JP2010181353A - Timepiece dial, method for manufacturing the same, and timepiece - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black timepiece dial having superior durability, sufficient high-grade feeling and a superior esthetic appearance; to provide a manufacturing method capable of manufacturing properly the timepiece dial; and to provide a timepiece including the timepiece dial. <P>SOLUTION: This timepiece dial 1 includes a substrate 2 constituted of a light-transmissible material, and a carbon film 3 provided on the first surface 21 side which is one main surface of the substrate 2 and constituted mainly of carbon. The substrate 2 includes fine irregularities 221 having a function for reflecting or scattering entering light from the first surface 21 side, on the second surface 22 which is a main surface on the opposite side to the first surface 21. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

A timepiece dial is required to have excellent aesthetic appearance as a decorative product as well as excellent visibility as a practical product. Conventionally, in order to achieve such an object, a metal material such as Au or Ag has generally been used as a constituent material of a timepiece dial.
Also, on the other hand, for the purpose of reducing production costs and improving the degree of freedom in forming the timepiece dial, an attempt is made to form a coating made of a metal material on the surface using plastic as a base material. (For example, refer to Patent Document 1).

However, plastics generally have poor adhesion to metal materials. For this reason, there is a problem that peeling between the base material and the coating film is likely to occur, and the durability of the timepiece dial is inferior.
On the other hand, there are various demands for timepiece dials, and in particular, there is a great demand for timepiece dials that have a dark color tone (particularly black) and a high-grade appearance. The dial for the purpose did not sufficiently satisfy such a requirement.

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

  An object of the present invention is to provide a timepiece dial that is excellent in durability, black, high-class and excellent in aesthetic appearance, and a manufacturing method capable of suitably producing the timepiece dial. Another object of the present invention is to provide a timepiece having the timepiece dial.

Such an object is achieved by the present invention described below.
In the timepiece dial of the present invention, a substrate made of a light-transmitting material,
A carbon film mainly composed of carbon provided on the first surface side which is one main surface of the substrate;
The substrate has minute irregularities having a function of reflecting and scattering light incident from the first surface side on a second surface which is a main surface opposite to the first surface. It is characterized by being.
As a result, it is possible to provide a timepiece dial that is excellent in durability, black, high-class and excellent in aesthetic appearance.

In the timepiece dial of the present invention, it is preferable that the irregularities are regularly arranged, and the average pitch is 10 to 28 μm.
Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent.
In the timepiece dial of the present invention, it is preferable that the height difference of the unevenness is 4 to 25 μm.
Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent.

In the timepiece dial of the present invention, the timepiece dial preferably includes a compound film made of silicon oxide, titanium oxide, or silicon carbide between the substrate and the carbon film. .
Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent, and the durability of the timepiece dial can be made particularly excellent.

In the timepiece dial of the present invention, it is preferable that the carbon film is provided so as to cover the entire substrate when the timepiece dial is viewed in plan.
Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent.
In the timepiece dial of the present invention, it is preferable that the average thickness of the carbon film is 50 to 400 nm.
Thereby, while making the aesthetic appearance of the timepiece dial sufficiently excellent, the light transmittance of the timepiece dial as a whole can be made particularly high. Therefore, the timepiece dial can be suitably applied to a solar timepiece.

In the timepiece dial of the present invention, the carbon film is preferably provided so as to partially cover the substrate when the timepiece dial is viewed in plan.
Thereby, the light transmittance as the whole timepiece dial can be reliably increased. Therefore, the timepiece dial can be suitably applied to a solar timepiece.
In the timepiece dial of the present invention, the carbon film is preferably provided in a number of island shapes.
Thereby, while making the aesthetic appearance of the timepiece dial sufficiently excellent, the light transmittance of the timepiece dial as a whole can be made particularly high.

In the timepiece dial of the present invention, the average thickness of the carbon film is preferably 50 to 800 nm.
Thereby, while making the aesthetic appearance of the timepiece dial sufficiently excellent, the light transmittance of the timepiece dial as a whole can be made particularly high.
In the timepiece dial of the present invention, the ratio of the area covered with the carbon film when the timepiece dial is viewed in plan is preferably 30 to 70%.
Thereby, while making the aesthetic appearance of the timepiece dial sufficiently excellent, the light transmittance of the timepiece dial as a whole can be made particularly high.

The method for manufacturing a timepiece dial of the present invention includes a substrate preparation step of preparing a substrate having minute irregularities on one main surface,
And a carbon film forming step of forming a carbon film mainly composed of carbon on a main surface opposite to the main surface on which the unevenness of the substrate is provided.
Thereby, while being excellent in durability, the manufacturing method which can manufacture suitably the dial for timepieces which is black, is full of high-class feelings, and was excellent in the aesthetic appearance can be provided.

In the timepiece dial manufacturing method of the present invention, in the carbon film forming step, a large number of openings are provided in a predetermined pattern on a main surface side of the substrate opposite to the main surface on which the unevenness is provided. It is preferable that the film is formed in a state in which the mask is arranged.
Thereby, the light transmittance as the whole timepiece dial can be reliably increased. Therefore, the timepiece dial can be suitably applied to a solar timepiece. Further, the productivity of the timepiece dial can be improved.

In the timepiece dial manufacturing method of the present invention, the carbon film forming step uses a material including a magnetic material as the mask, and a surface side of the substrate opposite to the surface facing the mask. It is preferable that the mask and the work on which the carbon film is to be formed are in close contact with each other by a magnet disposed on the surface.
As a result, it is possible to more reliably prevent film formation on a portion other than the target on the substrate, and to ensure excellent aesthetic appearance and light transmittance of the finally obtained dial for a watch. can do. That is, the reliability of the manufactured timepiece dial can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, prior to the carbon film forming step,
It is preferable to have a compound film forming step of forming a compound film made of silicon oxide, titanium oxide or silicon carbide on the main surface opposite to the main surface on which the unevenness of the substrate is provided.
Thereby, the aesthetic appearance of the manufactured timepiece dial can be made particularly excellent, and 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.
As a result, it is possible to provide a timepiece having a timepiece dial that is excellent in durability, black, high-class and excellent in aesthetic appearance.

  ADVANTAGE OF THE INVENTION According to this invention, while providing the timepiece dial which is excellent in durability, is black, is full of sense of quality, and was excellent in the external appearance, the manufacturing method which can manufacture the said timepiece dial suitably is provided. In addition, a timepiece having the timepiece dial can be provided.

