JP2008164525A - Watch, method of manufacturing dial plate for same, and dial plate for same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the dial plate of a watch excellent in optical transmittance having the sense of high quality in dark color, a method of manufacturing the dial plate of the watch, and the watch provided with the dial plate. <P>SOLUTION: The manufacturing method of the dial plate 1 for the watch is composed of the following processes: a reflection membrane forming process of forming a reflection membrane 4 constituted with metallic material on a base plate 2 constituted with light transmissive material; a light absorptive membrane forming process of forming the light absorptive membrane 3 constituted with material with function absorbing at least a part of incident light on the reflection membrane 4; a first aperture formation process of forming the first aperture part 31 on the light absorption membrane 3 by irradiating laser beam with a prescribed pattern from the surface side provided with the reflection membrane 4, and a light absorptive membrane 3 of the base plate 2; and a second aperture formation process of characteristically forming a second aperture 41 on the reflection membrane by removing a part of the reflection membrane 4 by performing the etching process. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a timepiece dial manufacturing method, 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.
On the other hand, there has been proposed a dial plate manufactured by molding and sintering using a mixture of a ceramic powder and a binder for the purpose of improving the sense of quality and decoration (see, for example, Patent Document 1). With such a configuration, it is possible to transmit a part of incident light while reflecting external light with a predetermined reflectance. As a result, a glossy dial can be obtained.

  On the other hand, there is a demand for applying a dial having a calm color tone and appearance such as black to a solar timepiece. However, in a dial plate made of a material with a color tone with a high light absorption rate such as black, minute irregularities on the surface are conspicuous, and the irregularities greatly affect the appearance of the dial. It was difficult to enhance the feeling. Further, in a color tone having a high light absorptance such as black, it has been impossible to achieve both light transmittance and excellent appearance. For example, when a material having a color tone with a high light absorptivity such as black is used, usually a sufficient amount of light transmittance cannot be secured, and a colorant is used to improve the light transmittance. When a material with a low content is used, a sufficiently deep color tone cannot be realized, and the luxury of the timepiece dial is lowered.

Japanese Patent Laid-Open No. 10-39048

  An object of the present invention is to provide a timepiece dial having excellent light transmittance and a dark-colored high-quality appearance, and to provide a manufacturing method capable of producing the timepiece dial. Another object is to provide a timepiece having the timepiece dial.

Such an object is achieved by the present invention described below.
The method for manufacturing a timepiece dial of the present invention includes a reflective film forming step of forming a reflective film made of a metal material on a substrate made of a light-transmitting material;
A light absorption film forming step of forming a light absorption film made of a material having a function of absorbing at least a part of incident light on the reflection film;
Forming a first opening for forming a first opening in the light absorption film by irradiating laser light with a predetermined pattern from the side of the substrate on which the reflection film and the light absorption film are provided Process,
And a second opening forming step of forming a second opening in the reflective film by removing a part of the reflective film by performing an etching process.
As a result, it is possible to efficiently manufacture a timepiece dial having excellent light transmittance and a dark, high-grade appearance.

The timepiece dial manufacturing method of the present invention preferably includes an oxide film forming step of forming an oxide film made of a metal oxide on the surface of the substrate prior to the reflective film forming step.
Thereby, the durability of the obtained timepiece dial can be made particularly excellent. In addition, the aesthetic appearance of the obtained timepiece dial can be more reliably improved.

In the timepiece dial manufacturing method of the present invention, it is preferable to use a material including a pigment, a resin material, and an organic solvent in the light absorption film forming step.
As a result, a light absorbing film having a smooth surface can be easily and reliably formed, and even a relatively thick light reflecting film can be efficiently formed. Further, in the first opening forming step, the portion where the first opening of the light absorption film is to be formed can be selectively removed, and the other portions are removed. It can be effectively prevented from being bent or deformed. As a result, the aesthetic appearance (high quality) of the finally obtained timepiece dial can be more reliably improved.

In the timepiece dial manufacturing method of the present invention, the light absorbing film is preferably formed using a material containing carbon black.
As a result, the deep black color peculiar to carbon black can be expressed, and in the first opening forming step, the portion where the first opening of the light absorption film should be formed is selected more reliably. Therefore, it is possible to effectively prevent other parts from being removed or deformed. As a result, the aesthetic appearance (high quality) of the finally obtained timepiece dial can be more reliably improved. In the first opening forming step, the energy of the laser beam can be efficiently absorbed by the light absorption film, so that the formation efficiency of the first opening can be made particularly excellent. As a result, the productivity of the timepiece dial can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, when the substrate is viewed in plan, a second aperture ratio as an area ratio in which the second opening is provided in the reflective film is the light absorbing film. It is preferable to perform the second opening forming step so as to be larger than the first opening ratio as the area ratio at which the first opening is provided.
Thereby, the aesthetic appearance (high-class feeling) of the timepiece dial obtained can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, when the first aperture ratio is X ₁ [%] and the second aperture ratio is X ₂ [%], 1.10 ≦ X ₂ / X ₁ It is preferable to perform the second opening forming step so as to satisfy the relationship of ≦ 1.15.
As a result, the aesthetic appearance (luxury feeling) can be made particularly excellent while the light transmittance of the timepiece dial obtained is sufficiently excellent.

In the timepiece dial manufacturing method of the present invention, when the substrate is viewed in plan, the first aperture ratio as an area ratio in which the first opening is provided in the light absorption film is 15 to 40. % Is preferable.
As a result, the aesthetic appearance (luxury feeling) can be made particularly excellent while the light transmittance of the timepiece dial obtained is sufficiently excellent.

In the timepiece dial manufacturing method of the present invention, when the substrate is viewed in plan, the second aperture ratio as an area ratio in which the second opening is provided in the reflective film is 20 to 60%. It is preferable that
As a result, the aesthetic appearance (luxury feeling) can be made particularly excellent while the light transmittance of the timepiece dial obtained is sufficiently excellent.

In the timepiece dial manufacturing method of the present invention, the difference (W ₂ −W ₁ ) between the width W ₂ [μm] of the _second opening and the width W ₁ [μm] of the _first opening. Is preferably 1 to 20 μm.
As a result, the aesthetic appearance (luxury feeling) can be made particularly excellent while the light transmittance of the timepiece dial obtained is sufficiently excellent.
In the timepiece dial manufacturing method of the present invention, it is preferable that the light absorbing film has a surface roughness Ra of 1.0 μm or less at a portion other than the first opening.
Thereby, the aesthetic appearance (luxury feeling) of the timepiece dial can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, it is preferable to form the reflective film using a material containing at least one selected from the group consisting of Ag and Al.
Thus, in the first opening forming step, a desired portion of the light absorption film can be selectively removed more efficiently and more reliably removed. As a result, the aesthetic appearance (luxury feeling) of the obtained timepiece dial can be made particularly excellent. Further, the light transmittance of the obtained timepiece dial can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, it is preferable that an average thickness of the reflective film is 0.005 to 2.5 μm.
As a result, it is possible to make the light transmittance particularly excellent while sufficiently improving the aesthetic appearance (luxury feeling) of the obtained timepiece dial.
In the timepiece dial manufacturing method of the present invention, it is preferable that an average thickness of the light absorbing film is 0.2 to 60 μm.
As a result, the aesthetic appearance (luxury feeling) can be made particularly excellent while the light transmittance of the timepiece dial obtained is sufficiently excellent.

