JP2008151549A - Clock dial and clock - Google Patents

Abstract

An object of the present invention is to provide a timepiece dial having excellent electromagnetic wave (radio wave, light) permeability, aesthetic appearance and durability, and a timepiece having the timepiece dial.
A timepiece dial 1 is provided with a base 2 mainly made of polycarbonate, a silicon oxide layer 3 mainly made of silicon oxide, and adjacent to the silicon oxide layer 3, and mainly. Dispersion of fine particles 51 in which fine particles 51 made of SiO ₂ are dispersed on a surface opposite to the surface opposite to the silicon oxide layer 3 of the zinc sulfide layer 4 made of zinc sulfide. Layer 5. The average particle diameter of the fine particles 51 is preferably 10 to 100 nm.
[Selection] Figure 1

Description

  The present invention relates to 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.

  In addition, for example, in radio timepieces and solar timepieces (timepieces equipped with solar cells), the timepiece dial is required to have electromagnetic wave (radiowave, light) permeability. For this reason, plastic dials have been used as such timepiece dials. However, since plastic lacks a high-class feeling, it is made of a metal material for the purpose of improving the aesthetic appearance of the timepiece dial. There is an attempt to coat with a thin film. However, as described above, there is a problem that plastic is inferior in adhesion to a metal material. In addition, in order to increase the transparency of electromagnetic waves (radio waves, light), it is necessary to reduce the thickness of the thin film sufficiently. However, in such a case, the aesthetic appearance of the watch dial as a whole deteriorates. There was a point.

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

  SUMMARY OF THE INVENTION An object of the present invention is to provide a timepiece dial having excellent electromagnetic wave (radio wave, light) permeability, aesthetic appearance and durability, and a timepiece having the timepiece dial. There is.

Such an object is achieved by the present invention described below.
The timepiece dial of the present invention, a base material mainly composed of polycarbonate,
A silicon oxide layer composed primarily of silicon oxide;
A zinc sulfide layer provided adjacent to the silicon oxide layer and composed mainly of zinc sulfide;
It is provided on the surface of the silicon oxide layer opposite to the surface facing the zinc sulfide layer, and has a fine particle dispersed layer in which fine particles composed of SiO ₂ are dispersed.
Thereby, while being excellent in the permeability | transmittance of electromagnetic waves (electric wave, light), the dial for timepieces excellent in the aesthetic appearance and durability can be provided. In particular, the timepiece dial can have a high-quality gloss and have a particularly excellent aesthetic appearance.

In the timepiece dial of the present invention, the fine particles preferably have an average particle diameter of 10 to 250 nm.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).
In the timepiece dial of the present invention, the content of the fine particles in the fine particle dispersed layer is preferably 3 to 35 vol%.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).

In the timepiece dial according to the aspect of the invention, it is preferable that the fine particle dispersed layer is formed by dispersing the fine particles in a resin material.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).
In the timepiece dial of the present invention, the fine particle dispersion layer preferably has a thickness of 0.5 to 30 μm.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).

In the timepiece dial according to the aspect of the invention, the fine particle dispersion layer is provided on the surface of the base opposite to the surface on which the zinc sulfide layer and the silicon oxide layer are provided. Preferably there is.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).

In the timepiece dial according to the aspect of the invention, it is preferable that the silicon oxide layer is provided adjacent to the substrate.
Thereby, the aesthetic appearance of the timepiece dial can be further improved.
In the timepiece dial of the present invention, the silicon oxide layer is preferably formed by vapor deposition.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).
In the timepiece dial of the present invention, the silicon oxide layer preferably has a thickness of 20 to 200 nm.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).

In the timepiece dial of the present invention, the zinc sulfide layer preferably has a thickness of 10 to 100 nm.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).
In the timepiece dial of the present invention, the total thickness of the silicon oxide layer and the zinc sulfide layer is preferably 50 to 250 nm.
Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light).

In the timepiece dial of the present invention, it is preferable to have a colored layer composed of a material containing a colorant between the silicon oxide layer and the fine particle dispersed layer.
Thereby, the aesthetic appearance of the timepiece dial can be further improved.
In the timepiece dial of the present invention, the color tone of the timepiece dial on the surface side of the base material on which the zinc sulfide layer is provided is L ^* a ^* b ^* as defined in JIS Z 8729. In the chromaticity diagram, it is preferable that a ^* is −10 to 10 and b ^* is −8 to 8.
Thereby, the aesthetic appearance of the timepiece dial is particularly excellent.

The timepiece of the present invention includes the timepiece dial of the present invention.
Thereby, it is possible to provide a timepiece having an aesthetic appearance and durability. In addition, it is possible to provide a timepiece (for example, a radio timepiece, a solar timepiece, a solar timepiece timepiece, etc.) that can effectively use electromagnetic waves (radio waves, light) from the outside.

  According to the present invention, it is possible to provide a timepiece dial having excellent electromagnetic wave (radio wave, light) permeability, aesthetic appearance and durability, and a timepiece having the timepiece dial. be able to.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
First, a preferred embodiment of the timepiece dial of the present invention will be described.
<Timepiece dial (first embodiment)>
FIG. 1 is a sectional view showing a first embodiment of a timepiece dial according to the present invention. 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. In the following description, the upper side in the figure is described as “upper”, and the lower side in the figure is described as “lower”.

As shown in FIG. 1, the timepiece dial 1 of the present embodiment includes a base material 2 mainly made of polycarbonate, a silicon oxide layer 3 mainly made of silicon oxide, and a silicon oxide layer 3. The zinc sulfide layer 4 provided adjacent to each other and mainly composed of zinc sulfide and the surface opposite to the surface facing the silicon oxide layer 3 of the base material 2 were provided and composed of SiO ₂ . A fine particle dispersion layer 5 in which fine particles 51 are dispersed. In the present invention, “mainly” means a component having the largest content among materials constituting the target portion, and the content is not particularly limited, but is 60 wt% or more of the material constituting the target portion. Preferably, it is 80 wt% or more, and more preferably 90 wt% or more.
Such a timepiece dial 1 is normally used such that the zinc sulfide layer 4 is on the outer surface side of the silicon oxide layer 3, that is, on the observer side. In the following description, unless otherwise specified, the timepiece dial 1 is described as being used with the upper side in the drawing facing the outer surface side.

[Base material]
The base material 2 is mainly composed of a material containing polycarbonate (PC). In the present invention, one of the requirements for the base material 2 is the permeability of electromagnetic waves (radio waves, light). Among various plastic materials, polycarbonate is particularly high in transparency and has excellent electromagnetic wave permeability, so that the electromagnetic wave permeability of the substrate 2 can be made particularly excellent. Further, due to the difference in refractive index between the base material 2 made of polycarbonate and the silicon oxide layer 3 described later, the interface between the base material 2 and the silicon oxide layer 3 and the silicon oxide layer 3 of the base material 2 Incident light is preferably reflected and refracted on the surface opposite to the coated surface side (lower side in the figure). Thereby, the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. Polycarbonate has a characteristic that it is not easily deformed by external stresses such as light and heat. For this reason, the adhesiveness of the base material 2 made of polycarbonate and the silicon oxide layer 3 described later can be made particularly excellent, and as a result, the durability of the timepiece dial 1 is particularly excellent. It can be. Moreover, when the base material 2 is made of a material containing polycarbonate, the strength of the timepiece dial 1 as a whole can be made particularly excellent. In addition, when the timepiece dial 1 is manufactured, since the degree of freedom of molding the base material 2 is increased (easiness of molding is improved), even if the timepiece dial 1 has a more complicated shape, It can be manufactured easily and reliably. Polycarbonate is relatively inexpensive among various plastic materials, and can contribute to the reduction of the production cost of the timepiece dial 1.

