JP2009210358A - Dial plate for timepiece, method of manufacturing dial plate for timepiece, and timepiece - Google Patents

Abstract

An object of the present invention is to provide a timepiece dial having excellent light transmittance and capable of stably maintaining a high-quality appearance with a dark color tone over a long period of time, and manufacturing the timepiece dial. And a timepiece having the timepiece dial.
A timepiece dial according to the present invention includes a substrate 11 made of a light-transmitting material, an oxide film 14 formed on the substrate 11 and made of titanium oxide, and an oxide. A Ti film 15 provided on the coating 14 and mainly made of Ti and having an opening, an Ag film 12 made of a material containing Ag and provided on the Ti film 15, and having an opening, and an Ag film 12 And a coat layer 13 provided thereon. The Ag film 12 is composed mainly of silver sulfide, silver halide, or silver oxide in the vicinity of the surface in contact with the coat layer 13.
[Selection] Figure 1

Description

  The present invention relates to a timepiece dial, a method for manufacturing a timepiece dial, and a timepiece.

A watch is required to have a function as a practical product and a decorative property (aesthetic appearance) as a decorative product. In particular, in solar timepieces equipped with solar cells, when solar cells (solar cells) are placed under the dial (solar watch dial), the dial has excellent light transmissivity and other decorative items. Decorative properties (aesthetic appearance) are required.
Specifically, the dial for a solar timepiece provides a sufficient amount of light for driving the timepiece through a solar cell disposed below the solar dial, while providing a decorative item. Decorative properties are also required.

Conventionally, in a solar timepiece, in order to make a sufficient amount of light incident on the solar cell, the solar cell itself is used as a dial plate, and a colored member (particularly a dark member) is not arranged on the solar cell. Designed the shape of the dial. However, such a watch is inferior in aesthetic appearance as a decorative product, and it is particularly difficult to give a high-class feeling.
Therefore, a dial plate obtained by sticking a metal film made of a metal material and provided with an opening through an adhesive on a plastic substrate has been proposed (see, for example, Patent Document 1). .

However, in the method as described above, when the metal film is stuck on the substrate, the metal film is likely to be wrinkled, and in order to prevent the occurrence of such wrinkles, it is necessary to perform a sticking operation carefully. Yes, the dial productivity is extremely low. Moreover, even when the sticking operation is performed with great care, it is difficult to sufficiently prevent the occurrence of relatively small wrinkles, etc., and the aesthetic appearance of the resulting dial is sufficiently excellent. It was difficult. In addition, the above-described method generates defective products at a relatively high rate, which is not preferable from the viewpoint of production yield and resource saving. The above problems are particularly noticeable when the metal film is relatively thin (for example, 10 μm or less). In addition, when the metal film is relatively thin (for example, 10 μm or less), the metal film is easily broken when performing the sticking operation, which is disadvantageous from the viewpoints of dial productivity, production cost, and resource saving. At the same time, a part of the torn metal film may be scattered as fine particles in the atmosphere, and there is a concern about human health. Further, with the dial as described above, it is difficult to reliably adhere the metal film, and the change in appearance over time (decrease in aesthetics) is remarkable.
On the other hand, there is a demand for applying a dial with a dark color tone and a high-quality appearance to a solar watch. However, since the above method uses a metal film, a high-quality dark color tone is used. It was not possible to obtain a dial with a pleasing appearance.

JP 11-326549 A (see page 3, right column, line 35 to page 4, left column, line 11)

  An object of the present invention is to provide a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-quality appearance in a dark color tone over a long period of time. It is to provide a manufacturing method capable of manufacturing the timepiece dial and to provide a timepiece including the timepiece dial.

Such an object is achieved by the present invention described below.
The timepiece dial of the present invention includes a substrate made of a light-transmitting material,
An Ag film made of a material containing Ag and having an opening;
A coating layer provided on the surface of the Ag film opposite to the surface facing the substrate;
In the Ag film, at least the vicinity of the surface in contact with the coating layer is mainly composed of silver sulfide, silver halide, or silver oxide.
Accordingly, it is possible to provide a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-quality appearance with a dark color tone over a long period of time.

In the timepiece dial of the present invention, it is preferable that the Ag film has a plurality of island-shaped regions when the timepiece dial is viewed in plan.
Thereby, the presence of the opening can be made less noticeable, and the aesthetic appearance of the timepiece dial can be made particularly excellent. In addition, even when the ratio of the area occupied by the opening (opening ratio) is relatively high when the timepiece dial is viewed in plan, the existence of the opening is surely made inconspicuous. Therefore, the light transmission can be made particularly excellent while sufficiently improving the aesthetic appearance of the timepiece dial.

In the timepiece dial of the present invention, the Ag film preferably has a thickness of 100 to 5000 nm.
Thereby, durability and aesthetic appearance of the timepiece dial can be made particularly excellent.
In the timepiece dial of the present invention, it is preferable that an oxide film mainly composed of a metal oxide is provided between the substrate and the Ag film.
Thereby, the durability of the timepiece dial can be made particularly excellent.

In the timepiece dial of the present invention, it is preferable to have a Ti film mainly composed of Ti and having an opening between the oxide film and the Ag film.
Thereby, the durability of the timepiece dial can be made particularly excellent.
In the timepiece dial of the present invention, a titanium oxide film mainly composed of titanium oxide is provided on the surface of the substrate,
On the surface of the titanium oxide film opposite to the surface in contact with the substrate, a Ti film composed mainly of titanium and having an opening is provided,
The Ag film is preferably provided on the surface of the Ti film opposite to the surface in contact with the titanium oxide film.
Thereby, the durability 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 Ag film is selectively sulfided, halogenated, or oxidized near the surface in contact with the coating layer in the thickness direction. .
Thereby, the durability of the timepiece dial can be made particularly excellent.
In the timepiece dial of the present invention, it is preferable that the coat layer is mainly composed of a urethane resin and / or an acrylic resin.
Thereby, discoloration of the Ag film over time can be more effectively prevented, and the aesthetic appearance of the timepiece dial can be made excellent for a longer period of time.

In the timepiece dial of the present invention, it is preferable that the coat layer is made of a material containing a colorant.
Thereby, the presence of the opening can be made less noticeable, and the aesthetic appearance of the timepiece dial can be made particularly excellent. In addition, even when the ratio of the area occupied by the opening (opening ratio) is relatively high when the timepiece dial is viewed in plan, the existence of the opening is surely made inconspicuous. Therefore, the light transmission can be made particularly excellent while sufficiently improving the aesthetic appearance of the timepiece dial.

The timepiece dial manufacturing method of the present invention includes a substrate preparation step of preparing a substrate made of a light-transmitting material,
Ag film formation that forms an Ag film mainly composed of Ag having a large number of island-like regions by performing film formation in a state where a mask having a large number of openings provided in a predetermined pattern is arranged Process,
A dark color in which at least the outer surface of the Ag film is mainly composed of silver sulfide, silver halide, or silver oxide by subjecting the Ag film to sulfidation, halogenation, or oxidation. Conversion process,
And a coat layer forming step of forming a coat layer on the side of the substrate on which the Ag film is provided.
Thus, a manufacturing method capable of manufacturing a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-quality appearance with a dark color tone over a long period of time. Can be provided.

The method for manufacturing a timepiece dial of the present invention includes a titanium oxide film forming step of forming a titanium oxide film mainly composed of titanium oxide on the surface of the substrate prior to the Ag film forming step. Is preferred.
Thereby, the durability of the timepiece dial can be made particularly excellent.
In the timepiece dial manufacturing method of the present invention, prior to the Ag film forming step, the titanium oxide is formed by forming a film with a mask having a large number of openings provided in a predetermined pattern. It is preferable to have a Ti film forming step of forming a Ti film mainly composed of Ti having a large number of island-like regions on the surface of the coating.
Thereby, the durability of the timepiece dial can be made particularly excellent.

The timepiece of the present invention includes the timepiece dial of the present invention.
Accordingly, it is possible to provide a timepiece having a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-quality appearance in a dark color tone over a long period of time. Can do. In addition, it is possible to provide a watch (for example, a solar watch) that can effectively use light from the outside.

The timepiece of the present invention includes a timepiece dial manufactured using the method of the present invention.
Accordingly, it is possible to provide a timepiece having a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-quality appearance in a dark color tone over a long period of time. Can do. In addition, it is possible to provide a watch (for example, a solar watch) that can effectively use light from the outside.

  According to the present invention, there is provided a timepiece dial that is excellent in light transmission (light transmission) and can stably maintain a high-grade appearance in a dark color tone over a long period of time. A manufacturing method capable of manufacturing the timepiece dial can be provided, and a timepiece including the 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, a preferred embodiment of the timepiece dial of the present invention will be described.
<Watch dial>
1 is a cross-sectional view showing a preferred embodiment of the timepiece dial of the present invention, FIG. 2 is a plan view showing a preferred embodiment of the timepiece dial of the present invention, and FIG. 3 is an arrangement of an Ag film. FIG. 4 is a schematic plan view for explaining another example of the arrangement pattern of the Ag film. 2 to 4, the coating layer is omitted.

