JP2006264315A - Ornament and watch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornament having a base material consisting mainly of a plastic material, being excellent in permeability for electromagnetic waves as well as in aesthetic appearance and durability, and a watch comprising the ornament. <P>SOLUTION: The ornament 1 comprises a base material 2 consisting mainly of a plastic material, an oxide film 3 provided on the base material 2 and consisting mainly of a metal oxide, and a metallic film 4 provided on the opposite side of the face opposed to the base material 2 of the oxide film 3 and consisting mainly of metallic material. An Openings 6 are provided on the metallic film 4 and the oxide film 3. An area rate occupied by the openings 6 is 25-35% when the metallic film 4 is viewed in plane. A width of the openings 6 is 10-100 μm. The metallic film 4 comprises a material containing at least one kind selected from the group consisting of Ag, Cr, Au, Al, Ti, Sn and In. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative article and a watch.

A decorative product such as a watch exterior part is required to have an excellent aesthetic appearance. Conventionally, in order to achieve such an object, a metal material such as Au or Ag has generally been used as a constituent material of an ornament.
On the other hand, there is an attempt to use a plastic as a base material and form a coating film made of a metal material on the surface for the purpose of reducing production costs and improving the degree of freedom of molding decorative items. (For example, refer to Patent Document 1).
However, plastics generally have poor adhesion to metal materials. For this reason, there is a problem that peeling between the base material and the coating film easily occurs and the durability of the decorative article is inferior.

  In addition, for example, in radio timepieces and solar timepieces (timepieces equipped with solar cells), the timepiece dial is required to have electromagnetic wave (radiowave, light) permeability. For this reason, plastic dials have been used as such timepiece dials. However, since plastic lacks a high-class feeling, it is made of a metal material for the purpose of improving the aesthetic appearance of the timepiece dial. There is an attempt to coat with a thin film. However, as described above, there is a problem that plastic is inferior in adhesion to a metal material. In addition, in order to increase the transparency of electromagnetic waves (radio waves, light), it is necessary to reduce the thickness of the thin film sufficiently. However, in such a case, the aesthetic appearance of the watch dial as a whole deteriorates. There was a point.

JP 2003-239083 A (page 4, left column, lines 37-42)

  An object of the present invention is to provide a decorative article that includes a base material mainly composed of a plastic material, has excellent electromagnetic wave (radio wave, light) permeability, and is excellent in aesthetic appearance and durability. It is to provide a watch equipped with goods.

Such an object is achieved by the present invention described below.
The decorative article of the present invention comprises a base material mainly composed of a plastic material,
An oxide film mainly composed of a metal oxide provided on the substrate;
A metal film mainly composed of a metal material provided on the surface of the oxide film opposite to the surface facing the substrate;
The metal coating is provided with an opening,
The area ratio occupied by the opening when the metal coating is viewed in plan is 25 to 35%.
As a result, it is possible to provide a decorative article that includes a base material mainly composed of a plastic material and is excellent in electromagnetic wave (radio wave, light) permeability and excellent in aesthetic appearance and durability.

In the decorative article of the present invention, it is preferable that the opening penetrates the oxide film.
Thereby, the transparency of electromagnetic waves can be further increased.
In the decorative article of the present invention, the width of the opening is preferably 10 to 100 μm.
Thereby, the aesthetic appearance of the decorative article can be made particularly excellent while the electromagnetic wave permeability is sufficiently high.

In the decorative article of the present invention, the substrate is preferably made of a material containing at least one selected from polycarbonate and acrylonitrile-butadiene-styrene copolymer (ABS resin).
Thereby, the strength of the entire decorative article can be made particularly excellent, and the degree of freedom of molding at the time of manufacturing the decorative article is increased (easiness of molding is improved).

In the decorative article of the present invention, the oxide film is preferably made of a material containing at least one selected from titanium oxide and chromium oxide.
Thereby, the adhesiveness of a base material and a metal film can be made more excellent.
In the decorative article of the present invention, the average thickness of the oxide film is preferably 0.005 to 1.0 μm.
As a result, the aesthetic appearance of the decorative article can be made particularly excellent, and the adhesion between the base material and the metal film is particularly excellent while sufficiently preventing the internal stress of the oxide film from becoming high. Can be.

In the decorative article of the present invention, the metal coating is preferably made of a material containing at least one selected from Ag, Cr, Au, Al, Ti, Sn, and In.
Thereby, while making the adhesiveness of a metal film and an oxide film especially excellent, the aesthetic appearance of a decorative article can be made especially excellent.
In the decorative article of the present invention, the average thickness of the metal film is preferably 0.005 to 1.5 μm.
Thereby, the adhesiveness between the oxide film and the metal film can be made particularly excellent while sufficiently preventing the internal stress of the metal film from becoming high.

In the decorative article of the present invention, the sum of the average thickness of the oxide film and the average thickness of the metal film is preferably 0.01 to 2.5 μm.
Thereby, the adhesiveness of a base material, an oxide film, and a metal film can be made especially excellent, fully preventing that the internal stress of an oxide film or a metal film becomes high. In addition, when the sum of the average thickness of the oxide coating and the average thickness of the metal coating is a value within the above range, the radio wave permeability of the entire decorative article is improved. As a result, the decorative article can be more suitably applied to a radio timepiece component.

In the decorative article of the present invention, it is preferable to have a coat layer mainly composed of a resin material on the metal film.
Thereby, for example, the aesthetic appearance of the decorative article can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light). In addition, deterioration, modification and the like of the metal coating due to the influence of the external environment can be more reliably prevented, and the durability as a decorative article can be made particularly excellent.
In the decorative product of the present invention, it is preferable that the coat layer is mainly composed of a urethane resin and / or an acrylic resin.
Thereby, the adhesiveness of the coat layer can be made particularly excellent.

The decorative article of the present invention is preferably a watch exterior part.
In general, a watch exterior part is a decorative product that is easily affected by external impacts, and is required to have a beautiful appearance as a decorative product and also to have durability as a practical product. These requirements can be satisfied at the same time.
The decorative article of the present invention is preferably a radio timepiece component.
The decorative article of the present invention is excellent in aesthetic appearance and durability, and is excellent in radio wave transmission because the base material is made of a plastic material. Therefore, the decorative article of the present invention can be suitably applied to a radio timepiece component.
The ornament of the present invention is preferably a timepiece dial.
A timepiece dial is required to have excellent electromagnetic wave permeability, radio wave timepiece, solar timepiece, etc., and excellent aesthetic appearance, excellent durability, etc., according to the present invention. Can be satisfied.

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 an aesthetic appearance and durability. In addition, it is possible to provide a timepiece (for example, a radio timepiece, a solar timepiece, a solar timepiece timepiece, etc.) that can effectively use electromagnetic waves (radio waves, light) from the outside.

  According to the present invention, it is provided with a base material mainly composed of a plastic material, and is provided with a decorative article having excellent electromagnetic wave (radio wave, light) permeability and excellent aesthetic appearance and durability. A watch equipped with a product can be provided.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
First, a preferred embodiment of the decorative article of the present invention will be described.
FIG. 1 is a sectional view showing a preferred embodiment of the decorative article of the present invention, and FIG. 2 is a plan view showing a preferred embodiment of the decorative article of the present invention.
As shown in FIG. 1, the decorative article 1 of the present embodiment includes a base material 2, an oxide film 3, a metal film 4, and a coat layer 5.

