JP2006257524A - Ornament having white coating film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornament which is an ornament composed of steel sheet, is highly resistant to corrosion, extremely little in elution of nickel and has a white film having excellent scratch resistance. <P>SOLUTION: The ornament is composed of: a base material for the ornament composed of the stainless steel; a barrier layer formed by a wet plating method on the base material surface; a primary coat formed by the wet plating method on the surface of the barrier layer; a wear resistant layer formed by the wet plating method on the surface of the under layer; and a color development layer composed of the outermost layer formed by the wet plating method on the surface of the wear resistant layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative article having a white coating and a method for producing the same, and more particularly, in particular, a hard, stainless steel-colored tone in which nickel is not more easily eluted from stainless steel as a base material even when used for a long period of time. The present invention relates to a decorative article having a white coating and a method for producing the same.

  Conventionally, many clock alloys, necklaces, pendants, brooches, etc., which are decorative items, have been made of copper alloys due to processability, material price, and the like. However, since the decorative article manufactured using this copper alloy as a raw material has poor corrosion resistance, a plating film is applied to the base material surface by a wet plating method. This plating film is usually composed of a nickel plating film formed by a wet plating method as a base plating film and an outermost layer plating film formed by a wet plating method on the surface of the coating film. When the outermost layer plating film is gold, a gold plating film is formed on the surface of the nickel plating film by a wet plating method. When the outermost layer is white, the surface of the nickel plating film is palladium plating film or palladium compound. A gold plating film or a rhodium plating film is formed by a wet plating method. The thickness of these plating films is generally formed in the range of 1 to 5 μm.

  However, in the decorative product as described above, since a plating film containing an expensive noble metal is formed as the outermost layer plating film in order to obtain corrosion resistance, there is a cost problem that the price of the decorative product is increased. . Therefore, in a low-priced decoration, the outermost layer plating film becomes thin, and the corrosion resistance for a long time becomes a problem. In addition, in the production of low-priced ornaments, maintenance of a precious metal plating bath is a major operational problem in order to obtain a stable thin outermost plating film. Furthermore, in order to obtain the outermost plating film having a stable color tone, the skill level of the worker is also a problem. Moreover, an inexpensive decorative article having an outermost layer plating film having a white color tone unique to stainless steel has not been obtained.

Therefore, the applicant of the present application disclosed in Japanese Patent Laid-Open No. 2003-253473 (Patent Document 1) as a white decorative article, a titanium plating film (underlayer) and a titanium carbide plating film (abrasion-resistant layer) on the surface of a metal substrate. And a white decorative article in which a platinum coating or a platinum alloy coating (outermost layer) is laminated by a dry plating method. The white hard coating formed on such a decorative article has a high-class feeling and is not easily scratched. In addition, a white tone specific to stainless steel required in the market is obtained.
JP 2003-253473 A

  However, if the white decorative base material is stainless steel, it will be slightly removed from the stainless steel base material due to human sweat and the action of the outermost platinum coating or platinum alloy coating as a catalyst during long-term use. Nickel elution was observed. (Within German standard range: no problem in carrying) This slight nickel elution could cause a decrease in the corrosion resistance of the substrate and cause metal allergies to those who are very sensitive to nickel. This is thought to be because sweat or the like comes into contact with the stainless steel of the base material from ultrafine pinholes that occur when the film is formed by the dry plating method. Moreover, as a method of preventing the occurrence of this pinhole, it can be solved by forming each film thickness thick. However, if the titanium carbide plating film (abrasion resistant layer) which is a hard film is coated thickly, the internal stress of the film The problem that a film peels arises. (Inadequate adhesion) In addition, it took a long time to form a film, and there was a problem in workability.

  The present invention is intended to solve the above-mentioned problems, nickel elution is difficult to occur from stainless steel as a base material, there is no problem of corrosion resistance and nickel allergy of the base material, and appearance quality due to scratches, etc. It is an object of the present invention to provide a decorative article having a high-quality white coating that is unlikely to deteriorate and that is close to a stainless steel coating, and a method for producing the same.

A decorative article having a white coating according to the present invention is:
In a decorative article in which a coating film having a white color tone made of a noble metal or a noble metal alloy is formed by a dry plating method as an outermost layer, the decorative article base material made of stainless steel is formed on the surface of the base material by a wet plating method. A barrier layer; an underlayer formed on the surface of the barrier layer by a dry plating method; an abrasion-resistant layer formed on the surface of the underlayer by a dry plating method; and a surface of the wear-resistant layer by a dry plating method A color developing layer composed of an outermost layer formed, and the color developing layer is composed of a wear-resistant layer having a thickness of 0.2 to 1.5 μm and an outermost layer having a thickness of 0.002 to 0.1 μm. It is a hard white film having

  In addition, a strike plating film layer made of gold or a gold alloy formed by a wet plating method is provided between the base material surface made of stainless steel and the barrier layer. The strike plating film layer has a thickness of 0.05 to 0.3 μm formed by a wet plating method, preferably 0.05 to 0.15 μm, and most preferably 0.05 to 0.1 μm. It is characterized by that.

  The barrier layer formed on the surface of the base material made of stainless steel is a film made of rhodium (Rh), gold (Au), or chromium (Cr) formed by a wet plating method. . The other barrier layer may be a film made of at least one of rhodium alloy, palladium alloy, platinum alloy, copper alloy, and gold alloy formed by a wet plating method. The barrier layer has a thickness of 0.3 to 3 μm, preferably 1.0 to 2.5 μm, and most preferably 1.5 to 2.0 μm.

  The underlayer formed on the surface of the barrier layer is formed by dry plating, titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb). Or it is a film which consists of tantalum (Ta). In addition, as the other underlayer, titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or carbonized carbon having a carbon atom content of 5 to 15 atomic% formed by a dry plating method is used. A metal compound film made of tantalum may be used. The thickness of the underlayer is preferably a film having a thickness of 0.02 to 0.2 μm.