  In addition, the base material 2 may contain components other than the said polycarbonate. Examples of such components include plasticizers, antioxidants, colorants (including various color formers, fluorescent materials, phosphorescent materials, etc.), brighteners, fillers, and resin components other than polycarbonate. For example, when the base material 2 is made of a material containing a colorant, variations in the color of the timepiece dial 1 can be widened.

  Although the refractive index of the base material 2 mainly composed of polycarbonate is not particularly limited, it is preferably 1.48 to 1.60, and more preferably 1.54 to 1.59. Thereby, light can be more preferably reflected and refracted at the interface between the substrate 2 and the silicon oxide layer 3 and the surface opposite to the surface side of the substrate 2 covered with the silicon oxide layer 3. it can. As a result, the aesthetic appearance of the timepiece dial 1 can be further improved. In the present specification, the refractive index means an absolute refractive index at 25 ° C. using sodium D-line unless otherwise specified.

Although the thickness of the base material 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 more preferable that it is 300-500 micrometers. When the thickness of the base material 2 is a value within the above range, the mechanical strength of the timepiece dial 1 is effectively prevented while the timepiece to which the timepiece dial 1 is applied is effectively prevented from being thickened. The shape stability and the like can be made sufficiently excellent. In general, as the thickness of the base material 2 increases, the electromagnetic wave permeability and aesthetic appearance of the timepiece dial 1 are inferior. However, since polycarbonate has a low refractive index, if the thickness of the base material 2 is within the above range, there will be no difference in electromagnetic wave permeability and aesthetic appearance depending on the thickness of the base material 2. 1 can have a particularly excellent aesthetic appearance and a particularly excellent electromagnetic wave permeability.
The substrate 2 may be formed by any method, and examples of the method for forming the substrate 2 include compression molding, extrusion molding, and injection molding.

[Silicon oxide layer]
A silicon oxide layer 3 mainly composed of silicon oxide is provided on the surface of the substrate 2.
Since silicon oxide has excellent electromagnetic wave permeability among various metal oxides, the electromagnetic wave transmission property of the timepiece dial 1 using the silicon oxide layer 3 is particularly excellent. be able to. In addition, the refractive index of the silicon oxide layer 3 is lower than that of the base material 2 made of a material containing polycarbonate. Incident light is suitably reflected and refracted at the interface between the physical layer 3 and the substrate 2. Similarly, the refractive index of the silicon oxide layer 3 is lower than that of the zinc sulfide layer 4, and incident light is suitably reflected and refracted at the interface between the silicon oxide layer 3 and the zinc sulfide layer 4. Thereby, the aesthetic appearance of the timepiece dial 1 can be made excellent. In addition, since silicon oxide has a high affinity with polycarbonate and zinc sulfide and has a characteristic that it is not easily deformed by external stress such as light or heat, the silicon oxide layer 3 is made of polycarbonate. The adhesion between the base material 2 and the zinc sulfide layer 4 is excellent. As a result, the durability of the timepiece dial 1 can be improved. In addition, the affinity between silicon oxide and polycarbonate is higher than the affinity between zinc sulfide and polycarbonate, which will be described later. For this reason, the timepiece dial 1 has a configuration in which the silicon oxide layer 3 is provided between the base material 2 and a zinc sulfide layer 4 described later, so that the surface of the base material is covered with the zinc sulfide layer. Compared to a watch dial, it has superior durability. Furthermore, even if the silicon oxide layer 3 is thick, cracks in the silicon oxide layer 3 and peeling failure at the interface between the substrate 2 and the silicon oxide layer 3 are unlikely to occur. Even when 3 is made relatively thick, the aesthetic appearance of the timepiece dial 1 can be made excellent while the electromagnetic wave permeability is excellent.

Although the refractive index of the silicon oxide layer 3 is not particularly limited, it is preferably 1.20 to 1.54, and more preferably 1.40 to 1.50. As a result, light can be more suitably reflected and refracted at the interface between the base 2 of the silicon oxide layer 3 and the zinc sulfide layer 4, and the aesthetic appearance of the timepiece dial 1 is particularly excellent. can do.
Further, when the refractive index of the silicon oxide layer 3 is n ₃ and the refractive index of the substrate 2 made of polycarbonate is n ₂ , n is a difference in refractive index between the silicon oxide layer 3 and the substrate 2. the value of ₂ -n ₃ is preferably from 0.05 to 0.30, and more preferably 0.03 to 0.20. Thereby, incident light is suitably reflected and refracted at the interface between the silicon oxide layer 3 and the base material 2, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent.

The silicon oxide layer 3 includes SiO, SiO _{2 and the} like as the silicon oxide, and among these, it is preferable that the silicon oxide layer 3 is mainly composed of SiO ₂ . As a result, it is possible to more suitably reflect and refract light at the interface between the base 2 of the silicon oxide layer 3 and the zinc sulfide layer 4 while making the transmission of electromagnetic waves more excellent. The aesthetic appearance of the dial 1 can be made particularly excellent.

  The thickness of the silicon oxide layer 3 is not particularly limited, but is preferably 20 to 200 nm, more preferably 30 to 150 nm, and even more preferably 50 to 100 nm. When the thickness of the silicon oxide layer 3 is a value within the above range, the aesthetic appearance of the timepiece dial 1 is further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light). be able to. If the thickness of the silicon oxide layer 3 is less than the lower limit, depending on the thickness of the zinc sulfide layer 4, it is difficult to sufficiently reflect and refract light, and it is difficult to obtain an excellent aesthetic appearance. There is a possibility. On the other hand, when the thickness of the silicon oxide layer 3 exceeds the upper limit, the electromagnetic wave permeability of the timepiece dial 1 may not be sufficiently obtained. Furthermore, when the thickness of the silicon oxide layer 3 exceeds the upper limit, a relatively large external stress (heat, heat) is applied to the timepiece dial 1 due to a difference in shrinkage between the silicon oxide layer 3 and the base material 2. There is a possibility that appearance defects such as cracks in the silicon oxide layer 3 due to the application of light) and peeling defects at the interface between the silicon oxide layer 3 and the zinc sulfide layer 4 may occur.

[Zinc sulfide layer]
A zinc sulfide layer 4 mainly composed of zinc sulfide is provided on the surface of the silicon oxide layer 3 opposite to the surface facing the substrate 2. The zinc sulfide layer 4 is provided adjacent to the silicon oxide layer 3.
The zinc sulfide constituting the zinc sulfide layer 4 is a compound of Zn and S. Since this zinc sulfide is generally a colorless and transparent material and has excellent electromagnetic wave permeability, the electromagnetic wave permeability of the timepiece dial 1 using the zinc sulfide layer 4 is particularly excellent. Can be. Moreover, the refractive index of the zinc sulfide layer 4 is higher than that of the silicon oxide layer 3, and the zinc sulfide layer 4 and the silicon oxide layer 3 are different due to the difference in refractive index between the zinc sulfide layer 4 and the silicon oxide layer 3. The incident light is preferably reflected and refracted at the interface. Thereby, the aesthetic appearance of the timepiece dial 1 can be made excellent. In addition, since zinc sulfide has a high affinity with silicon oxide and has a characteristic that it is not easily deformed by external stress such as light or heat, the zinc sulfide layer 4 is in close contact with the silicon oxide layer 3. Excellent in properties. As a result, the durability of the timepiece dial 1 can be improved.