[Base material]
The base material 2 is mainly composed of a plastic material.
As a plastic material which comprises the base material 2, various thermoplastic resins and various thermosetting resins are mentioned, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), etc. Polyolefin, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide (example: 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 ( Polyesters such as PBT) and polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, poly Ether sulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, Other thermoplastic resins such as fluorinated resins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, transpolyisoprene, fluororubber, chlorinated polyethylene, and epoxy Resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, Polypara-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, poly-monoethyl-para-xylylene, etc. Xylylene resin, etc., or copolymers, blends, polymer alloys, etc. mainly composed of these The recited, singly or in combination of two or more of these (e.g., a blend resin, polymer alloy, as a laminate or the like) can be used.

The base material 2 is composed of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin) among the above materials. preferable.
Thereby, the intensity | strength as the decoration 1 whole can be made especially excellent. Further, when the decorative article 1 is manufactured, since the degree of freedom of molding of the base material 2 is increased (easiness of molding is improved), even the decorative article 1 having a more complicated shape can be easily and reliably. Can be manufactured. 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 base material 2 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.
Moreover, the base material 2 should just be a thing by which at least a part of surface vicinity (site | part in which the oxide film 3 mentioned later is formed) was mainly comprised by the plastic material, for example, comprised by the material which does not contain a plastic material. It may have a part made.

Moreover, the base material 2 may have a substantially uniform composition at each site, or may have a different composition depending on the site. For example, the base material 2 may have a base portion and a surface layer provided on the base portion. When the base material 2 has such a structure, at least a part near the surface (a part where an oxide film 3 described later is formed) is mainly composed of a plastic material as described above. That's fine.
In addition, the shape and size of the base material 2 are not particularly limited, and are usually determined based on the shape and size of the decorative article 1.
Moreover, although the base material 2 may be shape | molded by what kind of method, as a shaping | molding method of the base material 2, compression molding, extrusion molding, injection molding, stereolithography, etc. are mentioned, for example.

[Oxide coating]
An oxide film 3 is provided on the surface of the substrate 2. As described above, the present invention is characterized in that the metal film is not directly provided on the surface of the base material mainly composed of the plastic material, and the oxide film is interposed between the base material and the metal film. . Thereby, the adhesiveness (adhesiveness through an oxide film) of a metal film and a base material can be improved, and the metal film can be effectively prevented from floating or peeling (peeling). As a result, the decorative article has excellent durability. Moreover, since such a decorative article has a metal film, it has an excellent aesthetic appearance.

The oxide film 3 is mainly composed of a metal oxide.
As the metal oxide constituting the oxide coating 3, 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 3 is made of a material containing at least one selected from titanium oxide (including a complex oxide) and chromium oxide (including a complex oxide), the substrate 2 and the metal film 4 can be made more excellent in adhesion. Further, the oxide film 3 is made of a colorless metal oxide (for example, an oxide of Zn, Mg, Mo, Nb, Zr, Sn, In, etc.), as will be described later on the oxide film 3. Even when the opening 6 is not formed (when the opening 6 is formed only in the metal coating 4), the transmittance of electromagnetic waves (particularly light) as the entire decorative article 1 is particularly excellent. Can be. In addition, the oxide film 3 may contain components other than a metal oxide.

  Moreover, although the average thickness of the oxide film 3 is not specifically limited, It is preferable that it is 0.005-1.0 micrometer, It is more preferable that it is 0.007-0.5 micrometer, 0.01-0. More preferably, it is 3 μm. When the average thickness of the oxide coating 3 is a value 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 coating 3 is increased. Adhesion between the substrate 2 and the metal coating 4 can be made particularly excellent while sufficiently preventing. On the other hand, when the average thickness of the oxide film 3 is less than the lower limit value, the adhesion between the base material 2 and the metal film 4 depends on the constituent materials of the oxide film 3, the base material 2, and the metal film 4. It may be difficult to sufficiently improve the performance. In addition, when the average thickness of the oxide film 3 is less than the lower limit value, depending on the formation method of the oxide film 3, pinholes are easily generated in the oxide film 3, and the oxide film 3 is provided. The effect may not be fully demonstrated. Moreover, when the average thickness of the oxide film 3 exceeds the upper limit, the variation in film thickness at each part of the oxide film 3 tends to increase. Moreover, when the average thickness of the oxide film 3 is particularly large, the internal stress of the oxide film 3 becomes high, and cracks and the like are likely to occur.

  Moreover, the oxide film 3 may have a uniform composition in each part, and may not be so. For example, the oxide film 3 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. The oxide film 3 may be a laminate having a plurality of layers. Thereby, for example, the adhesion between the base material 2 and the metal coating 4 can be further improved. More specifically, the layer on the side of the laminate that is in contact with the substrate 2 is made of a material having excellent adhesion to the substrate 2, and the layer on the side of the laminate that is in contact with the metal coating 4 is a metal coating. By using a material having excellent adhesion to 4, the adhesion between the substrate 2 and the metal coating 4 can be further improved. Moreover, when the oxide film 3 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 3 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 coating]
A metal coating 4 is provided on the surface of the oxide coating 3 (the surface opposite to the surface in contact with the substrate 2).
The metal coating 4 is mainly composed of a metal material.
Various metals (including alloys) can be used as the metal material constituting the metal coating 4, 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 coating 4 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. Thereby, the adhesion between the metal coating 4 and the oxide coating 3 can be made particularly excellent, and the aesthetic appearance of the decorative article 1 can be made particularly excellent. Further, when the metal coating 4 is made of the above-described material, the size of the opening 6 described later is relatively large, or the area ratio of the opening 6 occupying the entire surface of the metal coating 4 is relatively high. Even if it is large, the presence of the opening 6 can be made inconspicuous in appearance. The metal coating 4 may contain components other than the metal material.

Further, the constituent material of the metal coating 4 may include at least one of the elements constituting the oxide coating 3. In other words, the oxide film 3 and the metal film 4 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 3 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 4 has M May be included. Thereby, the adhesiveness of the oxide film 3 and the metal film 4 further improves.

  The average thickness of the metal coating 4 is not particularly limited, but is preferably 0.005 to 1.5 μm, more preferably 0.007 to 0.9 μm, and 0.01 to 0.5 μm. Is more preferable. When the average thickness of the metal coating 4 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 coating 4 from increasing. . Further, the adhesion between the oxide coating 3 and the metal coating 4 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 coating 4 is less than the lower limit, depending on the constituent material of the metal coating 4, it becomes difficult to fully exhibit the features such as gloss and color tone of the metal coating 4, 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 coating 4 is less than the lower limit value, pinholes are likely to be generated in the metal coating 4 depending on the formation method of the metal coating 4 and the like. In addition, depending on the constituent materials of the metal coating 4 and the oxide coating 3, it may be difficult to sufficiently improve the adhesion between the oxide coating 3 and the metal coating 4. Moreover, when the average thickness of the metal coating 4 exceeds the upper limit value, the variation in film thickness at each part of the metal coating 4 tends to increase. Further, when the average thickness of the metal coating 4 is particularly large, the internal stress of the metal coating 4 becomes high and cracks and the like are likely to occur. Moreover, when the average thickness of the metal coating 4 exceeds the said upper limit, the transmittance | permeability of the electromagnetic waves (radio wave, light) as the decoration 1 whole shows the tendency to reduce.

