JP2006249510A - Method for producing ornament, ornament and watch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornament capable of maintaining excellent hardness and aesthetic appearance over a long period, to provide a production method capable of providing the ornament, and to provide a watch provided with the ornament. <P>SOLUTION: The method for producing an ornament 1A comprises: a first film formation stage where a first film 3 mainly composed of TiN is formed on a base material 2; and a second film formation stage where a second film 4 composed of an Au-Pt-Pd-Cu-Ag-M based alloy comprising 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2.0 to 4.0 wt% Cu, 1.5 to 2.5 wt% Ag and 1.0 to 3.0 wt% M (wherein, M is at least one kind selected from the group consisting of Zn and In) is formed on the first film 3 by a dry plating process. Further, the production method provides the ornament, and the watch is provided with the ornament. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a decorative article, 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, a metal material such as Pt or Ag has generally been used as a constituent material of an ornament.
However, the hardness of metal materials is generally relatively low, and decorative articles (especially watch exterior parts and accessories) made of the above-mentioned materials 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 a problem, as a technique for hardening the base material, for example, a technique for hardening the surface by carburizing treatment in which carbon is injected into a base material made of stainless steel (for example, see Patent Document 1) is used. It has been.
However, since the carburizing process 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 by polishing and the hardness is lowered, or a shape that cannot be polished afterwards (a shape that does not hit the buff) cannot be processed.
Further, in the base material subjected to the carburizing treatment as described above, its color tone lacks a high-class feeling, so that it is difficult to apply to a decorative product that requires an excellent appearance (particularly whitish gold). .

JP-A-11-229114

  An object of the present invention is to provide a decorative product capable of maintaining excellent hardness and aesthetic appearance over a long period of time, to provide a production method capable of providing the decorative product, and to provide the decorative product. It is to provide a watch equipped with.

Such an object is achieved by the present invention described below.
The method for manufacturing a decorative article of the present invention includes a first film forming step of forming a first film mainly composed of TiN on a base material,
On the first coating, 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2.0 to 4.0 wt% Cu, 1.5 to 2.5 wt% Au—Pt—Pd—Cu—Ag—M alloy containing 1.0 to 3.0 wt% of M (wherein M is at least one selected from the group consisting of Zn and In) And a second film forming step of forming a second film by a dry plating method using as a target.
Thereby, the manufacturing method which manufactures the ornament which can hold | maintain the outstanding hardness and aesthetic appearance over a long period of time can be provided.

In the method for manufacturing a decorative article of the present invention, it is preferable that at least the vicinity of the surface of the base material is mainly composed of Ti and / or stainless steel.
Thereby, the hardness of the decorative product can be made particularly excellent, the dents such as scratches and dents can be made particularly difficult to adhere, and an excellent aesthetic appearance can be maintained for a longer period of time. it can.

In the method for manufacturing a decorative article according to the present invention, the N content in the first coating is preferably 2 to 29 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 method for manufacturing a decorative article of the present invention, the average thickness of the first coating is preferably 0.1 to 5.0 μm.
Thereby, it is possible to make the decorative article particularly difficult to have a dent such as a scratch or a dent while sufficiently preventing the internal stress of the first film from increasing, and it is excellent for a longer period of time. An aesthetic appearance can be maintained.

In the method for manufacturing a decorative article of the present invention, the average thickness of the second coating is preferably 0.01 to 2.0 μm.
Thereby, while making the hardness as a decorative article sufficiently high, the aesthetic appearance of the decorative article can be made particularly excellent, and the excellent aesthetic appearance can be maintained for a longer period of time.

In the method for manufacturing a decorative article of the present invention, it is preferable that the first film is formed by a dry plating method.
As a result, the first film having a uniform film thickness (small variation in film thickness) and particularly excellent adhesion to the substrate (including adhesion to the substrate via the base layer). A film can be reliably formed. As a result, the aesthetic appearance and durability as a decorative product can be made particularly excellent. Further, even if the first film to be formed is relatively thin, the variation in the film thickness can be made sufficiently small, which is advantageous in improving the reliability of the decorative article.

In the method for manufacturing a decorative article of the present invention, it is preferable that the first film is formed by ion plating.
As a result, the first film having a uniform film thickness (small variation in film thickness) and particularly excellent adhesion to the substrate (including adhesion to the substrate via the base layer). A film can be reliably formed. As a result, the aesthetic appearance and durability as a decorative product can be made particularly excellent. Further, even if the first film to be formed is relatively thin, the variation in the film thickness can be made sufficiently small, which is advantageous in improving the reliability of the decorative article.
In the method for manufacturing a decorative article of the present invention, it is preferable that the second film is formed by vacuum deposition.
Thereby, it is possible to obtain a decorative product having a particularly excellent aesthetic appearance.

In the method for manufacturing a decorative article of the present invention, it is preferable to have a base layer forming step of forming at least one base layer on the substrate prior to the first film forming step.
Thereby, the adhesiveness of a base material and a 1st film can be improved, for example, and the reliability and durability of a decorative article can be made more excellent.
In the method for producing a decorative article of the present invention, it is preferable to form a layer mainly composed of Ti as the underlayer.
Thereby, for example, the adhesion between the base material and the first coating can be further improved, and the reliability and durability of the decorative article can be made particularly excellent.
In the method for manufacturing a decorative article of the present invention, the average thickness of the base layer is preferably 0.1 to 2.0 μm.
Thereby, for example, the internal stress of the base layer is increased, and the adhesion between the substrate and the first coating can be made particularly excellent while sufficiently preventing the occurrence of cracks and the like.

The decorative article of the present invention is manufactured using the method of the present invention.
As a result, it is possible to provide a decorative article that can maintain excellent hardness and aesthetic appearance over a long period of time.
The decorative article of the present invention is on a substrate,
A first coating provided on the substrate and composed primarily of TiN;
By dry plating, the first coating is provided on the surface opposite to the surface facing the substrate, and is 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2. 0 to 4.0 wt% Cu, 1.5 to 2.5 wt% Ag, and 1.0 to 3.0 wt% M (where M is at least one selected from the group consisting of Zn and In) And a second film made of an Au—Pt—Pd—Cu—Ag—M alloy containing the seed.
As a result, it is possible to provide a decorative article that can maintain excellent hardness and aesthetic appearance over a long period of time.

In the decorative article of the present invention, it is preferable that the Vickers hardness Hv measured with a load of 10 gf is 500 to 1000 on the surface on which the second coating is provided.
Thereby, the outstanding aesthetic appearance as a decorative article can be hold | maintained over a longer period of time.
In the decorative product of the present invention, the color tone of the surface on which the second film is provided is such that a ^* is -1. In the chromaticity diagram of L ^* a ^* b ^* display defined by JIS Z 8729. It is preferable that it is 5-1.5 and b ^* is 7.0-15.0.
Thereby, the aesthetic appearance of the decorative article is particularly excellent.
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 external impacts, and is required to have a beautiful appearance as a decorative product and also 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.

  According to the present invention, it is possible to provide a decorative product that can maintain excellent hardness and aesthetic appearance over a long period of time, to provide a manufacturing method that can provide the decorative product, and to provide the decorative product. It is possible to provide a watch equipped with.

Hereinafter, preferred embodiments of a method for manufacturing a decorative article, a decorative article, and a timepiece according to the present invention will be described with reference to the accompanying drawings.
First, a first embodiment of the decorative article of the present invention and a preferred embodiment of the 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 1 </ b> A of the present embodiment has a base material 2, a first coating 3, and a second coating 4.

[Base material]
The base material 2 may be composed of any material, and may be composed of a metal material or a non-metal material.
When the base material 2 is comprised with a metal material, the ornament 1A which has the especially outstanding intensity | strength characteristic can be provided.
Moreover, when the base material 2 is comprised with a metal material, even if it is a case where the surface roughness of the base material 2 is comparatively large, leveling at the time of forming the 1st coating film 3 and the 2nd coating film 4 mentioned later is carried out. Due to the effect, the surface roughness of the resulting decorative article 1A can be reduced. For example, it is possible to perform mirror finishing even if machining by grinding, polishing, or the like on the surface of the substrate 2 is omitted, or the substrate 2 is formed by the MIM method, and the surface is Even when the surface is pear ground, it can be easily mirror-finished. As a result, a decorative article having excellent gloss can be obtained.