The timepiece dial of the present invention is manufactured using the method of the present invention.
As a result, it is possible to provide a timepiece dial having an excellent light transmittance and a dark, high-grade appearance.
The timepiece of the present invention includes the timepiece dial of the present invention.
Thereby, it is possible to provide a timepiece having a timepiece dial that has a dark and high-quality appearance. 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, it is possible to provide a timepiece dial having an excellent light transmittance and a dark, high-grade appearance, and a manufacturing method capable of producing the timepiece dial. Moreover, the timepiece provided with 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. Note that the drawings referred to in this specification show part of the configuration in an emphasized manner, and do not accurately reflect actual dimensions and the like.
<Manufacturing method of timepiece dial>
First, a method for manufacturing a timepiece dial according to the present invention will be described.
1 is a cross-sectional view showing a preferred embodiment of the timepiece dial manufacturing method of the present invention, FIG. 2 is a plan view showing a preferred embodiment of the timepiece dial of the present invention, and FIG. FIG. 4 is a schematic plan view for explaining an example of the shape (pattern) of the opening part of the absorption film, and FIG. 4 is a schematic diagram for explaining another example of the shape (pattern) of the opening part of the light absorption film. FIG.

  As shown in FIG. 1, in the timepiece dial manufacturing method of the present embodiment, a substrate preparation step (1 a) for preparing a substrate 2 and an oxide film 5 is formed on at least a part of the surface of the substrate 2. The oxide film forming step (1b), the reflective film forming step (1c) for forming the reflective film (metal film) 4 on the surface of the oxide film 5, and the light for forming the light absorbing film 3 on the surface of the reflective film 4 An absorption film forming step (1d), a first opening forming step (1e) for forming an opening (first opening) 31 in the light absorption film 3, and an opening (second opening) in the reflective film 4. Part) 41 and a second opening forming step (1f). In the following description, the upper side in FIG. 1 is described as “(external light) incident side”, and the lower side in FIG. 1 is described as “(external light) exit side” (the same applies to FIG. 5 described later).

[Board preparation process]
The board | substrate 2 is comprised with the material which has a light transmittance.
The light transmittance of the substrate 2 is preferably 80% or more, and more preferably 90% or more. As described above, since the light transmittance of the substrate 2 is sufficiently high, the light transmittance of the timepiece dial 1 as a whole can be sufficiently high. In this specification, unless otherwise specified, the light transmittance refers to the light transmittance when xenon white light defined in JIS Z 8902 is used as a light source. Further, in the present specification, the light reflectance and the absorptance are similar to the above, respectively, when xenon white light defined by JIS Z 8902 is used as a light source unless otherwise specified. It refers to the reflectance and absorption rate.

  Examples of the material constituting the substrate 2 include various plastic materials, various glass materials, and the like, but those made of plastic materials are preferable. The plastic material is generally excellent in moldability (freedom of molding), and can be suitably applied to manufacture the timepiece dial 1 having various shapes. Further, if the substrate 2 is made of a plastic material, it is advantageous for reducing the manufacturing cost of the timepiece dial 1. In addition, 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 2 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 2 is made of a plastic material will be mainly described.

Examples of the plastic material constituting the substrate 2 include various thermoplastic resins, various thermosetting resins, and the like. For example, polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethyl methacrylate (PMMA). ), Etc., polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyester resins such as polyethylene terephthalate (PET), etc., or copolymers, blends, polymer alloys, etc. mainly comprising these. These can be used, and one or more of these can be used in combination (for example, as a blend resin, a polymer alloy, a laminate, etc.). In particular, the substrate 2 is preferably composed mainly of polycarbonate and / or acrylonitrile-butadiene-styrene copolymer. Thereby, especially the intensity | strength as the timepiece dial 1 whole can be made excellent. Further, since the degree of freedom of molding of the substrate 2 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 2 is made of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin), the adhesion between the substrate 2 and the coating film is improved. It can be made particularly excellent. Polycarbonate is relatively inexpensive among various plastic materials, and can contribute to further reduction in production cost of the timepiece dial 1. The ABS resin also has particularly excellent chemical resistance, and the durability of the timepiece dial 1 as a whole can be further improved.
In addition, the board | substrate 2 may contain components other than a plastic material. Examples of such components include plasticizers, antioxidants, colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, fillers, and the like.

The substrate 2 may have a substantially uniform composition at each site, or may have a different composition depending on the site.
Further, the shape and size of the substrate 2 are not particularly limited, and are usually determined based on the shape and size of the timepiece dial 1 to be manufactured. In the illustrated configuration, the substrate (base material) 2 has a flat plate shape, but may have a curved plate shape, for example.

  Although the average thickness of the board | substrate 2 is not specifically limited, It is preferable that it is 200-700 micrometers, and it is more preferable that it is 300-600 micrometers. When the average thickness of the substrate 2 is a value within the above range, when the timepiece dial 1 is applied to a solar timepiece, the light transmission of the timepiece dial 1 is sufficiently high, It is possible to more effectively prevent the self color from being seen through, and to make the aesthetic appearance (luxury feeling) particularly excellent.

The substrate 2 may be formed by any method such as compression molding or injection molding. The surface of the substrate 2 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it becomes possible to give a variation in the glossiness of the surface of the timepiece dial 1 obtained.
In addition, various cleaning processes may be performed on the surface of the substrate 2 prior to a process described later. Thereby, for example, the adhesion between the substrate 2 and the oxide film 5 can be made particularly excellent.

[Oxide film forming step]
An oxide film 5 mainly composed of metal oxide is formed on the surface of the substrate 2 (1b).
Thus, in this embodiment, prior to the formation of the reflective film (metal film) 4, there is a step of forming the oxide film 5. This improves the adhesion between the substrate 2 and the metal coating 4 (adhesion through the oxide coating 5), in particular, the adhesion of the metal coating 4 formed by vapor deposition as described later. It is possible to effectively prevent the metal coating 4 from floating or peeling off. As a result, the durability of the timepiece dial 1 is particularly excellent.

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

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

  The average thickness of the oxide film 5 formed in this step is not particularly limited, but is preferably 0.005 to 1.0 μm, more preferably 0.007 to 0.5 μm, and More preferably, it is 01-0.3 micrometer. When the average thickness of the oxide film 5 is within the above range, the adhesion between the substrate 2 and the metal film 4 is particularly excellent while sufficiently preventing the internal stress of the oxide film 5 from increasing. Can be. Further, when the average thickness of the oxide coating 5 is within the above range, the function of preventing reflection of external light on the surface of the metal oxide coating 5 is efficiently exhibited, and the aesthetic appearance of the timepiece dial 1 is obtained. (Luxury) can be made particularly excellent. On the other hand, when the average thickness of the oxide film 5 is less than the lower limit, the adhesion between the substrate 2 and the metal film 4 may be increased depending on the constituent material of the oxide film 5, the substrate 2, and the metal film 4. There is a possibility that the function to be improved is not fully exhibited. In addition, when the average thickness of the oxide film 5 is less than the lower limit value, depending on the method of forming the oxide film 5, pinholes are easily generated in the oxide film 5, and the oxide film 5 is provided. The effect may not be fully demonstrated. Further, when the average thickness of the oxide film 5 exceeds the upper limit, the light transmittance in the oxide film 5 is lowered depending on the constituent material, the forming method, etc. of the oxide film 5, and the timepiece dial There is a possibility that the transmittance of light as a whole will be reduced, and the aesthetics (luxury) of the timepiece dial 1 may be reduced. Moreover, when the average thickness of the oxide film 5 exceeds the upper limit, the variation in film thickness at each portion of the oxide film 5 tends to increase. Further, when the average thickness of the oxide film 5 is particularly large, the internal stress of the oxide film 5 becomes high, and cracks and the like are likely to occur.