  In addition, the metal coating 4 may or may not have a uniform composition at each site. For example, the metal coating 4 may be a material (gradient material) whose content (composition) changes sequentially in the thickness direction. The metal coating 4 may be a laminate 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 3 is particularly excellent. That is, the layer on the side of the laminate that is in contact with the oxide coating 3 is made of a material having excellent adhesion to the oxide coating 3, and the outermost layer (the layer farthest from the oxide coating 3) of the laminate. ) 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 3 is particularly excellent. Moreover, when the metal film 4 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 coating 4 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.

  The sum of the average thickness of the oxide film 3 and the average thickness of the metal film 4 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 3 and the average thickness of the metal film 4 is a value within the above range, the internal stress of the oxide film 3 and the metal film 4 is sufficiently prevented from increasing, The adhesiveness of the material 2, the oxide film 3, and the metal film 4 can be made particularly excellent. In addition, when the sum of the average thickness of the oxide coating 3 and the average thickness of the metal coating 4 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.

[Aperture]
The metal coating 4 is provided with a large number of openings 6 penetrating in the thickness direction at a predetermined rate. By having such an opening 6, it is possible to sufficiently transmit electromagnetic waves incident from the outside (electromagnetic waves from the upper side in FIG. 1) while improving the aesthetic appearance of the decorative article 1 as a whole. Thereby, the ornament 1 can be suitably applied to, for example, a radio timepiece, a solar timepiece (a timepiece incorporating a solar cell), a solar timepiece, and the like.

The ratio of the area occupied by the opening 6 when the metal coating 4 is viewed in plan is 25 to 35%. When the area ratio occupied by the opening is less than the lower limit, the transmittance of the electromagnetic wave as the entire decorative article cannot be sufficiently increased. In addition, it is conceivable to reduce the thickness of the metal film for the purpose of improving the transmittance of electromagnetic waves. In such a case, however, the aesthetics of the entire decorative article is lowered. On the other hand, when the area ratio occupied by the opening exceeds the upper limit, the presence of the opening becomes conspicuous, and the aesthetics of the decorative article are significantly lowered.
As described above, the ratio of the area occupied by the opening 6 when the metal coating 4 is viewed in plan (ratio of the area occupied by the opening 6) is 25 to 35%, but 27 to 33%. Preferably, it is 28 to 32%. As a result, the effects as described above are exhibited more significantly.

  The shape of the opening 6 is not particularly limited. For example, the shape when viewed in plan may be any shape such as a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, a slit shape, or a lattice shape. As shown in FIG. 2, the presence of the opening 6 can be made inconspicuous in the appearance of the decorative article 1 when it has a substantially circular shape when seen in a plan view. Further, the opening 6 having such a shape can be easily formed, and the size thereof can be controlled more reliably.

  Moreover, it is preferable that the width | variety of the opening part 6 represented by W in a figure is 10-100 micrometers, It is more preferable that it is 40-60 micrometers, It is further more preferable that it is 45-55 micrometers. When the width W of the opening 6 is a value within the above range, the aesthetic appearance (aesthetics) of the decorative article 1 is particularly excellent while the electromagnetic wave permeability as the decorative article 1 is sufficiently high. be able to. On the other hand, if the width W of the opening 6 is less than the lower limit, it may be difficult to sufficiently increase the transmittance of the electromagnetic wave as the entire decorative article 1 depending on the ratio of the area occupied by the opening 6. There is sex. On the other hand, when the width W of the opening 6 exceeds the upper limit, depending on the constituent material, thickness, etc. of the metal coating 4, the presence of the opening 6 is conspicuous on the appearance of the decorative article 1, and the aesthetics of the decorative article 1 are present. Tends to decrease. When the opening 6 shows a substantially circular shape when viewed in plan, the diameter is the width W of the opening 6 and the opening 6 shows a substantially elliptical shape when viewed in plan. In some cases, the length in the minor axis direction can be the width W of the opening 6.

Moreover, it is preferable that the pitch of the opening part 6 represented by P in a figure is 60-300 micrometers, It is more preferable that it is 120-200 micrometers, It is further more preferable that it is 130-180 micrometers. When the pitch P of the openings 6 is a value within the above range, the aesthetic appearance (aesthetics) of the decorative article 1 is particularly excellent while the electromagnetic wave permeability as the decorative article 1 is sufficiently high. be able to. On the other hand, if the pitch P of the openings 6 is less than the lower limit value, the presence of the openings 6 is conspicuous on the appearance of the decorative article 1 depending on the constituent material, thickness, and the like of the metal coating 4. There is a tendency for the aesthetics of the to decrease. On the other hand, when the pitch P of the openings 6 exceeds the upper limit, depending on the ratio of the area occupied by the openings 6, it may be difficult to sufficiently increase the transmittance of electromagnetic waves as the entire decorative article 1. . Note that the pitch of the openings 6 refers to the center-to-center distance between the adjacent openings 6 and 6, and when there are a plurality of adjacent openings, the center between the adjacent openings 6. It refers to the distance between.
The opening 6 as described above may be provided at least in the metal coating 4 (particularly in the case where the oxide coating 3 is made of a material having transparency). In the configuration shown in FIG. 4, the oxide film 3 is also penetrated. Thereby, the transmittance | permeability of the electromagnetic wave as the decoration 1 whole can further be improved, making the aesthetic appearance of the decoration 1 excellent.

Further, as shown in FIG. 3, the opening 6 may be selectively provided in the metal film 4 and not provided in the oxide film 3. Thereby, while making the transmittance | permeability of electromagnetic waves sufficiently excellent, in the opening part 6, the light which injected from the outside permeate | transmits the oxide film 3 and the base material 2, and is reflected with a moderate reflectance, and is opened. The presence of the portion 6 becomes less conspicuous, and the aesthetic appearance of the decorative article 1 is particularly excellent. That is, when the oxide film 3 remains in the opening 6, a part of the light incident from the outside is reflected near the surface of the oxide film 3 and between the oxide film 3 and the base material 2. However, the reflection of light to the light incident side occurs, and the presence of the opening 6 becomes less noticeable. Such an effect is prominent when the refractive index (absolute refractive index) of the constituent material of the oxide film 3 is larger than the refractive index (absolute refractive index) of the constituent material of the substrate 2.
Further, when the refractive index (absolute refractive index) I _O of the material of the oxide coating _3, the refractive index of the constituent material of the substrate 2 (absolute refractive index) was I _B, 0.4 ≦ I _O -I it is preferable to satisfy the relation _B ≦ 1.5, and more preferably satisfy the relation: _{0.6 ≦ I O -I B ≦ 1.1} . By satisfying such a relationship, the above-described effects are exhibited as particularly remarkable.

[Coat layer]
A coat layer 5 is provided on the surface of the metal coating 4 (the surface opposite to the surface in contact with the oxide coating 3). By having such a coat layer 5, for example, glossiness, color tone and the like can be adjusted while sufficiently increasing the transmittance of electromagnetic waves, and the aesthetic appearance of the decorative article 1 is further improved. be able to. Moreover, by having such a coat layer 5, for example, the decorative article 1 as a whole has improved various properties such as corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, abrasion resistance, and discoloration resistance. It is possible to prevent the metal coating 4 and the like from being deteriorated or modified due to the influence of the external environment. As a result, the durability as the decorative article 1 can be made particularly excellent.

