JP2008139119A - Decorative product, method of manufacturing decorative product, and watch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an accessory excellent in transparency to electromagnetic waves (electric waves, light) and excellent in aesthetic appearance as well, and a method for manufacturing the accessory, and to provide a watch equipped with the accessory. <P>SOLUTION: The accessory 1 has a substrate 12 made of material having optical transparency, a coat 13 which is provided on the side of a first face 121 being one major face of the substrate 12 and reflects or absorbs at least a part of incident light, and a coat 14 which is provided on the side of a second face 122 being a major face opposite to the first face 121 of the substrate 12 and reflects or absorbs at least a part of incident light. The coat 13 is composed of openings 132 of a predetermined pattern, and a real part 131 as an area other than those. The coat 14 is composed of openings 142 of a predetermined pattern, and a real part 141 as an area other than those, and the real part 141 is arranged in at least a part of a substrate portion corresponding to each opening 132, in a plan view of the substrate 12. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  A dial for a solar timepiece (a timepiece equipped with a solar cell) is required to have a function (light transmittance) that transmits a sufficient amount of light (electromagnetic wave) for the solar cell to generate a sufficient electromotive force. For this reason, conventionally, a highly transparent plastic member has been used as a dial for a solar timepiece. However, plastics generally lack a sense of quality and are inferior in aesthetic appearance compared to metal materials such as Au and Ag. For this reason, a dial plate obtained by attaching a metal film made of a metal material and provided with an opening to one main surface of a plastic substrate via an adhesive has been proposed (for example, Patent Document 1).

  However, in order to take in a sufficient amount of external light, by increasing the size of each small hole or increasing the number of small holes sufficiently, etc. It is necessary to increase the total area (sum of the plurality of small hole areas). In such a case, small holes are conspicuous in the appearance of the timepiece dial, and the timepiece dial is inferior in aesthetics (aesthetic appearance). For the purpose of improving the aesthetic appearance of the timepiece dial, reducing the size of each small hole or reducing the number of small holes can transmit a sufficient amount of external light. It may not be possible. Thus, in the past, it has been difficult to obtain a timepiece dial that has both excellent decorativeness (aesthetic appearance) and excellent light (electromagnetic wave) transparency.

  Also, in recent years, radio timepieces that receive radio waves and adjust the time are rapidly spreading. Even in such a radio timepiece or the like, a dial or the like is required to have excellent permeability of electromagnetic waves (radio waves). Solar radio timepieces incorporating a solar battery and further incorporating a radio wave receiving antenna are becoming widespread. In the dial plate applied to the timepiece as described above, as in the above case, it is required to have both excellent decorativeness (aesthetic appearance) and excellent electromagnetic wave permeability. It was difficult.

JP 11-326549 A

  An object of the present invention is to provide a decorative article that is excellent in electromagnetic wave (radio wave, light) permeability and has an excellent aesthetic appearance, and a decorative article manufacturing method capable of manufacturing the decorative article. Another object of the present invention is to provide a watch provided with the ornament.

Such an object is achieved by the present invention described below.
The decorative article of the present invention includes a substrate made of a light transmissive material,
A coating A which is provided on the first surface side which is one main surface of the substrate and reflects or absorbs at least part of incident light;
A coating B that is provided on a second surface side that is a main surface opposite to the first surface of the substrate and reflects or absorbs at least part of incident light;
The coating A comprises an opening A having a predetermined pattern and a real part A as the other part,
The coating B is composed of an opening B having a predetermined pattern and a real part B as other parts.
When the substrate is viewed in plan, the real part B is arranged on at least a part of the part corresponding to each opening A.
As a result, it is possible to provide a decorative product that is excellent in electromagnetic wave (radio wave, light) permeability and excellent in aesthetic appearance.

In the decorative article of the present invention, the shape of the real part B is preferably substantially similar to the opening A.
As a result, it is possible to provide a decorative article that is particularly excellent in permeability of electromagnetic waves (radio waves, light) and that is particularly excellent in aesthetic appearance.
In the decorative article of the present invention, it is preferable that the center of the real part B is located at substantially the same place as the center of the corresponding opening A when the decorative article is viewed in plan.
As a result, it is possible to provide a decorative article that is particularly excellent in permeability of electromagnetic waves (radio waves, light) and that is particularly excellent in aesthetic appearance.
In the decorative article of the present invention, it is preferable that the real part B covers all of the opening A when the substrate is viewed in plan.
As a result, it is possible to provide a decorative product that is particularly excellent in aesthetic appearance.

The decorative article of the present invention is used so that external light enters from the first surface,
It is preferable that the coating A is made of a material that reflects light near the surface facing the substrate.
As a result, it is possible to provide a decorative article having particularly excellent electromagnetic wave (radio wave, light) permeability.
The decorative article of the present invention is used so that external light enters from the first surface,
The area ratio of the opening A in the coating A is preferably 25 to 60%.
As a result, it is possible to provide a decorative article that is particularly excellent in permeability of electromagnetic waves (radio waves, light) and that is particularly excellent in aesthetic appearance.

The decorative article of the present invention is used so that external light enters from the first surface,
The color tone on the first surface side of the coating A and the color tone on the first surface side of the coating B are preferably different.
Thereby, an opening part can be made especially inconspicuous and the ornament which was especially excellent in the aesthetic appearance can be provided.
In the decorative article of the present invention, the average thickness of the substrate is preferably 200 to 1000 μm.
As a result, it is possible to provide a decorative article that is particularly excellent in permeability of electromagnetic waves (radio waves, light) and that is particularly excellent in aesthetic appearance.

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 excellent in radio wave transmission. 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.
The timepiece dial is required to have excellent electromagnetic wave permeability and excellent aesthetic appearance, for example, in radio timepieces and solar timepieces, etc., but according to the present invention, these requirements must be satisfied at the same time. Can do.

The method for producing a decorative article of the present invention is a method for producing the decorative article of the present invention,
A substrate preparation process for preparing a substrate;
Forming the film with openings in a predetermined pattern by performing film formation in a state where a mask having openings in a predetermined pattern is arranged near the surface of at least one main surface of the substrate A film forming process to
And a mask removing process for removing the mask.
Thereby, while being excellent in the permeability | transmittance of electromagnetic waves (a radio wave, light), the manufacturing method of the decorative article excellent in the aesthetic appearance can be provided.
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 excellent electromagnetic wave permeability to the inside and excellent aesthetic appearance. 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 possible to provide a decorative article that is excellent in electromagnetic wave (radio wave, light) permeability and has an excellent aesthetic appearance, and a decorative article manufacturing method that can manufacture the decorative article. Moreover, the timepiece provided with the ornament can be provided.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
<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.
FIG. 1 is a schematic cross-sectional view showing a decorative article according to the first embodiment of the present invention, and FIG. 2 is a schematic diagram for explaining an example of the shape (pattern) of the opening included in the decorative article of the first embodiment. FIG. 3 is a schematic plan view for explaining another example of the shape (pattern) of the opening included in the decorative article of the first embodiment, and FIG. 4 shows the decorative article of the present invention. It is typical sectional drawing which shows the method to manufacture.

As shown in FIG. 1, the decorative article 1 according to the present embodiment is provided on the substrate 12 made of a light-transmitting material and the first surface 121 side which is one main surface of the substrate 12, and is incident on the substrate 12. The coating (coating A) 13 that reflects or absorbs at least a part of the emitted light and the second surface 122 side that is the main surface opposite to the first surface of the substrate, and at least one of the incident light And a coating (coating B) 14 that reflects or absorbs the portion.
The coating A13 includes an opening portion (opening portion A) 132 having a predetermined pattern and a real portion (real portion A) 131 as the other portion, and the coating B14 includes an opening portion (opening) having a predetermined pattern. Part B) 142 and a real part (real part B) 141 as other parts.

The real part A131 and the real part B141 are difficult to pass electromagnetic waves (light, radio waves). However, the openings A132 and B142 are provided, so that the coating A13 and the coating B14 sufficiently absorb the electromagnetic waves. Can be transmitted.
Note that either the first surface 121 side or the second surface 122 side may be the outer surface side, and electromagnetic waves may be incident on the substrate 12 from either side. Unless otherwise noted, the description will be made assuming that the upper side (first surface 121 side) in the figure is the outer surface side, and electromagnetic waves are incident on the substrate 12 from the coating A13.

