JP2017181084A - Ornament, manufacturing method for ornament and watch - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ornament having a plurality of differing tint ranges, excelling in esthetic appearance as well as excelling in durability.SOLUTION: An ornament 10 includes: metal base material 1 with at least a portion of a surface composed mainly by Ti or stainless steel; a first hard coat 2 composed mainly of Ti base hard compound; a stainless steel coat 3 composed mainly of stainless steel; a second hard coat 4 composed of material at least including one of Ti base hard chemical compound and Zr base hard chemical compound; and a different color coat 5 composed of material of different hue as the stainless steel coat 3 arranged in this order and the second hard coat 4 and the different color coat 5 selectively coat one portion of the surface of the stainless steel coat 3, and the stainless steel coat 3 and the different color coat 5 are composed to be capable of visual confirmation from outside.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative article, a method for manufacturing the decorative article, and a timepiece.

  A decorative product such as a watch exterior part is required to have an excellent aesthetic appearance.

  Conventionally, in order to achieve such an object, a plurality of materials having different colors have been used in combination.

  More specifically, a film (different color layer) made of a material different from that of the substrate is formed on the substrate, and then a part of the film is removed by masking. A decorative article having a portion having a color of a base material and a coating is manufactured (for example, see Patent Document 1).

  However, such a method has a problem that the durability of the decorative article is inferior because the substrate is exposed.

Japanese Patent No. 3601784

  An object of the present invention is to provide a decorative product having a plurality of different color areas and having an excellent aesthetic appearance and also having an excellent durability, and having a plurality of different color areas and an excellent aesthetic appearance, and having a durability It is another object of the present invention to provide a method for manufacturing a decorative product that can efficiently manufacture a decorative product that is also excellent, and to provide a watch equipped with the decorative product.

Such an object is achieved by the present invention described below.
The decorative article of the present invention comprises a metal base material, at least part of which is mainly composed of Ti or stainless steel,
A first hard film provided on the surface of the base material and mainly composed of a Ti-based hard compound;
A stainless steel coating that is provided on the opposite side of the first hard coating from the surface facing the substrate, and is mainly composed of stainless steel;
A second hard member formed of a material including at least one of a Ti-based hard compound and a Zr-based hard compound provided on a surface opposite to the surface facing the first hard coating of the stainless steel coating A coating;
The second hard coating is provided on a surface opposite to the surface facing the stainless steel coating, and is provided with a different color coating made of a material having a color tone different from that of the stainless steel coating,
The second hard coating and the different color coating selectively coat a part of the surface of the stainless steel coating, and the stainless steel coating and the different color coating are configured to be visible from the outside. It is characterized by being.

  As a result, it is possible to provide a decorative article having a plurality of different color regions and having an excellent aesthetic appearance and excellent durability.

  In the decorative article of the present invention, the different color coating is preferably an Au-based alloy coating composed of an Au-based alloy.

  Thereby, the aesthetic appearance of the decorative product can be further improved. Further, the adhesion between the second hard film made of a material containing at least one of the Ti hard compound and the Zr hard compound and the different color film (Au alloy film) shall be more excellent. And the durability of the decorative article can be further improved.

  In the decorative article of the present invention, the stainless steel film is preferably composed of austenitic stainless steel.

  Thereby, the corrosion resistance of the stainless steel coating can be made more excellent, and the durability of the decorative article can be made more excellent. In addition, at the time of manufacturing the decorative product, it is possible to more effectively prevent the stainless steel coating from being damaged during the removal of the second hard coating and the different color coating, and the reliability of the decorative product is further improved. Can be.

  In the decorative article of the present invention, the stainless steel film is preferably made of SUS316L.

  Thereby, the corrosion resistance of the stainless steel coating can be further improved, and the durability of the decorative article can be further improved. In addition, at the time of manufacturing the decorative product, it is possible to more effectively prevent the stainless steel coating from being damaged during the removal of the second hard coating and the different color coating, and the reliability of the decorative product is further improved. Can be.

The decorative article of the present invention is preferably a watch exterior part.
The exterior part for a watch is required to have a beautiful appearance as a decorative product and also to have durability as a practical product. However, according to the present invention, these requirements can be satisfied. Therefore, the effect of the present invention is more remarkably exhibited when the decorative article is a watch exterior part.

  In the decorative article of the present invention, the watch exterior part is preferably at least one selected from the group consisting of a case, a bezel, a back cover, and a band.

  These members have a great influence on the overall appearance of the watch, and are members that can be contacted by the user during normal use of the watch, and members that require particularly excellent durability in addition to an excellent aesthetic appearance. However, according to the present invention, these requirements can be satisfied. That is, when the present invention is applied to a watch exterior part as described above, the effects of the present invention are more remarkably exhibited.

In the method for producing a decorative article of the present invention, a first hard film mainly composed of a Ti-based hard compound is formed on a metal base material at least part of which is mainly composed of Ti or stainless steel. A first hard film forming step;
A stainless steel film forming step of forming a stainless steel film mainly composed of stainless steel on the first hard film;
A second hard film forming step of forming a second hard film made of a material containing at least one of a Ti-based hard compound and a Zr-based hard compound on the stainless steel film;
On the second hard film, a different color film forming step for forming a different color film made of a material having a color tone different from that of the stainless steel film,
A stainless steel film exposing step of selectively removing a part of the second hard film and the different color film to expose a part of the stainless steel film.

  Accordingly, it is possible to provide a method for manufacturing a decorative product that can efficiently manufacture a decorative product having a plurality of different color regions and having an excellent aesthetic appearance and also having excellent durability.

The timepiece of the present invention is characterized by including the decorative article of the present invention.
Accordingly, it is possible to provide a timepiece having a decorative product having a plurality of different color regions and having an excellent aesthetic appearance and excellent durability.

It is sectional drawing which shows typically suitable embodiment of the ornament of this invention. It is sectional drawing which shows typically the process (base material preparation process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (1st hard film formation process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (stainless steel film formation process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (2nd hard film formation process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (different color film formation process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (masking process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (stainless steel film exposure process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is sectional drawing which shows typically the process (mask removal process) of suitable embodiment of the manufacturing method of the decorative article of this invention. It is a flowchart which shows an example of the manufacturing method of the ornament of this invention. It is a fragmentary sectional view showing typically a suitable embodiment of a timepiece (portable timepiece) of the present invention.

Hereinafter, preferred embodiments will be described in detail with reference to the accompanying drawings.
《Decoration》
First, the decorative article of the present invention will be described.
FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the decorative article of the present invention.

  The decorative article 10 of this embodiment is provided on the surface of the base 1 made of metal, at least part of which is mainly made of Ti or stainless steel, and is mainly made of a Ti-based hard compound. A first hard coating 2 and a stainless steel coating 3 provided mainly on the surface of the first hard coating 2 opposite to the surface of the first hard coating 2 facing the substrate 1, and made of stainless steel; A second hard coating 4 that is provided on the surface opposite to the surface facing the first hard coating 2 and is made of a material containing at least one of a Ti-based hard compound and a Zr-based hard compound; The second hard coating 4 is provided on the surface opposite to the surface facing the stainless steel coating 3, and is provided with a different color coating 5 made of a material having a color tone different from that of the stainless steel coating 3.