  The coat layer 5 may be composed of any material, but is preferably composed of a material having appropriate transparency. Examples of such materials include various plastic materials (resin materials), various glasses, diamond-like carbon (DLC), etc. Among them, plastic has excellent transparency and excellent moldability (easy to mold). ) Is particularly preferable.

  Examples of the plastic material (resin material) constituting the coat layer 5 include various thermoplastic resins and various thermosetting resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer ( EVA) and other polyolefins, cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamides (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), poly Polyester such as butylene terephthalate (PBT) and polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, Polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyphenylene Various thermoplastic elastomers such as vinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene , Epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene ), Poly-dichloro-para-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, etc. Polyparaxylylene resin, etc., or copolymers and blends based on these, Rimaaroi and the like, singly or in combination of two or more of these (e.g., a blend resin, polymer alloy, as a laminate or the like) can be used.

The coat layer 5 is preferably composed of a material containing a urethane resin and / or an acrylic resin, among the materials described above, and is mainly composed of a urethane resin and / or an acrylic resin. More preferably. Thereby, the adhesiveness between the coat layer 5 and the metal coating 4 can be made particularly excellent while exhibiting the effects of having the coat layer 5 as described above more remarkably.
The coat layer 5 may contain components other than the above materials. Examples of such components include colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, plasticizers, antioxidants, fillers, and the like.

  The average thickness of the coat layer 5 is not particularly limited, but is preferably 0.01 to 50 μm, more preferably 0.1 to 20 μm, and further preferably 2 to 15 μm. When the average thickness of the coat layer 5 is within the above range, the adhesion between the coat layer 5 and the metal coating 4 is particularly excellent while sufficiently preventing the internal stress of the coat layer 5 from increasing. It can be. Moreover, the aesthetics of the decorative article 1 can be made particularly excellent. On the other hand, if the average thickness of the coat layer 5 is less than the lower limit value, the adhesion between the coat layer 5 and the metal coating 4 is sufficiently improved depending on the constituent material of the metal coating 4 and the coating layer 5. Can be difficult. Moreover, the function of the coat layer 5 may not be sufficiently exhibited. Moreover, when the average thickness of the coat layer 5 exceeds the upper limit, the variation in film thickness at each part of the coat layer 5 tends to increase. Further, when the average thickness of the coat layer 5 is particularly large, the internal stress of the coat layer 5 becomes high, and cracks and the like are likely to occur. Further, when the average thickness of the coat layer 5 is particularly large, depending on the constituent material (transparency) of the coat layer 5, the constituent material of the metal coating 4, etc., the characteristics of the metal coating 4 such as gloss and color tone are sufficiently exhibited. And it may be difficult to sufficiently enhance the aesthetics of the decorative article 1 as a whole.

When the opening 6 is selectively provided in the metal film 4 and not in the oxide film 3 as shown in FIG. 3 (the same applies to FIG. 6 described later), the oxide film When the refractive index (absolute refractive index) of the constituent material 3 is I _O and the refractive index (absolute refractive index) of the constituent material of the coat layer 5 is I _C , 0.4 ≦ I _O −I _C ≦ 1.5 It is preferable to satisfy this relationship, and it is more preferable to satisfy the relationship of 0.6 ≦ I _O −I _C ≦ 1.1. By satisfying such a relationship, a part of the light incident from the outside is reflected near the surface of the oxide film 3 or at the interface between the oxide film 3 and the substrate 2 toward the light incident side. Further, light is reflected toward the light incident side even at the interface between the oxide film 3 and the coat layer 5, and the presence of the opening 6 becomes more inconspicuous.

The coat layer 5 may or may not have a uniform composition at each site. For example, the coat layer 5 may be one in which the component (composition) changes sequentially in the thickness direction (gradient material). The coat layer 5 may be a laminate having a plurality of layers. Thereby, for example, the aesthetics as the decorative article 1 can be further enhanced while the adhesion with the metal coating 4 is particularly excellent.
Further, the coat layer 5 may be removed, for example, when the decorative article 1 is used.

[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.), dials, clock hands, bezels (for example, rotating bezels), crowns (for example, screw locks) Crowns, etc.), buttons, cover glass, glass edges, dial rings, parting plates, packings and other watch exterior parts, movement ground plates, gears, train wheels, rotating weights and other watch interior parts, glasses (for example, , Glasses frame), tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings, etc. Over or that 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, a watch exterior part is particularly preferable. In general, a watch exterior part is a decorative product that is easily affected by external impacts, and is required to have a beautiful appearance as a decorative product and also to have durability as a practical product. These requirements can be satisfied at the same time. The “watch exterior part” in this specification may be anything that can be visually recognized from the outside, and is not limited to the one exposed to the outside of the watch. Including built-in.

In addition, the decorative article of the present invention is preferably applied to a dial, particularly among timepiece exterior parts. The dial is a part that requires a particularly excellent aesthetic appearance among various parts constituting the timepiece. In addition, in radio timepieces and solar timepieces as described later (including solar radio timepieces), the dial is usually on the radio wave reception antenna so as to cover the radio wave reception antenna, It arrange | positions on a solar cell (on the light-receiving surface of a solar cell). Therefore, in radio timepieces and solar timepieces, the dial is required to have excellent radio wave permeability. However, according to the present invention, such a requirement can be sufficiently satisfied.
In addition, the decorative article of the present invention is preferably applied to a wristwatch, among watch exterior parts. In general, wristwatches are required to have excellent decorativeness and practicality in various environments because the conditions of the environment in which they are used are not constant.

In addition, the decorative article of the present invention is preferably a radio timepiece part (including a solar radio timepiece part) among timepiece parts (timepiece exterior parts) for the following reasons.
That is, since the decorative article of the present invention has the opening as described above, it is excellent in electromagnetic wave (light and radio wave) permeability. In addition, since the decorative article of the present invention has an oxide film between the base material and the metal film, the thickness of the metal film is relatively thin due to the color tone of the oxide film. In addition, the aesthetic appearance of the decorative product as a whole can be made excellent. In the decorative article of the present invention, the base material is made of a plastic material. For these reasons, the decorative article of the present invention can exhibit an excellent aesthetic appearance and durability, and can be particularly excellent in radio wave permeability. Therefore, the decorative article of the present invention can be suitably applied to a radio timepiece component.

Next, the manufacturing method of the ornament 1 mentioned above is demonstrated.
FIG. 4 is a cross-sectional view showing a preferred embodiment of the method for manufacturing a decorative article of the present invention.
As shown in FIG. 4, the method for manufacturing a decorative article according to this embodiment includes an oxide film forming step (1b) for forming an oxide film 3 on at least a part (1a) of the surface of the substrate 2, and an oxidation process. A metal film forming step (1c) for forming a metal film 4 on at least a part of the surface of the material film 3, an opening forming step (1d) for forming an opening 6 in the metal film 4 and the oxide film 3, A coating layer forming step (1e) for forming the coating layer 5 on the metal coating 4;

[Base material]
As the substrate 2, those described above can be used.
The surface of the substrate 2 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 base material 2 that has been subjected to such surface processing is compared with the oxide coating 3 and the metal coating 4 that are obtained by performing the surface processing, The glare of the metal coating 4 is suppressed, and the aesthetic appearance is particularly excellent. Moreover, since the base material 2 is mainly composed of a plastic material, the surface processing as described above can be performed relatively easily. In addition, since the oxide film 3 and the metal film 4 are usually relatively thin, when the oxide film 3 and the metal film 4 are subjected to a surface treatment, the oxide film at the portion subjected to the surface treatment. 3. Although the metal coating 4 may be completely removed, the occurrence of such a problem can be effectively prevented by subjecting the base material 2 to surface treatment.

