JP2007275144A - Ornament and watch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornament capable of maintaining an excellent beautiful appearance over a long period of time, and a watch equipped with the ornament. <P>SOLUTION: The ornament 1A has a base material 2 which has at least a part of the vicinity of a surface mainly composed of Ti and/or stainless steel, and a mixture layer 3 in which a gold-based material containing Au and TiN are mixed together. The rate of content of N in the mixture layer is in the range of 1-20 wt.%. The rate of content of Au in the mixture layer is in the range of 1-50 wt.%. The average thickness of the mixture layer is in the range of 0.04-1.5 μm. Preferably, the gold-based material is an Au-Fe-Pd-based alloy. Preferably, the mixture layer is provided in such a manner that vapor deposition by resistance heating, using the Au-containing gold-based material as an evaporation source, and vapor deposition by an electronic beam, using Ti as an evaporation source, are performed in the same apparatus. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a decorative article and a watch.

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, generally, a metal material such as Au has been used as a constituent material of an ornament.
However, the hardness of metal materials is generally relatively low, and ornaments made of the above materials (especially, watch exterior parts and accessories) are easily scratched on the surface and should be used for a long time. As a result, the aesthetic appearance is remarkably deteriorated.

In order to solve such problems, a technique for nitriding the surface of a base material made of, for example, stainless steel or Ti with nitrogen (for example, see Patent Document 1) is used as a technique for hardening the base material. .
However, since the nitriding treatment causes surface roughness, the polished appearance is changed. Mirror surface products are particularly rough and cloudy, and cannot be used as decorations as they are.

Therefore, as a post process, a method of polishing to a mirror surface by mechanical polishing has been adopted. However, this method has a drawback that the hardened layer is excessively scraped off by polishing and the hardness decreases, or a shape that cannot be polished afterwards (a shape that does not hit the buff) cannot be processed.
In addition, the base material that has been subjected to the nitriding treatment as described above is difficult to apply to a decorative product (especially gold-colored) that requires an excellent appearance because the color tone lacks a high-class feeling.

Japanese Patent Laid-Open No. 11-318520

  An object of the present invention is to provide a decorative article that can maintain an excellent aesthetic appearance over a long period of time, and to provide a timepiece including the decorative article.

Such an object is achieved by the present invention described below.
The decorative article of the present invention comprises a base material mainly composed of Ti and / or stainless steel at least in the vicinity of the surface;
It has a gold-based material containing Au and a mixed layer in which TiN is mixed.
Thereby, the ornament which can hold | maintain the outstanding aesthetic appearance over a long period of time can be provided.

In the decorative article of the present invention, the N content in the mixed layer is preferably 1 to 20 wt%.
This makes it possible to maintain an excellent aesthetic appearance for a longer period while making the aesthetic appearance of the decorative article particularly excellent.
In the decorative article of the present invention, the Au content in the mixed layer is preferably 1 to 50 wt%.
Thereby, the aesthetic appearance of the decorative article can be made particularly excellent.

In the decorative article of the present invention, the mixed layer preferably has an average thickness of 0.04 to 1.5 μm.
This makes it possible to prevent the internal stress of the mixed layer from becoming large and make the decorative article particularly difficult to have a dent such as a scratch or dent, and has an excellent aesthetic appearance over a longer period of time. Can be held.

In the decorative article of the present invention, it is preferable to have a TiN layer made of TiN between the base material and the mixed layer.
Thereby, durability (such as dent resistance) of the decorative article can be made particularly excellent, and an excellent aesthetic appearance can be maintained for a longer period of time.
In the decorative article of the present invention, the average thickness of the TiN layer is preferably 0.4 to 2.0 μm.
Thereby, durability (such as dent resistance) of the decorative article can be made particularly excellent, and an excellent aesthetic appearance can be maintained for a longer period of time.

In the decorative product of the present invention, the mixed layer is formed by performing vapor deposition by resistance heating using a gold-based material containing Au as an evaporation source and vapor deposition by an electron beam using Ti as an evaporation source in the same apparatus. It is preferable that it is provided.
As a result, the mixed layer can have a more uniform film thickness (small variation in film thickness) and particularly excellent adhesion to the substrate. As a result, the aesthetic appearance and durability as a decorative product can be made particularly excellent. Further, even if the mixed layer is relatively thin, the variation in film thickness can be made sufficiently small, which is advantageous in improving the reliability of the decorative article.

In the decorative article of the present invention, the metal material is preferably an Au—Fe—Pd alloy.
Thereby, the aesthetic appearance of the decorative article can be made particularly excellent.
In the decorative article of the present invention, the Vickers hardness Hv measured with a load of 10 gf is preferably 350 to 800 on the surface on the side where the mixed layer is provided.
Thereby, the outstanding aesthetic appearance as a decorative article can be hold | maintained over a longer period of time.

The decorative article of the present invention is preferably a watch exterior part.
In general, a watch exterior part is a decorative product that is easily affected by an external impact, and is required to have a beautiful appearance as a decorative product and to have durability as a practical product. These requirements can be satisfied at the same time.
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 that can maintain an excellent aesthetic appearance over a long period of time.

  ADVANTAGE OF THE INVENTION According to this invention, the timepiece provided with the ornament which can hold | maintain the outstanding aesthetic appearance over a long period of time, and the said ornament can be provided.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
<First Embodiment>
First, a first embodiment of a decorative article of the present invention and a preferred embodiment of a manufacturing method thereof will be described.
FIG. 1 is a cross-sectional view showing a first embodiment of the decorative article of the present invention, and FIG. 2 is a cross-sectional view showing a preferred embodiment of the method for manufacturing the decorative article shown in FIG.
As shown in FIG. 1, the decorative article 1A (1) of this embodiment includes a base material 2 and a mixed layer 3 in which a gold-based material containing Au and TiN are mixed.

[Base material]
The base material (metal base material) 2 is at least partly composed of mainly Ti and / or stainless steel near the surface. Examples of the material mainly composed of Ti include Ti (Ti as a simple substance), Ti alloy, and the like. Examples of stainless steel include Fe-Cr alloys, Fe-Cr-Ni alloys, and more specifically, SUS405, SUS430, SUS434, SUS444, SUS429, SUS430F, etc., SUS304, SUS303, SUS316, SUS316L, SUS316J1, SUS316J1L, etc. are mentioned. Examples of materials that can be nitrided or carburized include materials other than those composed of Ti and / or stainless steel as described above, but such materials (mainly Ti and / or stainless steel). In the case of using a configured material), it is difficult to sufficiently increase the hardness of the finally obtained decorative article. In addition, when a material mainly composed of Ti and / or stainless steel is not used, the final decorative product has an excellent aesthetic appearance for a sufficiently long period of time (especially in decorative products such as watch exterior parts). It is difficult to maintain an aesthetic appearance).