  The second hard coating 4 and the different color coating 5 selectively coat a part of the surface of the stainless steel coating 3, so that the stainless steel coating 3 and the different color coating 5 can be visually recognized from the outside. It is configured.

  With such a configuration, the decorative article 10 has a plurality of different color regions (a region where the stainless steel coating 3 can be visually recognized and a region where the different color coating 5 can be visually recognized), and has an excellent aesthetic appearance (aesthetics). It will be a thing. In addition, since a plurality of different color regions can be provided in a single part, it is possible to obtain a decorative product having an excellent aesthetic appearance as described above without combining a plurality of types of parts having different colors and materials. it can. For this reason, it is advantageous also for the suppression of the production cost of a decorative article. Further, the stainless steel film 3 and the different color film 5 that are visually recognized from the outside are provided with a first hard film 2 and a second hard film 4 as a base, respectively, and the base material 1 that is a base is an outer surface. Not exposed to the side. For this reason, the decorative article 10 is excellent in durability and can exhibit an excellent aesthetic appearance stably over a long period of time.

≪Base material≫
The base material 1 is a main part of the decorative article 10 and usually has a shape corresponding to the decorative article 10.

  The substrate 1 has a function of supporting the first hard coating 2, the stainless steel coating 3, the second hard coating 4, and the different color coating 5.

  The substrate 1 is made of metal having at least a part of its surface mainly composed of Ti or stainless steel.

  If the substrate 1 is made of such a material, the durability of the decorative article 10 can be made excellent. Further, when the coating (the first hard coating 2, the stainless steel coating 3, the second hard coating 4, and the different color coating 5) constituting the decorative article is relatively thin as will be described in detail later, 1 also greatly affects the appearance of the decorative article 10, but the aesthetic appearance of the decorative article 10 as a whole can be made excellent when the base material 1 is made of the material as described above. .

  In the present invention, “mainly” means that 50% by mass or more of the corresponding part is composed of the component, and in particular, 70% by mass or more of the corresponding part is composed of the component. It is preferable that 80% by mass or more of the corresponding part is composed of the component.

  When the base material 1 is mainly composed of Ti, examples of the constituent material of the base material 1 include metal Ti and Ti alloy.

  The Ti content in the Ti alloy is preferably 55% by mass or more, and more preferably 75% by mass or more.

  Examples of the stainless steel constituting the substrate 1 include martensitic stainless steel, ferritic stainless steel, austenitic stainless steel, austenitic / ferritic duplex stainless steel, precipitation hardening stainless steel, and the like.

  The substrate 1 only needs to have at least a part of the surface (the surface in contact with the first hard coating 2) made of the above material, and has a portion made of a material different from the above material. You may do it. For example, the base material 1 may have a base portion made of a material different from the above material and a surface layer made of the above material. In such a case, examples of the constituent material of the base include metal materials different from the above materials, various ceramic materials, and various resin materials.

  Moreover, the base material 1 may be comprised by the laminated body by which the layer from which a composition differs in the thickness direction, for example, and the gradient material from which a composition changes in gradient.

≪First hard coating≫
The first hard coating 2 is interposed between the base material 1 and the stainless steel coating 3 so as to be in contact with the base material 1 and the stainless steel coating 3.

The first hard coating 2 is mainly composed of a Ti-based hard compound.
By providing such a first hard coating 2, the adhesion between the substrate 1 and the stainless steel coating 3 can be made excellent. Further, by having the first hard coating 2 as a base (hard base) of the stainless steel coating 3, the stainless steel coating 3 is not easily damaged by wear or dents. For this reason, the durability of the decorative article 10 can be made excellent.

  Examples of the Ti-based hard compound that constitutes the first hard coating 2 include titanium carbide (TiC), titanium carbonitride (TiCN), titanium nitride (TiN), and titanium oxide. It is preferably composed of titanium carbonitride.

  Thereby, while being able to make the durability of the ornament 10 more excellent, the aesthetic appearance of the ornament 10 can also be made more excellent.

  The 1st hard film 2 should just be mainly comprised by the Ti type hard compound, and may contain another component (especially other component as an impurity).

  The content of components other than the Ti-based hard compound in the first hard coating 2 is preferably 5% by mass or less, and more preferably 1% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

  Moreover, the 1st hard film 2 may have a uniform composition in each site | part, and may have a different composition. For example, the first hard coating 2 may be composed of a laminate in which layers having different compositions are laminated in the thickness direction, or a gradient material in which the composition changes in an inclined manner.

  Although the thickness of the 1st hard film 2 is not specifically limited, It is preferable that they are 0.03 micrometer or more and 20 micrometers or less, and it is more preferable that they are 0.1 micrometer or more and 10 micrometers or less.

  Thereby, the durability and aesthetic appearance of the decorative article 10 can be further improved.

≪Stainless steel coating≫
The stainless steel coating 3 is interposed between the first hard coating 2 and the second hard coating 4 so as to be in contact with the first hard coating 2 and the second hard coating 4.

The stainless steel coating 3 is mainly composed of stainless steel.
By providing such a stainless steel coating 3, the aesthetic appearance of the decorative article 10 can be made excellent. In particular, the decorative article 10 can be provided with a silver region and excellent in aesthetic appearance.

  Further, the stainless steel coating 3 is only partially coated with the second hard coating 4 and the different color coating 5 on the surface opposite to the surface facing the first hard coating 2, and the other parts are , Exposed.

  With such a configuration, in the decorative article 10, the stainless steel coating 3 and the different color coating 5 are exposed, and both of these portions are configured to be directly visible from the outside.

  Therefore, the decorative article 10 has a plurality of different color regions (a region where the stainless steel coating 3 can be visually recognized and a region where the different color coating 5 can be visually recognized), and has an excellent aesthetic appearance (aesthetics).

  The stainless steel coating 3 is sufficiently resistant to the stainless steel coating exposure step of the method for manufacturing the decorative article 10 described in detail later, and is not easily damaged during the manufacturing process of the decorative article 10. . Therefore, the decorative article 10 having an excellent aesthetic appearance can be suitably manufactured.

  Examples of the stainless steel constituting the stainless steel coating 3 include martensitic stainless steel, ferritic stainless steel, austenitic stainless steel, austenitic / ferrite duplex stainless steel, and precipitation hardened stainless steel.

  In particular, the stainless steel coating 3 is preferably made of austenitic stainless steel.

  Thereby, the corrosion resistance of the stainless steel coating 3 can be made more excellent, and the durability of the decorative article 10 can be made more excellent. Further, when the decorative article 10 is manufactured, it is possible to more effectively prevent the stainless steel film 3 from being damaged when the second hard film 4 and the different color film 5 described later are removed. Can be made more reliable.