The wear-resistant layer is composed of titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide (WC). Or a metal compound film made of tantalum carbide (TaC). The wear-resistant layer has a thickness of 0.2 to 1.5 μm, preferably 0.5 to 1.0 μm.

  The outermost layer is a film made of platinum (Pt), palladium (Pd), or rhodium (Rh). The outermost layer may be a coating made of a platinum alloy, a palladium alloy, or a rhodium alloy. The outermost layer has a thickness of 0.002 to 0.1 μm, preferably 0.005 to 0.1 μm, more preferably 0.01 to 0.08 μm.

In addition, a mixed layer comprising a metal compound that forms the wear-resistant layer and a metal or alloy that forms the outermost layer is provided between the wear-resistant layer and the outermost layer. The thickness of the mixed layer is 0.005 to 0.1 μm.

  Further, the color evaluation of the coloring layer composed of the abrasion-resistant layer and the outermost layer by the L *, a *, b * display system (CIE surface system) is 70 <L * <91, −0.1 <a * <3. 0.0, 1.0 <b * <5.5.

  Each of the underlayer, the wear-resistant layer, the mixed layer, and the outermost layer is formed by at least one of a sputtering method, an ion plating method, and an arc method.

  In addition, a part of the surface of a white coating film having a color tone layer made of stainless steel has at least one coating film formed by a dry plating method or a wet plating method and having a color tone different from that of the coloring layer. And Further, the coating different from the color tone of the coloring layer is made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride or diamond-like carbon (DLC). Further, the coating different from the coloring layer may have a two-layer structure of a lower layer made of titanium nitride, zirconium nitride or hafnium nitride and an upper layer made of gold or a gold alloy. Furthermore, it is preferable to have a titanium coating and a silicon coating formed on the surface of the titanium coating between the coloring coating and a diamond-like carbon (DLC) coating that is a coating different from the coloring coating.

  The outermost layer is a mixed layer made of a metal compound that forms the wear-resistant layer and platinum (Pt), palladium (Pd), or rhodium (Rh). The outermost layer may be a mixed layer made of a metal compound that forms the wear-resistant layer and a platinum alloy, palladium alloy, or rhodium alloy.

  The decorative article having a white coating according to the present invention is characterized in that the surface hardness (Hv; micro Vickers hardness meter, 5 g load) of the coloring layer is usually 700 to 2000, preferably 1000 to 2000. Further, the decorative article is a watch exterior part.

The method for producing a decorative article having a white coating according to the present invention is as follows.
In a method for manufacturing a decorative article in which a coating having a white color tone made of a noble metal or a noble metal alloy is formed by a dry plating method as an outermost layer, a base material for a decorative article is manufactured by various processing means using a material made of stainless steel. A step of forming a barrier layer on the surface of the base material by a wet plating method, a step of forming a base layer on the surface of the barrier layer by a dry plating method, and a metal compound by a dry plating method on the surface of the base layer And forming a hard coloring layer having a stainless steel color by forming an outermost layer made of platinum or a platinum alloy by a dry plating method on the surface of the wear-resistant layer. It is characterized by.

  Further, a strike plating film layer made of gold or a gold alloy is formed between the base material surface made of stainless steel and the barrier layer by a wet plating method. The strike plating film layer has a thickness of 0.05 to 0.3 μm, preferably 0.05 to 0.15 μm, and most preferably 0.05 to 0.1 μm.

  In addition, a film made of rhodium (Rh), gold (Au), or chromium (Cr) is formed on the surface of the substrate as the barrier layer by a wet plating method. In addition, as another barrier layer, a film made of at least one of a rhodium alloy, a palladium alloy, a platinum alloy, a copper alloy, and a gold alloy may be formed by a wet plating method.

  Further, a film having a thickness of 0.3 to 3 μm is formed on the substrate surface as the barrier layer by a wet plating method, preferably 1.0 to 2.5 μm, most preferably 1.5 to 2.0 μm. Form.

  Further, on the surface of the barrier layer of the decorative article base material, as the base layer, titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum ( A film made of Ta) is formed by a dry plating method. As another underlayer, a metal compound film made of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or tantalum carbide having a carbon atom content of 5 to 15 atom% is dry-plated. It may be formed by a method. Moreover, it is good to form a 0.02-0.2 micrometer-thick film as a base layer on the barrier layer surface of a base material for decorative articles by a dry plating method.

The wear-resistant layer is composed of titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide (WC). ) Or a metal compound film made of tantalum carbide (TaC). Further, the thickness of the wear-resistant layer is usually 0.2 to 1.5 μm, preferably 0.5 to 1.0 μm.

  The outermost layer is formed of a film made of platinum (Pt), palladium (Pd), or rhodium (Rh). Moreover, it is good to form the thickness with 0.002-0.1 micrometer.

  In addition, a mixed layer comprising a metal compound that forms the wear-resistant layer and a metal or alloy that forms the outermost layer is formed between the wear-resistant layer and the outermost layer.

  Further, the color evaluation by the L *, a *, b * display system (CIE surface system) of the coloring layer is 70 <L * <91, −0.1 <a * <3.0, 1.0 <b *. <5.5.

  In the method for manufacturing a decorative article having a white coating according to the present invention, the underlayer, the wear-resistant layer, the mixed layer, and the outermost layer are formed by at least one of a sputtering method, an ion plating method, and an arc method. It is characterized by.

  In addition, a method for producing a decorative product having two or more color tones includes a dry plating method or a wet method in which at least one coating different from the color tone of the coloring layer is applied to a part of the surface of the white coating having a stainless steel tone consisting of the coloring layer. It is formed by a plating method.

  The coating film having a color tone different from that of the coloring layer is formed of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). Further, as a coating different from the coloring layer, a coating having a two-layer structure of a lower layer made of titanium nitride, zirconium nitride or hafnium nitride and an upper layer made of gold or a gold alloy may be formed.

  Further, the present invention is characterized in that a titanium film is formed between a coloring layer and a diamond-like carbon (DLC) film which is a film different from the coloring layer, and further a silicon film is formed on the surface of the titanium film.