As shown in FIG. 1, the timepiece dial 1 includes a substrate 11 made of a light-transmitting material, an oxide film 14 provided on the surface of the substrate 11 and mainly made of a metal oxide, The Ti film (metal film) 15 provided mainly on the surface of the oxide film 14 opposite to the surface facing the substrate 11 and mainly composed of titanium, and the surface of the Ti film 15 facing the oxide film 14 are It has an Ag film 12 that is provided on the opposite surface and is composed mainly of silver, and a coat layer 13 that is provided on the surface opposite to the surface of the Ag film 12 that faces the Ti film 15. That is, the timepiece dial 1 has a configuration in which the substrate 11, the oxide film 14, the Ti film 15, and the Ag film 12 are laminated in this order. The Ag film 12 has a large number of island-like regions (real parts), and the other regions are openings 121. Similarly, the oxide film 14 has a large number of island-shaped regions (real parts), and other regions have openings 141, and the Ti film 15 has a large number of island-shaped regions. It has a region (real part), and the other region is an opening 151.
The timepiece dial 1 is used such that the surface of the substrate 11 on which the Ag film 12 and the coat layer 13 are provided (the upper surface in FIG. 1) faces the observer side (outer surface side). It is.

[substrate]
The board | substrate 11 is comprised with the material which has a light transmittance. In the present invention, “having light transmittance” means having a property of transmitting at least part of light in the visible light region (wavelength region of 380 to 780 nm), and preferably transmitting light in the visible light region. The rate is 50% or more, and more preferably the light transmittance in the visible light region is 60% or more. Such light transmittance is, for example, using a white fluorescent lamp (manufactured by Toshiba Corporation, inspection fluorescent lamp FL20S-D65) as a light source, and a substrate to be measured (or a clock dial) under 1000 lux. Except that the measurement target substrate (or timepiece dial) is placed on the light source side surface of the solar cell for the current value (X) when power is generated by the solar cell (solar cell) of the same shape. The ratio ((Y / X) × 100 [%]) of the current value (Y) when power is generated in the same state can be adopted. Hereinafter, unless otherwise specified, in this specification, “light transmittance” refers to a value obtained under such conditions.

  Examples of the material constituting the substrate 11 include various plastic materials and various glass materials. The substrate 11 is preferably composed mainly of 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 11 is made of a plastic material, it is advantageous for reducing the manufacturing cost of the timepiece dial 1. In addition, since plastic materials are generally excellent in light (visible light) transmission and also in radio wave transmission, the timepiece dial 1 is assumed that the substrate 11 is made of a plastic material. Can be suitably applied to a radio timepiece as described later. In the following description, an example in which the substrate 11 is mainly composed of a plastic material will be mainly described. In the present invention, “mainly” means a component having the highest content among materials constituting the target portion (member), and the content is not particularly limited, but the target portion (member) It is preferable that it is 60 wt% or more of the material which comprises, More preferably, it is 80 wt% or more, It is further more preferable that it is 90 wt% or more.

  Examples of the plastic material constituting the substrate 11 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, polymer alloy, laminate, etc.). In particular, the substrate 11 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, since the degree of freedom of molding of the substrate 11 is increased (easiness of molding is improved), even the timepiece dial 1 having a more complicated shape can be easily and reliably manufactured. Further, when the substrate 11 is made of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin), the substrate 11 and the oxide coating 14 Adhesion 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 11 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. For example, when the substrate 11 is made of a material containing a colorant, variations in the color of the timepiece dial 1 can be widened.
The substrate 11 may have a substantially uniform composition at each site, or may have a different composition depending on the site.
Further, the shape and size of the substrate 11 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 11 has a flat plate shape, but may have a curved plate shape, for example.

Although the average thickness of the board | substrate 11 is not specifically limited, It is preferable that it is 150-700 micrometers, It is more preferable that it is 200-600 micrometers, It is further more preferable that it is 300-500 micrometers. When the average thickness of the substrate 11 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. Further, when the thickness of the substrate 11 is within the above range, the timepiece to which the timepiece dial 1 is applied is effectively prevented from being thickened while the timepiece dial 1 is mechanically mechanical. Strength, shape stability, etc. can be made sufficiently excellent.
The substrate 11 may be formed by any method. Examples of the method for forming the substrate 11 include compression molding, extrusion molding, injection molding, and stereolithography.

[Oxide coating]
On the surface of the substrate 11, an oxide film 14 mainly composed of a metal oxide is provided. As described above, in the timepiece dial 1, the Ag film 12 is not directly provided on the surface of the substrate 11 made of a plastic material or a glass material, and the oxide film 14 is interposed between the substrate 11 and the Ag film 12. Is intervening. As a result, adhesion between the substrate 11 and the Ag film 12 (particularly, adhesion through the Ti film 15 described later) can be improved, and the Ag film 12 and the like can be effectively lifted and peeled off (peeled). Can be prevented. As a result, the timepiece dial 1 is excellent in durability.
The oxide film 14 is mainly composed of a metal oxide.

  As the metal oxide constituting the oxide coating 14, oxides of various metals 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 14 is mainly composed of titanium oxide (including a complex oxide) (titanium oxide film), the adhesion between the substrate 11 and the Ag film 12 is more excellent. Can do. Further, when the oxide film 14 is composed of oxides of Ti, Zn, Mg, Mo, Nb, Zr, Sn, and In, the transparency of the oxide film 14 (particularly, a film as described later) (Transparency in thickness) can be very high. Thereby, even if it is a case where the oxide film 14 does not have an opening part, the light transmittance as the timepiece dial 1 whole can be made high enough.

Hereinafter, the case where the oxide film 14 is a titanium oxide film mainly composed of titanium oxide will be mainly described.
In the timepiece dial 1 of the present embodiment, the oxide coating (titanium oxide coating) 14 is formed at portions corresponding to the opening 151 of the Ti film 15 and the opening 121 of the Ag film 12 described later. , And has an opening 141 provided in a corresponding shape, size, and arrangement pattern. That is, the opening 141 of the oxide film 14 has the same shape and size as the opening 151 of the Ti film 15 and the opening 121 of the Ag film 12 and is provided in the same arrangement pattern. With such a configuration, even when the oxide coating 14 is relatively thick, the light transmission of the timepiece dial 1 as a whole can be very high. For this reason, light transmittance and aesthetic appearance can be made compatible at a very high level. In addition, even if the oxide film 14 has an opening as in the present embodiment, the opening 141 is formed into an Ag film by manufacturing the timepiece dial 1 using a method as described later. It can be easily and reliably formed in a portion corresponding to the 12 openings 121 with a size, shape, and arrangement pattern corresponding to the openings 121.

  Moreover, the average thickness of the oxide film (titanium oxide film) 14 is not particularly limited, but is preferably 5 to 1000 nm, more preferably 7 to 500 nm, and further preferably 10 to 300 nm. preferable. When the average thickness of the oxide coating 14 is within the above range, the durability of the timepiece dial 1 can be made particularly excellent. On the other hand, if the average thickness of the oxide film 14 is less than the lower limit, the effect of having the oxide film 14 may not be sufficiently exhibited. Moreover, when the average thickness of the oxide film 14 exceeds the upper limit, the variation in film thickness at each part of the oxide film 14 tends to increase. Further, when the average thickness of the oxide film 14 is particularly large, the internal stress of the oxide film 14 becomes high, and cracks and the like are likely to occur.

Further, the oxide film 14 may or may not have a uniform composition at each site. For example, the oxide film 14 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. The oxide film 14 may be a laminate having a plurality of layers. Thereby, for example, the adhesion between the substrate 11 and the Ag film 12 (adhesion through the oxide film 14 and the Ti film 15) can be further improved.
In the configuration shown in the drawing, conditions such as the size and shape of the opening 141 of the oxide coating 14 when the timepiece dial 1 is viewed in plan are the conditions of the opening 151 and the Ag film 12 of the Ti film 15. Since the conditions for the opening 121 are the same, the conditions such as the width and pitch of the real part of the oxide film 14 (regions other than the opening 141) are the real part of the Ti film 15 and the real part of the Ag film 12. The conditions are the same. The width and pitch of the Ag film 12 will be described in detail later.

[Ti film]
A Ti film 15 (as a metal film) mainly composed of titanium is provided on the surface of the oxide film 14 (surface opposite to the surface in contact with the substrate 11).
By having the Ti film 15, the adhesion between the oxide film 14 and the Ag film 12 (adhesion through the Ti film 15) can be made excellent, and the durability of the timepiece dial 1 as a whole. The property can be made excellent.

  The average thickness of the Ti film 15 is not particularly limited, but is preferably 50 nm or more, more preferably 60 to 900 nm, and even more preferably 70 to 500 nm. When the average thickness of the Ti film 15 is within the above range, the durability of the timepiece dial 1 can be made particularly excellent. On the other hand, if the average thickness of the Ti film 15 is less than the lower limit, the effect of having the Ti film 15 may not be sufficiently exhibited. Further, when the average thickness of the Ti film 15 exceeds the upper limit value, the variation in film thickness at each portion of the Ti film 15 tends to increase. Further, when the average thickness of the Ti film 15 is particularly large, the internal stress of the Ti film 15 becomes high and cracks and the like are likely to occur.

The Ti film 15 has an opening 151 provided with a corresponding shape, size, and arrangement pattern at a portion corresponding to the opening 121 of the Ag film 12 described in detail later. That is, the opening 151 of the Ti film 15 has the same shape and size as the opening 121 of the Ag film 12 and is provided in the same arrangement pattern. By having such a configuration, it is possible to prevent the Ti film 15 from being directly visually recognized by the user or the like while reliably exhibiting the effects of having the Ti film 15 as described above, The light transmittance of the timepiece dial 1 as a whole can be made sufficiently excellent. That is, since the Ti film 15 has the opening 151 as described above, the aesthetic appearance and light transmittance of the timepiece dial 1 are sufficiently excellent, and the durability of the timepiece dial 1 as a whole is improved. It can be made particularly excellent. By using a method as will be described later, the opening 151 is easily and reliably formed in a portion corresponding to the opening 121 of the Ag film 12 with a size, shape, and arrangement pattern corresponding to the opening 121. can do.
In the configuration shown in the drawing, the conditions such as the size and shape of the opening 151 of the Ti film 15 when the timepiece dial 1 is viewed in plan are the same as the conditions of the opening 121 of the Ag film 12. Therefore, the conditions such as the width and pitch of the real part (region other than the opening 151) of the Ti film 15 are the same as the conditions of the real part of the Ag film 12. The width and pitch of the Ag film 12 will be described in detail later.