  As austenitic stainless steel, for example, SUS301, SUS301L, SUS301J1, SUS302B, SUS303, SUS304, SUS304Cu, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J1, SUS304J2, SUS3, SUS3S, SUS3S, SUS3S, SUS311 SUS316LN, SUS316Ti, SUS316J1, SUS316J1L, SUS317, SUS317L, SUS317LN, SUS317J1, SUS317J2, SUS836L, SUS890L, SUS321, SUS347, SUSXM7, SUSXM15J1, etc. Steel coat 3 is preferably those composed of SUS316L.

  Thereby, the corrosion resistance of the stainless steel coating 3 can be further improved, and the durability of the decorative article 10 can be further improved. Further, when the decorative article 10 is manufactured, the stainless steel film 3 can be more effectively prevented from being damaged when the second hard film 4 and the different color film 5 described later are removed. The reliability can be further improved.

  The stainless steel coating 3 may be any as long as it is mainly composed of stainless steel, and may include other components (particularly, other components as impurities).

  The content of components other than stainless steel in the stainless steel coating 3 is preferably 5% by mass or less, and more preferably 1% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

  Further, the stainless steel coating 3 may have a uniform composition at each site, or may have a different composition. For example, the stainless steel coating 3 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 an inclined manner.

  The thickness of the stainless steel coating 3 is not particularly limited, but is preferably 0.01 μm or more and 1.0 μm or less, and more preferably 0.03 μm or more and 0.4 μm or less.

  Thereby, the durability and aesthetic appearance of the decorative article 10 can be further improved. Moreover, the productivity of the decorative article 10 can be made more excellent.

≪Second hard coating≫
The second hard coating 4 is interposed between the stainless steel coating 3 and the different color coating 5 and is provided so as to contact the stainless steel coating 3 and the different coating 5.

The second hard coating 4 is made of a material containing at least one of a Ti hard compound and a Zr hard compound.
By providing such a second hard coating 4, the adhesion between the stainless steel coating 3 and the different color coating 5 can be made excellent. In addition, by having the second hard coating 4 as the base (hard base) of the different color coating 5, the different color coating 5 is less likely to be damaged due to wear or dents. For this reason, the durability of the decorative article 10 can be made excellent.

  Examples of the Ti-based hard compound that constitutes the second hard coating 4 include the same materials as those described as the constituent material of the first hard coating 2, and in particular, composed of titanium carbonitride. It is preferable.

  Thereby, while being able to make the durability of the ornament 10 more excellent, the aesthetic appearance of the ornament 10 can also be made more excellent.

  Examples of the Zr-based hard compound constituting the second hard coating 4 include zirconium carbide (ZrC), zirconium carbonitride (ZrCN), zirconium nitride (ZrN), zirconium oxide, and the like. It is preferably composed of zirconium carbonitride or zirconium nitride.

  Thereby, while being able to make the durability of the ornament 10 more excellent, the aesthetic appearance of the ornament 10 can also be made more excellent.

  The second hard coating 4 only needs to contain at least one of a Ti-based hard compound and a Zr-based hard compound as a main component (those having the highest content), and other components (particularly, other impurities as impurities). Component).

  The content of components other than the Ti-based hard compound and the Zr-based hard compound in the second hard coating 4 is preferably 5% by mass or less, and more preferably 1% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

  Moreover, the 2nd hard film 4 may have a uniform composition in each site | part, and may have a different composition. For example, the second hard coating 4 may be composed of a laminated body in which layers having different compositions in the thickness direction are laminated, or a gradient material in which the composition changes in an inclined manner.

  Although the thickness of the 2nd hard film 4 is not specifically limited, It is preferable that they are 0.01 micrometer or more and 20 micrometers or less, and it is more preferable that they are 0.05 micrometer or more and 5 micrometers or less.

  Thereby, the durability and aesthetic appearance of the decorative article 10 can be further improved.

≪Different color film≫
The different color coating 5 is provided in contact with the outer surface of the second hard coating 4 (the surface opposite to the surface contacting the stainless steel coating 3), and is exposed on the outer surface of the decorative article 10. .

The different color coating 5 is made of a material having a color tone different from that of the stainless steel coating 3.
Thereby, the decorative article 10 has a plurality of different color regions (a region where the stainless steel coating 3 can be visually recognized and a region where the different color coating 5 can be visually recognized), and has an excellent aesthetic appearance (aesthetics). .

  The different color coating 5 may be any material as long as it is composed of a material having a color tone different from that of the stainless steel coating 3, but is preferably an Au based alloy coating composed mainly of an Au based alloy.

  As a result, the decorative article 10 can have a silver-based stainless steel coating 3 and a gold-colored different-colored coating (Au-based alloy coating) 5, and the aesthetic appearance of the decorative article 10 is more excellent. It can be. Further, the adhesion between the second hard coating 4 made of a material containing at least one of the Ti hard compound and the Zr hard compound and the different color coating (Au alloy coating) 5 is more excellent. And the durability of the decorative article 10 can be further improved.

As a constituent material of the different color coating (Au-based alloy coating) 5, various gold alloys can be used, and a gold alloy having an Au content of 80% by mass or more can be preferably used.
Thereby, the effects as described above are more remarkably exhibited.

  When the different color coating 5 is made of a material containing an Au alloy, the different color coating 5 may contain a component other than the Au alloy.

  The content of components other than the Au-based alloy in the different color coating (Au-based alloy coating) 5 is preferably 5% by mass or less, and more preferably 1% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

  In addition, the different color coating 5 may have a uniform composition at each site or may have a different composition. For example, the different color coating 5 may be composed of a laminated body in which layers having different compositions in the thickness direction are laminated, or a gradient material in which the composition changes in an inclined manner.

  The thickness of the different color coating 5 is not particularly limited, but is preferably 0.01 μm or more and 1.0 μm or less, and more preferably 0.03 μm or more and 0.4 μm or less.

  Thereby, the durability and aesthetic appearance of the decorative article 10 can be further improved. Moreover, the productivity of the decorative article 10 can be made more excellent.

  The decorative article 10 may be any article having a decorative property, for example, interiors such as figurines, exterior articles, jewelry, exterior parts for watches, glasses, tie pins, cufflinks, rings, necklaces, bracelets. , Accessories such as anklets, brooches, pendants, earrings, earrings, lighters or their cases, sports equipment such as automobile wheels, golf clubs, nameplates, panels, prize cups, other housing parts, etc. Although mentioned, it is preferable that the decorative article 10 is a watch exterior part.

  The exterior part for a watch is required to have a beautiful appearance as a decorative product and also to have durability as a practical product. However, according to the present invention, these requirements can be satisfied. Therefore, when the decorative article 10 is a watch exterior part, the effect of the present invention is more remarkably exhibited.