  Moreover, the base material 2 may have a substantially uniform composition at each site, or may have a different composition depending on the site. For example, the base material 2 may have a base portion and a surface layer provided on the base portion. If the base material 2 has such a configuration, for example, the degree of freedom in forming the base material 2 can be increased by selecting the constituent material of the base, and even if the decorative article 1A has a more complicated shape. Can be manufactured relatively easily. When the base material 2 has a base and a surface layer, the thickness (average value) of the surface layer is not particularly limited, but is preferably 0.1 to 50 μm, and preferably 1.0 to 10 μm. Is more preferable. When the thickness of the surface layer is within the above range, the strength of the base material 2 after the curing treatment can be made particularly excellent, and unintentional peeling from the base of the surface layer can be more reliably performed. Can be prevented.

When the base material 2 has a base and a surface layer, as the constituent material of the surface layer, for example, the materials described above can be suitably used. Moreover, as a constituent material of the base, for example, a metal material, a non-metal material, or the like can be used.
When the base is made of a metal material, it is possible to provide the decorative article 1A having particularly excellent strength characteristics.

  When the base is made of a metal material, the surface layer, the mixed layer 3 described later, the TiN layer 4 described in the second embodiment, and the like are formed even when the surface roughness of the base is relatively large. Due to the leveling effect, the surface roughness of the resulting decorative article 1A can be reduced. For example, it is possible to perform mirror finish even if machining such as cutting and polishing on the surface of the base is omitted, or the base is formed by the MIM method, and the surface is pear-ground. Even in this case, it can be easily mirror-finished. As a result, a decorative article having excellent gloss can be obtained.

When the base is made of a non-metallic material, for example, it is possible to provide a decorative article 1A that is relatively light and easy to carry and has a heavy appearance.
In addition, when the base is made of a non-metallic material, for example, it can be formed into a desired shape relatively easily.
Further, when the base is made of a nonmetallic material, an effect of shielding electromagnetic noise can be obtained.

  Examples of metal materials constituting the base include various metals such as Fe, Cu, Zn, Ni, Ti, Mg, Cr, Mn, Mo, Nb, Al, V, Zr, Sn, Au, Pd, Pt, and Ag. And alloys containing at least one of these. Among these, Cu, Zn, Ni, Ti, Al or an alloy containing at least one of these is preferable. When the base is made of the material as described above, the adhesion between the base and the surface layer can be made particularly excellent, the workability of the base is improved, and the base 2 as a whole is molded. The degree of freedom increases further.

Moreover, as a nonmetallic material which comprises a base, ceramics, plastics (especially heat resistant plastic), a stone material, wood, etc. are mentioned, for example.
As ceramics, for example, Al ₂ O ₃ , SiO ₂ , TiO ₂ , Ti ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , oxide-based ceramics such as barium titanate and strontium titanate, AlN, Si ₃ N ₄ , SiN, TiN, BN, ZrN, HfN, VN, TaN, NbN, CrN, Cr ₂ N and other nitride ceramics, graphite, SiC, ZrC, Al ₄ C ₃ , CaC ₂ , WC, TiC, HfC, VC , Carbide ceramics such as TaC and NbC, boride ceramics such as ZrB ₂ and MoB, or composite ceramics in which two or more of these are arbitrarily combined.
When the base is made of the ceramic as described above, a decorative article 1A having particularly excellent strength and hardness can be obtained.

Examples of the plastic material constituting the base 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 ( Polyesters such as PBT) and polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, poly Ether sulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride , Other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, transpolyisoprene, fluororubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy Resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, Polypara-xylylene, poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, poly-monoethyl-para-xylylene, etc. Xylylene resins, etc., or copolymers, blends, polymer Etc., and 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.
Further, the shape and size of the base material 2 are not particularly limited, and are usually determined based on the shape and size of the decorative article 1A.

[Mixed layer]
On the surface of the base material 2, a mixed layer 3 in which a gold-based material containing Au and TiN are mixed is provided.
By having such a mixed layer 3, the decorative product 1 A as a whole has an excellent aesthetic appearance (aesthetics) (particularly, a high-quality golden color tone), and the hardness of the decorative product 1 A as a whole (mixed layer) 3 can be made to be excellent, and a dent such as a scratch or a dent can be made difficult to attach. That is, the decorative article 1A can maintain an excellent aesthetic appearance over a long period of time. In particular, the metallic material constituting the mixed layer 3 and TiN are similar in color tone (chromaticity). For this reason, even if there is a microscopic composition variation in each part of the mixed layer 3, it is effectively prevented that the aesthetic appearance of the decorative article 1A is deteriorated. In addition, since the gold-based material and TiN are materials having high affinity, the mixed layer 3 includes a region mainly composed of a gold-based material and a region mainly composed of TiN. However, when a relatively large external force is applied to the decorative article 1A, the occurrence of cracks, separation, and the like in the vicinity of the interface between these regions is reliably prevented. For this reason, the durability of the decorative article 1A is very excellent.

On the other hand, when the decorative article does not have a mixed layer, for example, when the coating has a coating made of a gold-based material without containing TiN on the substrate, or it is made of TiN without containing a gold-based material. If the TiN layer composed of TiN and the gold-based material layer composed of the gold-based material are laminated on the base material, the above effects cannot be obtained. .
For example, when the base material has a coating film made of TiN that does not contain a gold-based material, the decorative article has an inferior aesthetic appearance (an appearance that is inferior to a high-class feeling). In addition, when the substrate has a coating made of a gold-based material that does not contain TiN, the coating from the substrate is caused by external forces (eg, frictional force), environmental changes such as temperature and humidity, etc. , And the like are relatively easily generated, and dents and the like are easily generated. That is, when the base material has a coating film made of a gold-based material that does not contain TiN, the durability of the decorative article is extremely inferior, and it is difficult to maintain an excellent aesthetic appearance over a long period of time. It becomes. In addition, when a TiN layer made of TiN and a gold-based material layer made of a gold-based material are laminated on the base material, external force (for example, frictional force, etc.), temperature, humidity, etc. Due to environmental changes or the like, the coating (gold-based material layer) is lifted or peeled off from the substrate relatively easily. That is, even when the TiN layer and the gold-based material layer are laminated on the base material, the decorative article is inferior in durability, and it is difficult to maintain an excellent aesthetic appearance over a long period of time.