When the substrate 2 is made of a non-metallic material, it is possible to provide a decorative article 1A that is relatively light and easy to carry and has a heavy appearance.
Moreover, when the base material 2 is comprised with a nonmetallic material, it can shape | mold to a desired shape comparatively easily. For this reason, even if it is the ornament 1A of a shape difficult to shape | mold directly, it can be provided comparatively easily.
Moreover, when the base material 2 is comprised with a nonmetallic material, the effect which shields electromagnetic noise is also acquired.

Examples of the metal material constituting the substrate 2 include various metals such as Fe, Cu, Zn, Ni, Mg, Cr, Mn, Mo, Nb, Al, V, Zr, Sn, Au, Pd, Pt, and Ag. And alloys containing at least one of these (for example, various stainless steels, brass, etc.).
If at least the vicinity of the surface of the substrate 2 is mainly composed of Ti and / or stainless steel, the decorative article 1A has a particularly excellent hardness, and is particularly provided with dents such as scratches and dents. It will be difficult. As a result, the decorative article 1A can maintain an excellent aesthetic appearance for a longer period of time. Further, when at least the vicinity of the surface of the base material 2 is mainly composed of Ti and / or stainless steel (particularly, the base material 2 is mainly composed of Ti), the base material 2 and the first to be described later The adhesion to the coating 3 is particularly excellent.

  Examples of the material mainly composed of Ti include Ti (Ti as a simple substance), Ti alloy, and the like. In addition, examples of the stainless steel include an Fe—Cr alloy and an Fe—Cr—Ni alloy. Examples of the Fe—Cr—Ni alloy include SUS304, SUS303, SUS316, SUS316L, SUS316J1, SUS316J1L, and the like, and examples of the Fe—Cr alloy include SUS405, SUS430, SUS434, SUS444, SUS429F, and SUS430F. Is mentioned.

Moreover, as a nonmetallic material which comprises the base material 2, plastics, ceramics, a stone material, wood, glass etc. are mentioned, for example.
Examples of the plastic include various thermoplastic resins and various thermosetting resins. For example, polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin , Polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide (eg, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), polyimide, polyamide Imide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile Rene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyester such as polycyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone , Polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, Tylene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy resins, phenol resins, urea Resin, melamine resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, polydichloroparaxylylene ( poly-dichloro-para-xylylene), poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene, etc., or Copolymers, blends, polymer alloys, etc. mainly composed of these are listed. Chino one or a combination of two or more (e.g., a blend resin, polymer alloy, as a laminate or the like) can be used.
When the substrate 2 is made of plastic, it is possible to obtain a decorative article 1A that is relatively light and easy to carry and has a heavy appearance.
Moreover, when the base material 2 is comprised with a plastic, it can shape | mold to a desired shape comparatively easily. For this reason, even the decorative article 1A having a complicated shape can be manufactured relatively easily.
Moreover, when the base material 2 is comprised with a plastic, the effect which shields electromagnetic noise is acquired.

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 material 2 is comprised with the above ceramics, the ornament 1A of high intensity | strength and high hardness can be obtained.

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. When 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 portion and a surface layer made of a metal material, the thickness (average value) of the surface layer is not particularly limited, but is preferably 0.1 to 50 μm, More preferably, it is 1.0-10 micrometers. When the thickness of the surface layer is within the above range, the strength of the substrate 2 can be made sufficiently excellent, and unintentional peeling from the base of the surface layer can be more reliably prevented. be able to.
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.

[First coating]
A first coating 3 is provided on the surface of the substrate 2. The first coating 3 is mainly composed of TiN.
By having such a first film 3, the decorative article 1 A as a whole has excellent hardness (hardness on the surface side on which the first film 3 and the second film 4 are provided; the same applies hereinafter). It is possible to make it difficult to attach a dent such as a scratch or dent. In addition, by having such a first coating 3, even if the thickness of the second coating 4 described later is relatively small, the aesthetic appearance of the decorative article 1A as a whole is excellent. Can do. That is, when the film thickness of the second film 4 to be described later is relatively small, the influence of the color tone of the first film 3 on the aesthetic appearance of the decorative article 1A is increased. The color tone (chromaticity) of the coating 3) and the color tone (chromaticity) of the second coating 4 are relatively similar (because the difference is small). The aesthetic appearance of 1A as a whole can be made excellent. Further, for example, even if the second coating 4 is worn or peeled off due to long-term use of the decorative article 1A, adverse effects on the aesthetic appearance of the decorative article 1A can be minimized. On the other hand, when the decorative article does not have the first film made of TiN, the hardness of the decorative article as a whole cannot be made sufficiently large. As a result, the decorative article is likely to have a dent such as a scratch or a dent. Further, when the decorative article does not have the first film made of TiN, the influence of the color tone of the base material or the like on the appearance as the decorative article becomes large. For this reason, depending on the combination of the constituent material of the base material, the constituent material of the second film, and the like, the aesthetic appearance as a decorative article may be significantly impaired.

The N content (X _1N ) in the first coating 3 is not particularly limited, but is preferably 2 to 29 wt%, more preferably 5 to 27 wt%, and 7 to 24 wt%. Is more preferable, and 8 to 16 wt% is most preferable. When the content of N in the first film 3 is a value within the above range, the color tone (chromaticity) of the first film 3 is optimized while the hardness of the decorative article 1A is sufficiently high. can do. As a result, the effects of the present invention as described above are more remarkably exhibited. On the other hand, if the content of N in the first coating 3 is less than the lower limit, the hardness of the decorative article 1A is sufficient depending on the thickness of the first coating, the composition of the second coating 4, and the like. Can be difficult to achieve. Further, if the N content in the first coating 3 exceeds the upper limit, the color tone of the first coating 3 becomes too dark (too gold), depending on the thickness of the second coating 4 and the like. The aesthetic appearance of the decorative article 1A may be adversely affected.

  Further, the first coating 3 may contain constituent components (constituent elements) other than Ti and N. For example, the first coating 3 may contain a predetermined amount of C (carbon). Thereby, the difference between the color tone of the first coating 3 and the color tone of the second coating 4 to be described later can be made smaller, and the hardness and the like of the first coating 3 are further improved. be able to. As a result, the effects of the present invention as described above can be exhibited more significantly.

When the first coating 3 is made of a material containing C (TiCN), the sum of the C content (X _1C ) and the N content (X _1N ) in the first coating 3 _{(X 1)} is not particularly limited, but is preferably 5-30 wt%, more preferably from 10～28Wt%, even more preferably 15-25 wt%.
Further, the C content (X _1C ) in the first coating 3 is preferably 0.5 to 12 wt%, more preferably 1 to 10 wt%, and 5 to 9 wt%. Further preferred. When the content of C in the first coating 3 is a value within the above range, the hardness of the decorative article 1A is sufficiently high, and the color tone (chromaticity) of the first coating 3 is optimal. can do. As a result, the effects of the present invention as described above are more remarkably exhibited. On the other hand, when the C content in the first coating 3 exceeds the upper limit, the color tone of the first coating 3 becomes too dark (too dark), depending on the thickness of the second coating 4 and the like. May adversely affect the aesthetic appearance of the decorative article 1A.

The C content X _1C [wt%] in the first coating 3 is preferably lower than the _N content X _1N [wt%] in the first coating 3. Thereby, it is possible to effectively prevent the color tone of the first coating 3 from becoming too dark, and as a result (particularly even when the thickness of the second coating 4 is relatively small). The aesthetic appearance of the ornament 1A can be made particularly excellent.

When the first coating 3 contains a predetermined amount of C (when it is made of TiCN as described above), the decorative article 1A can be used under normal use conditions (for example, temperature: −50 to 120 ° C., humidity: 0 to 100% RH) while having sufficient stability, the first coating 3 is not substantially damaged by using a specific chemical by using a specific chemical. Can be easily and reliably removed. Therefore, when the first coating 3 of the decorative article 1A is soiled, the first coating 3 can be removed and the first coating 3 can be suitably formed again. As described above, since the coating (first coating) can be peeled off and the coating can be re-formed easily and reliably by using a specific chemical, it can continue to exhibit its characteristics for an extremely long period of time. it can. Examples of the release agent that can be used for removing the first coating 3 include a solution containing nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ). When the stripping agent is such a solution, the concentration of nitric acid (HNO ₃ ) in the solution is preferably about 10 to 30 vol%, and the concentration of sulfuric acid (H ₂ SO ₄ ) is about 10 to 30 vol%. Preferably there is. Thereby, the 1st film 3 can be removed easily and reliably in a comparatively short time without giving the substantial damage with respect to the base material 2 grade | etc.,.