In the ornament 1, when the substrate 12 is viewed in plan, the real part B <b> 141 is disposed on at least a part of the part corresponding to the opening A <b> 132. Thereby, when the ornament is viewed from the outside, the opening A132 is less noticeable, and incident electromagnetic waves (light, radio waves) can be efficiently transmitted. That is, when viewed in plan, the real part B141 is arranged on at least a part of the part corresponding to the opening A132, so that the part (transmission part) where the opening A132 and the opening B142 overlap is minute. It becomes difficult, and it becomes difficult to look directly at the members and the like in the back of the decorative article 1. In addition, the opening A132 is difficult to be visually recognized as an opening due to the corresponding real part B141. Moreover, even if it is a case where it sees from diagonally, a part of opening part A132 can be covered by the real part B141, and while the opening part A132 becomes difficult to be noticed as an opening part, it depends on the angle which looks at the ornament 1 The variation in appearance can be reduced. As a result, the aesthetic appearance of the decorative article 1 can be made excellent.
Moreover, since the decorative article 1 can overlap the coating A13 and the coating B14 to hide the members and the like at the back of the decorative article 1, the area ratio of the opening A132 and the opening B142 can be made relatively large. . For this reason, the amount of electromagnetic waves incident on the substrate 12 can be increased, and the decorative article 1 has excellent electromagnetic wave permeability.

  An electromagnetic wave incident from the outside can take various paths, but there are a path through which the decorative article 1 is transmitted and a path through which it is reflected. The electromagnetic wave transmitted through the decorative article 1 can be used for power generation or the like when a solar cell or the like is installed, for example. On the other hand, the light reflected by the decorative article 1 can contribute to the improvement of the aesthetic appearance of the decorative article 1. As the incident path, for example, as shown in the incident path L1 shown in the figure, it can pass through the decorative article 1 without being reflected, and as in the incident path L2, the decorative article reflects the coating A13 and the coating B14. 1 can be passed. Further, there are cases where the light is reflected and not transmitted through the decorative article 1 as in the incident paths L3 and L4. In addition, the electromagnetic wave incident on the substrate 12 may be emitted to the outside of the decorative article 1 from various openings A132 or B142 after being repeatedly reflected a plurality of times by the coating A13 and the coating B14.

  Thus, since the ornament 1 can take a complicated path | route for the electromagnetic wave which injected into the board | substrate 12, the electromagnetic wave emitted from opening A132 becomes the thing by which the electromagnetic wave from these paths was averaged. For this reason, for example, even if there is a portion (transmission portion) where the opening A132 and the opening B142 overlap, this portion can be made inconspicuous. For example, even when light is incident not only from the opening A132 but also from the opening B142, the presence of the opening A132 can be made inconspicuous when observed from the first surface 121 side. In addition, since a large amount of electromagnetic waves can pass through the decorative article 1 through such a complicated path, most of the electromagnetic waves incident on the substrate 12 can pass through the decorative article 1. The electromagnetic wave permeability of the decorative article 1 is excellent.

  In addition, since the decorative article 1 can have a relatively large pattern of the opening A132 and the opening B142, it is easy to form the coating A13 and the coating B14 during manufacturing. Further, since the coating A13 and the coating B14 are formed on the opposite surface of the substrate 12, it is not necessary to strictly align the opening A132 and the real part B141, and the productivity is high at the time of manufacturing. The yield can be increased. Moreover, such a decorative article 1 can be manufactured particularly efficiently in a manufacturing method as described later.

  In particular, as shown in FIGS. 2 and 3, in the present embodiment, the decorative part 1 covers the entire opening A132 when the substrate 12 is viewed in plan. That is, when the ornament 1 is viewed in plan, the area of the opening when the ornament 1 is viewed as a whole is 0%. Thereby, even when solar cells or the like are present inside, they can be particularly difficult to visually recognize from the outside. Moreover, electromagnetic waves (light, radio waves) from the outside can sufficiently pass through the decorative article 1 through the incident path as described above. For this reason, the decorative article 1 is particularly excellent in aesthetic appearance, and can effectively transmit electromagnetic waves (light, radio waves) from the outside.

[substrate]
The substrate 12 is made of a material having electromagnetic wave permeability.
Examples of materials having electromagnetic wave transparency include organic polymer materials such as various plastic materials, and various glasses such as soda glass, crystalline glass, quartz glass, lead glass, potassium glass, borosilicate glass, and alkali-free glass. Materials and the like. Among these, organic polymer materials are preferable, and plastic materials are more preferable. Thereby, the transparency of electromagnetic waves (radio waves, light) can be made particularly excellent while the aesthetic appearance of the decorative article 1 is sufficiently excellent. Further, if the substrate 12 is mainly composed of a plastic material, the degree of freedom of molding of the substrate 12 at the time of manufacturing the ornament 1 is increased, and a relatively thin ornament or a complex ornament. Even so, it can be manufactured easily and reliably. Moreover, the productivity of the substrate 12 can be further improved, and as a result, the productivity of the decorative article 1 can be improved.

  Examples of the plastic material constituting the substrate 12 include various thermoplastic resins and various thermosetting resins. For example, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA). , 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 6-6) 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) ), Polyester such as polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyether Sulphone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride Other thermoplastic resins such as fluorine resins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene, etc. , Phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, poly Polyparaxylylene such as dichloroparaxylylene, poly-monofluoro-para-xylylene, and poly-monoethyl-para-xylylene Ren resin, etc., or copolymers, blends, polymer alloys mainly composed of these 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 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 substrate 12, the coating A13, and the coating B
Adhesion with 14 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 can further improve the durability of the decorative article 1 as a whole.

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.
Moreover, the board | substrate 12 may have a site | part comprised with the material which does not contain a plastic material, for example.

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.
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.

The thickness of the substrate 12 is not particularly limited, but is preferably 200 to 1000 μm, and more preferably 300 to 800 μm. As a result, the transparency of electromagnetic waves can be made particularly excellent, and internal devices and the like can be made inconspicuous from the outside.
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.

  Further, the substrate 12 may be subjected to a surface roughening process. For the roughening treatment, for example, streak processing, satin processing, or the like can be used. Thereby, for example, when the first surface 121 is subjected to the ancestralization treatment, the light reflected by the real part B141 and passing through the opening A132 can be scattered by the first surface 121, and the opening The presence of the part A132 can be made particularly difficult to notice, and the member at the tip of the decorative article 1 can be made particularly inconspicuous. For this reason, the decorative article 1 is particularly excellent in aesthetic appearance.

[Coating A]
The coating A is provided on the first surface 121 side, which is one main surface of the substrate 12, and includes an opening A132 having a predetermined pattern and a real part A131 which is the other part.
1. Real part A
The real part A131 is provided as a part other than the opening A132 in the coating A13, and has a function of reflecting or absorbing at least part of the light.
The material constituting the real part A (real part A131) may be any material, for example, various metal materials, various ceramic materials, various colored materials (for example, plastic materials including pigments and dyes) and the like. Of these, one type or two or more types can be used in combination.

  Among the above, when the real part A131 is mainly composed of a metal material, the following effects can be obtained. The metal material generally has a metallic luster and has a function of reflecting light (visible light). Therefore, the coating A13 made of metal functions as a reflective film that reflects light (visible light). Thereby, both surfaces of the real part A131 can have a reflecting function, and the decorative article 1 can obtain particularly excellent light transmission, a high-class feeling, and an aesthetic appearance. Moreover, by having such a real part A131, it is possible to reliably prevent the internal device and the like from being seen through the real part A131. Moreover, the ornament 1 can be manufactured easily and reliably by a method as described later. Further, by manufacturing such a real part A131 by a method described later, it is possible to reduce scratches, uneven thickness of the coating, and the like, and it is possible to accurately form the opening A132 having a desired shape. .

  When the real part A131 is composed of a metal material, various metals (including alloys) can be used as the metal material constituting the real part A131, 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 real part A131 is made of a material (including an alloy) containing 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 coating A13 and the oxide coating described later can be made particularly excellent, and the aesthetic appearance of the decorative article 1 can be made particularly excellent. Further, when the real part A131 is made of the material as described above, the size of the opening A132 is relatively large or the area ratio of the opening A132 occupying the entire surface of the coating A13 is relatively large. Even if it exists, presence of opening part A132 can be made not conspicuous on the external appearance. In addition, even if it is a case where it is comprised with a metal material in this way, real part A131 may contain components other than a metal material.

  Further, the real part A131 may or may not have a uniform composition in each part. For example, the real part A131 may be a stacked body having a plurality of layers. In this case, the material constituted by the layers may be different. Thereby, for example, the real part A131 is provided with a reflective layer (for example, a reflective layer made of a metal material) in the vicinity of the surface facing the substrate 12, and various colors and textures on the light incident side (external surface side) These materials (for example, plastic materials) can be used. In this case, the decorative article 1 can freely design variations in appearance while making the transmittance of electromagnetic waves particularly high. In addition, for example, the real part A131 is formed by using a material having excellent adhesion to the substrate 12 or another layer in contact with the real part A131 on the surface facing the substrate 12, so that the real part A131 has the substrate 12 or the real part A131. The adhesion to other layers in contact with the part A131 can be made excellent. Further, for example, the real part A131 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction.