[Reflective film forming step (metal film forming step)]
Next, a reflective film (metal film) 4 having a function of reflecting light is formed on the surface of the oxide film 5 (1c).
By providing such a reflective film 4, when the opening (first opening) 31 is formed in the light absorption film 3 in the first opening forming step described later, the substrate 2 is made to emit laser light. It can be surely prevented from being adversely affected by energy. Further, as will be described in detail later, in the first opening forming step, the portion other than the portion where the opening 31 of the light absorbing film 3 where the opening 31 is formed is removed by the energy of the laser beam. The occurrence of problems such as being deformed or deformed can be reliably prevented. Furthermore, by providing a reflective film, the light transmittance of the timepiece dial 1 finally obtained can be made particularly excellent.

  The reflective film 4 formed in this step may be made of any material as long as it has a function of reflecting light, but is preferably made of a metal material. Thereby, the light transmittance of the timepiece dial 1 as a whole to be manufactured can be stably and reliably increased. In the following description, the case where the reflective film 4 is a metal film mainly composed of a metal material will be mainly described.

As the metal material constituting the reflective film (metal coating) 4, various metals (including alloys) can be used. More specifically, for example, Fe, Cu, Zn, Ni, Mg, Cr, Mn, Examples include Mo, Nb, Al, V, Zr, Sn, Au, Pd, Pt, Ag, Co, In, W, Ti, Rh, and alloys containing at least one of these. The reflective film 4 is preferably made of a material (including an alloy) containing at least one selected from the group consisting of Ag and Al, among the materials described above. As a result, reflection on the reflective film 4 as will be described in detail later can be expressed more effectively, and the light transmittance of the timepiece dial 1 as a whole can be made particularly excellent. Further, when the reflective film (metal film) 4 is made of the above-described material, the adhesion between the reflective film (metal film) 4 and the oxide film 5 is particularly excellent. it can. In addition, since Ag and Al are also excellent in thermal conductivity, if the reflective film (metal coating) 4 is made of the material as described above, in the first opening forming step described later, The heat generated by the laser light can be efficiently removed and dissipated, and the adverse effects of heat can be prevented more effectively, and the aesthetic appearance of the finally obtained dial 1 for a watch can be obtained. , It can be surely superior.
Further, the reflective film 4 may or may not have a uniform composition in each part. For example, the reflective film 4 may be a material (gradient material) in which the contained component (composition) sequentially changes in the thickness direction. Further, the reflective film 4 may be a laminate having a plurality of layers. Moreover, when the reflective film 4 is a laminated body, you may have the layer comprised with the material which does not contain a metal material substantially, for example. More specifically, the reflective film 4 may have a configuration in which a layer made of a metal oxide or the like is interposed between two layers made of a metal material.

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

  The average thickness of the reflective film 4 formed in this step is not particularly limited, but is preferably 0.005 to 2.5 μm, more preferably 0.007 to 0.9 μm, and 0.01 More preferably, it is -0.5 micrometer. When the average thickness of the reflective film 4 is a value within the above range, the function of the reflective film 4 can be more effectively exhibited while sufficiently preventing the internal stress of the reflective film 4 from increasing. The light transmittance of the timepiece dial 1 as a whole can be made particularly excellent. Further, the adhesion between the reflective film (metal film) 4 and the oxide film 5 can be made particularly excellent. Further, when the average thickness of the reflective film 4 is a value within the above range, in the first opening forming step to be described later, the constituent material of the light absorption film 3 passes through the reflective film 4 and the oxide film 5. It is possible to more reliably prevent entry into the base 2 and the like, and it is possible to more reliably improve the aesthetic appearance of the timepiece dial 1 finally obtained. On the other hand, if the average thickness of the reflective film 4 is less than the lower limit value, depending on the constituent material of the reflective film 4 and the like, it is difficult to sufficiently exhibit the function of the reflective film 4, and the timepiece dial 1 There is a possibility that the light transmittance as a whole will be lowered, and the luxury of the timepiece dial 1 may be insufficient. Further, depending on the constituent materials of the reflective film (metal film) 4 and the oxide film 5, it may be difficult to sufficiently improve the adhesion between the reflective film (metal film) 4 and the oxide film 5. is there. On the other hand, when the average thickness of the reflective film 4 exceeds the upper limit value, the aesthetic appearance (luxury feeling) of the timepiece dial 1 is sufficiently excellent depending on the thickness of the light absorbing film 3 described later. Can be difficult. Moreover, when the average thickness of the reflective film 4 exceeds the upper limit, the variation in film thickness at each part of the reflective film 4 tends to increase. Further, when the average thickness of the reflective film 4 is particularly large, the internal stress of the reflective film 4 becomes high and cracks and the like are likely to occur. Further, when the average thickness of the reflective film 4 exceeds the upper limit value, the tendency of the radio wave transmittance of the timepiece dial plate 1 as a whole to be significantly reduced appears, and the timepiece dial plate 1 is applied to a radio timepiece. It becomes difficult.

[Light absorption film forming process]
Next, the light absorption film 3 having a function of absorbing at least a part of incident light (external light) is formed on the surface of the reflection film 4 (1d). By forming such a light absorbing film 3, the appearance of the timepiece dial 1 finally obtained can be dark and high-class.
The light absorption film 3 formed in this step may be any film that has a function of absorbing at least part of incident light (external light), but the light absorption rate of the light absorption film 3 is 80% or more. It is preferable that it is 90% or more. As described above, when the light absorption rate of the light absorbing film 3 is sufficiently high, the aesthetic appearance (luxury feeling) of the finally obtained timepiece dial 1 is particularly excellent. it can.
In addition, the light transmittance of the light absorption film 3 formed in this step is preferably 2% or less, and more preferably 1% or less. Thus, when the light transmittance of the light absorbing film 3 is sufficiently small, the aesthetic appearance (high quality) of the watch dial 1 finally obtained can be made particularly excellent.

