Manufacturing method for black components decorated with stones

Abstract

The present invention relates to an internal part or movement of a timepiece or a component of jewelry, said component comprising a substrate (2) partially coated with a black layer (3) and decorated with at least one stone (4), said black layer (3) comprising carbon nanotubes or aluminum oxide, said substrate (2) being free of said black layer (3) at least in the part facing the stone (4). The present invention further relates to a method for manufacturing this timepiece or jewelry component.

Description

[Technical field]

[0001] The present invention relates to a component intended for an internal part or movement of a timepiece or for a piece of jewellery. The invention further relates to a method for manufacturing said component. [Background technology]

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

[0003] The use of black coatings in the timepiece industry is well known. European patent document EP3327517 discloses a dial in which a first substrate facing the crystal of a watch is coated with a black nanotube layer, and a second substrate on the opposite side of the crystal is fixed to the first substrate. The first substrate is formed with an opening that serves as a window intended to form an index. The second substrate includes a luminescent coating at least in the area facing the opening, thereby generating a contrast between the black layer and the illuminated index in the first substrate.

[0004] Thus, contrast can be created by superimposing two substrates with different coatings. This superimposition allows both coatings to be selectively deposited on the same surface, eliminating the need for excessive manipulation of the particularly fragile nanotube layer. Nevertheless, this superimposition has the drawback of requiring the fabrication of two substrates, which increases the production costs.

[0005] Swiss patent document CH 711141 discloses a method for manufacturing a dial in which a decoration, i.e. the indexes, is attached to a carbon black coating. This decoration is manufactured separately from the dial and is then simply added to the dial. This greatly simplifies the manufacture of the dial. However, this manufacturing technique is not suitable for certain types of decoration, where the black color underneath the decoration would adversely affect the aesthetics and / or brilliance of the decoration.

[0006] In particular, this manufacturing technique is not well suited for decorations made with stones, especially diamonds. It is difficult to set stones on a dial covered with a black layer, which must completely surround the stone to create the desired contrast, but be interrupted at the location of the stone, otherwise the stone's brilliance will be reduced. In the manufacturing process, special care must be taken not to damage the carbon nanotube layer, which is so brittle that it is almost impossible to touch it without damaging the surface. Damaging this surface would result in the appearance of sparkling little dots or holes that would contrast with the original color of the carbon nanotubes. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a method for manufacturing a timepiece or a component of jewellery that is black coated and decorated with stones, in particular set with stones, the method being developed in such a way that the black coating is not damaged while the black layer is interrupted at the location of the stones. [Means for solving the problem]

[0008] The manufacturing method according to the invention therefore does not simply involve adding a decoration, in this case stones, to a coating, as in the prior art: according to the invention, the decoration formed by stones is made directly on the substrate from which the black layer has been selectively removed, thereby maintaining a surface free of the black layer underneath the decoration.

[0009] In particular, the invention relates to a method for manufacturing an internal component or movement of a timepiece or a component intended for a piece of jewellery, said component comprising a substrate at least partially coated with a black layer, said black layer comprising carbon nanotubes or aluminium oxide, said coated substrate being decorated with at least one stone arranged in a bed provided on said substrate, said substrate being free of said black layer, at least on the face of said bed, said method comprising a step a) of preparing said substrate, followed, in any order, by a step b) of depositing said black layer on said substrate, a step c) of forming said bed in said substrate and a step e) of positioning and fixing said stone within said bed, said method further comprising a step d) of selectively removing said black layer already deposited on said substrate, so that at least said face of said bed is free of black layer.

[0010] In another embodiment of the method applicable when the black layer comprises carbon nanotubes, step b) is replaced by a step b') of depositing a precursor layer comprising carbon nanotubes. The additional step d) is therefore replaced by an additional step d') of selectively removing the precursor layer so that at least the bed surface is free of the precursor layer. The method further comprises a step f) of chemically or laser etching the precursor layer to expose the black carbon nanotube layer.