  Further, the outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and platinum (Pt), palladium (Pd), or rhodium (Rh). The outermost layer may be formed of a mixed layer composed of a metal compound that forms the wear-resistant layer and a platinum alloy, a palladium alloy, or a rhodium alloy.

  Moreover, the surface hardness (Hv; micro Vickers hardness meter, 5 g load) of the coloring layer is formed to be 700 to 2000.

  According to the present invention, even if it is used for a long period of time, nickel is eluted in a very small amount from the stainless steel that is the base material of the decorative article. Therefore, the corrosion resistance of the base material is improved and the occurrence of nickel allergy is eliminated. In addition, there is provided a decorative article having a high-class white coating with a high-class feeling, which is high-quality, hard and excellent in scratch resistance, hardly deteriorates in appearance quality due to scratches, etc., and is close to a stainless steel coating, and a method for producing the same. Can be provided.

Hereinafter, a decorative article having a white coating according to the present invention and a method for producing the same will be described in detail.
A decorative article having a white coating according to the present invention is a decorative article base material made of stainless steel, a barrier layer formed on the surface of the base material by a wet plating method, and formed on the surface of the barrier layer by a dry plating method. And a coloring layer formed on the surface of the underlayer by a dry plating method. The coloring layer is composed of an abrasion resistant layer and an outermost layer, or an abrasion resistant layer, a mixed layer, and an outermost layer.

  Further, the decorative article having a white coating according to the present invention may have at least one coating different from the color tone of the coloring layer on a part of the surface of the white coating having the stainless steel color tone composed of the coloring layer. .

[Base material for decorative products]
The decorative article base material made of stainless steel is manufactured from the above-mentioned metal by conventionally known machining. Further, the decorative article base material is subjected to at least one surface finish among a mirror surface, a satin finish, a hairline pattern, a honing pattern, a stamping pattern, and an etching pattern by various means as required.

  Examples of the ornaments (including accessories) in the present invention (including parts) include watch case parts, wristwatch bands, wristwatch crowns, watch exterior parts such as wristwatch back covers, belt buckles, rings, necklaces, bracelets, and earrings. , Pendants, brooches, cufflinks, tie-stops, badges, medals, eyeglass frames, camera bodies, doorknobs, etc.

In the present invention, before forming the strike plating film layer and the barrier layer on the surface of the decorative article base material, it is preferable to previously wash and degrease the decorative article base material surface with a conventionally known organic solvent or the like. .
[Barrier layer]
The barrier layer constituting the decorative article having the white coating according to the present invention is composed of at least one plating coating formed by a wet plating method. Examples of the plating film include rhodium (Rh), gold (Au), and chromium (Cr). In order to make the adhesion between the surface of the decorative article base material and the barrier layer stronger, a strike plating film layer is provided between the decorative article base material surface and the barrier layer. Examples of the strike plating film layer include gold or a gold alloy.

[Underlayer]
The underlayer constituting the decorative article having a white coating according to the present invention is composed of at least one plated coating formed by a dry plating method. As this plating film,
Examples include titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), and tantalum (Ta).

On the surface of the underlayer, titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide as an abrasion resistant layer In the case of forming a metal compound film made of (WC) or tantalum carbide (TaC), from the viewpoint of further improving the adhesion between the base material and the wear-resistant layer, the underlayer was formed by a dry plating method. A metal compound film made of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or tantalum carbide having a carbon atom content of 5 to 15 atom% is particularly preferable. In this metal compound film, the carbon atom content of the metal compound gradually decreases as it approaches the surface of the decorative article substrate, and this metal compound film is called a so-called gradient film.

[Coloring layer]
The coloring layer constituting the decorative article having the white coating according to the present invention is composed of an abrasion resistant layer and an outermost layer, or an abrasion resistant layer, a mixed layer, and an outermost layer. These layers are formed by a dry plating method. Specific examples of the dry plating method include a sputtering method, an arc method, an ion plating method, a physical vapor deposition method (PVD) such as an ion beam, and CVD. Of these, the sputtering method, the arc method, and the ion plating method are particularly preferably used.

(Abrasion resistant layer)
The wear-resistant layer is made of a metal compound film formed on the surface of the underlayer by a dry plating method. Such metal compound coatings include titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide. A metal compound film made of (WC) or tantalum carbide (TaC) is desirable.

  The wear-resistant layer has a thickness of 0.2 to 1.5 μm, preferably 0.5 to 1.0 μm.

(Outermost layer)
The outermost layer is made of a noble metal (including alloy) film formed by a dry plating method on the surface of the wear-resistant layer or a mixed layer described later.

  As such a film made of a noble metal, a noble metal film made of platinum (Pt), palladium (Pd), rhodium (Rh), platinum alloy, palladium alloy or rhodium alloy is desirable. Moreover, in this invention, the mixed layer mentioned later can be made into an outermost layer. The thickness of the outermost layer is 0.002 to 0.1 μm, preferably 0.005 to 0.1 μm, and more preferably 0.01 to 0.08 μm. However, when a platinum film or a platinum alloy film is formed as the outermost layer, the thickness of the film is 0.002 to 0.01 μm, preferably 0.005 to 0.08 μm.

(Mixed layer)
In the present invention, the mixed layer that may be formed between the wear-resistant layer and the outermost layer as necessary is a coating formed by a dry plating method. This coating consists of a metal compound (for example, titanium carbide) that forms the wear-resistant layer and a metal or alloy (for example, platinum, platinum alloy) that forms the outermost layer. The thickness of this mixed layer is usually 0.005 to 0.1 μm, preferably 0.01 to 0.08 μm. By providing such a mixed layer, the adhesion between the wear-resistant layer and the outermost layer can be further strengthened.

  The color evaluation by the L *, a *, b * display system (CIE surface system) of the coloring layer composed of the abrasion resistant layer and the outermost layer or the abrasion resistant layer, the mixed layer and the outermost layer is 70 <L. * <91, −0.1 <a * <3.0, 1.0 <b * <5.5 are desirable. Among these, it is preferable that 75 <L * <85, 0 <a * <2.0, and 3.5 <b * <5.0.