  Although the content rate of N in the mixed layer 3 is not specifically limited, It is preferable that it is 1-20 wt%, and it is more preferable that it is 10-18 wt%. When the content of N in the mixed layer 3 is a value within the above range, the aesthetic appearance of the decorative article 1A is particularly excellent, and the scratch resistance (hardness to scratch) and scratch resistance ( It is possible to make the marks (e.g., difficult to be marked) particularly excellent. As a result, an excellent aesthetic appearance can be maintained over a longer period. On the other hand, if the N content in the mixed layer 3 is less than the lower limit, depending on the thickness of the mixed layer 3, the hardness, scratch resistance, dent resistance, etc. of the decorative article 1A as a whole It can be difficult to be good enough. On the other hand, when the N content in the mixed layer 3 exceeds the upper limit, it becomes difficult to make the appearance of the decorative article 1A sufficiently excellent depending on the Au content in the mixed layer 3 and the like. there is a possibility. If the N content in the mixed layer 3 exceeds the upper limit, depending on the thickness of the mixed layer 3 and the like, the internal stress of the mixed layer 3 becomes too large, and cracks and the like are likely to occur, and the decorative article 1A It may be difficult to make the durability of the steel sufficiently excellent.

  Moreover, the content rate of Au in the mixed layer 3 is not particularly limited, but is preferably 1 to 50 wt%, and more preferably 5 to 40 wt%. When the Au content in the mixed layer 3 is a value within the above range, the decorative article 1A is sufficiently excellent in durability (scratch resistance, scratch resistance, etc.), and the decorative article 1A is aesthetic. The appearance can be made particularly excellent. On the other hand, if the Au content in the mixed layer 3 is less than the lower limit, it is difficult to make the aesthetic appearance of the decorative article 1A sufficiently excellent depending on the thickness of the mixed layer and the like. there is a possibility. On the other hand, when the content ratio of Au in the mixed layer 3 exceeds the upper limit, the content ratio of TiN in the mixed layer 3 is relatively lowered, and depending on the thickness of the mixed layer 3 or the like, the decorative article 1A as a whole It may be difficult to make the hardness, scratch resistance, dent resistance, and the like sufficiently excellent.

  The gold-based material constituting the mixed layer 3 may be any material that contains at least Au, and may be, for example, pure gold or a gold alloy. Especially, as a gold-type material which comprises the mixed layer 3, an Au-Fe-Pd type alloy is preferable. When the gold-based material is an Au-Fe-Pd-based alloy, the color tone of the gold-based material can be made particularly excellent, and the affinity of the gold-based material to TiN can be made particularly excellent. In addition, it is possible to effectively prevent microscopic compositional variations from occurring in each part of the mixed layer 3. In addition, even when a microscopic compositional variation occurs in each part of the mixed layer 3, it is possible to more effectively prevent the aesthetic appearance of the decorative article 1A from being deteriorated. From these facts, when the gold-based material is an Au—Fe—Pd-based alloy, the aesthetic appearance of the decorative article 1A can be made particularly excellent. Further, when the gold-based material is an Au—Fe—Pd-based alloy, it is possible to more reliably prevent the mixed layer 3 from being cracked or peeled off when a relatively large external force is applied to the decorative article 1A. The durability of the decorative article 1A can be made particularly excellent.

  When the gold-based material constituting the mixed layer 3 is an Au—Fe—Pd-based alloy, the Fe content in the mixed layer is not particularly limited, but is preferably 0.1 to 4.0 wt%. More preferably, it is 0.3-3.0 wt%. When the content ratio of Fe in the mixed layer 3 is a value within the above range, the durability of the decorative article 1A can be made sufficiently excellent while the aesthetic appearance of the decorative article 1A is particularly excellent. .

  Moreover, when the gold-type material which comprises the mixed layer 3 is an Au-Fe-Pd-type alloy, the content rate of Pd in a mixed layer is although it does not specifically limit, It is 0.1-12.0 wt%. Preferably, it is 1.0 to 7.0 wt%. When the content ratio of Pd in the mixed layer 3 is a value within the above range, the durability of the decorative article 1A can be made sufficiently excellent while the aesthetic appearance of the decorative article 1A is particularly excellent. .

The average thickness of the mixed layer 3 is not particularly limited, but is preferably 0.04 to 1.5 μm, more preferably 0.05 to 0.3 μm, and 0.10 to 0.20 μm. More preferably. When the average thickness of the mixed layer 3 is a value within the above range, the internal stress of the mixed layer 3 is more effectively prevented from increasing while making the aesthetic appearance and hardness of the decorative article 1A particularly excellent. As a result, the reliability and durability of the decorative article 1A can be made particularly excellent. On the other hand, if the average thickness of the mixed layer 3 is less than the lower limit, it is difficult to make the aesthetic appearance of the decorative article 1A sufficiently excellent depending on the Au content in the mixed layer 3 and the like. There is a possibility. Further, if the average thickness of the mixed layer 3 is less than the lower limit, depending on the N content in the mixed layer 3, the hardness, scratch resistance, dent resistance, etc. of the decorative article 1A as a whole are sufficient. It may be difficult to make it excellent. On the other hand, when the average thickness of the mixed layer 3 exceeds the upper limit, depending on the N content in the mixed layer 3, the internal stress of the mixed layer 3 tends to increase.
In addition, the mixed layer 3 may be a layer in which a gold-based material containing Au and TiN are mixed in the same plane, but may have a plurality of regions having different compositions. For example, the mixed layer 3 may be configured by a laminate including a plurality of layers having different compositions in the thickness direction, and the composition changes in an inclined manner along the thickness direction. It may be a thing.