[Oxide film forming step]
An oxide film 3 mainly composed of a metal oxide is formed on the substrate 2 (1b).
As described above, the oxide film 3 has excellent adhesion to the base material 2 and the metal film 4. The present invention is characterized in that the durability of the entire decorative article is improved by forming such an oxide film.

  The method for forming the oxide film 3 is not particularly limited, and examples thereof include wet coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, and electrodeposition coating, electrolytic plating, immersion plating, and electroless plating. Examples include plating methods, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. Plating method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film forming method) as a method for forming the oxide coating 3, the oxide has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. The coating 3 can be reliably formed. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be made particularly excellent. Further, by applying a dry plating method (vapor phase film forming method) as a method for forming the oxide film 3, even if the oxide film 3 to be formed is relatively thin, the variation in film thickness is sufficiently obtained. It can be small. For this reason, the transparency of the electromagnetic wave of the ornament 1 can be improved, for example, while the durability of the ornament 1 obtained is sufficiently high. Therefore, the obtained decorative article 1 can be more suitably applied to timepiece parts such as radio timepieces and solar timepieces.

  Among the dry plating methods (vapor phase film forming methods) as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the oxide film 3, the above effects become more prominent. That is, by applying sputtering as a method for forming the oxide film 3, it is possible to more reliably form the oxide film 3 that has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. can do. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be further improved. Further, by applying sputtering as the method for forming the oxide film 3, even when the oxide film 3 to be formed is relatively thin, the variation in film thickness can be made particularly small. For this reason, the transparency of the electromagnetic wave of the ornament 1 can be further improved, for example, while making the durability of the ornament 1 obtained high. Therefore, the obtained decorative article 1 can be more suitably applied to timepiece parts such as radio timepieces and solar timepieces.

In the case of applying the dry plating method as described above, for example, by using a metal corresponding to the metal oxide constituting the oxide film 3 as a target and performing the treatment in an atmosphere containing oxygen gas, the oxide is obtained. The coating 3 can be formed easily and reliably.
The formation of the oxide film 3 may be performed by combining a plurality of different methods and conditions. Thereby, the oxide film 3 comprised by the laminated body as mentioned above can be formed suitably.

[Metal film forming process]
Next, a metal film 4 mainly composed of a metal material is formed on the oxide film 3 formed as described above (1c).
The formation method of the metal coating 4 is not particularly limited, and 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 thereof include chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. The method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film forming method) as a method for forming the metal film 4, the metal film has a uniform film thickness, is homogeneous, and has particularly good adhesion to the oxide film 3. 4 can be formed reliably. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be made particularly excellent. Further, by applying a dry plating method (vapor phase film formation method) as a method for forming the metal coating 4, even if the metal coating 4 to be formed is relatively thin, the variation in film thickness is sufficiently small It can be. For this reason, the transparency of the electromagnetic wave of the ornament 1 can be improved, for example, while the durability of the ornament 1 obtained is sufficiently high. Therefore, the obtained decorative article 1 can be more suitably applied to timepiece parts such as radio timepieces and solar timepieces.

  Among the dry plating methods (vapor phase film forming methods) as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the metal coating 4, the above effects become more prominent. That is, by applying sputtering as a method for forming the metal coating 4, the metal coating 4 having a uniform film thickness, uniform, and particularly excellent adhesion to the oxide coating 3 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 4, even if the metal film 4 to be formed is relatively thin, the variation in film thickness can be made particularly small. For this reason, the transparency of the electromagnetic wave of the ornament 1 can be further improved, for example, while making the durability of the ornament 1 obtained high. Therefore, the obtained decorative article 1 can be more suitably applied to timepiece parts such as radio timepieces and solar timepieces.

In addition, when applying the dry plating method as described above, for example, the metal film 4 can be easily and easily treated by performing treatment in an inert gas atmosphere such as argon gas using the metal constituting the metal film 4 as a target. It can be reliably formed. Further, when the above-described oxide film forming step is performed by a dry plating method, for example, the composition of the atmospheric gas in the vapor deposition apparatus (in the chamber) is replaced with an inert gas from an oxygen gas, If necessary, by changing the target, the oxide film forming step and the metal film forming step can be carried out in the same apparatus (without removing the substrate 2 from the apparatus). Thereby, the adhesiveness of the base material 2, the oxide film 3, and the metal film 4 is particularly excellent, and the productivity of the decorative article 1 is also improved.
Moreover, you may perform formation of the metal film 4 combining several different methods and conditions. Thereby, the metal film 4 comprised by the laminated body as mentioned above can be formed suitably.

[Opening Step]
Next, the opening 6 is formed (1d). The opening 6 may be formed at least in the metal film 4, but in the present embodiment, the opening 6 is formed so as to penetrate the oxide film 3.
The method for forming the opening 6 is not particularly limited. For example, a method of removing a part of the metal coating 4 (and the oxide coating 3) (a portion corresponding to the opening 6) by etching, the metal coating 4 (and oxidation). For example, a method of mechanically removing a part of the material coating 3) (a portion corresponding to the opening 6) by blasting or the like is used. In this embodiment, one of the metal coating 4 (and the oxide coating 3) is used. A method of removing a portion (a portion corresponding to the opening 6) by laser light irradiation is used. By using such a method, the opening 6 having a desired shape and arranged in a desired pattern can be easily and reliably formed. Further, by using laser light, the oxide film 3 can be removed together with the metal film 4, and the opening 6 can be efficiently formed.

  The laser light may be irradiated from either the base 2 side or the metal coating 4 side, but as shown in FIG. 4, it is preferable to irradiate from the base 2 side (lower side in the figure). Thereby, it is possible to easily and reliably form the opening 6 having a desired shape and arranged in a desired pattern while preventing the surface of the metal coating 4 from being unintentionally uneven. Can do. Moreover, the oxide film 3 can be removed efficiently together with the metal film 4 by irradiating the laser beam from the substrate 2 side. Further, when the laser beam is irradiated from the substrate 2 side, as shown in FIG. 3, only the metal film 4 is adjusted by adjusting the laser irradiation conditions and the like, and selecting the material of the metal film 4 and the oxide film 3. The decorative article 1 having the selectively provided opening 6 can be obtained easily and reliably. Further, when the laser beam is irradiated from the substrate 2 side, the shape (outside) shown in FIGS. 5 and 6 can be obtained by adjusting the laser irradiation conditions and selecting the material of the metal coating 4 and the oxide coating 3. It is possible to easily and reliably form the opening 6 having a tapered shape in which the opening area increases toward the surface. When the opening 6 has a shape as shown in FIGS. 5 and 6, since the light incident from the outside can be reflected on the inclined surface 61, the reflection direction of the light is widened, and the appearance of the decorative article 1 is The presence of the opening 6 becomes less conspicuous. As a result, the aesthetic appearance of the decorative article is further improved. In such a case, even if the width of the opening 6 (the area of the opening) is relatively large, the presence of the opening 6 is not noticeable. Therefore, the transmittance of electromagnetic waves can be further improved while sufficiently improving the aesthetic appearance of the decorative article 1. As shown in FIGS. 5 and 6, when the width of the opening 6 is not constant in the thickness direction of the metal coating 4, the width of the opening 6 is the smallest part of each opening 6. The value at can be adopted.