  In addition, each L * of the coloring layer formed on the base material for decorative articles having a mirror finish and the coloring layer formed on the base material for decorative articles having a hairline finish (fine line pattern) , A *, b * display system (CIE surface system), the color evaluation is 85 <L * <90, 0 <a * <2.0, 3.5 <b * <5.0, and 75 <L *. <85, 0 <a * <2.0, 3.5 <b * <5.0. In addition, the Δ values of L *, a *, and b * of the color forming layer formed on the decorative article base material with various surface finishes are ΔL * = ± 6.0, Δa * = ± 1.55. Δb * = ± 2.25.

  Further, the surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the color developing layer is usually 700 to 2000, preferably 1000 to 2000. In the present invention, by forming an outermost layer consisting of at least a wear-resistant layer having a thickness of 0.2 to 1.5 μm and a noble metal having a thickness of 0.002 to 0.1 μm on the surface of the base layer, there is a sense of quality. It is possible to obtain a decorative article having a high-quality white coating that is unlikely to deteriorate in appearance quality due to scratches or the like and that is close to a stainless steel coating.

[Coating different from coloring layer]
In the decorative article having a white coating according to the present invention, at least one coating different from the color tone of the coloring layer is formed on a part of the surface of the white coating having the stainless steel color tone made of the coloring layer by a dry plating method or a wet plating method. May be. As the coating different from the color tone of the coloring layer, a coating made of gold, a gold alloy (preferably a gold alloy not containing nickel), titanium nitride, zirconium nitride, hafnium nitride or diamond-like carbon (DLC) is desirable. This coating appears in the appearance of the decorative article together with the outermost layer forming the color forming layer. Therefore, the ornament according to the present invention includes so-called two-tone ornaments.

  The thickness of the plating film having a color tone different from that of the coloring layer is usually 0.1 to 1.0 μm, preferably 0.2 to 0.5 μm. Further, the coating film having a color tone different from that of the coloring layer may have a two-layer structure of a lower layer made of titanium nitride, zirconium nitride or hafnium nitride and an upper layer made of gold or a gold alloy (for example, a gold-iron alloy). . In this case, the thickness of the lower layer is usually 0.2 to 1.5 μm, preferably 0.5 to 1.0 μm, and the thickness of the upper layer is usually 0.03 to 0.2 μm, preferably 0.05 to 0. .1 μm.

  Furthermore, the coating film having a color tone different from that of the coloring layer may have a three-layer structure of a lower layer made of titanium, an intermediate layer made of titanium nitride, zirconium nitride, or hafnium nitride, and an upper layer made of gold or a gold alloy. . In this case, the thickness of the lower layer is usually 0.02 to 0.1 μm, preferably 0.03 to 0.08 μm, and the thickness of the intermediate layer is usually 0.2 to 1.5 μm, preferably 0.5 to It is 1.0 micrometer, and the thickness of an upper layer is 0.03-0.2 micrometer normally, Preferably it is 0.05-0.1 micrometer.

  Further, in the coating film having a color tone different from that of the coloring layer, a titanium coating, a silicon coating, and a diamond-like carbon (DLC) coating may be formed in this order on a part of the surface of the coloring layer. In this case, the thickness of the lower layer is usually 0.05 to 0.3 μm, preferably 0.08 to 0.2 μm, and the thickness of the intermediate layer is usually 0.05 to 0.3 μm, preferably 0.08 to The thickness of the upper layer is usually 0.5 to 3.0 μm, preferably 0.8 to 1.5 μm.

  Each layer constituting the single-layer structure, the two-layer structure, or the three-layer structure is usually formed by a dry plating method. Specific examples of the dry plating method include a sputtering method, an arc method, an ion plating method, a physical vapor deposition method (PVD) such as an ion beam, and CVD. Of these, the sputtering method, the arc method, and the ion plating method are particularly preferably used.

  In addition, the coating layer having a color tone different from that of the coloring layer is composed of a lower layer made of a gold strike plating film formed by a wet plating method and an upper layer made of a gold or gold alloy plating film formed by a wet plating method. It may be a structure. In this case, the thickness of the lower layer is usually 0.05 to 0.2 μm, preferably 0.05 to 0.1 μm, and the thickness of the upper layer is usually 1.0 to 10 μm, preferably 1.0 to 3.0 μm. It is.

  Such a decorative article having a coating film having a color tone different from that of the coloring layer on the surface of the coloring layer can be produced, for example, by the following method. First, a barrier layer and an underlayer are formed on the surface of a decorative material substrate, and after the color forming layer is formed on the surface of the underlayer, a masking treatment is applied to a part of the surface of the color developing layer. A plating film having a color tone different from that of the coloring layer is formed on the surface by a dry plating method or a wet plating method, and then the mask and the plating film on the mask are removed at least once, thereby having a stainless steel color tone. An outermost layer film having two or more color tones, which is composed of a white film and at least one plating film having a color tone different from that of the white film, can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.

First, a watch case base material and a watch band base material obtained by machining stainless steel (SUS316L) were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining. Next, the substrate is immersed in a plating solution having the following composition and electroplated under the following plating conditions to form a gold (or gold alloy) strike plating film layer having a thickness (0.1 μm) on the substrate surface. , Washed with water.
《Gold strike plating》
<Composition of plating solution>
Gold 3-5g / l
Sulfuric acid 10g / l
<Plating conditions>
pH 0.3 or more and less than 1 Liquid temperature 25 ° C
Current density (Dk) 3-5 A / dm ²
Time 30 seconds Next, the base material having the gold strike plating film is immersed in a plating solution having the following composition and electroplated under the following plating conditions to form a rhodium barrier layer having a thickness of 1.5 μm on the surface of the gold strike plating film. And washed with water.
<Rhodium plating>
<Composition of plating solution>
Sulfuric acid 60g / l
Rhodium 5-6g / l
<Plating conditions>
pH 0.3 to less than 1 Liquid temperature 45 ° C
Current density (Dk) 1-2 A / dm ²
Time 15 minutes Brightening agent Appropriate amount Next, these substrates were mounted in an ion plating apparatus, and the substrate surface was bombard cleaned in an argon atmosphere.