[Decoration]
The decorative article 1A (1) as described above may be any article having a decorative property. For example, an interior such as a figurine, an exterior article, a jewelry, a watch case (a trunk, a back cover, a trunk) And one-piece case with integrated back cover), watch band (including band clasp, band / bangle attaching / detaching mechanism, etc.), dial, watch hand, bezel (for example, rotating bezel, etc.), crown ( For example, screw lock-type crown, etc.), buttons, cover glass, glass edge, dial ring, parting plate, packing, etc. for watch exterior parts, movement base plate, gears, train wheel bridge, rotating weights, etc. Accessories such as glasses (eg, glasses frame), tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings, etc. , It is possible to apply lighter or its case, car wheel, sporting goods such as golf club, nameplate, panel, Shohai, various other equipment parts, including housing, etc., in various containers and the like. Among these, a watch exterior part is particularly preferable. A watch exterior part is required to have a beautiful appearance as a decorative product, and as a practical product, durability, corrosion resistance, scratch resistance, wear resistance, and excellent tactile sensation are required. Therefore, all these requirements can be satisfied. The “watch exterior part” in the present specification may be anything that can be visually recognized from the outside, and is not limited to the one that is exposed to the outside of the watch. Including built-in.
In addition, the decorative article 1A preferably has a Vickers hardness Hv of 350 to 800, more preferably 600 to 800, measured at a load of 10 gf on the surface on which the mixed layer 3 is provided. Thereby, the outstanding aesthetic appearance as a decorative article can be hold | maintained over a longer period of time.
Next, a method for manufacturing the above-described decorative article 1A will be described.
FIG. 2 is a cross-sectional view showing a preferred embodiment of the method for manufacturing the decorative article shown in FIG.
As shown in FIG. 2, the manufacturing method of the present embodiment includes a base material preparation step (1 a) for preparing the base material 2 and a mixed layer formation step (1 b) for forming the mixed layer 3 on the base material 2. Have.

[Base material preparation process]
As the substrate 2, those described above can be used.
The substrate 2 may be formed by any method. Examples of the method for forming the substrate 2 include press working, cutting, forging, casting, powder metallurgy sintering, metal Examples thereof include powder injection molding (MIM) and lost wax method.

  Moreover, when the base material 2 has a base and a surface layer as described above, the base material 2 can be manufactured as follows. That is, the base material 2 can be obtained by forming a surface layer on the base manufactured by the method as described above. Examples of the method for forming the surface layer include dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, and other wet plating methods such as electrolytic plating, immersion plating, and electroless plating, thermal CVD, plasma CVD, Examples thereof include chemical vapor deposition methods (CVD) such as laser CVD, vacuum deposition, sputtering, dry plating methods such as ion plating, and thermal spraying.

  The surface of the substrate 2 may be subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it becomes possible to give variation to the glossiness of the surface of the obtained decorative article 1A, and the decorativeness of the obtained decorative article 1A 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.

  Further, the decorative article 1A manufactured using the base material 2 subjected to such surface processing has less glare and the like than those obtained by directly performing the surface processing on the mixed layer 3. In particular, the aesthetic appearance is excellent. Further, as described above, the mixed layer 3 contains TiN, which is a hard material. Therefore, when the surface processing is performed directly on the mixed layer 3, when the surface processing is performed, the mixed layer 3 is not damaged. Although defects are likely to occur and the production yield of the decorative article 1A may be significantly reduced, the occurrence of such a problem can be effectively prevented by subjecting the base material 2 to surface treatment. Further, the surface treatment for the substrate 2 can be easily performed under mild conditions as compared with the surface treatment for the mixed layer 3.

[Mixed layer formation process]
A mixed layer 3 in which a gold-based material and TiN are mixed is formed on the surface of the substrate 2 (1b).
The formation method of the mixed layer 3 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., wet plating such as electrolytic plating, immersion plating, electroless plating, etc. And chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition (vapor deposition), dry plating methods (vapor phase deposition) such as sputtering and ion plating, and thermal spraying. However, a dry plating method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film formation method) as a method for forming the mixed layer 3, the mixed layer 3 has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. Can be reliably formed. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1A can be made particularly excellent. Moreover, even if the mixed layer 3 to be formed is relatively thin by applying a dry plating method (vapor phase film forming method) as a method for forming the mixed layer 3, the variation in film thickness is sufficiently small. It can be. For this reason, it is advantageous also in improving the reliability of the decorative article 1A. Moreover, the content rate of N in the mixed layer 3 can be more reliably controlled by applying a dry plating method (vapor phase film forming method) as a method for forming the mixed layer 3.

When the dry plating method as described above is applied, for example, the desired mixed layer 3 can be easily and reliably formed by performing the treatment in an atmosphere containing N (nitrogen). As such an atmospheric gas, for example, nitrogen gas (N ₂ gas) or the like can be used. And the composition (N content rate) etc. of the mixed layer 3 formed can be adjusted reliably by adjusting the partial pressure etc. suitably.

  Note that the atmosphere gas may contain, for example, an inert gas such as argon gas. Thereby, the dispersion | variation in the composition (N content rate) in each site | part (each site | part of a surface direction) of the mixed layer 3 can be prevented easily and reliably. As a result, the aesthetic appearance and durability of the decorative article 1A can be reliably improved, and the reliability of the decorative article 1A can be particularly improved.

  Moreover, vapor deposition is particularly preferable among the dry plating methods (vapor phase film forming methods) as described above. By applying vapor deposition as a method for forming the mixed layer 3, the above effects become more prominent. That is, by applying vapor deposition as a method for forming the mixed layer 3, it is possible to more reliably form the mixed layer 3 that has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. Can do. As a result, it is possible to further improve the aesthetic appearance and durability of the finally obtained decorative article 1A. Further, by applying vapor deposition as a method for forming the mixed layer 3, even if the mixed layer 3 to be formed is relatively thin, the variation in film thickness can be made particularly small. Further, by applying vapor deposition as a method for forming the mixed layer 3, the N content in the mixed layer 3 can be controlled more reliably.

  When the mixed layer 3 is formed by vapor deposition, it is preferable to perform vapor deposition by resistance heating using a gold-based material containing Au as an evaporation source and electron beam vapor deposition using Ti as an evaporation source in the same apparatus. . Thereby, the mixed layer 3 can have a more uniform film thickness (thickness variation is small), and the adhesiveness with the substrate 2 can be particularly excellent. As a result, the aesthetic appearance and durability as the decorative article 1A can be made particularly excellent. Even if the mixed layer 3 is relatively thin, the variation in film thickness can be made sufficiently small, which is advantageous in improving the reliability of the decorative article 1A. In addition, among the elements constituting the mixed layer 3, Ti is selectively nitrided while sufficiently preventing components other than Ti (for example, Fe that is relatively easily nitrided) from being nitrided. The mixed layer 3 composed of the gold-based material can be suitably formed. As a result, the aesthetic appearance and durability of the decorative article 1A can be reliably improved, and the reliability of the decorative article 1A can be particularly improved.

