JP2008164531A - Clock dial and clock - Google Patents

Abstract

An object of the present invention is to provide a timepiece dial having excellent electromagnetic wave permeability and an aesthetic appearance, and to provide a timepiece having the timepiece dial.
A timepiece dial 1 of the present invention includes a base material 2 made of an electromagnetic wave-transmitting material, a cover film 3 mainly made of a bag, and a reflective film 4 made of a metal material. And an oxide film 5 composed of a metal oxide. The substrate 2 is provided between the capsular film 3 and the reflective film 4. The base material 2 is made of a plastic material, and the reflective film 4 is made of a material containing one or more selected from the group consisting of Ag and Al.
[Selection] Figure 6

Description

  The present invention relates to a timepiece dial and a timepiece.

Timepieces and timepiece dials are required to have a function as a practical product and a decorative property (aesthetic appearance) as a decorative product.
Conventionally, a timepiece dial has generally been made of a metal material in order to obtain a high-quality appearance. There is also an attempt to use a dial plate made of an alloy having a complicated composition in order to obtain an appearance that is difficult to express with pure materials such as pure gold and pure silver (for example, see Patent Document 1).

  In recent years, radio timepieces having a function of receiving radio waves and automatically adjusting the time are becoming widespread. Such a dial for a radio timepiece is required to have excellent radio wave permeability. For this reason, in a radio timepiece, it is difficult to apply a dial made of a metal material, and a dial made of a plastic material is used. In addition, the plastic material is excellent in moldability and can suitably cope with the manufacture of a complicated-shaped dial. However, the dial plate made of a plastic material lacks luxury and has an inferior aesthetic appearance.

JP 2006-249510 A

  An object of the present invention is to provide a timepiece dial having excellent electromagnetic wave permeability and an aesthetic appearance, and to provide a timepiece having the timepiece dial.

Such an object is achieved by the present invention described below.
The timepiece dial of the present invention, a base material made of a material having electromagnetic wave permeability,
A capsule composed primarily of straw,
And a reflective film having a function of reflecting external light.
Thereby, while being excellent in the transmittance | permeability of electromagnetic waves, the dial for timepieces excellent in the aesthetic appearance can be provided.

In the timepiece dial of the present invention, it is preferable that the reflective film is provided in contact with the capsule.
As a result, the appearance of the timepiece dial can have a more vivid color tone.
In the timepiece dial according to the aspect of the invention, it is preferable that the base material is provided between the cap film and the reflective film.
This makes it possible to more effectively express the texture of the cocoon as a natural material with a deep and deep feeling while making the color of the dial for watches sufficiently bright. It can be made particularly excellent.

In the timepiece dial of the present invention, the thickness of the capsule is preferably 50 to 1000 μm.
Thereby, while making the color tone of the timepiece dial sufficiently bright, the texture of the bag can be expressed more effectively, and the aesthetic appearance of the timepiece dial can be made particularly excellent.

In the timepiece dial according to the aspect of the invention, it is preferable that the reflective film is made of a material containing one or more selected from the group consisting of Au and Cu.
Thereby, the texture of the bag can be expressed more effectively, and the aesthetic appearance of the timepiece dial can be made particularly excellent. Moreover, even if the thickness of the capsule is relatively thin, the texture of the cocoon can be sufficiently exhibited.

In the timepiece dial according to the aspect of the invention, it is preferable that the reflective film is made of a material including one or more selected from the group consisting of Ag and Al.
As a result, the appearance of the timepiece dial can have a more vivid color tone.
In the timepiece dial according to the aspect of the invention, it is preferable that the reflective film has a thickness of 0.005 to 2.5 μm.
Thereby, the external appearance of the timepiece dial can be made to have a more vivid color tone while sufficiently improving the electromagnetic wave permeability as the timepiece dial.

In the timepiece dial of the present invention, it is preferable that the base material is made of a plastic material.
Thereby, the transparency of the electromagnetic wave as the whole timepiece dial can be made particularly excellent. In addition, the plastic material has particularly excellent moldability among various materials, and can be suitably applied to manufacture a timepiece dial having a complicated shape. Moreover, it is preferable also from a viewpoint of suppression of the manufacturing cost of the timepiece dial.

In the timepiece dial of the present invention, the base material has light permeability, and
It is preferable that the reflective film has an opening.
Thereby, the light transmittance as the whole timepiece dial can be made excellent. For example, the timepiece dial can be suitably applied to a solar timepiece.
In the timepiece dial according to the aspect of the invention, it is preferable that the width of the opening provided in the reflective film is 10 to 150 μm.
Thereby, while making the aesthetic appearance of the timepiece dial plate sufficiently excellent, the light transmittance as the whole timepiece dial plate can be made particularly excellent.

In the timepiece dial according to the aspect of the invention, it is preferable that an area ratio occupied by the opening when the reflective film is viewed in plan is 15 to 55%.
Thereby, while making the aesthetic appearance of the timepiece dial plate sufficiently excellent, the light transmittance as the whole timepiece dial plate can be made particularly excellent.
The timepiece dial of the present invention is preferably a solar timepiece dial.
A timepiece dial for a solar timepiece is required to have excellent light transmittance and an excellent aesthetic appearance. However, according to the present invention, these requirements can be satisfied at the same time. That is, when the present invention is applied to a dial for a solar timepiece, the effect is more remarkably exhibited.
The timepiece of the present invention includes the timepiece dial of the present invention.
Thereby, it is possible to provide a timepiece having a timepiece dial having excellent electromagnetic wave permeability and excellent aesthetic appearance.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the transmittance | permeability of electromagnetic waves, the timepiece dial which was excellent in the aesthetic appearance can be provided, and the timepiece provided with the said timepiece dial can be provided.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
<< First Embodiment >>
<Watch dial>
First, a first embodiment of the timepiece dial of the present invention will be described.
FIG. 1 is a cross-sectional view showing a first embodiment of the timepiece dial of the present invention, and FIG. 2 is a schematic plan view for explaining an example of the shape (pattern) of the opening of the reflective film. FIG. 3 is a schematic plan view for explaining another example of the shape (pattern) of the opening included in the reflective film.

  As shown in FIG. 1, the timepiece dial 1 of the present embodiment includes a substrate (base material) 2, a cover film 3, a reflective film (metal film) 4, and an oxide film 5. . The timepiece dial 1 is normally used so that the surface side (the upper side in FIG. 1) of the substrate 2 covered with the capsule 3 faces the observer side (second embodiment to be described later). The same). In the following description, the upper side in FIG. 1 is described as “(external light) incident side” and the lower side in FIG. 1 is described as “(external light) exit side” (FIGS. 4, 5, and 5 to be described later). 6 and FIG. 7).

[substrate]
The substrate 2 is made of a material having electromagnetic wave permeability. Thereby, for example, the timepiece dial 1 can be suitably applied to a solar timepiece including a solar battery, a radio timepiece, or the like. In the present invention, the electromagnetic wave transmission property may be any electromagnetic wave transmission property such as visible light (hereinafter, also simply referred to as light), radio waves, etc., as long as it shows transparency with respect to electromagnetic waves in a predetermined wavelength region.

  In the case where the substrate 2 has light transmittance, the light transmittance of the substrate 2 is preferably 80% or more, and more preferably 90% or more. As described above, since the light transmittance of the substrate 2 is sufficiently high, the light transmittance of the timepiece dial 1 as a whole can be sufficiently high. As a result, the timepiece dial 1 can be suitably applied to a solar timepiece. In this specification, unless otherwise specified, the light transmittance refers to the light transmittance when xenon white light defined in JIS Z 8902 is used as a light source. Further, in the present specification, the light reflectance and the absorptance are similar to the above, respectively, when xenon white light defined by JIS Z 8902 is used as a light source unless otherwise specified. It refers to the reflectance and absorption rate.