[0011] The selective removal step d) or d') can be performed mechanically, for example with a setting tool, or preferably by laser ablation. It can also be performed indirectly during the step of forming the bed or during the step of growing the stone support on the substrate, such as with an additive manufacturing operation, in particular inkjet additive manufacturing.

[0012] The invention further relates to an internal part or movement of a timepiece or a component of a piece of jewelry, said component comprising a substrate partially covered with a black layer and decorated with at least one stone, said stone being arranged on said substrate or on a bed located on said substrate, said black layer comprising carbon nanotubes or aluminium oxide, said substrate being free of said black layer at least in the part facing said stone, i.e. on the face of the bed.

[0013] In the case of diamond decoration on a carbon nanotube coating, the invention proposes to produce a timepiece or a jewellery component containing two allotropes of carbon on its surface, one allotrope being very black thanks to the carbon nanotubes and the other allotrope being very white thanks to the diamonds, shining with a very striking contrast.

[0014] Other features and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings, in which: [Brief description of the drawings]

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

[0016] The present invention relates to an internal part or movement of a timepiece or a component intended for a piece of jewellery. This component may be selected from the group consisting of dials, hands, indexes, apexes, oscillating weights, plates and bridges, etc., which is not exhaustive. According to the invention, this component is at least partially covered with a black layer. The invention further relates to an assembly comprising two of said components, at least partially covered with a black layer.

[0017] The invention will be described below in relation to its application to a watch face 1 formed by a substrate 2 coated with a black layer 3, as shown in FIG. 1. The substrate can be made of a metallic material such as steel, titanium, aluminum, titanium or aluminum alloys, brass or other copper alloys. The substrate can also be made of ceramics, cermets, sapphire, composite materials or polymer materials. The substrate 2 is decorated and preferably set so that one or more stones 4 are distributed within the black layer 3. These stones 4 can be precious stones such as diamonds, semi-precious stones or synthetic stones such as zirconia. According to the invention, there is no black layer on the substrate, at least in the part facing the stones. The black layer can be present so as to be flush with the table of the stones. The substrate is also decorated to form an alignment of a number of stones, the substrate including a black layer between these alignments.

[0018] The substrate 2 has a bed 5, shown in FIG. 2, which serves as a seat for the stone 4, in particular the pavilion 4a of the stone 4. The stone 4 is fixed within the seat by setting, preferably by means of a setting element 6, shown in an enlarged view in FIG. 1. This setting element 6 can be a setting prong arranged within the bed, a grain forming a constituent part of the substrate, or a baguette or an undercut in the bed for an invisible setting. According to the invention, in order to make the setting invisible to the user, the setting element is preferably covered with a black layer. This setting is visually unnoticeable, blending in with the black background of the dial. Instead, the invention does not prevent the stone from being glued within the seat with a glue that does not deteriorate the brilliance of the stone.

[0019] In another embodiment of the invention, the black layer comprises carbon nanotubes. The carbon nanotube layer comprises at least 1% by weight, preferably at least 10% by weight, of carbon nanotubes. The carbon nanotube layer can be a varnish comprising at least 1% by weight, preferably at least 10% by weight, of carbon nanotubes. The higher the percentage, the darker the dark areas. The carbon nanotubes are randomly distributed within the varnish. The varnish can be deposited by spraying or the like. Alternatively, the carbon nanotube layer comprises at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight of carbon nanotubes aligned perpendicular to the plane of the substrate, with the remainder comprising other forms of carbon. Preferably, the carbon nanotube layer comprises 100% by weight of carbon nanotubes aligned perpendicular to the plane of the substrate. Such perpendicular alignment of the nanotubes produces a deeper black color than a varnish with random orientation of the carbon nanotubes, but has the drawback of having a lower mechanical strength than a varnish. To solve this problem, a protective layer can be deposited on the black layer, but this reduces the light absorption coefficient. This protective layer can be a varnish or an Al 2 O 3 , TiO 2 or SiO 2 The carbon nanotube layer can be a thin layer of a material such as , or a laminate of one or more of these materials deposited by ALD (Atomic Layer Deposition). The vertically aligned nanotubes are deposited by vacuum methods such as PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition) or laser ablation synthesis. The carbon nanotube layer has a thickness of 1-100 μm.