  The average thickness of the first coating 3 is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.8 to 3.0 μm, and 1.0 to 2 More preferably, it is 8 μm. When the average thickness of the first coating 3 is a value within the above range, it is more effective that the internal stress of the first coating 3 is increased while the hardness of the first coating 3 is sufficiently high. As a result, the reliability and durability of the decorative article 1A can be made particularly excellent. On the other hand, when the average thickness of the first coating 3 is less than the lower limit, the first coating as described above depends on the composition of the first coating 3 (for example, the N content). There is a possibility that the function 3 is not fully exhibited. When the average thickness of the first coating 3 exceeds the upper limit, the internal stress of the first coating 3 increases depending on the composition of the first coating 3 (for example, the N content). Show the trend.

  The first coating 3 may have a plurality of regions having different compositions. For example, the first coating 3 has a first region in which the N content is a predetermined value X and a second region in which the N content is a predetermined value X ′ greater than X. May be. In such a case, for example, by providing the first region closer to the base material 2 than the second region, the internal stress of the first coating 3 can be more effectively prevented and The hardness of the first coating 3 can be made higher, and the adhesion between the substrate 2 and the first coating 3 can be made particularly excellent. Therefore, the decorative article 1A can stably maintain an excellent aesthetic appearance for a longer period of time. Further, when the second region is provided closer to the base material 2 than the first region, the following effects can be obtained. By having the second region in which the sum of the C content and the N content is relatively large, the hardness of the first coating 3 as a whole (the hardness of the decorative article 1A as a whole) is particularly excellent. The influence of the second region having a relatively dark color tone on the aesthetic appearance of the decorative article 1A can be reduced. In other words, by having the first region on the second film 4 side (outer surface side of the decorative product) than the second region, the appearance of the decorative product 1A is more than the influence of the color tone of the second region, Since it becomes easy to be influenced by the color tone of the first region, the aesthetic appearance of the decorative article 1A as a whole is particularly excellent while the hardness of the first coating 3 as a whole (the hardness of the decorative article 1A as a whole) is particularly excellent. It can be excellent. Therefore, the decorative article 1A can stably maintain an excellent aesthetic appearance for a longer period of time.

When the first film 3 has a plurality of regions having different compositions (for example, when the first film 3 has the first region and the second region as described above), the first film 3 For example, it may be composed of a laminate including a plurality of layers having different compositions, or the composition may be changed in a gradient along its thickness direction.
Further, the first coating 3 is formed on the entire surface of the substrate 2 in the illustrated configuration, but it may be formed on at least a part of the substrate 2.

[Second coating]
A second coating 4 is provided on the surface of the first coating 3 (the surface opposite to the surface facing the substrate 2).
The second coating 4 comprises 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2.0 to 4.0 wt% Cu, and 1.5 to 2.5 wt%. An Au—Pt—Pd—Cu—Ag—M alloy containing Ag and 1.0 to 3.0 wt% of M (wherein M is at least one selected from the group consisting of Zn and In). It is formed by a dry plating method using a configured target (evaporation source). The second coating 4 formed by such a dry plating method has the same composition as the target. When the second coating 4 has the above composition, the decorative article 1A has a whitish gold color and an excellent appearance, and has sufficient corrosion resistance. In particular, it is possible to easily and surely provide a relatively white-stained golden ornament that has been difficult to manufacture.
On the other hand, in the Au-Pt-Pd-Cu-Ag-M-based alloy, when the content (content ratio) of each element is a value outside the above range, it has excellent corrosion resistance and is excellent in a whitish golden aesthetic appearance. It is difficult to obtain the ornament 1A.
Au, Pt, and In are materials that hardly cause allergic reactions. Therefore, the present invention can be suitably applied to a decorative article (for example, a watch) used in contact with the skin.

As described above, the Pt content (content rate) is set to 8.0 to 12 wt%. If the Pt content is less than the lower limit, sufficient hardness cannot be obtained. On the other hand, when the content of Pt exceeds the upper limit, problems such as crack generation due to increased stress and deterioration of corrosion resistance occur.
Further, as described above, the content (content ratio) of Pd is set to 6.0 to 8.0 wt%. If the Pd content is less than the lower limit, the second coating 4 has low hardness and inferior corrosion resistance. On the other hand, if the content of Pd exceeds the upper limit, the internal stress of the second coating 4 increases and cracks are likely to occur.

Moreover, as above-mentioned, content (content rate) of Cu shall be 2.0-4.0 wt%. When the Cu content is less than the lower limit, the coating becomes brittle (Cu malleability / ductility). On the other hand, if the Cu content exceeds the upper limit, problems such as insufficient corrosion resistance and reddish color tone occur.
Further, as described above, the Ag content (content rate) is set to 1.5 to 2.5 wt%. If the Ag content is less than the lower limit, the coating becomes brittle. On the other hand, if the Ag content exceeds the upper limit, sufficient corrosion resistance cannot be obtained.
Further, as described above, the content (content ratio) of M (where M is at least one selected from the group consisting of Zn and In) is 1.0 to 3.0 wt%. When the content of M is less than the lower limit, sufficient hardness cannot be obtained. On the other hand, when the content of M exceeds the upper limit, stress increases and cracks and the like are likely to occur.

In particular, when the second coating 4 is made of a material containing Zn as M, the strength and hardness of the coating are particularly excellent.
In addition, when the second coating 4 is made of a material containing In as M, the strength and hardness of the second coating 4 are particularly excellent, and the redness of the color tone can be further suppressed. An effect is obtained.

Further, as described above, the Pt content (content) is 8.0 to 12 wt%, preferably 8.5 to 11.5 wt%, and 9.0 to 11 wt%. Is more preferable. When the content of Pt is a value within the above range, particularly excellent hardness can be obtained, and occurrence of cracks and the like can be sufficiently prevented.
Further, as described above, the content of Pd is 6.0 to 8.0 wt%, preferably 6.3 to 7.7 wt%, and 6.5 to 7.5 wt%. Is more preferable. When the content of Pd is a value within the above range, the second coating 4 has particularly excellent corrosion resistance and low internal stress.

As described above, the Cu content is 2.0 to 4.0 wt%, preferably 2.3 to 3.7 wt%, and 2.5 to 3.5 wt%. Is more preferable. When the Cu content is a value within the above range, particularly excellent corrosion resistance can be obtained, and the color tone can be more effectively prevented from being reddish.
Further, as described above, the content of Ag is 1.5 to 2.5 wt%, but is preferably 1.7 to 2.3 wt%, and is 1.8 to 2.1 wt%. Is more preferable. When the Ag content is within the above range, particularly excellent corrosion resistance can be obtained.
Further, as described above, the content of M is 1.0 to 3.0 wt%, preferably 1.4 to 2.7 wt%, and 1.7 to 2.4 wt%. Is more preferable. When the content of M is a value within the above range, the strength and hardness of the coating can be made particularly excellent.

  The alloy constituting the second coating 4 may contain an element other than Au, Pt, Pd, Cu, Ag, and M (hereinafter also referred to as “essential elements”). Examples of such elements include Ni, Mg, Cr, Mn, Mo, Nb, W, Al, Au, Fe, V, Zr, and Sn, and one or more of these elements can be used. Can also be contained in combination. In the case where the second coating 4 contains an element other than the essential elements, Sn is particularly preferable among the elements described above. In this way, when the alloy constituting the second coating 4 contains an element other than the essential elements, the content (the total amount when containing two or more elements) is 1.5 wt% or less. It is preferable that it is 1.0 wt% or less.

  The second coating 4 is formed by a dry plating method (vapor phase film formation method). Thus, the present inventor has found that the color tone of the decorative product can be made whitish and have a high-class feeling by forming the second film by a dry plating method. In other words, when an Au-Pt-Pd-Cu-Ag-M alloy having the above-described composition is obtained by casting, wet plating, or the like, it becomes a silver-white color that does not have a gold color, and has been described above. The present inventor has found that an excellent aesthetic appearance of whitish gold can be obtained by adopting the dry plating method, while such an excellent appearance cannot be obtained. This is considered to be due to the following reasons.

