JP2015161621A - Timepiece dial, manufacturing method for the timepiece dial, and timepiece - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a timepiece dial which has sufficient optical transparency and is excellent in decorativeness (esthetic appearance); to provide a manufacturing method in which the timepiece dial having sufficient optical transparency and excellent in decorativeness (esthetic appearance) can be efficiently manufactured; and to provide a timepiece equipped with the timepiece dial.SOLUTION: A timepiece dial P10 includes a base material P1; and a coating film P3 which is formed by a particle accumulated by spraying aerosol obtained by dispersing the particle into gas from a nozzle. The coating film P3 is formed by accumulating a plurality of particles containing a second particle generated by causing a chemical reaction of a first particle constituted of a material having reactivity in a film forming process.

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 be practical, such as visibility, and to have decorativeness (aesthetic appearance). In particular, in solar timepieces equipped with solar cells, when solar cells (solar cells) are placed under the dial (solar watch dial), the dial has excellent light transmissivity and other decorative items. Decorative properties (aesthetic appearance) are required.

  Specifically, the dial for a solar timepiece provides a sufficient amount of light for driving the timepiece through a solar cell disposed below the solar dial, while providing a decorative item. Decorative properties are also required.

  As a dial for a solar watch, which tried to prevent the solar cell from being seen through the dial, it was made of a metal material with an adhesive on a plastic substrate. A dial plate obtained by pasting a provided metal film has been proposed (see, for example, Patent Document 1).

  However, with such a dial, it has been difficult to achieve both excellent light transmission and aesthetic appearance. That is, in order to ensure light transmittance, when the aperture ratio of the metal film (the ratio of the area occupied by the opening to the entire metal film when the metal film is viewed in plan) is relatively high, Even though the presence is conspicuous and a metal material (metal film) is used, a sufficiently excellent aesthetic appearance cannot be obtained. In solar timepieces, generally solar cells exhibiting a dark color such as black or dark purple are used, but when solar timepieces are provided with such solar cells, openings and openings in the metal film Differences in color tone and brightness from other parts (parts covered with a metal film) become conspicuous, and as a result, the presence of the opening becomes very conspicuous, and the timepiece dial when applied to a watch The aesthetic appearance is particularly inferior. On the other hand, when the aperture ratio of the metal film is lowered for the purpose of improving the aesthetic appearance, the light transmittance is lowered, and the power generation efficiency of the solar cell is significantly lowered. Moreover, the manufacturing method of the above dial plates is also inferior in productivity.

  A dial plate including a diffusion layer in which a diffusing agent is dispersed and a polarizing plate has also been proposed (see, for example, Patent Document 2). In such a dial plate, a white-colored appearance that prevents the observer from recognizing the presence of the solar cell can be obtained even when the solar cell is arranged on the back side due to light scattering and diffusion. However, since such a dial plate has a configuration including a polarizing plate, it is inevitably impossible to increase the transmittance to a predetermined value or more. For example, when the dial itself is colored. Could not secure a sufficient light transmittance.

JP 11-326549 A International Publication No. 2006/006390

  An object of the present invention is to provide a timepiece dial plate having sufficient light transmission and excellent decorativeness (aesthetic appearance), having sufficient light transmission, and decorative properties (aesthetic). An object of the present invention is to provide a timepiece dial manufacturing method capable of efficiently manufacturing a timepiece dial having an excellent appearance, and to provide a timepiece having the timepiece dial.

Such an object is achieved by the present invention described below.
The timepiece dial of the present invention comprises a base material,
A coating formed by spraying an aerosol formed by dispersing particles in a gas from a nozzle;
The coating film is formed by depositing a plurality of particles including second particles generated by chemically reacting first particles made of a reactive material in a film forming process. It is characterized by that.

  As a result, it is possible to provide a timepiece dial having sufficient light transmissivity and excellent in decorativeness (aesthetic appearance).

  In the timepiece dial of the present invention, the light transmittance is preferably 5% or more and 70% or less.

  As a result, it is possible to realize both the aesthetic appearance of the timepiece dial and the light transmission at a higher level.

  In the timepiece dial according to the aspect of the invention, it is preferable that the coating includes the first particles in addition to the second particles.

  Thereby, the film which has a color tone, a pattern, etc. which cannot be expressed only with a single kind of particle | grains can be formed. Further, in the coating, the first particles and the second particles can be arranged in a predetermined pattern, and for example, an appearance with gradation can be suitably expressed.

  In the timepiece dial according to the aspect of the invention, it is preferable that the coating includes a plurality of types of particles having different degrees of progress of the chemical reaction as the second particles.

  Thereby, the film which has a color tone, a pattern, etc. which cannot be expressed only with a single kind of particle | grains can be formed. In addition, in the coating, a plurality of types of second particles can be arranged in a predetermined pattern, and for example, a gradation-like appearance can be suitably expressed.

  In the timepiece dial of the present invention, it is preferable that the base material is made of a material including one or more selected from the group consisting of sapphire glass, quartz and plastic.

  Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent. Further, the durability of the timepiece provided with the timepiece dial can be further improved.

  The timepiece dial of the present invention preferably has at least one underlayer between the base material and the coating.

  Thereby, the adhesiveness of a base material and a film can be made especially excellent. Further, by making the underlayer function as a colored layer, the aesthetic appearance of the timepiece dial can be further improved. In addition, by making the underlayer function as a gap layer, it is possible to obtain a three-dimensional appearance such that the coating is lifted.

  In the timepiece dial of the present invention, it is preferable that the average particle diameter of the second particles is 10 nm or more and 100 μm or less.

  Thereby, the aesthetic appearance of the timepiece dial can be made particularly excellent. In addition, the durability of the timepiece dial can be made particularly excellent. Further, the productivity of the timepiece dial can be made particularly excellent.

  In the timepiece dial of the present invention, it is preferable that a protective film is provided on the surface of the coating opposite to the surface facing the substrate.

  Thereby, the unintended chemical reaction of the particle | grains which comprise a film can be prevented effectively, and the timepiece dial can maintain the outstanding aesthetic appearance stably over a long period of time. In addition, the timepiece dial can exhibit stable characteristics (for example, light transmittance) over a long period of time.

The method for manufacturing a timepiece dial of the present invention includes a base material preparation step of preparing a base material,
A film forming step of forming a film by spraying an aerosol formed by dispersing particles in a gas from a nozzle;
In the film forming step, first particles composed of a reactive material are used as a raw material, and the first particles are chemically reacted to generate second particles, which include the second particles. The film is formed by depositing a plurality of particles.

  Thereby, it is possible to provide a timepiece dial manufacturing method capable of efficiently manufacturing a timepiece dial having sufficient light transmittance and excellent decorativeness (aesthetic appearance).

In the timepiece dial manufacturing method of the present invention, the first particles are made of a material containing a metal material,
The second particles are preferably composed of a material including at least one selected from the group consisting of metal oxides, metal sulfides, and metal nitrides.

  Thereby, the coloring property of a film can be adjusted more suitably. Further, the chemical stability of the coating is improved by the passive state, and the durability of the timepiece dial can be made particularly excellent.

In the timepiece dial manufacturing method of the present invention, the first particles are made of a material containing a metal oxide,
It is preferable that the second particles are made of a metal material.

  Thereby, for example, when the metal particles as the constituent material of the film are relatively soft materials, and when stored in the state of particles as they are, they tend to cause aggregation or adhesion to the wall surface of the container. It is possible to suitably form a film while effectively preventing the occurrence of such a problem.

