JP2008150660A - Method for manufacturing ornament, ornament and timepiece - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture ornaments excellent in durability and aesthetic appearance having stereoscopic feeling by a method causing little environmental load by repeatedly using, especially, a mask for forming a coating in the manufacture of many dial plates for timepieces, and to provide a method for manufacturing the ornaments, the ornaments and timepieces with the ornaments. <P>SOLUTION: The method for manufacturing the ornament 1 includes the steps of: preparing a substrate 12 having a projecting part 121 on at least one surface; forming an oxide film 13 on the surface side provided with the projecting part 121 of the substrate 12; forming a metal film 14 by performing vapor-phase film deposition on the surface side provided with the projecting part 121 (surface side formed with the oxide film 13) of the substrate 12 in a state that a mask 21 having an opening part 2 provided at a part corresponding to the projecting part 121; and removing the mask 2. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a decorative article, a decorative article, and a watch.

In general, a timepiece dial uses characters and numerals (so-called time characters, etc.), scales, symbols, and various marks having functions such as indicating time.
Printing is widely used as a method for forming such an index.
By the way, the timepiece dial is required to have a function as a practical product (for example, a function that allows a user or the like to recognize the time easily and accurately) and an aesthetic appearance as a decorative product.

For this reason, a method of forming an index having a more three-dimensional feeling than printing by attaching and fixing a planting material referred to as a typesetting has been adopted particularly in high-class watches and the like (for example, patent documents) 1).
However, in a timepiece dial manufactured by attaching and fixing a planting material, when a relatively large external force (impact force) or the like is applied, the planting material may be detached from the dial body (substrate). there were. Moreover, the planting material used in such a method generally has a foot part for planting the dial body, but the foot part is thinner than other parts. . For this reason, when a comparatively large external force or the like is applied, there is a problem that the foot part breaks. The above problems tend to occur more easily as the height of the planting material is higher.

Japanese Patent Laid-Open No. 2003-247096

  An object of the present invention is to provide a decorative article having excellent durability and a three-dimensional appearance and an excellent aesthetic appearance, providing a manufacturing method capable of manufacturing the decorative article, and including the decorative article. Is to provide a watch.

Such an object is achieved by the present invention described below.
The method for manufacturing a decorative article of the present invention includes a substrate preparation step of preparing a substrate having a convex portion on at least one surface,
A film is formed on the convex portion by performing vapor phase film formation in a state where a mask having an opening is provided in a portion corresponding to the convex portion on the surface side of the substrate on which the convex portion is provided. A film forming step of forming
And a mask removing process for removing the mask.
Thereby, the manufacturing method which can manufacture the decorative goods excellent in durability and excellent in the three-dimensional aesthetic appearance can be provided.

In the method for manufacturing a decorative article of the present invention, the height of the convex portion is preferably 100 to 500 μm.
Thereby, the aesthetic appearance of the decorative article can be made particularly excellent while the durability of the decorative article is sufficiently excellent.
In the method for producing a decorative article of the present invention, the average thickness of the coating is preferably 0.005 to 2.5 μm.
Thereby, the aesthetic appearance of the decorative article can be made particularly excellent while the durability of the decorative article is sufficiently excellent.

In the decorative article manufacturing method of the present invention, the opening has a cross-sectional area increasing portion in which a cross-sectional area increases from a surface facing the substrate of the mask toward a surface on the opposite side. preferable.
Thereby, the durability and aesthetic appearance of the decorative article can be made particularly excellent.
In the method for manufacturing a decorative article of the present invention, the film forming step uses a material including a magnetic material as the mask, and is disposed on the surface of the substrate opposite to the surface facing the mask. It is preferable that the step is performed in a state where the mask and the work on which the film is to be formed are brought into close contact with each other by a magnet.
Thereby, it can prevent more reliably that it forms into a film | membrane in parts other than the objective on a board | substrate, and can make the aesthetic appearance of the ornament finally obtained more excellent.

In the method for producing a decorative article of the present invention, in the coating film forming step, the vapor phase composition composed of the constituent material of the coating film from a direction inclined by a predetermined angle θ with respect to the normal direction of the main surface of the substrate. It is preferable that the film particles are incident on the substrate.
Thereby, the film of a more suitable shape can be formed easily and reliably, and the aesthetic appearance of the resulting decorative article can be made particularly excellent.

In the method for manufacturing a decorative article of the present invention, the vapor-phase film-forming particles are preferably incident from a plurality of directions.
Thereby, the film of a more suitable shape can be formed easily and reliably, and the aesthetic appearance of the resulting decorative article can be made particularly excellent. In addition, it is possible to suppress variations in texture when the ornament is viewed from various directions.

In the method for manufacturing a decorative article of the present invention, it is preferable that the incident direction of the vapor-phase film-forming particles is changed with time.
Thereby, the film of a more suitable shape can be formed reliably and the aesthetic appearance of the resulting decorative article can be made particularly excellent. In addition, it is possible to suppress variations in texture when the ornament is viewed from various directions.

In the method for manufacturing a decorative article of the present invention, the incident direction of the vapor-phase film-forming particles is changed so that the incident direction of the vapor-phase film-forming particles rotates about the normal line of the main surface of the substrate. Is preferred.
Thereby, the aesthetic appearance of the obtained decorative article can be further improved. In addition, it is possible to more effectively suppress the variation in texture when the ornament is viewed from various directions.

In the method for manufacturing a decorative article of the present invention, the angle θ is preferably 1 to 50 °.
Thereby, the aesthetic appearance of the obtained decorative article can be made particularly excellent while sufficiently improving the productivity of the decorative article.
In the method for manufacturing a decorative article of the present invention, it is preferable that at least the outer surface of the coating is mainly composed of a metal material.
Thereby, the aesthetic appearance as a decorative article can be made especially excellent.

In the method for manufacturing a decorative article of the present invention, an oxide film forming step of forming an oxide film mainly composed of a metal oxide on the substrate;
It is preferable to have a metal film forming step of forming a metal film mainly composed of a metal material on the oxide film.
Thereby, the adhesiveness of a board | substrate and a film can be made more excellent, As a result, durability and reliability of a decorative article can be made especially excellent.

In the decorative article manufacturing method of the present invention, the decorative article is preferably a watch dial.
The timepiece dial is required to have an excellent aesthetic appearance, among other various decorative items having indices, and also to have practicality such as making the user recognize the time easily and accurately. According to this, since a three-dimensional index can be suitably formed, it is preferable not only from the viewpoint of improving the aesthetic appearance but also from the viewpoint of improving practicality. Therefore, the effect by this invention is notably exhibited when applied to the timepiece dial.

The decorative article of the present invention is manufactured using the method of the present invention.
Thereby, it is excellent in durability and can provide the ornament which was excellent in the aesthetic appearance with a three-dimensional effect.
The timepiece of the present invention is characterized by including the decorative article of the present invention.
Thereby, it is possible to provide a timepiece having a decorative article having excellent durability and a three-dimensional appearance and an excellent aesthetic appearance.

  According to the present invention, it is possible to provide a decorative product having excellent durability and a three-dimensional appearance, and having an excellent aesthetic appearance, providing a manufacturing method capable of manufacturing the decorative product, and including the decorative product. Watch can be provided. In particular, by repeatedly using a mask for film formation in the production of a large number of timepiece dials, it is possible to produce decorative items that are superior in durability and have a three-dimensional appearance with a low environmental impact. can do.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
In the present invention, the decorative article may be any article (member) that is required to have a decorative property. However, in the following description, the case where the decorative article is a timepiece dial is representatively shown. explain.
<First Embodiment>
First, a first embodiment of a decorative article and a method for manufacturing a decorative article according to the present invention will be described.

1 is a schematic cross-sectional view showing a decorative article according to the first embodiment of the present invention, FIG. 2 is a schematic cross-sectional view showing a method for manufacturing the decorative article according to the first embodiment of the present invention, and FIG. FIG. 5 is a diagram for explaining the traveling direction of vapor-phase film-forming particles when forming a metal film (film). Note that the drawings referred to in this specification show part of the configuration in an emphasized manner, and do not accurately reflect actual dimensions and the like.
As shown in FIG. 1, the ornament (clockface dial) 1 of this embodiment includes a substrate 12, an oxide film 13, and a metal film (coating) 14 having a function of reflecting light. Yes.

[substrate]
The substrate 12 may be composed of any material, but is preferably composed of plastic materials such as various thermoplastic resins and various thermosetting resins. The plastic material is generally excellent in moldability (freedom of molding), and can be suitably applied to the production of the decorative article 1 having various shapes. Further, if the substrate 12 is made of a plastic material, it is advantageous for reducing the manufacturing cost of the decorative article 1. Further, since plastic materials are generally excellent in electromagnetic wave permeability, if the substrate 12 is made of a plastic material, the decorative article 1 can be a solar watch (a watch equipped with solar cells), a radio wave watch, It can be suitably applied to a solar radio timepiece or the like. In the following description, an example in which the substrate 12 is made of a plastic material will be mainly described.