Although the refractive index of the zinc sulfide layer 4 is not particularly limited, it is preferably 2.20 to 2.60, more preferably 2.30 to 2.35. Thereby, light can be more suitably reflected and refracted at the interface between the zinc sulfide layer 4 and the silicon oxide layer 3, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. .
Further, when the refractive index of the zinc sulfide layer 4 was n _4, the value of n ₄ -n ₃ is a difference in refractive index between the zinc sulfide layer 4 and the silicon oxide layer 3 is 0.60 to 1 .40 is preferable, and 0.80 to 1.20 is more preferable. Thereby, incident light can be suitably reflected and refracted at the interface between the zinc sulfide layer 4 and the silicon oxide layer 3, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent.

Further, the value of n ₂ −n ₃ , which is the difference in refractive index between the substrate 2 and the silicon oxide layer 3, and the difference in refractive index between the zinc sulfide layer 4 and the silicon oxide layer 3, n ₄ −n. ₃ values, both satisfy the above conditions, and the value of _n 4 -n ₂ is the difference in refractive index between the zinc sulfide layer 4 and the substrate 2, that is 0.5 to 1.4 Preferably, it is 0.7-1.2. Thereby, incident light is suitably reflected and refracted at the interface between adjacent layers of the base material 2, the silicon oxide layer 3, and the zinc sulfide layer 4, and the aesthetic appearance of the timepiece dial 1 is particularly excellent. It can be.

  The thickness of the zinc sulfide layer 4 is not particularly limited, but is preferably 10 to 100 nm, more preferably 15 to 80 nm, and still more preferably 20 to 50 nm. When the thickness of the zinc sulfide layer 4 is a value within the above range, the aesthetic appearance of the timepiece dial 1 is further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light). be able to. On the other hand, if the thickness of the zinc sulfide layer 4 is less than the lower limit, depending on the thickness of the silicon oxide layer 3, it becomes difficult to sufficiently reflect and refract light, and an excellent aesthetic appearance is obtained. It can be difficult to get. On the other hand, if the thickness of the zinc sulfide layer 4 exceeds the upper limit, the electromagnetic wave permeability of the timepiece dial 1 may not be sufficiently obtained. Further, when the thickness of the zinc sulfide layer 4 exceeds the upper limit, cracks in the zinc sulfide layer 4 due to a relatively large external stress (heat, light) being applied to the timepiece dial 1, or zinc sulfide There is a possibility that poor appearance such as peeling failure occurs at the interface between the physical layer 4 and the silicon oxide layer 3.

  The formation method of the silicon oxide layer 3 and the zinc sulfide layer 4 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., electrolytic plating, immersion Wet plating methods such as plating and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods such as vacuum deposition, sputtering, and ion plating (vapor deposition methods), Although thermal spraying etc. are mentioned, the dry-type plating method (vapor phase film-forming method) is preferable. By applying a dry plating method (vapor phase film forming method) as a method for forming the silicon oxide layer 3 and the zinc sulfide layer 4, the substrate 2 and silicon have a uniform film thickness and are uniform. The timepiece dial 1 having particularly excellent adhesion between adjacent layers of the oxide layer 3 and the zinc sulfide layer 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 for forming the silicon oxide layer 3 and the zinc sulfide layer 4, the silicon oxide layer 3 and the zinc sulfide layer 4 to be formed are Even if it is relatively thin, the variation in the film thickness (layer thickness) can be made sufficiently small. 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.

  In addition, among the dry plating methods (vapor phase film forming methods) as described above, the above effects become more remarkable by applying vacuum deposition. That is, by applying vacuum deposition as a method for forming the silicon oxide layer 3 and the zinc sulfide layer 4, the film has a uniform thickness, is homogeneous, and has particularly excellent adhesion between adjacent layers. The silicon oxide layer 3 and the zinc sulfide layer 4 can be more reliably formed. As a result, the aesthetic appearance and durability of the finally obtained dial 1 for timepiece can be further improved. Moreover, even if the silicon oxide layer 3 and the zinc sulfide layer 4 to be formed are relatively thin by applying vacuum deposition as a method for forming the silicon oxide layer 3 and the zinc sulfide layer 4. The variation in film thickness can be made particularly small. For this reason, for example, it is possible to further improve the electromagnetic wave permeability of the timepiece dial 1 while making the obtained timepiece dial 1 highly durable. Therefore, the obtained timepiece dial 1 can be more suitably applied to a radio timepiece, a solar timepiece, or the like.

  The total thickness of the silicon oxide layer 3 and the zinc sulfide layer 4 is not particularly limited, but is preferably 50 to 250 nm, more preferably 80 to 220 nm, and even more preferably 100 to 200 nm. preferable. When the combined thickness of the silicon oxide layer 3 and the zinc sulfide layer 4 is a value within the above range, the transmittance of the electromagnetic wave (radio wave, light) is sufficiently high, and the timepiece dial 1 The aesthetic appearance can be further improved.

[Fine particle dispersion layer]
A fine particle dispersion layer 5 in which fine particles 51 made of SiO ₂ are dispersed in a dispersion medium 52 is provided on the surface opposite to the surface facing the silicon oxide layer 3 of the substrate 2. By having the fine particle dispersion layer 5, light (external light) incident from the upper side in the figure is emitted to the lower side in the figure, and part of the incident light is also emitted to the upper side (base material 2 side) in the figure. Can be scattered. Further, light incident from the lower side in the figure can be emitted while being scattered on the upper side (base material 2 side) in the figure. As a result, the timepiece dial is made to emit light (external light) incident from the upper side (base material 2 side) in the figure to the lower side (side where the solar cell 94 is arranged in the wristwatch 100 described later) in the figure. When viewing 1 from the outside (from the upper side in the figure), it is possible to effectively see the state of the inside (lower side in the figure) of the timepiece dial 1 through the timepiece dial 1. Can be prevented. In particular, in the timepiece dial 1, light is emitted (scattered) to the base material 2 side in the fine particle dispersion layer 5, so that the appearance as the timepiece dial 1 has a high glossiness and an excellent luxury feeling. It will have.

  Thus, in the present invention, the timepiece dial has a silicon oxide layer, a zinc sulfide layer, and a fine particle dispersed layer in a predetermined arrangement in addition to a base material mainly composed of polycarbonate. Thus, it is characterized in that excellent aesthetic appearance with excellent durability and high-quality feeling can be obtained while making the transmission of electromagnetic waves (light, radio waves) excellent. On the other hand, when it does not have even some of these structures, the above excellent effects cannot be obtained.

  For example, when the silicon oxide layer is not provided, it is not possible to realize suitable reflection and refraction of incident light due to the difference in refractive index between the silicon oxide layer and the zinc sulfide layer as described above. The dial is inferior in aesthetic appearance. Furthermore, it becomes impossible to realize suitable reflection and refraction of incident light due to the difference in refractive index between the silicon oxide layer and the substrate. In addition, the adhesion between the zinc sulfide layer and the base material cannot be made sufficiently excellent, and the timepiece dial is inferior in durability.

In addition, when the zinc sulfide layer is not provided, it is impossible to realize suitable reflection and refraction of incident light due to the difference in refractive index between the silicon oxide layer and the zinc sulfide layer as described above. The dial is inferior in aesthetic appearance.
Further, when the fine particle dispersed layer is not provided, suitable light scattering cannot be realized, and the aesthetic appearance of the timepiece dial cannot be sufficiently improved. In particular, it lacks gloss and is inferior to luxury. Moreover, since the state of the back side is easily visually recognized through the timepiece dial, it is difficult to apply to a solar timepiece or the like.