  In the timepiece dial manufacturing method of the present invention, it is preferable to include an underlayer forming step of forming at least one underlayer between the base material preparing step and the film forming step.

  Thereby, the adhesiveness of a base material and a film can be made especially excellent. Further, by making the underlayer function as a colored layer, the aesthetic appearance of the timepiece dial can be further improved. In addition, by making the underlayer function as a gap layer, it is possible to obtain a three-dimensional appearance such that the coating is lifted.

  In the timepiece dial manufacturing method of the present invention, it is preferable to have a protective film forming step of forming a protective film after the coating film forming step.

  Thereby, the unintended chemical reaction of the particle | grains which comprise a film can be prevented effectively, and the timepiece dial can maintain the outstanding aesthetic appearance stably over a long period of time. In addition, the timepiece dial can exhibit stable characteristics (for example, light transmittance) over a long period of time.

The timepiece of the present invention includes the timepiece dial of the present invention.
Thereby, it is possible to provide a timepiece having a timepiece dial plate having sufficient light transmissivity and excellent in decorativeness (aesthetic appearance).

  The timepiece of the present invention includes a timepiece dial manufactured using the method of the present invention.

  Thereby, it is possible to provide a timepiece having a timepiece dial plate having sufficient light transmissivity and excellent in decorativeness (aesthetic appearance).

It is typical sectional drawing which shows suitable embodiment of the timepiece dial of this invention. It is a typical top view which shows suitable embodiment of the timepiece dial of this invention. It is a typical top view which shows other suitable embodiment of the timepiece dial of this invention. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the dial for timepieces of this invention. It is a longitudinal cross-sectional side view which shows suitable embodiment of the film formation apparatus used for formation of a film. It is a longitudinal cross-sectional side view which shows an example of a structure of the crusher with which a film forming apparatus is provided. It is a block diagram of the principal part of the film formation apparatus shown in FIG. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (portable timepiece) of this invention.

  Hereinafter, a timepiece dial, a method for manufacturing a timepiece dial, and a timepiece according to the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

<< clock dial >>
First, the timepiece dial of the present invention will be described.

  1 is a schematic sectional view showing a preferred embodiment of the timepiece dial of the present invention, FIG. 2 is a schematic plan view showing a preferred embodiment of the timepiece dial of the present invention, and FIG. These are typical top views which show other suitable embodiment of the timepiece dial of this invention.

  As shown in FIG. 1, the timepiece dial P10 of this embodiment includes a base material (substrate) P1, a base layer P2, a coating P3, and a protective film P4.

  The timepiece dial P10 has light transmittance as a whole. For this reason, the timepiece dial P10 can be suitably applied to a solar timepiece (a timepiece having a solar cell) or the like. Further, the timepiece dial P10 is excellent in radio wave permeability, and therefore can be suitably applied to radio timepieces (including GPS timepieces).

<Base material>
The base material P1 has transparency.

  Specifically, the light transmittance (wavelength: 600 nm light transmittance) of the substrate P1 is preferably 70% or more, more preferably 85% or more, and 90% or more. Is more preferable.

  Thereby, the light transmittance as the whole timepiece dial P10 can be made particularly excellent.

  The substrate P1 is preferably made of a material including one or more selected from the group consisting of sapphire glass, quartz, and plastic.

  When the base material P1 is made of a material containing one or more selected from these groups, the aesthetic appearance of the timepiece dial P10 can be made particularly excellent. Further, the durability of the timepiece provided with the timepiece dial P10 can be further improved.

  Examples of the plastic material constituting the substrate P1 include various thermoplastic resins and various thermosetting resins, such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA). Polyolefin, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide (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), polybutylene terephthalate (PBT) ), Polyester such as polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyether Sulphone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride Other thermoplastic resins such as fluorine resins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene, etc. , Phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, poly Polyparaxylylene such as dichloro-para-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, etc. Ren resin, etc., or copolymers, blends, polymer alloys mainly composed of these And 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 base material P1 is composed of a material containing at least one selected from polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS resin) among the above materials. preferable.

  Thereby, the strength of the timepiece dial P10 as a whole can be made particularly excellent. In addition, when the timepiece dial P10 is manufactured, since the degree of freedom of molding the base material P1 is increased (easiness of molding is improved), even if the timepiece dial P10 has a more complicated shape, It can be manufactured easily and reliably. Polycarbonate is relatively inexpensive among various plastic materials, and can contribute to further reduction in the production cost of the timepiece dial P10. The ABS resin also has particularly excellent chemical resistance, and the durability of the timepiece dial P10 as a whole can be further improved.

  In addition, the base material P1 may contain components other than the above. Examples of such components include plasticizers, antioxidants, colorants (including various color formers, fluorescent substances, phosphorescent substances, etc.), brighteners, fillers, and the like.

  Moreover, the base material P1 may have a substantially uniform composition at each site, or may have a different composition depending on the site. For example, the base material P1 may have a base portion and a surface layer provided on the base portion. Further, it may be composed of a gradient material whose composition changes in a gradient manner.

  The shape and size of the base material P1 are not particularly limited, and are usually determined based on the shape and size of the timepiece dial P10.

  Moreover, although the base material P1 may be shape | molded by what kind of method, as a shaping | molding method of the base material P1, compression molding, extrusion molding, injection molding, stereolithography, etc. are mentioned, for example.

<Coating>
The coating P3 is formed by depositing particles P31 by spraying an aerosol formed by dispersing particles P31 in a gas from a nozzle.

  Such a method has a feature that, as will be described later in detail, the coating P3 can be selectively formed at a desired site, and waste of materials can be effectively prevented. . Further, pre-processing such as mask formation and post-processing such as removal of unnecessary film forming portions can be omitted or simplified. Moreover, the coating P3 having an excellent texture can be formed. Therefore, it is possible to provide a timepiece dial P10 that is excellent in aesthetic appearance, has little waste of materials during manufacture, and has a low environmental impact.

  In addition, with the above method, the film P3 having a desired pattern can be easily and reliably formed. For this reason, for example, even a coating film having a complicated shape and a fine shape with high design can be suitably formed. Moreover, the film P3 that functions as an index such as a time character can also be suitably formed. In addition, since a relatively thick coating P3 can be suitably formed, a three-dimensional expression can be achieved, and the watch dial P10 as a whole and the watch as a whole equipped with the watch dial P10 can be aesthetically aesthetic. The quality and luxury can be made particularly excellent. In particular, such an effect is remarkably exhibited when a part of the coating P3 is caused to function as an index such as a time letter.

  Further, in the above method, since it is not necessary to use a volatile solvent or the like, a problem caused by volatilization of a volatile component (volatile organic compound) in a state where the timepiece dial P10 is incorporated in the timepiece (movement of the movement). Failure, occurrence of trouble, fogging of cover glass, etc.) can be effectively prevented.

  Further, since the coating P3 is formed by depositing a plurality of particles P31, for example, the coating P3 is provided not only in the region where the coating P3 is not provided on the substrate P1. Even in the region, light can be transmitted. This is due to the following reasons. That is, since the plurality of particles P31 are stacked, there is a gap (gap) between the adjacent particles P31. A part of the light incident on the coating P3 enters the gap between the particles P31 and repeats reflection to be emitted to the surface opposite to the incident surface.

  Further, since the coating P3 is formed by spraying aerosol from a nozzle and depositing the particles P31, the texture and aesthetic appearance of the coating P3 are sufficient even when the coating P3 is relatively thin. It can be made excellent. For this reason, the texture and aesthetic appearance of the coating P3 can be made sufficiently excellent while increasing the proportion of light transmitted (not reflected) through the substance part of the coating P3.