  That is, when dry plating is employed, Au—Pt—Pd—Cu— is different depending on the melting point, boiling point, vapor pressure, etc. of each component (constituent element) of the Au—Pt—Pd—Cu—Ag—M alloy. Evaporation (volatilization) from the Ag-M alloy proceeds non-uniformly depending on each component. By the way, the Au-Pt-Pd-Cu-Ag-M alloy as described above generally has a composition capable of forming a solid solution. On the other hand, Au-Pt-Pd-Cu-Ag- Each component constituting the M-based alloy differs in crystallinity and easiness of precipitation as a solid due to a difference in melting point (freezing point). For this reason, when the non-uniform evaporation as described above occurs, the second coating 4 composed of a composite structure in which a plurality of different phases coexist microscopically is formed on the first coating 3. Thereby, the color tone which each phase has is combined, the external appearance as the decoration 1A whole is formed, and the outstanding aesthetics are obtained as a result. On the other hand, when a film composed of an Au—Pt—Pd—Cu—Ag—M alloy is formed by a method other than dry plating, the Au—Pt—Pd—Cu—Ag—M alloy is microscopically. However, since a uniform solid solution is formed, a whitish golden appearance as obtained when the dry plating method is adopted is not obtained, and a silver-white color having an inferior aesthetic appearance is obtained. In addition, although easiness of evaporation is different for each component, when dry plating is performed by the method and conditions described in detail later, the composition of the target and the composition of the second coating 4 (macro composition) Can be substantially the same.

  Moreover, the adhesiveness of the 1st film 3 and the 2nd film 4 can be made excellent by forming the 2nd film 4 using a dry-type plating method. As a result, the decorative article 1A has particularly excellent corrosion resistance and durability. Further, by using the dry plating method, it is possible to form the high-density second coating 4. For this reason, the second coating 4 has a high glossiness and is particularly excellent in aesthetic appearance.

Further, by using a dry plating method, even when the thickness of the second coating 4 is relatively thin, it can be formed with a uniform film thickness. Therefore, the present invention can be suitably applied to small decorative items (for example, a watch exterior part and a watch interior part as described later).
Further, by using the dry plating method, the second coating 4 can be easily and reliably formed even if the second coating 4 has a complicated composition containing elements other than essential elements.

The average thickness of the second coating 4 as described above is not particularly limited, but is preferably 0.01 to 2.0 μm, more preferably 0.05 to 1.5 μm, 0.05 More preferably, it is -1.2 micrometers. If the average thickness of the second coating 4 is less than the lower limit, pinholes are likely to be generated in the second coating 4 and the effects of the present invention may not be sufficiently exhibited. On the other hand, when the average thickness of the second coating 4 exceeds the upper limit, the internal stress of the second coating 4 increases, and the adhesion between the second coating 4 and the first coating 3 decreases. , Cracks are likely to occur. Moreover, when the average thickness of the 2nd film 4 exceeds the said upper limit, the hardness as 1 A of ornaments shows the tendency to fall.
Moreover, by having the second coating 4 as described above, the decorative article 1A is excellent in surface slipperiness. Thereby, the rough feeling of the surface can be reduced and prevented, and the uncomfortable feeling and uncomfortable feeling when the decorative article 1A comes into contact with the skin or the like can be reduced or prevented.

In addition, the composition in each site | part of the 2nd film 4 may be constant, or may not be constant. For example, the second coating 4 may be one whose composition changes sequentially along the thickness direction (graded material).
Moreover, the 2nd film 4 may be the laminated body of the several layer from which a composition differs, for example.
In addition, the second coating 4 is formed on the entire surface of the substrate 2 in the configuration shown in the drawing, but it may be formed on at least a part of the surface of the substrate 2.

[Decoration]
The decorative article 1A 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 a back cover) , One-piece case etc.), watch band (including band clasp, band / bangle attaching / detaching mechanism, etc.), dial, watch hand, bezel (eg, rotating bezel), crown (eg, screw lock) Crowns, etc.), buttons, cover glass, glass edges, dial rings, parting plates, packings and other watch exterior parts, movement ground plates, gears, train wheels, rotating weights and other watch interior parts, glasses (for example, , Glasses frame), tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings and other accessories, la Tar or its case, car wheel, sporting goods such as golf club, nameplate, panel, Shohai, various other equipment parts, including housing, etc., can be applied to various types of 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 this specification may be anything that can be visually recognized from the outside, and is not limited to the one exposed to the outside of the watch. Including built-in.

In addition, in the decorative article 1A, the Vickers hardness Hv measured with a load of 10 gf is preferably 500 to 1000, and more preferably 550 to 800, on the surface on which the second coating 4 is provided. . Thereby, the outstanding aesthetic appearance as a decorative article can be hold | maintained over a longer period of time.
Further, the color tone of the surface of the decorative article 1A on which the second film 4 is provided is, for example, in the chromaticity diagram of L ^* a ^* b ^* display defined by JIS Z 8729, where a ^* is −1. 0.5 to 1.5 and b ^* is preferably in the range of 7.0 to 15.0, a ^* is -1.2 to 1.2 and b ^* is 7.0 to 7.0. More preferably, it is in the range of 12.0, more preferably, a ^* is in the range of -1.0 to 1.0 and b ^* is in the range of 8.0 to 10.0. Thereby, the aesthetic appearance of the decorative article 1A is particularly excellent.

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 method for manufacturing a decorative article according to this embodiment includes a first film forming step (2b) for forming a first film 3 on at least a part (2a) of the surface of the substrate 2. And a second film forming step (2c) for forming the second film 4 on at least a part of the surface of the first film 3 by a dry plating method.

[Base material]
As the substrate 2, those described above can be used.
The manufacturing method of the base material 2 is not specifically limited.
When the base material 2 is made of a metal material, examples of the manufacturing method include press working, cutting, forging, casting, powder metallurgy sintering, metal powder injection molding (MIM), and lost wax method. Among these, casting or metal powder injection molding (MIM) is particularly preferable. Casting and metal powder injection molding (MIM) are particularly excellent in workability. For this reason, when these methods are used, the base material 2 having a complicated shape can be obtained relatively easily.

Metal powder injection molding (MIM) is usually performed as follows.
First, a material containing metal powder and an organic binder is mixed and kneaded to obtain a kneaded product.
Next, the kneaded product is injection molded to form a molded body.
Thereafter, the molded body is subjected to a degreasing process (debinding process) to obtain a degreased body. This degreasing treatment is usually performed by heating under reduced pressure conditions.
Furthermore, a sintered body is obtained by sintering the obtained degreased body. This sintering process is usually performed by heating at a higher temperature than the degreasing process.
In the present invention, the sintered body obtained as described above can be used as a base material.

Moreover, when the base material 2 is comprised with the above plastics, as the manufacturing method, compression molding, extrusion molding, injection molding, stereolithography etc. are mentioned, for example.
Moreover, when the base material 2 is comprised with the above ceramics, the manufacturing method is not specifically limited, However, It is preferable that it is metal powder injection molding (MIM). Since metal powder injection molding (MIM) is particularly excellent in processability, the base material 2 having a complicated shape can be obtained relatively easily.

  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 base material 2 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 1A, and the decorativeness of the obtained decorative article 1A can be further improved. Moreover, the decorative article 1A manufactured using the base material 2 subjected to such surface processing is obtained by directly performing the surface processing on the first coating 3 and the second coating 4. Compared to the above, glare and the like are suppressed, and the aesthetic appearance is particularly excellent. Further, as described above, since the first coating 3 is made of TiN, which is a hard material, when the surface treatment is directly applied to the first coating 3, the first coating 3 is applied when the surface treatment is performed. 1 may easily cause defects such as chipping, and the production yield of the decorative article 1A may be significantly reduced. However, by performing surface treatment on the base material 2, the occurrence of such a problem is also effective. Can be prevented. Further, the surface treatment for the substrate 2 can be easily performed under mild conditions as compared with the surface treatment for the first coating 3. In addition, since the second coating 4 is usually relatively thin, when the surface treatment as described above is performed after the second coating 4 is formed, the second coating 4 in the corresponding part is formed. The film thickness of the film may become extremely thin, or the first film may be exposed. In such a case, the aesthetic appearance of the decorative article 1A is remarkably impaired.

  In addition, for the purpose of improving the adhesion between the substrate 2 and the first coating 3, the substrate 2 may be pretreated prior to the formation of the first coating 3 described later. 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. Among these, the adhesion between the substrate 2 and the first coating 3 can be made particularly excellent by performing a cleaning treatment.