  When the decorative article 10 is a watch exterior part, examples of the watch exterior part include a case, a bezel, a back cover, a band (including a band piece, a band clasp, a band / bangle attaching / detaching mechanism, etc.), a character, and the like. There are at least one selected from the group consisting of a case, a bezel, a back cover and a band, including a plate, a clock hand, a crown (for example, a screw lock type crown), a button, a dial ring, and a parting plate. Preferably there is. Two or more of these may be linked or integrated.

  These members have a great influence on the overall appearance of the watch, and are members that can be contacted by the user during normal use of the watch, and members that require particularly excellent durability in addition to an excellent aesthetic appearance. However, according to the present invention, these requirements can be satisfied. That is, when the present invention is applied to a watch exterior part as described above, the effects of the present invention are more remarkably exhibited.

  In the present invention, the timepiece exterior component may be any member that can be seen from the outside when the timepiece is used, and is not limited to the one exposed to the outside of the timepiece.

《Method of manufacturing ornaments》
Next, the manufacturing method of the decorative article of the present invention will be described.
2-9 is sectional drawing which shows typically the process of suitable embodiment of the manufacturing method of the ornament of this invention. Moreover, FIG. 10 is a flowchart which shows an example of the manufacturing method of the ornament of this invention.

  The manufacturing method of the decorative article 10 of the present embodiment includes a base material preparation step of preparing a metal base material 1 having at least a part of the surface mainly made of Ti or stainless steel, A first hard film forming step for forming a first hard film 2 composed of a hard metal compound, and a stainless steel for forming a stainless steel film 3 composed mainly of stainless steel on the first hard film 2 A film forming process, and a second hard film forming process for forming a second hard film 4 made of a material containing at least one of a Ti-based hard compound and a Zr-based hard compound on the stainless steel film 3; A different color film forming step of forming a different color film 5 made of a material having a color tone different from that of the stainless steel film 3 on the second hard film 4, and a part of the second hard film 4 and the different color film 5 are formed. Selective removal And has a stainless steel coating exposing step for exposing a portion of the stainless steel coating 3.

  As a result, it is possible to manufacture a decorative article having a plurality of different color regions and having an excellent aesthetic appearance and also having excellent durability. In addition, in the relationship between the stainless steel constituting the stainless steel coating 3 and the constituent materials (particularly gold alloy) of the Ti-based hard compound, Zr-based hard compound, and the different-colored coating 5 constituting the second hard coating 4, There are various release agents (etchants) that have a very high etching rate for the constituent materials of the Ti-based hard compound, the Zr-based hard compound, and the different color coating 5 compared with the etching rate of stainless steel. Therefore, the decorative article 10 can be efficiently manufactured while sufficiently preventing the stainless steel coating 3 from being attacked.

≪Base material preparation process≫
In the base material preparation step, the base material 1 as described above is prepared.

  Prior to the process described later, the surface of the substrate 1 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing.

  Thereby, it becomes possible to give a variation in the glossiness of the surface of the obtained decorative article 10, and the decorativeness of the obtained decorative article 10 can be further improved. The mirror surface processing can be performed using, for example, a well-known polishing method, and for example, buffing (bedding) polishing, barrel polishing, and other mechanical polishing can be employed.

  Moreover, the decorative article 10 manufactured using the base material 1 that has been subjected to such surface processing has a coating (a first hard coating 2, a stainless steel coating 3, a second hard coating 4, and a different color coating 5). On the other hand, glare of the coating is suppressed as compared with the one obtained by directly performing the surface treatment, and particularly, the aesthetic appearance is excellent. In addition, when the thickness of the coating (first hard coating 2, stainless steel coating 3, second hard coating 4, and different color coating 5) is relatively thin as described above, surface processing is performed on the coating. In the case of direct application, the surface treatment is likely to cause defects such as chipping and peeling on the coating, and the production yield of the decorative article 10 may be significantly reduced. By doing so, the occurrence of such a problem can be effectively prevented. Moreover, the surface treatment with respect to the base material 1 can be easily performed under mild conditions as compared with the surface treatment for the coating film.

  Prior to the first hard film forming step, the base material 1 may be subjected to cleaning treatment such as blast treatment, alkali washing, acid washing, water washing, organic solvent washing, and bombardment treatment.

  Thereby, the adhesiveness of the base material 1 and the 1st hard film 2 can be made especially excellent.

≪First hard film forming process≫
In the first hard film forming step, the first hard film 2 is formed on the surface of the substrate 1.

  Although the formation method (film formation method) of the 1st hard film 2 is not specifically limited, It is preferable that it is a dry-type plating method.

  Thereby, the 1st hard film 2 which was homogeneous and was especially excellent in adhesiveness with the base material 1 can be formed comparatively easily. As a result, the durability of the resulting decorative article 10 is further improved. In addition, by using the dry plating method, it is possible to form the first hard coating 2 having a particularly high density. As a result, the decorative article 10 can maintain a particularly excellent aesthetic appearance over a long period of time. In addition, the composition of the first hard coating 2 can be controlled more easily.

  Examples of the dry plating method applied to the formation of the first hard coating 2 include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum vapor deposition, sputtering, ion plating, and the like. Of these, sputtering is preferable.

  As a result, the first hard coating 2 that is more homogeneous and has particularly excellent adhesion to the substrate 1 can be formed relatively easily. As a result, the durability of the resulting decorative article 10 is particularly excellent. Also, by using sputtering, it is possible to form the first hard coating 2 having a particularly high density, and the resulting decorative article 10 can maintain a particularly excellent aesthetic appearance over a long period of time.

For example, sputtering is preferably performed under the following conditions.
The sputtering voltage at the time of sputtering is preferably, for example, from 300 V to 800 V, and more preferably from 400 V to 650 V.

  When the sputtering voltage is a value within the above range, the first hard coating 2 having excellent adhesion to the substrate 1 can be formed. Further, the first hard coating 2 to be formed has a small variation in film thickness at each site, a small internal stress, and a crack is difficult to occur.

  The sputtering current at the time of sputtering is, for example, preferably from 5 A to 150 A, and more preferably from 10 A to 40 A.

  When the sputtering current is a value within the above range, the adhesion between the substrate 1 and the first hard coating 2 can be further improved. Further, the first hard coating 2 to be formed has a small variation in film thickness at each site, a small internal stress, and a crack is difficult to occur.

  The composition of the first hard coating 2 can be controlled by adjusting the composition of the atmospheric gas during sputtering.

Although the pressure of the atmosphere at the time of sputtering is not particularly limited, it is preferably 1 × 10 ⁻² Pa or more and 8 × 10 ⁻¹ Pa or less, preferably 1 × 10 ⁻¹ Pa or more and 6 × 10 ⁻¹ Pa or less. Is more preferable.

≪Stainless steel film formation process≫
In the stainless steel film forming step, the stainless steel film 3 is formed on the surface of the first hard film 2.

  Examples of the method for forming the stainless steel coating 3 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, sputtering, and ions. Examples thereof include dry plating methods such as plating, thermal spraying, joining metal foils, etc. Among these, dry plating methods are particularly preferable.