[Ag film]
An Ag film 12 made of a material containing Ag is provided on the surface of the Ti film 15 (the surface opposite to the surface in contact with the oxide film 14).
The Ag film 12 has an opening 121. As described above, the opening 121 is provided in a portion corresponding to the opening 151 included in the Ti film 15 with a corresponding shape, size, and arrangement pattern. That is, the opening 121 is provided in the same part as the opening 151 with the same shape, size, and arrangement pattern when the timepiece dial 1 is viewed in plan. Thereby, the light transmittance as the timepiece dial 1 as a whole can be made sufficiently excellent.

  The Ag film 12 is mainly composed of silver sulfide, silver halide, or silver oxide at least near the surface in contact with the coat layer 13 (near the surface opposite to the surface facing the substrate 11). The dark color portion 122 is formed. Such a dark color portion 122 can be formed by performing a sulfurization treatment or a halogenation treatment as will be described later, as compared with the Ag film 12 in a state before the sulfurization treatment or the halogenation treatment. And darkened.

By having such a dark color portion 122, it is difficult to realize the appearance of the timepiece dial 1 as a whole in the past (particularly difficult to realize as a dial for a solar timepiece). The color tone can be high-class.
In the illustrated configuration, the dark portion 122 is selectively provided near the surface of the Ag film 12 on the side in contact with the coat layer 13. Thereby, the durability of the timepiece dial 1 can be made particularly excellent.

  The real part (island-like region) of the Ag film 12 may have any shape, but in the configuration shown in FIG. 2, the shape when the timepiece dial 1 (substrate 11) is viewed in plan is substantially the same. It is circular. When the real part of the Ag film 12 has such a shape, the ratio of the area of the opening 121 when the timepiece dial 1 is viewed in plan (hereinafter also referred to as “aperture ratio of the Ag film 12”). Even when the aperture is relatively high, the presence of the opening 121 can be made sufficiently inconspicuous, and an excellent aesthetic appearance and light transmittance can be achieved at a higher level. Further, if the real part of the Ag film 12 has the shape as described above, the real part of the Ag film 12 having a desired shape can be easily and reliably formed by a method described later. Further, the productivity of the timepiece dial 1 can be made particularly excellent. Note that the shape of the real part of the Ag film 12 is not limited to that shown in FIG. 2, and may be, for example, as shown in FIGS. 3 and 4.

  The width of the real part of the Ag film 12 (or the diameter when the real part of the Ag film 12 is substantially circular) W is preferably 70 to 600 μm, more preferably 90 to 500 μm, and 100 More preferably, it is -300 micrometers. When the width W of the real part of the Ag film 12 is a value within the above range, the aesthetic appearance (aesthetics) of the timepiece dial 1 is sufficiently high while the light transmission as the timepiece dial 1 is sufficiently high. Can be made particularly excellent. On the other hand, when the width W of the real part of the Ag film 12 is less than the lower limit value, it is difficult to form the Ag film 12 with high accuracy during the manufacture of the timepiece dial 1, and the Ag film 12. Depending on the aperture ratio, it may be difficult to make the appearance of the timepiece dial 1 sufficiently excellent. On the other hand, when the width W of the real part of the Ag film 12 exceeds the upper 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 Ag film 12 and the like. there is a possibility.

  The pitch P of the real part of the Ag film 12 is preferably 100 to 750 μm, more preferably 130 to 600 μm, and further preferably 160 to 450 μm. When the pitch P of the real part of the Ag film 12 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 improved. It can be made particularly excellent. On the other hand, if the pitch P of the real part of the Ag film 12 is less than the lower limit value, it is difficult to form the Ag film 12 with high precision during the manufacture of the timepiece dial 1 and the Ag film 12 Depending on the aperture ratio or the like, it may be difficult to sufficiently increase the light transmittance of the timepiece dial 1 as a whole. On the other hand, if the pitch P of the real part of the Ag film 12 exceeds the upper limit, depending on the aperture ratio of the Ag film 12 or the like, it may be difficult to make the appearance of the timepiece dial 1 sufficiently excellent. There is sex. Note that the pitch of the real part of the Ag film 12 refers to the distance between the centers of the adjacent real parts and the real parts. When there are a plurality of adjacent real parts, the center between the adjacent real parts is the center. Refers to the distance.

  The average thickness of the Ag film 12 is not particularly limited, but is preferably 90 nm or more, more preferably 100 to 5000 nm, and further preferably 160 to 1500 nm. When the average thickness of the Ag film 12 is within the above range, the internal stress of the Ag film 12 is sufficiently prevented, and the aesthetic property of the timepiece dial 1 is particularly excellent. Can do. Further, the adhesion between the Ti film 15 and the Ag film 12 can be made particularly excellent. Further, the radio wave transmission of the timepiece dial 1 as a whole can be made particularly excellent. Thereby, for example, the timepiece dial 1 can be suitably applied to a solar radio timepiece. On the other hand, if the average thickness of the Ag film 12 is less than the lower limit value, the adhesion between the Ti film 15 and the Ag film 12 is sufficient depending on the thickness of the Ti film 15, the formation method of the Ag film 12, and the like. It may be difficult to make it excellent. On the other hand, when the average thickness of the Ag film 12 exceeds the upper limit, the variation in film thickness at each part of the Ag film 12 tends to increase. Further, when the average thickness of the Ag film 12 is particularly large, the internal stress of the Ag film 12 becomes high and cracks and the like are likely to occur.

The average thickness of the dark portion 122 is not particularly limited, but is preferably 80 nm or more, more preferably 100 to 2000 nm, and further preferably 150 to 1000 nm. Thereby, the aesthetics of the timepiece dial 1 can be made particularly excellent.
The aperture ratio of the Ag film 12 is preferably 20 to 70%, more preferably 30 to 70%, still more preferably 45 to 65%, and most preferably 50 to 65%. . When the aperture ratio of the Ag film 12 is a value within the above range, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent while the light transmittance is sufficiently excellent. On the other hand, when the aperture ratio of the Ag film 12 is less than the lower limit value, it becomes difficult to make the light transmission as the whole timepiece dial plate 1 sufficiently excellent. On the other hand, when the aperture ratio of the Ag film 12 exceeds the upper limit, it becomes difficult to make the aesthetic appearance of the timepiece dial 1 sufficiently excellent.

[Coat layer]
A coat layer 13 is provided on the surface of the Ag film 12 (surface opposite to the surface in contact with the Ti film 15). By having the coating layer 13, the dark color portion 122 of the Ag film 12 is prevented from being exposed to the outside, and the dark color portion 122 of the Ag film 12 is reacted with time by reaction (for example, desulfurization, dehalogenation reaction, etc.). Discoloration is reliably prevented. As a result, the timepiece dial 1 can maintain a stable appearance over a long period of time.
The coat layer 13 is made of a light transmissive material. Examples of such materials include various plastic materials (resin materials), various glasses, diamond-like carbon (DLC), etc. Among them, plastic has excellent transparency and excellent moldability (easy to mold). ) Is particularly preferable.

  Examples of the plastic material (resin material) constituting the coat layer 13 include various thermoplastic resins and various thermosetting resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer ( EVA) and other polyolefins, cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamides (eg nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6- 12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), Polycyclohexane terephthalate (PCT) and other polyesters, polyethers, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide , Polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, poly Various thermoplastics such as vinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene Elastomer, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para- xylylene), poly-dichloro-para-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, etc. Polyparaxylylene resins, etc., or copolymers and blends mainly containing these resins It includes polymer alloy or the like, singly or in combination of two or more of these (e.g., a blend resin, polymer alloy, as a laminate or the like) can be used.

  The coat layer 13 is preferably made of a material containing a urethane resin and / or an acrylic resin, and is mainly made of a urethane resin and / or an acrylic resin. More preferably. Thereby, it is possible to more effectively prevent the dark color portion 122 of the Ag film 12 from being discolored over time due to a reaction, and the aesthetic appearance of the timepiece dial 1 is excellent over a longer period of time. It can be. Further, the adhesion between the Ag film 12 and the coat layer 13 can be made particularly excellent.

  The coat layer 13 may contain components other than the above materials. Examples of such components include colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, plasticizers, antioxidants, fillers, and the like. Especially, it is preferable that the coating layer 13 is comprised with the material containing a coloring agent. When the coat layer 13 is made of a material containing a colorant, the opening 121 can be made inconspicuous in the timepiece dial 1, and the aesthetic appearance of the timepiece dial 1. Can be made particularly excellent. In addition, even when the aperture ratio of the timepiece dial 1 (the aperture ratio of the Ag film 12) is relatively high, the presence of the opening 12 can be reliably made inconspicuous, While making the aesthetic appearance of the timepiece dial 1 sufficiently excellent, the light transmittance can be made particularly excellent.