[First film forming step]
A first film 3 made of TiN is formed on the surface of the substrate 2 (2b).
The method for forming the first coating 3 is not particularly limited, and examples thereof include spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, and the like, electrolytic plating, immersion plating, electroless plating, and the like. Examples include wet plating methods, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. A dry plating method (vapor phase film forming method) is preferred. By applying the dry plating method as the method of forming the first coating 3, the first coating 3 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 2 can be assured. Can be formed. As a result, the aesthetic appearance and durability of the finally obtained decorative article 1A can be made particularly excellent. Further, by applying a dry plating method as a method for forming the first coating 3, even if the first coating 3 to be formed is relatively thin, the variation in film thickness is made sufficiently small. Can do. For this reason, it is advantageous also in improving the reliability of the decorative article 1A. In addition, by applying a dry plating method as a method for forming the first coating 3, the N content (and further the C content) in the first coating 3 can be more reliably controlled.

  Among the dry plating methods as described above, ion plating is particularly preferable. By applying ion plating as a method for forming the first coating 3, the above effects become more prominent. That is, by applying ion plating as a method for forming the first coating 3, the first coating 3 having a uniform film thickness, uniform, and particularly excellent adhesion to the substrate 2 is obtained. It can form more reliably. As a result, it is possible to further improve the aesthetic appearance and durability of the finally obtained decorative article 1A. Further, by applying ion plating as a method for forming the first film 3, even if the first film 3 to be formed is relatively thin, the variation in film thickness can be made particularly small. it can. Further, by applying ion plating as a method of forming the first coating 3, the N content (and further the C content) in the first coating 3 can be controlled more reliably.

When applying the dry plating method as described above, for example, the first coating 3 can be easily and reliably formed by performing treatment in an atmosphere containing N (nitrogen) using Ti as a target. Can do. As such an atmospheric gas, for example, nitrogen gas (N ₂ gas) or the like can be used. Then, the composition (N content) of the first coating 3 to be formed and the like can be adjusted by appropriately adjusting the pressure of the atmospheric gas and the like.

Note that the atmosphere gas may contain, for example, an inert gas such as argon gas. Thereby, the content rate of N in the 1st film 3 can be controlled comparatively low easily and reliably. Further, by including a gas component containing C (carbon) (for example, a hydrocarbon gas such as acetylene) in the atmospheric gas, a predetermined amount of C ( Carbon) can be contained (the first coating 3 made of TiCN can be formed). In addition, the atmospheric gas may contain, for example, a gas component containing O (oxygen) (for example, oxygen gas (O ₂ ) or the like). Thereby, the 1st film 3 of the composition containing oxygen (for example, TiNO, TiCNO, etc.) can be formed easily and reliably.

[Second film forming step]
Next, a second coating 4 is formed on the surface of the first coating 3 formed as described above (2c).
As described above, the formation of the second coating 4 is performed by a dry plating method (vapor phase film formation method), thereby obtaining an excellent appearance that cannot be obtained by other methods. be able to.

Moreover, the 2nd film 4 excellent in adhesiveness with the 1st film 3 can be formed by using a dry-type plating method. As a result, the resulting decorative article 1A has particularly excellent corrosion resistance and durability. Further, by using the dry plating method, it is possible to form the high-density second coating 4. As a result, the second coating 4 has a high glossiness and is particularly excellent in aesthetic appearance.
Further, by using a dry plating method, even when the thickness of the second coating 4 is relatively thin, it can be formed with a uniform film thickness.
Further, by using the dry plating method, the second coating 4 can be easily and reliably formed even if the second coating 4 has a complicated composition containing elements other than essential elements.

  Examples of the dry plating method include chemical vapor deposition (CVD) such as vacuum vapor deposition, sputtering, thermal CVD, plasma CVD, and laser CVD, ion plating, ion implantation, and the like. Among these, vacuum vapor deposition is particularly preferable. . By using vacuum deposition as the dry plating method, it is possible to obtain a decorative article 1A having a particularly excellent aesthetic appearance. Further, by using vacuum deposition as a dry plating method, it is possible to relatively easily obtain the second coating 4 that is homogeneous and particularly excellent in adhesion to the first coating 3 with a relatively simple apparatus. it can. As a result, the durability of the resulting decorative article 1A is further improved. In addition, by using vacuum deposition, it is possible to form the second coating 4 having a particularly high density. As a result, the decorative article 1A can maintain a particularly excellent aesthetic appearance over a long period of time.

The vacuum deposition is preferably performed under the following conditions, for example.
Examples of the method for heating the vapor deposition material include a method using a heat transfer crucible, an electron beam, a high frequency, a laser, and the like, and resistance heating, among which resistance heating is preferable. By using resistance heating as a method for heating the vapor deposition material, a homogeneous second coating 4 can be obtained by a simple method.

The atmospheric gas at the time of vacuum deposition is preferably mainly composed of an inert gas (for example, He gas, Ne gas, Ar gas, N ₂ gas).
The pressure of the atmosphere during vacuum deposition is not particularly limited, but is preferably about 1.3 × 10 ^{−4 to} 1.4 × 10 ⁻³ Pa, and preferably 3.9 × 10 ^{−4 to} 1.4 × 10. More preferably, it is about ^-4 Pa.

  Further, at the time of vacuum deposition, the output (current, voltage) of the apparatus may be constant or may be changed with time. For example, the vacuum deposition is a first stage in which the output of the apparatus is within a predetermined range, and a second stage after the first stage and having a higher output of the apparatus than the first stage. And a third stage after the first stage and the second stage and having a higher output of the apparatus than the second stage. By performing the vacuum deposition as having such a plurality of stages, the second coating 4 is formed with a particularly excellent color tone and particularly excellent adhesion to the first coating 3. can do. When performing vacuum deposition as having a plurality of stages as described above, the output in the second stage is preferably 1.02 to 1.10 times the output in the first stage. The output in stage 3 is preferably 1.02 to 1.10 times the output in stage 2. As a result, the effects as described above are exhibited more significantly.

  Further, when the above-described first step is performed by the dry plating method, for example, by changing the type of target, the composition of the atmospheric gas in the vapor deposition apparatus (in the chamber), etc., The first film formation step and the second film formation step can be performed successively (without removing the base material 2 from the apparatus). Thereby, the adhesiveness of the base material 2, the first coating 3, and the second coating 4 is particularly excellent, and the productivity of the decorative article 1 </ b> A is improved.

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 1 </ b> B of the present embodiment includes a base material 2, a base layer 5 provided on the surface of the base material 2, and a first coating 3 provided on the surface of the base layer 5. And a second coating 4 provided on the surface of the first coating 3. That is, the decorative product 1B is the same as the decorative product 1A described above except that the base layer 5 is provided between the base material 2 and the first coating 3. Therefore, the underlayer 5 will be described below.

[Underlayer]
The underlayer 5 is, for example, a function for improving the adhesion between the base material 2 and the first coating 3 (function as an adhesion improvement layer) and a function for repairing scratches on the base material 2 by leveling (leveling). (Function as a leveling layer) The obtained decorative article may have any function such as a function to reduce external impact (function as a cushion layer).

Examples of the constituent material of the underlayer 5 include metal materials such as Ti, Zr, Hf, V, Nb, Ta, Cr, Al and alloys containing at least one of these, among which Ti is used. preferable. When the foundation layer 5 is mainly composed of Ti, for example, the adhesion between the base material 2 and the first coating 3 can be further improved, and the reliability and durability of the decorative article 1B are particularly excellent. Can be. Further, when the underlayer 5 is mainly composed of Ti, the function as a leveling layer that relieves unevenness on the surface of the substrate 2 is more remarkably exhibited. Further, if the underlayer 5 is mainly composed of Ti, in the resulting decorative article 1B, the underlayer 5 functions more effectively as a cushion layer that reduces external impact, and as a result, the decorative article In 1B, a dent such as a dent is particularly unlikely to occur.
The average thickness of the underlayer 5 is not particularly limited, but is preferably 0.1 to 2.0 μm, and more preferably 0.5 to 1.0 μm. When the average thickness of the underlayer 5 is a value within the above range, the above-described functions of the underlayer 5 are more effectively exhibited while sufficiently preventing the internal stress of the underlayer 5 from increasing. be able to.

Next, the manufacturing method of the decorative article 1B described above 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 method for manufacturing a decorative article according to the present embodiment includes a step (4b) of forming a base layer 5 on at least a part (4a) of the surface of the substrate 2 and a surface of the base layer 5. A first film forming step (4c) for forming the first film 3 on at least a part, and a second film forming process for forming the second film 4 on at least a part of the surface of the first film 3 by dry plating. And a film forming step (4d). That is, this embodiment is the same as the above-described embodiment except that the base layer 5 is formed prior to the formation of the first coating 3.