[0020] In another alternative embodiment, the black layer comprises Al 2 O 3 Aluminum oxide such as Al x O y and further comprising a non-ferrous metal oxide such as an oxide of copper, zinc or manganese. x O yat least 90%, preferably 100%. The aluminum content of said aluminum oxide is 45-65% by weight, preferably 45-50% by weight. This layer has a thickness of 1-50 μm, preferably 2-10 μm, more preferably 4-7 μm. This layer can be deposited by PVD, CVD or PECVD (plasma enhanced chemical vapor deposition).

[0021] The components according to the invention can be manufactured according to several embodiments of the method, which are shown diagrammatically in figures 2 to 7. For the sake of clarity, in figures 2 to 7 only the substrate with the bed for the stone seat is shown, but no setting elements are shown. Any step involving the formation of the bed can, if necessary, be accompanied by the mechanical preparation of setting elements such as particles.

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

[0023] In the first embodiment shown in FIGS. 2 to 5, the method for producing this component comprises: a) a step of preparing a substrate 2 (FIGS. 2 to 5); - step b) of depositing a black layer 3 on all or part of the substrate 2, including the area (FIG. 2) intended to form the bed, the bed 5 (FIG. 3) or the upper surface of the stone 4, i.e. the table and crown of the ashlar (FIGS. 4-5), - a step d) of selectively removing the black layer 3 from the areas intended to form the bed 5 (Figure 2), the bed 5 (Figure 3) or the upper surface of the stone 4 (Figures 4-5).

[0024] The method further comprises the step c) of forming a bed 5 in the substrate 2 and the step e) of placing and fixing the stones 4 on the substrate 2. This fixing may include setting and other fixing techniques such as cementing.

[0025] In an alternative embodiment shown in figure 2, a black layer 3 is deposited on the substrate 2 before forming the bed 5. Then, the black layer 3 is removed during the formation of the bed 5. That is to say, steps c) and d) are one and the same step. Finally, step e) is performed.

[0026] In an alternative embodiment shown in Figure 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. This removal can be done mechanically, in particular manually, using a setting tool. In a preferred embodiment, this selective removal is done by laser ablation, preferably using a pulsed laser such as a nanosecond, picosecond or femtosecond laser. Finally, step e) is performed.

[0027] In the alternative embodiment shown in Fig. 4, the black layer 3 is deposited on a substrate 2 already decorated with stones 4. The black layer 3 on the stones 4 is then removed, which may be mechanically removed, but preferably 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, no surface treatment is required, unlike the alternative embodiment of Fig. 3, where the substrate still has to be set after the selective removal step.

[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 stones 4. The mask 8 can be a lacquer, an adhesive, a photosensitive film, etc. The mask 8 can be deposited, for example, by photolithography, stereolithography, digital printing, or manually in the case of an adhesive or film. Then, in step b), a black layer 3 is deposited on the substrate 2, including on the mask 8. Finally, in step d), the black layer 3 is selectively removed in the areas where the mask 8 is present. The mask can be removed by laser ablation or mechanically, for example manually with a dedicated tool. Alternatively (not shown), the mask can be placed within the bed before placing the stones. Thus, the black layer is deposited and selectively removed before placing the stones.