  In addition, the real part A131 is preferably made of a material that reflects light in the vicinity of the surface facing the substrate 12. Thereby, when light is incident on the substrate 12 from the opening A132, the light in the substrate 12 is reflected by the real part A131, so that it can efficiently pass through the opening B142. For example, when the electromagnetic wave passes through the incident path L3 shown in FIG. 1, the real part A131 can reflect light particularly efficiently and can pass through the opening B142. For this reason, the decorative article 1 is particularly excellent in light transmittance. Such a configuration can be easily obtained by using, for example, a metal material as the constituent material of the real part A131.

  When the real part A131 is made of a metal material, the surface of the real part A131 (the surface on the outer surface side) is substantially flat (smooth) except for the part where the opening A132 is provided, that is, The mirror surface is preferred. Thereby, the aesthetic appearance of the decorative article 1 is particularly excellent. More specifically, the surface roughness Ra of the coating A13 (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. Preferably, it is 0.001 to 0.1 μm. As a result, the above-described effects are exhibited more significantly.

  The average thickness of the real part A131 is not particularly limited, but is preferably 0.005 to 15 μm, more preferably 0.007 to 10 μm, and further preferably 0.01 to 3 μm. . When the average thickness of the real part A131 is a value within the above range, the aesthetic property of the decorative article 1 can be made particularly excellent while sufficiently preventing the internal stress of the real part A131 from increasing. . Further, the adhesion between the oxide film 15 and the real part A131 as described later 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.

2. Opening A
An opening A132 having a predetermined pattern is provided on the coating A13.
The shape of the opening A132 is not particularly limited, and the shape of the opening A132 when the substrate 12 is viewed in plan may be provided as a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, a slit shape, a lattice shape, or the like. Any shape is possible. For example, as shown in FIG. 2A and FIG. 3A, a large number of island-shaped openings A132 can be provided so as to surround the real part A131. If the shape of the opening A132 is such, the width and the like of the opening A132 can be easily and reliably controlled according to the specifications of the decorative article 1 to be manufactured.

  In the coating A13, the width of the opening A132 indicated by W in the drawing is preferably 50 to 200 μm, and more preferably 60 to 150 μm. When the width W of the opening A132 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 A132 is less than the lower limit value, 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 occupied area of the opening A132. There is sex. On the other hand, when the width W of the opening A132 exceeds the upper limit, it may be difficult to make the appearance of the decorative article 1 sufficiently excellent depending on the constituent material, thickness, and the like of the coating A13. .

  Moreover, it is preferable that it is 70-400 micrometers, as for the pitch of opening part A132 represented by P1 in a figure, it is more preferable that it is 80-350 micrometers, and it is further more preferable that it is 90-300 micrometers. When the pitch P1 of the opening A132 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 P1 of the opening A132 is less than the lower limit value, it may be difficult to make the appearance of the decorative article 1 sufficiently excellent depending on the constituent material, thickness, and the like of the coating A13. There is sex. On the other hand, when the pitch P1 of the opening A132 exceeds the upper limit, depending on the ratio of the occupied area of the opening A132, it may be difficult to sufficiently increase the transmittance of the electromagnetic wave as the entire decorative article 1. . Note that the pitch of the openings A132 refers to the distance between the centers of the adjacent openings A132 and A132, and when there are a plurality of adjacent openings A132, Refers to the distance between centers.

The area ratio of the opening A132 in the coating A13 is preferably 25 to 60%, and more preferably 30 to 55%. Thereby, the presence of the opening A132 can be made inconspicuous, and the electromagnetic wave can be sufficiently incident on the substrate 12. For this reason, the transparency of electromagnetic waves can be made particularly excellent while making the aesthetic appearance of the decorative article 1 particularly excellent.
Further, the shape of the pattern of the opening A132 may not be the same. That is, the shape of each opening A may be different.
Moreover, the pitch of the pattern of the openings A132 may be different between the openings A132.

[Coating B]
The coating B14 is provided on the second surface side opposite to the first surface of the substrate 12, and has an opening B142 having a predetermined pattern and a real part B141 which is other part. .
1. Real part B
The real part B141 is arranged corresponding to the opening A132 in the coating B14, and has a function of reflecting or absorbing at least a part of the light.

  The shape of the real part B141 is not particularly limited, but preferably corresponds to the shape of the opening A132. Thereby, since the opening A132 can be covered with the real part B141 having a small area, the area of the opening B142 can be particularly increased. For this reason, the electromagnetic wave permeability of the decorative article 1 is particularly excellent. In particular, for example, as shown in FIGS. 2B and 3B, it is preferable that the opening A132 has a substantially similar shape. Thereby, the opening A132 can be covered with the real part B141 having a smaller area, and the area of the opening B142 can be particularly increased. For this reason, the decorative article 1 has particularly excellent electromagnetic wave permeability.

  In addition, when the ornament 1 is viewed in plan, the center of the real part B141 is preferably substantially the same place as the center of the corresponding opening A132. As a result, the decorative article 1 is not particularly conspicuous in the opening A132, and is particularly excellent in aesthetic appearance. Here, the centers of the real part B141 and the opening A132 indicate the center of gravity in each shape. Specifically, when the distance d between the center of the real part B141 and the center of the corresponding opening A132 is d, the center distance d and the width W of the opening A132 have a relationship of d / W ≦ 0.05. It is preferable to satisfy, and it is more preferable to satisfy the relationship of d / W ≦ 0.02.

  The absolute value of the difference between the pitch P2 of the real part B141 indicated by P2 in the figure and the pitch P1 of the opening A132 is preferably smaller than 10 μm, and more preferably smaller than 5 μm. Thereby, the opening A132 can be covered with the real part B141 having a small area, and the decorative article 1 is particularly excellent in electromagnetic wave permeability. The pitch of the real part B141 indicates the distance between the centers of the adjacent real part B141 and the real part B141. When there are a plurality of adjacent real parts B141, the pitch between the real part B141 and the closest real part B141 is Refers to the distance between centers.

The material constituting the real part B141 may be any material, for example, various metal materials, various ceramic materials, various colored materials (for example, plastic materials including pigments and dyes), etc. One type or a combination of two or more types can be used.
Among these, it is preferable that the real part B141 is mainly composed of a metal material. The metal material generally has a metallic luster and has a function of reflecting light (visible light). In this case, the real part B141 functions as a reflective film that reflects light (visible light). Thereby, the surface facing the substrate of the real part B141 can have a reflection function as described later, and the decorative article 1 can obtain particularly excellent light transmittance, a high-class feeling, and an aesthetic appearance. Moreover, by having such a real part B141, it is possible to reliably prevent an internal device or the like from being seen through the real part B141. Moreover, the ornament 1 can be manufactured easily and reliably by a method as described later. Further, by manufacturing such a real part B141 by a method described later, it is possible to reduce scratches, uneven thickness of the coating, and the like, and it is possible to accurately form the real part B141 having a desired shape. .

  When the real part B141 is made of a metal material, various metals (including alloys) can be used as the metal material constituting the real part B141, 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 real part B141 is made of a material (including an alloy) containing 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 coating B14 and the oxide coating 15 as described later can be made particularly excellent, and the aesthetic appearance of the decorative article 1 can be made particularly excellent. In addition, even if it is the case where real part B141 is comprised with a metal material in this way, it may contain components other than a metal material.

  In addition, the real part B141 is preferably made of a material that reflects light in the vicinity of the surface facing the substrate 12. Thus, when the light is incident on the substrate 12 from the opening A132, the light is reflected by the real part B141, and is emitted from the opening A132 as in the optical path L4 in FIG. 1, for example. Thus, the real part A131 is absorbed or reflected. In the real part A131, part of the reflected light can pass through the opening B142. Further, the light emitted from the opening A132 can be used to improve the gloss of the decorative article 1. For this reason, the decorative article 1 is particularly excellent in light transmission and particularly in aesthetic appearance. Such a configuration can be easily obtained by using, for example, a metal material as the constituent material of the real part B141. In particular, when the vicinity of the surface of the real part A131 facing the substrate 12 is made of a material that reflects light, the decorative article 1 has significantly excellent light transmission.

The average thickness of the real part B141 is not particularly limited, but is preferably 0.005 to 15 μm, more preferably 0.007 to 10 μm, and further preferably 0.01 to 3 μm. . When the average thickness of the real part B141 is a value within the above range, the aesthetics of the decorative article 1 can be made particularly excellent while sufficiently preventing the internal stress of the real part B141 from increasing. . In addition, the adhesion between the oxide film 15 and the real part B141 as described later 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.
Further, the real part B141 may or may not have a uniform composition in each part. For example, the real part B141 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. Further, for example, the real part B141 may be a stacked body having a plurality of layers. In this case, the material constituted by the layers may be different.