In addition, when the arrangement of the silicon oxide layer and the zinc sulfide layer is changed, suitable reflection and refraction of external light (a surface facing the silicon oxide layer of the zinc sulfide layer realized in the present invention) Reflection and refraction at the surface opposite to the surface, reflection at the interface between the zinc sulfide layer and the silicon oxide layer, refraction, etc.), and the timepiece dial is inferior in aesthetic appearance It will be a thing.
In addition, when the fine particle dispersion layer is provided on the surface of the zinc sulfide layer opposite to the surface facing the silicon oxide layer, or when it is provided between the zinc sulfide layer and the silicon oxide layer, etc. However, similarly to the above, it is not possible to realize suitable reflection and refraction of external light, and the timepiece dial is inferior in aesthetic appearance.

The fine particles 51 may be any particles as long as they are mainly composed of SiO _2. For example, the particles 51 mainly composed of SiO ₂ may be subjected to a surface treatment. Thereby, for example, the aggregation of the fine particles 51 in the fine particle dispersion layer 5 can be more reliably prevented, the dispersibility of the fine particles 51 can be improved, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. it can. Examples of the surface treatment method for particles mainly composed of SiO ₂ include, for example, HMDS, silane coupling agents (which may have functional groups such as amino groups), titanate coupling agents, and fluorine-containing silanes. Examples include surface treatment with a coupling agent, silicone oil, and the like.

The average particle diameter of the fine particles 51 is preferably 10 to 250 nm, and more preferably 20 to 150 nm. When the average particle size of the fine particles 51 is a value within the above range, the incident light can be more efficiently scattered while the transmittance of electromagnetic waves (radio waves, light) is sufficiently high, and the timepiece dial The aesthetic appearance of 1 can be further improved. In the present specification, the average particle diameter means a volume-based average particle diameter unless otherwise specified.
The shape of the fine particles 51 is not particularly limited, and may be any shape such as a substantially spherical shape, a scale shape, a needle shape, or an indefinite shape.

  The content of the fine particles 51 in the fine particle dispersed layer 5 is preferably 3 to 35 vol%, more preferably 7 to 28 vol%. When the content of the fine particles 51 is a value within the above range, the transmittance of electromagnetic waves (radio waves, light) can be made sufficiently high, and incident light can be scattered more efficiently, and the timepiece dial 1 The aesthetic appearance can be further improved. In addition, the fine particle dispersion layer 5 can have excellent stability (impact resistance) against external force such as impact force, and the durability and reliability of the timepiece dial 1 as a whole are particularly excellent. can do.

  The dispersion medium 52 constituting the fine particle dispersion layer 5 is usually made of a transparent material. Examples of the constituent material of the dispersion medium 52 include various resin materials, various glass materials such as alkali-free glass, soda glass, crystalline glass, quartz glass, lead glass, potassium glass, and borosilicate glass. It is preferably made of a resin material. Thereby, the aesthetic appearance of the timepiece dial can be further improved while sufficiently increasing the transmittance of electromagnetic waves (radio waves, light). In addition, the fine particle dispersion layer 5 can have excellent stability (impact resistance) against external force such as impact force, and the durability and reliability of the timepiece dial 1 as a whole are particularly excellent. can do.

  Examples of the plastic material constituting the dispersion medium 52 include various thermoplastic resins, various thermosetting resins, and the like. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), Polyolefins such as vinyl acetate resin, cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamides (example: nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6 -12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene Copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET) , Polyesters such as polybutylene terephthalate (PBT) and polycyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene Oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, Various thermoplastics such as vinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene Elastomer, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para- xylylene), poly-dichloro-para-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, etc. Polyparaxylylene resins, etc., or copolymers mainly comprising these, Body mentioned polymer alloy or the like, singly or in combination of two or more of these (e.g., a blend resin, polymer alloy, as a laminate or the like) can be used.

  The refractive index of the dispersion medium 52 is not particularly limited, but is preferably 1.48 to 1.60, and more preferably 1.54 to 1.59. Thereby, an unfavorable reflection etc. at the interface between the base material 2 and the fine particle dispersion layer 5 can be prevented, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent. In addition, in the configuration in which the arrangement of the base material 2 and the fine particle dispersion layer 5 is changed from the configuration shown in the figure, it is possible to realize suitable reflection and refraction at the interface with the silicon oxide layer 3 as described above. And the aesthetic appearance of the timepiece dial can be made particularly excellent.

Further, when the refractive index of the substrate 2 is n ₂ and the refractive index of the dispersion medium 52 is n ₅ , | n ₂ −n ₅ | which is the absolute value of the difference in refractive index between the substrate 2 and the dispersion medium 52. The value of is preferably 0.11 or less, more preferably 0.09 or less, and even more preferably 0.03 or less. Thereby, an unfavorable reflection etc. at the interface between the base material 2 and the fine particle dispersion layer 5 can be prevented, and the aesthetic appearance of the timepiece dial 1 can be made particularly excellent.

Further, when the refractive index of the dispersion medium 52 is n ₅ and the refractive index of the silicon oxide layer 3 is n ₃ , the difference in refractive index between the dispersion medium 52 and the silicon oxide layer 3 is n ₅ −n ₃ . The value is preferably 0.03 to 0.30, and more preferably 0.07 to 0.20. Thereby, even in the configuration in which the arrangement of the base material 2 and the fine particle dispersion layer 5 is changed from the configuration as shown in the figure, suitable reflection and refraction at the interface with the silicon oxide layer 3 as described above are realized. And the aesthetic appearance of the timepiece dial can be made particularly excellent.

  The fine particle dispersion layer 5 may contain components other than those described above. 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 fine particle dispersion layer 5 is made of a material containing a colorant, variations in the color of the timepiece dial 1 can be widened.

  The thickness of the fine particle dispersion layer 5 is not particularly limited, but is preferably 0.5 to 30 μm, and more preferably 2 to 20 μm. When the thickness of the fine particle dispersion layer 5 is a value within the above range, the incident light can be more efficiently scattered while the transmittance of electromagnetic waves (radio waves, light) is sufficiently high, and the timepiece character The aesthetic appearance of the plate 1 can be further improved.

In the timepiece dial 1 as described above, the color tone of the surface on which the silicon oxide layer 3 and the zinc sulfide layer 4 are provided has an L ^* a ^* b ^* display defined by JIS Z 8729. in the chromaticity diagram, ^{a *} is -8～8, and is preferably ^{b *} is -8～8, ^{a *} is -4～4, and ^{b *} is at -4～4 More preferably. Thereby, the aesthetic appearance of the timepiece dial 1 is particularly excellent.

In addition, the timepiece dial 1 has a color tone of the surface on which the silicon oxide layer 3 and the zinc sulfide layer 4 are provided, the chromaticity of L ^* a ^* b ^* display defined by JIS Z 8729 In the figure, L ^* is preferably 50 to 85, and more preferably L ^* is 70 to 85. As a result, the aesthetic appearance of the timepiece dial 1 has a high degree of whiteness and a higher-grade appearance.

  The thickness of the timepiece dial 1 is not particularly limited, but is preferably 150 to 700 μm, more preferably 200 to 600 μm, and even more preferably 300 to 500 μm. When the thickness of the timepiece dial 1 is within the above range, the timepiece dial 1 is effectively prevented from becoming thicker while the timepiece to which the timepiece dial 1 is applied is prevented from being machined. The mechanical strength, the stability of the shape, etc. can be made sufficiently excellent.