  Examples of the plastic material constituting the substrate 12 include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, and polyvinylidene chloride. , Polystyrene, polyamide (eg, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly -(4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin) Butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. Polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, fragrance Polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin , Polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, melamine resins , Unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, poly-dichloro-xylylene para-xylylene), poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene and other polyparaxylylene resins, etc. Copolymer, blend, polymer alloy, etc., one or more of these Combination (e.g., blend resin, polymer alloy, as a laminate, etc.) may be used. The substrate 12 is preferably composed of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin) among the above materials. . Thereby, the intensity | strength as the decoration 1 whole can be made especially excellent. In addition, since the degree of freedom in forming the substrate 12 is increased during manufacture of the decorative article 1 (the ease of forming is improved), even the decorative article 1 having a more complicated shape can be easily and reliably manufactured. can do. Further, when the substrate 12 is made of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin), the adhesion between the substrate 12 and the coating ( In particular, the adhesion with the metal film (coating film) 14 via the oxide film 13 can be made particularly excellent. Polycarbonate is relatively inexpensive among various plastic materials, and can contribute to further reduction in the production cost of the decorative article 1. The ABS resin also has particularly excellent chemical resistance, and the durability of the decorative article 1 as a whole can be further improved.

In addition, the board | substrate 12 may contain components other than a plastic material. Examples of such components include plasticizers, antioxidants, colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, fillers, and the like.
Further, the substrate 12 may be formed of a material that does not include a plastic material, for example, as long as at least a portion near the surface (a portion where an oxide film 13 described later is formed) is mainly formed of a plastic material. It may have a different part.

  In addition, the substrate 12 may have a substantially uniform composition at each site, or may have a different composition depending on the site. For example, the substrate 12 may have a base and a surface layer provided on the base. When the substrate 12 has such a configuration, at least a portion near the surface (a portion where an oxide film 13 described later is formed) is mainly composed of a plastic material as described above. Good.

Moreover, the board | substrate 12 makes a substantially plate shape as a whole, and has the convex part 121 in the at least one surface (main surface). The convex portion 121 has a shape and a size corresponding to the index 15 such as letters / numbers (so-called time letters), scales, symbols, and various marks on the timepiece dial (decoration) 1.
Although the height of the convex part 121 is not specifically limited, It is preferable that it is 100-500 micrometers, It is more preferable that it is 200-350 micrometers, It is further more preferable that it is 220-330 micrometers. When the height of the convex portion 121 is a value within the above range, the aesthetic appearance of the decorative article 1 can be made particularly excellent while the durability of the decorative article 1 is sufficiently excellent.

The shape and size of the substrate 12 are not particularly limited, and are usually determined based on the shape and size of the decorative article 1. Moreover, the board | substrate 1 is not limited to what makes flat form, For example, what makes curved board shape may be sufficient.
The substrate 12 may be formed by any method, and examples of the method for forming the substrate 12 include compression molding, extrusion molding, injection molding, and stereolithography.

[Oxide film]
An oxide film 13 is provided on the surface of the substrate 12. Thus, in this embodiment, the metal film (film) 14 is not directly provided on the surface of the substrate 12 mainly made of a plastic material, and the oxide film 13 is formed between the substrate 12 and the metal film 14. Intervene. This improves the adhesion between the substrate 12 and the metal film 14 (adhesion through the oxide film 13), particularly the adhesion of the metal film 14 formed by vapor deposition as described later. It is possible to effectively prevent the metal film (coating) 14 from floating or peeling off (peeling). As a result, the decorative article 1 is excellent in durability. Moreover, since the decorative article 1 has the metal film 14, it has an excellent aesthetic appearance.

The oxide film 13 is mainly composed of a metal oxide.
As the metal oxide constituting the oxide film 13, oxides of various metals can be used, preferably Fe, Cu, Zn, Ni, Mg, Cr, Mn, Mo, Nb, Al, V, Zr. , Sn, Au, Pd, Pt, Ag, Co, In, W, Ti, and Rh oxides (including complex oxides). When the oxide film 13 is made of a material containing at least one selected from titanium oxide (including composite oxide) and chromium oxide (including composite oxide), the substrate 12 and the metal film 14 are formed. It is possible to make the adhesiveness to be more excellent.

  The average thickness of the oxide film 13 is not particularly limited, but is preferably 0.005 to 1.0 μm, more preferably 0.007 to 0.5 μm, and 0.01 to 0.00. More preferably, it is 3 μm. When the average thickness of the oxide film 13 is within the above range, the aesthetic appearance of the decorative article 1 as a whole can be made particularly excellent, and the internal stress of the oxide film 13 is increased. Adhesion between the substrate 12 and the metal film 14 can be made particularly excellent while sufficiently preventing. On the other hand, when the average thickness of the oxide film 13 is less than the lower limit, the adhesion between the substrate 12 and the metal film 14 may be increased depending on the constituent material of the oxide film 13, the substrate 12, and the metal film 14. There is a possibility that the function to be improved is not fully exhibited. Further, when the average thickness of the oxide film 13 is less than the lower limit value, depending on the formation method of the oxide film 13 or the like, pinholes are easily generated in the oxide film 13, and the oxide film 13 is provided. The effect may not be fully demonstrated. Moreover, when the average thickness of the oxide film 13 exceeds the upper limit, the variation in film thickness at each portion of the oxide film 13 tends to increase. Further, when the average thickness of the oxide film 13 is particularly large, the internal stress of the oxide film 13 becomes high, and cracks and the like are likely to occur.

The average thickness of the oxide film 13 is preferably smaller than the average thickness of the metal film 14 described later. Thereby, while making the adhesiveness of the board | substrate 12 and the metal film (coating film) 14 excellent enough, the aesthetic appearance of the ornament 1 can be made especially excellent. In particular, when the average thickness of the oxide film 13 is T ₁ [μm] and the average thickness of the metal film 14 is T ₂ [μm], the relationship of 0.005 ≦ T ₂ −T ₁ ≦ 1.5 is satisfied. It is preferable that the relationship is satisfied, 0.007 ≦ T ₂ −T ₁ ≦ 1.0 is more preferable, and 0.01 ≦ T ₂ −T ₁ ≦ 0.5 is further satisfied. preferable. By satisfying such a relationship, the above-described effects can be exhibited more significantly.

  Further, the oxide film 13 may or may not have a uniform composition at each part. For example, the oxide film 13 may be one in which the contained component (composition) changes sequentially in the thickness direction (gradient material). The oxide film 13 may be a stacked body having a plurality of layers. Thereby, for example, the adhesion between the substrate 12 and the metal film 14 can be further improved. More specifically, the layer on the side of the laminate that contacts the substrate 12 is made of a material having excellent adhesion to the substrate 12, and the layer on the side of the laminate that contacts the metal film 14 is the metal film 14. By using a material having excellent adhesion, the adhesion between the substrate 12 and the metal film 14 can be further improved. Moreover, when the oxide film 13 is a laminated body, you may have the layer comprised with the material which does not contain a metal oxide substantially, for example. More specifically, the oxide film 13 may have a configuration in which a layer made of a plastic material or the like is interposed between two layers made of a metal oxide.

[Metal film (film)]
A metal film (coating) 14 is provided so as to cover the convex portion 121 of the substrate 12. In particular, in the present embodiment, the metal film (coating film) 14 is provided on the surface of the oxide film 13 (the surface opposite to the surface in contact with the substrate 12) at a portion covering the convex portion 121 of the substrate 12. It has been.
Thus, in the decorative article (timepiece dial) 1, the metal film (coating) 14 is provided on the convex portion 121, thereby forming the index 15.

As described above, since the metal film 14 is provided on the convex portion 121 of the substrate 12, the index 15 has an excellent stereoscopic effect. Further, since the metal film 14 is formed by a method that will be described in detail later, the metal film 14 is reliably provided at a target portion, and the metal film 14 is not provided at an unintended portion.
The metal film 14 is mainly composed of a metal material. The metal material constituting the metal film 14 generally has a metallic luster and has a function of reflecting light (visible light). Therefore, the metal film 14 functions as a reflective film that reflects light (visible light).

  Various metals (including alloys) can be used as the metal material constituting the metal film 14, and preferably Fe, Cu, Zn, Ni, Mg, Cr, Mn, Mo, Nb, Al, V, Zr. Sn, Au, Pd, Pt, Ag, Co, In, W, Ti, Rh, and alloys containing at least one of these. The metal film 14 is composed of a material (including an alloy) including at least one selected from Ag, Cr, Au, Al, Ti, Sn, and In, among the materials described above. Is preferred. As a result, the adhesion between the metal film 14 and the oxide film 13 can be made particularly excellent, and the aesthetic appearance of the decorative article 1 can be made particularly excellent. In addition, the metal film 14 may contain components other than a metal material.