Next, a titanium plating film (underlayer) having a thickness of 0.05 μm was formed on the surface of these barrier layers by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 200-500 mA
Gas: Argon gas Deposition pressure: 0.004 to 0.009 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 50V
Filament voltage: 7V

Next, a titanium carbide plating film (abrasion resistant layer) having a thickness of 0.6 μm is formed on the surface of the titanium plating film formed on the surface of the base material by the ion plating method (hot cathode method) as described below. Formed under conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 300 mA
Gas: Methane gas Deposition pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V

Subsequently, a mixed plating film (mixed layer) of titanium carbide and platinum having a white color tone with a thickness of 0.05 μm is formed on the surface of the titanium carbide plating film formed on the surface of these substrates by an ion plating method (hot cathode method). Was formed under the following film forming conditions.
<Film formation conditions>
Evaporation source: titanium, platinum Electron gun: 10 kV, 300 mA (evaporation source: titanium),
10 kV, 500 mA (evaporation source: platinum)
Gas: Methane gas Deposition pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -50V
Anode voltage: 60V
Filament voltage: 7V

Next, a platinum coating (outermost layer) having a white color tone of 0.005 μm in thickness is formed on the surface of the mixed plating coating of titanium carbide and platinum formed on the surface of these substrates by the ion plating method (hot cathode method). Thus, a stainless steel-colored watch case and a watch band were obtained.
<Film formation conditions>
Evaporation source: Platinum Electron gun: 10 kV, 500 mA
Gas: Argon gas Film forming pressure: 0.2 Pa
Acceleration voltage (bias voltage): Ground to -50V
Anode voltage: 60V
Filament voltage: 7V
Surface hardness (Hv; micro Vickers hardness tester, 5 g load, holding time 10 seconds) of the platinum coating (including wear-resistant layer + mixed layer) formed on the surface of the watch case and watch band obtained as described above ) Was 1400. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  In addition, the color evaluation of the coloring layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2.0, 4.0 <b * <5. 0.

First, a watch case base material and a watch band base material obtained by machining stainless steel (SUS316L) were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining. Next, the substrate is immersed in a plating solution having the following composition and electroplated under the following plating conditions to form a gold (or gold alloy) strike plating film layer having a thickness (0.1 μm) on the substrate surface. , Washed with water.
《Gold strike plating》
<Composition of plating solution>
Gold 3-5g / l
Sulfuric acid 10g / l
<Plating conditions>
pH 0.3 or more and less than 1 Liquid temperature 25 ° C
Current density (Dk) 3-5 A / dm ²
Time 30 seconds Next, the substrate having the gold strike plating film is immersed in a plating solution having the following composition, electroplated under the following plating conditions, and a rhodium barrier layer having a thickness of 1.5 μm is formed on the surface of the gold strike plating film. And washed with water.
<Rhodium plating>
<Composition of plating solution>
Sulfuric acid 60g / l
Rhodium 5-6g / l
<Plating conditions>
pH 0.3 to less than 1 Liquid temperature 45 ° C
Current density (Dk) 1-2 A / dm ²
Time 15 minutes Brightening agent Appropriate amount Next, these substrates were mounted in an ion plating apparatus, and the substrate surface was bombard cleaned in an argon atmosphere.

Next, a titanium plating film (underlayer) having a thickness of 0.05 μm was formed on the surface of these barrier layers by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 200-500 mA
Gas: Argon gas Deposition pressure: 0.004 to 0.009 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 50V
Filament voltage: 7V

Next, a titanium carbide plating film (abrasion resistant layer) having a thickness of 0.6 μm is formed on the surface of the titanium plating film formed on the surface of the base material by the ion plating method (hot cathode method) as described below. Formed under conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 300 mA
Gas: Mixed gas of methane gas and argon gas Deposition pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V

Next, a platinum coating (outermost layer) having a white color tone of 0.005 μm in thickness is formed on the surface of the titanium carbide plating coating formed on the surface of these substrates by the ion plating method (hot cathode method) under the following film forming conditions. A stainless steel color watch case and watch band were obtained.
<Film formation conditions>
Evaporation source: Platinum Electron gun: 10 kV, 500 mA
Gas: Argon gas Deposition pressure: 0.2Pa
Acceleration voltage (bias voltage): Ground to -50V
Anode voltage: 60V
Filament voltage: 7V

  The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum coating (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is as follows: 1200. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  In addition, the color evaluation of the coloring layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2.0, 4.0 <b * <5. 0.

A plating film having a color tone different from that of the hard coating was formed on a part of the surface of the stainless steel hard coating (platinum coating) obtained in the same manner as in Example 2 by a dry plating method.
That is, a titanium plating film having a thickness of 0.05 μm was formed on the surface of the hard film by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 200-500 mA
Gas: Argon gas Deposition pressure: 0.2Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 40-50V
Filament voltage: 7V

Next, a titanium nitride plating film exhibiting a gold color with a thickness of 0.6 μm was formed on the surface of the titanium plating film by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 200-500 mA
Gas: Mixed gas of argon gas and nitrogen gas Film forming pressure: 0.2 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 40-50V
Filament voltage: 7V

Next, a gold-iron alloy plating film having a gold color with a thickness of 0.1 μm was formed on the surface of the titanium nitride plating film by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Gold-iron alloy Electron gun: 8 kV, 500 mA
Gas: Argon gas Deposition pressure: 0.26 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 10-30V
Filament voltage: 7V

Next, a part of the surface of the gold-iron alloy plating film is subjected to masking (using an epoxy resist as a mask material), and the gold-iron alloy plating film, titanium nitride plating film and titanium plating film are sequentially removed with an etching solution. Finally, the mask was removed to obtain a watch case and a watch band having two outermost layer coatings of different colors, each consisting of a stainless steel-colored hard coating and a gold-colored gold-iron alloy plating coating.