It is sectional drawing which shows 1st Embodiment of the dial for timepieces of this invention. It is a top view which shows typically the example of the uneven | corrugated arrangement pattern which a board | substrate has. It is a top view which shows typically the example of the uneven | corrugated arrangement pattern which a board | substrate has. It is a top view which shows typically the example of the uneven | corrugated arrangement pattern which a board | substrate has. It is a top view which shows typically the example of the uneven | corrugated arrangement pattern which a board | substrate has. It is a top view which shows typically the example of the uneven | corrugated arrangement pattern which a board | substrate has. It is sectional drawing which shows 1st Embodiment of the manufacturing method of the timepiece dial of this invention. It is sectional drawing which shows 2nd Embodiment of the dial for timepieces of this invention. It is a top view which shows an example of the dial for timepieces shown in FIG. It is a top view which shows another example of the timepiece dial shown in FIG. It is a top view which shows another example of the timepiece dial shown in FIG. It is sectional drawing which shows 2nd Embodiment of the manufacturing method of the dial for timepieces of this invention. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (portable timepiece) of this invention.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
<< First Embodiment >>
First, a first embodiment of a timepiece dial and a manufacturing method thereof according to the present invention will be described.
<Watch dial>
First, a first embodiment of the timepiece dial of the present invention will be described.

FIG. 1 is a cross-sectional view showing a first embodiment of the timepiece dial of the present invention, and FIGS. 2 to 6 are plan views schematically showing an example of an uneven pattern of the substrate.
As shown in FIG. 1, the timepiece dial 1 according to the present embodiment is provided on the substrate 2 made of a light-transmitting material and on the first surface 21 side which is one main surface of the substrate 2. Further, it has a carbon film 3 mainly composed of carbon, and a compound film 4 provided between the substrate 2 and the carbon film 3. That is, the timepiece dial 1 of the present embodiment has a configuration in which the substrate 2, the compound film 4, and the carbon film 3 are laminated in this order.

  In the timepiece dial 1, the first surface 21 side of the substrate 2, that is, the surface side covered with the carbon film 3 and the compound film 4 (upper side in FIG. 1) faces the observer side (outer surface side). It is used.

[substrate]
The board | substrate 2 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 2 include various plastic materials and various glass materials. The substrate 2 is preferably mainly composed 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 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 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 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 substrate 2 and the carbon film 3 are in close contact with each other. Property (adhesion through the compound film 4) 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.

Moreover, since the plastic materials as described above are all excellent in radio wave transmission, the timepiece dial 1 made of such a material can be suitably applied to a radio timepiece.
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. For example, when the substrate 2 is made of a material containing a colorant, variations in the color of the timepiece dial 1 can be widened.

The substrate 2 may have a substantially uniform composition at each site, or may have a different composition depending on the site.
The substrate 2 is provided with a carbon film 3 which will be described in detail later on the first surface 21 side. The first surface is formed on the second surface 22 which is the main surface opposite to the first surface 21. It has minute irregularities 221 having a function of reflecting / scattering light incident from the 21 side.

  By the way, in the timepiece dial 1, a part of light irradiated from the surface side (upper side in the drawing) on which the carbon film 3 is provided enters the substrate 2. In particular, in the timepiece dial 1 of the present embodiment, as will be described in detail later, the carbon film 3 has a relatively small thickness, and light from the outside of the timepiece dial 1 (in FIG. 1). Part of the light (from above) can enter the inside of the substrate 2. The light that has entered the substrate 2 through the carbon film 3 travels from the first surface 21 side toward the second surface 22 side, and part of the light exits from the second surface 22 side (that is, The other part is reflected / scattered by the unevenness 221 provided on the second surface 22. Thereby, the light that has once entered the substrate 2 from the first surface 21 side can be emitted again from the first surface 21 side. As a result, the carbon film 3 is irradiated and reflected from the back surface side (lower side in the figure) of the light reflected and scattered by the unevenness 221, and exhibits a glossy black appearance full of luxury. An aesthetic appearance that could not be obtained in the past can be obtained. In addition, since the black carbon film 3 is provided on the observer side of the timepiece dial 1 and the unevenness 221 is provided on the second surface 22 side of the substrate 2, the timepiece It is possible to make it difficult for an observer to visually recognize the state of the back side of the dial 1 for use (the lower side of the dial 1 for timepieces in FIG. 1). That is, it is possible to improve the aesthetic appearance of the timepiece dial 1 while improving the light transmittance of the timepiece dial 1 as a whole. For this reason, the timepiece dial 1 can be suitably applied to a solar timepiece (a timepiece having a solar cell).

  The irregularities 221 may be arranged in any manner, but are preferably arranged regularly when the substrate 2 is viewed in plan. Thereby, it is possible to effectively prevent unintentional color unevenness and the like from occurring in each part (each part in a plan view) of the timepiece dial 1. Examples of the arrangement pattern of the projections and depressions 221 (various arrangement patterns in plan view) include, for example, a pattern in which a large number of ridges and grooves are arranged in a spiral shape (see FIG. 2), and a pattern in which ridges and grooves are arranged in a concentric shape (See FIG. 3), a pattern in which a large number of ridges and grooves are arranged in a one-dimensional direction (see FIG. 4), and a pattern in which a large number of ridges and grooves are arranged in a two-dimensional direction (see FIGS. 5 and 6) Etc.

Pitch of the unevenness 221 (especially, on the second surface 22, ridges, the pitch in the direction perpendicular to the longitudinal direction of the groove) _{P 1} is not particularly limited, but is preferably 10～28Myuemu,. 20 to More preferably, it is 26 μm. When the pitch P _{1 of the} unevenness 221 is a value within the above range, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent.
Further, the height difference (the height difference between the top of the convex portion (projection) and the bottom of the concave portion (groove)) H of the unevenness 221 is not particularly limited, but is preferably 4 to 25 μm, preferably 8 to 13.5 μm. It is more preferable that When the height difference H of the irregularities 221 is a value within the above range, the aesthetic appearance of the timepiece dial 1 is particularly excellent while the light transmittance of the timepiece dial 1 is sufficiently high. be able to.

In the illustrated configuration, the cross-sectional shape of the projections and depressions 221 (the shape in the cross-section perpendicular to the longitudinal direction of the ridges and grooves) is an isosceles triangle. When the uneven shape 221 has such a cross-sectional shape, the light incident from the first surface 21 side can be appropriately reflected and scattered, and the light transmission and aesthetic appearance of the timepiece dial 1 can be achieved. , Especially at a high level.
The vertex angle (θ in the figure) of the unevenness 221 is not particularly limited, but is preferably 70 to 100 °. Thereby, the light incident from the first surface 21 side can be appropriately reflected and scattered, and the light transmission and the aesthetic appearance of the timepiece dial 1 can be made compatible at a very high level. .