  From the above, the timepiece dial P10 has an excellent aesthetic appearance and an excellent light transmission property. Therefore, the timepiece dial P10 can be suitably applied to a solar timepiece (a timepiece having a solar cell).

  Further, as described above, the coating P3 is formed by spraying an aerosol in which the particles P31 are dispersed in a gas from a nozzle, and satisfies the following conditions. That is, it is formed by depositing a plurality of particles P31 including the second particles P31B. The second particles P31B are obtained by chemically reacting the first particles P31A made of a reactive material in the film formation process.

  When the coating P3 includes such second particles P31B, the following effects can be obtained.

  For example, when the second particles are likely to agglomerate, it is difficult to stably form an aerosol using the second particles as a raw material, and the size of the particles ejected from the nozzle, The variation in shape becomes large, and the formed film has a large unintentional variation in film thickness and film quality. In addition, since the particle injection itself becomes unstable, it may be difficult to form a film having a desired shape. On the other hand, such a problem can be reliably prevented by including in the coating the second particles P31B formed in the film formation process using the first particles as a raw material.

  Further, for example, the coating P3 can be easily added to the second particle P31B and the first particle P31A can be included by adjusting the timing of the reaction with respect to the first particle P31A.

  Therefore, even when a single type of particle (first particle P31A) is used, the coating P3 including a plurality of types of particles (first particle P31A and second particle) is easily and reliably formed. be able to.

  Thus, since the coating P3 includes a plurality of types of particles (the first particles P31A and the second particles), for example, a coating having a color tone, a pattern, or the like that cannot be expressed by only a single type of particles. P3 can be formed.

In addition, when the coating P3 includes the first particles P31A in addition to the second particles P31B, for example, the first particles P31A and the second particles P31B are arranged in a predetermined pattern in the coating P3. Can be.
Thereby, for example, an appearance with gradation can be suitably expressed.

  In addition, for example, by adjusting the degree of reaction with respect to the first particle P31A, the second particle P31B includes a plurality of types of particles P31 (second particles P31B) having different degrees of progress of the chemical reaction. Can do.

  Therefore, even when a single type of particle (first particle P31A) is used, the coating P3 including a plurality of types of particles (a plurality of types of second particles) can be easily and reliably formed. .

  As described above, since the coating P3 includes a plurality of types of particles (a plurality of types of second particles), for example, the coating P3 having a color tone, a pattern, or the like that cannot be expressed only by a single type of particles is formed. can do.

Further, when the coating P3 includes a plurality of types of second particles P31B, for example, in the coating P3, these different types of particles P31 (second particles P31B) are arranged in a predetermined pattern. can do.
Thereby, for example, an appearance with gradation can be suitably expressed.

  Examples of the combination of the first particle P31A and the second particle P31B include a combination of a metal material and a metal oxide, a combination of a metal material and a metal sulfide, and the like.

  Examples of the metal material include Au, Pt, Ag, Pd, Rh, Al, Ti, Cr, Co, Ni, Fe, Mn, V, Cu, Zn, Nb, Zr, Mo, Y, Eu, Sr, and Si. , Ga, Ge, Sb, W, Ir, Ru, In, etc., and alloys containing one or more of these.

  More specific examples of the combination of the metal material and the metal oxide include a combination of nickel and nickel oxide, a combination of silver and silver oxide, and a combination of chromium and chromium oxide.

  By such a combination, a color range from black to gray (silver) can be expressed, and various patterns can be suitably formed.

Further, as a more specific example of the combination of a metal material and a metal oxide, a phosphor material such as Y ₂ O ₃ : Eu or SrTiO ₃ : Pr, a reductant of the phosphor material, and the like can be given. Thus, by using a phosphor material as one of the first particle P31A and the second particle P31B, a region exhibiting a fluorescent color such as red or blue by absorption of ultraviolet rays or the like and a fluorescent color are exhibited. A film P3 having no region can be formed.

  More specific examples of the combination of the metal material and the metal sulfide include a combination of silver and silver sulfide.

  By such a combination, a color range from yellow to gray (silver) can be expressed, and various patterns can be suitably formed.

  A more specific example of a combination of a metal material and a metal nitride includes a combination of Ti, TiN, and TiON.

  With such a combination, it is possible to express a color range from brown (black) to gold, and in particular, coloring can be performed while adjusting the transmittance more suitably.

  Adjustment of the composition of metal nitrides such as TiN and TiON can be suitably performed by adjusting the supply amount, ratio, and the like of an oxidizing gas such as oxygen and a nitriding gas such as ammonia gas.

  The average particle diameter of the second particles P31B is preferably 10 nm or more and 100 μm or less, and more preferably 100 nm or more and 80 μm or less.

  Thereby, reflection of light between the particles P31 and absorption of light in the gaps between the particles P31 as described above can be performed more efficiently, and the aesthetic appearance of the timepiece dial P10 is particularly excellent. can do. Further, the adhesion between the base material P1 and the coating P3 (adhesion through the underlayer P2) can be made particularly excellent, and the durability of the timepiece dial P10 can be made particularly excellent. it can. Moreover, the formation efficiency of the coating P3 becomes particularly excellent, and the productivity of the timepiece dial P10 can be made particularly excellent. Further, when the second particles P31B are made of a metal material, the gloss of the timepiece dial P10 is particularly excellent, and the light transmittance of the timepiece dial P10 as a whole is improved. It can be made particularly excellent.

  In the present specification, “average particle diameter” refers to an average particle diameter based on mass. This average particle diameter can be obtained, for example, by measuring the mobility of the aerosol and determining the aerodynamic diameter. For the measurement of the particle diameter, for example, a differential electrostatic classifier manufactured by TSI can be used. In addition, you may obtain | require an average particle diameter from the measurement result of a scanning electron microscope or a transmission electron microscope.

  In the illustrated configuration, the coating P3 includes the first particles P31A as well as the second particles P31B.

  The average particle diameter of the first particles P31A is preferably 10 nm or more and 100 μm or less, and more preferably 100 nm or more and 80 μm or less.

  Thereby, reflection of light between the particles P31 and absorption of light in the gaps between the particles P31 as described above can be performed more efficiently, and the aesthetic appearance of the timepiece dial P10 is particularly excellent. can do. Further, the adhesion between the base material P1 and the coating P3 (adhesion through the underlayer P2) can be made particularly excellent, and the durability of the timepiece dial P10 can be made particularly excellent. it can. Moreover, the formation efficiency of the coating P3 becomes particularly excellent, and the productivity of the timepiece dial P10 can be made particularly excellent. When the first particles P31A are made of a metal material, the gloss of the timepiece dial P10 is particularly excellent, and the light transmittance of the timepiece dial P10 as a whole is improved. It can be made particularly excellent.

  The coating P3 may be provided on the entire surface of the substrate P1, but is preferably provided so as to cover a part of the substrate P1. Thereby, the light transmittance of the timepiece dial P10 can be made particularly excellent. Further, conventionally, when the coating is provided so as to cover a part of the base material (the dial body), there is a problem that the waste of the material is particularly large at the time of manufacturing the timepiece dial. However, according to the present invention, the occurrence of such a problem can be reliably prevented. Therefore, when the coating P3 is provided so as to cover a part of the substrate P1, the effect of the present invention is more remarkably exhibited.