  Further, as described above, the timepiece dial 1 has the silicon oxide layer 3, the zinc sulfide layer 4, and the fine particle dispersion layer 5 on the base material 2. The variation of the reflectance at each wavelength in the visible light region (wavelength region of 380 to 780 nm) can be made sufficiently small. Thus, when the variation in reflectance at each wavelength in the visible light region is sufficiently small, an excellent aesthetic appearance that is high in whiteness and full of luxury can be obtained. In other words, in the visible light region (wavelength region of 380 to 780 nm), the reflectance A [%] at the wavelength where the reflectance is maximum and the reflectance B [%] at the wavelength where the reflectance is minimum. When the difference A−B is sufficiently small, the above effect can be obtained. Thus, the value of AB is preferably sufficiently small, but more specifically, it is preferably less than 25%, more preferably less than 20%, and less than 10%. More preferably. As a result, the above-described effects are exhibited more significantly.

As described above, the timepiece dial 1 is excellent in aesthetic appearance and excellent in electromagnetic wave permeability. For this reason, the timepiece dial 1 can be suitably applied to a radio timepiece, a solar timepiece (a timepiece having a built-in solar battery), a solar timepiece, and 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).

<Timepiece dial (second embodiment)>
Next, a second embodiment of the timepiece dial of the present invention will be described. In the following description, differences from the above-described embodiment (first embodiment) will be mainly described, and description of similar matters will be omitted.
FIG. 2 is a cross-sectional view showing a second embodiment of the timepiece dial of the present invention.

As shown in FIG. 2, the timepiece dial 1 ′ of the present embodiment includes a base material 2 mainly made of polycarbonate, a silicon oxide layer 3 mainly made of silicon oxide, and a silicon oxide layer 3. The zinc sulfide layer 4 that is provided adjacent to the surface of the base 2 and is provided on the opposite side of the surface of the substrate 2 that faces the silicon oxide layer 3 and is made of SiO _2. A fine particle dispersion layer 5 in which fine particles are dispersed, and a colored layer 6 provided between the substrate 2 and the fine particle dispersion layer 5 and made of a material containing a colorant. That is, the timepiece dial 1 ′ of the present embodiment has the colored layer 6 between the base material 2 and the fine particle dispersion layer 5, except for the timepiece dial 1 described in the first embodiment. It is the same. Hereinafter, the colored layer 6 will be described.

[Colored layer]
The colored layer 6 is made of a material containing a colorant. Thereby, light (external light) incident from the upper side in the figure, that is, light incident through the silicon oxide layer 3 and the zinc sulfide layer 4 (external light) is emitted to the fine particle dispersion layer 5 side. On the other hand, part of the incident light is colored by the colorant and reflected upward in the figure. Further, light incident from the fine particle dispersion layer 5 side (lower side in the figure) can also be emitted into the base material 2 side as colored light by the colorant. As a result, light (external light) incident from the side of the base material 2 is emitted from the outside to the lower side in the figure (the side where the solar cell 94 is arranged in the wristwatch 100 described later) while When viewed (from the upper side in the figure), the timepiece dial 1 ′ can be colored, and the inside of the timepiece dial 1 ′ (the lower side in the figure) via the timepiece dial 1 ′. ) Can be more effectively prevented from being seen through. As a result, the decorativeness (aesthetic appearance) of the timepiece dial 1 ′ can be made particularly excellent. In particular, in the timepiece dial 1 ′ having the silicon oxide layer 3, the zinc sulfide layer 4, the fine particle dispersed layer 5 and the colored layer 6, the silicon oxide layer 3, the zinc sulfide layer 4, the fine particle dispersed layer 5, A radio timepiece or solar timepiece (a timepiece equipped with a solar cell) having an excellent decorative property (aesthetic appearance) while adding the color developed by the colored layer 6 to the luster of the colorant and making the electromagnetic wave permeability sufficiently high It is effective as a dial for a watch. Further, the timepiece dial 1 ′ provided with the colored layer 6 can express colors that could not be expressed only by the silicon oxide layer 3, the zinc sulfide layer 4, and the fine particle dispersed layer 5. Moreover, since the color of the timepiece dial can be controlled by changing the constituent material of the colored layer, it is also effective for multi-item production.

Examples of the colorant include pigments and dyes.
Moreover, it is preferable that the colored layer 6 is comprised with the material which has adhesiveness and adhesiveness. Thereby, the adhesiveness with the base material 2 and the fine particle dispersion layer 5 can be improved, and as a result, the durability (impact resistance, etc.) of the timepiece dial 1 ′ can be improved. The reliability of the timepiece dial 1 ′ as an ornament can be made particularly excellent.

  As a material having the above-mentioned tackiness and adhesiveness (adhesive / adhesive material), for example, a material used for an adhesive, an adhesive, etc. can be used. As an adhesive / adhesive material, for example, urethane Resin, acrylic resin, and urethane resin is particularly preferable. Thereby, the adhesiveness with the base material 2 and the fine particle dispersed layer 5 can be made particularly excellent while sufficiently maintaining the light transmission and aesthetic appearance of the timepiece dial 1 ′ as a whole.

When the colored layer 6 includes the above-mentioned adhesive / adhesive material, the colored layer 6 is preferably mainly composed of an adhesive / adhesive material. Thereby, the adhesiveness with the base material 2 and the fine particle dispersion layer 5 can be made especially excellent.
Although the thickness of the colored layer 6 is not specifically limited, It is preferable that it is 1-25 micrometers, and it is more preferable that it is 5-15 micrometers. When the thickness of the colored layer 6 is a value within the above range, light is more preferably refracted and reflected at the interface between the colored layer 6 and the substrate 2 and at the interface between the colored layer 6 and the fine particle dispersed layer 5. The decorativeness (aesthetic appearance) of the timepiece dial 1 ′ can be made particularly excellent.

  By using the base material 2 containing a colorant, it is possible to give the same color as the timepiece dial 1 'with the colored layer introduced, but if this method is used, it is included in the base material. The adhesion between the substrate and the silicon oxide layer may be deteriorated due to the influence of the colorant. Moreover, there is a possibility that the electromagnetic wave permeability required for the substrate 2 cannot be sufficiently obtained. Moreover, the aesthetic appearance of the timepiece dial 1 ′ generated by refraction and reflection caused at the interface between the base material 2 and the adjacent layer by incident light may be impaired. Therefore, in this embodiment, by introducing the colored layer, the aesthetic appearance of the timepiece dial 1 ′ can be easily and reliably improved.

As described above, the timepiece dial 1 ′ has the colored layer 6 in addition to the base material 2, the silicon oxide layer 3, the zinc sulfide layer 4, and the fine particle dispersed layer 5. For this reason, as described above, even when a relatively thin material (150 to 700 μm) is used as the base material 2, the mechanical strength and shape stability of the timepiece dial 1 ′ are sufficiently excellent. Can be.
Further, the thickness of the timepiece dial 1 ′ is not particularly limited, but is preferably 150 to 700 μm, more preferably 200 to 600 μm, and further preferably 300 to 500 μm. When the thickness of the timepiece dial 1 ′ is within the above range, the timepiece dial 1 ′ is effectively prevented from being thickened by the timepiece to which the timepiece dial 1 ′ is applied. The mechanical strength, shape stability, etc. can be made particularly excellent.

As described above, the timepiece dial 1 ′ is excellent in aesthetic appearance and excellent in electromagnetic wave permeability. For this reason, the timepiece dial 1 ′ can be suitably applied to a radio timepiece, a solar timepiece (a timepiece incorporating a solar battery), a solar radio timepiece, and 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).