  Moreover, it is preferable that the 1st surface 121 side of real part B141 has a different color tone from the 1st surface 121 side of real part A131. As a result, a contrast is generated in the pattern composed of the real part A131 and the real part B141 as shown in FIGS. 2 (c) and 3 (c). For this reason, even when a device or the like behind the decorative article 1 is seen through the opening A132 and the opening B142, it is difficult to recognize the inside and can be inconspicuous. The appearance can be made particularly excellent. Moreover, since the color tone is different, the pattern formed by the real part A131 and the real part B141 can contribute to the improvement of decorativeness as a fine pattern.

In addition, the first surface 121 side of the real part B141 may have the same color tone as the first surface 121 side of the real part A131. Thereby, a sense of unity is obtained in the appearance of the decorative article 1, and the luxury and aesthetic appearance are particularly excellent.
Further, the shape of the real part B141 may not be the same. That is, the shape of each real part B141 may be different.
Moreover, the pitch of the real part B141 may be different for each real part B141.

2. Opening B
Opening B142 is provided in parts other than real part B141 in coat B14. The electromagnetic wave incident on the substrate 12 can be emitted from the decorative article 1 through the opening B142.
In the present embodiment, when viewed in plan from the second surface 122 side, the area ratio of the opening B142 in the coating B14 is preferably 30 to 75%, and more preferably 35 to 70%. . Thereby, it becomes easy for the real part B141 to cover the opening A132, the aesthetic appearance of the decorative article 1 can be made excellent, and the electromagnetic wave permeability of the decorative article 1 is made particularly excellent. be able to.

[Oxide coating]
In the present embodiment, the oxide film 15 is provided on both surfaces of the substrate 12. Thus, in the present embodiment, the coating film A13 or the coating film B14 is not directly provided on the surface of the substrate 12, but the oxide film 15 is interposed between the substrate 12 and the coating film A13 or the coating film B14. Thereby, the electromagnetic wave incident on the substrate 12 can be reflected or refracted at the boundary between the substrate 12 and the oxide film 15. Therefore, for example, when the real part B141 is made of a material that absorbs light, the electromagnetic wave incident substantially perpendicular to the substrate 12 passes through the oxide film 15 and is absorbed by the real part B141. However, electromagnetic waves incident from an oblique direction of the substrate 12 can be reflected at the boundary between the oxide film 15 and the substrate 12 and can pass through the decorative article 1. For this reason, by having such an oxide film 15, the real part B141 can have a mat-like appearance, and the electromagnetic wave permeability of the decorative article 1 can be made excellent. Moreover, the interface which reflects can be increased by interposing the oxide film 15, and therefore, the path of the electromagnetic wave as described above can be made particularly complicated. For this reason, even if a member or the like is present in the back of the ornament 1, it can be particularly difficult to visually recognize, and the aesthetic appearance of the ornament 1 can be particularly excellent. In addition, the interposition of the oxide film 15 can improve the adhesion between the substrate 12 and the film A13 or the film B14 (adhesion through the oxide film 15). In particular, when the coating A13 or the coating B14 is a metal coating, the adhesion to the substrate 12 can be particularly improved, and the floating or peeling (peeling) of the coating A13 and the coating B14 can be effectively prevented. . As a result, the decorative article 1 is excellent in durability.

The oxide film 15 is mainly composed of a metal oxide.
As the metal oxide constituting the oxide film 15, various metal oxides can be used, and 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 15 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 12 and the film A13 or The adhesiveness with the coating B14 can be further improved. The oxide film 15 is made of a transparent material (colorless metal oxide), and transmits light from the substrate 12, the opening A and the opening B, and is a solar cell (power generation unit). To irradiate. Examples of such a material include Ti, Zn, Mg, Mo, Nb, Zr, Sn, and In oxides. Note that the oxide film 15, the components other than the metal oxide (eg, SiO ₂₎ may include a.

Further, when the coating A13 or the coating B14 is a metal coating made of a metal material, the constituent material of the oxide coating 15 may include at least one of the elements constituting the metal coating. In other words, the oxide film 15 and the metal film 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 15 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 has M It may be included. Thereby, the adhesiveness of the oxide film 15 and a metal film further improves.
The constituent material of the oxide film 15 on the first surface 121 and the second surface 122 may be different.

Moreover, although the average thickness of the oxide film 15 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 15 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 coating 15 is increased. Adhesion between the substrate 12 and the film A13 or the film B14 can be made particularly excellent while sufficiently preventing. On the other hand, when the average thickness of the oxide film 15 is less than the lower limit, depending on the constituent materials of the oxide film 15, the substrate 12, the film A13, and the film B14, the substrate 12, the film A13, and the film B14 There is a possibility that the function of improving the adhesiveness of the film will not be sufficiently exhibited. Further, if the average thickness of the oxide film 15 is less than the lower limit value, depending on the method of forming the oxide film 15, pinholes are likely to be generated in the oxide film 15, and the oxide film 15 is provided. The effect may not be fully demonstrated. Moreover, when the average thickness of the oxide film 15 exceeds the upper limit, the variation in film thickness at each portion of the oxide film 15 tends to increase. Further, when the average thickness of the oxide film 15 is particularly large, the internal stress of the oxide film 15 becomes high, and cracks and the like are likely to occur.
Further, the thickness of the oxide film 15 on the first surface 121 and the second surface 122 may be different.

  Further, the oxide film 15 may or may not have a uniform composition at each part. For example, the oxide film 15 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. The oxide film 15 may be a laminate having a plurality of layers. Thereby, for example, the adhesion between the substrate 12 and the coating A13 or the coating B14 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 coating A13 or B14 is coated with the coating A13. Alternatively, the adhesiveness between the substrate 12 and the coating A13 or the coating B14 can be further improved by using a material having excellent adhesiveness with the coating B14. Moreover, when the oxide film 15 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 15 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.

[Decoration]
The ornament 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, 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.

Moreover, it is preferable that the decorative article 1 is applied to a dial plate, particularly among watch 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 decorative article 1 of the present invention, such a requirement can be sufficiently satisfied.
Moreover, it is preferable that the decorative article 1 is applied to a wristwatch, among the exterior parts for a watch. In general, a wristwatch is not necessarily constant in the environment in which it is used, and is required to have excellent decorativeness and practicality under various environments. According to the decorative article 1 of the present invention, such a requirement is required. Can be fully satisfied.

  Further, the decorative article 1 is preferably a radio timepiece part (including a solar radio timepiece part) among the timepiece parts (timepiece exterior parts) for the reasons described below. That is, since the decorative article 1 has the coating A13 and the coating B14 as described above, the decorative article 1 is excellent in electromagnetic wave (light and radio wave) permeability and in aesthetic appearance. In particular, in this embodiment, since the decorative article 1 has the oxide film 15 between the substrate 12 and the coating A13 and the coating B14, the coating A13 and the coating B14 are hardly peeled off and the durability of the decorative article 1 is increased. Excellent in properties. Moreover, even if the thickness of the coating A13 and the coating B14 is relatively thin due to the color tone of the oxide coating 15, the aesthetic appearance of the decorative article 1 as a whole can be made excellent. For these reasons, the decorative article 1 can exhibit an excellent aesthetic appearance and durability, and can have a particularly excellent radio wave permeability. Therefore, the decorative article 1 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 schematic cross-sectional view showing a method for suitably manufacturing the decorative article 1 of the present invention.
Since the decorative article 1 of the present invention can form the opening A132 and the opening B142 having a relatively large pattern as described above, the coating A13 having the opening A132 and the opening B142 easily and efficiently, and The coating B14 can be formed.

The above-described decorative article 1 may be of any method, but as shown in FIG. 4, the decorative article manufacturing method of the present embodiment includes a substrate preparation step (1 a) for preparing the substrate 12, and the substrate 12. Opening is provided in a predetermined pattern by performing vapor phase film formation in a state where a mask (vapor phase film formation mask) 2 having a predetermined pattern in the vicinity of at least one surface is provided. It is preferable to have a film forming process (film forming process) (1c, 1d) for forming the coated film A13 or B14 and a mask removing process (1e) for removing the mask 2. Thereby, the opening part of the film A13 and the film B14 can be manufactured with high accuracy and particularly efficiently. For this reason, according to such a manufacturing method, the decorative article of the present invention can be manufactured easily and reliably. Moreover, since the resulting decorative article can be coated with a uniform thickness, the aesthetic appearance is particularly excellent.
In this embodiment, in addition to these steps, an oxide film forming step (1b) for forming the oxide film 15 on both surfaces of the substrate, and a film forming step similar to the above for the other main surface (Film formation step) (1f, 1g) and mask removal step (1h) are performed.

[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 subjected to such surface processing is compared with that obtained by applying the surface processing to the oxide film 15, the film A13, or the film B14. Further, the glare of the coating A13 or the coating B14 is suppressed, and the aesthetic appearance is particularly excellent. Further, since the substrate 12 is mainly composed of a plastic material, the surface processing as described above can be performed relatively easily. Further, when the coating A13 and / or the coating B14 is formed using a metal material, the oxide coating 15, the coating A13, and the coating B14 are usually relatively thin. When the surface treatment is applied to B14, the oxide film 15, the film A13, or the film B14 at the portion subjected to the surface treatment is completely removed or the surrounding oxide film 15, the film A13, or the film B14 is removed. However, such a problem can be effectively prevented by subjecting the substrate 12 to surface treatment.