  The average thickness of the coat layer 13 is not particularly limited, but is preferably 0.01 to 50 μm, more preferably 0.1 to 20 μm, and further preferably 2 to 15 μm. When the average thickness of the coat layer 13 is within the above range, it is possible to more effectively prevent discoloration of the Ag film 12 over time while sufficiently preventing the internal stress of the coat layer 13 from increasing. In addition, the adhesion between the coating layer 13 and the Ag film 12 can be made particularly excellent. Further, the presence of the opening 121 can be made less noticeable, and the aesthetics of the timepiece dial 1 can be made particularly excellent. On the other hand, if the average thickness of the coat layer 13 is less than the lower limit value, depending on the constituent material of the coat layer 13 and the like, it may be difficult to reliably prevent discoloration of the Ag film 12 over time. There is. Further, depending on the constituent material of the coat layer 13, it may be difficult to sufficiently improve the adhesion between the coat layer 13 and the Ag film 12. On the other hand, when the average thickness of the coat layer 13 exceeds the upper limit, the variation in film thickness at each portion of the coat layer 13 tends to increase. Further, when the average thickness of the coat layer 13 is particularly large, the internal stress of the coat layer 13 becomes high, and cracks and the like are likely to occur. In addition, when the average thickness of the coat layer 13 is particularly large, depending on the constituent material of the coat layer 13 and the like, it becomes difficult to fully exhibit the characteristics such as the color tone of the Ag film 12, and the watch dial 1 as a whole It may be difficult to sufficiently enhance the aesthetics of As shown in the figure, when a part of the coat layer 13 penetrates into the opening 16, the average thickness of the coat layer 13 is a portion (opening part) provided on the real part of the Ag film 12. The value of the average thickness for the part excluding the part corresponding to 121) is adopted.

  The thickness of the timepiece dial 1 is not particularly limited, but is preferably 160 to 710 μm, more preferably 210 to 610 μm, and still more preferably 310 to 510 μm. When the thickness of the timepiece dial 1 is within the above range, the timepiece dial 1 is effectively prevented from becoming thicker while the timepiece to which the timepiece dial 1 is applied is prevented from being machined. The mechanical strength, the stability of the shape, etc. can be made sufficiently excellent.

The light transmittance of the timepiece dial 1 is preferably 20% or more, more preferably 25% or more, even more preferably 29% or more, and most preferably 32% or more. preferable.
As described above, the timepiece dial 1 is excellent in aesthetic appearance and light transmittance. For this reason, the timepiece dial 1 can be suitably applied to a solar timepiece (a timepiece incorporating a solar cell) or the like.
Moreover, since the timepiece dial 1 is excellent in durability, it can be suitably applied to a portable timepiece (for example, a wristwatch).

<Manufacturing method of timepiece dial>
Next, the manufacturing method of the timepiece dial 1 described above will be described.
FIG. 5 is a cross-sectional view showing a preferred embodiment of the timepiece dial manufacturing method of the present invention.
As shown in FIG. 5, the manufacturing method of this embodiment includes a substrate preparation step (1 a) for preparing the substrate 11, and a mask 2 in which a large number of openings 21 are provided in a predetermined pattern on the surface of the substrate 11. The oxide film forming step (1b, 1c) for forming the oxide film (titanium oxide film) 14 having the opening 141 by performing film formation in a state where the oxide film 14 is disposed, and the oxide film 14 on the substrate 11 are formed. A Ti film forming step of forming the Ti film 15 having the openings 151 by performing film formation in a state where the mask 2 provided with a large number of openings 21 in a predetermined pattern is arranged on the provided surface side. (1d) and forming a film in a state where the mask 2 provided with a large number of openings 21 in a predetermined pattern is arranged on the surface of the substrate 11 on which the oxide film 14 and the Ti film 15 are provided. Thus, Ag having an opening 121 is obtained. Forming an Ag film 12 (1e), a mask removing process (1f) for removing the mask 2 from the substrate 11, and subjecting the Ag film 12 to sulfidation or halogenation, at least the Ag film 12 The darkening step (1g) in which the vicinity of the outer surface is mainly composed of silver sulfide or silver halide, and the formation of a coat layer 13 on the surface of the substrate 11 on which the Ag film 12 is provided Step (1h).

[Board preparation process]
As the substrate 11, those described above can be used.
The surface of the substrate 11 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it is possible to give variations to the appearance of the obtained timepiece dial 1, and the aesthetic appearance of the obtained timepiece dial 1 can be further improved.

  Moreover, the timepiece dial 1 manufactured using the substrate 11 subjected to such surface processing is obtained by performing the surface processing on the oxide film 14, the Ti film 15, and the Ag film 12. Compared to the above, glare and the like are suppressed in appearance, and in particular, the aesthetic appearance is excellent. Further, if the substrate 11 is mainly composed of a plastic material, the surface processing as described above can be performed relatively easily. In addition, the oxide film 14, the Ti film 15, and the Ag film 12 are usually relatively thin, and are provided as having a plurality of island-shaped regions. When surface processing is performed on the film 15 and the Ag film 12, there is a possibility that problems such as complete removal of the oxide film 14, the Ti film 15, and the Ag film 12 at the portion subjected to the surface treatment may occur. However, the occurrence of such a problem can be effectively prevented by performing the surface treatment on the substrate 11.

[Oxide film formation process (titanium oxide film formation process)]
An oxide film (titanium oxide film) 14 is formed by forming a film on the surface of the substrate 11 in a state where the mask 2 provided with the openings 21 in a predetermined pattern is arranged (1b, 1c). .
As described above, the oxide film (titanium oxide film) 14 has excellent adhesion to the substrate 11 and the Ti film 15. By forming such an oxide film 14, the durability of the timepiece dial 1 as a whole can be made particularly excellent.

In this embodiment, the oxide film 14 is formed by performing film formation with the mask 2 disposed. Thereby, the oxide film 14 having a large number of island-like regions (real parts) can be easily and reliably formed in a shape, size, and pattern corresponding to the opening 21 of the mask 2. Further, by using the mask 2, the opening 141 is formed simultaneously with the formation of the oxide film 14. In other words, since the opening 141 is formed without the need for post-processing after film formation, it is possible to reliably prevent the occurrence of unintentional irregularities and the like, and the opening having a desired shape. 141 can be formed, and the productivity of the timepiece dial 1 can be improved. In addition, since the mask 2 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 quality variation among the timepiece dials 1 is increased. Can be suppressed. That is, the reliability of the quality of the timepiece dial 1 is improved. Further, by preparing a plurality of types of masks 2 having openings 21 having patterns corresponding to the oxide film 14 (real part) to be formed, various patterns can be obtained without greatly changing the formation conditions of the oxide film 14. It can respond suitably also to the production of the timepiece dial 1 having the oxide film 14. That is, it is possible to efficiently cope with multi-product production.
Further, by forming the oxide film 14 by film formation using the mask 2, the openings 141 having the same shape, size, and pattern as the openings 151 of the Ti film 15 and the openings 121 of the Ag film 12 are provided. The oxide film 14 can be easily and reliably formed. As a result, the light transmission and aesthetic appearance of the timepiece dial 1 can be made particularly excellent easily and reliably.

  The formation method (film formation method) of the oxide film 14 is not particularly limited, and examples thereof include spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, and the like, electrolytic plating, immersion plating, and nothing. Examples include wet plating methods such as electrolytic plating, 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. A phase deposition method is preferred. By applying a vapor deposition method as a method of forming the oxide film 14, it has a uniform film thickness (suppressing unintentional variation in thickness), is homogeneous, and adheres well to the substrate 11. However, it is possible to reliably form a particularly excellent oxide film 14. As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. Further, when used as a timepiece component such as a radio timepiece, since particularly excellent radio wave permeability is required, it is generally preferable that the oxide film 14 be relatively thin as described above. By applying a vapor deposition method as the forming method 14, even if the oxide film 14 to be formed is relatively thin as described above, the variation in film thickness can be made sufficiently small. . For this reason, for example, while the durability of the timepiece dial 1 to be obtained is sufficiently high, the radio wave transmission and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Therefore, the obtained timepiece dial 1 can be suitably applied to a radio timepiece. 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 14, the above effects become more prominent.

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 14 as a target and performing the treatment in an atmosphere containing oxygen gas, The oxide film 14 can be easily and reliably formed.
Further, the oxide film 14 may be formed by combining a plurality of different methods and conditions. Thereby, the oxide film 14 comprised by the laminated body as mentioned above can be formed suitably.

The mask 2 used in this step has openings 21 arranged in a corresponding pattern at a portion corresponding to the real part of the oxide film 14 to be formed.
Such a mask 2 is prepared by, for example, preparing a plate-like member and subjecting it to chemical treatment such as etching, irradiation of energy rays such as laser light, mechanical treatment such as lathe treatment (physical treatment). ) Or the like to form the opening 21.
The thickness of the mask 2 depends on the thickness of the oxide film 14 and the like to be formed, but is preferably 30 to 200 μm, and more preferably 40 to 120 μm.

  The mask 2 may be composed 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 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 11 (timepiece 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. Further, one type of mask 2 can be used in common for substrates 11 having different shapes (for example, a flat substrate 11 and a curved plate substrate 11).