  Examples of the material having light transmissivity and radio wave transmissivity include various plastic materials, various glass materials, various ceramic materials, and the like. The material constituting the substrate 2 is preferably a plastic material. The plastic material is generally excellent in moldability (freedom of molding), and can be suitably applied to manufacture the timepiece dial 1 having various shapes. Further, if the substrate 2 is made of a plastic material, it is advantageous for reducing the manufacturing cost of the timepiece dial 1. In addition, plastic materials are generally superior in light (visible light) and radio wave permeability as compared to other materials. In the following description, an example in which the substrate 2 is made of a plastic material will be mainly described.

  Examples of the plastic material constituting the substrate 2 include various thermoplastic resins, various thermosetting resins, and the like. For example, polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethyl methacrylate (PMMA). ), Etc., polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyester resins such as polyethylene terephthalate (PET), etc., or copolymers, blends, polymer alloys, etc. mainly comprising these. These can be used, and one or more of these can be used in combination (for example, as a blend resin, a polymer alloy, a laminate, etc.). In particular, the substrate 2 is preferably composed mainly of polycarbonate and / or acrylonitrile-butadiene-styrene copolymer. Thereby, especially the intensity | strength as the timepiece dial 1 whole can be made excellent. Further, when the timepiece dial 1 is manufactured, the degree of freedom in forming the substrate 2 is increased (easiness of forming is improved), so that even a more complicated shape of the timepiece dial 1 can be easily obtained. And it can manufacture reliably. Further, when the substrate 2 is made of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin), the adhesion between the substrate 2 and the coating film is improved. It can be made particularly excellent. Polycarbonate is relatively inexpensive among various plastic materials, and can contribute to further reduction in production cost of the timepiece dial 1. The ABS resin also has particularly excellent chemical resistance, and the durability of the timepiece dial 1 as a whole can be further improved.

In addition, the board | substrate 2 may contain components other than a plastic material. Examples of such components include plasticizers, antioxidants, colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, fillers, and the like.
The substrate 2 may have a substantially uniform composition at each site, or may have a different composition depending on the site.

The shape and size of the substrate 2 are not particularly limited, and are usually determined based on the shape and size of the timepiece dial 1. In the illustrated configuration, the substrate (base material) 2 has a flat plate shape, but may have a curved plate shape, for example.
Although the average thickness of the board | substrate 2 is not specifically limited, It is preferable that it is 100-700 micrometers, and it is more preferable that it is 200-600 micrometers. When the average thickness of the substrate 2 is a value within the above range, when the timepiece dial 1 is applied to a solar timepiece, the light transmission of the timepiece dial 1 is sufficiently high, It is possible to more effectively prevent the self color from being seen through, and to make the aesthetic appearance (luxury feeling) particularly excellent.

[Capsule]
On the outside light incident side of the substrate 2, a capsular film 3 mainly composed of ridges is provided. Persimmon is generally collected as a fossil of a resin of the genus Pinus, and has a unique texture (color tone, transparency, gloss, etc.) and has an appearance that is difficult to express with other materials. is there. By having such a cap 3, the appearance of the timepiece dial 1 can be made excellent with a texture specific to the watch. Further, the bag has a low density, usually about 1.05 to 1.10 g / cm ³ , and is advantageous for reducing the weight of the timepiece dial 1 and the timepiece including the timepiece. In the present specification, “mainly” means that the content in the target structure (for example, the content of soot in the capsule 3) is 50 wt% or more, and in particular, 90 wt%. It is preferable that it is above, and it is more preferable that it is 95 wt or more.

  Examples of the type of ridges that form the capsular membrane 3 include succinite, gedanit, gresit, and allingit. Examples of the constituent material of the capsule 3 include succinoresene, succinoabietinolic acid, succinoabietol, succinoresinol, succinosylvinic acid, succinic acid, succioxyabietic acid, succinogilic acid, and succinoabietic And the like. The total content of the constituent substances in the capsule 3 is preferably 80 wt% or more, and more preferably 90 wt% or more. In addition to the above substances, the capsule 3 may include, in addition to the above substances, an analogous compound thereof and an ester compound containing at least one selected from them. In the present invention, the cocoons are not limited to natural cocoons but may be artificial cocoons (such as those obtained using colophonium). Note that the capsule 3 may contain components other than soot, such as plastic components.

  The bag generally has radio wave transparency and light transparency. The light transmittance of the capsular membrane 3 varies depending on the thickness of the capsular membrane 3 and the type of ridges, but is preferably 5 to 90%, more preferably 10 to 70%. If the light transmittance of the capsule 3 is within the above range, the light transmission of the timepiece dial 1 as a whole is sufficiently excellent, while the aesthetic appearance (high-grade) of the timepiece dial 1 is high. (Feel) can be made particularly excellent. In addition, since the permeability | transmittance of the radio wave of a bag is very high, it can be applied suitably to a radio timepiece. Even when the thickness of the timepiece dial 1 is relatively thick, Usually not a problem.

  Moreover, although the average thickness of the capsule 3 is not specifically limited, It is preferable that it is 50-1200 micrometers, and it is more preferable that it is 70-500 micrometers. When the average thickness of the capsule 3 is a value within the above range, the light transmission of the watch dial 1 as a whole is sufficiently excellent, and the texture of the bag is deeper and deeper. It can be expressed as having a feeling, and the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be particularly excellent.

By the way, wrinkles have a unique texture (color tone, transparency, gloss, etc.) and have an appearance that is difficult to express with other materials. However, when a dial made of a spear is simply incorporated into a watch, the appearance of the dial has a dark and dull tone, and the texture inherent to the spear cannot be fully exhibited. This is considered to be due to the following reasons. That is, in a timepiece having a dial, generally, a movement or the like housed in the case is arranged on the back side of the dial, so the back side of the dial is shaded and is unique to the bag. It is thought that transparency, glossiness, etc. are not expressed.
Therefore, in the present invention, a reflective film having a function of reflecting external light is provided on the back side of the capsule.

[Reflective film (metal coating)]
A reflective film 4 is provided between the substrate 2 and the coating film 3 described above.
A part of the light incident from the outer surface (upper side in the figure) of the timepiece dial 1 is reflected by the first surface 31 of the capsule 3 (the surface opposite to the surface facing the reflective film 4). And enters the inside of the capsule 3. The light that has entered the capsular film 3 is reflected on the surface of the reflective film 4 (the surface facing the capsular film 3). As described above, the reflective film 4 is disposed on the back side of the capsular film 3 so that the light reflected by the first surface 31 of the capsular film and the inside of the capsular film 3 are transmitted from the second surface 32 side. Light can be emitted to the viewer side. As a result, the texture inherent to the bag can be sufficiently exhibited, and the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be sufficiently improved.

  The reflective film 4 may be made of any material as long as it has a function of reflecting light, but is preferably made of a metal material. As a result, the texture inherent to the bag can be expressed more effectively, and the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent. In the following description, the case where the reflective film 4 is a metal film mainly composed of a metal material will be mainly described.

  As the metal material constituting the reflective film (metal coating) 4, various metals (including alloys) can be used. More specifically, for example, Fe, Cu, Zn, Ni, Mg, Cr, Mn, Examples include Mo, Nb, Al, V, Zr, Sn, Au, Pd, Pt, Hf, Ag, Co, In, W, Ti, Rh, and alloys containing at least one of these. In particular, when the reflective film 4 is made of a material containing one or more selected from the group consisting of Au and Cu, the unique texture inherent in the cocoon is more effectively obtained. The aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Moreover, even if the thickness of the capsular membrane 3 is relatively thin, the texture of the cocoon can be sufficiently exhibited. Further, when the reflective film 4 is made of a material (including an alloy) containing at least one selected from the group consisting of Ag and Al, the reflection by the reflective film 3 as described above is more effective. The appearance of the timepiece dial 1 can have a more vivid color tone. Further, when the reflective film (metal film) 4 is made of the above-described material, the adhesion between the reflective film (metal film) 4 and the oxide film 5 described later is particularly excellent. be able to. Further, the reflective film 4 may or may not have a uniform composition in each part. For example, the reflective film 4 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. Further, the reflective film 4 may be a laminate having a plurality of layers. Moreover, when the reflective film 4 is a laminated body, you may have the layer comprised with the material which does not contain a metal material substantially, for example. More specifically, the reflective film 4 may have a configuration in which a layer made of a metal oxide or the like is interposed between two layers made of a metal material.