[0029] In a second embodiment, shown in FIG. 6, step b) is replaced by step b') of depositing a precursor layer 7 on the substrate 2, including on the surface of the bed 5. Step b') consists of depositing a precursor layer and annealing to polymerize the precursor. This alternative embodiment applies to carbon nanotube-based black layers. The precursor comprises a polymer and carbon nanotubes. The proportion of carbon nanotubes is between 0.1 and 15% by weight and the proportion of polymer is between 85 and 99.9% by weight. The polymer can be chosen from thermoplastics such as polyamides, polybutenes, polyethylenes, polyimides, polypropylenes, polystyrenes, polyvinyl acetates and polymethylmethacrylates, or thermosetting materials such as polyepoxides and polyurethanes. To improve the adhesion between the polymer and the carbon nanotubes, the carbon nanotubes can be pre-functionalized. For example, in the case of a polyimide matrix, the carbon nanotubes can be pre-functionalized by etching in an acidic medium, for example nitric acid. A precursor containing a mixture of carbon nanotubes distributed in a polyimide matrix is ​​deposited and polymerized at temperatures between 150 and 350°C for 1 to 7 hours.

[0030] Then, a step d) of selectively removing the precursor layer 7 deposited in the bed 5 is performed. This selective removal is preferably performed by laser ablation, but can also be performed manually with a suitable tool. This is followed by a step e) of placing and fixing the stone 4 within the bed 5 of the substrate 2. Finally, in step f), the precursor layer 7 is chemically or laser-etched to expose the carbon nanotubes therein and form the black layer 3. Depending on the nature of the polymer matrix, chemical etching can be performed in an acidic medium (for example, formic acid, acetic acid, sulfuric acid, nitric acid, hydrochloric acid or hydrofluoric acid) or in a suitable solvent (for example, m-cresol). This etching step partially dissolves the polymer matrix of the precursor layer, roughening the surface and thus exposing a microstructure rich in carbon nanotubes and suitable for trapping light. Laser etching using a pulsed laser (for example, femtosecond or picosecond laser) can also be considered to create such surface microstructures.

[0031] Alternatively (not shown), step b') can be performed before step c) of forming the bed, so that steps c) and d') are a single concomitant step of forming the bed and selectively removing the precursor layer from the bed. Alternatively (not shown), the precursor layer can be deposited on a substrate on which the stone is set, so that selective removal of the precursor can be performed on the stone.

[0032] In a third embodiment, shown in figure 7, the method further comprises an additional step h) of growing a material on the substrate 2 covered with the black layer to form a support 11 intended to receive the stone 4. The method thus comprises: a) a step of providing a substrate 2; - a step b) of depositing a black layer 3 on the substrate 2; a step h) of growing a material on the coated substrate 2 to form a support 11, which step d) is carried out simultaneously with the step of selectively removing the black layer 3; - step e) of placing and fixing the stones 4 within a bed 5 provided in a support 11 on the substrate 2.

[0033] Said material growth step h) is carried out by additive manufacturing such as digital printing, electroforming, selective laser melting or any other additive method. The material can be a metallic, ceramic or polymeric material. During this step, the black layer 3 is automatically selectively removed from the support 11 so that the part of the substrate 2 facing the stone 4 to be set is free of the black layer 3.

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

[0035] All embodiments show the setting elements being covered with a black layer so as to blend in and be unobtrusive with the dial background, but the invention does not exclude that selective removal of the black layer from the bed also includes removal from the setting elements.

[0036] Finally, the invention also relates to an assembly comprising a first component and a second component, each of which is intended for an internal part or movement of a timepiece or for a piece of jewellery. According to the invention, the first and second components comprise at least one part coated with a black layer. Preferably, the first component is movable relative to the second component and is mounted facing the second component. This first component is decorated with one or more stones. For example, the first component is a hand coated with a black layer and decorated with a stone set or bonded to the tip of the hand, and the second component is a dial coated 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 part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); and d) selectively removing said black layer (3) already deposited on said substrate (2) so that at least the surface of said bed (5) is free of said black layer (3), Step a) of providing the substrate (2); b) depositing said black layer (3) on said substrate (2); step d) of selectively removing said black layer (3) from said bed (5) made in step c) of forming said bed (5) on said substrate (2), wherein step c) and step d) are one and the same step; and step e) of placing and fixing the stones (4) within the bed (5) of the substrate (2). A method comprising:

2. 1. A method for manufacturing an internal part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); and d) selectively removing said black layer (3) already deposited on said substrate (2) so that at least the surface of said bed (5) is free of said black layer (3), Step a) of providing the substrate (2); c) forming said bed (5) in said substrate (2); b) depositing said black layer (3) on said substrate (2); d) selectively removing said black layer (3) from the surface of said bed (5); and step e) of placing and fixing the stones (4) within the bed (5) of the substrate (2). A method comprising:

3. 1. A method for manufacturing an internal part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); The method further comprises a step d) of selectively removing the black layer (3) already deposited on the substrate (2) so that at least the surface of the bed (5) is free of the black layer (3), Step a) of providing the substrate (2); c) forming said bed (5) in said substrate (2); e) placing and fixing the stones (4) within the bed (5) of the substrate (2); b) depositing said black layer (3) on said substrate (2) including on the surface free of said stones (4); and step d) selectively removing the black layer (3) deposited on the surface free of the stones (4). A method comprising:

4. 1. A method for manufacturing an internal part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); d) selectively removing said black layer (3) already deposited on said substrate (2) so that at least the surface of said bed (5) is free of said black layer (3); and f) placing a mask (8) on said face free of stones (4), Step a) of providing the substrate (2); c) forming said bed (5) in said substrate (2); e) placing and fixing the stones (4) within the bed (5) of the substrate (2); f) placing a mask (8) on said face free of stones (4); b) depositing said black layer (3) on said substrate (2) including on said mask (8); and step d) selectively removing said black layer (3) by removing said mask (8). A method comprising:

5. 1. A method for manufacturing an internal part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); d) selectively removing said black layer (3) already deposited on said substrate (2) so that at least the surface of said bed (5) is free of said black layer (3); f) placing a mask (8) on the surface of said bed (5); Including, Step a) of providing the substrate (2); c) forming said bed (5) in said substrate (2); f) placing a mask (8) on the surface of said bed (5); b) depositing said black layer (3) on said substrate (2) including on said mask (8); d) selectively removing said black layer (3) by removing said mask (8); and step e) of placing and fixing the stones (4) within the bed (5) of the substrate (2). A method comprising:

6. 1. A method for manufacturing an internal part or movement of a timepiece or a component intended for a piece of jewellery, comprising the steps of: The component comprises a substrate (2) at least partially covered with a black layer (3) and decorated with at least one stone (4) arranged in a bed (5) provided in or on the substrate (2), The black layer (3) contains carbon nanotubes or aluminum oxide, 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 providing the substrate (2); b) depositing a black layer (3) on said substrate (2); c) forming the bed (5) in or on the substrate (2); e) placing and fixing said stone (4) within the confines of said bed (5); d) selectively removing said black layer (3) already deposited on said substrate (2) so that at least the surface of said bed (5) is free of said black layer (3); a material growth step h) of growing a material on said substrate (2) to form a support (11), whereby a step d) of selectively removing said black layer (3) from said support (11) on said substrate (2) is performed; Including, Step a) of providing the substrate (2); b) depositing said black layer (3) on said substrate (2); a material growth step h) of growing a material on said substrate (2) to form a support (11), whereby a step d) of selectively removing said black layer (3) from said support (11) on said substrate (2) is performed; and step e) of placing and fixing the stones (4) on the substrate (2) within the bed (5) provided on the support (11). A method comprising:

7. The material depositing step h) is performed by additive manufacturing, electroforming, or selective laser melting.

7. The method of claim 6.

8. Step d) is carried out mechanically or by laser ablation.

8. The method according to any one of claims 1 to 7.

9. The stone (4) is fixed in place by a setting.

9. The method according to any one of claims 1 to 8.

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