<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 transmission (electromagnetic wave transmission) and decoration (aesthetic appearance). For this reason, the timepiece of the present invention provided with such a timepiece dial can sufficiently satisfy the requirements required as a solar timepiece or a radio timepiece. As a part other than the timepiece dial (the timepiece dial of the present invention) that constitutes the timepiece of the present invention, known parts can be used. Hereinafter, an example of the configuration of the timepiece of the present invention will be described. explain.

FIG. 3 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 3, a wristwatch (portable watch) 100 according to the present embodiment includes a case (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 (or timepiece dial 1 ′) of the present invention, the solar battery 94, and the movement 81 as described above are housed, and a hand (not shown) is further illustrated. (Guidelines) etc. are stored.
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 (or 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. 3, in the movement 81, for example, an electric double layer capacitor for storing the electromotive force of the solar cell 94, a lithium ion secondary battery, a crystal oscillator as a time reference source, and a crystal vibration A semiconductor integrated circuit that generates a driving pulse for driving a clock based on the oscillation frequency of the child, a step motor that drives the pointer every second in response to this driving pulse, and a wheel that transmits the movement of the step motor to the pointer A row mechanism is provided.
The movement 81 includes a radio wave receiving antenna (not shown). And it has the function to perform time adjustment etc. using the received electromagnetic wave.

The solar cell 94 has a function of converting light energy into electric energy. The electric energy converted by the solar cell 94 is used for driving the movement.
In the solar cell 94, for example, a p-type impurity and an n-type impurity are selectively introduced into a non-single-crystal silicon thin film, and a p-type non-single-crystal silicon thin film and an n-type non-single-crystal silicon thin film are used. It has a pin structure provided with an i-type non-single-crystal silicon thin film with a low impurity concentration in between.

A winding stem pipe 86 is fitted into and fixed to the barrel 82, and a shaft 871 of a crown 87 is rotatably inserted into the winding stem pipe 86.
The body 82 and the bezel 84 are fixed by a plastic packing 88, and the bezel 84 and the glass plate 85 are fixed by a plastic packing 89.
Further, a back cover 83 is fitted (or screwed) to the body 82, and a ring-shaped rubber packing (back cover packing) 92 is inserted in a compressed state in these joint portions (seal portions) 93. Has been. With this configuration, the seal portion 93 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove 872 is formed on the outer periphery of the middle portion of the shaft portion 871 of the crown 87, and a ring-shaped rubber packing (crown packing) 91 is fitted in the groove 872. The rubber packing 91 is in close contact with the inner peripheral surface of the winding stem pipe 86 and is compressed between the inner peripheral surface and the inner surface of the groove 872. With this configuration, the space between the crown 87 and the winding stem pipe 86 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 87 is rotated, the rubber packing 91 rotates together with the shaft portion 871 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 86.

Since the above portable watch (watch) is required to have particularly excellent durability (for example, impact resistance, etc.) among various types of watches, a book with excellent aesthetic appearance and excellent durability can be obtained. The invention can be applied more suitably.
In the above description, a wristwatch (portable clock) as a solar radio timepiece has been described as an example of a clock. However, the present invention is applicable to other types of clocks such as a portable clock, a table clock, and a wall clock other than a wristwatch. Can be applied similarly. Further, the present invention can be applied to any timepiece such as a solar timepiece excluding a solar radio timepiece and a radio timepiece excluding a solar radio timepiece.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above.
For example, in the timepiece dial and timepiece of the present invention, the configuration of each part can be replaced with any configuration that exhibits the same function, and any configuration can be added. For example, you may have a printing part formed by various printing methods.

In the above-described embodiment, the fine particle dispersion layer has been described as being provided on the surface of the substrate opposite to the surface facing the silicon oxide layer. However, the fine particle dispersion layer is formed of the silicon oxide layer. What is necessary is just to be provided in the surface opposite to the surface facing the zinc sulfide layer, for example, it may be provided so as to be adjacent to the silicon oxide layer.
In the above-described embodiment, the zinc sulfide layer and the silicon oxide layer have been described as being provided on the side of the substrate opposite to the side on which the fine particle dispersion layer is provided. The sulfide layer and the silicon oxide layer may be adjacent to each other. For example, the sulfide layer and the silicon oxide layer may be provided between the base material and the fine particle dispersion layer.
Moreover, in 2nd Embodiment mentioned above, although the colored layer demonstrated as what was provided between the base material and fine particle dispersion layer, a colored layer is between a silicon oxide layer and a base material, for example. It may be provided. Thus, if the colored layer is provided between the silicon oxide layer and the fine particle dispersed layer, the same effect as described above can be obtained.

Further, the surface of the timepiece dial (the surface of the fine particle dispersion layer 5 (the surface opposite to the surface facing the silicon oxide layer 3, the zinc sulfide layer 4, and the base material 2), the zinc sulfide layer 4 At least one layer (coat layer) may be provided on the surface (the surface opposite to the surface facing the substrate 2). Such a layer may be removed, for example, when the timepiece dial is used.
Each of the above-described layers constituting the timepiece dial (for example, between the silicon oxide layer and the base material, the base material and the fine particle dispersed layer, the base material and the colored layer, and the colored layer and the fine particle dispersed layer) One or two or more intermediate layers may be provided.

Next, specific examples of the present invention will be described.
1. Manufacture of timepiece dial (Example 1)
A timepiece dial was manufactured by the following method.
First, the base material which has the shape of the timepiece dial was produced by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained base material was substantially disk-shaped and had a diameter: 27 mm × thickness: 500 μm.

Next, this base material was washed. As the substrate cleaning, ultrasonic cleaning in a neutral detergent was performed for 10 minutes, water cleaning for 10 seconds, and pure water cleaning for 10 seconds.
Thereafter, a silicon oxide layer and a zinc sulfide layer were sequentially formed on one surface (main surface) of the substrate cleaned as described above. As described in detail below, the silicon oxide layer and the zinc sulfide layer are formed by using a plurality of thin film materials made of a metal material as an evaporation source, heating the evaporation source in a high vacuum chamber, By evaporating the thin film material.
First, the cleaned substrate was mounted in a vacuum deposition apparatus, and then the inside of the vacuum deposition apparatus was evacuated (depressurized) to 1.3 × 10 ⁻⁴ Pa while preheating the interior of the apparatus.
In such a state, a laser is irradiated on a thin film composed of SiO ₂ having a purity of 99% or more as an evaporation source, and a silicon oxide layer composed of 99 wt% or more of SiO ₂ is processed under the condition of a processing time of 2 minutes. Formed. The silicon oxide layer thus formed had a thickness of 100 nm.

Subsequently, on the surface of the silicon oxide layer formed as described above, the inside of the vacuum evaporation apparatus was exhausted (reduced pressure) to 1.3 × 10 ⁻⁴ Pa, and ZnS having a purity of 99% or more was used as an evaporation source. The thin film thus formed was irradiated with a laser to form a zinc sulfide layer composed of 99 wt% or more of ZnS under the condition of a processing time of 1 minute. The thickness of the zinc sulfide layer thus formed was 20 nm.
The total thickness of the silicon oxide layer and the zinc sulfide layer obtained as described above was 120 nm.