In the present embodiment, the reflective film 4 is provided in contact with the cap film 3. Thereby, the light reflected on the surface of the reflective film 4 is directly incident on the cap film 3, and the appearance of the timepiece dial 1 can have a more vivid color tone.
The average thickness of the reflective film 4 is not particularly limited, but is preferably 0.005 to 2.5 μm, more preferably 0.007 to 0.9 μm, and 0.01 to 0.5 μm. Is more preferable. When the average thickness of the reflective film 4 is within the above range, the function of the reflective film 4 described above can be more effectively exhibited while sufficiently preventing the internal stress of the reflective film 4 from increasing. The aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Further, the adhesion between the reflective film (metal film) 4 and the oxide film 5 described later can be made particularly excellent. On the other hand, if the average thickness of the reflective film 4 is less than the lower limit value, depending on the constituent material of the reflective film 4 and the like, it is difficult to fully exhibit the function of the reflective film 4 described above. It may be difficult to make the aesthetic appearance of the entire plate 1 sufficiently excellent. Further, depending on the constituent materials of the reflective film (metal film) 4 and the oxide film 5, it may be difficult to sufficiently improve the adhesion between the reflective film (metal film) 4 and the oxide film 5. is there. On the other hand, when the average thickness of the reflective film 4 exceeds the upper limit value, the tendency of the transmittance of electromagnetic waves (radio waves) as the whole timepiece dial plate 1 appears significantly, and the timepiece dial plate 1 becomes a radio timepiece. It becomes difficult to apply. Moreover, when the average thickness of the reflective film 4 exceeds the upper limit, the variation in film thickness at each part of the reflective film 4 tends to increase. Further, when the average thickness of the reflective film 4 is particularly large, the internal stress of the reflective film 4 becomes high and cracks and the like are likely to occur.

  The reflective film 4 has an opening 41 provided in a predetermined pattern. Thus, by having the opening 41, a part of the light incident on the timepiece dial 1 can be guided to the substrate 2, and as a result, can be emitted from the side opposite to the incident side. . That is, a part of the light incident on the timepiece dial 1 can be transmitted. As described above, the coating film 3 is provided on the light incident side of the reflective film 4 while ensuring the light transmission of the timepiece dial 1 as a whole by having the opening 41 in this manner. Therefore, the presence of the opening 41 is difficult to be visually recognized by an observer due to the appearance unique to the eyelid. Therefore, by setting it as such a structure, the outstanding light transmittance and the outstanding aesthetic appearance can be made to make compatible.

  When the substrate 2 (timepiece dial 1) is viewed in plan, the aperture ratio occupied by the opening 41 in the reflective film 4 is preferably 15 to 55%, and preferably 25 to 50%. More preferred. When the aperture ratio of the reflection film 4 is a value within the above range, the aesthetic appearance (luxury feeling) of the timepiece dial 1 is particularly excellent while sufficiently improving the transmittance of light (external light). can do. On the other hand, if the aperture ratio of the reflective film 4 is less than the lower limit value, it becomes difficult to sufficiently improve the light transmittance of the timepiece dial 1 as a whole. On the other hand, when the aperture ratio of the reflective film 4 exceeds the upper limit, it becomes difficult to make the aesthetic appearance of the timepiece dial 1 sufficiently excellent depending on the thickness of the cap film 3 or the like.

  The opening 41 may have any shape. Examples of the shape of the opening 41 when the substrate 2 (timepiece dial 1) is viewed in plan include a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, and a slit shape. As shown in FIGS. 2 and 3, the opening 41 has a large number of island-shaped regions (reflective films) formed of the reflective film 4 when the substrate 2 (clock dial 1) is viewed in plan view. 4 real part) may be provided. Thereby, in the external appearance of the timepiece dial 1, the presence of the opening 41 can be made inconspicuous, and the productivity of the timepiece dial 1 can be made particularly excellent.

  Further, the width of the opening 41 represented by W in the figure (the diameter when the opening 41 is substantially circular) is preferably 10 to 150 μm, more preferably 30 to 140 μm. More preferably, it is 35-130 micrometers. When the width W of the opening 41 is a value within the above range, the light transmission as the timepiece dial 1 is sufficiently high, and the aesthetic appearance (aesthetics) of the timepiece dial 1 is particularly excellent. Can be. On the other hand, if the width W of the opening 41 is less than the lower limit, it becomes difficult to sufficiently increase the light transmittance of the timepiece dial 1 as a whole, depending on the aperture ratio of the reflective film 4 and the like. there is a possibility. On the other hand, if the width W of the opening 41 exceeds the upper limit, depending on the thickness of the capsule 3 or the like, it may be difficult to make the appearance of the timepiece dial 1 sufficiently excellent. .

  Moreover, it is preferable that the pitch of the opening part 41 represented by P in a figure is 70-550 micrometers, it is more preferable that it is 80-500 micrometers, and it is further more preferable that it is 90-450 micrometers. When the pitch P of the openings 41 is a value within the above range, the light transmission as the timepiece dial 1 is sufficiently high, and the aesthetic appearance (aesthetics) of the timepiece dial is particularly excellent. Can be. Note that the pitch of the openings 41 refers to the center-to-center distance between the adjacent openings 41 and 41, and when there are a plurality of adjacent openings 41, the pitch between the adjacent openings 41 Refers to the distance between centers.

[Oxide coating]
An oxide film 5 is provided between the substrate 2 and the reflective film (metal film) 4, in other words, on the surface of the reflective film (metal film) 4 opposite to the surface facing the cap film 3. . Thus, in this embodiment, the metal film 4 as a reflective film is not directly provided on the surface of the substrate 2 mainly composed of a plastic material, and the oxide film 5 is interposed between the substrate 2 and the metal film 4. Is intervening. This improves the adhesion between the substrate 2 and the metal coating 4 (adhesion through the oxide coating 5), in particular, the adhesion of the metal coating 4 formed by vapor deposition as described later. It is possible to effectively prevent the metal coating 4 from floating or peeling off. As a result, the timepiece dial 1 is excellent in durability.

The oxide film 5 is mainly composed of a metal oxide. As the metal oxide constituting the oxide coating 5, oxides of various metals can be used, preferably Fe, Cu, Zn, Ni, Mg, Cr, Mn, Mo, Nb, Al, V, Zr. , Sn, Au, Pd, Pt, Ag, Co, In, W, Ti, and Rh oxides (including complex oxides). When the oxide film 5 is made of a material containing at least one selected from titanium oxide (including a complex oxide) and chromium oxide (including a complex oxide), the substrate 2 and the metal film 4 It is possible to make the adhesiveness to be more excellent. Further, the constituent material of the oxide coating 5 may include at least one of the elements constituting the metal coating 4. In other words, the oxide coating 5 and the metal coating 4 may be made of a material containing a common element at least at a site where they are in contact with each other. For example, when the metal film 4 contains M (where M represents a metal element), the oxide film 5 has a composition formula of MO _{n / 2} (where M represents a metal element and n represents the valence of M). May be included. Thereby, the adhesiveness of the oxide film 5 and the metal film 4 further improves. In addition, the oxide film 5 may or may not have a uniform composition at each site. For example, the oxide film 5 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. The oxide film 5 may be a laminate having a plurality of layers. Moreover, when the oxide film 5 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 5 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.