  In particular, in the present embodiment, the mask 2 is made of a material including a magnetic material (a material having ferromagnetism). A magnet (not shown) is disposed on the surface (second surface) opposite to the surface (first surface) facing the mask 2 of the substrate 11, whereby the mask 2 and the oxide film are arranged. 14 (further, the Ti film 15 and the Ag film 12) can be reliably brought into close contact with the substrate 11 as a work to be formed. As a result, on the substrate 11, it is possible to more reliably prevent the oxide film 14 (in addition, the Ti film 15 and the Ag film 12 in a process described later) from being formed on a part other than the target. The aesthetic appearance and light transmittance of the finally obtained timepiece dial 1 can be surely made 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 2 is composed of a material containing a magnetic material, but the mask 2 may be composed substantially of only a magnetic material, for example. However, it may contain other components.
The mask 2 may have a surface layer (not shown). Thereby, for example, the durability of the mask 2 can be made particularly excellent, or the constituent materials of the oxide film 14 (in addition, the Ti film 15 and the Ag film 12 are formed on the mask 2 during vapor deposition. Can be effectively prevented from adhering firmly. 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.

[Ti film forming step]
Next, a film is formed in a state where a mask 2 provided with a large number of openings 21 in a predetermined pattern is disposed on the surface of the substrate 11 on which the oxide film 14 is provided. A Ti film 15 is formed on the coating 14 (1d).
As described above, the Ti film 15 has excellent adhesion to the oxide film (titanium oxide film) 14 and the Ag film 12. By forming such a Ti film 15, the durability of the timepiece dial 1 as a whole can be made particularly excellent.

  In this step, film formation is performed with the mask 2 disposed on the surface of the substrate 11 on which the oxide film 14 is provided. Thereby, the Ti film 15 having a large number of island-like regions (real parts) can be easily and reliably formed in a shape, size, and pattern corresponding to the opening 21 of the mask 2. Further, by using the mask 2, the opening 151 is formed simultaneously with the formation of the Ti film 15. In other words, since the opening 151 is formed without the need for post-treatment after film formation, it is possible to reliably prevent the occurrence of unintentional irregularities and the like, and the opening having a desired shape. 151 can be formed, and the productivity of the timepiece dial 1 can be improved. In addition, since the mask 2 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 quality variation among the timepiece dials 1 is increased. Can be suppressed. That is, the reliability of the quality of the timepiece dial 1 is improved. Further, by preparing a plurality of types of masks 2 having openings 21 having patterns corresponding to the Ti film 15 (real part) to be formed, Ti having various patterns can be obtained without greatly changing the formation conditions of the Ti film 15. The production of the timepiece dial 1 having the film 15 can be suitably handled. That is, it is possible to efficiently cope with multi-product production.

Further, by forming the Ti film 15 by film formation using the mask 2, the Ti film 15 having the opening 151 having the same shape, size and pattern as the opening 121 of the Ag film 12 can be easily and reliably formed. can do. As a result, the light transmission and aesthetic appearance of the timepiece dial 1 can be made particularly excellent easily and reliably.
As the mask 2, a mask different from that used in the oxide film forming process described above (for example, a mask having a larger opening than the mask used in the oxide film forming process) may be used. The same material as that used in the oxide film forming step may be used. In this step, the manufacturing cost of the timepiece dial 1 can be suppressed by using the same mask 2 as that used in the oxide film forming step. Further, in this step, when the same mask 2 as that used in the oxide film forming step is used, the mask 2 is continuously removed without removing the mask 2 from the substrate 11 after the oxide film forming step described above. It is preferable to carry out the process. As a result, it is possible to reliably prevent an unintended displacement between the oxide film 14 and the Ti film 15 and improve the productivity of the timepiece dial 1.

  The formation method (film formation method) of the Ti film 15 is not particularly limited, and for example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, inkjet coating, etc., electrolytic plating, immersion plating Examples include wet plating methods such as electroless plating, 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. The vapor phase film forming method is preferable. By applying a vapor deposition method as a method of forming the Ti film 15, it has a uniform film thickness (suppressing unintentional thickness variation), is homogeneous, and has an adhesion to the substrate 11 ( It is possible to reliably form the Ti film 15 having particularly excellent adhesion (through the oxide film 14). As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. Further, when used as a timepiece component such as a radio timepiece, since particularly excellent radio wave permeability is required, it is generally preferable that the Ti film 15 be relatively thin as described above. By applying the vapor phase film forming method as the forming method, even if the Ti film 15 to be formed is relatively thin, the variation in film thickness can be made sufficiently small. For this reason, for example, while the durability of the timepiece dial 1 to be obtained is sufficiently high, the radio wave transmission and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Therefore, the obtained timepiece dial 1 can be suitably applied to a radio timepiece. Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the Ti film 15, the above effects become more prominent.

  In the vapor phase film formation as described above, for example, the Ti film 15 can be easily and reliably formed by performing processing in an inert gas atmosphere such as argon gas using titanium as a target. Moreover, when performing the oxide film formation process (titanium oxide film formation process) mentioned above by a vapor phase film-forming method, the composition of the atmospheric gas in a vapor-phase film-forming apparatus (inside a chamber) contains oxygen gas, for example. By substituting one with an inert gas, the oxide film forming step and the Ti film forming step can be performed successively (without removing the substrate 11 from the device) in the same apparatus. Thereby, the adhesion between the oxide film 14 and the Ti film 15 is particularly excellent, and the productivity and reliability of the timepiece dial 1 are also improved.

In the present embodiment, this step is also the surface (second surface) opposite to the surface (first surface) facing the mask 2 of the substrate 11 as in the oxide film forming step described above. A magnet (not shown) is disposed on the mask 2 so that the mask 2 and the substrate 11 (the substrate 11 provided with the oxide film 14) as the work on which the Ti film 15 is to be formed are in close contact with each other. Do. As a result, it is possible to more reliably prevent the Ti film 15 from being formed on a portion other than the target on the substrate 11, and to improve the aesthetic appearance and light transmittance 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.
Further, the Ti film 15 may be formed by combining a plurality of different methods and conditions.

[Ag film forming step]
Next, film formation is performed in a state where the mask 2 provided with a large number of openings 21 in a predetermined pattern is arranged on the surface of the substrate 11 on which the oxide film 14 and the Ti film 15 are provided. Thus, the Ag film 12 is formed on the Ti film 15 (1e).
By providing the Ag film 12 in this manner, the dark color portion 122 can be suitably formed in the process described later, and the watch dial 1 finally obtained has a high-quality appearance with a dark color tone. Can be.
Further, as described above, the Ag film 12 is excellent in adhesion with the Ti film 15 and the coat layer 13. By forming such an Ag film 12, the durability of the timepiece dial 1 as a whole can be made particularly excellent.

  In this step, film formation is performed with the mask 2 disposed on the surface of the substrate 11 on which the oxide film 14 and the Ti film 15 are provided. Thereby, the Ag film 12 having a large number of island-like regions (real parts) can be easily and reliably formed with a shape, size, and pattern corresponding to the opening 21 of the mask 2. Further, by using the mask 2, the opening 121 is formed simultaneously with the formation of the Ag film 12. In other words, since the opening 121 is formed without the need for post-processing after film formation, it is possible to reliably prevent the occurrence of unintentional irregularities and the like, and the opening having a desired shape. 121 can be formed, and the productivity of the timepiece dial 1 can be improved. In addition, since the mask 2 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 variation in quality 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. Further, by preparing a plurality of types of masks 2 having openings 21 having patterns corresponding to the Ag film 12 (real part) to be formed, various patterns of Ag can be obtained without greatly changing the formation conditions of the Ag film 12. The production of the timepiece dial 1 having the film 12 can be suitably handled. That is, it is possible to efficiently cope with multi-product production.

Further, by forming the Ag film 12 by film formation using the mask 2, the Ag film 12 having the opening 131 having the same shape, size and pattern as the opening 151 of the Ti film 15 can be easily and reliably formed. can do. As a result, the light transmission and aesthetic appearance of the timepiece dial 1 can be made particularly excellent easily and reliably.
As the mask 2, a mask different from that used in the Ti film forming process (for example, a mask having a larger opening than the mask used in the Ti film forming process) may be used. You may use the same thing used at the film formation process. In this step, the manufacturing cost of the timepiece dial 1 can be suppressed by using the same mask 2 as that used in the Ti film forming step. Further, in this process, when the same mask 2 used in the Ti film forming process is used, the process is continued without removing the mask 2 from the substrate 11 after the Ti film forming process described above. It is preferred to do so. As a result, unintentional displacement between the Ti film 15 and the Ag film 12 can be surely prevented, and the productivity of the timepiece dial 1 is improved.

  The formation method (film formation method) of the Ag film 12 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, inkjet coating, etc., electrolytic plating, immersion plating Examples include wet plating methods such as electroless plating, 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. The vapor phase film forming method is preferable. By applying a vapor deposition method as a method of forming the Ag film 12, the film has a uniform film thickness (suppressing unintentional thickness variation), is homogeneous, and has an adhesiveness to the substrate 11 ( It is possible to reliably form the Ag film 12 having particularly excellent adhesion (through the oxide film 14 and the Ti film 15). As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. Further, when used as a timepiece component such as a radio timepiece, since particularly excellent radio wave permeability is required, it is generally preferable that the Ag film 12 be relatively thin as described above. By applying the vapor deposition method as the forming method, even if the Ag film 12 to be formed is relatively thin as described above, the variation in film thickness can be made sufficiently small. For this reason, for example, while the durability of the timepiece dial 1 to be obtained is sufficiently high, the radio wave transmission and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Therefore, the obtained timepiece dial 1 can be suitably applied to a radio timepiece. Of the vapor phase film forming methods as described above, sputtering is particularly preferable. By applying sputtering as a method for forming the Ag film 12, the above effects become more prominent.