[Underlayer forming process]
In the present embodiment, the base layer 5 is formed on the surface of the substrate 2 (4b).
The formation method of the underlayer 5 is not particularly limited. For example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, etc., wet plating such as electrolytic plating, immersion plating, electroless plating, etc. Examples thereof include chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating methods (vapor deposition methods) such as vacuum deposition, sputtering, and ion plating, and thermal spraying. The method is preferred. By applying a dry plating method as a method for forming the underlayer 5, it is possible to reliably form the underlayer 5 that has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2. it can. 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 as a method for forming the underlayer 5, even if the underlayer 5 to be formed is relatively thin, the variation in film thickness can be made sufficiently small. For this reason, it is advantageous also in improving the reliability of the decorative article 1B.

  Moreover, when performing the 1st film formation process (and 2nd film formation process) mentioned above by a dry-type plating method, the kind of target, the composition of atmospheric gas in a vapor-phase film-forming apparatus (chamber interior), etc. are mentioned, for example. By changing, the underlayer forming process and the first coating film forming process (and the second coating film forming process) can be continuously performed in the same apparatus (without removing the base material 2 from the apparatus). it can. Thereby, the adhesiveness of the base material 2, the base layer 5, and the first coating 3 (and the second coating 4) is particularly excellent, and the productivity of the decorative article 1B is also improved. In particular, when the underlayer 5 is made of Ti, the same target is used, and by changing the composition of the atmospheric gas in the vapor deposition apparatus (in the chamber), the underlayer is preferably used. 5 and the first coating 3 can be formed successively (continuously).

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 first film forming process and the second film forming process, or between the base layer forming process and the first film forming process. The base material may be subjected to pretreatment such as cutting, grinding, polishing, and honing.
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.

Further, in the above-described embodiment, it has been described that one target is used as a target (evaporation source) in the second film forming step. However, a plurality of targets (for example, a plurality of targets having different compositions from each other) are used. It may be used. In such a case, the dry plating conditions may be set so that the formed second film has the composition described above. In other words, the alloy composition as a whole of the target used in the dry plating method may satisfy the above-described conditions. Thus, by using a plurality of targets having different compositions, for example, each target can be heated separately, and the volatilization amount of each target can be adjusted. As a result, a second film having a desired composition can be easily formed.
In the embodiment described above, the first coating and the second coating have been described as being provided adjacent to each other. However, at least one layer is provided between the first coating and the second coating. The intermediate layer may be provided. Thereby, the further improvement of the adhesiveness of a 1st coating film and a 2nd coating film etc. can be aimed at, for example.

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 as 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 first film mainly composed of TiN was formed on the substrate cleaned as described above using a vapor deposition apparatus as follows.
First, while preheating the processing chamber of the vapor deposition apparatus, the processing chamber was evacuated (depressurized) to 2 × 10 ⁻³ Pa.
Next, a cleaning argon gas was introduced into the processing chamber, and a cleaning process was performed for 5 minutes. The cleaning process was performed by applying a DC voltage of 350V.

Next, after exhausting (reducing pressure) the processing chamber to 2 × 10 ⁻³ Pa, nitrogen gas was introduced at a flow rate of 40 ml / min, and the atmospheric pressure (total pressure) in the processing chamber was 1.8 × 10 ⁻³ Pa. It was. In such a state (a state in which nitrogen gas was continuously introduced), Ti was used as a target, an ionization voltage was set to 50 V, and an ionization current was set to 40 A. In this state, ion plating was performed for 90 minutes (first 1 Film formation step). As a result, a first film made of TiN and having an average thickness of 2.4 μm was formed. Moreover, the content rate of N in the formed 1st film was 15.0 wt%.
After that, a second film composed of an Au—Pt—Pd—Cu—Ag—M alloy was formed on the surface of the first film by vacuum vapor deposition using the vapor phase film forming apparatus (first) 2 film forming step). The second film was formed as follows.

First, while preheating the processing chamber of the vapor deposition apparatus, the processing chamber was evacuated (depressurized) to 2.7 × 10 ⁻³ Pa. Thereafter, the inside of the chamber is further evacuated to 8.0 × 10 ⁻⁴ Pa. In such a state, the target formed by casting is dissolved and evaporated by resistance heating using a tungsten board, and Au—Pt— A second film composed of a Pd—Cu—Ag—M alloy was formed to obtain a decorative article. In addition, the vacuum deposition includes a first stage (1 minute) in which the output is maintained at 62%, a second stage (in 7 minutes) in which the output is maintained at 66%, and a third stage in which the output is maintained at 70%. Stage (27 minutes). The average thickness of the formed second film was 1.0 μm.
In addition, the thickness of the 1st coating film and the 2nd coating film was measured with the microscope cross-section test method of JISH5821.

(Examples 2 and 3)
The average thickness of the first film by changing the flow rate of the nitrogen gas in the first film forming step, and further changing the processing time of the first film forming step, the N content in the first film A decorative article (a watch case (back cover)) was manufactured in the same manner as in Example 1 except that as shown in Table 1.
(Examples 4 to 8)
By changing the alloy composition of the target used in the second film formation step, the composition of the second film was changed as shown in Table 1, and the decorative article (watch case ( Back cover)) was manufactured.

Example 9
In the first film formation step, a decorative article (watch) is formed in the same manner as in Example 1 except that the first film is formed of TiCN by using nitrogen gas and acetylene gas as the atmospheric gas. Case (back cover) was manufactured.
In the first film formation step (ion plating), nitrogen gas and acetylene gas are introduced at flow rates of 30 ml / min and 20 ml / min, respectively, and the atmospheric pressure (total pressure) in the processing chamber is set to 3.0 × 10. ^-3 Pa, the ionization voltage was set to 50 V, and the ionization current was set to 40 A.

(Examples 10 and 11)
By changing the flow rates of nitrogen gas and acetylene gas in the first film forming step, and further changing the processing time of the first film forming step, the average thickness of the first film, N in the first film A decorative article (watch case (back cover)) was produced in the same manner as in Example 1 except that the content of C and the content of C were as shown in Table 1.

(Example 12)
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 material 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 body 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 80 ° C. for 1 hour and then to 400 ° C. at a rate of 10 ° C./hour in an argon gas atmosphere of 1.0 × 10 ⁻¹ Pa. 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, after cutting the necessary part and grinding | polishing, 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 13 and 14)
The average thickness of the first film by changing the flow rate of the nitrogen gas in the first film forming step, and further changing the processing time of the first film forming step, the N content in the first film A decorative article (a watch case (back cover)) was produced in the same manner as in Example 12 except that as shown in Table 1.
(Examples 15 to 17)
By changing the alloy composition of the target used in the second film forming step, the composition of the second film was changed as shown in Table 1, and the decorative article (watch case ( Back cover)) was manufactured.

(Example 18)
In the first film formation step, a decorative article (watch) is formed in the same manner as in Example 12 except that the first film is formed of TiCN by using nitrogen gas and acetylene gas as the atmospheric gas. Case (back cover) was manufactured.
In the first film formation step (ion plating), nitrogen gas and acetylene gas are introduced at flow rates of 30 ml / min and 20 ml / min, respectively, and the atmospheric pressure (total pressure) in the processing chamber is set to 3.0 × 10. ^-3 Pa, the ionization voltage was set to 50 V, and the ionization current was set to 40 A.

(Examples 19 and 20)
By changing the flow rates of nitrogen gas and acetylene gas in the first film forming step, and further changing the processing time of the first film forming step, the average thickness of the first film, N in the first film A decorative article (watch case (back cover)) was produced in the same manner as in Example 18 except that the content of C and the content of C were as shown in Table 1.

(Example 21)
Prior to the formation of the first coating film, a decorative article (watch case (back cover)) was produced in the same manner as in Example 1 except that a base layer was formed on the surface of the substrate.
The underlayer was formed as follows.
First, the base material cleaned in the same manner as in Example 1 was placed in the processing chamber of the vapor deposition apparatus.

Next, the processing chamber was evacuated (depressurized) to 3 × 10 ⁻³ Pa while preheating the processing chamber of the vapor deposition apparatus.
Next, a cleaning argon gas was introduced into the processing chamber, and a cleaning process was performed for 5 minutes. The cleaning process was performed by applying a DC voltage of 350V.
Thereafter, argon gas was introduced into the processing chamber at a gas pressure of 53 Pa, and a DC voltage of 400 V was applied and held for 30 to 60 minutes. In such a state, using Ti as a target, setting an ionization voltage: 30 V, an ionization current: 20 A, and a processing time: 20 minutes, an underlayer composed of Ti was formed (underlayer formation step). The average thickness of the formed underlayer was 0.5 μm.