Further, the constituent material of the metal film 14 may include at least one of the elements constituting the oxide film 13. In other words, the oxide film 13 and the metal film 14 may be composed of a material containing an element common to each other at least at a site where they are in contact with each other. For example, when the oxide film 13 includes a metal oxide represented by a composition formula of MO _{n / 2} (where M represents a metal element and n represents a valence of M), the metal film 14 has M May be included. Thereby, the adhesion between the oxide film 13 and the metal film 14 is further improved.

  The surface of the metal film 14 (the surface opposite to the surface facing the substrate 12) is preferably substantially flat (smooth), that is, a mirror surface. Thereby, the aesthetic appearance of the decorative article 1 is particularly excellent. More specifically, the surface roughness Ra of the metal film 14 (surface roughness Ra on the surface opposite to the surface facing the substrate 12) is not particularly limited, but is 0.001 to 0.5 μm. Is preferable, and it is more preferable that it is 0.001-0.1 micrometer. As a result, the above-described effects are exhibited more significantly.

  The average thickness of the metal film (coating) 14 is not particularly limited, but is preferably 0.005 to 2.5 μm, more preferably 0.007 to 0.9 μm, and 0.01 to 0.00. More preferably, it is 5 μm. When the average thickness of the metal film 14 is within the above range, the aesthetics of the decorative article 1 can be made particularly excellent while sufficiently preventing the internal stress of the metal film 14 from increasing. . Further, the adhesion between the oxide film 13 and the metal film 14 can be made particularly excellent. Moreover, the transmittance | permeability of the electromagnetic waves (radio wave, light) as the decoration 1 whole can be made large enough. On the other hand, if the average thickness of the metal film 14 is less than the lower limit value, depending on the constituent material of the metal film 14, it becomes difficult to fully exhibit the features such as gloss and color tone of the metal film 14, It may be difficult to sufficiently enhance the aesthetics of the decorative article 1 as a whole. Further, if the average thickness of the metal film 14 is less than the lower limit value, pinholes are likely to be generated in the metal film 14 depending on the formation method of the metal film 14 and the like. Further, if the average thickness of the metal film 14 is less than the lower limit value, it is difficult to sufficiently express the three-dimensional effect of the index 15, and the aesthetic appearance as a decorative article (timepiece dial) 1 is sufficiently excellent. Can be difficult to maintain. Further, depending on the constituent materials of the metal film 14 and the oxide film 13, it may be difficult to sufficiently improve the adhesion between the oxide film 13 and the metal film 14. On the other hand, when the average thickness of the metal film 14 exceeds the upper limit, the variation in film thickness at each part of the metal film 14 tends to increase. In addition, when the average thickness of the metal film 14 is particularly large, the internal stress of the metal film 14 becomes high and cracks and the like are likely to occur. Moreover, when the average thickness of the metal film 14 exceeds the said upper limit, the transmittance | permeability of the electromagnetic wave (radio wave, light) as the decoration 1 whole shows the tendency to reduce.

  Further, the metal film 14 may or may not have a uniform composition at each part. For example, the metal film 14 may be a material (gradient material) whose content (composition) changes sequentially in the thickness direction. Further, the metal film 14 may be a stacked body having a plurality of layers. Thereby, for example, the aesthetics as the decorative article 1 can be further enhanced while the adhesion with the oxide film 13 is particularly excellent. That is, the layer on the side of the laminate that is in contact with the oxide film 13 is made of a material having excellent adhesion to the oxide film 13, and the outermost layer of the laminate (the layer farthest from the oxide film 13). ) Is made of a material having excellent aesthetics, the aesthetics as the decorative article 1 can be further enhanced while the adhesion to the oxide film 13 is particularly excellent. Moreover, when the metal film 14 is a laminated body, you may have the layer comprised with the material which does not contain a metal material substantially, for example. More specifically, the metal film 14 may have a configuration in which a layer made of a metal oxide or the like is interposed between two layers made of a metal material.

  Further, the sum of the average thickness of the oxide film 13 and the average thickness of the metal film 14 is preferably 0.01 to 2.5 μm, more preferably 0.014 to 1.5 μm, More preferably, it is 0.02-0.8 micrometer. When the sum of the average thickness of the oxide film 13 and the average thickness of the metal film 14 is a value within the above range, the substrate can be sufficiently prevented from increasing the internal stress of the oxide film 13 and the metal film 14. 12, the adhesion of the oxide film 13 and the metal film 14 can be made particularly excellent. Further, when the sum of the average thickness of the oxide film 13 and the average thickness of the metal film 14 is a value within the above range, the radio wave permeability of the decorative article 1 as a whole is improved. As a result, the decorative article 1 can be more suitably applied to the radio timepiece component.

[Decoration]
The decorative item 1 as described above may be any item as long as it has a decorative property. For example, interiors such as figurines, exterior items, jewelry items, watch cases (body, back cover, case and back cover) , One-piece cases, etc.), watch bands (including band clasps, band / bangle attachment / detachment mechanisms, etc.), watch dials, watch hands, bezels (eg, rotating bezels), crowns (eg, , Screw lock-type crown, etc.), watch parts such as buttons, cover glass, glass edges, dial rings, parting plates, packing, etc., interior parts for watches, such as movement base plates, gears, train wheel supports, rotating weights, glasses ( For example, eyeglass frames), tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings and other accessories, la Tar or its case, car wheel, sporting goods such as golf club, nameplate, panel, Shohai, various other equipment parts, including housing, etc., can be applied to various types of containers and the like. Among these, the decorative article 1 is particularly preferably applied to a timepiece dial. The timepiece dial is a part that requires a particularly excellent aesthetic appearance among various parts constituting the timepiece. In addition, the timepiece dial generally has a large number of portions that become uneven portions such as time letters among various ornaments, and thereby, the effect of improving the aesthetic appearance can be obtained efficiently. That is, the effect of the present invention can be exhibited more remarkably by applying to a timepiece dial. Further, the timepiece dial has a three-dimensional time character, so that the time display by the hands (hands) can be easily and accurately recognized. Therefore, by applying the present invention to a timepiece dial, it is possible to obtain an excellent aesthetic appearance as a decorative product and to improve the function as a practical product.

Next, the manufacturing method of the ornament 1 mentioned above is demonstrated.
FIG. 2 is a schematic cross-sectional view showing a method for manufacturing a decorative article according to the first embodiment of the present invention.
As shown in FIG. 2, the method for manufacturing a decorative article of this embodiment includes a substrate preparation step (1a) for preparing a substrate 12, and an oxide film formation step (1b) for forming an oxide film 13 on the surface of the substrate 12. ) And a mask (vapor phase deposition mask) 2 having an opening 21 provided in a portion corresponding to the convex portion 121 of the substrate 12 on the surface of the oxide film 13 (on the substrate 12). Then, a metal film forming step (film forming step) (1c, 1d) for forming the metal film 14 on the convex portion 121 by performing vapor phase film formation, and a mask removing step (1e) for removing the mask 2 are performed. Have.

[Board preparation process]
As the substrate 12, those described above can be used.
Further, the surface of the substrate 12 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it becomes possible to give a variation in the glossiness of the surface of the obtained decorative article 1, and the decorativeness of the obtained decorative article 1 can be further improved.

  Moreover, the decorative article 1 manufactured using the substrate 12 that has been subjected to such surface processing is more metal than that obtained by performing the surface processing on the oxide film 13 and the metal film 14. Glare and the like of the film 14 are suppressed, and particularly, the aesthetic appearance is excellent. Further, when the substrate 12 is mainly composed of a plastic material, the surface processing as described above can be easily performed. In addition, since the oxide film 13 and the metal film 14 are usually relatively thin, when the surface treatment is performed on the oxide film 13 and the metal film 14, the oxide film at a portion where the surface treatment is performed. 13. The metal film 14 may be completely removed, or the surrounding oxide film 13 and the metal film 14 may be peeled off. By doing so, the occurrence of such a problem can be effectively prevented.

[Oxide film forming step]
An oxide film 13 mainly composed of metal oxide is formed on the surface of the substrate 12 (1b).
As described above, the oxide film 13 has excellent adhesion with the substrate 12 and the metal film 14. By forming such an oxide film 13, the durability of the decorative article 1 as a whole can be made particularly excellent.