  The coverage of the coating P3 when the timepiece dial P10 is viewed in plan is preferably 50% or more and 95% or less, and more preferably 70% or more and 90% or less.

  As a result, it is possible to realize both the aesthetic appearance of the timepiece dial P10 and the light transmission at a higher level.

  The average thickness of the coating P3 is preferably 0.01 μm or more and 300 μm or less, more preferably 0.05 μm or more and 160 μm or less, and further preferably 0.10 μm or more and 70 μm or less.

  Thereby, the aesthetic appearance of the timepiece dial P10 can be made particularly excellent. Further, the light transmission of the timepiece dial P10 can be made particularly excellent. Further, the durability of the timepiece dial P10 can be made particularly excellent.

2 and 3 are schematic plan views showing a preferred embodiment of the timepiece dial of the present invention.
In the configuration shown in FIG. 2, a spiral pattern is formed by a region (first region) configured by the first particles P31A and a region (second region) configured by the second particles P31B. Yes.

  Thus, according to the present invention, even a pattern having a plurality of color regions can be suitably formed.

  In the configuration shown in FIG. 3, a plurality of dot-like regions (first regions) composed of the first particles P31A are scattered in the second region composed of the second particles P31B. It has the composition which has. By having such a configuration, for example, a pattern imitating a starry sky can be provided.

  In the configuration shown in FIG. 3, the first particles P31A and the second particles P31B may be made of any material. For example, the first particles P31A are made of a phosphor material. By doing so, the state of the night sky can be expressed when observed in a dark environment, and the aesthetic appearance of the timepiece dial P10 can be made particularly excellent.

  In the description of FIGS. 2 and 3, the relationship between the first particles P31A and the second particles P31B may be opposite to that described above.

<Underlayer>
In the illustrated configuration, a base layer P2 is provided between the substrate P1 and the coating P3.

  Thereby, for example, the adhesion between the substrate P1 and the coating P3 (adhesion via the base layer P2) can be made particularly excellent. Further, for example, by making the base layer P2 function as a colored layer, the aesthetic appearance of the timepiece dial P10 can be further improved. Further, by making the underlayer P2 function as a gap layer, it is possible to obtain a three-dimensional appearance such that the coating P3 is lifted.

The average thickness of the underlayer P2 is preferably 0.01 μm or more and 10 μm or less.
Thereby, the foundation layer P2 can more effectively exhibit the functions as described above.

  The underlayer P2 may be made of any material, and examples of the constituent material of the underlayer P2 include TiN, AlN, SiN, GaN, SiO, SiON, etc. , TiN, AlN, and SiN are preferably made of a material containing one or more selected from the group consisting of TiN, AlN, and SiN.

  As a result, adhesion between the substrate P1 and the coating P3 (adhesion through the underlayer P2), particularly when the coating P3 is made of a material containing a metal material, metal oxide, or metal nitride. In particular, the adhesion can be made excellent. Further, since TiN, AlN and SiN are materials having high transparency as described above, it is more effective to adversely affect the appearance and light transmittance of the timepiece dial P10 as a whole. Can be prevented.

  In the configuration shown in the figure, the base layer P2 is provided on the entire surface of the base material P1 on which the coating P3 is provided. For example, the base layer P2 is selectively applied only to a portion in contact with the coating P3. It may be provided. Further, the base layer P2 may be provided only in a part of the portion where the coating P3 is provided.

  Further, in the configuration shown in the figure, the case where the single base layer P2 is provided has been described, but the timepiece dial may be provided with two or more base layers.

  The underlayer P2 may have a uniform composition at each site or may have a different composition. For example, it may be composed of a laminated body in which layers having different compositions in the thickness direction are laminated, or a gradient material whose composition changes in a gradient manner.

<Protective film>
In the illustrated configuration, a protective film P4 is provided on the surface of the coating P3 opposite to the surface facing the substrate P1.

  Thereby, the unintentional chemical reaction of particle | grains P31 (1st particle | grain P31A, 2nd particle | grain P31B) which comprises the film P3 can be prevented effectively. As a result, the timepiece dial P10 can stably maintain an excellent aesthetic appearance over a long period of time. In addition, the timepiece dial P10 can exhibit stable characteristics (for example, light transmittance) over a long period of time.

  The protective film P4 may be any film that covers the film P3 and has a function of protecting the film P3. For example, an antireflection film may be used as the protective film P4.

  As a result, the function as a protective film as described above is exhibited, and unintentional reflection of external light can be effectively prevented, and the aesthetic appearance of the timepiece dial P10 is particularly excellent. can do.

  The thickness of the protective film P4 is not particularly limited, but is preferably 0.2 μm or more and 10 μm or less, and more preferably 0.3 μm or more and 7 μm or less.

  Thereby, the function as described above can be more effectively exhibited while effectively preventing the timepiece dial P10 from being thickened.

  In the illustrated configuration, the protective film P4 is provided on the entire surface of the base material P1 on which the coating film P3 is provided. For example, the protective film P4 is provided on the side on which the coating film P3 of the base material P1 is provided. It may be selectively provided only on a part of the surface.

  The light transmittance (wavelength: light transmittance at 600 nm) of the timepiece dial P10 is preferably 5% to 70%, more preferably 7% to 65%, and more preferably 10% or more. More preferably, it is 62% or less.

  As a result, it is possible to realize both the aesthetic appearance of the timepiece dial P10 and the light transmission at a higher level.

<< Method for manufacturing timepiece dial >>
Next, a method for manufacturing a timepiece dial according to the present invention will be described.

  FIG. 4 is a cross-sectional view schematically showing each step in a preferred embodiment of the timepiece dial manufacturing method of the present invention.

  As shown in FIG. 4, the manufacturing method of the present embodiment includes a base material preparation step (1a) for preparing the base material P1, a base layer formation step (1b) for forming the base layer P2 on the surface of the base material P1, and A film forming step (1c) for forming a film P3 on the surface of the underlayer, and a protective film forming step (1d) for forming a protective film P4 on the surface side of the base material P1 on which the film P3 is provided. Yes.

<Base material preparation process>
In the base material preparation step, the base material P1 as described above is prepared (1a).

  The substrate P1 prepared in this step may be subjected to a cleaning treatment such as water washing, alkali washing, acid washing, washing with an organic solvent, or the like.

  Moreover, the surface treatment may be performed for the purpose of improving the adhesion with the layer formed on the substrate P1.

<Underlayer formation process>
Next, the base layer P2 is formed on the surface of the substrate P1 (1b).

  The underlayer P2 formed in this step preferably satisfies the conditions described above.

  The underlayer P2 can be formed by, for example, a vapor deposition method (dry plating method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD), wet plating method, dipping, or the like.

  The underlayer P2 is formed in the same manner as the coating P3, that is, an aerosol in which particles (particles made of the constituent material of the underlayer P2) are dispersed in a gas is directed from the nozzle toward the substrate P1. A method of spraying and forming the base layer P2 by the impact force may be employed. Thereby, the foundation layer P2 can be selectively and efficiently formed at a desired site.

<Film formation process>
Next, a coating P3 is formed on a part of the surface of the base layer P2 (1c).

  In particular, an aerosol in which particles P31 are dispersed in a gas is sprayed from a nozzle toward the substrate P1, and the particles P31 are deposited (attached) by the impact force to form a coating P3.

  In this step, the first particle P31A is used as a raw material, and this is reacted to obtain the second particle P31B. Then, a plurality of particles P31 including the second particles P31B are deposited to form a coating P3. Thereby, the effects as described above can be obtained.