(Examples 22 and 23)
By selecting and adjusting the target constituent material and processing time in the base layer forming step, the constituent material and average thickness of the base layer are shown in Table 2, and the flow rate of nitrogen gas in the first film forming step is changed. In addition, the above-mentioned implementation was performed except that the average thickness of the first coating and the N content in the first coating were changed as shown in Table 2 by changing the processing time of the first coating forming step. In the same manner as in Example 21, a decorative article (watch case (back cover)) was produced.

(Examples 24-26)
Table 2 shows the constituent material and average thickness of the target layer by selecting and adjusting the target constituent material and processing time in the base layer forming step, and the alloy composition of the target used in the second film forming step. By changing, the decorative article (watch case (back cover)) was manufactured in the same manner as in Example 21 except that the composition of the second coating was changed as shown in Table 2.

(Example 27)
In the first film forming step, a decorative article (watch) is formed in the same manner as in Example 21 except that the first film is formed of TiCN by using nitrogen gas and acetylene gas as the atmospheric gas. Case (back cover) was manufactured.
In the first film formation step (ion plating), nitrogen gas and acetylene gas are introduced at flow rates of 30 ml / min and 20 ml / min, respectively, and the atmospheric pressure (total pressure) in the processing chamber is set to 3.0 × 10. ^-3 Pa, the ionization voltage was set to 50 V, and the ionization current was set to 40 A.

(Examples 28 and 29)
By selecting and adjusting the target constituent material and processing time in the base layer forming step, the constituent material and average thickness of the base layer are shown in Table 2, and the nitrogen gas and acetylene gas in the first film forming step Table 2 shows the average thickness of the first coating, the N content in the first coating, and the C content by changing the flow rate and further changing the processing time of the first coating forming step. A decorative article (watch case (back cover)) was produced in the same manner as in Example 27 except for the above.

(Example 30)
A decorative article (watch case (back cover)) was manufactured in the same manner as in Example 21 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 material 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 body 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 80 ° C. for 1 hour and then to 400 ° C. at a rate of 10 ° C./hour in an argon gas atmosphere of 1.0 × 10 ⁻¹ Pa. 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, after cutting the necessary part and grinding | polishing, 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 31 and 32)
By selecting and adjusting the target constituent material and processing time in the base layer forming step, the constituent material and average thickness of the base layer are shown in Table 2, and the flow rate of nitrogen gas in the first film forming step is changed. In addition, the above-mentioned implementation was performed except that the average thickness of the first coating and the N content in the first coating were changed as shown in Table 2 by changing the processing time of the first coating forming step. In the same manner as in Example 30, a decorative article (watch case (back cover)) was produced.

(Examples 33 to 35)
Table 2 shows the constituent material and average thickness of the target layer by selecting and adjusting the target constituent material and processing time in the base layer forming step, and the alloy composition of the target used in the second film forming step. By changing, the decorative article (watch case (back cover)) was manufactured in the same manner as in Example 30 except that the composition of the second coating was changed as shown in Table 2.

(Example 36)
In the first film formation step, a decorative article (watch) was formed in the same manner as in Example 30 except that nitrogen gas and acetylene gas were used as the atmospheric gas, so that the first film was formed of TiCN. Case (back cover) was manufactured.
In the first film formation step (ion plating), nitrogen gas and acetylene gas are introduced at flow rates of 30 ml / min and 20 ml / min, respectively, and the atmospheric pressure (total pressure) in the processing chamber is set to 3.0 × 10. ^-3 Pa, the ionization voltage was set to 50 V, and the ionization current was set to 40 A.

(Examples 37 and 38)
By selecting and adjusting the target constituent material and processing time in the base layer forming step, the constituent material and average thickness of the base layer are shown in Table 2, and the flow rate of nitrogen gas in the first film forming step is changed. In addition, the above-mentioned implementation was performed except that the average thickness of the first coating and the N content in the first coating were changed as shown in Table 2 by changing the processing time of the first coating forming step. In the same manner as in Example 36, a decorative article (watch case (back cover)) was produced.
(Example 39)
A decorative article (watch case (back cover) was used in the same manner as in Example 1 except that the base material was a Cu—Zn alloy (alloy composition: Cu 60 wt% —Zn 40 wt%) and was molded by casting. )) Was manufactured.

(Comparative Example 1)
A decorative article (watch case (back cover)) was obtained in the same manner as in Example 1 except that the second film was directly formed on the surface of the substrate without forming the first film.
(Comparative Example 2)
After the first film was formed, an ornament (watch case (back cover)) was obtained in the same manner as in Example 1 except that the second film was not formed.

(Comparative Example 3)
A decorative article (watch case (back cover)) was manufactured by the method as described below.
First, a Ti substrate was prepared in the same manner as in Example 12.
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.
The carburized layer (TiC layer) comprised by TiC was formed by performing the carburizing process with respect to the base material which wash | cleaned as mentioned above.

The carburizing process was performed by a plasma carburizing process as described below.
That is, it has a processing chamber surrounded by a heat insulating material such as graphite fiber in a heating furnace, the processing chamber is heated by a heating element made of rod graphite, and a positive electrode of a direct current glow discharge is connected to the upper portion of the processing chamber. In addition, a cathode is connected to the processing table and a gas manifold is installed at a key point in the processing chamber to introduce hydrocarbons, nitrogen, argon, hydrogen and other process gases (carburizing gas and dilution gas) as appropriate. A carburizing apparatus was prepared.
And first, the base material was installed in the processing chamber of the carburizing apparatus, and the processing chamber was depressurized to 1.3 Pa. In this way, the substrate was heated to about 300 ° C. by the heater while the processing chamber was decompressed.

Thereafter, a cleaning argon gas was introduced into the processing chamber to perform a cleaning process for 5 minutes. The cleaning process was performed by applying a DC voltage of 350V.
Thereafter, by introducing propane gas into the processing chamber, the gas composition in the processing chamber is almost 100% propane gas, the gas pressure is 53 Pa, a DC voltage of 400 V is applied, and the plasma is held for 90 to 180 minutes. Carburizing treatment was performed. Thereafter, argon gas and nitrogen gas were injected into the processing chamber to cool the substrate to room temperature. By such a carburizing process, a carburized layer having a thickness of about 15 μm was formed.
Thereafter, a second film was formed on the surface of the carburized layer in the same manner as in Example 1 to obtain a decorative article (watch case (back cover)).

(Comparative Examples 4 to 21)
As shown in Table 3, a decorative article (watch case (back cover)) was obtained in the same manner as in Example 1 except that the target used in the second film formation step was changed and the composition of the second film was changed. Manufactured.
In addition, when the chromaticity of the surface of the target (evaporation source) used for forming the second film in each of the above examples was measured using a chromaticity meter (manufactured by Minolta, CM-2022), a ^* is −1.5 to 1.5 and b ^* is not included in the range of 7.0 to 15.0, a ^* is −1.5 to 1.5 and b ^* is It was included in the range of 0.0 to 6.9.

In addition, the second film formed in each of the examples and the comparative examples has substantially the same composition as the target (evaporation source) used for the formation, and the target and the second film The difference in the content of each component was less than 0.01 wt%.
Tables 1, 2 and 3 collectively show the structures of the decorative articles of each Example and each Comparative Example and the conditions of the targets used for forming the second film. In Tables 1 to 3, stainless steel is indicated by SUS and Cu—Zn alloy is indicated by BS. In Table 3, for Comparative Example 3, values relating to the carburized layer formed by carburizing treatment are shown in the column of the first coating.

2. Visual appearance evaluation Each decorative article manufactured in each of the above Examples and Comparative Examples was visually and observed with a microscope, and the appearance was evaluated in accordance with the following four criteria.
A: Appearance is excellent.
○: Good appearance.
Δ: Appearance is slightly poor.
X: Appearance defect.