  Further, the first surface 21 of the substrate 2 is preferably relatively flat (smooth). Thereby, the aesthetic appearance of the timepiece dial 1 is particularly excellent. Further, the first surface 21 of the substrate 2 may be provided with a pattern such as a radial pattern or a vortex pattern. Thereby, the variation of the design of the timepiece dial 1 can be expanded, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. The surface roughness Ra of the first surface 21 is preferably 0.001 to 5.0 μm, and more preferably 0.001 to 2.5 μm. As a result, the above-described effects are exhibited more significantly.

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 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 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. Further, when the thickness of the substrate 2 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 2 may be formed by any method. Examples of the method for forming the substrate 2 include compression molding, extrusion molding, injection molding, and stereolithography.

[Carbon film]
A carbon film 3 mainly composed of carbon is provided on the first surface 21 side of the substrate 2.
The carbon film 3 exhibits a black color. In the present embodiment, the carbon film 3 has a relatively small thickness, and a part of the light from the outside of the timepiece dial 1 (light from the upper side in FIG. 1) is transferred to the inside of the substrate 2. Can be entered. Thereby, combined with the effect of the unevenness 221 described above, the timepiece dial 1 can have a glossy black appearance full of luxury, and an aesthetic that cannot be obtained in the past. It can have an appearance.

In addition, since the carbon constituting the carbon film 3 is excellent in radio wave permeability, the timepiece dial 1 made of such a material can be suitably applied to a radio timepiece.
In the present embodiment, the average thickness of the carbon film 3 is 50 to 400 nm. Thereby, the aesthetic appearance of the timepiece dial 1 can be made sufficiently excellent. Thus, in the present embodiment, the average thickness of the carbon film 3 is 50 to 400 nm, but is preferably 80 to 300 nm. Thereby, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Further, the durability of the timepiece dial 1 can be made particularly excellent. Further, the light transmission of the timepiece dial 1 as a whole can be secured, and for example, the timepiece dial 1 can be suitably applied to a solar timepiece.
The carbon film 3 is formed by sputtering, and the method for forming the carbon film 3 will be described in detail later.

[Compound film]
A compound film 4 made of silicon oxide, titanium oxide, or silicon carbide is provided between the substrate 2 and the carbon film 3.
By having such a compound film 4, the adhesion between the substrate 2 and the carbon film 3 can be made excellent, and the durability of the timepiece dial 1 can be made excellent.

Further, by having the compound film 4, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. This is considered to be due to the following reasons. That is, in the timepiece dial 1 of the present embodiment, the carbon film 3 described above is black, but has a function of transmitting part of the irradiated light. The light transmitted through the carbon film 3 is suitably reflected and refracted at the interface between the carbon film 3 and the compound film 4 and the interface between the compound film 4 and the substrate 2, and the light reflected and scattered by the unevenness 221 is By appropriately reflecting and refracting at the interface between the substrate 2 and the compound film 4 and at the interface between the compound film 4 and the carbon film 3, the timepiece dial 1 has a better aesthetic appearance to the observer. Be recognized.
In addition, since silicon oxide, titanium oxide, and silicon carbide are all excellent in radio wave transmission, the timepiece dial 1 made of such a material is preferably applied to a radio timepiece. Can do.

  The average thickness of the compound film 4 is not particularly limited, but is preferably 10 to 100 nm, and more preferably 15 to 80 nm. When the average thickness of the compound film 4 is a value within the above range, the aesthetic appearance of the timepiece dial 1 is sufficiently excellent, and the durability of the timepiece dial 1 is particularly excellent. Can do. Further, the light transmittance of the timepiece dial 1 as a whole can be made particularly excellent.

In particular, when the compound film 4 is composed of silicon oxide, the average thickness of the compound film 4 is preferably 15 to 100 nm, and more preferably 20 to 80 nm.
Moreover, when the compound film 4 is comprised by the titanium oxide, it is preferable that the average thickness of the compound film 4 is 15-100 nm, and it is more preferable that it is 20-80 nm.
Further, when the compound film 4 is composed of silicon carbide, the average thickness of the compound film 4 is preferably 10 to 80 nm, and more preferably 15 to 60 nm.

The compound film 4 may have a uniform composition throughout, or may have a different composition at each site. For example, the compound film 4 may be configured by a laminate including a plurality of layers having different compositions in the thickness direction, or configured by a gradient material in which the composition changes in a gradient manner in the thickness direction. It may be what was done.
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, a first embodiment of the method for manufacturing a timepiece dial according to the invention will be described.
FIG. 7 is a cross-sectional view showing a first embodiment of a method for manufacturing a timepiece dial according to the present invention.
As shown in FIG. 7, the timepiece dial manufacturing method of this embodiment includes a substrate preparation step (1 a) for preparing the substrate 2, and silicon oxide and titanium oxide on the first surface 21 of the substrate 2. A compound film forming step (1b) for forming a compound film 4 composed of an oxide or silicon carbide, and a carbon film forming step for forming a carbon film 3 composed mainly of carbon on the compound film 4 by sputtering ( 1c).

[Board preparation process]
As the substrate 2, those described above can be used.
The substrate 2 may be prepared in advance with the second surface 22 provided with irregularities 221. Alternatively, the substrate 2 having a flat surface shape may be subjected to a predetermined treatment, as described above. The substrate 2 having the unevenness 221 may be used. For example, the substrate 2 manufactured by using a mold having irregularities corresponding to the irregularities 221 on the surface corresponding to the second surface 22 may be used, or by cutting using a cutting tool or the like. Alternatively, the substrate 2 on which the unevenness 221 is formed may be used.
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 compound film 4 can be made particularly excellent.

[Compound film forming step]
Next, the compound film 4 made of silicon oxide, titanium oxide, or silicon carbide is formed on the surface of the substrate 2.
The formation method of the compound 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. Examples thereof include chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. The method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film formation method) as a method of forming the compound film 4, the film has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 and the carbon film 3. The compound film 4 can be reliably formed. As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. Further, by applying a dry plating method (vapor phase film forming method) as a method of forming the compound film 4, even if the compound film 4 to be formed is relatively thin, the variation in film thickness is sufficiently small. It can be. Therefore, for example, the electromagnetic wave permeability of the timepiece dial 1 can be improved while the durability of the obtained timepiece dial 1 is sufficiently high. Therefore, the obtained timepiece dial 1 can be more suitably applied to a radio timepiece, a solar timepiece, or the like.
Further, among the dry plating methods (vapor phase film forming methods) as described above, the above effects become more remarkable by applying sputtering.
The formation of the compound film 4 may be performed by combining a plurality of different methods and conditions. Thereby, for example, the compound film 4 composed of a laminate can be suitably formed.