Second Embodiment
Next, a second embodiment of the decorative article of the present invention and a preferred embodiment of the manufacturing method thereof will be described.
FIG. 3 is a sectional view showing a second embodiment of the decorative article of the present invention, and FIG. 4 is a sectional view showing a preferred embodiment of the method for manufacturing the decorative article shown in FIG.

Hereinafter, the decorative article and the manufacturing method thereof according to the second embodiment will be described with a focus on differences from the above-described embodiment, and description of similar matters will be omitted.
As shown in FIG. 3, the decorative article 1B (1) of the present embodiment has a configuration in which a base material 2, a TiN layer 4 made of TiN, and a mixed layer 3 are laminated in this order. . That is, the ornament 1B is the same as the ornament 1A described above except that the TiN layer 4 is provided between the base material 2 and the mixed layer 3. Therefore, the TiN layer 4 will be described below.

[TiN layer]
The TiN layer 4 is mainly composed of TiN. By having the TiN layer 4, the adhesion between the substrate 2 and the mixed layer 3 can be made particularly excellent. In addition, by having the TiN layer 4, the function of repairing scratches on the base material 2 by leveling (leveling) (function as a leveling layer) and the function of cushioning external shocks in the decorative article 1B (cushion layer) As a function). For this reason, the aesthetic appearance, durability, and reliability as a decorative product can be made particularly excellent.
Further, by including the TiN layer 4, even when the mixed layer 3 is relatively thin, the aesthetic appearance, durability, and the like as a decorative product can be made particularly excellent. For this reason, the usage-amount of Au which is a noble metal can be suppressed and it is advantageous also from viewpoints, such as resource saving and reduction of manufacturing cost.

Although the content rate of N in the TiN layer 4 is not specifically limited, It is preferable that it is 5-35 wt%, and it is more preferable that it is 10-25 wt%. When the content of N in the TiN layer 4 is a value within the above range, the aesthetic appearance of the decorative article 1B is particularly excellent, and the scratch resistance (hardness to scratch) and scratch resistance ( It is possible to make the marks (e.g., difficult to be marked) particularly excellent. As a result, an excellent aesthetic appearance can be maintained over a longer period. On the other hand, if the content of N in the TiN layer 4 is less than the lower limit, the effect of having the TiN layer 4 may not be sufficiently exhibited depending on the thickness of the TiN layer 4 and the like. On the other hand, if the N content in the TiN layer 4 exceeds the upper limit, depending on the thickness of the TiN layer 4 and the like, the internal stress of the TiN layer 4 becomes too large, and cracks and the like are likely to occur. It may be difficult to make the durability of the steel sufficiently excellent.
The average thickness of the TiN layer 4 is not particularly limited, but is preferably 0.4 to 2.0 μm, and more preferably 0.5 to 1.0 μm. When the average thickness of the TiN layer 4 is within the above range, the above-described functions of the TiN layer 4 are more effectively exhibited while sufficiently preventing the internal stress of the TiN layer 4 from increasing. be able to.

Next, a method for manufacturing the above-described decorative item 1B will be described.
FIG. 4 is a cross-sectional view showing a preferred embodiment of the method for manufacturing the decorative article shown in FIG.
As shown in FIG. 4, the manufacturing method of the present embodiment includes a base material preparing step (2a) for preparing the base material 2, a TiN layer forming step (2b) for forming the TiN layer 4 on the base material 2, and A mixed layer forming step (2c) for forming the mixed layer 3 on the TiN layer 4;
The manufacturing method of this embodiment is the same as that of embodiment mentioned above except having a TiN layer formation process between a base material preparation process and a mixed layer formation process. Therefore, the TiN layer forming process will be described below.

[TiN layer forming step]
In the TiN layer forming step, a TiN layer 4 made of TiN is formed on the surface of the substrate 2 (1b).
The formation method of the TiN layer 4 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., wet plating such as electrolytic plating, immersion plating, electroless plating, etc. And chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition (vapor deposition), dry plating methods (vapor phase deposition) such as sputtering and ion plating, and thermal spraying. However, a dry plating method (vapor phase film forming method) is preferable. By applying a dry plating method (vapor phase film formation method) as a method for forming the TiN layer 4, the TiN layer 4 has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. Can be reliably formed. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1B can be made particularly excellent. Further, by applying a dry plating method (vapor phase film forming method) as a method for forming the TiN layer 4, even if the TiN layer 4 to be formed is relatively thin, the variation in film thickness is sufficiently small. It can be. For this reason, it is advantageous also in improving the reliability of the decorative article 1B. Further, by applying a dry plating method (vapor phase film forming method) as a method of forming the TiN layer 4, the N content in the TiN layer 4 can be controlled more reliably.

When applying the dry plating method as described above, for example, the desired TiN layer 4 can be easily and reliably formed by performing the treatment in an atmosphere containing N (nitrogen). As such an atmospheric gas, for example, nitrogen gas (N ₂ gas) or the like can be used. Then, by appropriately adjusting the partial pressure and the like, the composition (N content) of the TiN layer 4 to be formed can be reliably adjusted.

  Note that the atmosphere gas may contain, for example, an inert gas such as argon gas. Thereby, the dispersion | variation in the composition (N content rate) in each site | part (each site | part of a surface direction) of the TiN layer 4 can be prevented easily and reliably. As a result, the aesthetic appearance and durability of the decorative article 1B can be reliably improved, and the reliability of the decorative article 1B can be particularly improved.

  Moreover, vapor deposition is particularly preferable among the dry plating methods (vapor phase film forming methods) as described above. By applying vapor deposition as a method for forming the mixed layer 3, the above effects become more prominent. That is, by applying vapor deposition as a method for forming the mixed layer 3, the TiN layer 4 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 2 can be more reliably formed. Can do. As a result, it is possible to further improve the aesthetic appearance and durability of the finally obtained decorative article 1B. Further, by applying vapor deposition as a method of forming the TiN layer 4, even if the TiN layer 4 to be formed is relatively thin, the variation in film thickness can be made particularly small. Further, by applying vapor deposition as a method of forming the TiN layer 4, the N content in the TiN layer 4 can be controlled more reliably.