The color tone of the light absorbing film 3 formed in this step is not particularly limited, but is preferably black. Thereby, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent.
Examples of the constituent material of the light absorption film 3 formed in this step include colorants such as various pigments and various dyes, and metal compounds such as metal carbides and metal oxides. Among these, carbon black, acetylene, etc. Black pigments such as black, ivory black, bone black, peach black, vine black, lamp black, furnace black, charcoal black, iron black, manganese ferrite black, cobalt ferrite black, copper chrome black and copper chrome manganese black are preferably used. It is done. In particular, when carbon black is used among the above pigments, a deep black characteristic of carbon black can be expressed in the finally obtained dial 1 for timepiece, and a first opening forming step described later , The part where the first opening 31 of the light absorption film 3 is to be formed can be selectively removed more reliably, and other parts may be removed or deformed. Can be effectively prevented. As a result, the aesthetic appearance (luxury feeling) of the timepiece dial 1 finally obtained can be more reliably improved. Further, in the first opening forming step, the energy of the laser light can be efficiently absorbed by the light absorption film 3, and therefore the formation efficiency of the first opening 31 can be made particularly excellent. As a result, the productivity of the timepiece dial 1 can be made particularly excellent.

  Moreover, the material used for formation of the light absorption film 3 in this process may contain components other than the above. Examples of such components include resin components and precursors thereof (for example, corresponding monomers, dimers, oligomers, prepolymers, etc.), liquid media such as solvents and dispersion media, plasticizers, antioxidants, and brighteners. And fillers. As the resin component, for example, various thermoplastic resins, various thermosetting resins, and the like can be used. Examples of the liquid medium include organic solvents such as hydrocarbon solvents, ketone solvents, and alcohol solvents, and inorganic solvents such as water, carbon tetrachloride, and carbon disulfide.

  In particular, when a material containing a pigment, a resin material, and an organic solvent is used for forming the light absorption film 3, the following effects can be obtained. That is, the light absorption film 3 having a smooth surface can be easily and reliably formed, and even a relatively thick light absorption film 3 can be efficiently formed. Further, in the first opening forming step to be described later, the portion where the first opening 31 of the light absorbing film 3 is to be formed can be selectively removed more reliably, and other portions can be removed. It can be effectively prevented from being removed or deformed. As a result, the aesthetic appearance (luxury feeling) of the timepiece dial 1 finally obtained can be more reliably improved.

  The method for forming the light absorbing film 3 is not particularly limited, and examples thereof include wet coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, and electrodeposition coating, electrolytic plating, immersion plating, and electroless plating. Examples include plating, chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vapor deposition such as vacuum deposition, sputtering, and ion plating, and thermal spraying. In particular, even the light absorption film 3 having a relatively large film thickness can be efficiently formed by coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, and electrodeposition coating. When the light absorbing film 3 is formed by the above method, for example, a material for forming the light absorbing film 3 (light absorbing film forming material) includes a liquid medium such as a solvent or a dispersion medium. By using, the formation efficiency of the light absorption film 3 can further be improved. In such a case, after the coating film is formed, the liquid medium may be removed (desolvent or dedispersed medium) as necessary. Moreover, when the light absorption film 3 to be formed is made of a material containing a resin, for example, the material for forming the light absorption film 3 includes a monomer, a dimer, an oligomer, a prepolymer corresponding to the resin. For example, a precursor (precursor) may be used. Moreover, when the light absorption film 3 to be formed is composed of a material containing a curable resin such as a thermosetting resin or a photocurable resin, for example, heating, light (energy rays) as necessary. You may perform processes, such as irradiation.

  Moreover, the average thickness of the light absorption film 3 formed in this step is not particularly limited, but is preferably 0.2 to 60 μm, and more preferably 0.5 to 50 μm. When the average thickness of the light-absorbing film 3 is within the above range, the light transmittance of the timepiece dial 1 as a whole is sufficiently excellent, and the aesthetic appearance (luxury) of the timepiece dial 1 is achieved. Can be made particularly excellent. In particular, the aesthetic appearance when the timepiece dial 1 is viewed from a direction inclined by a predetermined angle from the normal (perpendicular) direction of the main surface can be made particularly excellent.

[First opening forming step]
Next, an opening (first opening) 31 is formed in the light absorption film 3 (1e). The opening 31 is formed by laser light irradiation. Thereby, for example, the energy of the irradiated laser beam is absorbed by the light absorption film 3 and a part of the light absorption film 3 is removed, whereby the opening 31 can be efficiently formed. Further, by controlling the irradiation pattern of the laser beam, even the opening 31 having a complicated pattern can be easily and reliably formed. Further, by using laser light for forming the opening 31, for example, even when manufacturing a plurality of types of timepiece dials 1 having different shapes, sizes, and arrangement patterns of the opening 31, the laser irradiation pattern can be changed. It can respond suitably by changing. That is, it can respond suitably also to multi-product production.

  In addition, since the reflection film 4 is provided on the back surface of the light absorption film 3 where the opening 31 is to be formed in this step, the energy of the irradiated laser beam is used to form the opening 31 more efficiently. can do. That is, even if a part of the laser light irradiated from the light incident side (upper side in FIG. 1) and incident on the light absorption film 3 is not used for forming the opening 31, the laser light is reflected on the reflective film 4 Therefore, it is possible to reliably prevent the occurrence of defective openings in the light absorbing film 3 (defects such as the absence of an opening at a portion where the opening is to be formed). it can. In addition, since the metal material constituting the reflective film 4 generally has excellent thermal conductivity, it is possible to prevent a temperature other than the irradiated portion of the laser light from becoming high temperature. As a result, the light absorbing film 3 Of these, the portion irradiated with the laser beam can be selectively removed. That is, the portion of the light absorption film 3 that is directly irradiated with the laser light is removed by the energy of the laser light, while the portion that is not directly irradiated with the laser light is heat generated by the irradiation of the laser light. Is efficiently removed and dissipated by the metal coating 4. As a result, it is possible to effectively prevent the portion of the light absorption film 3 that has not been directly irradiated with the laser light from becoming high temperature, and the opening 31 having a desired shape and size can be formed in a desired manner. The pattern can be formed more reliably.

  On the other hand, when laser light irradiation is performed in a state where no reflective film is arranged on the back surface of the light absorption film (the surface opposite to the side on which the laser light is irradiated), The aesthetic appearance of the watch dial finally obtained cannot be made sufficiently excellent. That is, when the metal film is not disposed on the back surface of the light absorption film, when the laser beam is applied, the constituent material of the light absorption film that has absorbed the laser beam and has become a high energy state is the substrate, the oxide film. Or the like (hereinafter referred to as a substrate). As a result, even in the portion where the opening of the light absorption film is formed, the substrate or the like is colored by the constituent material of the light absorption film, and the light transmission as a whole of the timepiece dial is low End up. Further, when the constituent material of the light absorption film such as the substrate enters, the substrate or the like easily absorbs the energy of the laser beam. As a result, the temperature of the substrate or the like is likely to increase due to the irradiation of the laser beam, and the deformation or the like of the substrate or the like is likely to occur. Moreover, since it does not have a metal film, heat removal and heat dissipation do not proceed efficiently, and not only the part directly irradiated with the laser beam but also its surroundings are likely to be in a high temperature state. As a result, in addition to the deformation of the substrate and the like as described above, the light absorption film is deformed, and the opening formed in the light absorption film becomes larger than necessary.