[Carbon film formation process]
Next, a carbon film 3 made of carbon is formed on the surface of the compound film 4 by sputtering.
The treatment conditions in this step are not particularly limited, but the degree of vacuum: 0.1 to 10 Pa, the film formation rate: 3.0 to 20.0 nm / min, the gas used: Ar, the power source power (input power): 800 to It is preferable to carry out under the condition of 1500W. Thereby, the aesthetic appearance and durability of the obtained timepiece dial 1 can be made particularly excellent, and the productivity of the timepiece dial 1 can be made excellent.

The degree of vacuum in this step is preferably 0.1 to 10 Pa as described above, but more preferably 0.3 to 8.0 Pa.
In addition, the film formation rate in this step is preferably 3.0 to 20.0 nm / min as described above, but more preferably 5.0 to 15.0 nm / min.
Further, the power source power of the sputtering apparatus used in this step is preferably 800 to 1500 W as described above, but more preferably 900 to 1300 W.

As described above, the timepiece dial 1 can be obtained.
The compound film forming step and the carbon film forming step as described above may be performed on the substrate 2 having a size and shape corresponding to the timepiece dial 1 to be manufactured. May be applied to the substrate 2 and then processed into a desired size and shape by punching, cutting or the like.

<< Second Embodiment >>
Next, a second embodiment of the timepiece dial and the manufacturing method thereof according to the present invention will be described. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.
<Watch dial>
First, a second embodiment of the timepiece dial of the present invention will be described.

8 is a sectional view showing a second embodiment of the timepiece dial of the present invention, FIG. 9 is a plan view showing an example of the timepiece dial shown in FIG. 8, and FIGS. 10 and 11 are shown in FIG. It is a top view which shows another example of the dial for timepieces shown.
As shown in FIG. 8, the timepiece dial 1 of the present embodiment is provided on the substrate 2 made of a light-transmitting material and on the first surface 21 side which is one main surface of the substrate 2. Further, it has a carbon film 3 mainly composed of carbon, and a compound film 4 provided between the substrate 2 and the carbon film 3, and the carbon film 3 and the compound film 4 are composed of the timepiece dial 1. Is provided so as to partially cover the substrate 2 when viewed in a plan view (provided in a number of islands). That is, in the first embodiment described above, the carbon film 3 and the compound film 4 are provided so as to cover the entire substrate 2 when the timepiece dial 1 is viewed in plan. In the present embodiment, the watch dial 1 is provided so as to partially cover the substrate 2 when viewed in plan (provided in a large number of islands). With such a configuration, the light transmittance of the timepiece dial 1 as a whole can be made particularly excellent. In addition, the light reflected and scattered by the unevenness 221 can be effectively used by improving the aesthetic appearance of the timepiece dial 1, and the appearance of the timepiece dial 1 is more excellent in gloss. be able to. Further, even when the film thickness of the carbon film 3 is relatively large, the amount of light incident on the substrate 2 (the amount of light reflected and scattered by the unevenness 221 of the substrate 2) can be made sufficiently large. The external appearance of the dial 1 can have a more profound feeling of black and a sufficient gloss.

  The above effect is obtained when the carbon film 3 is provided so as to partially cover the substrate 2 when the timepiece dial 1 is viewed in plan view. When the compound film 4 is provided so as to partially cover the substrate 2 when the timepiece dial 1 is viewed in plan, or the carbon film 3 is provided in a number of island shapes. In some cases, it is more prominently exhibited, and even more prominently when the carbon film 3 and the compound film 4 are provided in a number of islands.

  In the timepiece dial 1 of the present embodiment, the average thickness of the carbon film 3 is not particularly limited, but is preferably 50 to 800 nm, and more preferably 100 to 600 nm. When the average thickness of the carbon film 3 is a value within the above range, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Further, the light transmission of the timepiece dial 1 as a whole can be secured, and for example, the timepiece dial 1 can be suitably applied to a solar timepiece. Further, the durability of the timepiece dial 1 can be made particularly excellent.

  When the substrate 2 (timepiece dial 1) is viewed in plan, the ratio (coverage) of the area covered with the carbon film 3 is preferably 30 to 70%, and preferably 35 to 55%. Is more preferable, and it is still more preferable that it is 40 to 50%. When the coverage 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 (external light) transmittance is sufficiently excellent. . On the other hand, when the coverage is less than the lower limit value, it is difficult to make the timepiece dial 1 sufficiently excellent in aesthetic appearance depending on the thickness of the carbon film 3 and the like. On the other hand, when the coverage exceeds the upper limit, the effect of providing the carbon film 3 (and the compound film 4) so as to partially cover the substrate 2 as described above is sufficiently exhibited. It becomes difficult.

  Each carbon film 3 (each island-like region) may have any shape and arrangement pattern. In the configuration shown in FIG. 9, the shape of the carbon film 3 is substantially circular. If the carbon film 3 has such a shape, a number of island-like carbon films 3 can be easily and reliably formed by a method as described later. Further, when the carbon film 3 has such a shape, the appearance of the timepiece dial 1 is more likely to have a region where the carbon film 3 is not provided when the timepiece dial 1 is viewed in plan. In addition to being inconspicuous, the productivity of the timepiece dial 1 can be made particularly excellent. The carbon film 3 may have a shape and an arrangement pattern as shown in FIGS. 9 to 11, the display of the unevenness 221 included in the substrate 2 is omitted.

The width W ₂ of the carbon film 3 (when the carbon film 3 is substantially circular) W ₂ is preferably 70 to 600 μm, more preferably 90 to 500 μm, and 100 to 300 μm. Is more preferable. If the width W ₂ of the carbon film 3 is within this range, while a particularly high light permeability of the timepiece dial 1, particularly outstanding appearance of the timepiece dial 1 (aesthetics) Can be.

Further, the pitch P _{2 of the} carbon film 3 is preferably 100 to 750 μm, more preferably 130 to 600 μm, and further preferably 160 to 450 μm. When the pitch P ₂ of the carbon film 3 is within this range, while a particularly high light permeability of the timepiece dial 1, a particularly outstanding appearance of the timepiece dial (aesthetics) Can be. The pitch of the carbon film 3 refers to the distance between the centers of the adjacent carbon films 3 to 3, and when there are a plurality of adjacent carbon films 3, Refers to the distance between centers.
In the present embodiment, the compound film 4 is provided in a shape and pattern corresponding to the carbon film 3, that is, in a shape and pattern that completely overlaps with the carbon film 3 when the timepiece dial 1 is viewed in plan. ing. Thereby, the aesthetic appearance of the timepiece dial 1 is particularly excellent.