  In the vapor phase film formation as described above, for example, the Ag film 12 can be easily and reliably formed by performing processing in an inert gas atmosphere such as argon gas using silver as a target. Further, when the Ti film forming process described above is performed by a vapor deposition method, for example, by changing the target, the Ti film forming process and the Ag film forming process are performed in the same apparatus (the substrate 11 is placed in the apparatus). (Without taking it out of). Thereby, the adhesion between the Ti film 15 and the Ag film 12 becomes particularly excellent, and the productivity and reliability of the timepiece dial 1 are also improved.

In the present embodiment, this step is also performed on the surface (second surface) opposite to the surface (first surface) facing the mask 2 of the substrate 11 as in the Ti film forming step described above. By arranging a magnet (not shown), the mask 2 and the substrate 11 (the substrate 11 provided with the oxide film 14 and the Ti film 15) as the work on which the Ag film 12 is to be formed are securely adhered. In the state. As a result, it is possible to more reliably prevent the Ag film 12 from being formed on a portion other than the target on the substrate 11, and to improve the aesthetic appearance and light transmittance of the finally obtained dial 1 for timepiece. It can be surely excellent. That is, the reliability of the manufactured timepiece dial 1 can be made particularly excellent.
Further, the Ag film 12 may be formed by combining a plurality of different methods and conditions.

[Mask removal process]
Next, the mask 2 is removed from the substrate 11 (1f). As a result, the portion corresponding to the opening 21 of the mask 2 is covered with the oxide film 14, the Ti film 15, and the Ag film 12, and the other portions are in a state where the surface of the substrate 11 is exposed. It becomes.
The removal of the mask 2 can be performed by peeling the mask 2 from the substrate 11 provided with the oxide film 14, the Ti film 15, and the Ag film 12.

[Darkening process]
Next, the Ag film 12 is subjected to sulfurization treatment or halogenation treatment (1 g). As a result, at least the vicinity of the outer surface of the Ag film 12 is a dark color portion 122 mainly composed of silver sulfide or silver halide.
Examples of the compound (reagent) that can be used for the sulfurization treatment of the Ag film 12 include sulfur, sulfur dioxide, hydrogen sulfide, ammonium sulfide, and the like. Among these, ammonium sulfide is preferably used for the sulfidation treatment of the Ag film 12. Thereby, it is possible to easily form the dark color portion 122 having a suitable appearance while preventing the adverse effects on the substrate 11, the Ti film 15, and the like more reliably.

Examples of the compound (reagent) that can be used for the halogenation treatment of the Ag film 12 include fluorine (F ₂ ), chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), and the like. . Among these, fluorine (F ₂ ) is preferably used for the halogenation treatment of the Ag film 12. Thereby, it is possible to easily form the dark color portion 122 having a suitable appearance while preventing the adverse effects on the substrate 11, the Ti film 15, and the like more reliably.
Further, examples of the compound (reagent) that can be used for the oxidation treatment of the Ag film 12 include ozone (O ₃ ). By using ozone for the oxidation treatment of the Ag film 12, it is possible to easily form the dark color portion 122 having a suitable appearance while more reliably preventing adverse effects on the substrate 11, the Ti film 15 and the like. .

[Coat layer forming step]
Next, the coat layer 13 is formed on the surface side on which the Ag film 12 is provided (1h). Thereby, the timepiece dial 1 is obtained.
The formation method of the coat layer 13 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. Examples of the method include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and thermal spraying. When it is made of such a material, it is preferably formed by painting. Thereby, the coat layer 13 can be formed relatively easily. Further, when the coat layer 13 is formed by painting, it is easy to add a component such as a colorant to the material for forming the coat layer and to adjust the amount of addition.

As described above, the timepiece dial 1 can be obtained.
The oxide film forming step, the Ti film forming step, the Ag film forming step, the darkening step, and the coat layer forming step as described above are performed in the size and shape of the substrate 11 corresponding to the timepiece dial 1 to be manufactured. However, it may be applied to the sheet-like substrate 11 and then processed into a desired size and shape by punching, cutting, or the like.

<Clock>
Next, the timepiece of the present invention provided with the timepiece dial 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. As described above, the timepiece dial of the present invention is excellent in light transmittance and decorativeness (aesthetic appearance). For this reason, the timepiece of the present invention provided with such a timepiece dial can sufficiently satisfy the requirements for a solar timepiece. As a part other than the timepiece dial (the timepiece dial of the present invention) that constitutes 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. explain.

FIG. 6 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 6, the wristwatch (portable timepiece) 100 according to the present embodiment includes a trunk (case) 82, a back cover 83, a bezel (edge) 84, and a glass plate (cover glass) 85. . Further, in the case 82, the timepiece dial 1 of the present invention as described above, the solar cell 94, and the movement 81 are accommodated, and further, hands (pointers) not shown are accommodated. . The timepiece dial 1 is provided between a solar cell 94 and a glass plate (cover glass) 85, and is provided with an oxide film 14, a Ti film 15, an Ag film 12, and a coat layer 13 of a substrate 11. The surface (first surface) is arranged so as to face the glass plate (cover glass) 85 side.

The glass plate 85 is usually made of transparent glass or sapphire having high transparency. Thereby, while being able to fully exhibit the aesthetics of the timepiece dial 1 of the present invention, a sufficient amount of light can be incident on the solar cell 94.
The movement 81 uses the electromotive force of the solar cell 94 to drive the pointer.
Although omitted in FIG. 6, in the movement 81, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 94, a lithium ion secondary battery, a crystal oscillator as a time reference source, and a crystal vibration A semiconductor integrated circuit that generates a driving pulse for driving a clock based on the oscillation frequency of the child, a step motor that drives the pointer every second in response to this driving pulse, and a wheel that transmits the movement of the step motor to the pointer A row mechanism is provided.

The movement 81 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 94 has a function of converting light energy into electric energy. The electric energy converted by the solar cell 94 is used for driving the movement.
In the solar cell 94, 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 86 is fitted into and fixed to the barrel 82, and a shaft 871 of a crown 87 is rotatably inserted into the winding stem pipe 86.

The body 82 and the bezel 84 are fixed by a plastic packing 88, and the bezel 84 and the glass plate 85 are fixed by a plastic packing 89.
Further, a back cover 83 is fitted (or screwed) to the body 82, and a ring-shaped rubber packing (back cover packing) 92 is inserted in a compressed state in these joint portions (seal portions) 93. Has been. With this configuration, the seal portion 93 is sealed in a liquid-tight manner, and a waterproof function is obtained.
A groove 872 is formed on the outer periphery of the middle portion of the shaft portion 871 of the crown 87, and a ring-shaped rubber packing (crown packing) 91 is fitted in the groove 872. The rubber packing 91 is in close contact with the inner peripheral surface of the winding stem pipe 86 and is compressed between the inner peripheral surface and the inner surface of the groove 872. With this configuration, the space between the crown 87 and the winding stem pipe 86 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 87 is rotated, the rubber packing 91 rotates together with the shaft portion 871 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 86.

Since the above portable watch (watch) is required to have particularly excellent durability (for example, impact resistance, etc.) among various types of watches, a book with excellent aesthetic appearance and excellent durability can be obtained. The invention can be applied more suitably.
In the above description, a wristwatch (portable clock) as a solar radio timepiece has been described as an example of a clock. However, the present invention is applicable to other types of clocks such as a portable clock, a table clock, and a wall clock other than a wristwatch. Can be applied similarly. Further, the present invention can be applied to any timepiece such as a solar timepiece excluding a solar radio timepiece and a radio timepiece excluding a solar radio timepiece.
The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above.

For example, in the timepiece dial and timepiece of the present invention, the configuration of each part can be replaced with any configuration that exhibits the same function, and any configuration can be added. For example, you may have a printing part formed by various printing methods.
In the above-described embodiments, the Ag film (the same applies to the oxide film and Ti film) is typically described with a configuration in which openings are provided so as to surround a large number of island-like real parts. However, the structure of the Ag film (the same applies to the oxide film and the Ti film) is not limited to this. For example, the Ag film may have a large number of openings in one real part.

In the above-described embodiment, the oxide film 14 has been described as having the opening 141 at the portion corresponding to the opening 151 of the Ti film 15 and the opening 121 of the Ag film 12. May not have an opening. In such a case, for example, the oxide film can be suitably formed by performing film formation without using a mask in the oxide film forming step of the manufacturing method as described above.
In the present invention, the timepiece dial may not have the oxide film and the Ti film as described above. For example, in the present invention, the timepiece dial may be one in which an Ag film is directly provided on the surface of the substrate.

Moreover, the coating layer should just be provided so that the real part (dark color part 122) of the Ag film | membrane 12 may be covered at least, for example, an opening part is provided in the site | part corresponding to the opening part 121 of the Ag film | membrane 12. You may have.
Further, in the above-described embodiment, the case where the Ag film has a dark color part in a part in the thickness direction thereof has been representatively described. However, the entire Ag film may be formed of a dark color part.
In the above-described embodiment, it has been described that the darkening process is performed after the mask is removed after the Ag film is formed. However, the darkening process may be performed in a state where the mask is in close contact. The coat layer forming step may also be performed with the mask in close contact.

Moreover, in the manufacturing method of the timepiece dial according to the present invention, an optional process can be added as necessary.
Further, in the above-described embodiment, a mask made of a material containing a magnetic material is used, and the mask and the substrate as a work are provided by a magnet disposed on the surface opposite to the surface facing the mask of the substrate. However, it is not necessary to use a magnet.
Further, the timepiece dial of the present invention is not limited to the one manufactured by the method described above as long as it includes a substrate, an Ag film having an opening and a dark portion, and a coat layer. .