[Oxide film forming step]
An oxide film 15 mainly composed of metal oxide is formed on the surface of the main surface of the substrate 12 (1b). The oxide film 15 may be formed on both sides of the main surface, or may be formed only on one side. In the latter case, it may be formed on either main surface. In this embodiment, it shall form on both surfaces.
As described above, the oxide film 15 has excellent adhesion with the substrate 12, the film A13, and the film B14. By forming such an oxide film 15, the durability of the decorative article 1 as a whole can be made particularly excellent.

  The method for forming the oxide film 15 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, and other wet processes such as electroplating, immersion plating, and electroless plating. 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 of forming the oxide film 15, the oxide film 15 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 15, even if the oxide film 15 to be formed is relatively thin, the variation in film thickness is made sufficiently small. Can do. 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. Further, as will be described in detail later, when the coating A13 or the coating B14 is formed by vapor phase film formation, the vapor phase film formation method is applied as the method for forming the oxide film 15 to manufacture the decorative article 1. The present step and the film forming step can be subsequently performed without once removing the substrate 12 in the manufacturing process from the vapor deposition 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 a method for forming the oxide film 15, the above effects become more prominent. That is, by applying sputtering as a method of forming the oxide film 15, the oxide film 15 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 15, even if the oxide film 15 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 above vapor phase film-forming method, for example, by using a metal corresponding to the metal oxide constituting the oxide film 15 as a target and performing the treatment in an atmosphere containing oxygen gas, The oxide film 15 can be easily and reliably formed.
The oxide film 15 may be formed by combining a plurality of different methods and conditions. Thereby, the oxide film 15 comprised by the laminated body as mentioned above can be formed suitably.

[Film Forming Step (Film Forming Step on First Surface Side)]
Next, film formation is performed in a state where a mask (film formation mask) 2 provided with openings 21 in a predetermined pattern is arranged on the oxide film 15 formed as described above. One coating (coating A13 or coating B14) is formed (1c, 1d). In the present embodiment, the coating A13 is described as being formed on the first surface 121 side.

  In this way, the film A13 having the opening A132 is formed by performing film formation with the mask 2 disposed. That is, the opening A132 is formed simultaneously with the formation of the coating A13. By forming the coating A13 in this way, the opening A132 (inverted pattern) corresponding to the pattern of the opening 21 of the mask 2 can be easily and reliably formed. 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. Moreover, since it is not necessary to form an opening by a chemical method (chemical treatment) or a physical method (physical treatment), it is possible to suitably form the coating A13 without unintentional unevenness. Also, by preparing the mask 2 having the openings 21 having a pattern (inverted pattern) corresponding to the openings A132 to be formed, the openings A132 having various patterns can be obtained without greatly changing the formation conditions of the coating A13. It can respond suitably also to the production of the decorative article 1 having That is, it is possible to efficiently cope with multi-product production.

  The method for forming the coating A13 is not particularly limited. For example, a wet coating method such as spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, electrolytic plating, immersion plating, electroless plating, or the like. And chemical vapor deposition (CVD) such as thermal CVD, plasma CVD and laser CVD, vapor deposition such as vacuum deposition, sputtering and ion plating, and thermal spraying.

  When the coating A13 is made of a metal material, the coating A13 is preferably formed by vapor deposition. Examples of the vapor deposition method that can be applied to the formation of the coating A13 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 for forming the coating A13, the coating A13 has a uniform thickness (suppressing unintentional variation in thickness), is uniform, and adheres well to the oxide coating 15. However, it is possible to reliably form a particularly excellent coating A13. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1 can be made particularly excellent. Further, when used as a timepiece component such as a radio timepiece or a solar timepiece, since particularly excellent electromagnetic wave permeability is required, it is generally preferable that the coating A13 be relatively thin as described above, but the coating A13. By applying the vapor phase film forming method as the forming method, even if the film A13 to be formed is relatively thin as described above, the variation in film thickness can be made sufficiently small. For this reason, for example, the durability of the obtained decorative article 1 can be made sufficiently high, and the electromagnetic wave permeability and aesthetic appearance of the decorative article 1 can be made particularly excellent. Therefore, the obtained decorative article 1 can be suitably applied to timepiece parts such as radio timepieces and solar timepieces.

  Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as the method for forming the coating A13, the above effects become more prominent. That is, by applying sputtering as a method for forming the coating A13, it is possible to more reliably form the coating A13 that has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the oxide coating 15. it can. 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 coating A13, even when the coating A13 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 vapor phase film formation as described above, for example, the film A13 is easily and reliably formed by performing processing in an inert gas atmosphere such as argon gas using the metal constituting the film A13 as a target. be able to. Further, when the oxide film forming step 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 film forming step can be performed in the same apparatus (without removing the substrate 12 from the apparatus). As a result, the adhesion of the substrate 12, the oxide coating 15, and the coating A13 is particularly excellent, and the productivity and reliability of the decorative article 1 are also improved.
Further, the coating A13 may be formed by combining a plurality of different methods and conditions. Thereby, film A13 comprised with the above laminated bodies can be formed suitably.

The mask 2 used in this step has openings 21 arranged in a pattern corresponding to the openings A132 of the coating A13 to be formed. That is, it can be said that the mask 2 has the opening 21 other than the portion corresponding to the opening A132 to be formed, and has the opening 21 having a pattern reverse to the opening A132.
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 thickness of the mask 2 is not particularly limited, but it is usually preferable that the thickness be equal to or greater than the thickness of the coating A13 to be formed. Thereby, the coating A13 having the opening A132 having the target shape can be more reliably formed.
When the thickness of the coating A13 to be formed is T _R [μm] and the thickness of the mask 2 is T _M [μm], it is preferable to satisfy the relationship of 29 ≦ T _M −T _R ≦ 199, 49 ≦ It is more preferable to satisfy the relationship of T _M −T _R ≦ 149. Thereby, the effect mentioned above becomes more remarkable.
The specific thickness of the mask 2 is preferably 30 to 200 μm, more preferably 50 to 150 μm, although it depends on the thickness of the coating A13 to be formed.

  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 side of the substrate 12 opposite to the surface facing the mask 2, whereby the mask 2 and the substrate 12 (oxide) as a workpiece on which the coating A 13 is to be formed. The substrate 12) coated with the coating 15 can be reliably adhered. As a result, it is possible to more reliably prevent the coating A13 from being formed on a portion other than the target on the substrate 12, and to ensure excellent aesthetic appearance and electromagnetic wave permeability of the finally obtained decorative article 1. Can be. 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.
In the formation of the coating A13, when the mask 2 is divided into a plurality of members, for example, the mask 2 can be disposed on the oxide coating 15 as follows.

  First, a temporary mask having an opening having a pattern reverse to that of the mask 2 is prepared and disposed on the oxide film 15. Here, the temporary mask has an opening having the same shape as the coating A13 to be formed. Next, the mask 2 is formed on the oxide film 15 with the temporary mask disposed. Next, the mask 2 can be disposed on the oxide film 15 by peeling off the temporary mask.

Although the thickness of the temporary mask depends on the thickness of the coating A13 to be formed, etc., it is preferably 30 to 200 μm, more preferably 50 to 150 μm.
Further, the temporary mask may be made of any material, and various metal materials, various ceramic materials, various plastic materials, and the like as described above can be used.
In this case, the material constituting the mask 2 may be any material, but it adheres to the oxide film 15 when the film A13 is formed, but when the mask 2 is removed, the oxide is formed. It is preferable that the film 15 is easily peeled off. Thereby, the mask 2 can be disposed without damaging the oxide film 15. Further, when forming the coating A13, the coating A13 having a uniform thickness can be formed with high accuracy.

  Examples of such materials include various plastic materials. The plastic material can be coated by dissolving in an organic solvent or the like, and the mask 2 can be easily formed and disposed on the substrate 12. In addition, the mask 2 formed of a plastic material can be dissolved by an organic solvent or the like at the time of peeling, and can be easily peeled off from the oxide film 15.

  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 coating A13 can be effectively prevented from firmly adhering to the mask 2 during film formation. . 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.

[Mask Removal Step (Mask Removal Step on First Surface Side)]
Next, the mask 2 is removed (1e). Thereby, on the surface of the substrate 12 on the side coated with the oxide film 15 and the film A13, the portion corresponding to the opening 21 of the mask 2 is exposed, and the other portions are the real parts. It will be in the state covered with A131.
The removal of the mask 2 can be performed by peeling the mask 2 from the substrate 12 provided with the oxide film 15 and the film A13.