  By using a dry plating method as a method of forming the stainless steel coating 3, the adhesion between the first hard coating 2 and the stainless steel coating 3 can be made particularly excellent. As a result, the durability of the resulting decorative article 10 is particularly excellent.

  Prior to the formation of the stainless steel coating 3, the first hard coating 2 may be pretreated. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, bombarding and other cleaning treatment, etching treatment, etc., among which cleaning treatment is particularly preferable.

  By performing a cleaning treatment on the surface of the first hard coating 2, the adhesion between the first hard coating 2 and the stainless steel coating 3 can be made particularly excellent.

≪Second hard film forming process≫
In the second hard film forming step, the second hard film 4 is formed on the surface of the stainless steel film 3.

  The method for forming the second hard coating 4 (film formation method) is not particularly limited, but is preferably a dry plating method.

  As a result, the second hard coating 4 which is homogeneous and particularly excellent in adhesion to the stainless steel coating 3 can be formed relatively easily. As a result, the durability of the resulting decorative article 10 is further improved. In addition, by using the dry plating method, it is possible to form the second hard coating 4 having a particularly high density. As a result, the decorative article 10 can maintain a particularly excellent aesthetic appearance over a long period of time. In addition, the composition of the second hard coating 4 can be controlled more easily.

  Examples of the dry plating method applied to the formation of the second hard coating 4 include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum vapor deposition, sputtering, and ion plating. Of these, sputtering is preferable.

  As a result, the second hard coating 4 that is more homogeneous and particularly excellent in adhesion to the stainless steel coating 3 can be formed relatively easily. As a result, the durability of the resulting decorative article 10 is particularly excellent. Further, by using sputtering, it is possible to form the second hard coating 4 having a particularly high density, and the resulting decorative article 10 can maintain a particularly excellent aesthetic appearance over a long period of time.

For example, sputtering is preferably performed under the following conditions.
For example, the sputtering voltage at the time of sputtering is preferably 300 V or more and 800 V or less, and more preferably 450 V or more and 600 V or less.

  When the sputtering voltage is a value within the above range, the second hard coating 4 having excellent adhesion to the stainless steel coating 3 can be formed. Further, the second hard coating 4 to be formed has a small variation in film thickness at each portion, a small internal stress, and a crack is difficult to occur.

  The sputtering current at the time of sputtering is, for example, preferably from 5 A to 150 A, and more preferably from 10 A to 40 A.

  When the sputtering current is within the above range, the adhesion between the stainless steel coating 3 and the second hard coating 4 can be further improved. Further, the second hard coating 4 to be formed has a small variation in film thickness at each portion, a small internal stress, and a crack is difficult to occur.

  The composition of the second hard coating 4 can be controlled by adjusting the composition of the atmospheric gas during sputtering.

Although the pressure of the atmosphere at the time of sputtering is not particularly limited, it is preferably 1 × 10 ⁻² Pa or more and 8 × 10 ⁻¹ Pa or less, preferably 1 × 10 ⁻¹ Pa or more and 6 × 10 ⁻¹ Pa or less. Is more preferable.

  Prior to the formation of the second hard coating 4, the stainless steel coating 3 may be pretreated. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, cleaning treatment such as bombardment treatment, etching treatment, and the like.

  By performing a cleaning treatment on the surface of the stainless steel coating 3, the adhesion between the stainless steel coating 3 and the second hard coating 4 can be made particularly excellent.

≪Different color film formation process≫
In the different color film forming step, a different color film 5 made of a material having a color tone different from that of the stainless steel film 3 is formed on the surface of the second hard film 4.

  Examples of the method for forming the different color coating 5 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, sputtering, and ion plating. Examples thereof include dry plating methods such as coating, thermal spraying, joining of metal foils, etc. Among these, dry plating methods are particularly preferable.

  By using a dry plating method as a method for forming the different color film 5, the adhesion between the second hard film 4 and the different color film 5 can be made particularly excellent. As a result, the durability of the resulting decorative article 10 is particularly excellent.

  Prior to the formation of the different color coating 5, the second hard coating 4 may be pretreated. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, bombarding and other cleaning treatment, etching treatment, etc., among which cleaning treatment is particularly preferable.

  By performing a cleaning treatment on the surface of the second hard coating 4, the adhesion between the second hard coating 4 and the different color coating 5 can be made particularly excellent.

≪Masking process≫
In the present embodiment, prior to a stainless steel coating exposure process described later, a masking process for coating the mask 7 on a part of the surface of the different color coating 5 is provided. This mask 7 has a function of protecting the second hard coating 4 and the different color coating 5 at the coated site in the stainless steel coating exposure step.

  By forming such a mask 7, the selectivity of the removal of the second hard film 4 and the different color film 5 in the stainless steel film exposure step can be made more excellent, and more reliably desired. The second hard coating 4 and the different color coating 5 can be removed in a pattern.

  The mask 7 may be any mask as long as it has a function of protecting the second hard film 4 and the different color film 5 in the coated portion in the step of removing the second hard film 4 and the different color film 5. It is preferable that the mask can be easily removed in a mask removing process described later.

  Examples of the material constituting the mask 7 include acrylic resin, polyimide resin, polysulfone resin, epoxy resin, fluorine resin, vinyl resin, rubber resin, and the like.

  The method for forming the mask 7 is not particularly limited. For example, coating such as dipping, brush coating, spray coating, electrostatic coating, and electrodeposition coating, wet plating methods such as electrolytic plating, immersion plating, and electroless plating, and thermal CVD. And chemical vapor deposition (CVD) such as plasma CVD and laser CVD, dry plating such as vacuum deposition, sputtering and ion plating, and thermal spraying.

  Although the average thickness of the mask 7 is not specifically limited, For example, it is preferable that it is 100 micrometers or more and 2000 micrometers or less, and it is more preferable that it is 500 micrometers or more and 1000 micrometers or less.

  The mask 7 is preferably transparent. Thereby, it becomes possible to visually recognize the contact state with the different color coating 5 from the outside.

  The mask 7 is not limited to that formed directly on the surface of the different color coating 5 so as to have a desired shape. For example, the mask 7 having a desired pattern may be obtained by covering substantially the entire surface of the different color coating 5 with the constituent material of the mask 7 and then removing a part thereof.

Examples of a method for removing a part of the mask 7 that covers almost the entire surface of the different color coating 5 include a method of irradiating the mask 7 at a site to be removed with laser light. Examples of the laser used at this time include a gas laser such as a Ne—He laser, an Ar laser, and a CO ₂ laser, a ruby laser, a semiconductor laser, a YAG laser, and a glass laser.

≪Stainless steel coating exposure process≫
In the stainless steel film exposing step, a part of the second hard film 4 and the different color film 5 (part not covered with the mask 7) is selectively removed, and a part of the stainless steel film 3 is exposed.