  Moreover, although the average thickness of the oxide film 5 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 film 5 is within the above range, the adhesion between the substrate 2 and the metal film 4 is particularly excellent while sufficiently preventing the internal stress of the oxide film 5 from increasing. Can be. Further, when the average thickness of the oxide coating 5 is within the above range, the function of preventing reflection of external light on the surface of the metal oxide coating 5 is efficiently exhibited, and the aesthetic appearance of the timepiece dial 1 is obtained. (Luxury) can be made particularly excellent. On the other hand, when the average thickness of the oxide film 5 is less than the lower limit, the adhesion between the substrate 2 and the metal film 4 may be increased depending on the constituent material of the oxide film 5, the substrate 2, and the metal film 4. There is a possibility that the function to be improved is not fully exhibited. In addition, when the average thickness of the oxide film 5 is less than the lower limit value, depending on the method of forming the oxide film 5, pinholes are easily generated in the oxide film 5, and the oxide film 5 is provided. The effect may not be fully demonstrated. Further, when the average thickness of the oxide film 5 exceeds the upper limit, the light transmittance in the oxide film 5 is lowered depending on the constituent material, the forming method, etc. of the oxide film 5, and the timepiece dial There is a possibility that the transmittance of light as a whole will be reduced, and the aesthetics (luxury) of the timepiece dial 1 may be reduced. Moreover, when the average thickness of the oxide film 5 exceeds the upper limit, the variation in film thickness at each portion of the oxide film 5 tends to increase. Further, when the average thickness of the oxide film 5 is particularly large, the internal stress of the oxide film 5 becomes high, and cracks and the like are likely to occur.

  The timepiece dial 1 as described above may be applied to any timepiece, but is preferably applied to a solar timepiece having a solar cell. In solar timepieces, in general, the dial (timepiece dial) is required to have excellent light transmission, and the solar cell placed on the back side is required to have a function to prevent deterioration of the aesthetic appearance of the watch as a whole. However, according to the present invention, these requirements can be satisfied simultaneously. That is, when the timepiece dial of the present invention is applied to a solar timepiece, the effect is remarkably exhibited.

<Manufacturing method of timepiece dial>
Next, the manufacturing method of the timepiece dial 1 described above will be described.
FIG. 4 is a cross-sectional view showing a preferred embodiment of the method for manufacturing the timepiece dial shown in FIG. 1, and FIG. 5 is a diagram for explaining the traveling direction of vapor-phase film-forming particles when forming a reflective film. It is.
As shown in FIG. 4, in the method for manufacturing a timepiece dial according to this embodiment, a substrate preparation step (1 a) for preparing the substrate 2 and an oxide film 5 is formed on at least a part of the surface of the substrate 2. An oxide film forming step (1b), a reflecting film forming step (1c, 1d) for forming a reflecting film (metal coating) 4 having an opening 41 on the surface of the oxide film 5, and a surface of the reflecting film 4 A film forming step (1e) for forming the film 3;

[Board preparation process]
As the substrate 2, those described above can be used.
The surface of the substrate 2 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it becomes possible to give a variation in the glossiness of the surface of the timepiece dial 1 obtained.
In addition, various cleaning processes may be performed on the surface of the substrate 2 prior to a process described later. Thereby, for example, the adhesion between the substrate 2 and the oxide film 5 can be made particularly excellent.

[Oxide film forming step]
An oxide film 5 mainly composed of metal oxide is formed on the surface of the substrate 2 (1b).
As described above, the oxide film 5 has excellent adhesion to the substrate 2 and the metal film 4. By forming such an oxide coating 5, the durability of the timepiece dial 1 as a whole can be made particularly excellent.

  The method for forming the oxide film 5 is not particularly limited, and for example, wet coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, electrolytic plating, immersion plating, electroless plating, and the like. Examples include plating methods, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and thermal spraying. preferable. By applying a vapor deposition method as a method for forming the oxide film 5, the oxide film 5 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 2 is reliably formed. can do. As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. In addition, by applying a vapor deposition method as a method of forming the oxide film 5, even if the oxide film 5 to be formed is relatively thin, the variation in film thickness is made sufficiently small. Can do. When the reflective film 4 is formed by vapor deposition, the vapor deposition method is applied as the method for forming the oxide film 5, so that the substrate 2 in the manufacturing process can be taken into account in the production of the timepiece dial 1. This process and the reflective film forming process (metal film forming process) can be performed successively without taking out from the phase film forming apparatus. For this reason, the productivity of the timepiece dial 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 5, the above effects become more prominent. That is, by applying sputtering as a method of forming the oxide film 5, the oxide film 5 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 2 is more reliably formed. be able to. As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be further improved. Further, by applying sputtering as a method for forming the oxide film 5, even if the oxide film 5 to be formed is relatively thin, the variation in film thickness can be made particularly small. In addition, when applying the vapor phase film forming method as described above, for example, by using a metal corresponding to the metal oxide constituting the oxide film 5 as a target and performing the treatment in an atmosphere containing oxygen gas, The oxide film 5 can be formed easily and reliably. The formation of the oxide film 5 may be performed by combining a plurality of different methods and conditions. Thereby, the oxide film 5 comprised by the laminated body as mentioned above can be formed suitably.

[Reflective film forming step (metal film forming step)]
Next, a reflective film (metal film) 4 is formed on the surface of the oxide film 5 (1c, 1d).
The method for forming the reflective film 4 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., wet plating such as electrolytic plating, immersion plating, electroless plating, etc. And chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vapor deposition methods such as vacuum deposition, sputtering, and ion plating, thermal spraying, etc., but vapor deposition methods are preferred. . By applying a vapor deposition method as a method for forming the reflective film 4, the reflective film (metal film) 4 has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the oxide film 5. Can be reliably formed. As a result, the aesthetic appearance and durability of the timepiece dial 1 finally obtained can be made particularly excellent. Further, by applying a vapor deposition method as a method of forming the reflective film 4, even if the reflective film 4 to be formed is relatively thin, the variation in film thickness can be made sufficiently small. . Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the reflective film 4, the above effects become more prominent. That is, by applying sputtering as a method for forming the reflective film 4, the reflective film 4 having a uniform film thickness, uniform, and particularly excellent adhesion with the oxide film 5 is more reliably formed. be able to. As a result, the aesthetic appearance, durability, and light transmittance of the finally obtained timepiece dial 1 can be further improved. Further, by applying sputtering as the method for forming the reflective film 4, even if the reflective film 4 to be formed is relatively thin, the variation in film thickness can be made particularly small. The reflective film 4 may be formed by combining a plurality of different methods and conditions. Thereby, the reflective film 4 comprised by the laminated body as mentioned above can be formed suitably.

  The reflective film 4 formed in this step has the opening 41 as described above. In this step, the reflective film that does not have the opening 41 may be formed once, and then the opening may be formed in the reflective film. However, in this embodiment, as described below, At the same time as the film 4 is formed, the opening 41 is formed. That is, in this embodiment, the oxide film 5 formed as described above is formed with a mask (vapor phase film formation mask) 8 provided with openings 81 in a predetermined pattern. By performing the film, the reflective film 4 is formed (1c, 1d).

  Thus, the reflective film 4 having the opening 41 is formed by performing film formation with the mask 8 disposed. That is, the opening 41 is formed simultaneously with the formation of the reflective film 4. By forming the reflective film 4 (opening 41) as the reflective film in this manner, the opening 41 corresponding to the pattern of the opening 81 of the mask 8 (inverted pattern) can be easily and reliably formed. Can do. In addition, since the mask 8 can be used repeatedly in the production of a large number of timepiece dials 1, the productivity of the timepiece dial 1 is improved and the quality variation among the timepiece dials 1 is also improved. Can be suppressed. That is, the reliability of the quality of the timepiece dial 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 reflective film 4 without unintentional unevenness. Also, by preparing the mask 8 having the openings 81 of the pattern corresponding to the openings 41 to be formed (inverted pattern), the openings of various patterns can be obtained without greatly changing the formation conditions of the reflective film 4. The production of the timepiece dial 1 having 41 can be suitably handled. That is, it is possible to efficiently cope with multi-product production.