The type of laser light irradiated in this step is not particularly limited. For example, ruby laser, semiconductor laser, YAG laser, femtosecond laser, glass laser, YVO ₄ laser, Ne-He laser, Ar laser, CO ₂ laser, Excimer laser etc. are mentioned. Moreover, you may use wavelengths, such as SHG of each laser, THG, and FHG.
The laser light irradiation may be performed through a mask in which a light transmission part (opening part) is formed in a predetermined pattern. Alternatively, for example, the laser light source and the base material 2 may be moved relative to each other while the laser light is irradiated intermittently.

[Coat layer forming step]
Next, a coat layer 5 is formed on the metal coating 4 (1e). Thereby, the decorative article 1 is obtained.
The formation method of the coat layer 5 is not particularly limited, and 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. Coating methods such as chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. When 5 is mainly composed of a resin material as described above, it is preferably formed by painting. Thereby, the coat layer 5 can be formed relatively easily. Further, when the coat layer 5 is formed by painting, it is easy to add a component such as a colorant to the material for forming the coat layer and to adjust the addition amount.

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. As described above, the decorative article of the present invention is excellent in light transmission (electromagnetic wave transmission) and decoration (aesthetic appearance). For this reason, the timepiece of the present invention provided with such a decorative article can sufficiently satisfy the requirements required as a solar timepiece or a radio timepiece. 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. 7 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 7, a wristwatch (portable timepiece) 100 according to this embodiment includes a case (case) 22, a back cover 23, a bezel (edge) 24, and a glass plate (cover glass) 25. . Further, in the case 22, a dial (clock dial) 10 as a decoration of the present invention as described above, a solar cell 9, and a movement 21 are housed, and a hand (not shown) Etc.) are stored.
The glass plate 25 is usually made of a highly transparent transparent glass, sapphire, or the like. Thereby, while being able to fully exhibit the aesthetics of the dial 10 as a decorative article of the present invention, a sufficient amount of light can be incident on the solar cell 9.
The movement 21 uses the electromotive force of the solar cell 9 to drive the pointer.

Although omitted in FIG. 7, in the movement 21, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 9, a lithium ion secondary battery, a crystal oscillator as a time reference source, and 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.
In addition, the movement 21 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 9 has a function of converting light energy into electric energy. The electric energy converted by the solar cell 9 is used for driving the movement.
In the solar cell 9, 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 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 26 is fitted and fixed to the barrel 22, and a shaft portion 271 of a crown 27 is rotatably inserted into the winding stem pipe 26.
The body 22 and the bezel 24 are fixed by a plastic packing 28, and the bezel 24 and the glass plate 25 are fixed by a plastic packing 29.
Further, the back cover 23 is fitted (or screwed) to the body 22, and a ring-shaped rubber packing (back cover packing) 60 is inserted in a compressed state in these joint portions (seal portions) 50. Has been. With this configuration, the seal portion 50 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove 272 is formed on the outer periphery of the shaft portion 271 of the crown 27, and a ring-shaped rubber packing (crown packing) 30 is fitted in the groove 272. The rubber packing 30 is in close contact with the inner peripheral surface of the winding stem pipe 26 and is compressed between the inner peripheral surface and the inner surface of the groove 272. With this configuration, the space between the crown 27 and the winding stem pipe 26 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 27 is rotated, the rubber packing 30 rotates together with the shaft portion 271 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 26.

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. For example, an intermediate process such as cleaning may be performed between the oxide film forming process and the metal film forming process, or between the opening forming process and the coat layer forming process. Further, post-treatment such as polishing (lapping) may be performed after the formation of the coating layer. Moreover, you may pre-process with respect to the base material before an oxide film formation process.

In the embodiment described above, the coating layer 5 has been described as being present on the outer surface side of the metal coating, but an opening in which a part of the coating layer 5 is provided in the metal coating 4 and the oxide coating 3. 6 may be used. Thereby, the adhesiveness of the coat layer 5 is further improved.
Moreover, although embodiment mentioned above demonstrated as a thing in which an ornament is provided with a coat layer, the ornament does not need to be provided with the coat layer.
In the above-described embodiment, the base material and the oxide film are adjacent to each other, and the oxide film and the metal film are adjacent to each other. For example, at least one intermediate layer is provided between them. There may be.

  In the above-described embodiment, as shown in FIG. 2, the decorative article 1 has been described as having a plurality (large number) of openings 6. However, in the present invention, the decorative article 1 has at least the openings. You only need one. For example, as shown in FIGS. 8 and 9, the opening 6 is provided with a number of island-shaped regions (light reflecting regions) that can reflect light formed of a metal film. Also good. In such a case, the shape of the light reflection region (the shape when the metal coating is viewed in plan) may be any shape such as a substantially triangular shape, a substantially quadrangular shape, a substantially pentagonal shape, a substantially hexagonal shape or the like, a substantially circular shape, or a substantially oval shape. However, it is preferably substantially polygonal. Thereby, the transmittance of electromagnetic waves (radio waves, light) can be further increased, and the aesthetic appearance of the decorative article can be further improved.

Next, specific examples of the present invention will be described.
1. Manufacture of decorative products (Example 1)
Decorative articles (watch exterior parts (dial plates)) were produced by the method described below.
First, a base material having the shape of a wristwatch exterior part (a dial plate) was produced by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained base material was substantially disc-shaped and had a diameter of about 27 mm × thickness: about 0.5 μm. Absolute refractive index I _B of the polycarbonate constituting the substrate was 1.58.
Next, this base material was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.

An oxide film composed of TiO ₂ was formed on the surface of the substrate thus cleaned by sputtering as described below (oxide film formation step).
First, the cleaned substrate was mounted in a sputtering apparatus, and then the inside of the sputtering apparatus was evacuated (depressurized) to 3 × 10 ⁻³ Pa while preheating 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 such a state, Ti is used as a target, and discharge is performed under the conditions of input power: 1500 W and processing time: 4.0 minutes, so that it is composed of TiO ₂ (absolute refractive index I _O : 2.51). An oxide film was formed.
The average thickness of the oxide film thus formed was 0.08 μm.

Subsequently, a metal film composed of Ag was formed on the surface of the oxide film formed as described above by sputtering as described below (metal film forming step).
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: 1500 W and treatment time: 2.5 minutes, thereby forming a metal film composed of Ag.
The average thickness of the metal film thus formed was 0.20 μm.

Next, the base material coated with the oxide film and the metal film obtained as described above was washed. As washing, first, alkali immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, water washing for 10 seconds, and pure water washing for 10 seconds.
Next, an opening penetrating the metal film and the oxide film was formed.
The opening was formed by irradiating laser light from the substrate side (the surface side opposite to the surface on which the oxide film or metal film of the substrate was coated).
A YVO ₄ laser was used as the laser. At this time, laser light was intermittently irradiated while relatively moving the laser light source and the substrate. Laser light irradiation was performed under the conditions of current value: 40 [A], frequency: 35 kHz, and processing speed: 1500 [mm / s].
Thereby, a large number of circular openings penetrating the oxide film and the metal film were formed. The width (diameter) W of the formed openings was 50 μm, and the pitch P of the openings was 160 μm. Further, the ratio of the area occupied by the opening (the ratio of the occupied area of the opening) when the metal film was viewed in plan was 30%.