  The method for forming the oxide film 13 is not particularly limited. For example, wet coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., electrolytic plating, immersion plating, electroless plating, etc. Examples include plating methods, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and thermal spraying. preferable. By applying a vapor deposition method as a method for forming the oxide film 13, the oxide film 13 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 12 is reliably formed. can do. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be made particularly excellent. In addition, by applying a vapor deposition method as a method for forming the oxide film 13, even if the oxide film 13 to be formed is relatively thin, the variation in film thickness is made sufficiently small. Can do. Further, as will be described in detail later, since the metal film 14 is formed by vapor phase film formation, the vapor phase film formation method is applied as the method for forming the oxide film 13 to manufacture the decorative article 1. In the manufacturing process, the present step and the metal film forming step can be carried out continuously without once removing the substrate 12 from the vapor phase film forming apparatus. For this reason, the productivity of the decorative article 1 can be made particularly excellent. Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as the method for forming the oxide film 13, the above effects become more prominent. That is, by applying sputtering as a method of forming the oxide film 13, the oxide film 13 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 12 is more reliably formed. be able to. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be further improved. Further, by applying sputtering as a method for forming the oxide film 13, even if the oxide film 13 to be formed is relatively thin, the variation in film thickness can be made particularly small. In addition, when applying the above vapor phase film forming method, for example, by using a metal corresponding to the metal oxide constituting the oxide film 13 as a target and performing the treatment in an atmosphere containing oxygen gas, The oxide film 13 can be easily and reliably formed. In addition, the oxide film 13 may be formed by combining a plurality of different methods and conditions. Thereby, the oxide film 13 comprised by the laminated body as mentioned above can be formed suitably.

[Metal film forming step (film forming step)]
Next, a mask (vapor phase film formation mask) 2 in which an opening 21 is provided in a portion corresponding to the convex portion 121 of the substrate 12 is arranged on the surface of the oxide film 13 (on the substrate 12). Then, the metal film 14 is formed on the convex portion 121 by performing vapor deposition (1c, 1d).
In this way, by performing vapor phase film formation with the mask 2 disposed, the surface of the substrate 12 covered with the oxide film 13 is selectively applied to a portion corresponding to the opening 21 of the mask 2. The membrane 14 is covered and the index 15 is formed.

In addition, the following effects can be obtained by performing vapor phase film formation with the mask 2 disposed.
That is, compared to the conventional method using printing or the method of attaching and fixing the planting material, the three-dimensional effect of the index can be improved and the adhesion of the index to the substrate can be increased.

In addition, since the mask 2 can be repeatedly used for the production of a large number of ornaments 1, the productivity of the ornaments 1 can be improved and quality variations among the ornaments 1 can be suppressed. That is, the reliability of the quality of the decorative article 1 is improved.
Further, by preparing the mask 2 having the openings 21 of the pattern corresponding to the index 15 to be formed (inverted pattern), the index 15 of various patterns can be changed without largely changing the formation conditions of the metal film 14. It can respond suitably also to production of the ornament 1 which has. In addition, by changing the material used for vapor phase film formation (vapor phase film formation material), the processing time of vapor phase film formation, and the like, it is possible to easily manufacture a wide variety of decorative articles 1 having completely different appearances. it can. That is, it is possible to efficiently cope with multi-product production.

  As described above, the metal film 14 is formed by vapor deposition. Examples of the vapor deposition method that can be applied to the formation of the metal film 14 include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, sputtering, and ion plating. . By applying a vapor deposition method as a method of forming the metal film 14, it has a uniform film thickness (suppressing unintentional thickness variation), is homogeneous, and is in close contact with the oxide film 13. It is possible to reliably form the metal film 14 with particularly excellent properties. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be made particularly excellent. Further, by applying a vapor deposition method as a method for forming the metal film 14, even if the metal film 14 to be formed is relatively thin, the variation in film thickness can be made sufficiently small. .

  Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the metal film 14, the above effects become more prominent. That is, by applying sputtering as a method for forming the metal film 14, the metal film 14 having a uniform film thickness, uniform, and particularly excellent adhesion to the oxide film 13 is more reliably formed. be able to. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be further improved. Further, by applying sputtering as a method for forming the metal film 14, even if the metal film 14 to be formed is relatively thin, the variation in film thickness can be made particularly small.

  In the vapor phase film formation as described above, for example, the metal film 14 is easily and reliably formed by performing processing in an inert gas atmosphere such as argon gas using the metal constituting the metal film 14 as a target. Can be formed. Further, when the oxide film forming process described above is performed by a vapor deposition method, for example, the composition of the atmospheric gas in the vapor deposition apparatus (in the chamber) is replaced with an inert gas from one containing oxygen gas. Then, if necessary, by changing the target, the oxide film forming step and the metal film forming step can be continuously performed in the same apparatus (without removing the substrate 12 from the apparatus). Thereby, the adhesion of the substrate 12, the oxide film 13, and the metal film 14 is particularly excellent, and the productivity and reliability of the decorative article 1 are also improved.

The formation of the metal film 14 may be performed by combining a plurality of different methods and conditions. Thereby, the metal film 14 comprised by the laminated body as mentioned above can be formed suitably.
As described above, the metal film formation step (film formation step) is performed by vapor phase film formation, and thus the above excellent effects can be obtained. On the other hand, when the metal film (film) 14 is formed by a method other than vapor phase film formation, the above effects cannot be obtained. For example, when wet plating is performed in a state where a mask having an opening is provided, it is difficult to sufficiently reduce variation in the thickness of the formed metal film (coating film). In particular, when the thickness of the coating to be formed is relatively thin, variations in thickness at each part and minute irregularities on the coating surface become particularly remarkable, and the aesthetic appearance of the decorative article is sufficiently excellent. It cannot be assumed. In addition, when wet plating is performed, there is a possibility that the plating solution remains in the inside of the formed film or in the vicinity of the interface with the member to be coated with the film. Thus, if the plating solution remains, the durability of the decorative article is significantly reduced. Moreover, even when washing is performed after wet plating, it is difficult to completely remove the plating solution. In particular, if the coating is relatively thin as described above, the formed coating may be damaged. In addition, it is difficult to reliably remove the plating solution. In addition, when wet plating is performed, it is difficult to control the film thickness and the film becomes relatively thick, so that there is a problem that repeated use of the mask becomes difficult (the size of the opening of the mask becomes small).

  In the present embodiment, the mask 2 is a second surface that is the opposite surface (main surface) from the first surface 22 side that is the surface (main surface) facing the substrate 12 (oxide film 13). A cross-sectional area increasing portion 212 in which the cross-sectional area of the opening 21 increases toward the surface 23 side is provided. In other words, the opening 21 is formed on the second surface 23 from the first surface 22 facing the substrate 12 of the mask 2 by an inclined surface 211 inclined by a predetermined angle with respect to a direction perpendicular to the main surface of the mask 2. A cross-sectional area increasing portion 212 whose cross-sectional area increases toward the side is provided. By using such a mask 2, the metal film (coating film) 14 can be formed so as to reliably cover the entire convex portion 121. In other words, the vapor deposition material can be reliably attached to the side surface of the convex portion 121 and the like. As a result, the aesthetic appearance of the decorative article 1 can be made particularly excellent.

In the opening portion 21 (cross-sectional area increasing portion 212) of the mask 2, the cross-sectional area at the cross-sectional area minimum portion 213 that minimizes the cross-sectional area of the opening portion 21 (in the illustrated configuration, the opening portion 21 of the first surface 22 Cross-sectional area) is S ₀ ′ [μm ² ], and the cross-sectional area at the maximum cross-sectional area 214 where the cross-sectional area of the opening 21 is the maximum (in the configuration shown, the cross-sectional area of the opening 21 on the second surface 23). Is preferably S ₁ ′ [μm ² ], the relationship of 0.10 ≦ S ₀ ′ / S ₁ ′ ≦ 0.95 is preferably satisfied, and 0.15 ≦ S ₀ ′ / S ₁ ′ ≦ 0. It is more preferable to satisfy the relationship of 90, and it is even more preferable to satisfy the relationship of 0.20 ≦ S ₀ ′ / S ₁ ′ ≦ 0.85. By satisfying such a relationship, the metal film (film) 14 can be more reliably formed so as to cover the entire convex portion 121. On the other hand, if the value of S ₀ ′ / S ₁ ′ is less than the lower limit value, the effect of having the cross-sectional area increasing portion 212 as described above may not be sufficiently exhibited. Further, when the value of S ₀ ′ / S ₁ ′ is less than the lower limit value, depending on the thickness of the metal film (coating film) 14 to be formed, when removing the mask 2 in the mask removal step described later, Along with the mask 2, at least a part of the formed metal film (coating film) 14 is removed from the substrate 12 (on the oxide film 13), and the aesthetic appearance of the finally obtained decorative article 1 is deteriorated. There is a possibility. Further, depending on the constituent material of the mask 2, the stability of the shape of the mask 2 may be reduced, and the mask 2 may be deformed when the metal film 14 is formed. In addition, the durability of the mask 2 may decrease, and the tendency for the productivity of the decorative article 1 to decrease may become significant. On the other hand, when the value of S ₀ ′ / S ₁ ′ exceeds the upper limit value, the effect of having the cross-sectional area increasing portion 212 is sufficient depending on the constituent material of the mask 2, the constituent material of the metal film 14, and the like. It may be difficult to make the aesthetic appearance of the decorative article 1 sufficiently excellent.