  The second hard coating 4 and the different color coating 5 can be removed by removing the second hard coating 4 and the different color coating 5 and substantially not dissolving or peeling the stainless steel coating 3 and the mask 7. It can be performed using an agent.

  The release agent used for the removal of the second hard film 4 and the different color film 5 can remove the second hard film 4 and the different color film 5, and substantially removes the stainless steel film 3 and the mask 7. As long as it does not dissolve or peel off, it is not particularly limited, but it is preferably a fluid such as a liquid or a gas, and among these, a liquid is particularly preferable. Thereby, it is possible to easily and reliably remove the second hard coating 4 and the different color coating 5.

Examples of release agents include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), and methyl. Ketone solvents such as isopropyl ketone (MIPK) and cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG) and glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), Ether solvents such as 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), methyl cellosolve, ethyl cellosolve, Cellosolve solvents such as enylcellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane and cyclohexane, aromatic hydrocarbon solvents such as toluene, xylene and benzene, and fragrances such as pyridine, pyrazine, furan, pyrrole and thiophene Group heterocyclic solvents, amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate , Ester solvents such as methyl acetate and ethyl formate, sulfur compound solvents such as dimethyl sulfoxide (DMSO) and sulfolane, nitrile solvents such as acetonitrile and propionitrile, organic solvents such as formic acid, acetic acid, trichloroacetic acid and trifluoroacetic acid From organic solvents such as acid solvents 1 type or a mixture of 2 or more types selected from these, acidic substances such as nitric acid, sulfuric acid, hydrogen chloride, hydrogen fluoride, phosphoric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide Alkaline substances such as calcium, magnesium hydroxide, and ammonia, potassium permanganate (KMnO ₄ ), manganese dioxide (MnO ₂ ), potassium dichromate (K ₂ Cr ₂ O ₇ ), ozone, concentrated sulfuric acid, nitric acid, and white powder , Oxidizing agents such as hydrogen peroxide and quinones, and mixtures of reducing agents such as sodium thiosulfate (Na ₂ S ₂ O ₃ ), hydrogen sulfide, hydrogen peroxide, hydroquinones, etc. A solution (particularly an aqueous solution) containing 0.1% by volume or more and 5% by volume or less of potassium hydroxide and 30% by volume or more and 60% by volume or less of hydrogen peroxide is preferable. .

  By using such a solution as a release agent, the stainless steel coating 3 and the second hard coating 4 (particularly, TiCN, which is not coated with the mask 7 without causing substantial damage to the mask 7). The second hard film 4) and the different color film 5 made of ZrCN can be easily removed.

  Examples of methods for removing the second hard coating 4 and the different color coating 5 include a method of spraying a release agent, a method of dipping in a liquid release agent (dipping), and electrolysis in a state of being immersed in a liquid release agent. Among them, the method of immersing in a liquid release agent is particularly preferable. This makes it possible to remove the second hard coating 4 and the different color coating 5 more easily and reliably. Further, the removal of the second hard coating 4 and the different color coating 5 may be performed while applying ultrasonic vibration, for example.

  When the removal of the second hard coating 4 and the different color coating 5 is performed by immersing in a release agent in a liquid state, the temperature of the release agent is not particularly limited, but is preferably 15 ° C. or more and 100 ° C. or less, for example. The temperature is more preferably 20 ° C. or more and 50 ° C. or less, and further preferably 30 ° C. or more and 40 ° C. or less.

  The immersion time in the release agent is not particularly limited, but is preferably, for example, from 5 minutes to 120 minutes, and more preferably from 20 minutes to 60 minutes.

≪Mask removal process≫
In the present embodiment, after the stainless steel film exposing step, a mask removing step for removing the mask 7 is further provided.

  Thereby, the different color film 5 can be exposed to the outside, and the aesthetic appearance of the decorative article 10 can be further improved.

  The mask 7 may be removed by any method, but a mask remover that can remove the mask 7 and that does not substantially damage the stainless steel coating 3 and the different-color coating 5 is used. It is preferable to use.

  By using such a mask remover, the mask 7 can be easily and reliably removed.

The mask removing agent used for removing the mask 7 is not particularly limited, but is preferably a fluid such as a liquid or a gas. Among them, a liquid is particularly preferable.
This makes it possible to remove the mask 7 more easily and reliably.

Examples of the mask remover include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), Ketone solvents such as methyl isopropyl ketone (MIPK) and cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME) 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, ether solvents such as diethylene glycol dimethyl ether (diglyme), methyl cellosolve, ethyl celloso Cellosolve solvents such as butyl, phenylcellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, aromatic hydrocarbon solvents such as toluene, xylene, benzene, pyridine, pyrazine, furan, pyrrole, thiophene, etc. Aromatic heterocyclic compound solvents, amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane, Ester solvents such as ethyl acetate, methyl acetate, ethyl formate, sulfur compound solvents such as dimethyl sulfoxide (DMSO), sulfolane, nitrile solvents such as acetonitrile, propionitrile, formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, Organic acid solvents such as hydrofluoric acid A mixture of one or more selected from organic solvents, etc., and acidic substances such as nitric acid, sulfuric acid, hydrogen chloride, hydrogen fluoride, phosphoric acid, sodium hydroxide, potassium hydroxide, hydroxide Alkaline substances such as lithium, calcium hydroxide, magnesium hydroxide, ammonia, potassium permanganate (KMnO ₄ ), manganese dioxide (MnO ₂ ), potassium dichromate (K ₂ Cr ₂ O ₇ ), ozone, concentrated sulfuric acid, Examples thereof include a mixture of an oxidizing agent such as nitric acid, white powder, hydrogen peroxide, and quinones, and a reducing agent such as sodium thiosulfate (Na ₂ S ₂ O ₃ ), hydrogen sulfide, hydrogen peroxide, and hydroquinones.

  Examples of the method for removing the mask 7 include a method of spraying a mask remover, a method of immersing in a liquid mask remover, and a method of electrolysis in a state of being immersed in a liquid mask remover. Among these, a method of immersing in a mask remover in a liquid state is particularly preferable.

  This makes it possible to remove the mask 7 more easily and reliably. The removal of the mask 7 may be performed while applying ultrasonic vibration, for example.

  When removing the mask 7 by immersing it in a mask remover in a liquid state, the temperature of the mask remover is not particularly limited, but is preferably 15 ° C. or higher and 100 ° C. or lower, for example, 30 ° C. or higher and 50 ° C. or higher. It is more preferable that the temperature is not higher than ° C.

  Further, the immersion time in the mask remover is not particularly limited, but is preferably, for example, from 5 minutes to 60 minutes, and more preferably from 5 minutes to 30 minutes.

  FIG. 10 shows a flowchart of the method for manufacturing the decorative product as described above.

"clock"
Next, the timepiece of the invention will be described.
FIG. 11 is a partial cross-sectional view schematically showing a preferred embodiment of the timepiece (portable timepiece) of the present invention.