  In the vapor phase film formation as described above, for example, the metal constituting the reflection film 4 is used as a target and the treatment is performed in an inert gas atmosphere such as argon gas, so that the reflection film 4 is easily and reliably formed. Can be formed. 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 metal film forming step can be continuously performed in the same apparatus (without removing the substrate 2 from the apparatus). As a result, the adhesion of the substrate 2, the oxide film 5 and the reflective film 4 is particularly excellent, and the productivity and reliability of the timepiece dial 1 are also improved.

The reflective film 4 may be formed by combining a plurality of different methods and conditions. Thereby, the reflective film 4 comprised by the laminated body as mentioned above can be formed suitably.
The mask 8 used in this step has openings 81 arranged in a pattern corresponding to the openings 41 of the reflective film 4 to be formed. That is, it can be said that the mask 8 has the opening 81 other than the portion corresponding to the opening 41 to be formed, and has the opening 81 of the pattern in which the opening 41 is reversed.

  Further, the mask 8 used in this step has a cross-sectional area of the opening 81 from the first surface 82 side which is the main surface facing the substrate 2 toward the second surface 83 side which is the opposite main surface. It has a cross-sectional area decreasing portion 812 that decreases. In other words, the opening 81 is inclined from the first surface 82 side facing the substrate 2 of the mask 8 by the inclined surface 811 inclined by a predetermined angle with respect to the direction perpendicular to the main surface of the mask 8. It is provided as having a cross-sectional area reducing portion 812 whose cross-sectional area decreases toward the side. Furthermore, in other words, the mask 8 has the opening 81 on the second surface 83 side so that the area of the opening 81 on the second surface 83 side is smaller than the opening 81 on the first surface 82 side. A protruding portion 84 that protrudes toward the central direction is provided. By using such a mask 8, when the mask 8 is removed after the reflective film 4 is formed, it is possible to effectively prevent the formed reflective film 4 from being defective. As a result, the reliability of the obtained timepiece dial 1 can be improved.

In the opening 81 (cross-sectional area reducing portion 812) of the mask 8, the cross-sectional area at the minimum cross-sectional area 813 where the cross-sectional area of the opening 81 is minimum is S ₀ ′ [μm ² ], and the cross-sectional area of the opening 81 is When the cross-sectional area at the maximum cross-sectional area maximum portion 814 (the cross-sectional area of the opening 81 in the first surface 82 in the illustrated configuration) is S ₁ ′ [μm ² ], 0.01 ≦ S ₀ ′ / S ₁ ′ ≦ 0.95 is preferably satisfied, 0.05 ≦ S ₀ ′ / S ₁ ′ ≦ 0.90 is more preferable, and 0.10 ≦ S ₀ ′ / More preferably, the relationship of S ₁ ′ ≦ 0.85 is satisfied. By satisfying such a relationship, when the mask 8 is removed in a subsequent mask removing step, it is possible to more effectively prevent defects and the like from being formed in the formed reflective film 4, and an obtained timepiece can be obtained. The reliability of the dial 1 can be made particularly excellent. On the other hand, if the value of S ₀ ′ / S ₁ ′ is less than the lower limit value, the stability of the shape of the mask 8 decreases depending on the constituent material of the mask 8, and the mask 8 is formed when the reflective film 4 is formed. May be deformed. When such deformation occurs, it may be difficult to form the reflective film 4 having the opening 41 having a desired shape. In addition, the durability of the mask 8 may be reduced, and the tendency for the productivity of the timepiece dial 1 to be reduced may become significant. On the other hand, when the value of S ₀ ′ / S ₁ ′ exceeds the upper limit, depending on the constituent material of the mask 8, the constituent material of the reflective film 4, etc., the effect of the mask 8 having the cross-sectional area reducing portion 812 is sufficient. It is difficult to make the aesthetic appearance of the timepiece dial 1 sufficiently excellent.

The thickness of the mask 8 is not particularly limited, but it is usually preferable that the thickness be equal to or greater than the thickness of the reflective film 4 to be formed. Thereby, the reflective film 4 having the opening 41 having a target shape can be more reliably formed.
When the thickness of the reflective film 4 to be formed is T _R [μm] and the thickness of the mask 8 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.

Although the specific thickness of the mask 8 depends on the thickness of the reflective film 4 to be formed, etc., it is preferably 30 to 200 μm, more preferably 50 to 150 μm.
Such a mask 8 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 81.

  The mask 8 may be made of any material, and examples of the constituent material of the mask 8 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 8. When the mask 8 is made of a metal material, the durability of the mask 8 can be made particularly excellent. As a result, the productivity of the timepiece dial 1 can be made particularly excellent, and variations in quality among a large number of timepiece dials 1 can be suppressed, and the reliability of the timepiece dial 1 can be reduced. Will improve. In addition, metal materials generally have moderate elasticity, and many have high shape followability, and the substrate 2 (watch dial 1 to be manufactured) is not limited to a flat plate, but a curved plate. Even if it is in a shape, it can be suitably applied. In addition, one type of mask 8 can be used in common for differently shaped substrates 2 (for example, flat substrate 2 and curved plate substrate 2).

  In particular, in the present embodiment, the mask 8 is made of a material including a magnetic material (a material having paramagnetism and ferromagnetism). A magnet (not shown) is disposed on the surface of the substrate 2 opposite to the surface facing the mask 8, whereby the mask 8 and the work to be formed with the reflective film 4 as the reflective film are provided. The substrate 2 (the substrate 2 covered with the oxide film 5) can be reliably adhered. As a result, it is possible to more reliably prevent the reflective film 4 from being formed on a portion other than the target on the substrate 2, and to improve the aesthetic appearance and electromagnetic wave permeability of the finally obtained timepiece dial 1. It can be surely excellent. That is, the reliability of the manufactured timepiece dial 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 8 is made of a material containing a magnetic material, but the mask 8 may be made of substantially only a magnetic material, for example. However, it may contain other components.
The mask 8 may have a surface layer (not shown). Thereby, for example, the durability of the mask 8 can be made particularly excellent, or the constituent material of the reflective film 4 can be effectively prevented from firmly adhering onto the mask 8 during film formation. it can. 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.

  When this step is performed by vapor phase film formation, for example, the vapor phase film formation is inclined by a predetermined angle θ with respect to the normal direction of the main surface of the substrate 2 (main surface to be covered with the reflective film 4). From this direction, vapor deposition particles (for example, sputtered particles in the case of sputtering) made of the constituent material of the reflective film 4 may be incident on the substrate 2. Thereby, it is possible to effectively prevent unintentional film thickness variation from occurring in the formed reflective film 4. Further, vapor-phase film-forming particles composed of the constituent material of the reflective film 4 from a direction inclined by a predetermined angle θ with respect to the normal direction of the main surface of the substrate 2 (main surface to be coated with the reflective film 4). By making the light incident on the substrate 2, the vapor-phase film-forming particles can be reliably supplied to the region on the back side of the protruding portion 84 in the opening 81, and the shape corresponding to the opening 81 of the mask 8. The reflective film 4 can be more reliably formed.

  In such a case, the angle θ formed by the incident direction of the vapor-phase film-forming particles and the normal direction of the main surface of the substrate 2 is not particularly limited, but is preferably 1 to 50 °, and preferably 3 to 40 °. More preferably, it is 5 to 30 °. When the angle θ is a value within the above range, it is possible to more effectively prevent unintentional film thickness variation from occurring in the formed reflective film 4.

  Moreover, it is preferable that the vapor-phase film-forming particles are incident not only from one direction but also from a plurality of directions on the substrate 2. Thereby, the suitable reflective film 4 with which the dispersion | variation in unintentional film thickness was suppressed can be formed easily and reliably, and the aesthetic appearance and light transmittance about the timepiece dial 1 obtained are especially excellent. Can be. Further, it is possible to obtain the timepiece dial 1 as a material in which variations in texture when viewed from various directions are more effectively suppressed.