The opening 21 has a shape and a size (a shape and a size when viewed in plan) corresponding to the index 15 (metal film (coating) 14 to be formed). It is preferable that the width is slightly larger than the width of the convex portion 121 (more precisely, the width of the convex portion 121 covered with the oxide film 13). More specifically, the difference between the width W _O [μm] of the opening 21 and the width of the convex 121 (more precisely, the width of the convex 121 covered with the oxide film 13) W _C [μm]. (W 2 _{O 3} -W _C ) is preferably 2 to 50 μm, and more preferably 5 to 30 μm. Thereby, the metal film (coating) 14 can be more reliably formed so as to cover the entire convex portion 121. In the case where the opening 21 has the cross-sectional area minimum portion 213 as in the configuration shown in the drawing, the width at the cross-sectional area minimum portion 213 is adopted as the width W _O of the opening 21.

The specific thickness of the mask 2 depends on the thickness of the metal film 14 to be formed, etc., but is preferably 30 to 200 μm, and more preferably 50 to 150 μm.
Such a mask 2 is prepared, for example, by a member on a plate and subjected to chemical processing such as etching, irradiation of energy rays such as laser light, and mechanical processing (physical processing) such as lathe processing. ) Or the like to form the opening 21.

  The mask 2 may be made of any material, and examples of the constituent material of the mask 2 include various metal materials, various ceramic materials, various plastic materials, and the like. Among these, a metal material is preferable as the constituent material of the mask 2. When the mask 2 is made of a metal material, the durability of the mask 2 can be made particularly excellent. As a result, the productivity of the decorative article 1 can be made particularly excellent, and variations in quality among a large number of the decorative articles 1 can be suppressed, and the reliability of the decorative article 1 is improved. In addition, metal materials generally have moderate elasticity, and many have high shape followability, and the substrate 12 (decoration 1 to be manufactured) is not limited to a flat plate, but a curved plate or the like. Even if it is a thing, it can apply suitably. Further, one type of mask 2 can be used in common for substrates 12 having different shapes (for example, a flat substrate 12 and a curved plate substrate 12).

  In particular, in the present embodiment, the mask 2 is made of a material including a magnetic material (a material having paramagnetism and ferromagnetism). A magnet (not shown) is disposed on the surface of the substrate 12 opposite to the surface facing the mask 2, whereby the mask 2 and the substrate as a workpiece on which the metal film 14 as the coating is to be formed. 12 (the substrate 12 covered with the oxide film 13) can be reliably adhered. As a result, it is possible to more reliably prevent the metal film 14 from being formed on a portion other than the target on the substrate 12, and to make sure the aesthetic appearance of the finally obtained decorative article 1 is excellent. be able to. That is, the reliability of the manufactured decorative article 1 can be made particularly excellent.

The magnet may be, for example, a permanent magnet or an electromagnet.
As described above, in the present embodiment, the mask 2 is composed of a material containing a magnetic material, but the mask 2 may be composed substantially of only a magnetic material, for example. However, it may contain other components.
The mask 2 may have a surface layer (not shown). Thereby, for example, the durability of the mask 2 can be made particularly excellent, and the constituent material of the metal film 14 can be effectively prevented from firmly adhering to the mask 2 during vapor deposition. be able to. Examples of the material constituting such a surface layer include fluorine resins such as polytetrafluoroethylene (PTFE), silicone resins, diamond-like carbon (DLC), and the like.

  Moreover, the mask 2 should just have the opening part 21 in the site | part corresponding to the convex part 121 of the board | substrate 12, for example, has an opening part in parts other than the site | part corresponding to the convex part 121 of the board | substrate 12. There may be. Thereby, in the finally obtained ornament 1, a pattern having a predetermined pattern or the like can be provided in a portion other than the portion where the index 15 of the substrate 121 is provided, and the aesthetic appearance of the ornament 1 is further improved. Can be.

  When this step is performed by vapor phase film formation, the vapor phase film formation is, for example, inclined by a predetermined angle θ with respect to the normal direction of the main surface of the substrate 12 (main surface to be covered with the metal film 14). From this direction, vapor deposition particles (for example, sputtering particles in the case of sputtering) made of the constituent material of the metal film 14 may be incident on the substrate 12. Thereby, the metal film (coating) 14 can be more reliably formed so as to cover the entire convex portion 121.

In such a case, the angle θ formed by the incident direction of the vapor-phase film-forming particles and the normal direction of the main surface of the substrate 12 is not particularly limited, but is preferably 1 to 50 °, preferably 3 to 40 °. More preferably, it is 5 to 30 °. When the angle θ is a value within the above range, the metal film (coating film) 14 can be more reliably formed so as to cover the entire convex portion 121.
Further, it is preferable that the vapor-phase film-forming particles are incident not only from one direction but also from a plurality of directions on the substrate 12. Thereby, the metal film 14 of a suitable shape can be formed easily and reliably, and the aesthetic appearance of the resulting decorative article 1 can be made particularly excellent. In addition, it is possible to obtain the decorative article 1 in which the variation in texture when viewed from various directions is more effectively suppressed.

  As a method for injecting vapor-phase film-forming particles from a plurality of directions, for example, a plurality of vapor-phase film-formation sources (targets, vapor deposition sources, etc.), which are materials for vapor-phase film-formation, are prepared, There is also a method of installing and generating vapor deposition particles simultaneously or sequentially from the plurality of vapor deposition sources. For example, the substrate 12 and the vapor deposition source are relatively moved (displaced). On the other hand, there is a method of generating vapor-phase film-forming particles from a vapor-phase film-formation source. As a method of relatively moving (displacement) the substrate 12 and the vapor deposition source, for example, a method of moving (displacement) the vapor deposition source while the substrate 12 is fixed, Examples thereof include a method of moving (displacement) the substrate 12 in a fixed state, and a method of moving (displacement) both the vapor deposition source and the substrate 12. In particular, when the substrate 12 is moved (displaced), it is possible to obtain an effect that it is easy to use a conventional vapor deposition apparatus for fixing a vapor deposition source.

Hereinafter, a method for moving (displacement) the substrate 12 will be described more specifically with reference to FIG.
In the configuration shown in FIG. 3, the substrate 12 is rotated on the shaft 9 so that the angle between the normal of the main surface of the substrate 12 and the longitudinal direction of the shaft 9 maintains a predetermined angle θ. It has a configuration to let you. In other words, in the configuration shown in FIG. 3, the normal of the main surface of the substrate 12 where the extension line of the shaft 9 is in contact with the surface (incident surface) of the substrate 12 is a conical circumferential surface about the shaft 9. The substrate 12 rotates to form. With such a configuration, for example, the incidence of the vapor-phase film-forming particles is maintained while the normal line of the main surface of the substrate 12 is inclined by the angle θ with respect to the incident direction of the vapor-phase film-formation particles. The direction can be changed over time. Thereby, the metal film 14 of a suitable shape can be formed easily and reliably, and the aesthetic appearance of the resulting decorative article 1 can be made particularly excellent. In addition, it is possible to obtain the decorative article 1 in which the variation in texture when viewed from various directions is more effectively suppressed.

The value of the angle θ may change over time. Thus, when the value of the angle θ changes with time, it is preferable that the maximum value is included in the above-described range. Further, for example, there may be a time point when the angle θ becomes zero during vapor phase film formation.
As the angle θ, an angle formed by a straight line connecting a vapor deposition source and a substrate on which a metal film is to be formed and a normal line of the substrate can be employed.

[Mask removal process]
Next, the mask 2 is removed (1e). As a result, on the surface of the substrate 12 on the side coated with the oxide film 13 and the metal film 13, the portion corresponding to the opening 21 of the mask 2 is covered with the metal film 14, and the other portions are oxidized. The material film 13 is exposed.
The mask 2 can be removed by peeling the mask 2 from the substrate 12 provided with the oxide film 13 and the metal film 14.
In this way, the decorative article 1 is obtained.

<Second Embodiment>
Next, a second embodiment of the decorative article and the method for manufacturing the decorative article of the present invention will be described.
FIG. 4 is a schematic sectional view showing a decorative article according to the second embodiment of the present invention, and FIG. 5 is a schematic sectional view showing a method for manufacturing the decorative article according to the second embodiment of the present invention.
Hereinafter, the decorative article and the manufacturing method according to the second embodiment will be described with a focus on differences from the above-described embodiment, and description of similar matters will be omitted.

As shown in FIG. 4, in the decorative article 1 of the present embodiment, the oxide film 13 is provided only at a portion corresponding to the metal film 14. In other words, in the decorative article 1 of this embodiment, the entire oxide film 13 is completely covered with the metal film 14.
When the oxide film 13 is provided only in a portion corresponding to the metal film 14 as in the present embodiment, for example, the oxide film 13 is made of a colored material (particularly, a dark material). Even if it is a thing, it can prevent the oxide film 13 having a bad influence on the external appearance of the ornament 1.