  In addition, by performing this process by the dry plating method (particularly, vapor deposition) as described above, the adhesion between the TiN layer 4 and the mixed layer 3 formed in the subsequent process may be further improved. It is possible to further improve the aesthetic appearance and durability of the decorative article 1B. In particular, when the subsequent mixed layer forming step is performed by a dry plating method (particularly, vapor deposition) similarly to the TiN layer forming step, the adhesion between the TiN layer 4 and the mixed layer 3 can be further improved. Further, the base material 2 provided with the TiN layer 4 can be continuously subjected to a mixed layer forming step without being once taken out from the film forming apparatus. As a result, the productivity of the decorative article 1B becomes particularly excellent, and it is possible to effectively prevent unintentional contamination from occurring between the TiN layer 4 and the mixed layer 3. The reliability of the decorative article 1B can be made particularly excellent.

<Clock>
Next, the timepiece of the present invention provided with the decorative product of the present invention as described above will be described.
FIG. 5 is a partial cross-sectional view showing a preferred embodiment of the timepiece (portable timepiece) of the present invention.
As shown in FIG. 5, the wristwatch (portable timepiece) 10 of this 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 10 of the present invention 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 is the aforementioned. It is configured.
As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

For example, in the method for manufacturing a decorative article of the present invention, an optional process can be added as necessary. For example, intermediate processing such as cleaning may be performed between the TiN layer forming step and the mixed layer forming step. Moreover, you may perform pre-processing, such as cutting, grinding, grinding | polishing, and honing, with respect to a base material.
In addition, 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 second embodiment described above, the base material and the TiN layer are provided adjacent to each other, and the TiN layer and the mixed layer are provided adjacent to each other. At least one intermediate layer may be provided between the TiN layer and the mixed layer.
In addition, for example, at least one intermediate layer other than the TiN layer may be provided between the base material and the mixed layer.

Next, specific examples of the present invention will be described.
1. Manufacture of decorative products (Example 1)
A decorative article (watch case (back cover)) was manufactured by the method described below.
First, a base material having the shape of a watch case (back cover) was produced by casting using stainless steel (SUS444), 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 mixed layer in which a gold-based material containing Au and TiN were mixed was formed as follows using a vapor deposition device on the substrate cleaned as described above (mixed layer forming step).

First, while preheating the processing chamber of the vapor deposition apparatus, the processing chamber was evacuated (depressurized) to 2 × 10 ⁻³ Pa. Thereafter, nitrogen gas was introduced at a flow rate of 30 ml / min, and the atmospheric pressure (total pressure) in the processing chamber was set to 3.0 × 10 ⁻³ Pa. In such a state (a state in which nitrogen gas is continuously introduced), an Au—Fe—Pd alloy as a gold material (Au: 68.0 wt%, Fe: 12.0 wt%, Pd: 20.0 wt%) Vapor deposition using resistance heating (resistance heating vapor deposition) using Ti as an evaporation source and electron beam vapor deposition (electron beam deposition) using Ti as an evaporation source were performed in the same apparatus (same processing chamber) for 20 minutes. Resistance heating is performed by placing an Au—Fe—Pd alloy on a tungsten board under the condition of a set current of 250 mA. Electron beam irradiation is performed under the condition of a set current of 650 mA by placing a Ti material in a crucible made of Cu alloy. I went there. As a result, a decorative article having a mixed layer in which a gold-based material and TiN were mixed was obtained. The average thickness of the formed mixed layer was 0.14 μm. In addition, the thickness of the mixed layer was measured in accordance with a microscope cross-sectional test method defined in JIS H 5821.

(Examples 2 to 5)
Example 1 except that the composition of the gold-based material used in the mixed layer forming step, the flow rate of nitrogen gas, and the vapor deposition treatment time are as shown in Table 1, and the treatment conditions for resistance heating vapor deposition and electron beam vapor deposition are adjusted. In the same manner as in Example 1, a decorative article (watch case (back cover)) was manufactured.
(Example 6)
A decorative article (watch case (back cover)) was manufactured in the same manner as in Example 1 except that a substrate made of Ti was used.

As a base material, what was produced by metal powder injection molding (MIM) as described below was used.
First, a Ti powder having an average particle diameter of 52 μm manufactured by a gas atomization method was prepared.
A material composed of Ti powder: 75 vol%, polyethylene: 8 vol%, polypropylene: 7 vol%, and paraffin wax: 10 vol% was kneaded. A kneader was used for kneading the materials. Moreover, the material temperature at the time of kneading | mixing was 60 degreeC.

Next, the obtained kneaded product was pulverized and classified into pellets having an average particle diameter of 3 mm. Using these pellets, metal powder injection molding (MIM) was performed with an injection molding machine to produce a molded article having the shape of a watch case. At this time, the molded body was molded in consideration of debinding treatment and shrinkage during sintering. The molding conditions at the time of injection molding were a mold temperature of 40 ° C., an injection pressure of 80 kgf / cm ² , an injection time of 20 seconds, and a cooling time of 40 seconds.

Next, the molded body was subjected to a debinding process using a degreasing furnace to obtain a degreased body. In this debinding treatment, the temperature was raised to 400 ° C. at a rate of 10 ° C./hour in an argon gas atmosphere of 1.0 × 10 ⁻¹ Pa at 80 ° C. for 1 hour. The weight of the sample at the time of heat treatment was measured, and the point at which the weight reduction disappeared was defined as the end of debinding.
Next, the degreased body thus obtained was sintered using a sintering furnace to obtain a base material. This sintering was performed by performing a heat treatment at 900 to 1100 ° C. for 6 hours in an argon gas atmosphere of 1.3 × 10 ^{−3 to} 1.3 × 10 ⁻⁴ Pa.
About the base material obtained by making it above, the required location was cut and grind | polished, Then, this base material was wash | cleaned. 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.
(Examples 7 to 10)
Example 1 except that the composition of the gold-based material used in the mixed layer forming step, the flow rate of nitrogen gas, and the vapor deposition treatment time are as shown in Table 1, and the treatment conditions for resistance heating vapor deposition and electron beam vapor deposition are adjusted. In the same manner as in Example 6, a decorative article (watch case (back cover)) was produced.