Next, specific examples of the present invention will be described.
1. Manufacture of watch dials 100 watch dials (watch dials) were manufactured for each example and each comparative example by the following method.
Example 1
First, a base material having the shape of a watch dial was manufactured by injection molding using polycarbonate, and then a necessary portion was cut out, and unnecessary burrs and the like were cut and polished to obtain a substrate. The obtained substrate was substantially disc-shaped and had a diameter: 27 mm × thickness: 450 μm.

Next, this substrate was cleaned. As the cleaning of the substrate, first, the substrate was washed with a neutral detergent for plastic for 30 seconds, and then washed with water for 30 seconds and with pure water for 60 seconds. Then, it dried for 20 minutes in oven (80 degreeC).
An oxide film (titanium oxide film) composed of TiO ₂ (titanium oxide) was formed on the surface of the substrate thus cleaned by sputtering as described below (oxide film formation). Process).

The oxide coating is a mask in which circular openings are arranged in a staggered pattern on the surface of the substrate (positioned so that the center of the opening is located at a portion corresponding to each vertex of the equilateral triangle). It formed by performing sputtering in the state which arranged (refer to Drawing 2).
The mask was made of stainless steel (SUS430), and its thickness was 50 μm. The diameter of the opening was 168 μm. Further, the opening ratio of the mask represented by the area ratio occupied by the opening when the mask was viewed in plan was 42%.

In this step, a magnet (neodymium magnet) is disposed on the surface (second surface) opposite to the surface (first surface) facing the mask of the substrate, and the substrate, mask, and Was carried out in close contact.
Sputtering in this step was performed under the following conditions.
First, the cleaned substrate was mounted in a sputtering apparatus, and then the inside of the sputtering apparatus was evacuated (depressurized) to 1.0 × 10 ⁻⁴ Pa while preheating the apparatus.

Next, while introducing argon gas at an argon flow rate: 20 ml / min, oxygen was introduced at an oxygen flow rate: 10 ml / min. In this state, Ti was used as a target, and discharge was performed under the conditions of input power: 1400 W and processing time: 5.0 minutes, thereby forming an oxide film composed of TiO ₂ . 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 oxide film thus formed was 10 nm.

Subsequently, a Ti film composed of Ti was formed by sputtering on the surface of the oxide film formed as described above (Ti film forming step).
The Ti film was formed following the above-described process without removing the substrate coated with the oxide film from the sputtering apparatus and without relatively moving the substrate and the mask.
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 25 ml / min. In this state, Ti was used as a target, and discharge was performed under the conditions of input power: 1000 W and processing time: 10 minutes, thereby forming a Ti film composed of Ti. 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 Ti film thus formed was 100 nm.

Subsequently, an Ag film made of Ag was formed on the surface of the Ti film formed as described above by sputtering (Ag film forming step).
The Ag film was formed following the above-described process without removing the substrate coated with the oxide film and the Ti film from the sputtering apparatus and without relatively moving the substrate and the mask.

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 25 ml / min. In this state, Ag was used as a target, and discharge was performed under the conditions of input power: 1000 W and treatment time: 5.0 minutes, thereby forming an Ag film 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 Ag film thus formed was 200 nm.

Next, the substrate provided with the oxide film having an opening, the Ti film, and the Ag film was taken out from the sputtering apparatus, and the mask was removed.
Next, acid cleaning using 5 wt% sulfuric acid was performed on the substrate provided with the oxide coating, Ti film, and Ag film, followed by water cleaning.
Next, a dark color portion (black portion) composed of silver sulfide (Ag ₂ S) was formed by performing the following sulfurization treatment (darkening step).
First, a substrate (a substrate provided with an oxide film, a Ti film, and an Ag film) subjected to cleaning as described above and ammonium sulfide were placed in a sealed container. After leaving for 2 hours, the substrate was taken out from the container. As a result, the Ag film was provided with a black dark color portion having a predetermined thickness from the outer surface. The formed dark color part had a thickness of 150 nm.

Thereafter, a coating layer mainly composed of an acrylic resin was formed on the side of the substrate on which the Ag film was provided, using a mixture of carbon black (colorant) and polyar clear. Thus, a wristwatch dial as shown in FIGS. 1 and 2 was obtained (coat layer forming step). The coating layer was formed by a spray coating method. The average thickness of the formed coating layer was 10 μm.
In addition, the thickness of the substrate, oxide film, Ti film, Ag film, dark portion, coat layer, and mask was measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 6)
Table 1 shows the constituent materials of the substrate, mask conditions, types of targets used in the oxide film forming process, oxide film forming process, Ti film forming process, Ag film forming process, and darkening treatment By adjusting the treatment time, the composition of the oxide film, Ti film, and Ag film (dark color part) is as shown in Table 1, and the content of the colorant contained in the coating layer is adjusted. In addition, a watch dial was manufactured in the same manner as in Example 1 except that the thickness of the coat layer was as shown in Table 1.

(Example 7)
A watch dial was manufactured in the same manner as in Example 1 except that the formation of the dark portion (darkening step) was performed by halogenation.
The halogenation treatment in this example was performed as follows.
That is, the substrate (substrate provided with the oxide film, Ti film, and Ag film) subjected to the above cleaning is placed in a sealed container and heated, and in this state, fluorine gas (F ₂ ) is sealed in the sealed container. The inside was filled and left for 2 hours.
As a result, the Ag film had a predetermined thickness from the outer surface and was provided with a black-brown dark color portion composed of silver fluoride (AgF ₂ ). The formed dark portion had a thickness of 80 nm.

(Examples 8 to 10)
Table 1 shows the constituent materials of the substrate, mask conditions, types of targets used in the oxide film forming process, oxide film forming process, Ti film forming process, Ag film forming process, and darkening treatment By adjusting the treatment time, the composition of the oxide film, Ti film, and Ag film (dark color part) is as shown in Table 1, and the content of the colorant contained in the coating layer is adjusted. In addition, a watch dial was manufactured in the same manner as in Example 7 except that the thickness of the coat layer was as shown in Table 1.

(Example 11)
A watch dial was manufactured in the same manner as in Example 1 except that the dark portion was formed (darkening step) by oxidation.
The oxidation treatment in this example was performed as follows.
That is, the substrate (substrate provided with the oxide film, Ti film, and Ag film) that has been cleaned as described above is placed in a sealed container, and in this state, ozone (O ₃ ) is filled in the sealed container. , Left for 15 minutes.
As a result, the Ag film had a predetermined thickness from the outer surface and was provided with a black dark color portion made of silver oxide (AgO). The formed dark color part had a thickness of 120 nm.

(Examples 12 to 15)
Table 1 shows the constituent materials of the substrate, mask conditions, types of targets used in the oxide film forming process, oxide film forming process, Ti film forming process, Ag film forming process, and darkening treatment By adjusting the treatment time, the composition of the oxide film, Ti film, and Ag film (dark color part) is as shown in Table 1, and the content of the colorant contained in the coating layer is adjusted. In addition, a watch dial was manufactured in the same manner as in Example 10 except that the thickness of the coat layer was as shown in Table 1.

(Comparative Example 1)
A watch dial was manufactured in the same manner as in Example 1 except that the mask was not used in the oxide film forming step, the Ti film forming step, and the Ag film forming step.
(Comparative Example 2)
A watch dial was manufactured in the same manner as in Example 1 except that the coating layer forming step was omitted. That is, the timepiece dial of this comparative example is in a state where the Ag film is exposed.
(Comparative Example 3)
A watch dial was manufactured in the same manner as in Example 1 except that the oxide film forming step, the Ti film forming step, the Ag film forming step, and the darkening step were omitted. That is, the timepiece dial of this comparative example has a coating layer directly provided on the surface of the substrate.

(Comparative Example 4)
A watch dial was manufactured in the same manner as in Example 1 except that the darkening step was omitted. That is, in the timepiece dial of this comparative example, the Ag film has no dark color portion.
In addition, the board | substrate used by each said Example and each comparative example has the transmittance | permeability of visible light when using a white fluorescent lamp (the Toshiba company make, fluorescent lamp FL20S-D65 for a test | inspection) as a light source, It was 60% or more.

  Table 1 summarizes the structures of the mask (gas phase film formation mask) and the timepiece dial used in the production of the timepiece dial of each example and each comparative example. In the table, polycarbonate is represented by PC, acrylonitrile-butadiene-styrene copolymer (ABS resin) is represented by ABS, acrylic resin is represented by Ac, and carbon black is represented by CB. In Table 1, in the “shape and arrangement pattern” column for the Ag film, the shape and arrangement pattern as shown in FIG. 2 are indicated by “A”, and the shape and arrangement pattern as shown in FIG. The shape and arrangement pattern shown in FIG. 4 are indicated by “C”, and those provided in the form of a film on the entire surface (first surface) of the substrate are indicated by “D”. However, the aperture ratio may be different from that shown in FIGS. In Table 1, the formation method of the dark color portion is indicated by “SU” by the sulfurization treatment, by “HA” by the halogenation treatment, and by “OX” by the oxidation treatment. Each part of the timepiece dial plate was composed mainly of the components shown in Table 1, and the content of other components was less than 1 wt%.