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

The first opening 31 formed in this step functions as an entrance for transmitting external light to the opposite surface side through the substrate 2 or the like in the timepiece dial 1 to be manufactured. .
When the substrate 2 (timepiece dial 1) is viewed in plan, an aperture ratio (first aperture ratio) as an area ratio occupied by the opening 31 in the light absorption film 3 is not particularly limited, but is 15 to 40%. It is preferable that it is 25 to 35%. When the aperture ratio (first aperture ratio) of the light absorbing film 3 is a value within the above range, the aesthetic appearance of the timepiece dial 1 to be obtained is made sufficiently excellent in light (external light) transmittance. (Luxury) can be made particularly excellent. On the other hand, if the aperture ratio (first aperture ratio) of the light absorbing film 3 is less than the lower limit value, it is difficult to sufficiently improve the light transmittance of the timepiece dial 1 as a whole. become. On the other hand, when the aperture ratio (first aperture ratio) of the light absorbing film 3 exceeds the upper limit, the aesthetic appearance of the timepiece dial 1 to be obtained is sufficiently excellent depending on the thickness of the light absorbing film 3 and the like. It becomes difficult to do.

  The opening 31 may have any shape. In the configuration shown in FIG. 2, the shape of the opening 31 when the substrate 2 (timepiece dial 1) is viewed in plan view is substantially circular. For example, the substrate 2 (timepiece dial 1) is viewed in plan view. The shape at this time may be a substantially elliptical shape, a substantially polygonal shape, a slit shape, or the like. Further, as shown in FIGS. 3 and 4, the opening 31 surrounds a large number of island-like regions formed of the light absorption film 3 when the substrate 2 (clock dial 1) is viewed in plan. It may be provided. Thereby, in the external appearance of the timepiece dial 1, the presence of the opening 31 can be made inconspicuous, and the productivity of the timepiece dial 1 can be made particularly excellent.

The width of the opening 31, represented in the figure _{W 1} (when the opening 31 is substantially circular, the diameter) is not particularly limited, but is preferably 10 to 150 m, 15～140Myuemu More preferably, it is 20-130 micrometers. When the width W ₁ of the opening 31 is a value within the above range, the aesthetic appearance (aesthetics) of the timepiece dial 1 is particularly enhanced while the light transmission as the timepiece dial 1 is sufficiently high. It can be excellent. On the other hand, when the width W ₁ of the opening 31 is less than the lower limit value, the aperture ratio (first aperture ratio) of the light absorption film 3 and the aperture ratio (second aperture ratio) of the reflection film 4 described later. In some cases, it may be difficult to sufficiently increase the light transmittance of the timepiece dial 1 as a whole. On the other hand, if the width W ₁ of the opening 31 exceeds the above upper limit value, the aperture ratio of the light absorbing layer 3 by a (first aperture rate) and the like, provided with excellent appearance of the timepiece dial 1 sufficiently Can be difficult.

The pitch of the opening 31, represented in the figure _{P 1} is preferably from 70～400Myuemu, more preferably from 80～350Myuemu, even more preferably 90～300Myuemu. When the pitch P ₁ of the opening 31 is within this range, while a sufficiently high transmittance of light of the timepiece dial 1, particularly outstanding appearance of the timepiece dial (aesthetics) Can be. On the other hand, when the pitch P ₁ of the openings 31 is less than the lower limit value, the appearance of the timepiece dial 1 is sufficiently excellent depending on the aperture ratio (first aperture ratio) of the light absorbing film 3 and the like. It can be difficult to do. On the other hand, when the pitch P ₁ of the openings 31 exceeds the upper limit value, depending on the aperture ratio (first aperture ratio) of the light absorption film 3, the aperture ratio (second aperture ratio) of the reflection film 4 described later, and the like. Therefore, it may be difficult to sufficiently increase the light transmittance of the timepiece dial 1 as a whole. The pitch of the openings 31 refers to the center-to-center distance between the adjacent openings 31 and 31. When there are a plurality of adjacent openings 31, the pitch between the adjacent openings 31 Refers to the distance between centers.

[Second opening forming step]
Thereafter, an opening (second opening) 41 is formed in the reflective film 4 (1f). Thus, the timepiece dial 1 capable of transmitting light through the first opening 31 and the second opening 41 is obtained.
The opening 41 is formed by etching. As a result, an opening (second opening 41) can be selectively and efficiently applied to a portion of the reflective film 4 corresponding to the portion where the opening (first opening) 31 of the light absorption film 3 is provided. ) Can be formed. In other words, the second opening 41 is formed so as to correspond to the shape and arrangement pattern of the first opening 31. Further, by forming the opening 41 by etching, it is possible to reliably prevent adverse effects on the light absorption film 3, the oxide film 5, and the substrate 2 by adjusting the etching time, selecting the composition of the etching solution, and the like. However, the second opening 41 larger than the first opening 31 can be easily formed. In particular, by adjusting the etching amount, it is possible to easily and reliably form the second opening 41 that satisfies the relationship described later with the first opening 31. Moreover, since the light absorption film 3 having the first opening 31 can be used as a mask by forming the second opening 41 by etching, it is not necessary to add a new process and is excellent. The second opening 41 having a desired shape and size can be formed with positional accuracy.

As etching for forming the second opening 41, dry etching, wet etching, or the like can be used, but wet etching is preferable. Thereby, the 2nd opening part 41 which satisfies the relationship which is mentioned later between the 1st opening parts 31 can be formed more easily and reliably.
The second opening 41 formed in this step is provided at a site corresponding to the opening (first opening) 31 of the light absorption film 3. In other words, the second opening 41 is provided so as to overlap the first opening 31 when the substrate 2 (timepiece dial 1) is viewed in plan. Thereby, the external light which passed the opening part (1st opening part) 31 of the light absorption film 3 can be efficiently entered in the board | substrate 2, and the transmittance | permeability of the light as the timepiece dial 1 whole is sufficient. It can be made excellent.

The shape of the second opening 41 (the shape when the substrate 2 is viewed in plan) is not particularly limited, but is preferably substantially similar to the corresponding first opening 31. Thereby, it is possible to make the light transmittance particularly excellent while sufficiently improving the aesthetic appearance (luxury) of the timepiece dial 1.
Further, the arrangement pattern of the second openings 41 is not particularly limited, but is preferably the same as the arrangement pattern of the first openings 31 in the light absorption film 3. Thereby, it is possible to make the light transmittance particularly excellent while sufficiently improving the aesthetic appearance (luxury) of the timepiece dial 1.

  The second opening 41 only needs to be provided so that at least a part of the second opening 41 overlaps the first opening 31 when the substrate 2 (timepiece dial 1) is viewed in plan view. 2 (timepiece dial 1) is preferably provided so that the first opening 31 is completely included in the region where the second opening 41 is provided when viewed in plan. . Thereby, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent.

  Further, when the substrate 2 (timepiece dial 1) is viewed in plan, the first aperture ratio as the area ratio in which the first opening 31 is provided in the light absorption film 3 is the second aperture ratio in the reflection film 4. It is preferable that the opening ratio is smaller than the second opening ratio as the area ratio in which the opening 41 is provided. Thereby, for example, even when the timepiece dial 1 is observed from a direction inclined by a predetermined angle from the normal direction (perpendicular line) of the main surface, the viewer can more reliably see the reflective film 4 visually. Can be prevented. In particular, even when the thickness of the light absorption film 3 is relatively thin, the viewer can more reliably prevent the reflection film 4 from being visually recognized. As a result, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent.

