion via covalent bonds. The promoters can, for example, be based on ethylene glycol (EG), paraphenylenediamine (PPD), polyimide (PI), or polyazomethine (PAM).

[0093] Each precursor of said organic material may include a chain with at least two carbon atoms to provide flexibility to the coating, reduce internal stress, or promote crystal orientation. Naturally, the longer the chain, the more flexible it will be. Preferably, the organic material comprises between 4 and 30 carbon atoms per chain, and even more preferably between 5 and 10 carbon atoms per chain. The carbon chain of said at least one functional 20A or hybrid 20C layer may also contain aromatic rings or carbon-carbon double bonds to further reduce flexibility.

[0094] Of course, each chain can contain at least one heteroatom such as sulfur (S), oxygen (O), or nitrogen (N). Furthermore, each chain can contain at least one aromatic and / or aliphatic ring. Finally, each chain can be saturated or unsaturated and / or have a linear or non-linear structure (for example, three, four, or five branches allowing for the addition of chemical functionalities).

[0095] Said at least one precursor of said organic material may have at least one functional site on at least one termination. This termination allows interaction with the substrate 10 or on the opposite side of the substrate 10. Thus, the functional sites may have different functions depending on the termination chosen. Some terminations may To improve chemical adsorption with metals, lacquers, varnishes, or oxides. The precursor can be homofunctional or heterofunctional, bipodal or tripodal. If the precursor has only one reactive active site, this improves its preferential orientation. Thiols and amines form strong bonds with precious metals such as gold and silver, and organosilanes form strong bonds with metal oxides.

[0096] According to a first example, said at least one functional site may include an amine, a thiol, an amine, an acrylate, a silane or an organosilane in order to improve the adhesion of the coating 20 to the substrate 10 or another layer 20A, 20B above and / or below.

[0097] According to a second example, said at least one functional site may comprise a polyurea, glycine, glucose, alkane, alcohol, carboxylic acid, organosilane, organosilicone or perfluorinated compound in order to form an external surface of the coating 20 hydrophilic, hydrophobic and / or lipophobic.

[0098] Said precursor of said organic material may be based on 4-aminophenol (AP), 1,4-butanediol (BDO), 1,6-hexanediol (HDO), ethylene glycol (EG), hydroquinone (HQ), benzene-1,4-dicarboxylic acid (BDC) or ethylanoamine (EA).

[0099] It is also possible to complete the injection sequence using an organic precursor with at least one termination compatible with a precursor from step c and with interesting physicochemical properties depending on the specific characteristics of watch component 1. The deposition of this precursor ensures good adhesion to at least one mechanical layer 20B and exhibits hydrophilic, hydrophobic, or epilame-like characteristics, depending on the molecular examples mentioned above. These structures can also improve the surface tribological properties, notably by decreasing the abrasiveness coefficient to reduce wear and increase lubrication.

[0100] Organosilanes form strong bonds with metal oxides; aliphatic chains, polar chains, and fluorinated chains confer hydrophobic, hydrophilic, and epilame properties, respectively. This significantly improves their physicochemical properties.

[0101] The process may therefore further include the following step: c. depositing, by ALD method, at least one mechanical layer based on a precursor of an inorganic material in order to improve the mechanical strength and / or optical quality of said coating.

[0102] It is understood that the process can perform a step b followed by a step c, or vice versa. Since the ALD and MLD methods are compatible, the substrate does not necessarily need to be moved between controlled chambers. The injection phases of precursors and purge can therefore follow one another in the same enclosure to implement at least one step b and at least one step c.

[0103] The said precursor of the said mechanical layer may be ceramic-based, that is to say, based on a material (crystalline and / or amorphous) based on an oxide, carbide, sulfide or nitride.

[0104] The process may consist of several steps b and / or several steps c. Preferably, steps b and c are alternated. However, two successive steps b (identical or not) and / or two successive steps c (identical or not) may be carried out. Depending on the intended applications, the process parameters are adapted to selectively modify the thickness and material of each layer (mechanical or functional).