<Manufacturing method of timepiece dial>
Next, a second embodiment of the timepiece dial manufacturing method of the present invention will be described.
FIG. 12 is a cross-sectional view showing a second embodiment of the method for manufacturing a timepiece dial according to the invention.
As shown in FIG. 12, in the manufacturing method of the present embodiment, a substrate preparation step (2 a) for preparing the substrate 2 and a large number of openings 61 are provided in a predetermined pattern on the first surface 21 of the substrate 2. In the state where the mask 6 is disposed, the compound film forming step (2b, 2c) for forming a large number of compound films 4 on the first surface 21 of the substrate 2 and the first of the substrate 2 are performed. In the state where the mask 6 provided with a large number of openings 61 in a predetermined pattern is arranged on the surface 21 side, a film is formed by a sputtering method, so that a large number of island-shaped elements mainly composed of carbon are formed. A carbon film forming step (2d) for forming the carbon film 3 and a mask removing step (2e) for removing the mask 6 are included. That is, the manufacturing method of the present embodiment is different from the above-described embodiment in that the mask 6 is used in the compound film forming step and the carbon film forming step, and the mask removing step is included. Thus, by forming the compound film 4 and the carbon film 3 by film formation using the mask 6, the desired shape, pattern compound film 4 and carbon film 3 can be reliably formed. For this reason, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent, and the light transmittance of the timepiece dial 1 as a whole can be reliably increased. Therefore, the timepiece dial 1 can be suitably applied to a solar timepiece. Also, the productivity of the timepiece dial 1 can be improved.

[Compound film forming step]
In this embodiment, silicon oxide, titanium oxide, or silicon is formed by performing film formation in a state where the mask 6 having openings 61 provided in a predetermined pattern is disposed on the first surface 21 of the substrate 2. A compound film 4 made of carbide is formed (2b, 2c).
As described above, in the present embodiment, the compound film 4 is formed by performing the film formation with the mask 6 disposed, thereby forming a large number of shapes, sizes, and patterns corresponding to the openings 61 of the mask 6. The individual island-shaped compound films 4 can be formed easily and reliably. Further, since the mask 6 can be used repeatedly in the production of a large number of timepiece dials 1, the productivity of the timepiece dial 1 is improved and the quality variation among the timepiece dials 1 is also 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 6 having openings 61 having patterns corresponding to the compound film 4 to be formed, the compound film 4 having various patterns can be obtained without greatly changing the formation conditions of the compound film 4. The production of the timepiece dial 1 can be suitably handled. That is, it is possible to efficiently cope with multi-product production.

In addition, by forming the compound film 4 by film formation using the mask 6, the compound film 4 having the same shape, size and pattern as the carbon film 3 can be formed easily and reliably. 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 of the compound 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. Examples thereof include chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. The method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film formation method) as a method of forming the compound film 4, the film has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 and the carbon film 3. The compound film 4 can be reliably formed. As a result, the aesthetic appearance and durability of the finally obtained timepiece dial 1 can be made particularly excellent. Further, by applying a dry plating method (vapor phase film forming method) as a method of forming the compound film 4, even if the compound film 4 to be formed is relatively thin, the variation in film thickness is sufficiently small. It can be. Therefore, for example, the electromagnetic wave permeability of the timepiece dial 1 can be improved while the durability of the obtained timepiece dial 1 is sufficiently high. Therefore, the obtained timepiece dial 1 can be more suitably applied to a radio timepiece, a solar timepiece, or the like.

Further, among the dry plating methods (vapor phase film forming methods) as described above, the above effects become more remarkable by applying sputtering.
The formation of the compound film 4 may be performed by combining a plurality of different methods and conditions. Thereby, for example, the compound film 4 composed of a laminate can be suitably formed.
The mask 6 used in this step has openings 61 arranged in a pattern corresponding to a large number of compound films 4 to be formed. That is, the mask 6 has openings 61 at portions corresponding to a large number of compound films 4 to be formed.

Such a mask 6 is prepared, for example, as a plate-like member, and subjected 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 61.
Although the thickness of the mask 6 depends on the thickness of the compound film 4 and the carbon film 3 to be formed, it is preferably 30 to 200 μm, more preferably 40 to 120 μm.

  The mask 6 may be made of any material, and examples of the constituent material of the mask 6 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 6. When the mask 6 is made of a metal material, the durability of the mask 6 can be made particularly excellent. As a result, the productivity of the timepiece dial 1 can be made particularly excellent, and variations in quality among a large number of timepiece dials 1 can be suppressed, and the reliability of the timepiece dial 1 can be reduced. Will improve. In addition, metal materials generally have moderate elasticity, and many have high shape followability, and the substrate 2 (watch dial 1 to be manufactured) is not limited to a flat plate, but a curved plate. Even if it is in a shape, it can be suitably applied. In addition, one type of mask 6 can be used in common for differently shaped substrates 2 (for example, flat substrate 2 and curved plate substrate 2).

  In particular, in this embodiment, the mask 6 is made of a material including a magnetic material (a material having ferromagnetism). A magnet (not shown) is disposed on the surface (second surface 22) opposite to the surface (first surface 21) facing the mask 6 of the substrate 2, so that the mask 6 and the compound can be combined. The substrate 4 as the work on which the film 4 (and the carbon film 3) is to be formed can be reliably adhered. As a result, it is possible to more reliably prevent the compound film 4 (and the carbon film 3 in the later-described process) from being formed on the substrate 2 at a site other than the target, and the finally obtained timepiece The aesthetic appearance and light transmittance of the dial 1 can be reliably improved. 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 6 is made of a material containing a magnetic material, but the mask 6 may be made of substantially only a magnetic material, for example. However, it may contain other components.
The mask 6 may have a surface layer (not shown). Thereby, for example, the durability of the mask 6 can be made particularly excellent, or the constituent material of the compound film 4 (and the constituent material of the carbon film 3) is formed on the mask 6 at the time of vapor deposition. It is possible to effectively prevent the strong adhesion. 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.

[Carbon film formation process]
Next, a carbon film 3 is formed by performing film formation on the compound film 4 formed as described above in a state where the mask 6 is disposed (2d).
In this way, by forming a film with the mask 6 arranged, a large number of island-like carbon films 3 can be easily and reliably formed in a shape, size, and pattern corresponding to the opening 61 of the mask 6. Can be formed. In addition, when the timepiece dial 1 is viewed in plan without requiring post-treatment after film formation, an area not covered with the carbon film 3 is formed. The carbon film 3 having a desired shape can be formed, and the productivity of the timepiece dial 1 can be improved. Further, since the mask 6 can be used repeatedly in the production of a large number of timepiece dials 1, the productivity of the timepiece dial 1 is improved and the quality variation among the timepiece dials 1 is also 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 6 having openings 61 having patterns corresponding to the carbon film 3 to be formed, the carbon film 3 having various patterns can be obtained without greatly changing the formation conditions of the carbon film 3. The production of the timepiece dial 1 can be suitably handled. That is, it is possible to efficiently cope with multi-product production.