3. Appearance evaluation using a chromaticity meter The chromaticity of the surface on which the coating film was formed was measured using a chromaticity meter (CM-2022, manufactured by Minolta Co., Ltd.) for the decorative products manufactured in the above Examples and Comparative Examples. Evaluation was performed according to the following four-stage criteria.
A: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is -1.0 to 1.0 and b ^* is in the range of 8.0 to 10.0.
○: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is in the range of -1.2 to 1.2 and b ^* is in the range of 7.0 to 12.0 (excluding the range of）).
Δ: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is in the range of -1.5 to 1.5 and b ^* is in the range of 7.0 to 15.0 (except for the range of ◎ and ○).
×: In the chromaticity diagram of L ^* a ^* b ^* display specified by JIS Z 8729, a ^*
Is -1.5 to 1.5 and b ^* is outside the range of 7.0 to 15.0.
As the light source of the colorimeter was a _{D 65} defined in JIS Z 8720, and measurements were taken at a viewing angle 2 °.

4). Long-term stability evaluation The decorative article produced in each of the above Examples and Comparative Examples is formed into a decorative article film after being left for 90 days in an environment of normal temperature (25 ° C.), normal pressure, and humidity 70% RH. The color tone on the surface side was measured using a chromaticity meter (CM-2022, manufactured by Minolta Co., Ltd.), and evaluated according to the above-mentioned criteria for “appearance evaluation by chromaticity meter”.

5. Oxidation resistance evaluation The decorative articles produced in the above Examples and Comparative Examples were allowed to stand at 200 ° C. in an atmospheric atmosphere at normal pressure for 8 hours, and then the color tone of the surface side on which the decorative article coating film was formed, It measured using the chromaticity meter (Minolta company make, CM-2022), and evaluated in accordance with the standard of the above-mentioned "appearance evaluation by a chromaticity meter".

6). Evaluation of chemical resistance The decorative articles manufactured in the above Examples and Comparative Examples were evaluated for chemical resistance by performing an aeration test as shown below.
Artificial sweat was placed in a desiccator and left at 40 ° C. for 24 hours. Thereafter, each decorative article was put in a desiccator and further left at 40 ° C. At this time, each decorative article was arranged so as not to be immersed in artificial sweat. After 24 hours, each decorative article was taken out from the desiccator, and the color tone of the surface side on which the decorative article film was formed was measured using a chromaticity meter (CM-2022, manufactured by Minolta Co., Ltd.). Evaluation was performed according to the criteria of “Appearance Evaluation by”.

7). Evaluation of Adhesiveness of Coating Films The decorative articles manufactured in the respective Examples and Comparative Examples were subjected to the following tests to evaluate the adhesiveness of the coating films (first coating film, second coating film, underlayer). .
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.
(Double-circle): The float of a film, peeling, etc. are not recognized at all.
○: Almost no floating of the film is observed.
(Triangle | delta): The lift of a film is recognized clearly.
X: Cracks and peeling of the film are clearly recognized.

8). Scratch resistance evaluation Each decorative article produced in each of the above Examples and Comparative Examples was subjected to the following test to evaluate the scratch resistance.
Using a Suga Abrasion Tester (Suga Test Instruments Co., Ltd., NUS-ISO-1) under the condition of load: 200 gf, the surface on which the coating film of each decorative article was formed (the surface of the base material was exposed) The surface of each decorative article after a total of 300 DS (double stroke) wear 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. Or peeling of a film is recognized.

9. Evaluation of dent resistance (difficulty of marking) The dent resistance was evaluated by performing the following tests on the decorative articles manufactured in the respective Examples and Comparative Examples.
A stainless steel ball (diameter 1 cm) is dropped from a position of 60 cm in height toward the surface on which the coating film of each ornament is formed, and the size of the recess on the surface of the ornament (the diameter of the recess mark). Was measured and evaluated according to the following four-stage 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 in Table 4, Table 5, and Table 6 together with the Vickers hardness Hv of the coating. In addition, as Vickers hardness Hv, the value measured by the measurement load 10gf about the surface (surface by which the film is provided) of each ornament is shown.

As is clear from Tables 4 to 6, the decorative article of the present invention had an excellent aesthetic appearance, particularly an excellent aesthetic appearance showing a whitish gold color. In addition, the decorative article of the present invention was excellent in long-term stability, oxidation resistance, chemical resistance, and film adhesion. Moreover, the decorative article of the present invention had high hardness and was excellent in scratch resistance and dent resistance. From these results, it can be seen that the decorative article of the present invention can maintain an excellent aesthetic appearance over a long period of time.
Moreover, all the decorative articles of the present invention had an excellent tactile sensation without a rough feeling.

  On the other hand, all of the comparative examples were inferior in aesthetic appearance, and satisfactory results were not obtained. In particular, in Comparative Example 1 having no first coating, the long-term stability, the adhesion of the coating, the scratch resistance, the dent resistance, and the like were remarkably inferior. Moreover, in the comparative example 2 which does not have a 2nd film, the aesthetic appearance was especially inferior. Further, in Comparative Example 3, the surface roughness during the formation of the carburized layer was remarkable, and thereafter the appearance of the decorative article covered with the second coating was also extremely inferior.

In each of the above examples, the first coating is composed of TiN (TiCN) containing a predetermined amount of C. Nitric acid (HNO ₃ ): 15 vol%, sulfuric acid (H ₂ SO ₄ ): 15 vol By using an aqueous solution containing 1%, the coating (first coating, second coating) can be preferably removed, and the subsequent coating (first coating, second coating) is re-formed. Can be suitably performed, and a decorative product having an excellent aesthetic appearance can be reproduced.
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 wristwatches 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 1A, 1B ... Decoration 2 ... Base material 3 ... 1st film 4 ... 2nd film 5 ... Underlayer 10 ... Wristwatch (portable clock) 22 ... Body (case) 23 ... Back cover 24 ... Bezel (edge) 25 ... Glass plate 26 ... Wind 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 part)

Claims (17)

A first film forming step of forming a first film mainly composed of TiN on a substrate;
On the first coating, 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2.0 to 4.0 wt% Cu, 1.5 to 2.5 wt% Au—Pt—Pd—Cu—Ag—M alloy containing 1.0 to 3.0 wt% of M (wherein M is at least one selected from the group consisting of Zn and In) And a second film forming step of forming a second film by a dry plating method using as a target.   The method for producing a decorative article according to claim 1, wherein at least the vicinity of the surface of the base material is mainly composed of Ti and / or stainless steel.   The method for producing a decorative article according to claim 1 or 2, wherein the content of N in the first coating is 2 to 29 wt%.   The method for manufacturing a decorative article according to any one of claims 1 to 3, wherein an average thickness of the first coating is 0.1 to 5.0 µm.   The method for producing a decorative article according to any one of claims 1 to 4, wherein an average thickness of the second coating is 0.01 to 2.0 µm.   The method for manufacturing a decorative article according to any one of claims 1 to 5, wherein the first film is formed by a dry plating method.   The method for manufacturing a decorative article according to claim 6, wherein the first film is formed by ion plating.   The method for manufacturing a decorative article according to any one of claims 1 to 7, wherein the second coating is formed by vacuum deposition.   The method for manufacturing a decorative article according to any one of claims 1 to 8, further comprising a base layer forming step of forming at least one base layer on the substrate prior to the first film forming step.   The method for manufacturing a decorative article according to claim 9, wherein a layer mainly composed of Ti is formed as the underlayer.   The method for manufacturing a decorative article according to claim 9 or 10, wherein an average thickness of the underlayer is 0.1 to 2.0 µm.   A decorative article manufactured using the method according to claim 1. On the substrate
A first coating provided on the substrate and composed primarily of TiN;
By dry plating, the first coating is provided on the surface opposite to the surface facing the substrate, and is 8.0 to 12 wt% Pt, 6.0 to 8.0 wt% Pd, 2. 0 to 4.0 wt% Cu, 1.5 to 2.5 wt% Ag, and 1.0 to 3.0 wt% M (where M is at least one selected from the group consisting of Zn and In) And a second coating film made of an Au—Pt—Pd—Cu—Ag—M alloy containing the seed).   The decorative article according to claim 12 or 13, wherein a Vickers hardness Hv measured with a load of 10 gf is 500 to 1000 on the surface on the side on which the second film is provided. The color tone of the surface on which the second film is provided is such that a ^* is −1.5 to 1.5 in the chromaticity diagram of L ^* a ^* b ^* display defined by JIS Z 8729. The decorative article according to any one of claims 12 to 14, wherein b ^* is 7.0 to 15.0.   The decorative article according to any one of claims 12 to 15, wherein the decorative article is a watch exterior part.   A timepiece comprising the decorative article according to any one of claims 12 to 16.

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