[0105] An example of the sequence of the process according to the invention with steps b and c combined is shown below: - Initialization: setting up the enclosure (pressure, temperature, purging with an inert gas, etc.) in order to have a controlled, non-reactive atmosphere with the products that will be used during the process; - first injection: Introduction of a first precursor in the form of a metallic gas (for example trimethylaluminium (TMA, A^CHsJe) or titanium tetrachloride (TiCU)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This first precursor will be absorbed onto the surface and adhere by forming metallic bonds with residual groups (for example: amine or hydroxyl); - first purge: Once the surface is saturated with the first precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - second injection: Introduction of the second precursor in the form of an inorganic gas (for example: water (H2O)) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This second precursor will adsorb onto the surface and adhere by forming bonds with the metallic sites of the first precursor; - second purge: Once the surface is saturated with the second precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 5 to 360 s; - third injection: Introduction of a third precursor in the form of a metallic gas (for example trimethylaluminium (TMA, Ah(CH3)6) or titanium tetrachloride (TiCU)) for 0.1 to 60 s (seconds) at flow rates ranging from 1 to 1000 sccm. This third precursor will be absorbed onto the surface and adhere by forming metallic bonds with residual groups (for example: amine or hydroxyl); - third purge: Once the surface is saturated with the third precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s; - fourth injection: Introduction of the fourth precursor in gaseous form of an organic type (for example ethylene glycol (EG, C2H6O2) or hydroquinone (HQ, CeH4(OH)2) for 0.1 to 60 s at flow rates ranging from 1 to 1000 sccm. This fourth precursor will be absorbed onto the surface and adhere by forming bonds with the metallic sites of the third precursor; - fourth purge: Once the surface is saturated with the fourth precursor, the enclosure must be purged with an inert gas (for example argon (Ar) or nitrogen (N2)) for 1 to 360 s.

[0106] The cyclic process can then be repeated to increase thickness and form deposits ranging from a few angstroms (0.1 nm) to 500 nm. The cycles can have multiple heads.

[0107] The ratio between step b and step c allows the properties of the coating 20 to be modified. The ratio between step b and step c can, for example, allow thicknesses on the total deposit thickness according to, for example, ratios 2:1, 10:1, 100:1, 1:1, 1:2, 1:100, etc.

[0108] Alternating stages b and c showed resistance to bending work with radii of curvature ranging from 1 to 10 cm without propagating cracks large enough to compromise the sealing of the coating 20.

[0109] The invention is not limited to the embodiments and variations presented, and other embodiments and variations will be readily apparent to those skilled in the art. Thus, the embodiments above are examples. Although the description refers to one or more embodiments, this does not necessarily mean that each reference relates to the same embodiment, or that the features apply only to a single embodiment. Simple features of different embodiments can also be combined and / or interchanged to provide other embodiments. By way of no limitation, other coating variations 20, for example, combining two variations shown in Figures 6 to 11, can be considered without departing from the scope of the invention.

[0110] In addition, the coating comprises at least two layers, i.e. functional 20A and / or hybrid 20C and / or mechanical 20B, to generate at least one color by interference effect in order to decorate according to a predetermined color the watch component 1.

[0111] Finally, the invention is not limited to a timepiece. Thus, the invention could also be applied in other fields such as, for example, the jewelry, fine jewelry, leather goods, tableware, optical instruments, firearms or writing instruments. LIST OF REFERENCES 1 - watch component 1 A - Watch case component 1 B - watch movement component 2 - timepiece 3 - clockwork movement 10 - substrate 20 - coating 20A - functional layer 20B - mechanical layer 20C - hybrid layer 30 - outer layer 30A - functional layer 30B - mechanical layer 30C - hybrid layer 40 - inner layer 40A - functional layer 40B - mechanical layer 40C - hybrid layer B - break C - alumina layer S - substrate

Claims

1. DEMANDS 1. Watch component (1) formed of a substrate (10) which is at least partially covered by a coating (20), characterized in that said coating comprises at least one functional layer (20A), deposited by MLD method, based on an organic material in order to improve the durability of said coating (20).