In addition, as a stripping solution for the gold-iron alloy plating film, a stripping solution containing cyan as a main component and containing an oxidizing agent is used. As a stripping solution for a titanium nitride plating film and a titanium plating film, nitric acid is used as a main component. Was used, and methylene chloride was used as a mask remover.
The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum coating (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is as follows: The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the gold-iron alloy plating film (including the titanium nitride plating film) was 1000. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  The color evaluation of the outermost layer (white coating) constituting the color developing layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2. It was 0, 4.0 <b * <5.0.

A plating film having a color tone different from that of the hard coating was formed on a part of the surface of the stainless steel-colored hard coating (platinum coating) obtained in the same manner as in Example 3.
That is, the substrate on which the hard film was formed was cleaned by performing electrolytic degreasing, neutralization, and water washing as pretreatment.

Next, the substrate having the hard coating was immersed in a plating solution having the following composition and electroplated under the following plating conditions to form a gold strike plating coating having a thickness of 0.1 μm on the surface of the hard coating and washed with water. .
《Gold strike plating》
<Composition of plating solution>
Gold 3-5g / l
Sulfuric acid 10g / l
<Plating conditions>
pH 0.3 or more and less than 1 Liquid temperature 25 ° C
Current density (Dk) 3-5 A / dm ²
Time 30 seconds

Next, the substrate having the gold strike plating film is immersed in a plating solution having the following composition, and electroplated under the following plating conditions to form a gold-iron alloy plating film having a thickness of 3.0 μm on the surface of the gold strike plating film. And washed with water.
《Gold-iron alloy plating》
<Composition of plating solution>
Gold 4.6g / l
Iron 0.6g / l
Indium 3.5g / l
Appropriate amount of brightener <Plating conditions>
pH 3.5-3.7
Bath temperature 37-40 ° C
Current density (Dk) 1.0 to 1.5 A / dm ²
30 minutes

  Next, a part of the surface of the gold-iron alloy plating film is subjected to a masking process, the gold-iron alloy plating film and the gold strike plating film are sequentially removed with an etching solution, and finally the mask is removed, thereby obtaining a stainless steel color. Thus, a watch case and a watch band having two outermost layer coatings having different color tones comprising a hard coating and a gold-iron alloy plating coating of gold were obtained.

  In addition, as a stripping solution for the gold-iron alloy plating film and the gold strike plating film, a stripping solution containing cyan as a main component and an oxidizing agent was used, and methylene chloride was used as a mask stripping solution. The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum coating (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is 1100. The surface hardness (Hv; micro Vickers hardness tester, 5 g load, holding time 10 seconds) of the gold-iron alloy plating film was 120. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  The color evaluation of the outermost layer (white coating) constituting the color developing layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2. It was 0, 4.0 <b * <5.0.

In part of the surface of the hard coating (platinum coating) of stainless steel color obtained in the same manner as in Example 3,
A plating film having a color tone different from that of the hard film was formed by a dry plating method. That is, after a mask material (epoxy resist) is applied to a part of the hard coating surface and dried, a 0.05 μm-thick titanium plating coating is sputtered on the hard coating surface and the mask material surface (magnetron sputtering method). Was formed under the following film forming conditions.
<Film formation conditions>
Target: Titanium Sputtering gas: Argon gas Deposition pressure: 0.02 Pa
Target applied power: 0.3 to 0.5 kW
Bias voltage (acceleration voltage): -50 to -100V

Next, a silicon plating film having a thickness of 0.1 μm was formed on the surface of the titanium plating film by a sputtering method (magnetron sputtering method) under the following film forming conditions.
<Film formation conditions>
Target: Silicon Sputtering gas: Argon gas Deposition pressure: 0.05Pa
Target applied power: 0.3 to 0.5 kW
Bias voltage (acceleration voltage): -50 to -100V

Next, a black diamond-like carbon (DLC) plating film having a thickness of 0.1 μm was formed on the surface of the silicon plating film by plasma CVD (Chemical Vaper Deposition) under the following film formation conditions.
<Film formation conditions>
Gas: Benzene Deposition pressure: 0.2Pa
Filament current: 20A
Anode current: 2.0A
Cathode voltage (acceleration voltage): -1.0 to -5.0 kV

  Next, the masking material is peeled off with methylene chloride, and the titanium plating film, silicon plating film, and DLC film formed immediately above the masking material are lifted off to form a stainless steel-colored hard film and a black DLC plating film. A watch case and a watch band having an outermost layer coating having two different colors were obtained.

  The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum coating (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is as follows: The surface hardness (Hv; micro Vickers hardness tester, 5 g load, holding time 10 seconds) of the DLC plating film was 1,800. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  The color evaluation of the outermost layer (white coating) constituting the color developing layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2. It was 0, 4.0 <b * <5.0.

First, a wristwatch case base material and a wristwatch band base material obtained by machining stainless steel were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining. Next, the substrate is immersed in a plating solution having the following composition, and electroplated under the following plating conditions to form a gold (or gold alloy) strike plating film layer having a thickness of 0.1 μm on the substrate surface, and washed with water. did.
《Gold strike plating》
<Composition of plating solution>
Gold 3-5g / l
Sulfuric acid 10g / l
<Plating conditions>
pH 0.3 or more and less than 1 Liquid temperature 25 ° C
Current density (Dk) 3-5 A / dm ²
Time 30 seconds Next, the base material having the gold strike plating film was immersed in a plating solution having the following composition, and electroplated twice under the following plating conditions to obtain a total thickness of 1.5 μm (first time A rhodium barrier layer was formed on the surface of the gold strike plating film and washed with water. The plating was formed with a thickness of 1.0 μm and washed with water, and then the second plating was formed with a thickness of 0.5 μm. The reason why the barrier layer was formed twice was to reduce the number of fine pinholes in the barrier layer as much as possible.
<Rhodium plating>
<Composition of plating solution>
Sulfuric acid 60g / l
Rhodium 5-6g / l
Appropriate amount of brightener <Plating conditions>
pH 0.3 to less than 1 Liquid temperature 45 ° C
Current density (Dk) 1-2 A / dm ²
Time 1st: 10 minutes, 2nd: 5 minutes Next, these substrates were mounted in a sputtering apparatus, and the substrate surface was bombarded cleaned in an argon atmosphere.