Next, on the surface (main surface) opposite to the surface on which the silicon oxide layer and zinc sulfide layer of the base material are formed, a fine particle dispersion layer is formed as follows. I got a dial. That is, first, fine particles having an average particle diameter of 80 nm composed of SiO ₂ were dispersed in a mixture of melamine resin and methyl ethyl ketone to obtain a dispersion. Next, this dispersion was applied to the surface opposite to the surface on which the silicon oxide layer and the zinc sulfide layer were formed. Thereafter, the mixture was left for 1 minute in an environment of atmospheric pressure: 1.0 Pa and temperature: 30 ° C. to remove methyl ethyl ketone, thereby forming a fine particle dispersion layer in which fine particles were dispersed in a solid melamine resin. The thickness of the fine particle dispersion layer thus formed was 10 μm. The content of fine particles in the fine particle dispersed layer was 25 vol%.
The total thickness of the silicon oxide layer, the zinc sulfide layer, the fine particle dispersion layer, and the silicon oxide layer and the zinc sulfide layer was measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 2 to 4)
Change the content of each component in the dispersion used to form the fine particle dispersion layer, and process time in the vacuum evaporation system in the formation process of the substrate thickness, silicon oxide layer, and zinc sulfide layer Example 1 except that the content of the fine particles in the fine particle dispersed layer and the thickness of each layer were changed as shown in Table 1 by changing the coating amount of the dispersion used for forming the fine particle dispersed layer. A watch dial was manufactured in the same manner.
(Examples 5-7)
Except that the configuration of the fine particle dispersion layer was changed as shown in Table 1 by changing the size of the fine particles contained in the dispersion used for forming the fine particle dispersion layer and / or the type of the resin material, the above-described implementation was performed. A watch dial was manufactured in the same manner as in Example 1.

(Example 8)
First, the base material which has the shape of the timepiece dial was produced by compression molding using polycarbonate, and then necessary portions were cut and polished. The obtained base material was substantially disc-shaped and had a diameter: 27 mm × thickness: 490 μm.
Next, this base material was washed. As the substrate cleaning, ultrasonic cleaning in a neutral detergent was performed for 10 minutes, water cleaning for 10 seconds, and pure water cleaning for 10 seconds.

Thereafter, a silicon oxide layer and a zinc sulfide layer were sequentially formed on one surface (main surface) of the substrate cleaned as described above. As described in detail below, the silicon oxide layer and the zinc sulfide layer are formed by using a plurality of thin film materials made of a metal material as an evaporation source, heating the evaporation source in a high vacuum chamber, By evaporating the thin film material.
First, the cleaned substrate was mounted in a vacuum deposition apparatus, and then the inside of the vacuum deposition apparatus was evacuated (depressurized) to 1.3 × 10 ⁻⁴ Pa while preheating the interior of the apparatus.
In such a state, a laser is irradiated on a thin film composed of SiO ₂ having a purity of 99% or more as an evaporation source, and a silicon oxide layer composed of 99 wt% or more of SiO ₂ is processed under the condition of a processing time of 2 minutes. Formed. The silicon oxide layer thus formed had a thickness of 100 nm.

Subsequently, on the surface of the silicon oxide layer formed as described above, the inside of the vacuum evaporation apparatus was exhausted (reduced pressure) to 1.3 × 10 ⁻⁴ Pa, and ZnS having a purity of 99% or more was used as an evaporation source. The thin film thus formed was irradiated with a laser to form a zinc sulfide layer composed of 99 wt% or more of ZnS under the condition of a processing time of 1 minute. The thickness of the zinc sulfide layer thus formed was 20 nm.
The total thickness of the silicon oxide layer and the zinc sulfide layer obtained as described above was 120 nm.

Next, a colored layer and a fine particle dispersion layer are sequentially formed on the surface (main surface) opposite to the surface on which the silicon oxide layer and zinc sulfide layer of the substrate are formed as follows. Thus, a timepiece dial was obtained. That is, first, a colored layer composition composed of a cyan pigment and a urethane paint was applied to the surface of the substrate opposite to the surface on which the silicon oxide layer and the zinc sulfide layer were formed. Then, by leaving for 1 minute in an environment of atmospheric pressure: 1.0 Pa and temperature: 30 ° C., and removing the solvent contained in the urethane paint, the colorant and the urethane adhesive (urethane resin) are used. A structured colored layer was formed. The colored layer thus formed had a thickness of 10 μm. Next, a dispersion obtained by dispersing fine particles having an average particle diameter of 80 nm composed of SiO ₂ in a mixture of melamine resin and methyl ethyl ketone was applied to the surface of the formed colored layer. Thereafter, the mixture was left for 1 minute in an environment of atmospheric pressure: 1.0 Pa and temperature: 30 ° C. to remove methyl ethyl ketone, thereby forming a fine particle dispersion layer in which fine particles were dispersed in a solid melamine resin. The thickness of the fine particle dispersion layer thus formed was 10 μm. The content of fine particles in the fine particle dispersed layer was 25 vol%.
The total thickness of the silicon oxide layer, the zinc sulfide layer, the fine particle dispersed layer, the colored layer, and the silicon oxide layer and the zinc sulfide layer is in accordance with the microscope cross-section test method defined in JIS H5821. It was measured.

(Examples 9 to 11)
Change the content of each component in the dispersion used to form the fine particle dispersion layer, and process time in the vacuum evaporation system in the formation process of the substrate thickness, silicon oxide layer, and zinc sulfide layer By changing the coating amount of the colored layer composition used for forming the colored layer and the coating amount of the dispersion used for forming the fine particle dispersion layer, the content of fine particles in the fine particle dispersion layer and the thickness of each layer are shown in Table 1. A timepiece dial was manufactured in the same manner as in Example 8 except that the change was made as shown in FIG.
(Examples 12 and 13)
Example 8 except that the configuration of the fine particle dispersion layer was changed as shown in Table 1 by changing the size of the fine particles contained in the dispersion liquid used for forming the fine particle dispersion layer or the type of the resin material. A watch dial was manufactured in the same manner as described above.

(Comparative Example 1)
A timepiece dial was manufactured in the same manner as in Example 1 except that the step of forming the zinc sulfide layer was omitted.
(Comparative Example 2)
Except for changing the thickness of the silicon oxide layer as shown in Table 1 by changing the processing time in the vacuum deposition apparatus in the process of forming the silicon oxide layer, the same as in Comparative Example 1 above. A watch dial was manufactured.

(Comparative Example 3)
A timepiece dial was manufactured in the same manner as in Example 1 except that the step of forming the silicon oxide layer was omitted.
(Comparative Example 4)
Except for changing the thickness of the silicon oxide layer as shown in Table 1 by changing the treatment time in the vacuum deposition apparatus in the step of forming the zinc sulfide layer, the same as in Comparative Example 3 above. A watch dial was manufactured.

(Comparative Example 5)
A timepiece dial was manufactured in the same manner as in Example 1 except that the step of forming the fine particle dispersion layer was omitted.
(Comparative Example 6)
The surface of the zinc sulfide layer (silicon oxide of the zinc sulfide layer), not the surface (main surface) opposite to the surface on which the silicon oxide layer and zinc sulfide layer of the base material are formed A timepiece dial was manufactured in the same manner as in Example 1 except that it was formed on the surface opposite to the surface facing the physical layer.

(Comparative Example 7)
Without forming the fine particle dispersion layer on the surface (main surface) opposite to the surface on which the silicon oxide layer and zinc sulfide layer of the base material are formed, the silicon oxide layer and the zinc sulfide layer A timepiece dial was manufactured in the same manner as in Example 1 except that it was formed in between.
(Comparative Example 8)
A watch dial was manufactured in the same manner as in Example 1 except that the base material was made of acrylonitrile-butadiene-styrene copolymer (ABS resin) instead of the base material made of polycarbonate. .

Table 1 summarizes the configuration of the timepiece dial of each example and each comparative example. In Table 1, polycarbonate is represented by PC, ABS resin is represented by ABS, melamine resin is represented by MF, and vinyl acetate resin is represented by PVAc. The refractive indexes of the metal compound layers formed in the above examples and comparative examples were as follows. That is, the refractive index of the zinc sulfide (ZnS) layer was 2.30, and the refractive index of the silicon oxide (SiO ₂ ) layer was 1.46.