  The particles P31 (first particles P31A and second particles P31B) used in this step and the coating P3 to be formed preferably satisfy the above-described conditions.

  In this step, for example, the first particle P31A is composed of a material including a metal material, and is a material including at least one selected from the group consisting of metal oxides, metal sulfides, and metal nitrides. The configured second particles P31B can be formed.

  Thereby, the color development property of the film P3 can be adjusted more suitably. Moreover, the chemical stability of the coating P3 is improved by the passive state, and the durability of the timepiece dial P10 can be made particularly excellent.

  When the first particle P31A is made of a material containing a metal material and the second particle P31B made of a material containing a metal oxide is formed, oxidation of oxygen or the like as a carrier gas is performed. A sex gas can be preferably used.

  In addition, when the second particle P31B made of a material containing a metal sulfide is formed as the first particle P31A using a material containing a metal material, hydrogen sulfide or the like is used as a carrier gas. A sulfide gas can be suitably used.

  In addition, when the first particle P31A is made of a material containing a metal material and the second particle P31B made of a material containing a metal nitride is formed, nitridation of ammonia or the like as a carrier gas A sex gas can be preferably used.

  In this step, for example, the first particles P31A made of a material containing a metal oxide can be used to form the second particles P31B made of a material containing a metal material.

  Thereby, for example, when the metal particles as the constituent material of the coating P3 is a relatively soft material, and when it is stored as it is in the state of particles, it tends to cause aggregation and adhesion to the wall surface of the container. The coating P3 can be suitably formed while effectively preventing the occurrence of such a problem.

  In addition, when using the thing comprised with the material containing a metal oxide as the 1st particle P31A and forming the 2nd particle P31B comprised with the material containing a metal material, reduction | restoration of hydrogen etc. as carrier gas A sex gas can be preferably used.

The processing conditions in this step may be constant or may change over time.
For example, by changing the composition of the carrier gas of the particles P31 over time, the composition of the deposited particles (first particle P31A, second particle P31B) and the composition of the coating P3 can be adjusted easily and reliably. Can do. As a result, the color tone, characteristics, and the like of the part of the coating P3 can be suitably adjusted. In addition, formation of a pattern composed of a plurality of colors (including a gradation pattern) can be suitably performed.

Alternatively, the incident angle of the particles P31 and the spray pressure of the aerosol containing the particles P31 may be changed over time. Thereby, the shape of the film P3 to be formed can be suitably adjusted.
The film forming apparatus used in this step will be described in detail later.

<Protective film formation process>
Next, a protective film P4 is formed on the side of the substrate P1 on which the coating P3 is provided (1d).

  The protective film P4 formed in this step preferably satisfies the conditions described above.

  The protective film P4 can be formed by, for example, a vapor deposition method (dry plating method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD), wet plating method, dipping, or the like.

<Film forming device>
Next, a film forming apparatus used for forming the film P3 will be described.

  FIG. 5 is a longitudinal sectional side view showing a preferred embodiment of a coating film forming apparatus used for forming a coating film, FIG. 6 is a longitudinal sectional side view showing an example of the configuration of a crusher included in the coating film forming apparatus, and FIG. These are block diagrams of the principal part of the film formation apparatus shown in FIG. In the following, for convenience of explanation, in FIG. 5, the x axis, the y axis, and the z axis are illustrated as three axes orthogonal to each other. The x-axis is an axis along one of the horizontal directions, the y-axis is an axis along the horizontal direction and perpendicular to the x-axis, and the z-axis is a vertical direction (up and down Direction). In addition, the tip side of each illustrated arrow is a “positive side (+ side)” and the base end side is a “negative side (− side)”. Further, the upper side in FIG. 5 is referred to as “upper (upper)”, and the lower side is referred to as “lower (lower)”. Moreover, in FIG. 5, illustration of the foundation | substrate layer P2 provided on the base material P1 is abbreviate | omitted.

  As shown in FIGS. 5, 6, and 7, the film forming apparatus 1 includes an aerosol generator 15, a disintegrator 4, a film forming chamber 16, a connecting pipe 2, a connecting pipe 8, and a gas supply unit. 3 (3A, 3B, 3C, 3D), pressure adjusting means 5, moving means 6, and control unit 7.

  The aerosol generator 15 is configured to maintain airtightness, and can accommodate therein particles P31 used for forming the coating P3.

The crusher 4 is connected to an aerosol generator 15 by a connecting pipe 8.
The crusher 4 has a function of crushing the particles P31 contained in the aerosol generated by the aerosol generator 15.

  The film forming chamber 16 is provided independently of the aerosol generator 15 and the crusher 4. The film forming chamber 16 is also configured to maintain airtightness, and a plurality of base materials P1 can be accommodated therein.

  The room temperature in the film forming chamber 16 is adjusted to 25 ° C. or higher and 30 ° C. or lower by, for example, water cooling, that is, by a refrigerant passing through the piping.

  The connecting pipe 2 connects the crusher 4 and the film forming chamber 16, and the inner cavity portion 22 functions as a flow path through which the particles P31 used for forming the coating P3 pass.

  The connecting pipe 2 has a first opening (one end opening) 25 opened at one end thereof facing the inside of the crusher 4, and a second opening (other end opening) 21 opened at the other end. It faces the film forming chamber 16.

  With such a configuration, the aerosol generator 15 and the film forming chamber 16 communicate with each other via the connecting pipe 8, the disintegrator 4 and the connecting pipe 2.

  The second opening 21 is arranged in parallel to the surface direction of the base material P <b> 1 accommodated in the film forming chamber 16. And the particle | grains P31 which pass through the connection pipe 2 (lumen part 22) are sprayed on the base material P1 from the 2nd opening part 21. FIG. Thereby, the coating P3 is formed on the base material P1 (in particular, in this embodiment, the surface of the foundation layer P2). Thus, in the connecting pipe 2, the portion on the second opening 21 side functions as the nozzle portion 24.

  The average inner diameter of the connecting tube 2 is not particularly limited, but is preferably 1 mm or more and 10 mm or less, for example. Moreover, the internal diameter of the 2nd opening part 21 is although it does not specifically limit, For example, it is preferable that they are 0.1 mm or more and 1 mm or less.

  Moreover, it does not specifically limit as a constituent material of the connection pipe 2, For example, metal materials, such as stainless steel, can be used.

  In addition, a temperature adjustment mechanism 90 that adjusts the temperature of the connection pipe 2 is provided on the outer periphery of the connection pipe 2. By this temperature adjusting mechanism 90, the temperature of the particle P31 passing through the connecting pipe 2 can be adjusted suitably, and as a result, the reaction of the particle P31 can be adjusted suitably. Further, by heating the connecting pipe 2 by the temperature adjusting mechanism 90, it is possible to prevent the particles P31 passing through the connecting pipe 2 from adhering to the inner peripheral portion (inner wall) of the connecting pipe 2-. In addition, it does not specifically limit as heating temperature, For example, 100 to 300 degreeC is preferable and 250 to 300 degreeC is more preferable.

  As shown in FIG. 5, the gas supply means 3 supplies gas into the aerosol generator 15.

  In the configuration shown in the figure, five gas supply means 3 (3A, 3B, 3C, 3D, 3E) are provided, and these supply different types of gas into the aerosol generator 15, respectively.

  For example, the gas supply means 3A supplies an inert gas such as nitrogen, helium or argon, the gas supply means 3B supplies an oxidizing gas such as oxygen, and the gas supply means 3C uses hydrogen sulfide or the like. The gas supply means 3D supplies a nitriding gas such as ammonia, and the gas supply means 3E supplies a reducing gas such as hydrogen. Can do.