Thereafter, a coat layer made of polyurethane was formed on the metal coating (coat layer forming step). As a result, a decorative article (a wristwatch exterior part (a dial)) was obtained (see FIGS. 1 and 2). The coating layer was formed by a spin coating method. The average thickness of the formed coating layer was 10 μm. The absolute refractive index I _C of the material constituting the coat layer was 1.54.
In addition, the thickness of the oxide film, the metal film, and the coat layer was measured according to a microscope cross-section test method defined in JIS H5821.

(Examples 2 to 4)
By changing the treatment time of the oxide film forming process and the metal film forming process, the average thickness of the oxide film and the metal film is shown in Table 1, and by changing the laser light irradiation conditions, A decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 1 except that the shape of the opening, the width W, the pitch P, and the ratio of the occupied area were as shown in Table 1.
(Example 5)
A decorative article (exterior part for watch (character plate)) was produced in the same manner as in Example 1 except that acrylonitrile-butadiene-styrene copolymer (ABS resin) was used as a constituent material of the base material.

(Example 6)
When forming an oxide film (oxide film formation step), Cr is used as a target, argon flow rate: 40 ml / min, oxygen flow rate: 10 ml / min, input power: 1000 W, treatment time: 3.5 minutes A decorative article (a watch exterior part (a dial)) was produced in the same manner as in Example 1 except that the discharge was performed in the same manner as in Example 1. The formed oxide film was composed of CrO, and the average thickness was 0.08 μm.

(Example 7)
When carrying out the metal coating (metal coating forming step), the above-mentioned implementation was performed except that the discharge was performed using Cr as a target, argon gas flow rate: 20 ml / min, input power: 500 W, treatment time: 5 minutes. In the same manner as in Example 6, a decorative article (watch exterior part (dial plate)) was produced. The formed metal film was made of Cr, and the average thickness was 0.20 μm.

(Examples 8 to 10)
By changing the treatment time of the oxide film forming process and the metal film forming process, the average thickness of the oxide film and the metal film is shown in Table 1, and by changing the laser light irradiation conditions, A decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 7 except that the shape of the opening, the width W, the pitch P, and the ratio of the occupied area were as shown in Table 1.

(Example 11)
The above-described implementation was performed except that, when the metal film was formed (metal film formation step), the discharge was performed using Sn as a target, argon gas flow rate: 20 ml / min, input power: 1000 W, treatment time: 2 minutes. In the same manner as in Example 1, a decorative article (watch exterior part (dial plate)) was produced. The formed metal film was composed of Sn, and the average thickness was 0.15 μm.

(Example 12)
Except that the metal coating is formed as a laminate of an Al layer composed of Al and an In layer composed of In, a decorative article (watch exterior part (dial plate)) in the same manner as in Example 5 above. Manufactured.
Both the Al layer and the In layer were formed by sputtering.
The Al layer was formed by performing discharge under the conditions of using Al as a target, argon gas flow rate: 30 ml / min, input power: 1500 W, and processing time: 1 minute.

The In layer was formed by performing discharge under the conditions of using In as a target, argon gas flow rate: 30 ml / min, input power: 1600 W, and processing time: 1 minute.
The average thicknesses of the formed Al layer and In layer were 0.05 μm and 0.05 μm, respectively. Note that the Al layer is a layer in contact with the oxide film, and the In layer is a layer in contact with the coat layer.

(Example 13)
Except that the metal coating was formed as a laminate of a Ti layer composed of Ti and a Cr layer composed of Cr, a decorative article (watch exterior part (dial plate)) in the same manner as in Example 1 Manufactured.
Both the Ti layer and the Cr layer were formed by sputtering.
The Ti layer was formed by performing discharge under the conditions of using Ti as a target, argon gas flow rate: 20 ml / min, input power: 600 W, treatment time: 3 minutes.

The Cr layer was formed by performing discharge under the conditions of using Cr as a target, argon gas flow rate: 30 ml / min, input power: 500 W, and processing time: 1.5 minutes.
The average thicknesses of the formed Ti layer and Cr layer were 0.05 μm and 0.05 μm, respectively. Note that the Ti layer is the layer in contact with the oxide film, and the Cr layer is the layer in contact with the coat layer.

(Example 14)
A decorative article (watch exterior part (dial plate)) in the same manner as in Example 6 except that the metal coating was formed as a laminate of an Ag layer made of Ag and an Au layer made of Au. Manufactured.
Both the Ag layer and Au layer were formed by sputtering.
The Ag layer was formed by performing discharge under the conditions of using Ag as a target, argon gas flow rate: 35 ml / min, input power: 1700 W, treatment time: 1 minute.

The Au layer was formed by performing discharge under the conditions of using Au as a target, argon gas flow rate: 30 ml / min, input power: 1700 W, and processing time: 30 seconds.
The average thicknesses of the formed Ag layer and Au layer were 0.10 μm and 0.03 μm, respectively. The Ag layer is a layer in contact with the oxide film, and the Au layer is a layer in contact with the coat layer.

(Example 15)
Except for forming the opening by selectively removing only the metal film while leaving the oxide film by changing the condition of the opening forming process (laser light irradiation condition), In the same manner, a decorative article (a watch exterior part (a dial)) was manufactured (see FIG. 3). In the obtained decorative article, the oxide film and the coat layer were in close contact with each other at the site corresponding to the opening.
The laser beam was irradiated under the conditions of current value: 25 [A], frequency: 35 kHz, and processing speed: 1500 [mm / s].

(Example 16)
A decorative article (watch exterior part (character plate)) is manufactured in the same manner as in Example 15 except that the shape of the opening is changed as shown in FIG. 8 by changing the laser light irradiation pattern. did.
(Example 17)
A decorative article (watch exterior part (character plate)) was produced in the same manner as in Example 16 except that the coat layer was made of an acrylic resin (absolute refractive index I _C : 1.50). .

(Comparative Example 1)
A decorative article (watch exterior part (dial)) was prepared in the same manner as in Example 3 except that a metal film was formed directly on the surface of the cleaned substrate without forming an oxide film. Manufactured.
(Comparative Example 2)
A decorative article (watch exterior part (dial plate)) was produced in the same manner as in Example 3 except that the step of forming the metal film and the step of forming the coat layer were omitted.

(Comparative Example 3)
A decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 1 except that the step of forming the opening was omitted.
(Comparative Examples 4 and 5)
A decorative article (for wristwatches) was used in the same manner as in Example 1 except that the shape, width W, pitch P, and occupied area ratio of the openings were changed as shown in Table 1 by changing the laser light irradiation conditions. An exterior part (a dial) was manufactured.
Table 1 summarizes the structures of the decorative articles of each example and each comparative example. In Table 1, polycarbonate was indicated by PC, and acrylonitrile-butadiene-styrene copolymer (ABS resin) was indicated by ABS.

2. Appearance evaluation of ornaments Each ornament produced in each of the above Examples and Comparative Examples was visually and microscopically observed, and the appearance was evaluated according to the following four criteria.
A: Appearance is excellent.
○: Good appearance.
Δ: Appearance is slightly poor.
X: Appearance defect.