Next, a method for manufacturing the decorative article 1 according to this embodiment will be described.
FIG. 5 is a schematic cross-sectional view showing a method for manufacturing a decorative article according to a second embodiment of the present invention.
As shown in FIG. 5, the decorative article manufacturing method according to the present embodiment includes a substrate preparation step (2 a) for preparing the substrate 12, and openings on the surface of the substrate 12 corresponding to the convex portions 121 included in the substrate 12. An oxide film forming step (2b) for forming the oxide film 13 on the convex portion 121 by performing vapor phase film formation in a state where the mask (vapor phase film formation mask) 2 provided with the portion 21 is disposed. 2c) and the surface of the oxide film 13 (on the substrate 12) with the mask (vapor phase film formation mask) 2 disposed on the surface of the oxide film 13, vapor phase film formation is performed on the convex portion 121 (oxide). A metal film forming step (film forming step) (2d) for forming the metal film 14 on the surface of the film 13 and a mask removing step (2e) for removing the mask 2 are provided. That is, the oxide film forming step is the same as that of the first embodiment described above except that the oxide film forming step is performed in a state where the mask 2 is arranged on the surface of the substrate 12 and the metal film forming step is subsequently performed.

  In this way, by successively forming the oxide film 13 and the metal film 14 with the mask 2 disposed on the surface of the substrate 12 being generated, it is possible to effectively generate the positional deviation between the oxide film 13 and the metal film 14. Therefore, the aesthetic appearance of the resulting decorative article 1 can be more reliably improved. Further, the oxide film 13 can function as a part of the coating. That is, a film as a laminate of an oxide film and a metal film can be provided on the convex portion of the substrate.

<Clock>
Next, the timepiece of the present invention provided with the decorative product of the present invention as described above will be described.
The timepiece of the present invention has the ornament of the present invention as described above. In addition, as a part other than the decorative article (the decorative article of the present invention) constituting the timepiece of the present invention, known parts can be used. Hereinafter, an example of the configuration of the timepiece of the present invention will be described.

FIG. 6 is a schematic partial sectional view showing a preferred embodiment of the timepiece (portable timepiece) of the present invention.
As shown in FIG. 6, a wristwatch (portable timepiece) 100 according to this embodiment includes a case (case) 72, a back cover 73, a bezel (edge) 74, and a glass plate (cover glass) 75. . Further, in the case 72, the timepiece dial plate 1, the solar battery 88, and the movement 71 as the ornaments of the present invention as described above are housed, and a hand (pointer) (not shown) or the like is further provided. It is stored.

The glass plate 75 is usually made of transparent glass or sapphire having high transparency. Thereby, while being able to fully exhibit the aesthetics of the timepiece dial 1 as the ornament of the present invention, a sufficient amount of light can be incident on the solar cell 88.
The movement 71 uses the electromotive force of the solar cell 88 to drive the pointer.
Although omitted in FIG. 6, in the movement 71, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 88, a lithium ion secondary battery, a crystal oscillator as a time reference source, a crystal vibration A semiconductor integrated circuit that generates a driving pulse that drives the clock based on the oscillation frequency of the child, a step motor that drives the wheel train mechanism every second in response to this driving pulse, and a movement of the step motor A train wheel mechanism for transmitting to the vehicle is provided.

The movement 71 includes a radio wave receiving antenna (not shown). And it has the function to perform time adjustment etc. using the received electromagnetic wave.
The solar cell 88 has a function of converting light energy into electric energy. The electric energy converted by the solar battery 88 is used for driving the movement.
In the solar cell 88, for example, a p-type impurity and an n-type impurity are selectively introduced into a non-single-crystal silicon thin film, and a p-type non-single-crystal silicon thin film and an n-type non-single-crystal silicon thin film are used. It has a pin structure provided with an i-type non-single-crystal silicon thin film with a low impurity concentration in between.

A winding stem pipe 76 is fitted and fixed to the barrel 72, and a shaft 771 of a crown 77 is rotatably inserted into the winding stem pipe 76.
The body 72 and the bezel 74 are fixed by a plastic packing 78, and the bezel 74 and the glass plate 75 are fixed by a plastic packing 79.
Further, a back cover 73 is fitted (or screwed) to the barrel 72, and a ring-shaped rubber packing (back cover packing) 84 is inserted into the joint portion (seal portion) 85 in a compressed state. Has been. With this configuration, the seal portion 85 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove 772 is formed in the outer periphery of the shaft 771 of the crown 77, and a ring-shaped rubber packing (crown packing) 83 is fitted in the groove 772. The rubber packing 83 is in close contact with the inner peripheral surface of the winding stem pipe 76 and is compressed between the inner peripheral surface and the inner surface of the groove 772. With this configuration, the space between the crown 77 and the winding stem pipe 76 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 77 is rotated, the rubber packing 83 rotates together with the shaft portion 771 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 76.

In the above description, a wristwatch (portable clock) is described as an example of a clock, but the present invention is similarly applied to other types of clocks such as a portable clock, a table clock, and a wall clock other than the wristwatch. be able to.
In the above description, the dial to which the ornament of the present invention is applied has been described. However, the ornament of the present invention may be applied to parts (decorations) other than the dial. For example, a case (case), hands, etc. constituting the timepiece may be constituted by the decorative article of the present invention. Further, a plurality of parts (decorative items) constituting the timepiece may be constituted by the ornamental items of the present invention.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.
For example, in the method for manufacturing a decorative article of the present invention, an optional process can be added as necessary.
In the above-described embodiment, the film forming process uses a mask made of a material containing a magnetic material, and the mask is formed by a magnet disposed on the surface opposite to the surface facing the mask of the substrate. In the film forming process, a magnet need not be used. However, in the film forming process, the magnet is not used.

In the above-described embodiment, the mask having the cross-sectional area increasing portion is used as the mask. However, a mask having no cross-sectional area increasing portion may be used.
In the embodiment described above, the substrate and the oxide film are adjacent to each other, and the oxide film and the metal film are adjacent to each other. However, for example, there is at least one intermediate layer between them. May be.

In the above-described embodiment, the decorative article has been described as having a substrate, an oxide film, and a metal film. However, the decorative article of the present invention is not limited to such a configuration, for example, The oxide film may not be provided.
In the above-described embodiment, the coating is mainly composed of a metal material and has been described as functioning as a reflective film. However, in the present invention, the coating may be composed of any material, for example, It may be composed of a ceramic material, a resin material containing a colorant, or the like. The coating may not function as a reflective film.

  Further, for example, a coat layer may be provided on the outer surface of the decorative article (such as the outer surface of the coating). As a result, for example, the glossiness, color tone, etc. are adjusted to further improve the aesthetic appearance of the decorative product, or the overall decorative product has corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, abrasion resistance. Various properties such as color resistance and discoloration resistance can be improved. Such a coat layer may be removed, for example, when a decorative article is used.

Next, specific examples of the present invention will be described.
1. Manufacture of Decorative Items 100 decorative items (watch exterior parts (watch dials)) were manufactured for each Example and each Comparative Example by the method described below.
(Example 1)
First, a substrate having the shape of a wristwatch exterior part (watch dial) was prepared by compression molding using polycarbonate colored with a white pigment, and then necessary portions were cut and polished. The obtained substrate had a substantially disk shape, and had a convex portion of a corresponding shape at a portion where an index of one surface (main surface) was to be provided. The obtained substrate had a diameter of 27 mm, and the thickness of the portion excluding the convex portion was 0.5 mm. In addition, the height of each convex portion was 300 μm.

Next, this substrate was cleaned. As the cleaning of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, washing with water for 10 seconds, and cleaning with pure water for 10 seconds.
An oxide film composed of TiO ₂ was formed by sputtering as described below on the surface of the substrate on which the convex portions of the substrate thus cleaned were provided (oxide film forming step).

First, the cleaned substrate was mounted in a sputtering apparatus, and then the inside of the sputtering apparatus was exhausted (reduced pressure) to 3 × 10 ⁻³ Pa while preheating the inside of the apparatus.
Next, while introducing argon gas at an argon flow rate: 40 ml / min, oxygen was introduced at an oxygen flow rate: 10 ml / min. In this state, Ti was used as a target, and discharge was performed under the conditions of input power: 1400 W and processing time: 3.0 minutes, whereby an oxide film composed of TiO ₂ was formed. The average thickness of the oxide film thus formed was 0.01 μm.