  Thus, by being configured to be able to supply a plurality of types of gases, it is possible to more suitably control the presence or absence of the reaction of the particles P31 and the degree of the reaction. Further, different types of reactions (for example, oxidation reaction of metal material and sulfurization reaction) can be performed in combination. Thereby, for example, the aesthetic appearance of the timepiece dial P10 to be manufactured can be further improved.

  The gas supply means 3 (3A, 3B, 3C, 3D, 3E) includes a tank 31 (31A, 31B, 31C, 31D, 31E) filled with gas, and a connecting pipe that connects the tank 31 and the aerosol generator 15. 32 (32A, 32B, 32C, 32D, 32E) and an electromagnetic valve 33 (33A, 33B, 33C, 33D, 33E) installed in the middle of the connecting pipe 32.

The tank 31 can store gas in an airtight manner.
The tank 31 and the aerosol generator 15 are in communication with each other via a connecting pipe 32. The connecting tube 32 may be hard or flexible.

  The connecting pipe 32 is provided with an electromagnetic valve 33 in the middle of the longitudinal direction. The electromagnetic valve 33 opens and closes the connecting pipe 32. When the electromagnetic valve 33 is in the open state, the tank 31 and the aerosol generator 15 communicate with each other. Thereby, the gas is supplied from the tank 31 to the aerosol generator 15. Further, when the electromagnetic valve 33 is closed, the communication between the tank 31 and the aerosol generator 15 is blocked. Thereby, the supply of gas from the tank 31 to the aerosol generator 15 is stopped.

Further, the electromagnetic valves 33A, 33B, 33C, 33D, and 33E are each configured to be able to adjust the opening degree.
Thereby, the flow volume of gas can be adjusted suitably.

  Moreover, since the flow rate of the gas accommodated in each tank 31A, 31B, 31C, 31D, 31E can be adjusted individually, the flow rate (compounding ratio, partial pressure) of each gas can be suitably adjusted. . As a result, the degree of reaction of the particles P31 can be suitably adjusted.

By supplying gas from the tank 31 to the aerosol generator 15, an aerosol is generated in which the particles P <b> 31 stored in the aerosol generator 15 are dispersed in the gas.
The aerosol generated in the aerosol generator 15 in this way is introduced into the crusher 4 through the connecting pipe 8 when the gas from the tank 31 functions as a carrier gas.

  As shown in FIG. 6, the crusher 4 includes a container 41 into which an aerosol containing particles P31 is introduced, an aerosol inlet 42 into which an aerosol containing particles P31 is introduced from a connecting pipe 8, and crushing of the particles P31. A crushing tool 43 for performing the above, an aerosol outlet 44 for leading the aerosol containing the crushed particles P31 to the connecting pipe 2, a brush 45 for removing the particles P31 when they adhere to the crushing tool 43, Gas inlets 46 a and 46 b for introducing gas into the container 41 and an ultrasonic vibration device 47 are provided.

  In the crusher 4, an aerosol inlet 42 is installed in a container 41, and a cylindrical crusher 43 is disposed at the tip of the crusher 4 so that the shaft can be rotated by a motor (not shown). The opening of the aerosol inlet 42 has a slit shape in which the cylindrical axis direction of the crushing tool 43 has a long side. The width of the slit is not particularly limited, but is preferably 1 mm or less.

  As the crushing tool 43, it is preferable that the cylindrical side surface on which the aerosol collides is made of a high hardness material such as titanium carbide.

  An aerosol outlet 44 is disposed above the crusher 43. Moreover, the brush 45 is installed so that the crushing tool 43 may be contact | connected. Gas inlets 46 a and 46 b are arranged in a space from the crushing tool 43 to the aerosol outlet 44, and an ultrasonic vibration device 47 is installed on the outer periphery of the aerosol outlet 44.

  The aerosol generated in the aerosol generator 15 is accelerated at the aerosol inlet 42 and collides with the cylindrical side surface of the crushing tool 43. Thick arrows in the figure indicate the traveling direction of the aerosol. The crushing tool 43 rotates in the clockwise direction as shown by the arrow in the figure. Therefore, the aerosol which changes the introduced position one after another collides with the cylindrical side surface of the crushing tool 43 while always changing the collision surface. Thereby, even if the aerosol generated in the aerosol generator 15 contains a relatively large amount of aggregated particles, the aggregated particles can be efficiently crushed.

  The particles P31 in the aerosol may adhere to the side surface of the cylinder to some extent, but the adhering powder is scraped off by the brush 45 and accumulated on the bottom of the container 41. Colliding with the crushing tool 43, the aggregated particles are crushed and converted into an aerosol rich in primary particles. Since the aerosol introduced from the aerosol inlet 42 obliquely collides with the cylindrical side surface of the crushing tool 43, most of the aerosol reflects along the tangential direction of the cylindrical side surface, but has a certain diffusion width. It is conceivable to collide with and adhere to the inner wall of the aerosol outlet 44. To prevent this, gas is introduced from the gas inlets 46a and 46b, and a curtain-like gas film is formed on the inner surface of the aerosol outlet 44. It is preferable to prevent the adhesion or to operate the ultrasonic vibration device 47 to vibrate the aerosol outlet 44 so that the adhesion does not proceed. The small arrows from the gas inlets 46a and 46b indicate the flow of gas introduced from here. Furthermore, it is preferable to neutralize the surface charge of the pulverized particles P31 by previously ionizing the gas to be introduced and prevent reaggregation in the aerosol.

  The aerosol converted into the primary particle-rich aerosol in this way is led to a nozzle (not shown), and thus can efficiently form a structure with no defects over a long period of time with few defects. Is possible.

  The aerosol that has been converted into a material rich in primary particles in the crusher 4 is introduced into the connecting pipe 2 and sprayed onto the base material P1 from the second opening 21. And this particle | grain P31 will collide and adhere to the base material P1, As a result, the film P3 is formed.

  The pressure adjusting means 5 makes the pressure in the film forming chamber 16 lower than the pressure in the aerosol generator 15 and the pressure in the disintegrator 4.

  As shown in FIG. 5, the pressure adjusting means 5 is installed in the middle of the connection pipe 52, a pump 51 that sucks the inside of the film formation chamber 16, a connection pipe 52 that connects the pump 51 and the film formation chamber 16. And an electromagnetic valve 53.

The pump 51 sucks the gas G ₂ in the film forming chamber 16. Due to this suction, the gas G ₂ in the film forming chamber 16 is discharged through the connecting pipe 52, so that the pressure in the film forming chamber 16 is higher than the pressure in the aerosol generator 15 and the pressure in the disintegrator 4. Definitely lower. Thus, the particles P31 can surely flow out into the film forming chamber 16, and thus the coating P3 can be reliably formed.

  The pressure in the film forming chamber 16 depends on the pressure in the aerosol generator 15 and the like, but can be, for example, less than 10 kPa when the pressure in the aerosol generator 15 is 10 kPa or more and 1 MPa or less. .

  Moreover, it does not specifically limit as the pump 51, For example, a turbo-molecular pump, a dry pump, a mechanical booster pump, a rotary pump etc. can be used.

  The pump 51 is connected to the film forming chamber 16 through a connecting pipe 52. The connecting pipe 52 may be hard or flexible.