(Example 11)
A decorative article (watch case (back cover)) was manufactured by the method described below.
First, a base material having the shape of a watch case (back cover) was produced by casting using stainless steel (SUS444), 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 TiN layer composed of TiN was formed on the substrate cleaned as described above using a vapor deposition apparatus as follows (TiN layer forming step).
First, while preheating the processing chamber of the vapor deposition apparatus, the processing chamber was evacuated (depressurized) to 2 × 10 ⁻³ Pa. Thereafter, nitrogen gas was introduced at a flow rate of 30 ml / min, and the atmospheric pressure (total pressure) in the processing chamber was set to 3.0 × 10 ⁻³ Pa. In such a state (a state in which nitrogen gas was continuously introduced), vapor deposition by electron beam (electron beam vapor deposition) using Ti as an evaporation source was performed for 60 minutes. The electron beam was irradiated under the condition of a set current of 780 mA with a Ti material placed in a crucible made of Cu alloy. As a result, a TiN layer composed of TiN was formed. The average thickness of the formed TiN layer was 1.0 μm.

Then, using the vapor deposition apparatus that performed the TiN layer forming step, a mixed layer in which a gold-based material containing Au and TiN coexist was formed (without taking out the substrate coated with the TiN layer from the processing chamber). (Mixed layer forming step). The mixed layer forming step was performed as follows.
First, while preheating the processing chamber of the vapor deposition apparatus, the processing chamber was evacuated (depressurized) to 2 × 10 ⁻³ Pa. Thereafter, nitrogen gas was introduced at a flow rate of 30 ml / min, and the atmospheric pressure (total pressure) in the processing chamber was set to 3.0 × 10 ⁻³ Pa. In such a state (a state in which nitrogen gas is continuously introduced), an Au—Fe—Pd alloy as a gold material (Au: 68.0 wt%, Fe: 12.0 wt%, Pd: 20.0 wt%) Vapor deposition using resistance heating (resistance heating vapor deposition) using Ti as an evaporation source and electron beam vapor deposition (electron beam deposition) using Ti as an evaporation source were performed in the same apparatus (same processing chamber) for 20 minutes. Resistance heating is performed by placing an Au—Fe—Pd alloy on a tungsten board under the condition of a set current of 250 mA. Electron beam irradiation is performed under the condition of a set current of 650 mA by placing a Ti material in a crucible made of Cu alloy. I went there. As a result, a decorative article was obtained in which a mixed layer containing a gold-based material and TiN was formed on the TiN layer. The average thickness of the formed mixed layer was 0.14 μm. In addition, the thickness of the TiN layer and the mixed layer was measured according to a microscope cross-sectional test method defined in JIS H5821.

(Examples 12 to 15)
Tables 1 and 2 show the flow rate of nitrogen gas in the TiN layer forming process, the deposition process time, the composition of the gold-based material used in the mixed layer forming process, the flow rate of nitrogen gas, and the deposition process time, and resistance heating. A decorative article (watch case (back cover)) was produced in the same manner as in Example 11 except that the processing conditions for vapor deposition and electron beam vapor deposition were adjusted.

(Example 16)
A decorative article (watch case (back cover)) was produced in the same manner as in Example 11 except that a substrate composed of Ti was used.
As a base material, what was produced by metal powder injection molding (MIM) as described below was used.

First, a Ti powder having an average particle diameter of 52 μm manufactured by a gas atomization method was prepared.
A material composed of Ti powder: 75 vol%, polyethylene: 8 vol%, polypropylene: 7 vol%, and paraffin wax: 10 vol% was kneaded. A kneader was used for kneading the materials. Moreover, the material temperature at the time of kneading | mixing was 60 degreeC.
Next, the obtained kneaded product was pulverized and classified into pellets having an average particle diameter of 3 mm. Using these pellets, metal powder injection molding (MIM) was performed with an injection molding machine to produce a molded article having the shape of a watch case. At this time, the molded body was molded in consideration of debinding treatment and shrinkage during sintering. The molding conditions at the time of injection molding were a mold temperature of 40 ° C., an injection pressure of 80 kgf / cm ² , an injection time of 20 seconds, and a cooling time of 40 seconds.

Next, the molded body was subjected to a debinding process using a degreasing furnace to obtain a degreased body. In this debinding treatment, the temperature was raised to 400 ° C. at a rate of 10 ° C./hour in an argon gas atmosphere of 1.0 × 10 ⁻¹ Pa at 80 ° C. for 1 hour. The weight of the sample at the time of heat treatment was measured, and the point at which the weight reduction disappeared was defined as the end of debinding.
Next, the degreased body thus obtained was sintered using a sintering furnace to obtain a base material. This sintering was performed by performing a heat treatment at 900 to 1100 ° C. for 6 hours in an argon gas atmosphere of 1.3 × 10 ^{−3 to} 1.3 × 10 ⁻⁴ Pa.
About the base material obtained by making it above, the required location was cut and grind | polished, Then, this base material was wash | cleaned. 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.

(Examples 17 to 20)
The flow rate of nitrogen gas in the TiN layer forming process, the deposition process time, the composition of the gold-based material used in the mixed layer forming process, the flow rate of nitrogen gas, and the deposition process time are shown in Table 2, and resistance heating deposition, electron A decorative article (watch case (back cover)) was produced in the same manner as in Example 16 except that the processing conditions for beam deposition were adjusted.

(Comparative Example 1)
A decorative article (watch case (back cover)) was prepared in the same manner as in Example 1 except that only the electron beam evaporation of Ti was performed without performing resistance heating evaporation of the gold-based material during the evaporation process. Manufactured.
(Comparative Example 2)
A decorative article (watch case (back cover)) was produced in the same manner as in Comparative Example 1 except that the vapor deposition time was changed as shown in Table 2.

(Comparative Example 3)
When performing the vapor deposition process, the decorative article (watch case (back cover)) was prepared in the same manner as in Example 6 except that only the electron beam vapor deposition of Ti was performed without performing the resistance heating vapor deposition of the metal-based material. Manufactured.
(Comparative Example 4)
A decorative article (watch case (back cover)) was produced in the same manner as in Comparative Example 3 except that the vapor deposition time was changed as shown in Table 2.