  A wristwatch (portable timepiece) 100 according to the present embodiment includes a case (case) 22, a back cover 23, a bezel (edge) 24, and a glass plate 25. Further, in the case 22, a movement (not shown) (for example, a dial and one with hands) is accommodated.

  A winding stem pipe 26 is fitted and fixed to the barrel 22, and a shaft portion 271 of a crown 27 is rotatably inserted into the winding stem pipe 26.

  The body 22 and the bezel 24 are fixed by a plastic packing 28, and the bezel 24 and the glass plate 25 are fixed by a plastic packing 29.

  Further, a back cover 23 is fitted (or screwed) to the barrel 22, and a ring-shaped rubber packing (back cover packing) 40 is inserted in a compressed state in these joint portions (seal portions) 50. Has been. With this configuration, the seal portion 50 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove 272 is formed on the outer periphery of the shaft portion 271 of the crown 27, and a ring-shaped rubber packing (crown packing) 30 is fitted in the groove 272. The rubber packing 30 is in close contact with the inner peripheral surface of the winding stem pipe 26 and is compressed between the inner peripheral surface and the inner surface of the groove 272. With this configuration, the space between the crown 27 and the winding stem pipe 26 is liquid-tightly sealed, and a waterproof function is obtained. When the crown 27 is rotated, the rubber packing 30 rotates together with the shaft portion 271 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe 26.

  The wristwatch 100 according to the present embodiment is a decorative product according to the present invention in which at least one of the decorative items (particularly, the watch exterior parts) such as the bezel 24, the trunk 22, the crown 27, the back cover 23, and the watch band has been described above. It is composed of In other words, the timepiece of the present embodiment is provided with the decorative article of the present invention.

  Accordingly, it is possible to provide a timepiece having a decorative product having a plurality of different color regions and having an excellent aesthetic appearance and excellent durability.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the decorative article and watch 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, at least a part of the surface of the decorative article is given corrosion resistance, weather resistance, water resistance, oil resistance, scratch resistance, abrasion resistance, discoloration resistance, etc. A coat layer (protective layer) or the like that improves the effect of scratches or the like may be formed. Such a coat layer may be removed when a decorative article is used.

  In the embodiment described above, the decorative article has a five-layer configuration in which the base material, the first hard coating, the stainless steel coating, the second hard coating, and the different color coating are laminated in this order. As described above, at least one intermediate layer may be provided between two adjacent structures among these structures. More specifically, the decorative article of the present invention has, for example, a structure in which a first hard film and a stainless steel film are repeatedly laminated on the surface of a base material, The first hard film in which the stainless steel film in contact with the second hard film contacts with the surface opposite to the surface in contact with the second hard film may have a different configuration (same It may not be the first hard coating).

  Moreover, in the method for manufacturing a decorative article of the present invention, an optional process can be added as necessary.

  Further, in the above-described embodiment, the case of having a mask forming step before the stainless steel coating exposing step and using the mask to remove a part of the second hard coating and the different color coating has been representatively described. In the present invention, the mask forming step may be omitted. Even in such a case, for example, with respect to a laminate including a base material, a first hard coating, a stainless steel coating, a second hard coating, and a different color coating, a release agent is applied in a predetermined pattern using an inkjet method or the like. The second hard coating and the different color coating can be removed in a desired pattern.

  In the above-described embodiment, the case where the mask is removed after the different color film removal step is representatively described. However, the mask removal step after the different color film removal step may be omitted. That is, the decorative article of the present invention may include a mask as a part of the configuration.

Next, specific examples of the present invention will be described.
[1] Manufacture of decorative products (Example 1)
A decorative article (a piece of a wristwatch band) was manufactured by performing a surface treatment as shown below.

  First, a base material having the shape of a wristwatch band piece was produced by forging using titanium, and then necessary portions were cut and polished.

Next, this base material was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
A first hard film was formed on the surface of the substrate thus cleaned.

The first hard coating was formed by sputtering as described below.
First, the substrate was attached to the sputtering apparatus, and then the inside of the sputtering apparatus was evacuated (depressurized) to 1.0 × 10 ⁻³ Pa while preheating the apparatus.

Further, the inside of the sputtering apparatus was evacuated (depressurized) to 2.8 × 10 ⁻³ Pa, and bombardment was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

Subsequently, the atmosphere gas in the sputtering apparatus is replaced with a mixed gas of nitrogen and acetylene to 4.0 × 10 ⁻¹ Pa, and film formation by sputtering is performed, and titanium carbonitride (TiCN) is formed. A first hard coating was formed. Titanium was used as the target. The average thickness of the formed first hard film was 1.0 μm.

Next, a stainless steel film was formed on the surface of the first hard film.
The stainless steel film was formed by sputtering as described below.

First, in the state where the base material provided with the first hard coating as described above is continuously mounted in the above-described sputtering apparatus, the inside of the sputtering apparatus is preheated to 1.0 × 10 ^−3. Exhaust (reduced pressure) to Pa.

Further, the inside of the sputtering apparatus was evacuated (depressurized) to 2.8 × 10 ⁻³ Pa, and bombardment was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

  Thereafter, argon gas was introduced into the processing chamber, and film formation by sputtering was performed to form a stainless steel film composed of SUS316L. Note that SUS316L was used as a target. The average thickness of the formed stainless steel coating was 0.1 μm.

Next, a second hard coating was formed on the surface of the stainless steel coating.
The second hard film was formed by sputtering as described below.

First, in the state where the base material provided with the first hard film and the stainless steel film as described above is continuously mounted in the above-described sputtering apparatus, the inside of the sputtering apparatus is preheated to 1.0. It exhausted (reduced pressure) to * 10 < ^-3 > Pa.

Further, the inside of the sputtering apparatus was evacuated (depressurized) to 2.8 × 10 ⁻³ Pa, and bombardment was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

Subsequently, the atmosphere gas in the sputtering apparatus is replaced with a mixed gas of nitrogen and acetylene to be 3.0 × 10 ⁻¹ Pa, and then film formation by sputtering is performed, which is composed of titanium carbonitride (TiCN). A second hard coating was formed. Titanium was used as the target. The average thickness of the formed second hard film was 0.5 μm.

Next, a different color film was formed on the surface of the second hard film.
The formation of the different color film was performed by sputtering as described below.

First, in the state where the base material provided with the first hard coating, the stainless steel coating, and the second hard coating as described above is mounted in the sputtering apparatus described above, sputtering is performed while preheating the apparatus. The inside of the apparatus was evacuated (depressurized) to 1 × 10 ⁻³ Pa.

Further, the inside of the sputtering apparatus was evacuated (depressurized) to 2.8 × 10 ⁻³ Pa, and bombardment was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

  Thereafter, argon gas was introduced into the processing chamber, and film formation by sputtering was performed to form a different color film composed of a gold alloy. As a target, a gold alloy of Au 75 mass% -Cu 25 mass% was used. The average thickness of the formed different color film was 0.1 μm.