Subsequently, a zirconium film (underlayer) having a thickness of 0.05 μm was formed on the surface of these base materials by a sputtering method (magnetron sputtering method) under the following film forming conditions.
<Film formation conditions>
Target: Zirconium sputtering Gas: Argon gas Deposition pressure: 0.5 Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V

Next, a zirconium carbide plating film (abrasion resistant layer) having a white color tone with a thickness of 0.6 μm is formed on the surface of the zirconium plating film formed on these substrate surfaces by sputtering (magnetron sputtering method) under the following film formation conditions. Formed.
<Film formation conditions>
Target: Zirconium sputtering Sputtering gas: Mixed gas of methane gas and argon gas Deposition pressure: 0.665 Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V

Then, on the surface of the zirconium carbide plating film formed on these substrate surfaces,
A platinum film (outermost layer) having a white color tone of 0.005 μm in thickness was formed by sputtering (magnetron sputtering method) under the following film forming conditions to obtain a stainless steel-colored watch case and watch band.
<Film formation conditions>
Target: Platinum Sputtering gas: Argon gas Deposition pressure: 0.2Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V
The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum coating (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is as follows: 1300. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

  In addition, the color evaluation of the coloring layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2.0, 4.0 <b * <5. 0.

First, a watch case base material and a watch band base material obtained by machining stainless steel (SUS316L) were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining. Next, the substrate is immersed in a plating solution having the following composition, and electroplated under the following plating conditions to form a gold (or gold alloy) strike plating film layer having a thickness of 0.1 μm on the substrate surface, and washed with water. did.
《Gold strike plating》
<Composition of plating solution>
Gold 3-5g / l
Sulfuric acid 10g / l
<Plating conditions>
pH 0.3 or more and less than 1 Liquid temperature 25 ° C
Current density (Dk) 3-5 A / dm ²
Time 30 seconds Next, the base material having the gold strike plating film is immersed in a plating solution having the following composition and electroplated under the following plating conditions to form a gold-iron alloy barrier layer having a thickness of 1.5 μm as a gold strike. It was formed on the surface of the plating film and washed with water.
《Gold-Iron Plating》
<Composition of plating solution>
Gold 4.6g / l
Iron 0.6g / l
Indium 3.5g / l
Appropriate amount of brightener <Plating conditions>
pH 4.7
Liquid temperature 50 ℃
Current density (Dk 1.0 A / dm ²
15 minutes

Next, these substrates were mounted in a sputtering apparatus, and the substrate surface was bombarded cleaned in an argon atmosphere.

Next, a titanium carbide plating film (underlayer) having a gradient structure with a carbon atom content of 5 to 15 atomic% having a thickness of 0.05 μm is formed on the surface of the barrier layer of these substrates by an ion plating method (hot cathode method). It formed on the following film-forming conditions.
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 200-500 mA
Gas: Mixed gas of argon gas and methane gas Film forming pressure: 0.004 to 0.009 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 50V
Filament voltage: 7V

Next, a titanium carbide plating film (abrasion resistant layer) having a white color tone with a thickness of 0.6 μm and a carbon atom content of 40 ± 10 atomic% is formed on the surface of the titanium carbide plating film formed on the surface of these base materials. The film was formed under the following film forming conditions by an ion plating method (hot cathode method).
<Film formation conditions>
Evaporation source: Titanium Electron gun: 10 kV, 300 mA
Gas: Mixed gas of methane gas and argon gas Deposition pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V

Next, a platinum coating (outermost layer) having a white color tone of 0.005 μm in thickness is formed on the surface of the titanium carbide plating coating formed on the surface of these substrates by the ion plating method (hot cathode method) under the following film forming conditions. A stainless steel color watch case and watch band were obtained.
<Film formation conditions>
Evaporation source: Platinum Electron gun: 10 kV, 500 mA
Gas: Argon gas Deposition pressure: 0.2Pa
Acceleration voltage (bias voltage): Ground to -50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness (HV; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum film (including the wear-resistant layer) formed on the surface of the watch case and watch band obtained as described above is: 1200. These watch cases and watch bands are excellent in scratch resistance, and have a white coat with a high-class feeling close to a stainless steel coat.

In addition, the color evaluation of the coloring layer by the L *, a *, b * display system (CIE surface system) is 82 <L * <85, 0 <a * <2.0, 4.0 <b * <5. 0. Further, the wristwatch case and wristband obtained as described above and the wristwatch case and wristband obtained in Example 2 were each subjected to a scratch test, and the adhesion of the coating to the base material was compared. The measuring instrument used for the scratch test is a HEIDON-14 type surface property measuring instrument.

  Hereinafter, a decorative part sample of Example 2 having a base layer made of a titanium plating film and a titanium carbide plating film (a wear-resistant layer) having a white color tone with a carbon atom content of 40 ± 10 atomic%, and a carbon atom content of 5 to 5 A decorative part sample of Example 7 having a base layer made of a titanium carbide plating film of 15 atomic% and a titanium carbide plating film (abrasion resistant layer) having a white color tone with a carbon atom content of 40 ± 10 atomic% was prepared and coated. The adhesion force (critical load described later) was measured.

  The measurement conditions were such that a diamond indenter with a tip angle of 90 ° and a tip curvature radius of 50 μm was used, the scratching speed was 30 mm / min, and the scratching load was changed from 50 gf to 300 gf every 50 gf. This measurement result shows that the resistance value changes abruptly when the scratch load exceeds a certain value due to the scratch load and the resistance value after scratching. This is because the scratch resistance value increases linearly as the load increases, but when the critical load is exceeded, cracks occur in the coating formed on the substrate and chipping peeling occurs. . Then, due to the generated cracks and chipping peeling, the scratch resistance value increases rapidly, and the friction coefficient increases. The adhesion force of the film to the substrate can be evaluated by the value of the critical load. Here, the point of the scratch load which changed rapidly was observed with an optical microscope, and the adhesion strength of the coating was evaluated.