  As the mask 6, a mask different from that used in the above-described compound film forming process (for example, a mask having a larger opening than the mask used in the compound 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 6 as that used in the compound film forming step. Further, in this process, when the same mask 6 used in the compound film forming process is used, the process is continued without removing the mask 6 from the substrate 2 after the compound film forming process described above. It is preferred to do so. As a result, it is possible to reliably prevent an unintentional displacement between the compound film 4 and the carbon film 3 and improve the productivity of the timepiece dial 1.

The processing method (sputtering method) and processing conditions (vacuum degree, film forming speed, gas used, power supply power (input power)) in this step are preferably the same as those described in the above-described embodiment.
In the present embodiment, this step is also the surface (second surface 22) opposite to the surface (first surface 21) facing the mask 6 of the substrate 2 as in the above-described compound film forming step. A magnet (not shown) is arranged on the side, whereby the mask 6 and the substrate 2 as the workpiece on which the carbon film 3 is to be formed (the substrate 2 provided with the compound film 4) are in close contact with each other. Do. As a result, it is possible to more reliably prevent the carbon film 3 from being formed on a portion other than the target on the substrate 2, 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.

[Mask removal process]
Next, the mask 6 is removed from the substrate 2 (2e). Thereby, in the first surface 21 of the substrate 2, the portion corresponding to the opening 61 of the mask 6 is in a state where the surface of the substrate 2 is exposed, and the other portion is covered with the compound film 4 and the carbon film 3. It will be in the state.
The mask 6 can be removed by peeling the mask 6 from the substrate 2 on which the compound film 4 and the carbon film 3 are provided.

As described above, the timepiece dial 1 can be obtained.
The compound film forming step and the carbon film forming step as described above may be performed on the substrate 2 having a size and shape corresponding to the timepiece dial 1 to be manufactured. May be applied to the substrate 2 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, but an example of the configuration of the timepiece of the present invention is described below. explain.

FIG. 13 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 13, a 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 the solar cell 94 and a glass plate (cover glass) 85, and the first surface 21 is disposed so as to face the glass plate (cover glass) 85 side. Yes. That is, the carbon film 3 is disposed between the substrate 2 and the glass plate (cover glass) 85.

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. 13, 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. Further, at least one layer may be provided on the surface of the timepiece dial (the surface on the side where the carbon film is provided or the surface on the side where the unevenness of the substrate is provided). Such a layer may be removed, for example, when the timepiece dial is used.

  Further, in the second embodiment described above, the compound film 4 is described as being provided in an island shape at a portion corresponding to a large number of carbon films 3, but the compound film 4 is provided in an island shape. It does not have to be. In such a case, for example, in the compound film forming step of the manufacturing method as described above, the compound film can be suitably formed by performing film formation without using a mask.

Further, the timepiece dial of the present invention may not be provided with the compound film as described above.
In the above-described embodiment, the unevenness of the substrate is described as being provided on the entire second surface. However, the unevenness may be provided on a part of the second surface. . For example, as in the second embodiment described above, when the timepiece dial is viewed in plan, when the carbon film is provided so as to partially cover the substrate, the unevenness is When the dial is viewed in plan, it may be selectively provided in a region including a portion that overlaps the region between the carbon film and the carbon film.

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.

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: 500 μm. Further, the obtained substrate is such that the first surface which is one main surface is smooth, and regularly over the entire second surface which is the main surface opposite to the first surface, It had the uneven | corrugated pattern which consists of the protruding item | line and groove | channel provided in the spiral shape (refer FIG. 2). The pitch of the unevenness was 25 μm. Moreover, the height difference of the unevenness (the height difference between the top of the ridge and the bottom of the groove) was 12.5 μm. The cross-sectional shape of the unevenness is an isosceles triangle, and the angle of the apex of the unevenness (θ in FIG. 1) was 90 °.

Next, this substrate was cleaned. The substrate was first washed with a neutral plastic detergent for 30 seconds, then neutralized for 10 seconds, washed with water for 30 seconds, and washed with pure water for 60 seconds. Then, it dried for 20 minutes in oven (80 degreeC).
A compound film composed of silicon oxide was formed on the surface of the substrate thus cleaned by sputtering as described below (compound film forming step).

First, a cleaned substrate is mounted in a film forming apparatus, and then the inside of the apparatus is evacuated (depressurized) to 3 × 10 ⁻³ Pa, and then argon gas is introduced at an argon gas flow rate of 35 ml / min. The pressure (degree of vacuum) was 1.2 Pa. In such a state, silicon oxide (SiO ₂ ) is used as a target, and discharge is performed under the conditions of input power (power supply power): 1000 W and processing time: 10 minutes, so that silicon is formed on the first surface of the substrate. A compound film composed of oxide (SiO ₂ ) was formed. The average thickness of the compound film thus formed was 50 nm.

Subsequently, a timepiece dial was obtained by forming a carbon film on the surface of the compound film as follows (carbon film forming step). That is, 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 to set the pressure (degree of vacuum) in the apparatus to 1.2 Pa. . In such a state, carbon (C) is used as a target, discharge is performed under the conditions of input power (power supply power): 1000 W, film formation rate: 8.3 nm / min, and processing time: 30 minutes. A carbon film composed of C) was formed. The carbon film thus formed had an average thickness of 250 nm.
In addition, the thickness of the substrate, the compound film, and the carbon film was measured in accordance with a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 4)
By changing the processing conditions in the carbon film forming step as shown in Table 1, and changing the processing time in the compound film forming step, the thickness of the substrate, the constituent material, and the unevenness conditions of the substrate, A timepiece dial was manufactured in the same manner as in Example 1 except that the structure shown in the figure was used.

(Example 5)
In the compound film forming step, a timepiece dial was manufactured in the same manner as in Example 1 except that a thin film composed of TiO ₂ having a purity of 99% or more was used as a target.
(Examples 6 to 8)
By changing the processing conditions in the carbon film forming step as shown in Table 1, and changing the processing time in the compound film forming step, the thickness of the substrate, the constituent material, and the unevenness conditions of the substrate, A timepiece dial was manufactured in the same manner as in Example 5 except that the structure shown in the figure was used.

Example 9
In the compound film forming step, a timepiece dial was manufactured in the same manner as in Example 1 except that a thin film composed of SiC having a purity of 99% or more was used as a target.
(Examples 10 to 12)
By changing the processing conditions in the carbon film forming step as shown in Table 1, and changing the processing time in the compound film forming step, the thickness of the substrate, the constituent material, and the unevenness conditions of the substrate, A timepiece dial was manufactured in the same manner as in Example 9 except that the structure shown in the figure was used.