Next, a mask was formed in a predetermined shape on part of the surface of the different color coating.
The mask was formed by brushing a rubber-based resin to cover a part of the surface of the different color film and then drying at 200 ° C. for 30 minutes. The average thickness of the formed mask was 500 μm.

  Next, using the release agent, the different color film at the part where the mask was not coated and the second hard film corresponding to the part were removed.

  The removal of the different color coating and the second hard coating was performed by immersing the substrate coated with the mask in a release agent. At this time, an aqueous solution composed of 0.1% by weight potassium hydroxide, 140% by volume hydrogen peroxide, and 60% by volume water was used as the release agent. Further, the temperature of the release agent and the immersion time in the release agent in this step were 35 ° C. and 30 minutes, respectively.

Thereafter, the mask was removed by dipping in a mask remover comprising a halogen compound solvent and a ketone solvent. Moreover, the temperature of the mask removing agent and the immersion time in the mask removing agent in this step were 30 ° C. and 30 minutes, respectively.
In addition, the thickness of each coating film was measured by the microscope cross-section test method of JIS H 5821.

(Example 2)
A decorative article (watch band piece) was manufactured in the same manner as in Example 1 except that the base material was made of stainless steel (SUS316L).

(Example 3)
An ornament (watch band piece) was manufactured in the same manner as in Example 1 except that the second hard coating was formed of zirconium carbonitride (ZrCN).

Example 4
A decorative article (a piece of a wristwatch band) was manufactured in the same manner as in Example 3 except that a substrate made of stainless steel (SUS316L) was used.

  Table 1 summarizes the structures of the decorative articles of the respective examples. In addition, about each site | part which comprises an ornament, all the content rate of the component shown in a table | surface was 99.9 mass% or more.

[2] Appearance evaluation of ornaments Each ornament manufactured in each of the above examples was observed visually and with a microscope, and the appearance was evaluated according to the following four-stage criteria.
A: Appearance is excellent.
B: Appearance is good.
C: Appearance is slightly poor.
D: Appearance defect.

[3] Evaluation of film adhesion The test as shown below was performed on each decorative article manufactured in each of the above examples to evaluate the adhesion of the film.
Each decorative article was subjected to the following thermal cycle test.

  First, the decorative article 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 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).

Then, the external appearance of the ornament was visually observed, and the external appearance was evaluated according to the following four criteria.
A: No floating or peeling of the film is observed.
B: Floating of the film is hardly recognized.
C: The float of the film is clearly recognized.
D: Cracking and peeling of the film are clearly recognized.

[4] Evaluation of scratch resistance Each decorative article produced in each of the above examples was subjected to the following test to evaluate the scratch resistance.

  A stainless steel brush was pressed onto the surface on the side where the coating of each decorative article was provided and slid 50 times. The pressing load at this time was 0.2 kgf.

Thereafter, the surface of the decorative article was visually observed, and the appearance was evaluated according to the following four criteria.
A: No scratches are observed on the surface of the coating.
B: Scratches are hardly observed on the surface of the coating.
C: Scratches are slightly observed on the surface of the coating.
D: Scratches are significantly observed on the surface of the coating.

[5] Evaluation of dent resistance (difficulty of marking) The dent resistance was evaluated by performing the following test on each decorative article manufactured in each of the above examples.

A stainless steel ball (diameter 1 cm) is dropped from a position of 50 cm in height above each ornament, and the size of the dent on the surface of the ornament (the diameter of the dent mark) is measured. Evaluation was made according to the criteria.
A: The diameter of the dent mark is less than 1 mm, or the dent mark is not required.
B: The diameter of the dent mark is 1 mm or more and less than 2 mm.
C: The diameter of the dent mark is 2 mm or more and less than 3 mm.
D: The diameter of the dent mark is 3 mm or more.
These results are shown in Table 2.

  As is clear from Table 2, all the decorative articles of the present invention have excellent aesthetic appearance (particularly, having a plurality of different color regions and excellent aesthetic appearance) and excellent durability. Met.

  In addition, a wristwatch as shown in FIG. 11 was assembled using the decorative articles manufactured in the above-described examples. When these wristwatches were evaluated in the same manner as described above, the same results as described above were obtained.

  DESCRIPTION OF SYMBOLS 10 ... Ornament, 1 ... Base material, 2 ... 1st hard coating, 3 ... Stainless steel coating, 4 ... 2nd hard coating, 5 ... Different color coating (Au type alloy coating), 7 ... Mask, 100 ... Wristwatch (Portable watch), 22 ... trunk (case), 23 ... back cover, 24 ... bezel (edge), 25 ... glass plate, 26 ... winding stem pipe, 27 ... crown, 271 ... shaft, 272 ... groove, 28 ... Plastic packing, 29 ... Plastic packing, 30 ... Rubber packing (Crown packing), 40 ... Rubber packing (back cover packing), 50 ... Joint part (seal part)

Claims (8)

A metal substrate at least part of which is mainly composed of Ti or stainless steel;
A first hard film provided on the surface of the base material and mainly composed of a Ti-based hard compound;
A stainless steel coating that is provided on the opposite side of the first hard coating from the surface facing the substrate, and is mainly composed of stainless steel;
A second hard member formed of a material including at least one of a Ti-based hard compound and a Zr-based hard compound provided on a surface opposite to the surface facing the first hard coating of the stainless steel coating A coating;
The second hard coating is provided on a surface opposite to the surface facing the stainless steel coating, and is provided with a different color coating made of a material having a color tone different from that of the stainless steel coating,
The second hard coating and the different color coating selectively coat a part of the surface of the stainless steel coating, and the stainless steel coating and the different color coating are configured to be visible from the outside. Decorative product characterized by being.   The decorative product according to claim 1, wherein the different color coating is an Au-based alloy coating mainly composed of an Au-based alloy.   The decorative article according to claim 1 or 2, wherein the stainless steel coating is made of austenitic stainless steel.   The decorative article according to claim 3, wherein the stainless steel film is made of SUS316L.   The decorative article according to any one of claims 1 to 4, wherein the decorative article is a watch exterior part.   The decorative article according to claim 5, wherein the watch exterior part is at least one selected from the group consisting of a case, a bezel, a back cover, and a band. A first hard film forming step of forming a first hard film mainly composed of a Ti-based hard compound on a metal substrate at least a part of which is mainly composed of Ti or stainless steel;
A stainless steel film forming step of forming a stainless steel film mainly composed of stainless steel on the first hard film;
A second hard film forming step of forming a second hard film made of a material containing at least one of a Ti-based hard compound and a Zr-based hard compound on the stainless steel film;
On the second hard film, a different color film forming step for forming a different color film made of a material having a color tone different from that of the stainless steel film,
A method for producing a decorative article, comprising: a stainless steel coating exposing step of selectively removing a part of the second hard coating and the different color coating to expose a part of the stainless steel coating.   A timepiece comprising the ornament according to any one of claims 1 to 6.

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