Subsequently, a metal film composed of Ag was formed on the surface of the oxide film formed as described above by sputtering (metal film formation step (film formation step)).
The metal film was formed by performing sputtering in a state where a mask provided with an opening in a portion corresponding to the convex portion of the substrate was disposed on the surface of the oxide film.
The mask was made of stainless steel (SUS444), and its thickness was 150 μm. In addition, as shown in FIG. 2, this mask is provided with a cross-sectional area increasing portion in which the cross-sectional area increases from the first surface facing the substrate toward the second surface on the opposite side. Met. Further, in the cross-sectional area increasing portion, the cross-sectional area S ₀ ′ [μm ² ] at the cross-sectional area minimum portion where the cross-sectional area of the opening is minimum and the cross-sectional area at the maximum cross-sectional area where the cross-sectional area of the opening is maximum. The ratio (S ₀ ′ / S ₁ ′) to S ₁ ′ [μm ² ] was 0.70. Further, the difference (W _O −W _C ) between the width W _O [μm] of the opening of the mask and the width W _C [μm] of the convex portion covered with the oxide film was 10 μm.

In addition, this step was performed in a state where a magnet was disposed on the surface of the substrate opposite to the surface facing the mask, and the substrate provided with the oxide film and the mask were in close contact with the magnet.
Sputtering in this step was performed under the following conditions.
First, the inside of the apparatus was evacuated (depressurized) to 3 × 10 ⁻³ Pa, and then argon gas was introduced at an argon gas flow rate of 35 ml / min. In this state, Ag was used as a target, and discharge was performed under the conditions of input power: 1400 W and treatment time: 2.0 minutes, thereby forming a metal film composed of Ag. At this time, as shown in FIG. 3, the substrate is rotated on the shaft in such a manner that the angle formed between the normal line of the main surface of the substrate and the longitudinal direction of the shaft is maintained at 15 °. Vapor phase film-forming particles (sputtered particles) composed of the constituent material of the metal film from a direction inclined by 15 ° (angle θ) with respect to the normal direction of the main surface of the substrate (main surface to be coated with the metal film) ) On the substrate. The average thickness of the metal film thus formed was 0.20 μm.
Next, the substrate provided with the oxide film and the metal film was taken out from the sputtering apparatus, and the mask was removed (mask removal process). As a result, a decorative article as shown in FIG. 1 was obtained.
In addition, the height of the convex part, the thickness of the oxide film, the metal film, and the mask were measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 7)
The configuration of the substrate and the configuration of the mask used in the manufacture of the decorative product are as shown in Table 1, and the processing conditions of each process are adjusted so that the oxide film and the metal film have the configuration as shown in Table 1. Except for the above, an ornament was manufactured in the same manner as in Example 1.
(Example 8)
In the metal film forming step, a decorative article was manufactured in the same manner as in Example 4 except that the substrate was fixed so that the perpendicular direction of the main surface of the substrate and the traveling direction of the sputtered particles were substantially parallel.

Example 9
First, a cleaned substrate was prepared in the same manner as in Example 1.
An oxide film composed of TiO ₂ was formed by sputtering on the surface of the substrate on which the convex portions of the substrate thus cleaned were provided (oxide film forming step).
The oxide film is formed by sputtering in a state where a mask having an opening provided in a portion corresponding to the convex portion of the substrate is arranged on the surface of the substrate (surface on the side where the convex portion is provided). did.

The mask was made of stainless steel (SUS444), and its thickness was 150 μm. In addition, as shown in FIG. 5, this mask is provided with a cross-sectional area increasing portion in which the cross-sectional area increases from the first surface facing the substrate toward the second surface opposite to the substrate. Met. Further, the difference (W _O −W _C ) between the width W _O [μm] of the opening of the mask and the width W _C [μm] of the convex portion was 10 μm.

Moreover, this process was performed in the state which provided the magnet on the surface side opposite to the surface facing the mask of a board | substrate, and contact | adhered the board | substrate and the mask with this magnet.
Sputtering was performed as shown below.
First, the cleaned substrate was attached to the sputtering apparatus in a state of being in close contact with the mask with a magnet, and then the inside of the sputtering apparatus was evacuated (depressurized) to 3 × 10 ⁻³ Pa while preheating the inside of the apparatus.

Next, while introducing argon gas at an argon flow rate: 40 ml / min, oxygen was introduced at an oxygen flow rate: 10 ml / min. In this state, Ti was used as a target, and discharge was performed under the conditions of input power: 1400 W and processing time: 3.0 minutes, whereby an oxide film composed of TiO ₂ was formed. At this time, as shown in FIG. 3, the substrate is rotated on the shaft in such a manner that the angle formed between the normal line of the main surface of the substrate and the longitudinal direction of the shaft is maintained at 15 °. Vapor-phase film-forming particles composed of the constituent material of the oxide film (from the direction inclined by 15 ° (angle θ) with respect to the normal direction of the main surface of the substrate (main surface to be coated with the oxide film) ( Sputtered particles) were incident on the substrate. The average thickness of the oxide film thus formed was 0.01 μm.

Subsequently, a metal film composed of Ag was formed by sputtering on the surface of the oxide film formed as described above in a state where the mask was adhered to the substrate with a magnet (metal film formation step (film formation) Process)).
Sputtering in this step was performed under the following conditions.
First, the inside of the apparatus was evacuated (depressurized) to 3 × 10 ⁻³ Pa, and then argon gas was introduced at an argon gas flow rate of 35 ml / min. In this state, Ag was used as a target, and discharge was performed under the conditions of input power: 1400 W and treatment time: 2.0 minutes, thereby forming a metal film composed of Ag. At this time, as shown in FIG. 3, the substrate is rotated on the shaft in such a manner that the angle formed between the normal line of the main surface of the substrate and the longitudinal direction of the shaft is maintained at 15 °. Vapor phase film-forming particles (sputtered particles) composed of the constituent material of the metal film from a direction inclined by 15 ° (angle θ) with respect to the normal direction of the main surface of the substrate (main surface to be coated with the metal film) ) On the substrate. The average thickness of the metal film thus formed was 0.20 μm.
Next, the substrate provided with the oxide film and the metal film was taken out from the sputtering apparatus, and the mask was removed (mask removal process). As a result, a decorative article as shown in FIG. 4 was obtained.
In addition, the height of the convex part, the thickness of the oxide film, the metal film, and the mask were measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 10 to 15)
The configuration of the substrate and the configuration of the mask used in the manufacture of the decorative product are as shown in Table 1, and the processing conditions of each process are adjusted so that the oxide film and the metal film have the configuration as shown in Table 1. Except for the above, an ornament was manufactured in the same manner as in Example 9.
(Example 16)
In the metal film formation step, a decorative article was manufactured in the same manner as in Example 12 except that the substrate was fixed so that the perpendicular direction of the main surface of the substrate and the traveling direction of the sputtered particles were substantially parallel.

(Comparative Example 1)
First, using a material having the same composition as that used in Example 1 (polycarbonate colored with a white pigment), a substrate having the shape of a wristwatch exterior part (watch dial) is produced by compression molding. After that, necessary portions were cut and polished. The obtained substrate was substantially disk-shaped and had a smooth surface. That is, the substrate used in Example 1 did not have unevenness. The obtained substrate had a diameter of 27 mm and a thickness of 0.5 mm.

Next, this substrate was cleaned. As the cleaning of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, washing with water for 10 seconds, and cleaning with pure water for 10 seconds.
By performing printing (octopus printing) on the surface of the substrate thus cleaned, an index was formed at a site corresponding to the site where the index was provided in Example 1 to obtain a decorative article. For forming the index, an ink (dispersion) containing Ag fine particles, an acrylic resin, and methyl ethyl ketone was used. The thickness of the formed indicator was 40 μm.

(Comparative Example 2)
By repeatedly performing printing, a decorative article was manufactured in the same manner as in Comparative Example 1 except that the thickness of the index was 250 μm.
(Comparative Example 3)
First, using a material having the same composition as that used in Example 1 (polycarbonate colored with a white pigment), a substrate having the shape of a wristwatch exterior part (watch dial) is produced by compression molding. After that, necessary portions were cut and polished. At this time, openings having a diameter of 150 μm were formed in the vicinity of the centers of a plurality of portions corresponding to the portions provided with the index in Example 1. The obtained substrate was substantially disk-shaped and had a smooth surface. That is, the substrate used in Example 1 did not have unevenness. The obtained substrate had a diameter of 27 mm and a thickness of 0.5 mm.

Next, this substrate was cleaned. As the cleaning of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, washing with water for 10 seconds, and cleaning with pure water for 10 seconds.
By attaching a planting material having a foot to the opening of the substrate thus cleaned and fixing with an adhesive, an index is formed at a site corresponding to the site where the index was provided in Example 1 And got an ornament. As the planting material, a base made of a material having the same composition as that of the substrate was coated with an oxide film and a metal film in this order. The oxide film and the metal film were formed under the same conditions as in Example 1. The foot part of the planting material had a thickness of 150 μm and a length of 1.0 mm. Moreover, the height of the site | part except the leg part of the planting material was 100 micrometers.