(Comparative Example 5)
A decorative article (watch case (back cover)) was prepared in the same manner as in Example 1 except that only the resistance heating vapor deposition of the gold-based material was performed without performing the Ti electron beam vapor deposition. Manufactured.
(Comparative Example 6)
A decorative article (watch case (back cover)) was produced in the same manner as in Comparative Example 5 except that the vapor deposition time was changed as shown in Table 2.

(Comparative Example 7)
A decorative article (watch case (back cover)) was prepared in the same manner as in Example 6 except that only the resistance heating vapor deposition of the gold-based material was performed without performing the electron beam vapor deposition of Ti. Manufactured.
(Comparative Example 8)
A decorative article (watch case (back cover)) was manufactured in the same manner as in Comparative Example 7 except that the vapor deposition time was changed as shown in Table 2.
Tables 1 and 2 collectively show the processing conditions at the time of manufacturing the decorative articles of each example and each comparative example, and Tables 3 and 4 collectively show the configurations of the decorative articles. In Tables 3 and 4, stainless steel is indicated by SUS. In Tables 2 and 4, for each comparative example, data relating to a layer composed of TiN and a layer composed of a gold-based material is shown in the mixed layer column.

2. Appearance Evaluation The decorative articles of the respective Examples and Comparative Examples were observed visually and with a microscope, and their appearance was evaluated according to the following four-stage criteria.
A: Appearance is excellent.
○: Good appearance.
Δ: Appearance is slightly poor.
X: Appearance defect.

3. Evaluation of scratch resistance The decorative articles of the respective Examples and Comparative Examples were subjected to the following tests to evaluate the scratch resistance.
Using a Suga Abrasion Tester (Suga Test Instruments Co., Ltd., NUS-ISO-1) under the condition of load: 400 gf, each decorative film (mixed layer for each example, TiN for each comparative example) The layer on the side where the layer made of or a layer made of a metal-based material) was formed (the surface on the side opposite to the surface of the base material exposed) was worn for a total of 200 DS (double stroke). The appearance of each subsequent decorative article was visually observed, and the appearance was evaluated according to the following four-stage criteria. In addition, the said test was done using Sumitomo 3M Co., Ltd. product and the wrapping film (aluminum oxide, particle size: 30 micrometers).
A: No scratches are observed on the surface of the coating.
○: Scratches are hardly observed on the surface of the coating.
Δ: Slight scratches are observed on the surface of the coating.
X: Scratches are significantly observed on the surface of the coating.

4). Evaluation of dent resistance (difficulty of being indented) The dent resistance was evaluated by performing the following tests on the decorative articles of the examples and the comparative examples.
Stainless steel toward the surface on which the coating of each decorative article (a mixed layer for each example, a layer made of TiN or a layer made of a gold-based material for each comparative example) is formed A manufactured sphere (diameter 1 cm) was dropped from a position with a height of 50 cm, and the size of the dent on the surface of the decorative article (diameter of the dent mark) was measured, and evaluated according to the following four criteria.
(Double-circle): The diameter of a dent mark is less than 1 mm, or a dent mark is not calculated | required.
○: The diameter of the dent mark is 1 mm or more and less than 2 mm.
(Triangle | delta): The diameter of a dent mark is 2 mm or more and less than 3 mm.
X: The diameter of a dent mark is 3 mm or more.
These results are shown together with the Vickers hardness Hv on the surface provided with the coating (a mixed layer for each example, a layer made of TiN or a layer made of a gold-based material for each comparative example). As shown in FIG. In addition, as Vickers hardness Hv, the value measured with the measurement load of 10 gf about the surface of each ornament is shown.

As is clear from Table 5, the decorative articles of the present invention all had excellent aesthetic appearance, high hardness, and excellent scratch resistance and dent resistance.
Moreover, all the decorative articles of the present invention had an excellent tactile sensation without a rough feeling.
In the present invention, a coating (mixed layer, TiN layer) having a desired composition and characteristics can be easily formed by appropriately selecting the atmospheric composition during vapor deposition.
On the other hand, in the comparative example, a satisfactory result was not obtained.
In addition, a wristwatch as shown in FIG. 5 was assembled using the decorative articles manufactured in the respective Examples and Comparative Examples. When these watches were evaluated in the same manner as described above, the same results as described above were obtained.

It is sectional drawing which shows 1st Embodiment of the decorative article of this invention. It is sectional drawing which shows suitable embodiment of the manufacturing method of the ornament shown in FIG. It is sectional drawing which shows 2nd Embodiment of the decorative article of this invention. It is sectional drawing which shows suitable embodiment of the manufacturing method of the ornament shown in FIG. It is a fragmentary sectional view which shows suitable embodiment of the timepiece (portable timepiece) of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 1A, 1B ... Decoration 2 ... Base material 3 ... Mixed layer 4 ... TiN layer 10 ... Wristwatch (portable watch) 22 ... Body (case) 23 ... Back cover 24 ... Bezel (edge) 25 ... Glass plate 26 ... Winding True 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 (seal)

Claims (11)

A substrate at least partially near the surface mainly composed of Ti and / or stainless steel;
A decorative product comprising a gold-based material containing Au and a mixed layer containing TiN.   The decorative article according to claim 1, wherein a content ratio of N in the mixed layer is 1 to 20 wt%.   The decorative article according to claim 1 or 2, wherein a content ratio of Au in the mixed layer is 1 to 50 wt%.   The decorative article according to any one of claims 1 to 3, wherein an average thickness of the mixed layer is 0.04 to 1.5 µm.   The decorative article according to any one of claims 1 to 4, further comprising a TiN layer made of TiN between the base material and the mixed layer.   The decorative article according to any one of claims 1 to 5, wherein an average thickness of the TiN layer is 0.4 to 2.0 µm.   The mixed layer is provided by performing vapor deposition by resistance heating using a gold-based material containing Au as an evaporation source and vapor deposition by an electron beam using Ti as an evaporation source in the same apparatus. Item 7. The decorative article according to any one of Items 1 to 6.   The decorative article according to any one of claims 1 to 7, wherein the gold-based material is an Au-Fe-Pd-based alloy.   The decorative article according to any one of claims 1 to 8, wherein a Vickers hardness Hv measured with a load of 10 gf is 350 to 800 on the surface on which the mixed layer is provided.   The decorative article according to any one of claims 1 to 9, wherein the decorative article is a watch exterior part. A timepiece comprising the decorative article according to claim 1.

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