2. Visual appearance evaluation About each timepiece dial manufactured in each of the above Examples and Comparative Examples, visual observation is performed from the surface side on which the metal compound layer is formed, and these appearances are in accordance with the following six-stage criteria. ,evaluated.
A: Glossy and has a very good appearance.
A: Excellent appearance.
○: Good appearance.
Δ: Appearance is slightly poor.
X: Appearance is poor.
Xx: The appearance is extremely poor.

3. Appearance evaluation by chromaticity meter The chromaticity (a ^* b ^* ) of the surface side on which the metal compound layer was formed was measured with respect to the dial for timepiece manufactured in each of the above Examples and Comparative Examples. , CM-2022), and evaluated according to the following four-stage criteria.
A: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is in the range of -5 to 5 and b ^* is in the range of -4 to 4.
○: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is -10 to 10 and b ^* is in the range of -8 to 8 (excluding the range of ◎).
Δ: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is in the range of -15 to 15 and b ^* is in the range of -13 to 13 (except for the range of ◎ and ○).
×: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is −15 to 15 and b ^* is out of the range of −13 to 13.
As the light source of the colorimeter was a _{D 65} defined in JIS Z 8720, and measurements were taken at a viewing angle 2 °.

Further, according to the ^L * ^a * ^{b *} display ^{L *} values to the following four levels of the chromaticity diagram defined in JIS Z 8729, were evaluated.
A: In the chromaticity diagram of L ^* a ^* b ^* display defined by JIS Z 8729, L ^* is 75 ≦ L ^* ≦ 85.
○: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, L ^* is 55 ≦ L ^* <75.
Δ: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, L ^* is 45 ≦ L ^* <55.
×: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, L ^* is L ^* <45.

4). Variation in reflectance in visible light region Each wavelength in the visible light region (wavelength region of 380 to 780 nm) on the surface side on which the metal compound layer is formed in the timepiece dial plate manufactured in each of the examples and comparative examples. The reflectance at was measured. From this measurement result, in the visible light region (wavelength region of 380 to 780 nm), the reflectance A [%] at the wavelength where the reflectance is maximum and the reflectance B [%] at the wavelength where the reflectance is minimum. The difference AB was obtained and evaluated according to the following five-stage criteria. It can be said that the smaller the value of AB, the smaller the variation in reflectance in the visible light region. The reflectance was measured in a state where a solar cell was arranged on the back side of the timepiece dial.
A: The AB value is less than 8%.
A: AB value is 8% or more and less than 18%.
A: The value of AB is 18% or more and less than 23%.
(Triangle | delta): The value of AB is 23% or more and less than 28%.
X: The value of AB is 28% or more.

5. 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 as described above was made incident on the upper surface of the light receiving surface of the solar cell in a state where the timepiece dial was 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 four criteria. It can be said that the larger the light transmittance, the better the light transmittance of the timepiece dial. The timepiece dial was overlapped so that the surface of the base material on which the metal compound was formed faced the fluorescent lamp (light source) side.
A: 25% or more.
○: 20% or more and less than 25%.
Δ: 15% or more and less than 25%.
X: Less than 15%.

  Thereafter, a watch as shown in FIG. 3 was manufactured by 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, the movement of all of the timepieces of the present invention and the timepieces of the comparative examples was driven even when the irradiation intensity was relatively small.

6). 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 timepiece dial is. The timepiece dial was overlapped so that the surface of the base material on which the metal compound layer was formed faced the fluorescent lamp (light source) side.
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.

7). Durability evaluation of timepiece dials The following two types of tests were performed on the timepiece dials manufactured in the above-described examples and comparative examples to evaluate the durability of the timepiece dials.
7-1. 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.
A: No lifting or peeling of the metal compound layer or fine particle dispersion layer is observed.
A: Almost no floating of the metal compound layer and the fine particle dispersed layer is observed.
(Triangle | delta): The floating of a metal compound layer and a fine particle dispersion layer is recognized clearly.
X: Cracks and peeling of the metal compound layer and the fine particle dispersed layer are clearly recognized.

7-2. 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.
A: No lifting or peeling of the metal compound layer or fine particle dispersion layer is observed.
A: Almost no floating of the metal compound layer and the fine particle dispersed layer is observed.
(Triangle | delta): The floating of a metal compound layer and a fine particle dispersion layer is recognized clearly.
X: Cracks and peeling of the metal compound layer and the fine particle dispersed layer are clearly recognized.
These results are shown in Table 2.

As is apparent from Table 2, the timepiece dial of the present invention had an excellent aesthetic appearance and was excellent in electromagnetic wave (light and radio wave) permeability and durability.
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 simultaneously satisfy the excellent aesthetic appearance, the excellent electromagnetic wave permeability, and the durability as a timepiece dial.
Further, a timepiece as shown in FIG. 3 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 1st Embodiment of the dial for timepieces of this invention. It is sectional drawing which shows 2nd Embodiment 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.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1, 1 '... Timepiece dial 2 ... Base material 3 ... Silicon oxide layer 4 ... Zinc sulfide layer 5 ... Fine particle dispersion layer 51 ... Fine particle 52 ... Dispersion medium (resin) 6 ... Colored layer 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 ... Joint part (seal part) 100 ... Watch (portable watch)

Claims (14)

A substrate composed primarily of polycarbonate;
A silicon oxide layer composed primarily of silicon oxide;
A zinc sulfide layer provided adjacent to the silicon oxide layer and composed mainly of zinc sulfide;
A timepiece dial comprising: a silicon oxide layer provided on a surface opposite to a surface facing the zinc sulfide layer; and a fine particle dispersion layer in which fine particles made of SiO ₂ are dispersed. .   The timepiece dial according to claim 1, wherein the fine particles have an average particle diameter of 10 to 250 nm.   The timepiece dial according to claim 1 or 2, wherein a content ratio of the fine particles in the fine particle dispersed layer is 3 to 35 vol%.   The timepiece dial according to claim 1, wherein the fine particle dispersed layer is formed by dispersing the fine particles in a resin material.   The timepiece dial according to claim 1, wherein the fine particle dispersion layer has a thickness of 0.5 to 30 μm.   6. The fine particle dispersion layer is provided on a surface side of the substrate opposite to a surface on which the zinc sulfide layer and the silicon oxide layer are provided. The dial for clocks described in 1.   The timepiece dial according to claim 1, wherein the silicon oxide layer is provided adjacent to the substrate.   The timepiece dial according to claim 1, wherein the silicon oxide layer is formed by vapor deposition.   The timepiece dial according to claim 1, wherein the silicon oxide layer has a thickness of 20 to 200 nm.   The timepiece dial according to claim 1, wherein the zinc sulfide layer has a thickness of 10 to 100 nm.   The timepiece dial according to claim 1, wherein the total thickness of the silicon oxide layer and the zinc sulfide layer is 50 to 250 nm.   The timepiece dial according to claim 1, further comprising a colored layer made of a material containing a colorant, between the silicon oxide layer and the fine particle dispersed layer. The color tone of the timepiece dial on the surface side of the base material on which the zinc sulfide layer is provided is as follows. In the chromaticity diagram of L ^* a ^* b ^* display defined by JIS Z 8729, a ^* is − The timepiece dial according to any one of claims 1 to 12, wherein the dial is 10 to 10 and b ^* is -8 to 8.   A timepiece comprising the timepiece dial according to claim 1.

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