2. Watch component (1) formed of a substrate (10) which is at least partially covered by a coating (20), characterized in that said coating comprises at least one hybrid layer (20C), deposited by a hybrid MLD / ALD method, based on an organic material and an inorganic material in order to improve the durability of said coating (20).

3. Watch component (1) according to claim 1 or 2, wherein the organic material comprises a chain with at least two carbon atoms in order to provide flexibility to the coating (20).

4. Watch component (1) according to any one of the preceding claims, wherein the organic material comprises at least one functional site on at least one termination.

5. Watch component (1) according to the preceding claim, wherein said at least one functional site comprises a polyurea, a glycine, a glucose, an alkane, an alcohol, a carboxylic acid, an organosilane, an organosilicone or a perfluorinated compound in order to form a hydrophilic, hydrophobic and / or lipophobic coating (20).

6. Watch component (1) according to any one of the preceding claims, wherein the coating (20) further comprises at least one mechanical layer (20B), deposited by ALD method, based on an inorganic material in order to improve the mechanical resistance and / or optical quality of said coating (20).

7. Watch component (1) according to any one of the preceding claims, wherein each mechanical layer (20B) is ceramic-based.

8. Watch component (1) according to any one of the preceding claims, forming a dial, a spiral, a wheel or a hand.

9. Watch component (1) according to any one of the preceding claims, wherein the coating (20) comprises at least two layers (20A, 20B, 20C) to generate at least one color by interference effect.

10. Method for manufacturing a watch component (1) comprising a substrate (10) at least partially covered by a coating (20), characterized in that the method comprises the following steps: a. forming the substrate (10) of the watch component (1); b. deposit, by an MLD method, at least one functional layer (20A) based on at least one precursor of an organic material on the substrate (10) in order to improve the durability of said coating (20).

11. A method for manufacturing a watch component (1) comprising a substrate (10) at least partially covered by a coating (20), characterized in that the method comprises the following steps: a. forming the substrate (10) of the watch component (1); b. depositing, by a hybrid MLD / ALD method, at least one hybrid layer (20C) based on at least one precursor of an organic material and at least one precursor of an inorganic material on the substrate (10) in order to improve the durability of said coating (20).

12. Manufacturing method according to claim 10 or 11, wherein said at least one precursor of said organic material comprises a chain with at least two carbon atoms in order to provide flexibility to the coating (20).

13. A manufacturing method according to any one of claims 10 to 12, wherein said at least one precursor of said organic material comprises at least one functional site on at least one termination.

14. A manufacturing method according to the preceding claim, wherein said at least one functional site comprises an amine, a thiol, a hydroxyl, an epoxide, a carboxylic acid, an acrylate, a silane or an organosilane in order to improve the adhesion of the coating (20).

15. Manufacturing method according to claim 13 or 14, wherein said at least one functional site comprises a polyurea, glycine, glucose, alkane, alcohol, carboxylic acid, organosilane, organosilicone or perfluorinated compound in order to form a hydrophilic, hydrophobic and / or lipophobic coating (20).

16. A manufacturing process according to any one of claims 10 to 15, wherein said precursor of said organic material is based on 4-aminophenol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, hydroquinone, benzenedicarboxylic acid or ethylanoamine.

17. A manufacturing method according to any one of claims 10 to 16, further comprising the following step: c. depositing, by ALD method, at least one mechanical layer (20B) based on a precursor of an inorganic material in order to improve the mechanical strength and / or optical quality of said coating (20).

18. Manufacturing process according to the preceding claim, comprising several steps b and / or several steps c.

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