Also, the first aperture ratio _X 1 [%], when the second aperture ratio was _X 2 [%], to satisfy the relationship of _{1.10 ≦ X 2 / X 1 ≦} 2.30 preferably More preferably, the relationship of 1.15 ≦ X ₂ / X ₁ ≦ 1.80 is satisfied. By satisfying such a relationship, for example, even when the timepiece dial 1 is observed from a direction inclined by a predetermined angle from the normal direction (perpendicular line) of the main surface, the reflective film 4 is provided to the observer. It can prevent more reliably that it is visually recognized. In particular, even when the thickness of the light absorption film 3 is relatively thin, the viewer can more reliably prevent the reflection film 4 from being visually recognized. As a result, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent. On the other hand, if the value of X ₂ / X ₁ is less than the lower limit, depending on the thickness of the light absorbing film 3, the timepiece dial 1 is set at a predetermined angle from the normal direction (perpendicular) of the main surface. It may be difficult to make the aesthetic appearance sufficiently excellent when observed from an inclined direction. On the other hand, if the value of X ₂ / X ₁ exceeds the upper limit value, depending on the pitch of the opening 31 and the opening 41, it becomes difficult to fully exhibit the function of the reflective film 4, and the timepiece dial 1 It may be difficult to make the overall light transmittance (light utilization efficiency) sufficiently excellent.

  When the substrate 2 (timepiece dial 1) is viewed in plan, the second aperture ratio as the area ratio where the second opening 41 is provided in the reflective film 4 is preferably 20 to 60%. 30 to 55% is more preferable. When the second aperture ratio 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.

The width of the opening 41, represented in the figure _{W 2} (if opening 41 is substantially circular, the diameter) is preferably from 11～170Myuemu, more in the range of 17~150μm preferable.
The pitch of the opening 41, represented in the figure _{P 2} is preferably from 70～400Myuemu, more preferably from 80～350Myuemu, even more preferably 90～300Myuemu. In the configuration shown in the figure, P ₁ and P ₂ are equal. The pitch of the openings 41 refers to the distance between the centers of the adjacent openings 41 and 41, and when there are a plurality of adjacent openings 41, the distance between the centers of the adjacent openings 41 is the closest. Refers to distance.

The difference (W ₂ −W ₁ ) between the width W ₂ [μm] of the second opening 41 and the width W ₁ [μm] of the first opening 31 is preferably _{1 to 30} μm. 2 to 25 μm is more preferable. By satisfying such a relationship, for example, even when the timepiece dial 1 is observed from a direction inclined by a predetermined angle from the normal direction (perpendicular line) of the main surface, the reflective film 4 is provided to the observer. It can prevent more reliably that it is visually recognized. In particular, even when the thickness of the light absorption film 3 is relatively thin, the viewer can more reliably prevent the reflection film 4 from being visually recognized. As a result, the aesthetic appearance (luxury feeling) of the timepiece dial 1 can be made particularly excellent. On the other hand, if the value of (W ₂ −W ₁ ) is less than the lower limit value, the timepiece dial 1 may be moved from the normal direction (perpendicular) of the main surface depending on the thickness of the light absorbing film 3 or the like. It may be difficult to make the aesthetic appearance sufficiently excellent when observed from a direction inclined by a predetermined angle. On the other hand, if the value of (W ₂ −W ₁ ) exceeds the upper limit, depending on the pitch of the opening 31 and the opening 41, it becomes difficult to fully exhibit the function of the reflective film 4. It may be difficult to make the light transmittance (light utilization efficiency) of the plate 1 as a whole excellent.

  Further, when the substrate 2 (timepiece dial 1) is viewed in plan, the total aperture ratio as the area ratio where the first opening 31 and the second opening 41 overlap (the timepiece dial 1 as a whole). (Opening ratio) is preferably 15 to 40%, more preferably 25 to 35%. When the total aperture ratio 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.

<Watch dial>
The timepiece dial 1 obtained by the method as described above has an excellent aesthetic appearance and excellent light transmittance. In particular, the timepiece dial 1 obtained by the method as described above is particularly excellent because the surface of the light absorbing film 3 is prevented from being undesirably rough (particularly, near the opening 31). It has a beautiful aesthetic appearance.
The surface roughness Ra of the light absorbing film 3 in the timepiece dial 1 is not particularly limited, but is preferably 1.0 μm or less. Thereby, the aesthetic appearance of the timepiece dial 1 is particularly excellent.

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

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

FIG. 5 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 5, a wristwatch (portable watch) 100 according to this embodiment includes a case (case) 102, a back cover 103, a bezel (edge) 104, and a glass plate (cover glass) 105. . Further, in the case 102, the timepiece dial 1, the solar battery 11, and the movement 101 as described above are housed, and hands (pointers) (not shown) and the like are housed.

The glass plate 105 is usually made of transparent glass or sapphire having high transparency. Thereby, the aesthetic appearance of the timepiece dial 1 can be sufficiently exhibited, and a sufficient amount of light can be incident on the solar cell 11.
The movement 101 uses the electromotive force of the solar cell 11 to drive the pointer.
Although omitted in FIG. 5, in the movement 101, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 11, a lithium ion secondary battery, a crystal oscillator as a time reference source, a crystal oscillation A semiconductor integrated circuit that generates a driving pulse that drives the clock based on the oscillation frequency of the child, a step motor that drives the wheel train mechanism every second in response to this driving pulse, and a movement of the step motor A train wheel mechanism for transmitting to the vehicle is provided.
The movement 101 also includes a radio wave receiving antenna (not shown). And it has the function to perform time adjustment etc. using the received electromagnetic wave.

The solar cell 11 has a function of converting light energy into electric energy. The electric energy converted by the solar cell 11 is used for driving the movement.
In the solar cell 11, for example, a p-type impurity and an n-type impurity are selectively introduced into a non-single-crystal silicon thin film, and a p-type non-single-crystal silicon thin film and an n-type non-single-crystal silicon thin film are used. It has a pin structure provided with an i-type non-single-crystal silicon thin film with a low impurity concentration in between.

A winding stem pipe 106 is fitted and fixed to the barrel 102, and a shaft 1071 of a crown 107 is rotatably inserted into the winding stem pipe 106.
The body 102 and the bezel 104 are fixed by a plastic packing 108, and the bezel 104 and the glass plate 105 are fixed by a plastic packing 109.
Further, a back cover 103 is fitted (or screwed) to the body 102, and a ring-shaped rubber packing (back cover packing) 114 is inserted in a compressed state in these joint portions (seal portions) 115. Has been. With this configuration, the seal portion 115 is liquid-tightly sealed, and a waterproof function is obtained.