(Example 13)
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: 500 μm. Further, the obtained substrate is such that the first surface which is one main surface is smooth, and regularly over the entire second surface which is the main surface opposite to the first surface, It had the uneven | corrugated pattern which consists of the protruding item | line and groove | channel provided in the spiral shape (refer FIG. 2). The pitch of the unevenness was 25 μm. Moreover, the height difference of the unevenness (the height difference between the top of the ridge and the bottom of the groove) was 12.5 μm. The cross-sectional shape of the unevenness is an isosceles triangle, and the angle of the apex of the unevenness (θ in FIG. 1) was 90 °.

Next, this substrate was cleaned. The substrate was first washed with a neutral plastic detergent for 30 seconds, then neutralized for 10 seconds, washed with water for 30 seconds, and washed with pure water for 60 seconds. Then, it dried for 20 minutes in oven (80 degreeC).
A compound film composed of silicon oxide was formed on the surface of the substrate thus cleaned by sputtering as described below (compound film forming step).

In the compound film, circular openings are arranged in a staggered pattern on the surface (first surface) of the substrate (so that the center of the opening is located at a portion corresponding to each vertex of the equilateral triangle) It was formed by sputtering in a state where a mask (see FIG. 9) was placed.
The mask was made of stainless steel (SUS430), and its thickness was 50 μm. The diameter of the opening was 160 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 40%.
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, a cleaned substrate is mounted in a film forming apparatus, and then the inside of the apparatus is evacuated (depressurized) to 3 × 10 ⁻³ Pa, and then argon gas is introduced at an argon gas flow rate of 35 ml / min. The pressure (degree of vacuum) was 1.2 Pa. In such a state, silicon oxide (SiO ₂ ) is used as a target, and discharge is performed under the conditions of input power (power supply power): 1000 W and processing time: 10 minutes, so that silicon is formed on the first surface of the substrate. A compound film composed of oxide (SiO ₂ ) was formed. The average thickness of the compound film thus formed was 50 nm.

Subsequently, a timepiece dial was obtained by forming a carbon film on the surface of the compound film (carbon film forming step).
The carbon film was formed following the above-described process without removing the substrate covered with the compound film from the sputtering apparatus and without relatively moving the substrate and the mask.

This step was performed under the following conditions. That is, 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 to set the pressure (degree of vacuum) in the apparatus to 1.2 Pa. . In such a state, carbon (C) is used as a target, discharge is performed under the conditions of input power (power supply power): 1000 W, film formation rate: 8.3 nm / min, and processing time: 42 minutes. A carbon film composed of C) was formed. The carbon film thus formed had an average thickness of 350 nm.
In addition, the thickness of the substrate, the compound film, and the carbon film was measured in accordance with a microscope cross-sectional test method defined in JIS H5821.

(Examples 14 to 16)
The processing conditions in the carbon film forming process are changed as shown in Tables 1 and 2, and the processing time in the compound film forming process, the thickness of the substrate, the constituent materials, the unevenness conditions of the substrate, the compound film forming process, and A timepiece dial was manufactured in the same manner as in Example 13 except that the conditions shown in Table 1 and Table 2 were changed by changing the conditions of the mask used in the carbon film forming step.
(Example 17)
In the compound film forming step, a timepiece dial was manufactured in the same manner as in Example 13 except that a thin film made of TiO ₂ having a purity of 99% or more was used as a target.

(Examples 18 to 20)
While changing the processing conditions in the carbon film forming process as shown in Table 2, the processing time of the compound film forming process, the thickness of the substrate, the constituent materials, the conditions of the unevenness of the substrate, the compound film forming process and the carbon film forming A timepiece dial was manufactured in the same manner as in Example 17 except that the configuration shown in Table 2 was obtained by changing the conditions of the mask used in the process.

(Example 21)
In the compound film forming step, a timepiece dial was manufactured in the same manner as in Example 13 except that a thin film composed of SiC having a purity of 99% or more was used as a target.
(Examples 22 to 24)
While changing the processing conditions in the carbon film forming process as shown in Table 2, the processing time of the compound film forming process, the thickness of the substrate, the constituent materials, the conditions of the unevenness of the substrate, the compound film forming process and the carbon film forming A timepiece dial was manufactured in the same manner as in Example 21 except that the configuration shown in Table 2 was obtained by changing the conditions of the mask used in the process.

(Comparative Example 1)
A timepiece dial was manufactured in the same manner as in Example 1 except that a black coating film was formed by brushing instead of forming a carbon film by sputtering. For the formation of the coating film, a paint composed of carbon black, polyurethane resin and cyclohexane was used. The formed coating film was mainly composed of a polyurethane resin.

(Comparative Example 2)
A watch dial was manufactured in the same manner as in Example 1 except that a substrate having a smooth second surface and no minute irregularities was used. The surface roughness Ra of the second surface of the substrate was 0.1 μm.
(Comparative Example 3)
A watch dial was manufactured in the same manner as Comparative Example 2 except that a carbon film was formed directly on the surface of the cleaned substrate without forming a compound film.

  In addition, as for the board | substrate used for manufacture of the timepiece dial of each said Example and each comparative example, surface roughness Ra of the 1st surface is the value in the range of 0.07-0.15 micrometer in all. Met. In the timepiece dial of each of the above examples and comparative examples, the surface roughness Ra of the carbon film (surface roughness Ra of the surface opposite to the surface facing the substrate) is 0. The value was within the range of 07 to 0.10 μm. In addition, the substrates used in each of the above examples and comparative examples each have a visible light transmittance when a white fluorescent lamp (manufactured by Toshiba Corporation, inspection fluorescent lamp FL20S-D65) is used as a light source. It was 60% or more.