  As a method for injecting vapor-phase film-forming particles from a plurality of directions, for example, a plurality of vapor-phase film-formation sources (targets, vapor deposition sources, etc.), which are materials for vapor-phase film-formation, are prepared, There may be a method of installing and generating vapor deposition particles simultaneously or sequentially from the plurality of vapor deposition sources. For example, the substrate 2 and the vapor deposition source are relatively moved (displaced). On the other hand, there is a method of generating vapor-phase film-forming particles from a vapor-phase film-formation source. As a method of moving (displace) the substrate 2 and the vapor deposition source relatively, for example, a method of moving (displacement) the vapor deposition source while the substrate 2 is fixed, Examples thereof include a method of moving (displacement) the substrate 2 in a fixed state, and a method of moving (displacement) both the vapor deposition source and the substrate 2. In particular, when the substrate 2 is moved (displaced), an effect that it is easy to use a conventional vapor deposition apparatus that fixes a vapor deposition source as it is can be obtained.

Hereinafter, a method of moving (displacement) the substrate 2 will be described more specifically with reference to FIG.
In the configuration shown in FIG. 5, the substrate 2 is rotated on the shaft 9 so that the angle between the normal of the main surface of the substrate 2 and the longitudinal direction of the shaft 9 maintains a predetermined angle θ. It has a configuration to let you. In other words, in the configuration shown in FIG. 5, the normal line of the main surface of the substrate 2 where the extension line of the shaft 9 is in contact with the surface (incident surface) of the substrate 2 is a conical circumferential surface about the shaft 9. The substrate 2 rotates to form. With this configuration, for example, the incidence of the vapor-phase film-forming particles is maintained while maintaining the state where the normal line of the main surface of the substrate 2 is inclined by the angle θ with respect to the incident direction of the vapor-phase film-formation particles. The direction can be changed over time. Thereby, the reflective film 4 having the opening 41 of a suitable shape can be easily and reliably formed, and the aesthetic appearance and electromagnetic wave permeability of the obtained timepiece dial 1 are particularly excellent. be able to. Further, it is possible to obtain the timepiece dial 1 as a material in which variations in texture when viewed from various directions are more effectively suppressed.

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

After forming the reflective film 4, the mask 8 is removed (1d). As a result, on the surface of the substrate 2 on the side coated with the oxide film 5 and the reflective film 4, the part corresponding to the opening 81 of the mask 8 is exposed, and the other parts are reflected. It will be in the state coat | covered with the film | membrane 4 (real part).
The mask 8 can be removed by peeling the mask 8 from the substrate 2 on which the oxide film 5 and the reflective film 4 are provided. As described above, since the mask 8 has a reduced cross-sectional area, when the mask is removed in this step, inconvenience such as unintentional peeling occurs in the reflective film 4 formed in the previous step. Can be more reliably formed.

[Capsule formation process]
Next, the coating 3 is formed on the surface of the reflective film 4 (1e). Thereby, the timepiece dial 1 is obtained.
The formation of the covering film 3 is not particularly limited, but can be performed, for example, by bonding a covering material previously formed into a film shape to the surface of the reflective film 4. The joining of the brazing material and the reflective film 4 can be performed, for example, by bringing the brazing material into close contact with the reflective film 4 in a state where the brazing material and / or the reflective film 4 is heated. Further, the coating 3 may be formed by applying a molten soot on the reflective film 4. Wrinkles are generally a relatively soft material that is easy to process and softens at relatively low temperatures. For this reason, the capsule 4 can be easily formed by using the above method. In addition, you may perform joining of a brazing material and the reflecting film 4 through the layer comprised with the adhesive and the adhesive agent.

  In addition, a liquid obtained by dissolving or dispersing soot in a material generally used as a solvent (solvent) may be used as the material for forming the capsule. By using it as such a film forming material, the method of forming the film 3 and the degree of freedom of forming conditions are widened, and even a relatively thin film can be formed suitably. Examples of the method for forming the film 3 using the film forming material include spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, and the like.

<< Second Embodiment >>
Next, a timepiece dial according to a second embodiment of the present invention and a manufacturing method thereof will be described. Hereinafter, the difference from the above-described embodiment will be mainly described, and the description of the same matters will be omitted.
<Watch dial>
FIG. 6 is a cross-sectional view showing a second embodiment of the timepiece dial of the present invention.

  As shown in FIG. 6, the timepiece dial 1 of the present embodiment is provided on the surface of the substrate (base material) 2, the capsule 3, and the surface of the substrate 2 opposite to the surface facing the capsule 3. A reflective film (metal film) 4 and an oxide film 5 provided in contact with the substrate 2 and the reflective film 4. That is, it is the same as that of embodiment mentioned above except the arrangement | positioning of the board | substrate (base material) 2, the coating film 3, the reflective film (metal film) 4, and the oxide film 5 differing.

As shown in FIG. 6, in the timepiece dial 1 of the present embodiment, the capsular film 3 is not in contact with the reflective film 4, and the substrate 2 and the oxidation film are interposed between the capsular film 3 and the reflective film 4. It has the structure by which the material film 5 was inserted. By having such a configuration, the light reflected by the surface of the reflective film 4 (the surface facing the cap film 3) does not directly enter the cap film 3, but enters the cap film 3 via the substrate 2 or the like. It will be incident. This allows the observer to recognize that the capsule 3 is thicker than the actual thickness, and the appearance of the timepiece dial 1 can be made more profound. Moreover, even if the thickness of the capsular membrane 3 is relatively thin, the texture of the cocoon can be sufficiently exhibited. Further, since the substrate 2 and the oxide film 5 are interposed between the covering film 3 and the reflective film 4, the presence of the opening 41 can be made inconspicuous, and the timepiece This is advantageous in improving the aesthetic appearance of the dial 1 for use. Further, even when the size of the opening 41 is relatively large or the aperture ratio is relatively large, the presence of the opening 41 can be made sufficiently inconspicuous, so that the timepiece dial 1 The light transmission property of the timepiece dial 1 as a whole can be made particularly excellent while the aesthetic appearance of the watch is sufficiently excellent.
In the present embodiment, the capsule 3 is in contact with the substrate 2. In general, the bag has an affinity for the plastic material constituting the substrate 2 rather than the affinity for the metal material. Therefore, with the configuration as shown in FIG. 6, the adhesion of the capsule 3 is excellent, and the durability and reliability of the timepiece dial 1 as a whole is improved.

<Manufacturing method of timepiece dial>
Next, the manufacturing method of the timepiece dial 1 described above will be described.
FIG. 7 is a cross-sectional view showing a preferred embodiment of the method for manufacturing the timepiece dial shown in FIG.
As shown in FIG. 7, in the method for manufacturing a timepiece dial according to this embodiment, a substrate preparation step (2 a) for preparing the substrate 2 and an oxide film 5 is formed on at least a part of the surface of the substrate 2. An oxide film forming step (2b), a reflective film forming step (2c, 2d) for forming a reflective film (metal film) 4 having an opening 41 on the surface of the oxide film 5, and a reflective film 4 on the substrate 2 A film forming step (2e) for forming the film 3 on the surface opposite to the surface on which the film is provided. That is, it is the same as that of embodiment mentioned above except the site | parts which form the capsule 3 differ.

"clock"
Next, the timepiece of the present invention provided with the timepiece dial 1 of the present invention as described above will be described.
The timepiece of the present invention has the timepiece dial of the present invention as described above. In addition, as components other than the timepiece dial (the timepiece dial of the invention) constituting the timepiece of the invention, known parts can be used. Hereinafter, an example of the configuration of the timepiece of the invention will be described. Will be described.

FIG. 8 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 8, a wristwatch (portable timepiece) 100 according to this embodiment includes a case (case) 102, a back cover 103, a bezel (edge) 104, and a glass plate (cover glass) 105. . Further, in the case 102, the timepiece dial 1, the solar battery 11, and the movement 101 as described above are housed, and hands (pointers) (not shown) and the like are housed.
The glass plate 105 is usually made of transparent glass or sapphire having high transparency. Thereby, the aesthetic appearance of the timepiece dial 1 can be sufficiently exhibited, and a sufficient amount of light can be incident on the solar cell 11.