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

In the above description, a wristwatch (portable clock) is described as an example of a clock, but the present invention is similarly applied to other types of clocks such as a portable clock, a table clock, and a wall clock other than the wristwatch. be able to.
In the above description, a solar timepiece (in particular, a solar radio timepiece) is described as an example of a timepiece. However, the present invention can be similarly applied to a timepiece other than a solar timepiece.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.
For example, the manufacturing method of the present invention may include steps other than those described above. For example, you may have the process of forming a coating layer in the surface side provided with the light absorption film, or the surface side opposite to the reflective film of a board | substrate, and the surface facing a light absorption film. As a result, for example, the color tone and the like can be adjusted to further improve the aesthetic appearance of the timepiece dial, or as a whole timepiece dial, the corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, Various characteristics such as wear and discoloration resistance can be improved. Such a coat layer may be removed, for example, when a timepiece dial is used.
In the above-described embodiment, the oxide film forming process for forming the oxide film is described prior to the reflective film forming process. However, such a process may be omitted.

Next, specific examples of the present invention will be described.
1. Manufacture of timepiece dial (Example 1)
A timepiece dial was manufactured by the following method.
First, a substrate having the shape of a timepiece dial was produced by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained substrate was substantially disc-shaped and had a diameter: 27 mm × thickness: 0.5 mm.
Next, this substrate was cleaned. As the cleaning of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, washing with water for 10 seconds, and cleaning with pure water for 10 seconds.

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

Subsequently, a metal film as a reflection film composed of Ag was formed on the surface of the oxide film formed as described above by sputtering as described below (reflection film formation step).
First, the inside of the apparatus was evacuated (depressurized) to 3 × 10 ⁻³ Pa, and then argon gas was introduced at an argon gas flow rate of 35 ml / min. In this state, Ag was used as a target, and discharge was performed under the conditions of input power: 1400 W and treatment time: 4.0 minutes, thereby forming a metal film (reflective film) composed of Ag. The average thickness of the metal film thus formed was 0.30 μm.

Next, the substrate coated with the oxide film and the metal film obtained as described above was washed. As washing, first, alkali immersion degreasing was performed for 30 seconds, then neutralization was performed for 10 seconds, water washing for 10 seconds, and pure water washing for 10 seconds.
Next, a light absorption film made of a material containing carbon black was formed on the surface of the metal film formed as described above (reflection film forming step). The light absorbing film is formed by applying a composition containing carbon black, an acrylic resin, and methyl ethyl ketone (light absorbing film forming material) to the surface of the metal film by brush coating, and then at 60 ° C. under normal pressure. By volatilizing methyl ethyl ketone by heating. The average thickness of the light absorption film thus formed was 10 μm.

Next, the light absorption film provided on the metal film was irradiated with a YVO ₄ laser from the outer surface side (the surface side opposite to the surface facing the metal film) of the light absorption film (first surface). Opening forming step). At this time, the laser light was intermittently irradiated while relatively moving the laser light source and the substrate. Laser light irradiation was performed under the conditions of current value: 25 [A], frequency: 35 kHz, and processing speed: 1500 [mm / s]. As a result, as shown in FIG. 2, a large number of circular openings penetrating the light absorption film were formed in a staggered pattern. The width (diameter) W ₁ of the formed openings was 52 μm, and the pitch P _{1 of the} openings was 90 μm. In addition, when the substrate was viewed in plan, the aperture ratio (first aperture ratio) was 30% as the area ratio occupied by the aperture (first aperture) in the light absorption film.

Next, an opening (second opening) was formed in the metal film by wet etching (second opening forming step). As a result, a timepiece dial as shown in FIGS. 1 and 2 was obtained. Wet etching was performed using a 45 wt% nitric acid aqueous solution as an etchant. In addition, the temperature of the etching solution and the etching time in this step were 25 ° C. and 5 minutes, respectively.
The thicknesses of the substrate, oxide coating, metal coating (reflection film), and light absorption film were measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 10)
The constituent materials and thickness of the substrate used for manufacturing the timepiece dial are as shown in Table 1, and the oxide coating, the metal coating, and the light absorption film are configured as shown in Table 1 in each step. A timepiece dial was manufactured in the same manner as in Example 1 except that the processing conditions were adjusted (including changes in materials used in each step).

(Comparative Example 1)
A timepiece dial was manufactured in the same manner as in Example 1 except that the reflective film forming step and the second opening forming step were omitted. The timepiece dial manufactured in this comparative example had the same configuration as the timepiece dial of Example 1 except that it did not have a reflective film (metal coating).
(Comparative Example 2)
A timepiece dial was manufactured in the same manner as in Comparative Example 1 except that the first opening forming step was omitted.

(Comparative Example 3)
In this comparative example, a timepiece dial having the same configuration as in Example 1 was manufactured except that the light absorbing film was not provided. The timepiece dial was manufactured as follows.
First, in the same manner as in Example 1, an oxide film and a metal film were formed on a substrate made of polycarbonate, and then the substrate coated with the oxide film and the metal film was washed.

Next, a composition (mask forming material) containing an acrylic resin and methyl ethyl ketone was applied to the surface of the metal coating using a spin coater. Then, methyl ethyl ketone was removed by heating to 60 ° C.
Thereafter, the formed acrylic resin film was irradiated with laser light in the same manner as in Example 1 with respect to the light absorption film. As a result, a mask having a large number of circular openings arranged in a staggered pattern was obtained. The width (diameter) of the formed openings was 47 μm, and the pitch of the openings was 150 μm. Further, when the substrate was viewed in plan, the aperture ratio as an area ratio occupied by the openings in the mask was 30%.

Next, an opening was formed in the metal film by wet etching. Wet etching was performed using a 45 wt% nitric acid aqueous solution as an etchant. In addition, the temperature of the etching solution and the etching time in this step were 25 ° C. and 5 minutes, respectively.
Thereafter, the mask made of acrylic resin was removed using methyl ethyl ketone to obtain a timepiece dial.

(Comparative Example 4)
A timepiece dial was manufactured in the same manner as Comparative Example 3 except that the oxide film forming step was omitted.
(Comparative Example 5)
A timepiece dial was manufactured in the same manner as in Example 1 except that the second opening forming step was omitted.

  Table 1 summarizes the configuration of the timepiece dial of each example and each comparative example. In Table 1, polycarbonate is represented by PC, acrylonitrile-butadiene-styrene copolymer (ABS resin) is ABS, polyethylene terephthalate is PET, acrylic resin is PMMA, carbon black is CB, cobalt violet (C.I. Violet 14) was indicated in CV.

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

3. Evaluation of light transmittance of timepiece dial The light transmittance of each timepiece dial manufactured in each of the above Examples and Comparative Examples was evaluated by the following method.
First, the solar cell and each clock dial were placed in a dark room. Thereafter, light from a fluorescent lamp (light source) separated by a predetermined distance was made incident on the light receiving surface of the solar cell alone. At this time, the power generation current of the solar cell was A [mA]. Next, light from a fluorescent lamp (light source) separated by a predetermined distance was made incident in the same manner as described above with the timepiece dial overlapped on the upper surface of the light receiving surface of the solar cell. In this state, the generated current of the solar cell was B [mA]. Then, the light transmittance of the timepiece dial represented by (B / A) × 100 was calculated and evaluated according to the following six criteria. It can be said that the larger the light transmittance of the timepiece dial, the better the light transmittance of the timepiece dial.
A: 35% or more.
A: 32% or more and less than 35%.
○: 28% or more and less than 32%.
Δ: 25% or more and less than 28%.
X: 17% or more and less than 25%.
Xx: Less than 17%.