  Tables 1 and 2 collectively show the structure of the timepiece dial of each example and each comparative example. In Tables 1 and 2, polycarbonate is PC, acrylonitrile-butadiene-styrene copolymer (ABS resin) is ABS, acrylic resin is Ac, and polyethylene terephthalate is PET. In Tables 1 and 2, in the column of “concave / convex arrangement pattern”, as shown in FIG. 2, a pattern in which a large number of ridges and grooves are arranged in a spiral shape is indicated by “a”, and FIG. As shown in FIG. 4, a pattern in which ridges and grooves are concentrically arranged is indicated by “b”, and as shown in FIG. 4, a pattern in which a large number of ridges and grooves are arranged in a one-dimensional direction is indicated by “c”. It showed in. In Tables 1 and 2, the coverage column shows the ratio of the area covered with the carbon film (the occupation ratio of the carbon film) when the timepiece dial (substrate) is viewed in plan. In Tables 1 and 2, in the column of “shape and arrangement pattern” for the carbon film, the shape and arrangement pattern as shown in FIG. 9 are indicated by “A”, and the shape and arrangement as shown in FIG. A pattern is indicated by “B”, a shape and an arrangement pattern as shown in FIG. 11 are indicated by “C”, and a film provided on the entire first surface side of the substrate is indicated by “D”. However, the coverage may be different from that shown in FIGS. Moreover, about the comparative example 1, the conditions of the coating film formed using the coating material were shown in the column about a carbon film. Moreover, the content rate of the material shown in Table 1 and Table 2 in each site | part of the timepiece dial of each said Example and each comparative example was 99.9 wt% or more.

2. Appearance evaluation of wristwatch dial For each wristwatch dial manufactured in each of the above examples and comparative examples, from the first surface side of the substrate (surface side provided with the carbon film), visual observation is performed, These appearances were evaluated according to the following seven-stage criteria.
A: It has a high-class feeling and has an extremely excellent appearance.
B: It has a high-class feeling and has a very good appearance.
C: It has an excellent appearance.
D: It has a good appearance.
E: Appearance is slightly poor.
F: Appearance is poor.
G: 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 six criteria. It can be said that the larger the light transmittance, the better the light transmittance of the timepiece dial. The timepiece dial was superimposed on the solar cell so that the first surface of the substrate (the surface on which the carbon film was provided) faced the white fluorescent lamp (light source) side. Further, as the white fluorescent lamp, a white fluorescent lamp (manufactured by Toshiba, fluorescent lamp for inspection FL20S-D65) was used.

A: 40% or more.
B: 34% or more and less than 40%.
C: 28% or more and less than 34%.
D: 22% or more and less than 28%.
E: 17% or more and less than 22%.
F: Less than 17%.

  Thereafter, a wristwatch as shown in FIG. 13 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 carbon film was 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.

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 carbon film was 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). Durability Evaluation of Watch Dials Each watch dial plate manufactured in each of the above Examples and Comparative Examples was subjected to the following two tests to evaluate the durability of the watch dial plate.
5-1. Bending test Each watch dial was bent at 25 ° with respect to the center of the watch dial, using an iron bar with a diameter of 3.5 mm as a fulcrum, 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 coating film (carbon film, compound film or coating film) is observed at all.
B: Floating of the coating (carbon film, compound film or coating) is hardly observed.
C: The float of the film (carbon film, compound film or paint film) is clearly recognized.
D: Cracking and peeling of the coating (carbon film, compound film or coating) are clearly recognized.

5-2. 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 at −25 ° 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 coating film (carbon film, compound film or coating film) is observed at all.
B: Floating of the coating (carbon film, compound film or coating) is hardly observed.
C: The float of the film (carbon film, compound film or paint film) is clearly recognized.
D: Cracking and peeling of the coating (carbon film, compound film or coating) are clearly recognized.
These results are shown in Table 3.

As can be seen from Table 3, all of the timepiece dials of the present invention had an excellent aesthetic appearance (aesthetic appearance exhibiting a high-quality black color) and were excellent in durability. The timepiece dial of the present invention was also excellent in electromagnetic wave (light, radio wave) permeability.
On the other hand, in the comparative example, a satisfactory result was not obtained. That is, the timepiece dial of each comparative example could not achieve both excellent aesthetic appearance and durability as a timepiece dial.
Further, a timepiece as shown in FIG. 13 was assembled using the timepiece dials obtained in each Example and each Comparative Example. Each timepiece thus obtained was tested and evaluated in the same manner as described above, and the same results as described above were obtained.

  DESCRIPTION OF SYMBOLS 1 ... Timepiece dial 2 ... Board | substrate (base material) 21 ... 1st surface 22 ... 2nd surface 221 ... Concavity and convexity 3 ... Carbon film 4 ... Compound film 6 ... Mask 61 ... Opening part 94 ... Solar cell 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 (sealing part) 100 ... Watch (portable watch)

Claims (15)

A substrate made of a light-transmitting material;
A carbon film mainly composed of carbon provided on the first surface side which is one main surface of the substrate;
The substrate has minute irregularities having a function of reflecting and scattering light incident from the first surface side on a second surface which is a main surface opposite to the first surface. A clock dial characterized by being.   The timepiece dial according to claim 1, wherein the unevenness is regularly arranged, and an average pitch thereof is 10 to 28 μm.   The timepiece dial according to claim 1 or 2, wherein the height difference of the unevenness is 4 to 25 µm.   The timepiece dial according to any one of claims 1 to 3, wherein the timepiece dial plate includes a compound film made of silicon oxide, titanium oxide, or silicon carbide between the substrate and the carbon film. Dial.   5. The timepiece dial according to claim 1, wherein the carbon film is provided so as to cover the entire substrate when the timepiece dial is viewed in plan.   The timepiece dial according to claim 5, wherein the carbon film has an average thickness of 50 to 400 nm.   The timepiece dial according to any one of claims 1 to 4, wherein the carbon film is provided so as to partially cover the substrate when the timepiece dial is viewed in plan.   The timepiece dial according to claim 7, wherein the carbon film is provided in a number of island shapes.   The timepiece dial according to claim 7 or 8, wherein the carbon film has an average thickness of 50 to 800 nm.   The timepiece dial according to any one of claims 7 to 9, wherein a ratio of the area covered with the carbon film when the timepiece dial is viewed in plan is 30 to 70%. A substrate preparation step of preparing a substrate having minute irregularities on one main surface;
And a carbon film forming step of forming a carbon film mainly composed of carbon on a main surface opposite to the main surface on which the unevenness of the substrate is provided. .   In the carbon film forming step, film formation is performed in a state where a mask having a large number of openings in a predetermined pattern is arranged on the main surface side of the substrate opposite to the main surface on which the unevenness is provided. The method for manufacturing a timepiece dial according to claim 11, wherein the timepiece dial is used.   In the carbon film forming step, the mask is made of a material containing a magnetic material, and the mask is formed by a magnet disposed on the surface of the substrate opposite to the surface facing the mask. The timepiece dial manufacturing method according to claim 12, wherein the timepiece dial is performed in close contact with a work on which a carbon film is to be formed. Prior to the carbon film forming step,
14. The compound film forming step of forming a compound film made of silicon oxide, titanium oxide or silicon carbide on a main surface opposite to the main surface on which the unevenness of the substrate is provided. A method for manufacturing a timepiece dial described in any one of the above.   A timepiece comprising the timepiece dial according to claim 1.

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