The movement 101 uses the electromotive force of the solar cell 11 to drive the pointer.
Although omitted in FIG. 8, in the movement 101, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 11, a lithium ion secondary battery, a crystal resonator as a time reference source, and a crystal vibration A semiconductor integrated circuit that generates a driving pulse that drives the clock based on the oscillation frequency of the child, a step motor that drives the wheel train mechanism every second in response to this driving pulse, and a movement of the step motor A train wheel mechanism for transmitting to the vehicle is provided.
The movement 101 also 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 11 has a function of converting light energy into electric energy. The electric energy converted by the solar cell 11 is used for driving the movement.
In the solar cell 11, 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 106 is fitted and fixed to the barrel 102, and a shaft 1071 of a crown 107 is rotatably inserted into the winding stem pipe 106.
The body 102 and the bezel 104 are fixed by a plastic packing 108, and the bezel 104 and the glass plate 105 are fixed by a plastic packing 109.
Further, a back cover 103 is fitted (or screwed) to the body 102, and a ring-shaped rubber packing (back cover packing) 114 is inserted in a compressed state in these joint portions (seal portions) 115. Has been. With this configuration, the seal portion 115 is liquid-tightly sealed, and a waterproof function is obtained.

  A groove 1072 is formed on the outer periphery of the shaft 1071 of the crown 107, and a ring-shaped rubber packing (crown packing) 113 is fitted in the groove 1072. The rubber packing 113 is in close contact with the inner peripheral surface of the winding stem pipe 106 and is compressed between the inner peripheral surface and the inner surface of the groove 1072. With this configuration, the space between the crown 107 and the winding stem pipe 106 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 107 is rotated, the rubber packing 113 rotates together with the shaft portion 1071 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 106.

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, a solar timepiece (particularly, a solar radio timepiece) has been described as an example of a timepiece. However, the present invention is not limited to a solar timepiece (for example, a radio timepiece other than a solar radio timepiece). Can be applied similarly.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.
For example, the timepiece dial of the present invention is not limited to the one manufactured by the method described above, and may be manufactured by any method.
In the above-described embodiment, the reflective film has been described as having an opening, but the reflective film may not have an opening.

In the above-described embodiment, the description has been made on the assumption that the oxide film is provided between the substrate and the reflective film. However, the timepiece dial of the present invention does not necessarily have the oxide film. .
Further, the timepiece dial of the present invention may have another configuration in addition to the above-described configuration. For example, a coating layer may be provided on the surface of the capsule. As a result, for example, the color tone and the like can be adjusted to further improve the aesthetic appearance of the timepiece dial, or as a whole timepiece dial, the corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, Various characteristics such as wear and discoloration resistance can be improved. Such a coat layer may be removed, for example, when a timepiece dial is used. Further, for example, at least one intermediate layer is provided between the substrate and the oxide film, between the oxide film and the metal film, between the metal film and the film, between the substrate and the film, and the like. May be provided.

Next, specific examples of the present invention will be described.
1. Manufacture of timepiece dial (Example 1)
A timepiece dial was manufactured by the following method.
First, a substrate (base material) having the shape of a timepiece dial was prepared by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained substrate was substantially disk-shaped and had a diameter: 27 mm × thickness: 0.4 mm.

Next, this substrate was cleaned. As the cleaning of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, washing with water for 10 seconds, and cleaning with pure water for 10 seconds.
An oxide film composed of TiO ₂ was formed on the surface of the substrate thus cleaned by sputtering as described below (oxide film forming step).
First, the cleaned substrate was mounted in a sputtering apparatus, and then the inside of the sputtering apparatus was exhausted (reduced pressure) to 3 × 10 ⁻³ Pa while preheating the inside of the apparatus. Next, while introducing argon gas at an argon flow rate: 40 ml / min, oxygen was introduced at an oxygen flow rate: 10 ml / min. In this state, Ti was used as a target, and discharge was performed under the conditions of input power: 1400 W and treatment time: 2.5 minutes, thereby forming an oxide film composed of TiO ₂ . The average thickness of the oxide film thus formed was 0.05 μm.

Subsequently, a reflective film (metal film) composed of an Ag—Au alloy was formed on the surface of the oxide film by sputtering as follows (reflective film forming process (metal film forming process)).
First, in a state where a mesh (square lattice) mask (see FIG. 2) in which square openings are regularly arranged is arranged on the surface of the oxide film, this mask is provided on the substrate on which the oxide film is provided. It was made to adsorb | suck to the magnet installed in the sputtering device via. As a result, the substrate and the mask are brought into close contact with each other, and the relative movement between the substrate and the mask is regulated. The mask was made of stainless steel (SUS444), and its thickness was 120 μm. Moreover, this mask had a cross-sectional area reduction part as shown in FIG. Further, the cross-sectional area at the minimum cross-sectional area where the cross-sectional area of the opening of the mask is minimum is S ₀ ′ [μm ² ], and the cross-sectional area at the maximum cross-sectional area where the cross-sectional area of the opening is maximum is S _1. When “[μm ² ]” was set, the value of S ₀ ′ / S ₁ ′ was 0.65.

Next, 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, an Ag—Au alloy was used as a target, and discharge was performed under the conditions of input power: 1400 W and processing time: 2.5 minutes, thereby forming a reflective film made of Ag. At this time, as shown in FIG. 5, the substrate is rotated on the shaft in such a manner that the angle formed between the normal line of the main surface of the substrate and the longitudinal direction of the shaft maintains 15 °. Vapor-phase deposited particles (sputtered particles) composed of the constituent material of the reflective film from a direction inclined by 15 ° (angle θ) with respect to the normal direction of the main surface of the substrate (main surface to be coated with the reflective film) ) On the substrate. The average thickness of the reflective film thus formed was 0.25 μm. Further, the formed reflective film had an opening at a portion covered with a mask.

Next, the substrate provided with the oxide film and the reflective film having the opening was taken out from the sputtering apparatus, and the mask was removed.
Next, the substrate coated with the oxide film and the reflective film obtained as described above was washed. As washing, first, alkali immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, water washing for 10 seconds, and pure water washing for 10 seconds.

On the other hand, a plate-shaped brazing material was prepared, and hot pressing was performed to obtain a smooth film having an average thickness of about 250 μm.
Next, the capsule was bonded to the surface of the reflective film formed as described above, thereby obtaining a timepiece dial (capsule forming step). Bonding of the coating was carried out by bringing the oxide coating, the substrate coated with the reflective coating, and the coating in close contact with each other while being heated to 140 ° C., and then allowing to cool.
The thicknesses of the substrate, oxide film, metal film (reflection film), and capsule were measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 5)
The constituent materials and thickness of the substrate used for the production of the timepiece dial are as shown in Table 1, and the oxide film, the reflective film, and the coating film are configured as shown in Table 1 in each step. A timepiece dial was manufactured in the same manner as in Example 1 except that the processing conditions were adjusted (including changes in materials used in each step).

(Example 6)
A timepiece dial was manufactured in the same manner as in Example 1 except that a coating film was formed on the surface of the substrate opposite to the surface on which the oxide film and the reflective film were provided.
(Examples 7 to 10)
The constituent materials and thickness of the substrate used for the production of the timepiece dial are as shown in Table 1, and the oxide film, the reflective film, and the coating film are configured as shown in Table 1 in each step. A timepiece dial was manufactured in the same manner as in Example 6 except that the processing conditions were adjusted (including changes in materials used in each step).
(Example 11)
In the reflective film forming step, a timepiece dial was manufactured in the same manner as in Example 6 except that no mask was used.

(Comparative Example 1)
A plate-shaped watch material was prepared and heat-pressed to obtain a timepiece dial made of a watch and having a substantially disk shape with a diameter of 27 mm × thickness: 0.6 mm.
(Comparative Example 2)
A timepiece dial was manufactured in the same manner as in Example 1 except that the reflective film forming step was omitted.