  Thereafter, a wristwatch as shown in FIG. 5 was manufactured using the timepiece dial manufactured in each of the above Examples and Comparative Examples. Then, each manufactured wristwatch was put in a dark room. Thereafter, light from a fluorescent lamp (light source) spaced a predetermined distance was made incident from a surface on the dial side (surface on the glass plate) of the watch. At this time, the irradiation intensity was changed at a constant speed so that the irradiation intensity of light gradually increased. As a result, in the timepiece of the present invention, the movement was driven even when the irradiation intensity was relatively small. On the other hand, in the timepieces of Comparative Examples 2 and 5, 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 watch internal module (movement) and a watch dial were assembled in the watch case, and the radio wave reception sensitivity in this state was measured.

Using the reception sensitivity in a state where the timepiece dial is not incorporated as a reference, the reduction amount (dB) of the reception sensitivity when the timepiece dial is incorporated was evaluated according to the following four criteria. It can be said that the lower the radio wave reception sensitivity is, the better the radio wave transmission of the dial is.
A: No decrease in sensitivity is observed (below the detection limit).
○: A decrease in sensitivity is observed at less than 0.7 dB.
(Triangle | delta): The fall of a sensitivity is 0.7 dB or more and less than 1.0 dB.
X: The reduction in sensitivity is 1.0 dB or more.

5. Adhesion evaluation (durability evaluation) of coating (oxide coating, reflective film, light absorption film)
Each timepiece dial produced in each of the above Examples and Comparative Examples was subjected to the following two tests to evaluate the adhesion of the coating (oxide coating, reflection film, light absorption film).
5-1. Bending test For each timepiece dial, a steel bar with a diameter of 4 mm was used as a fulcrum, and after bending 30 ° with respect to the center of the timepiece dial, the appearance of the timepiece dial was visually observed, These appearances were evaluated according to the following four criteria. Bending was performed in both compression / tension directions.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.

5-2. Thermal cycle test Each timepiece dial was subjected to the following thermal cycle test.
First, the watch dial is placed in a 20 ° C. environment for 1.5 hours, then in a 60 ° C. environment for 2 hours, then in a 20 ° C. environment for 1.5 hours, and then in a −20 ° C. environment. It was left to stand for 3 hours. Thereafter, the environmental temperature was returned again to 20 ° C., which was set as one cycle (8 hours), and this cycle was repeated three times in total (24 hours in total).
Thereafter, the appearance of the timepiece dial was visually observed, and the appearance was evaluated according to the following four-stage criteria.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.
These results are shown in Table 2.

As can be seen from Table 2, all of the timepiece dials of the present invention had an excellent aesthetic appearance and excellent light transmittance.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, the timepiece dial of Comparative Example 1 having no reflective film has a low light transmittance as the whole timepiece dial. In addition, the timepiece dials of Comparative Examples 3 and 4 having a reflective film but not having a light absorbing film did not exhibit a sufficiently high-quality appearance. Further, although the light-absorbing film is provided, the timepiece dial of Comparative Example 2 in which the light-absorbing film is not provided with an opening has very poor light transmission. Further, the timepiece dial of Comparative Example 5 having a light absorption film and a reflection film, but having no opening in the reflection film, was very poor in light transmission and inferior in aesthetic appearance. .
Further, a timepiece as shown in FIG. 5 was assembled using the timepiece dials obtained in the respective examples and comparative examples. Each timepiece thus obtained was tested and evaluated in the same manner as described above, and the same results as described above were obtained.

It is sectional drawing which shows suitable embodiment of the manufacturing method 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 shape (pattern) of the opening which a light absorption film has. It is a typical top view for demonstrating another example of the shape (pattern) of the opening which a light absorption film has. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (watch) of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Timepiece dial 2 ... Board | substrate (base material) 3 ... Light absorption film 31 ... Opening part (1st opening part) 4 ... Reflective film (metal film) 41 ... Opening part (2nd opening part) 5 ... Oxide coating 11 ... Solar cell 101 ... Movement 102 ... Body (case) 103 ... Back cover 104 ... Bezel (edge) 105 ... Glass plate (cover glass) 106 ... Winding pipe 107 ... Crown 1071 ... Shaft portion 1072 ... Groove DESCRIPTION OF SYMBOLS 108 ... Plastic packing 109 ... Plastic packing 113 ... Rubber packing (Crown packing) 114 ... Rubber packing (back cover packing) 115 ... Joint part (seal part) 100 ... Wristwatch (portable clock)

Claims (15)

A reflective film forming step of forming a reflective film made of a metal material on a substrate made of a light-transmitting material;
A light absorption film forming step of forming a light absorption film made of a material having a function of absorbing at least a part of incident light on the reflection film;
Forming a first opening for forming a first opening in the light absorption film by irradiating laser light with a predetermined pattern from the side of the substrate on which the reflection film and the light absorption film are provided Process,
A timepiece dial having a second opening forming step of removing a part of the reflective film by performing an etching process and forming a second opening in the reflective film. Method.   2. The timepiece dial manufacturing method according to claim 1, further comprising an oxide film forming step of forming an oxide film made of a metal oxide on the surface of the substrate prior to the reflecting film forming step.   The timepiece dial manufacturing method according to claim 1 or 2, wherein a material containing a pigment, a resin material, and an organic solvent is used in the light absorption film forming step.   4. The timepiece dial manufacturing method according to claim 1, wherein the light absorption film is formed using a material containing carbon black.   When the substrate is viewed in plan, the second aperture ratio as the area ratio where the second opening is provided in the reflective film is the area where the first opening is provided in the light absorption film. The timepiece dial manufacturing method according to any one of claims 1 to 4, wherein the second opening forming step is performed so as to be larger than a first opening ratio as a rate. Wherein the 1 _X 1 [%] the aperture ratio of the second aperture ratio when the _X 2 [%], so as to satisfy the relationship of _{1.10 ≦ X 2 / X 1 ≦} 1.15, The timepiece dial manufacturing method according to claim 5, wherein the second opening forming step is performed.   The first aperture ratio as an area ratio in which the first opening is provided in the light absorption film when the substrate is viewed in plan is 15 to 40%. A manufacturing method of the timepiece dial described in the above.   The second aperture ratio as an area ratio in which the second opening is provided in the reflective film when the substrate is viewed in plan is 20 to 60%. Of manufacturing a dial for a watch. The difference (W ₂ -W ₁ ) between the width W ₂ [μm] of the _second opening and the width W ₁ [μm] of the _first opening is set to ₁ to 20 μm. The manufacturing method of the dial for timepieces in any one of.   10. The timepiece dial manufacturing method according to claim 1, wherein the light absorbing film has a surface roughness Ra of 1.0 μm or less at a portion other than the first opening. 11.   The timepiece dial manufacturing method according to claim 1, wherein the reflective film is formed using a material including at least one selected from the group consisting of Ag and Al.   The timepiece dial manufacturing method according to claim 1, wherein an average thickness of the reflective film is 0.005 to 2.5 μm.   The timepiece dial manufacturing method according to claim 1, wherein an average thickness of the light absorbing film is 0.2 to 60 μm.   A timepiece dial manufactured using the method according to claim 1.   A timepiece comprising the timepiece dial according to claim 14.

Images