(Comparative Example 4)
A decorative article was manufactured in the same manner as in Comparative Example 3 except that the height of the portion excluding the foot portion of the planting material was set to 300 μm.
The configuration of the mask used in the manufacture of the ornaments of each example and each comparative example, the angle θ formed by the perpendicular direction of the main surface of the substrate when forming the metal film and the traveling direction of the sputtered particles, the configuration of the ornament, etc. Table 1 summarizes the results. In the table, polycarbonate is represented by PC, acrylonitrile-butadiene-styrene copolymer (ABS resin) is represented by ABS, and polyethylene terephthalate is represented by PET. In the table, the surface roughness Ra of the metal film (surface roughness Ra of the surface opposite to the surface facing the substrate) is also shown.

2. Appearance evaluation of ornaments 2-1. Evaluation of stereoscopic effect Each decorative product manufactured in each of the above Examples and Comparative Examples was visually observed, and these stereoscopic effects were evaluated according to the following five-stage criteria.
A: Extremely excellent.
A: Excellent.
○: Good.
Δ: Slightly poor
X: Defect.

2-2. Comprehensive Appearance Evaluation Each decorative product manufactured in each of the above Examples and Comparative Examples was visually and microscopically observed, and their appearance was evaluated according to the following five criteria.
A: Extremely excellent.
A: Excellent.
○: Good.
Δ: Slightly poor
X: Defect.

3. Durability Evaluation For each decorative article manufactured in each of the above Examples and Comparative Examples, the following three types of tests were performed to evaluate the durability of the decorative article.
3-1. Evaluation by drop test Each of the ornaments manufactured in each of the above examples and comparative examples is a watch dial after being repeatedly dropped 50 times onto a 10 cm thick block made of stainless steel from a height of 3 m. The appearances of were visually observed, and these appearances were evaluated according to the following four criteria.
A: No damage (distortion, floating, cracking, peeling, etc.) of the index is observed at all.
○: Index damage (distortion, floating, cracking, peeling, etc.) is hardly observed.
(Triangle | delta): The damage (a distortion, a float, a crack, peeling, etc.) of a parameter | index is recognized slightly.
X: Index damage (distortion, floating, cracking, peeling, etc.) is noticeable.

3-2. Evaluation by Bending Test For each of the ornaments manufactured in each of the above examples and comparative examples, after bending at 30 ° with respect to the center of the ornament as a fulcrum with an iron bar having a diameter of 4 mm as a fulcrum, The appearance was visually observed, and the appearance was evaluated according to the following four-stage criteria. Bending was performed in both compression / tension directions.
A: No lifting or peeling of the indicators (coating, planting material, paint) is observed.
○: Floating indicators (film, planting material, paint) are hardly observed.
(Triangle | delta): The lift of a parameter | index (a film, a planting material, a paint) is recognized clearly.
X: Cracks and peeling of the indicators (coating, planting material, paint) are clearly recognized.

3-3. Evaluation by Thermal Cycle Test Each decorative article manufactured in each of the above Examples and Comparative Examples was subjected to the following thermal cycle test.
First, the decorative article is placed in a 20 ° C. environment for 1.5 hours, then in a 60 ° C. environment for 2 hours, then in a 20 ° C. environment for 1.5 hours, and then in a −20 ° C. environment. It was left for 3 hours. Thereafter, the environmental temperature was returned again to 20 ° C., which was set as one cycle (8 hours), and this cycle was repeated three times in total (24 hours in total).

Then, the external appearance of the ornament was visually observed, and the external appearance was evaluated according to the following four criteria.
A: No lifting or peeling of the indicators (coating, planting material, paint) is observed.
○: Floating indicators (film, planting material, paint) are hardly observed.
(Triangle | delta): The lift of a parameter | index (a film, a planting material, a paint) is recognized clearly.
X: Cracks and peeling of the indicators (coating, planting material, paint) are clearly recognized.
These results are shown in Table 2.

As is clear from Table 2, all the decorative articles of the present invention had an excellent aesthetic appearance with a three-dimensional effect and were also excellent in durability.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, in Comparative Examples 1 and 2 in which the index was formed by printing, the three-dimensional effect could not be sufficiently clear. Further, in Comparative Example 2 in which printing was repeatedly performed for the purpose of improving the three-dimensional effect, a part of the ink superimposed on the printing layer flowed down to the surface of the substrate, resulting in a so-called sagging state, and the formed index Was unclear. Moreover, in Comparative Examples 3 and 4 in which the index was formed using the planting material, the adhesiveness of the index was inferior and did not have sufficient durability. Further, the decorative article of Comparative Example 4 in which the height of the planting material was increased for the purpose of improving the three-dimensional effect was particularly low in durability.
Moreover, the timepiece as shown in FIG. 6 was assembled using the dials (decorative items) obtained in the respective examples and comparative examples. Each timepiece thus obtained was tested and evaluated in the same manner as described above, and the same results as described above were obtained.

It is typical sectional drawing which shows the ornament of 1st Embodiment of this invention. It is typical sectional drawing which shows the manufacturing method of the ornament of 1st Embodiment of this invention. It is a figure for demonstrating the advancing direction of the gaseous-phase film-forming particle | grains at the time of forming a metal film (coating). It is typical sectional drawing which shows the ornament of 2nd Embodiment of this invention. It is typical sectional drawing which shows the manufacturing method of the ornament of 2nd Embodiment of this invention. It is a typical fragmentary sectional view showing a suitable embodiment of a timepiece (portable timepiece) of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Decorative article (Watch dial) 12 ... Substrate 121 ... Protruding part 13 ... Oxide film 14 ... Metal film (coating) 15 ... Index 2 ... Mask (gas phase film forming mask) 21 ... Opening 211 ... Inclination Surface 212 ... Cross-sectional area increasing portion 213 ... Cross-sectional area minimum portion 214 ... Cross-sectional area maximum portion 22 ... First surface 23 ... Second surface 9 ... Shaft 71 ... Movement 72 ... Body (case) 73 ... Back cover 74 ... Bezel (Rim) 75 ... Glass plate (cover glass) 76 ... Winding pipe 77 ... Crown 771 ... Shaft portion 772 ... Groove 78 ... Plastic packing 79 ... Plastic packing 83 ... Rubber packing (crown packing) 84 ... Rubber packing (back) Lid packing) 85 ... Joint (seal part) 88 ... Solar cell 100 ... Wristwatch (portable watch)

Claims (15)

A substrate preparation step of preparing a substrate having a convex portion on at least one surface;
A film is formed on the convex portion by performing vapor phase film formation in a state where a mask having an opening is provided in a portion corresponding to the convex portion on the surface side of the substrate on which the convex portion is provided. A film forming step of forming
And a mask removing step for removing the mask.   The method for manufacturing a decorative article according to claim 1, wherein the height of the convex portion is 100 to 500 μm.   The method for producing a decorative article according to claim 1 or 2, wherein an average thickness of the coating is 0.005 to 2.5 µm.   The decoration according to any one of claims 1 to 3, wherein the opening includes a cross-sectional area increasing portion in which a cross-sectional area increases from a surface facing the substrate of the mask toward an opposite surface thereof. Product manufacturing method.   In the film forming step, the mask is made of a material containing a magnetic material, and the mask and the film are formed by a magnet disposed on a surface of the substrate opposite to the surface facing the mask. The method for manufacturing a decorative article according to any one of claims 1 to 4, wherein the method is performed in a state where the workpiece is to be in close contact with the workpiece to be formed.   In the coating film forming step, vapor-phase film-forming particles made of a constituent material of the coating film are incident on the substrate from a direction inclined by a predetermined angle θ with respect to the normal direction of the main surface of the substrate. Item 6. A method for producing a decorative article according to any one of Items 1 to 5.   The method for manufacturing a decorative article according to claim 6, wherein the vapor-phase film-forming particles are incident from a plurality of directions.   The method for manufacturing a decorative article according to claim 6 or 7, wherein an incident direction of the vapor-phase film-forming particles is changed with time.   The incident direction of the vapor-phase film-forming particles is changed so that the incident direction of the vapor-phase film-forming particles rotates around a normal line of the main surface of the substrate. A method for manufacturing ornaments.   The method for manufacturing a decorative article according to any one of claims 6 to 9, wherein the angle θ is 1 to 50 °.   The method for producing a decorative article according to any one of claims 1 to 10, wherein at least the outer surface of the coating is mainly composed of a metal material. An oxide film forming step of forming an oxide film mainly composed of a metal oxide on the substrate;
The method for manufacturing a decorative article according to any one of claims 1 to 11, further comprising a metal film forming step of forming a metal film mainly composed of a metal material on the oxide film.   The method for manufacturing a decorative product according to any one of claims 1 to 12, wherein the decorative product is a timepiece dial.   A decorative article manufactured using the method according to any one of claims 1 to 13.   A timepiece comprising the decorative article according to claim 14.

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