(Comparative Example 3)
First, a substrate having the shape of a timepiece dial was produced by casting using Ag, and then necessary portions were cut and polished. The obtained substrate was substantially disk-shaped and had a diameter: 27 mm × thickness: 0.4 mm.
Thereafter, a watch dial was obtained by forming a capsule on the surface of the obtained substrate in the same manner as in Example 1.

  Along with the configuration of the timepiece dial of each example and each comparative example, the configuration of the mask used to manufacture the dial, the angle θ formed by the perpendicular direction of the main surface of the substrate and the traveling direction of the sputtered particles when forming the metal film Are summarized in Table 1. In Table 1, polycarbonate is represented by PC, acrylonitrile-butadiene-styrene copolymer (ABS resin) is represented by ABS, and polyethylene terephthalate is represented by PET. In addition, each of the capsules used in each example and each comparative example had a light transmittance in the range of 10 to 70%. In addition, the wrinkles used in each example and each comparative example are all natural wrinkles, and succinoresene, succinoabietinolic acid, succinoabietol, succinoresinol, succinosylvinic acid in the capsule, The total content of succinic acid, succioxyabietic acid, succinogiruic acid, and succinoabieticol was all 90 wt% or more.

2. Appearance evaluation of timepiece dials Each timepiece dial produced in each of the above examples and comparative examples was visually observed, and the appearance was evaluated according to the following six-stage criteria.
A: It has a high-class feeling and has a very good appearance.
A: It has a high-class feeling and has an excellent appearance.
○: There is a high-class feeling and a good appearance is exhibited.
Δ: Inferior to luxury. Or the aesthetic appearance is somewhat poor.
X: Aesthetic appearance is poor.
XX: The aesthetic appearance is extremely poor.

3. Evaluation of radio wave permeability The radio wave permeability of each timepiece dial 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 watch internal module (movement) and a watch dial were assembled in the watch case, and the radio wave reception sensitivity in this state was measured.
Using the reception sensitivity in a state where the timepiece dial is not incorporated as a reference, the reduction amount (dB) of the reception sensitivity when the timepiece dial is incorporated was evaluated according to the following five 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 decrease in sensitivity is 1.0 dB or more and less than 1.5 dB.
Xx: The reduction in sensitivity is 1.5 dB or more.

4). Evaluation of light transmittance of timepiece dial The light transmittance of each timepiece dial manufactured in each of the above Examples and Comparative Examples was evaluated by the following method.
First, the solar cell and each clock 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) separated by a predetermined distance was made incident in the same manner as described above with the timepiece dial overlapped 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 timepiece dial represented by (B / A) × 100 was calculated and evaluated according to the following six criteria. It can be said that the larger the light transmittance of the timepiece dial, the better the light transmittance of the timepiece dial.

A: 35% or more.
A: 32% or more and less than 35%.
○: 28% or more and less than 32%.
Δ: 25% or more and less than 28%.
X: 17% or more and less than 25%.
Xx: Less than 17%.

  Thereafter, a wristwatch as shown in FIG. 8 was manufactured using the timepiece dial manufactured in each of the above 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 watch of Comparative Example 3, the movement was not confirmed even when the irradiation intensity was relatively high.

5. Evaluation of adhesion (durability evaluation) of coatings (oxide coatings, reflective films, and capsules)
Each timepiece dial manufactured in each of the above Examples and Comparative Examples was subjected to the following two tests to evaluate the adhesion of the coating (oxide coating, reflective coating, capsule).
5-1. Bending test For each timepiece dial, a steel bar with a diameter of 4 mm is used as a fulcrum, and after bending 20 ° with respect to the center of the timepiece dial, the appearance of the timepiece dial is visually observed, These appearances were evaluated according to the following four criteria. Bending was performed in both compression / tension directions.

(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.

5-2. Thermal cycle test Each timepiece dial was subjected to the following thermal cycle test.
First, the watch dial is placed in a 20 ° C. environment for 1.5 hours, then in a 60 ° C. environment for 2 hours, then in a 20 ° C. environment for 1.5 hours, and then in a −20 ° C. environment. It was left to stand for 3 hours. Thereafter, the environmental temperature was returned again to 20 ° C., which was set as one cycle (8 hours), and this cycle was repeated three times in total (24 hours in total).

Thereafter, the appearance of the timepiece dial was visually observed, and the appearance was evaluated according to the following four-stage criteria.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.
These results are shown in Table 2.

As is apparent from Table 2, the timepiece dial of the present invention had an excellent aesthetic appearance and was excellent in electromagnetic wave permeability.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, the timepiece dials of Comparative Examples 1 and 2, which did not have a reflective film, were inferior in aesthetic appearance. Further, the timepiece dial of Comparative Example 3 using a metal substrate was inferior in electromagnetic wave permeability.
Further, a timepiece as shown in FIG. 8 was assembled using the timepiece dials obtained in each Example and each Comparative Example. Each timepiece thus obtained was tested and evaluated in the same manner as described above, and the same results as described above were obtained.

It is sectional drawing which shows 1st Embodiment of the dial for timepieces of this invention. It is a typical top view for explaining an example of the shape (pattern) of the opening which a reflective film has. It is a typical top view for demonstrating another example of the shape (pattern) of the opening part which a reflecting film has. It is sectional drawing which shows the manufacturing method of the timepiece dial shown in FIG. It is a figure for demonstrating the advancing direction of the gaseous-phase film-forming particle | grains at the time of forming a reflecting film. It is sectional drawing which shows 2nd Embodiment of the dial for timepieces of this invention. It is sectional drawing which shows the manufacturing method of the timepiece dial shown in FIG. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (portable timepiece) of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Timepiece dial 2 ... Board | substrate (base material) 3 ... Capsule 31 ... 1st surface 32 ... 2nd surface 4 ... Reflective film (metal film) 41 ... Opening part 5 ... Oxide film 8 ... Mask ( 81 ... Opening part 811 ... Inclined surface 812 ... Cross sectional area reducing part 813 ... Cross sectional area minimum part 814 ... Cross sectional area maximum part 82 ... First surface 83 ... Second surface 84 ... Protruding part 9 ... Shaft 11 ... Solar cell 101 ... Movement 102 ... Body (case) 103 ... Back cover 104 ... Bezel (edge) 105 ... Glass plate (cover glass) 106 ... Winding pipe 107 ... Crown 1071 ... Shaft part 1072 ... Groove 108 ... Plastic packing 109 ... Plastic packing 113 ... Rubber packing (Crown packing) 114 ... Rubber packing (back cover packing) 115 ... Junction (seal part) 100 Wristwatch (portable timepiece)

Claims (13)

A base material made of a material having electromagnetic wave permeability;
A capsule composed primarily of straw,
A timepiece dial having a reflective film having a function of reflecting outside light.   The timepiece dial according to claim 1, wherein the reflective film is provided in contact with the cap film.   The timepiece dial according to claim 1, wherein the base material is provided between the cap film and the reflective film.   The timepiece dial according to any one of claims 1 to 3, wherein a thickness of the capsule is 50 to 1000 µm.   The timepiece dial according to any one of claims 1 to 4, wherein the reflective film is made of a material containing one or more selected from the group consisting of Au and Cu.   The timepiece dial according to claim 1, wherein the reflective film is made of a material containing one or more selected from the group consisting of Ag and Al.   The timepiece dial according to claim 1, wherein the reflective film has a thickness of 0.005 to 2.5 μm.   The timepiece dial according to claim 1, wherein the base material is made of a plastic material. The base material is light transmissive, and
The timepiece dial according to claim 1, wherein the reflective film has an opening.   The timepiece dial according to claim 9, wherein a width of the opening provided in the reflective film is 10 to 150 μm.   The timepiece dial according to claim 9 or 10, wherein an area ratio occupied by the opening when the reflective film is viewed in plan is 15 to 55%.   The timepiece dial according to any one of claims 9 to 11, wherein the timepiece dial is a solar timepiece dial.   A timepiece comprising the timepiece dial according to claim 1.

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