2. Appearance evaluation of wristwatch dial For each wristwatch dial manufactured in each of the above examples and comparative examples, the first surface side of the substrate (surface provided with oxide coating, Ti film, Ag film, and coating layer) From the side), visual observation was performed, and these appearances were evaluated according to the following 6-step criteria.
A: It has a dark color tone, a high-class feeling, and an extremely excellent appearance.
B: It is a dark color tone, has a high-class feeling, and has an excellent appearance.
C: Dark color tone, high-class feeling, and good appearance.
D: A high-quality dark color tone is not obtained. Or, the appearance is slightly poor.
E: Appearance is poor.
F: The appearance is extremely poor.

3. Evaluation of Light Transmittance of Wristwatch Dial The light transmission of each watch dial manufactured in each of the above Examples and Comparative Examples was evaluated by the following method.
First, the solar cell and each watch dial were placed in a darkroom. Thereafter, light from a white 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 white fluorescent lamp (light source) separated by a predetermined distance as described above was made incident on the upper surface of the light receiving surface of the solar cell with a wristwatch dial overlapped. 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 five criteria. It can be said that the larger the light transmittance, the better the light transmittance of the timepiece dial. The timepiece dial is a solar cell so that the first surface of the substrate (the surface on which the oxide film, Ti film, Ag film, and coating layer are provided) faces the white fluorescent lamp (light source) side. Superimposed. Further, as the white fluorescent lamp, a white fluorescent lamp (manufactured by Toshiba, fluorescent lamp for inspection FL20S-D65) was used.
A: 32% or more.
B: 29% or more and less than 32%.
C: 25% or more and less than 29%.
D: 19% or more and less than 25%.
E: Less than 19%.

  Thereafter, a wristwatch as shown in FIG. 6 was manufactured using the timepiece dial manufactured in each of the above Examples and Comparative Examples. At this time, the timepiece dial was such that the first surface of the substrate (the surface on which the oxide film, Ti film, Ag film, and coating layer were provided) faced the glass plate side. Then, each manufactured wristwatch was put in a dark room. Thereafter, light from a white fluorescent lamp (light source) separated by a predetermined distance was made incident from a surface on the timepiece dial side (surface on the glass plate side) of the timepiece. 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 1, 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 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 wristwatch internal module (movement) and a wristwatch dial were assembled in the watch case, and the radio wave reception sensitivity in this state was measured. At this time, the timepiece dial was such that the first surface of the substrate (the surface on which the oxide film, Ti film, Ag film, and coating layer were provided) faced the outer surface.

Based on the reception sensitivity in a state where the wristwatch dial is not incorporated, the reduction amount (dB) of the reception sensitivity when the wristwatch 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 wristwatch dial is.
A: No decrease in sensitivity is observed (below the detection limit).
B: A decrease in sensitivity is observed at less than 0.7 dB.
C: The decrease in sensitivity is 0.7 dB or more and less than 1.0 dB.
D: The decrease in sensitivity is 1.0 dB or more.

5. Stability evaluation of color tone Each watch dial plate manufactured in each of the above examples and comparative examples was left to stand in an environment of temperature: 50 ° C. and humidity: 90% RH for 90 days. From the surface side (surface side on which the oxide film, Ti film, Ag film, and coating layer were provided), visual observation was performed and evaluation was performed according to the following five-step criteria.
A: No decrease in aesthetics is observed.
B: Almost no deterioration in aesthetics is observed.
C: A slight decrease in aesthetics is observed.
D: A decrease in aesthetics is clearly observed.
E: A significant decrease in aesthetics is observed.

6). Evaluation of Adhesiveness of Coating Film Each watch dial plate manufactured in each of the above Examples and Comparative Examples was subjected to two kinds of tests as shown below, and the coating film (oxide film, Ti film, Ag film, coating layer) The adhesion was evaluated.
6-1. Bending test Each watch dial was bent at 25 ° with the iron bar of 3.3mm in diameter as the fulcrum, and the watch dial was centered, and then the appearance of the watch dial was visually observed. These appearances were evaluated according to the following four criteria. Bending was performed in both compression / tension directions.
A: No floating or peeling of the film is observed.
B: Floating of the film is hardly recognized.
C: The float of the film is clearly recognized.
D: Cracking and peeling of the film are clearly recognized.

6-2. Thermal cycling test Each watch dial was subjected to the following thermal cycling test.
First, the watch dial is placed in a 15 ° C. environment for 1.5 hours, then in a 65 ° C. environment for 2 hours, then in a 15 ° C. environment for 1.5 hours, and then in a −15 ° C. environment. It was left to stand for 3 hours. Thereafter, the environmental temperature was returned again to 15 ° C., which was set as one cycle (8 hours), and this cycle was repeated a total of 4 times (total 32 hours).
Thereafter, the appearance of the watch dial was visually observed, and the appearance was evaluated according to the following four criteria.
A: No floating or peeling of the film is observed.
B: Floating of the film is hardly recognized.
C: The float of the film is clearly recognized.
D: Cracking and peeling of the film are clearly recognized.
These results are shown in Table 2.

As can be seen from Table 2, all of the timepiece dials of the present invention had an excellent aesthetic appearance with a dark color tone and a high-class appearance, and were excellent in light transmittance. In addition, the timepiece dial of the present invention was excellent in color tone stability and could stably maintain an excellent appearance over a long period of time. Moreover, the timepiece dial of the present invention was excellent in the adhesion of the film (oxide film, Ti film, Ag film, coat layer) and had excellent durability. In addition, the timepiece dial of the present invention was excellent in radio wave permeability.
On the other hand, in the comparative example, a satisfactory result was not obtained.
Moreover, the timepiece as shown in FIG. 6 was assembled using the timepiece dials obtained in each of the examples and the comparative examples. Each timepiece thus obtained was tested and evaluated in the same manner as described above, and the same results as described above were obtained.

It is sectional drawing which shows suitable embodiment of the timepiece dial of this invention. It is a top view which shows suitable embodiment of the timepiece dial of this invention. It is a typical top view for demonstrating an example of the arrangement pattern of Ag film | membrane. It is a typical top view for demonstrating another example of the arrangement pattern of Ag film | membrane. It is sectional drawing which shows suitable embodiment of the manufacturing method of the timepiece dial of this invention. 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 11 ... Board | substrate 12 ... Ag film | membrane 121 ... Opening part 122 ... Dark color part 13 ... Coat layer 14 ... Oxide film (titanium oxide film) 141 ... Opening part 15 ... Ti film | membrane (metal film) 151 ... Opening 2 ... Mask (mask for vapor phase deposition) 21 ... Opening 81 ... Movement 82 ... Body (case) 83 ... Back cover 84 ... Bezel (edge) 85 ... Glass plate (cover glass) 86 ... Winding pipe 87 ... Crown 871 ... Shaft part 872 ... Groove 88 ... Plastic packing 89 ... Plastic packing 91 ... Rubber packing (Crown packing) 92 ... Rubber packing (back cover packing) 93 ... Junction (seal part) 94 ... Solar cell 100 ... Wrist watch

Claims (14)

A substrate made of a light-transmitting material;
An Ag film made of a material containing Ag and having an opening;
A coating layer provided on the surface of the Ag film opposite to the surface facing the substrate;
The timepiece dial according to claim 1, wherein the Ag film is mainly composed of silver sulfide, silver halide, or silver oxide at least near the surface in contact with the coating layer.   The timepiece dial according to claim 1, wherein the Ag film has a plurality of island-shaped regions when the timepiece dial is viewed in plan.   The timepiece dial according to claim 1 or 2, wherein the thickness of the Ag film is 100 to 5000 nm.   The timepiece dial according to any one of claims 1 to 3, further comprising an oxide film mainly composed of a metal oxide between the substrate and the Ag film.   The timepiece dial according to claim 4, further comprising a Ti film mainly composed of Ti and having an opening between the oxide film and the Ag film. A titanium oxide film mainly composed of titanium oxide is provided on the surface of the substrate,
On the surface of the titanium oxide film opposite to the surface in contact with the substrate, a Ti film composed mainly of titanium and having an opening is provided,
4. The timepiece dial according to claim 1, wherein the Ag film is provided on a surface of the Ti film opposite to a surface in contact with the titanium oxide film.   The timepiece according to any one of claims 1 to 6, wherein the Ag film is selectively sulfided, halogenated, or oxidized in the thickness direction in the vicinity of the surface in contact with the coat layer. Dial for use.   The timepiece dial according to claim 1, wherein the coat layer is mainly composed of a urethane resin and / or an acrylic resin.   The timepiece dial according to claim 1, wherein the coat layer is made of a material containing a colorant. A substrate preparation step of preparing a substrate made of a light-transmitting material;
Ag film formation that forms an Ag film mainly composed of Ag having a large number of island-like regions by performing film formation in a state where a mask having a large number of openings provided in a predetermined pattern is arranged Process,
A dark color in which at least the outer surface of the Ag film is mainly composed of silver sulfide, silver halide, or silver oxide by subjecting the Ag film to sulfidation, halogenation, or oxidation. Conversion process,
And a coating layer forming step of forming a coating layer on a surface side of the substrate on which the Ag film is provided.   The timepiece dial manufacturing method according to claim 10, further comprising a titanium oxide film forming step of forming a titanium oxide film mainly composed of titanium oxide on the surface of the substrate prior to the Ag film forming step. .   Prior to the Ag film forming step, by forming a film with a mask provided with a large number of openings in a predetermined pattern, a large number of island-shaped regions are formed on the surface of the titanium oxide film. The timepiece dial manufacturing method according to claim 11, further comprising a Ti film forming step of forming a Ti film mainly composed of Ti.   A timepiece comprising the timepiece dial according to claim 1.   A timepiece comprising a timepiece dial manufactured using the method according to claim 10.

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