  The connecting pipe 52 is provided with an electromagnetic valve 53 in the middle of its longitudinal direction. The electromagnetic valve 53 opens and closes the connecting pipe 52. When the electromagnetic valve 53 is in the open state, the inside of the film forming chamber 16 can be sucked by the suction force of the pump 51, and thus the inside of the film forming chamber 16 can be decompressed. Further, when the electromagnetic valve 53 is in a closed state, the suction force of the pump 51 is prevented from reaching the film forming chamber 16.

  As shown in FIG. 5, the moving means 6 moves the base material P <b> 1 with respect to the second opening 21 in the y-axis direction. As shown in FIGS. 5 and 7, the moving means 6 includes a stage (table) 61 that transports a plurality of base materials P1, a y-axis motor 62y that moves the stage 61 in the y-axis direction, and a y-axis motor. A y-axis motor driver 63y for controlling the driving of 62y. The moving means 6 can also move the stage 61 in the x-axis direction, and has an x-axis motor 62x that moves the x-axis motor driver 63x that controls the driving of the x-axis motor 62x. ing.

  The stage 61 is a plate-like member made of a metal material such as stainless steel. This stage 61 is supported horizontally.

  The y-axis motor 62y is a servomotor, for example, and is connected to the stage 61 via a ball screw (not shown) or the like. Then, as the y-axis motor 62y rotates, the rotational force is transmitted to the stage 61 via the ball screw. Accordingly, the plurality of base materials P1 placed on the stage 61 can be moved together with the stage 61 in the y-axis direction.

  The y-axis motor 62y is electrically connected to the y-axis motor driver 63y.

  The number of rotations of the y-axis motor 62y can be changed by the control of the y-axis motor driver 63y. As a result, the speed at which the stage 61 moves, that is, the speed when the moving means 6 is actuated is variable. And according to the magnitude of the said speed, the thickness of the coating film P3 formed can be adjusted, respectively. For example, when the speed is “large”, a “thin” film P3 is formed, and when the speed is “small”, a “thick” film P3 is formed.

  Similar to the y-axis motor 62y, the x-axis motor 62x is a servo motor, for example, and is connected to the stage 61 via a ball screw (not shown) or the like. Then, when the x-axis motor 62x rotates, the rotational force is transmitted to the stage 61 via the ball screw. Thereby, the plurality of substrates P1 placed on the stage 61 can be moved together with the stage 61 in the x-axis direction.

  The x-axis motor 62x is electrically connected to the x-axis motor driver 63x.

  Each operation | movement of the gas supply means 3, the pressure adjustment means 5, the movement means 6, etc. is controlled by the control part 7, respectively. The control unit 7 is, for example, a personal computer (PC) with a built-in CPU (Central Processing Unit).

  As shown in FIG. 7, the control unit 7 includes the electromagnetic valve 33 of the gas supply means 3, the pump 51 and the electromagnetic valve 53 of the pressure adjusting means 5, and the x-axis motor driver 63x and the y-axis motor driver 63y of the moving means 6. Are electrically connected to each other. And the control part 7 can operate these each independently. The control program is stored in advance in a storage unit (recording medium) 71 built in the control unit 7.

  The storage unit 71 includes, for example, RAM (Random Access Memory: including both volatile and nonvolatile), FD (Floppy Disk (Floppy is a registered trademark)), HD (Hard Disk), CD-ROM (Compact It is composed of a magnetic or optical recording medium such as a disc read-only memory or a semiconductor memory.

Next, the operation of the film forming apparatus 1 in the film forming process will be described in detail.
In the film forming step, as shown in FIG. 5, the stage 61 is aligned with the second opening 21 of the connecting pipe 2 so that the second opening 21 of the connecting pipe 2 faces the base material P1. Do. This alignment is performed using a CCD (Charge Coupled Device) camera based on an image captured by the CCD camera.

  At this time, the pressure adjusting means 5 is operating in the film forming apparatus 1. Thereby, the pressure in the film forming chamber 16 becomes lower than the pressure in the aerosol generator 15. This state is maintained until the formation of the coating P3 on the substrate P1 is completed.

In the film forming apparatus 1, the gas supply means 3 is also operating.
Then, the moving means 6 is operated, that is, the stage 61 is moved in the positive y-axis direction.

  As described above, the gas supply means 3, the pressure adjusting means 5, the moving means 6, etc. are operated, so that the aerosol containing the particles P 31 generated in the aerosol generator 15 passes through the connecting pipe 2 toward the film forming chamber 16. Pass through reliably. The particles P31 can pass through the connecting pipe 2 smoothly by the carrier gas. Thereafter, the particles P31 are discharged from the second opening 21, and are sprayed and adhered to the respective substrates P1 in order. Thereby, the coating P3 which has a desired shape can be rapidly formed in the desired site | part of the base material P1.

  According to the method for manufacturing a timepiece dial of the present invention as described above, it is possible to efficiently manufacture a timepiece dial having sufficient light transmittance and excellent decorativeness (aesthetic appearance). A method for manufacturing a timepiece dial can be provided. In addition, it is possible to provide a timepiece dial manufacturing method capable of efficiently manufacturing a timepiece dial by a method with less waste of materials and less burden on the environment.

<< Clock >>
Next, the timepiece of the invention will be described.

The timepiece of the present invention has the timepiece dial of the present invention as described above.
Thereby, the timepiece having an excellent aesthetic appearance can be provided. In addition, since the timepiece dial is excellent in light transmittance, it is possible to provide a timepiece (for example, a solar timepiece) capable of effectively using light from the outside. In addition, it is possible to provide a timepiece having a timepiece dial with less waste of materials during manufacture and less environmental load. In addition, the entire timepiece can be made less wasteful during production and less burden on the environment.

  In addition, the timepiece of the present invention only needs to be provided with the timepiece dial of the present invention, and other parts can be known ones. An example will be described.

FIG. 8 is a cross-sectional view showing a preferred embodiment of the timepiece (watch) of the present invention.
As shown in FIG. 8, the wristwatch (portable watch) P100 of this embodiment includes a trunk (case) P82, a back cover P83, a bezel (edge) P84, and a glass plate (cover glass) P85. . Further, in the case P82, a timepiece dial P10, a solar battery P94, and a movement P81 are housed, and a hand (pointer) (not shown) and the like are housed.

  The glass plate P85 is usually made of highly transparent transparent glass, sapphire, or the like. As a result, the visibility of the timepiece dial P10, hands, etc. can be made sufficiently excellent, and a sufficient amount of light can be made incident on the solar cell P94.

Movement P81 drives the pointer using the electromotive force of solar cell P94.
Although omitted in FIG. 8, in the movement P81, for example, an electric double layer capacitor for storing the electromotive force of the solar battery P94, 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 P81 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 P94 has a function of converting light energy into electric energy. The electric energy converted by the solar battery P94 is used for driving the movement.

  In the solar cell P94, 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 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 P86 is fitted and fixed to the trunk P82, and a shaft portion P871 of a crown P87 is rotatably inserted into the winding stem pipe P86.

  The body P82 and the bezel P84 are fixed by a plastic packing P88, and the bezel P84 and the glass plate P85 are fixed by a plastic packing P89.

  Further, a back cover P83 is fitted (or screwed) to the body P82, and a ring-shaped rubber packing (back cover packing) P92 is inserted in a compressed state at the joint (seal part) P93. Has been. With this configuration, the seal portion P93 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove P872 is formed on the outer periphery of the shaft portion P871 of the crown P87, and a ring-shaped rubber packing (crown packing) P91 is fitted in the groove P872. The rubber packing P91 is in close contact with the inner peripheral surface of the winding stem pipe P86 and is compressed between the inner peripheral surface and the inner surface of the groove P872. With this configuration, the space between the crown P87 and the winding stem pipe P86 is sealed in a liquid-tight manner to obtain a waterproof function. When the crown P87 is rotated, the rubber packing P91 rotates together with the shaft portion P871 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe P86.