3. Evaluation of Light Transmittance of Wristwatch Dial The light transmittance of each decorative article (dial plate) manufactured in each of the above Examples and Comparative Examples was evaluated by the following method.
First, the solar cell and each dial were placed in a dark room. Thereafter, light from a fluorescent lamp (light source) separated by a predetermined distance was made incident on the light receiving surface of the solar cell alone. At this time, the power generation current of the solar cell was A [mA]. Next, light from a fluorescent lamp (light source) spaced a predetermined distance was made incident in the same manner as described above in a state where the dial plate was superimposed on the upper surface of the light receiving surface of the solar cell. In this state, the generated current of the solar cell was B [mA]. Then, the light transmittance of the dial represented by (B / A) × 100 was calculated and evaluated according to the following four-stage criteria. It can be said that the greater the light transmittance of the dial, the better the light transmittance of the dial.
A: 32% or more.
○: 25% or more and less than 32%.
Δ: 17% or more and less than 25%.
X: Less than 17%.

  Thereafter, a wristwatch as shown in FIG. 7 was manufactured using the dial plates manufactured in the respective Examples and Comparative Examples. Then, each manufactured wristwatch was put in a dark room. Thereafter, light from a fluorescent lamp (light source) spaced a predetermined distance was made incident from a surface on the dial side (surface on the glass plate) of the watch. At this time, the irradiation intensity was changed at a constant speed so that the irradiation intensity of light gradually increased. As a result, in the timepiece of the present invention, the movement was driven even when the irradiation intensity was relatively small. On the other hand, in the timepieces of Comparative Examples 3 and 4, the movement was not confirmed even when the irradiation intensity was relatively high.

4). Evaluation of radio wave permeability The radio wave permeability of each decorative article manufactured in each of the above Examples and Comparative Examples was evaluated by the following method.
First, a watch case and a wristwatch internal module (movement) equipped with an antenna for receiving radio waves were prepared.
Next, a wristwatch internal module (movement) and a dial as a decoration were incorporated in the watch case, and the radio wave reception sensitivity in this state was measured.

Using the reception sensitivity in a state where no dial is incorporated as a reference, the reduction amount (dB) of reception sensitivity when the dial is incorporated was evaluated according to the following four criteria. It can be said that the lower the radio wave reception sensitivity is, the better the radio wave transmission of the dial is.
A: No decrease in sensitivity is observed (below the detection limit).
○: A decrease in sensitivity is observed at less than 0.7 dB.
(Triangle | delta): The fall of a sensitivity is 0.7 dB or more and less than 1.0 dB.
X: The reduction in sensitivity is 1.0 dB or more.

5. Evaluation of Adhesiveness of Film (Oxide Film, Metal Film) Each decorative article manufactured in each of the above Examples and Comparative Examples was subjected to two kinds of tests as shown below to form a film (oxide film, metal film). The adhesion was evaluated.
5-1. Bending test For each decorative product, an iron bar with a diameter of 4 mm was used as a fulcrum, and after bending at 30 ° with respect to the center of the decorative product, the appearance of the decorative product was visually observed. Evaluation was carried out according to a four-stage standard. Bending was performed in both compression / tension directions.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.

5-2. Thermal cycle test Each decorative article 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.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.
These results are shown in Table 2.

As is clear from Table 2, the decorative articles of the present invention all have an excellent aesthetic appearance, and are excellent in electromagnetic wave (light, radio wave) permeability, and coating (oxide coating, metal coating). The adhesion was also excellent.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, the decorative article of Comparative Example 1 having no oxide film was inferior in the adhesion of the film (metal film). Moreover, the decorative article of Comparative Example 2 having no metal film was inferior in aesthetic appearance. In addition, in the decorative article of Comparative Example 3 that does not have an opening and the decorative article of Comparative Example 4 in which the ratio of the occupied area of the opening is small, sufficient electromagnetic wave (light, radio wave) permeability could not be obtained. Moreover, the decorative article of Comparative Example 5 having a large proportion of the area occupied by the openings was inferior in aesthetic appearance.
Moreover, the timepiece as shown in FIG. 7 was assembled using the dials (decorative items) obtained in the examples and the 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 sectional drawing which shows suitable embodiment of the ornament of this invention. It is a top view which shows suitable embodiment of the ornament of this invention. It is sectional drawing which shows other suitable embodiment of the decorative article of this invention. It is sectional drawing which shows suitable embodiment of the manufacturing method of the ornament of this invention. It is sectional drawing which shows other suitable embodiment of the decorative article of this invention. It is sectional drawing which shows other suitable embodiment of the decorative article of this invention. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (portable timepiece) of this invention. It is a top view which shows other suitable embodiment of the decorative article of this invention. It is a top view which shows other suitable embodiment of the decorative article of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Ornament 2 ... Base material 3 ... Oxide film 4 ... Metal film 5 ... Coat layer 6 ... Opening 61 ... Inclined surface 10 ... Dial (clock face dial) 9 ... Solar cell 21 ... Movement 22 ... Body ( Case) 23 ... Back cover 24 ... Bezel (edge) 25 ... Glass plate (cover glass) 26 ... Winding pipe 27 ... Crown 271 ... Shaft 272 ... Groove 28 ... Plastic packing 29 ... Plastic packing 30 ... Rubber packing (Ryu) 60 ... Rubber packing (back cover packing) 50 ... Joint part (seal part) 100 ... Watch (portable watch)

Claims (15)

A substrate composed mainly of plastic material;
An oxide film mainly composed of a metal oxide provided on the substrate;
A metal film mainly composed of a metal material provided on the surface of the oxide film opposite to the surface facing the substrate;
The metal coating is provided with an opening,
The decorative article characterized in that the area ratio occupied by the opening when the metal coating is viewed in plan is 25 to 35%.   The ornament according to claim 1, wherein the opening penetrates the oxide film.   The decorative article according to claim 1 or 2, wherein the opening has a width of 10 to 100 µm.   The decorative article according to any one of claims 1 to 3, wherein the base material is made of a material containing at least one selected from polycarbonate and acrylonitrile-butadiene-styrene copolymer (ABS resin).   The decorative article according to any one of claims 1 to 4, wherein the oxide film is made of a material containing at least one selected from titanium oxide and chromium oxide.   The decorative article according to any one of claims 1 to 5, wherein an average thickness of the oxide film is 0.005 to 1.0 µm.   The decorative article according to any one of claims 1 to 6, wherein the metal coating is made of a material containing at least one selected from Ag, Cr, Au, Al, Ti, Sn, and In.   The decorative article according to any one of claims 1 to 7, wherein an average thickness of the metal coating is 0.005 to 1.5 µm.   The decorative article according to any one of claims 1 to 8, wherein a sum of an average thickness of the oxide coating and an average thickness of the metal coating is 0.01 to 2.5 µm.   The decorative article according to any one of claims 1 to 9, further comprising a coat layer mainly made of a resin material on the metal film.   The decorative article according to any one of claims 1 to 10, wherein the coat layer is mainly composed of a urethane resin and / or an acrylic resin.   The ornament according to any one of claims 1 to 11, wherein the ornament is a watch exterior part.   The decorative article according to any one of claims 1 to 12, wherein the decorative article is a radio timepiece component.   The decorative article according to any one of claims 1 to 13, wherein the decorative article is a timepiece dial.   A timepiece comprising the decorative article according to claim 1.

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