[Film Forming Step (Film Forming Step on Second Surface Side)]
Next, vapor phase film formation is performed in a state where a mask (vapor phase film formation mask) 2 having openings 21 in a predetermined pattern is arranged on the oxide film 15 provided on the other main surface. To form a coating B14 (1f, 1g).
The coating B14 can be formed in the same manner as the above-described coating formation step except that the mask 2 having a predetermined pattern to be formed is used.

[Mask Removal Step (Mask Removal Step on Second Surface Side)]
Finally, the mask 2 is removed (1h). As a result, on the surface of the substrate 12 on the side coated with the oxide film 15 and the film B14, the portion corresponding to the opening 21 of the mask 2 is exposed, and the other portions are the real parts. The decorative article 1 is obtained after being covered with B141.

<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. 5 is a schematic plan view showing an example of the shape (pattern) of the opening included in the decorative article of the second embodiment of the present invention, and FIG. 6 shows the opening of the decorative article of the second embodiment of the present invention. It is a typical top view which shows another example of the shape (pattern) of a part.

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 FIGS. 5C and 6C, in the present embodiment, when the decorative article 1 is viewed in plan, the real part B141 of the coating B14 is only part of the opening A132 of the coating A13. The covering, the opening A132 and the opening B142 form the transmissive portion 16 that is an overlapping portion, that is, a portion that is not covered by either the real part A131 or the real part B141. Thereby, the decorative article 1 has particularly excellent electromagnetic wave permeability. Moreover, in this embodiment, since the transmissive part 16 is formed by the coating A13 and the coating B14 on both surfaces of the substrate, the width of the transmissive part 16 can be easily narrowed. For this reason, the decorative article 1 can make the transmittance of electromagnetic waves particularly excellent while improving the aesthetic appearance.

  By the way, it is also conceivable that a film is formed only on one side without forming a film on both surfaces of the substrate, and an electromagnetic wave is transmitted by providing a fine opening. However, in this case, it is difficult to form a fine opening and it is difficult to form the opening with high accuracy. Further, when viewed in a plan view, even when an opening having the same area as that of the transmissive portion 16 in the present embodiment is formed, the electromagnetic wave permeability cannot be improved as in the present embodiment. . That is, in the ornament 1 of the present embodiment, the thickness of the substrate 12 is added, so that light incident from an oblique direction can be effectively transmitted, and the substantial area through which the electromagnetic wave passes through the transmission part 16 can be increased. . For this reason, the transparency of electromagnetic waves can be made particularly excellent. In addition, in the decorative article 1 of the present embodiment, a large amount of electromagnetic waves can enter the substrate 12, and can pass through the decorative article 1 through many complicated paths as described above. For this reason, the decorative article 1 can make the presence of the opening A132 less conspicuous as compared with the case where a film is formed only on one side, and can further improve the electromagnetic wave permeability.

Further, the shape (pattern) of the opening A132 is not particularly limited, and for example, a pattern similar to that of the first embodiment can be used as shown in FIG. Further, for example, a shape (pattern) as shown in FIG.
Further, the shape of the real part B141 is not particularly limited, and the same shape as that of the first embodiment can be used, but it preferably corresponds to the shape of the opening A132. Thereby, the width W ′ of the transmission part 16 can be easily narrowed, and the transmission part 16 is particularly difficult to be visually recognized. For this reason, the decorative article 1 is particularly excellent in aesthetic appearance. Moreover, since the transmission part 16 can be formed by the real part B141 having a small area, the light transmittance of the decorative article 1 is particularly excellent. In particular, as shown in FIGS. 5B and 6B, it is preferable that the opening A132 has a substantially similar shape. As a result, the transmissive part 16 has a shape as shown in FIGS. 5C and 6C, and the width W ′ of the transmissive part 16 is particularly narrow, while the real part B141 having a particularly small area. The transmission part 16 can be formed. For this reason, the above-mentioned effect can be acquired especially notably.

In the present embodiment, the area ratio of the opening B142 with respect to the coating B14 is preferably 50 to 85%, and more preferably 55 to 80%. As a result, the decorative article 1 can make the transmission part 16 inconspicuous, while making the transmission of electromagnetic waves particularly excellent, and the aesthetic appearance is particularly excellent.
In addition, when the decorative article 1 is viewed in plan, the width W ′ of the transmission part 16 is preferably 5 to 30 μm, and more preferably 10 to 20 μm. Thereby, the ornament 1 can make the presence of the transmission part 16 inconspicuous while making the electromagnetic wave permeability particularly excellent. Note that the width of the transmissive part 16 is equal to PA at an arbitrary point on the boundary between the real part A131 and the opening A132 in the plan view of the decorative article 1, and is equal to the boundary between the real part B141 and the opening B142. When the point close to the number A is PB, it indicates the distance on the plane from PA to PB.

In addition, when the decorative article 1 is viewed in plan, the area ratio of the transmission part 16 is preferably 10 to 45%, and more preferably 15 to 30%. As a result, the decorative article 1 can make the transmission part 16 inconspicuous, while making the transmission of electromagnetic waves particularly excellent, and the aesthetic appearance is particularly excellent.
Moreover, in this embodiment, when the ornament 1 is viewed in plan, it is only necessary that the transmission part 16 is formed, and the real part A131 and the real part B141 may overlap each other.
Moreover, the shape of the transmission part 16 may be different between the transmission parts 16.
Further, the pitch between the transmission parts 16 may be different.
Further, the openings A132 may not be formed by all the openings A132 forming the transmissive part 16.

<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. 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 schematic partial sectional view showing a preferred embodiment of the timepiece (portable timepiece) of the present invention.
As shown in FIG. 7, the wristwatch (portable timepiece) 100 of 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, a dial (clock dial) 10 as a decoration of the present invention as described above, a solar cell 88, and a movement 71 are housed, and a hand (not shown) Etc.) are 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 dial 10 as a decorative article 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. 7, in the movement 71, for example, an electric double layer capacitor for storing the electromotive force of the solar battery 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 above-described method for manufacturing a decorative article, an optional process can be added as necessary.
Further, the steps may be performed in any order as long as they are performed in the above order on each surface of the substrate. For example, each step may be performed alternately on the first surface and the second surface, or the steps for the first surface may be performed after completing all the steps for the second surface. You may do it. Further, for example, either the coating A or the coating B may be formed first, or may be formed simultaneously. Further, for example, the oxide film forming step may be performed at any time after preparing the substrate and before arranging the mask on each surface.

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 is provided and the film is formed. However, the mask may not be used.

In the embodiment described above, the decorative article has been described as having a substrate, an oxide film, a film A, and a film B. However, the decorative article of the present invention is limited to such a configuration. For example, it may not have an oxide film.
In the above-described embodiment, the substrate and the oxide film are adjacent to each other, and the oxide film and the film A or B are adjacent to each other. There may be layers.

In the above-described embodiment, the coating A and the coating B have been described as having a uniform thickness. However, the coating A and the coating B may have different thicknesses at each portion.
Moreover, you may provide the coating layer mainly comprised with the material which has transparency on the surface of the film A and the film B. By having such a coat layer, for example, the glossiness, color tone, etc. can be adjusted while the electromagnetic wave transmittance is sufficiently high, and the aesthetic appearance of the decorative article 1 is further improved. Can do. Further, by having such a coat layer, for example, various properties such as corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, abrasion resistance, and discoloration resistance as the entire decorative article 1 are improved. It is possible to prevent the coating A, the coating B 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.

  In the above-described embodiment, the opening is described as having an oxide film, but the oxide film may not be provided in these portions. Thereby, the transparency of the electromagnetic wave as the whole decorative article 1 can be further improved. In this case, an oxide film having an opening can be obtained by arranging a mask and performing vapor phase film formation of a metal oxide as in the film formation step. Further, a film having an opening can be formed by performing film formation in a state where a mask is provided.

  Further, the opening of the coating A and the corresponding real part of the coating B may have the same shape. Thereby, in the manufacturing method as mentioned above, the temporary mask of the film A and the mask of the film B can be made the same, for example. For this reason, it is not necessary to make two temporary masks and masks, and work efficiency can be improved. Further, when the masks are different, it is possible to prevent subtle deviations in the pitch and width of the openings between the masks, and the openings of the coating A and the coating B having desired shapes can be formed with high accuracy. .

Next, specific examples of the present invention will be described.
1. Manufacture of Decorative Items 100 decorative items (watch exterior parts (dial plates)) 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 (a dial) was produced by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained substrate was substantially disk-shaped and had a diameter of about 27 mm × thickness: about 0.5 mm. Absolute refractive index _{I B} of the polycarbonate constituting the substrate was 1.58.
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 (absolute refractive index I _{2 O} : 2.51) was formed on both surfaces of the substrate thus cleaned by sputtering as described below (oxide film formation) Process).
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 treatment time: 3.0 minutes, thereby forming an oxide film composed of TiO ₂ . The average thickness of the oxide coating on each surface thus formed was 0.01 μm.
Subsequently, a film A composed of Ag was formed on the surface of the oxide film on the first surface side formed as described above (film formation step).
The coating A was formed by performing sputtering with a square mask (see FIG. 2) regularly arranged on the surface of the oxide coating on the first surface side.