  In the above description, a wristwatch (portable clock) as a solar radio timepiece has been described as an example of a clock. 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.

  In the embodiment described above, the case where the timepiece dial includes a base layer and a protective film in addition to the base material and the coating has been mainly described. However, the timepiece dial of the present invention includes the base material and the coating. May be provided, and at least one of the base layer and the protective film may not be provided.

  Moreover, although embodiment mentioned above demonstrated the case where the film was provided in the one surface side of the base material, the film may be provided in the both surface sides of the base material.

  In the above-described embodiment, the coating has been described as including the first particles in addition to the second particles, but the first particles may not be included in the coating.

  In the embodiment described above, the case where the first particles having reactivity are used as the raw material particles has been described. However, as the raw material particles, together with the first particles, particles that are not subjected to a chemical reaction in the film formation process (first 3 particles) may be used in combination.

  Moreover, in the manufacturing method of the timepiece dial according to the present invention, a pre-processing step, an intermediate processing step, and a post-processing step may be performed as necessary.

  In the above-described embodiment, the temperature adjustment mechanism that adjusts the temperature of the communication pipe has been described, and thus the case where the chemical reaction of the particles proceeds inside the communication pipe has been described. It may be one that proceeds at the site. For example, the chemical reaction of the particles may proceed inside the aerosol generator or inside the crusher, or may proceed upon collision with the substrate.

  In addition, the film forming apparatus may include a temperature adjustment mechanism that adjusts the temperature of these parts, for example, for the purpose of suitably controlling the chemical reaction of the particles at these parts.

  Moreover, although the opening part of the connecting pipe of the film forming apparatus faces the z-axis negative direction in the above-described embodiment, it is not limited to this. For example, the x-axis positive direction, x-axis negative direction, y-axis positive direction, You may face the y-axis negative direction or the z-axis positive direction.

  Moreover, although the moving means of the film forming apparatus is configured to move the base material in the positive y-axis direction with respect to the nozzle portion of the connecting pipe in the embodiment, the moving means is not limited to this. The nozzle portion may be configured to move in the positive y-axis direction with respect to the base material.

  Further, the moving means of the film forming apparatus may be configured to move the stage also in the z-axis direction. Further, the stage may be configured to be rotatable.

  Further, when the film forming apparatus forms the film on the base material, the film forming apparatus performs the formation while moving the stage in the above embodiment. However, the present invention is not limited to this. Each time the nozzle is positioned, the movement of the stage may be stopped and the formation may be performed.

  Moreover, although embodiment mentioned above demonstrated as a film forming apparatus having a crusher, you may use what does not have a crusher for formation of a film.

  In the above-described embodiment, the film forming apparatus has been described as including a temperature adjusting mechanism that adjusts the temperature of the connecting pipe. However, a film that does not include the temperature adjusting mechanism may be used for forming the film. .

  In addition, when the timepiece dial of the present invention is provided with a film such as an antireflection film, the part where the film is formed is not particularly limited, and may be, for example, the part described in the above-described embodiment. It may be on the surface opposite to the surface on which the coating film of the substrate is provided.

P100 …… Watch (portable watch)
P10 …… Timepiece dial P1 …… Base material (substrate)
P2: Underlayer P3 ... Coating P31 ... Particle P31A ... First particle P31B ... Second particle P4 ... Protective film P81 ... Movement P82 ... Body (case)
P83 …… Back cover P84 …… Bezel (edge)
P85 …… Glass plate (cover glass)
P86 ... Winding pipe P87 ... Crown P871 ... Shaft P872 ... Groove P88 ... Plastic packing P89 ... Plastic packing P91 ... Rubber packing (Crown packing)
P92 …… Rubber packing (back cover packing)
P93 …… Joint part (seal part)
P94 …… Solar cell 1 …… Film forming device 2 …… Connecting pipe 21 …… Second opening (other end opening)
22 …… Luminous part 24 …… Nozzle part 25 …… First opening (one-end opening)
3, 3A, 3B, 3C, 3D, 3E ... Gas supply means 31, 31A, 31B, 31C, 31D, 31E ... Tank 32, 32A, 32B, 32C, 32D, 32E ... Connecting pipe 33, 33A, 33B 33C, 33D, 33E ... Solenoid valve 4 ... Crusher 41 ... Container 42 ... Aerosol inlet 43 ... Crusher 44 ... Aerosol outlet 45 ... Brush 46a ... Gas inlet 46b ... ... Gas inlet 47 ... Ultrasonic vibration device 5 ... Pressure adjusting means 51 ... Pump 52 ... Connecting pipe 53 ... Solenoid valve 6 ... Moving means 61 ... Stage (table)
62x …… x-axis motor 62y …… y-axis motor 63x …… x-axis motor driver 63y …… y-axis motor driver 7 …… control unit 71 …… storage unit (recording medium)
15 ...... aerosol generator 16 ...... deposition chamber 90 ...... temperature regulator G ₂ ...... gas

Claims (15)

A substrate;
A coating formed by spraying an aerosol formed by dispersing particles in a gas from a nozzle;
The coating film is formed by depositing a plurality of particles including second particles generated by chemically reacting first particles made of a reactive material in a film forming process. A timepiece dial characterized by that.   The timepiece dial according to claim 1, wherein the light transmittance is 5% or more and 70% or less.   The timepiece dial according to claim 1, wherein the coating includes the first particles in addition to the second particles.   4. The timepiece dial according to claim 1, wherein the coating includes a plurality of types of particles having different degrees of progress of the chemical reaction as the second particles. 5.   The timepiece character according to any one of claims 1 to 4, wherein the base material is made of a material containing one or more selected from the group consisting of sapphire glass, quartz, and plastic. Board.   The timepiece dial according to claim 1, wherein the timepiece dial has at least one underlayer between the base material and the coating.   The timepiece dial according to any one of claims 1 to 6, wherein the second particles have an average particle size of 10 nm or more and 100 µm or less.   The timepiece dial according to any one of claims 1 to 7, wherein a protective film is provided on a surface of the coating opposite to the surface facing the base material. A substrate preparation step of preparing a substrate;
A film forming step of forming a film by spraying an aerosol formed by dispersing particles in a gas from a nozzle;
In the film forming step, first particles composed of a reactive material are used as a raw material, and the first particles are chemically reacted to generate second particles, which include the second particles. A method for manufacturing a timepiece dial, wherein the coating is formed by depositing a plurality of particles. The first particles are made of a material containing a metal material,
10. The timepiece dial manufacturing method according to claim 9, wherein the second particles are made of a material containing at least one selected from the group consisting of a metal oxide, a metal sulfide, and a metal nitride. . The first particles are made of a material containing a metal oxide,
The timepiece dial manufacturing method according to claim 9 or 10, wherein the second particles are made of a material containing a metal material.   The method for manufacturing a timepiece dial according to claim 9, further comprising an underlayer forming step of forming at least one underlayer between the base material preparing step and the film forming step. .   The timepiece dial manufacturing method according to claim 9, further comprising a protective film forming step of forming a protective film after the film forming step.   A timepiece comprising the timepiece dial according to claim 1.   A timepiece comprising a timepiece dial manufactured using the method according to any one of claims 9 to 13.

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