  The mask was installed as follows. First, a temporary mask having the same shape as the coating A to be formed was placed on the oxide coating. Next, the mask 2 was formed by coating the oxide film 15 with a resin solution obtained by dissolving a polyester resin with methyl ethyl ketone in a state where a temporary mask is arranged, and then drying. The coating was performed by a spin coat method. Next, a square mask was regularly arranged on the surface of the oxide film by peeling off the temporary mask. The provided mask had a thickness of 130 μm, and this mask had a constant area in the thickness direction as shown in FIG. The temporary mask used had a thickness of 150 μm, and this temporary mask had a constant area in the thickness direction.

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 coating A composed of Ag. At this time, the perpendicular direction of the main surface of the substrate and the traveling direction of the sputtered particles were made substantially parallel. The average thickness of the coating A thus formed was 0.20 μm.

Next, the substrate provided with the oxide film and the film A having the opening A was taken out from the sputtering apparatus and removed by dissolving the mask with methyl ethyl ketone (mask removal process).
Next, a film forming process and a mask removing process were performed on the other main surface (second surface) on which the film was not formed.
In the coating step, the same conditions as described above are provided with a mask having a reversed pattern (a mesh (square lattice) mask (see FIG. 2) in which square openings are regularly arranged) as shown in the figure. Sputtering was performed to form a coating B. The mask was made of stainless steel (SUS444), and its thickness was 150 μm. Further, as shown in FIG. 4, this mask had a constant cross-sectional area in the thickness direction. Moreover, this process was performed in the state which provided the magnet on the surface opposite to the surface which opposes the mask of a board | substrate, and contact | adhered the board | substrate with which the oxide film was provided, and the mask. The formed coating film B had an average thickness of 0.20 μm.
Next, after the coating B was formed, the mask was removed.
As a result, a decorative article as shown in FIG. 2 was obtained.
The thicknesses of the oxide film, the film and the mask were measured in accordance with a microscope cross-sectional test method defined in JIS H5821.

(Example 2)
As shown in Table 1, a decorative article (watch exterior part (dial)) was obtained in the same manner as in Example 1 except that the thickness of the substrate, the material of the coating A and the coating B, the width of the opening, and the pitch were changed. ) Was manufactured.
When forming the film B (film forming process), the film is formed by sputtering, Cr is used as a target, discharge is performed under the conditions of argon gas flow rate: 20 ml / min, input power: 500 W, and processing time of 5 minutes. Went. The formed coating B was composed of Cr, and the average thickness was 0.20 μm.

(Example 3)
As shown in Table 1, a decorative article (watch exterior part (dial)) was obtained in the same manner as in Example 1 except that the thickness of the substrate, the material of the coating A and the coating B, the width of the opening, and the pitch were changed. ) Was manufactured.
When forming the film A (film forming process), the film is formed by sputtering, using Ag as a target, and discharging under conditions of argon gas flow rate: 35 ml / min, input power: 1700 W, and processing time of 1 minute. Went. Further, with the mask disposed, discharge was performed using Au as a target under the conditions of an argon gas flow rate: 30 ml / min, input power: 1700 W, and a processing time of 30 seconds. The formed coating A was composed of an Ag layer and an Au layer, and the average thicknesses were 0.10 μm and 0.03 μm, respectively. The Ag layer is a layer on the side in contact with the oxide film, and the Au layer is a layer on the outer surface side.

Example 4
As shown in Table 1, a decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 1 except that the material of the coating A and the coating B, the width of the opening, and the pitch were changed.
When forming the film A (film forming process), the film is formed by sputtering, Al is used as a target, and discharge is performed under the conditions of argon gas flow rate: 30 ml / min, input power: 1500 W, and processing time of 1 minute. Went. Further, in the state where the mask was arranged, discharging was performed using In as a target, argon gas flow rate: 30 ml / min, input power: 1600 W, and processing time of 1 minute. The formed coating A was composed of an Al layer and an In layer, and the average thicknesses were 0.05 μm and 0.05 μm, respectively. The Al layer is a layer on the side in contact with the oxide film, and the In layer is a layer on the outer surface side.

(Example 5)
As shown in Table 1, a decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 1 except that the material of the coating A and the coating B, the width of the opening, and the pitch were changed.
(Example 6)
As shown in Table 1, a decorative article (watch exterior part (dial)) was obtained in the same manner as in Example 1 except that the thickness of the substrate, the material of the coating A and the coating B, the width of the opening, and the pitch were changed. ) Was manufactured.
When forming the film B (film forming process), the film is formed by sputtering, Cr is used as a target, discharge is performed under the conditions of argon gas flow rate: 20 ml / min, input power: 500 W, and processing time of 5 minutes. Went. The formed coating B was composed of Cr, and the average thickness was 0.20 μm.

(Example 7)
As shown in Table 1, a decorative article (watch exterior part (dial)) was obtained in the same manner as in Example 1 except that the thickness of the substrate, the material of the coating A and the coating B, the width of the opening, and the pitch were changed. ) Was manufactured.
When forming the film A (film forming process), the film is formed by sputtering, using Ag as a target, and discharging under conditions of argon gas flow rate: 35 ml / min, input power: 1700 W, and processing time of 1 minute. Went. Further, with the mask disposed, discharge was performed using Au as a target under the conditions of an argon gas flow rate: 30 ml / min, input power: 1700 W, and a processing time of 30 seconds. The formed coating A was composed of an Ag layer and an Au layer, and the average thicknesses were 0.10 μm and 0.03 μm, respectively. The Ag layer is a layer on the side in contact with the oxide film, and the Au layer is a layer on the outer surface side.

(Example 8)
As shown in Table 1, a decorative article (a watch exterior part (a dial)) is manufactured in the same manner as in Example 1 except that the material of the substrate, the coating A and the coating B, the width of the opening, and the pitch are changed. did. As the substrate material, acrylonitrile-butadiene-styrene copolymer (ABS resin) was used.
When forming the coating B (coating forming step), the coating is formed by sputtering, Ti is used as a target, discharge is performed under the conditions of argon gas flow rate: 20 ml / min, input power: 600 W, and processing time of 6 minutes. Went. The formed coating B was composed of Ti, and the average thickness was 0.10 μm.

Example 9
As an opening formed in the coating film A and the coating film B, a pattern as shown in FIG. 3 was used, and as shown in Table 1, the decorative article was the same as in Example 1 except that the materials of the coating film A and the coating film B were changed. (Exterior parts for watch (dial)) were manufactured.
When forming the film A (film forming process), the film is formed by sputtering, Sn is used as a target, and the discharge is performed under the conditions of argon gas flow rate: 20 ml / min, input power: 1000 W, and processing time of 2 minutes. Went. The formed coating A was composed of Sn, and the average thickness was 0.15 μm.

(Example 10)
As shown in Table 1, a decorative article (a watch exterior part (a dial)) was manufactured in the same manner as in Example 1 except that the material of the coating A and the coating B, the width of the opening, and the pitch were changed.
When forming the film A (film forming process), the film is formed by sputtering, Al is used as a target, and discharge is performed under the conditions of argon gas flow rate: 30 ml / min, input power: 1500 W, and processing time of 1 minute. Went. Further, in the state where the mask was arranged, discharging was performed using In as a target, argon gas flow rate: 30 ml / min, input power: 1600 W, and processing time of 1 minute. The formed coating A was composed of an Al layer and an In layer, and the average thicknesses were 0.05 μm and 0.05 μm, respectively. The Al layer is a layer on the side in contact with the oxide film, and the In layer is a layer on the outer surface side.

(Example 11)
A substrate was prepared and washed in the same manner as in Example 1 to form an oxide film on both sides of the substrate.
Next, a square lattice mask as shown in Table 1 (the one used for forming the coating film B in Example 1) was arranged to form the coating film A.
The coating was formed as follows.
First, sputtering was performed using Ag as a target. 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 such a state, Ag was used as a target, discharge was performed under the conditions of input power: 1400 W, treatment time: 2.0 minutes, and an Ag layer was formed.

Next, coating was performed on the Ag layer in the state where the mask was continuously arranged to form a coating layer. The coating was performed by spin coating, and the coating material was acrylic resin. After the applied paint was dried, the mask was peeled off to obtain a coating A. The formed coating A was composed of an Ag layer and a coating layer, and the average thickness thereof was 0.05 μm and 2.0 μm. The Ag layer is the layer on the side in contact with the oxide coating, and the coating layer is the layer on the outer surface side.
Then, the film B was formed on the conditions which formed the film A of Example 1, and the ornamental article (watch exterior parts (character board)) was manufactured.

(Example 12)
Similar to Example 1, a substrate preparation step and an oxide film formation step were performed.
Subsequently, a metal film composed of Ag was formed on the surface of the oxide film formed on the first surface side and the second surface side by sputtering as described below.
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.
The average thickness of the metal coatings thus formed was 0.20 μm.

Next, a mask forming film was coated on the surface of the metal film formed on the first surface side and the second surface side.
Formation of the mask forming film was performed by coating the surface of the metal film using a spin coater under the condition of a rotational speed of 3000 rpm and then drying at 70 to 100 ° C. for 20 minutes. The average thickness of the formed mask forming film was about 10 μm.

Next, an opening having a predetermined pattern was formed in the mask forming film to obtain a mask having an opening. The shape of the mask was the same as in Example 1. That is, the mask on the first surface side is a regular arrangement of square masks (see FIG. 2), and the mask on the second surface side is a mask with an inverted pattern (a mesh having square openings arranged regularly). (A square lattice-like mask) (see FIG. 2)). The opening was formed in the mask forming film by exposure. An ultra-high pressure mercury lamp was used as the light source. At this time, laser light was intermittently irradiated while relatively moving the light source and the base material. Irradiation from the light source was performed under the condition of a light amount of 100 mJ / cm ² .

Next, by performing etching using an etching solution, an opening was formed in a portion of the metal film that was not covered with a mask, and a film A and a film B made of a metal material were formed.
Etching was performed by a shower method using an etching solution on a base material (a laminate of a base material, an oxide film, and a metal film) coated with a mask. At this time, an aqueous solution of 40-50 wt% nitric acid was used as an etching solution. The temperature of the etching solution and the etching time in this step were about 20 ° C. and about 5 minutes, respectively.
Next, the mask was removed by immersing it in a mask remover composed of a sodium hydroxide solution to produce a decorative article (watch exterior part (dial plate)). Moreover, the temperature of the mask remover and the immersion time in the mask remover were 30 to 40 ° C. and 5 to 10 minutes, respectively.

(Example 13)
A substrate was prepared and washed in the same manner as in Example 1. A printed pattern having an opening pattern similar to that of Example 1 as shown in Table 1 was printed on both surfaces of the obtained substrate by screen printing to obtain a coating film having openings on both surfaces of the substrate. Exterior parts (dial plates)) were manufactured.

(Example 14)
A substrate was prepared and washed in the same manner as in Example 1. A printed pattern having an opening pattern similar to that of Example 5 as shown in Table 1 is printed on both surfaces of the obtained substrate by screen printing, and a coating having openings on both surfaces of the substrate is decorated with a transmissive portion. Product (watch exterior parts (dial plate)) was manufactured.

(Comparative Example 1)
A decorative article (watch) is formed in the same manner as in Example 1 except that the coating A is formed without a mask in the coating forming process on the first surface, and each process is not performed on the second surface. Exterior parts (dial plates)) were manufactured.
(Comparative Examples 2-3)
Except that each step is not performed on the second surface and the shape of the opening formed on the first surface is as shown in Table 1, a decorative article (watch exterior part ( Dial)) was manufactured.

(Comparative Example 4)
In the same manner as in Example 4, a substrate was prepared and washed on the first surface, and then an oxide coating process was performed.
In the film forming process, a mask was disposed on the first surface to form the film twice so as to have the same transmissive part pattern as that of the decorative article obtained in Example 4. That is, sputtering is performed in a state where square masks (see FIG. 5) are regularly arranged, and then a mask with a reversed pattern (a square (square lattice) mask with regularly arranged square openings) (see FIG. 5). Sputtering was performed with the Thereafter, a coating layer forming step was performed in the same manner as in Example 1. In addition, for the second surface, a decorative article (a watch exterior part (a dial)) was manufactured without performing each step. As a result, in the film forming process performed on the first surface, the first pattern and the second pattern shifted in the film, and a part of the film overlapped.

(Comparative Example 5)
A decorative article (watch exterior part (character plate)) is formed in the same manner as in Example 1 except that the same mask as that used in the first face was used in the coating formation process on the second face. Manufactured.
Table 1 summarizes the structures of the decorative articles of each example and each comparative example. In the table, polycarbonate is indicated by PC, and acrylonitrile-butadiene-styrene copolymer is indicated by ABS. Moreover, the shape of the opening part in the film A of Comparative Example 4 is the same shape as the transmission part in FIG.

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.
A: Appearance is good.
○: Appearance is normal.
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: 30% or more.
A: 25% or more and less than 30%.
○: 20% or more and less than 25%.
Δ: 15% or more and less than 20%.
X: Less than 15%.

  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 watches of Comparative Examples 1, 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.
These results are shown in Table 3.

As is clear from Table 2, all the decorative articles of the present invention had an excellent aesthetic appearance and were excellent in electromagnetic wave (light, radio wave) permeability.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, in the decorative article of Comparative Example 1 in which no opening was formed, sufficient electromagnetic wave (light) permeability was not obtained. Moreover, in the decorative article of Comparative Example 3, as a result of the opening being too small, sufficient electromagnetic wave (light) permeability was not obtained.

Moreover, in the decorative article of Comparative Example 4, the formation of the film was not good, and an excellent appearance could not be obtained. Moreover, in the decorative articles of Comparative Examples 2 and 5, the opening could be visually recognized, and an excellent appearance could not be obtained.
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 typical sectional drawing which shows the ornament of 1st Embodiment of this invention. It is a typical top view for demonstrating an example of the shape (pattern) of the opening which an ornament has. It is a typical top view for demonstrating another example of the shape (pattern) of the opening which an ornament has. It is typical sectional drawing which shows the manufacturing method of the ornament of 1st Embodiment of this invention. It is a typical top view for demonstrating an example of the shape (pattern) of the opening which the ornament of 2nd Embodiment of this invention has. It is a typical top view for demonstrating another example of the shape (pattern) of the opening which the ornament of 2nd Embodiment of this invention has. 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 12 ... Board | substrate 121 ... 1st surface 122 ... 2nd surface 13 ... Coating A 131 ... Real part A 132 ... Opening part A 14 ... Coating B 141 ... Real part B 142 ... Opening part B 15 ... Oxidation Material coating 16 ... Transmission part 2 ... Mask (gas phase film formation mask) 21 ... Opening 10 ... Dial (clock dial) 71 ... Movement 72 ... Body (case) 73 ... Back cover 74 ... Bezel (edge) 75 ... Glass plate (cover glass) 76 ... Winding pipe 77 ... Crown 771 ... Shaft 772 ... Groove 78 ... Plastic packing 79 ... Plastic packing 83 ... Rubber packing (crown packing) 84 ... Rubber packing (back cover packing) 85 ... Joint part (seal part) 88 ... Solar cell 100 ... Watch (portable watch)

Claims (12)

A substrate made of a light-transmitting material;
A coating A which is provided on the first surface side which is one main surface of the substrate and reflects or absorbs at least part of incident light;
A coating B that is provided on a second surface side that is a main surface opposite to the first surface of the substrate and reflects or absorbs at least part of incident light;
The coating A comprises an opening A having a predetermined pattern and a real part A as the other part,
The coating B is composed of an opening B having a predetermined pattern and a real part B as other parts.
An ornamental article characterized in that, when the substrate is viewed in plan, the real part B is arranged on at least a part of a part corresponding to each opening A.   The decorative article according to claim 1, wherein the shape of the real part B is substantially similar to the opening A.   The ornament according to claim 2, wherein when the ornament is viewed in plan, the center of the real part B is at substantially the same location as the center of the corresponding opening A.   The ornament according to any one of claims 1 to 3, wherein when the substrate is viewed in plan, the real part B covers the entire opening A. The decorative article is used so that external light enters from the first surface,
The decorative article according to any one of claims 1 to 4, wherein the coating A is made of a material that reflects light near a surface facing the substrate. The decorative article is used so that external light enters from the first surface,
The decorative article according to any one of claims 1 to 5, wherein an area ratio of the opening A in the coating A is 25 to 60%. The decorative article is used so that external light enters from the first surface,
The decorative article according to any one of claims 1 to 6, wherein a color tone on the first surface side of the coating A and a color tone on the first surface side of the coating B are different.   The decorative article according to any one of claims 1 to 7, wherein an average thickness of the substrate is 200 to 1000 µm.   The ornament according to any one of claims 1 to 8, wherein the ornament is a radio timepiece component.   The ornament according to any one of claims 1 to 8, wherein the ornament is a timepiece dial. A method for manufacturing the decorative article according to any one of claims 1 to 10,
A substrate preparation process for preparing a substrate;
Forming the film with openings in a predetermined pattern by performing film formation in a state where a mask having openings in a predetermined pattern is arranged near the surface of at least one main surface of the substrate A film forming process to
And a mask removing step for removing the mask.   A timepiece comprising the decorative article according to claim 1.

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