  In Example 2, chipping peeling occurred when the scratch load was 200 gf. On the other hand, in Example 7, chipping peeling occurred when the scratch load was 250 gf. That is, the critical load in Example 2 was 200 gf, and the critical load in Example 7 was 250 gf. From this, it is understood that the decorative part of Example 7 has a coating adhesion strength of 25% higher than that of the decorative part of Example 2.

Next, the same coating as in Examples 1 to 7 was formed on a test piece of stainless steel (SUS316L, dimension (mm): 20 (diameter) × 1 (thickness)), and each test piece was made into a small desiccator ( The test was performed under the following conditions.
In addition, the test piece which remove | excluded the barrier layer from the sample of Example 1 was made as a comparative sample (the place which does not have a barrier layer differs from Example 1), and tested simultaneously.
"Test method"
<Artificial sweat composition>
Sodium chloride 0.5% (m / m)
Lactic acid 0.1% (m / m)
Urea 0.1% (m / m)
Amount necessary to adjust ammonium pH to 6.5-The amount of artificial sweat per unit area shall be ml / cm ² .
<Test conditions>
A small desiccator is placed in a thermostatic bath and maintained at 30 ± 2 ° C. for 168 hours.

上記ニッケルの溶出量の分析は、試験が終わった各デシケータ内の液中に含まれるニッケル濃度を、誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ）で測定し、その後、試験片の表面積で換算したものである。

In the analysis of the nickel elution amount, the nickel concentration contained in the liquid in each desiccator after the test was measured with an inductively coupled plasma mass spectrometer (ICP-MS), and then converted into the surface area of the test piece. Is.

From the above test results (Table 1), according to the present invention, the elution amount of nickel is one order of magnitude less than that of the comparative example, and furthermore, in Example 6, it is two orders of magnitude less. . Further, as a German standard, a nickel elution amount of 0.5 μg / cm ² / week is used as a reference value, and a sample exceeding this reference value is rejected, and those below are accepted.

In Examples 1 to 7, the barrier layer is a rhodium alloy, a palladium alloy, a platinum alloy, a copper alloy, or a gold alloy, and the underlayer is chromium, hafnium, vanadium, or niobium. It goes without saying that a plating film made of hafnium carbide, vanadium carbide, niobium carbide or tungsten carbide can be formed as the layer, and a rhodium film, a rhodium alloy film, a palladium alloy film or a platinum alloy film can be formed as the outermost layer. In Examples 1-7, watch cases and wristbands are manufactured. Needless to say, the techniques described in Examples 1-7 can also be applied to decorative items such as necklaces, pendants, brooches and the like. .

Claims (51)

In a decorative article in which a coating film having a white color tone made of a noble metal or a noble metal alloy is formed by a dry plating method as an outermost layer, the decorative article base material made of stainless steel is formed on the surface of the base material by a wet plating method. A barrier layer; an underlayer formed on the surface of the barrier layer by a dry plating method; an abrasion-resistant layer formed on the surface of the underlayer by a dry plating method; and a surface of the wear-resistant layer by a dry plating method A color developing layer composed of an outermost layer formed, and the color developing layer is composed of a wear-resistant layer having a thickness of 0.2 to 1.5 μm and an outermost layer having a thickness of 0.002 to 0.1 μm. A decorative article having a white coating, characterized by being a hard white coating having 2. The white color according to claim 1, further comprising a strike plating film layer made of gold or a gold alloy formed by a wet plating method between the base material surface made of stainless steel and the barrier layer. A decorative article with a coating. 3. The decorative article having a white coating according to claim 2, wherein the strike plating coating layer is a coating having a thickness of 0.05 to 0.3 [mu] m formed by a wet plating method. The barrier layer formed on the surface of the base material made of stainless steel is a film made of rhodium (Rh), gold (Au) or chromium (Cr) formed by a wet plating method. A decorative article having a white coating according to claim 1. The barrier layer formed on the surface of the base material is a film made of at least one of rhodium alloy, palladium alloy, platinum alloy, copper alloy, and gold alloy formed by a wet plating method. A decorative article having the white coating according to claim 1. The said barrier layer is a film with a thickness of 0.3 to 3 μm formed by a wet plating method, and has a white film according to any one of claims 1, 2, and 4 to 5. Ornaments. Titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or a base layer formed on the surface of the barrier layer is formed by dry plating. 2. The decorative article having a white coating according to claim 1, wherein the decorative article is a coating made of tantalum (Ta). The underlayer formed on the surface of the barrier layer is formed by dry plating, and has a carbon atom content of 5 to 15 atomic percent titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, carbonized carbon. 2. The decorative article having a white coating according to claim 1, which is a metal compound coating made of tungsten or tantalum carbide. The decorative article having a white coating according to claim 1, wherein the underlayer is a coating having a thickness of 0.02 to 0.2 µm formed by a dry plating method. The wear-resistant layer is made of titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide (WC). 2. The decorative article having a white film according to claim 1, wherein the decorative article is a metal compound film made of tantalum carbide (TaC). The decorative article having a white coating according to claim 1 or 10, wherein the wear-resistant layer has a thickness of 0.5 to 1.0 µm. 2. The decorative article having a white coating according to claim 1, wherein the outermost layer is a coating made of platinum (Pt), palladium (Pd), or rhodium (Rh). 2. The decorative article having a white coating according to claim 1, wherein the outermost layer is a coating made of a platinum alloy, a palladium alloy, or a rhodium alloy. 14. The decorative article having a white coating according to claim 1, wherein the outermost layer has a thickness of 0.01 to 0.08 [mu] m. The mixed layer comprising a metal compound that forms the wear-resistant layer and a metal or an alloy that forms the outermost layer is provided between the wear-resistant layer and the outermost layer. The ornamental article which has the white film in any one of Claims 1-14. 16. The decorative article having a white coating according to claim 1, wherein the mixed layer has a thickness of 0.005 to 0.1 [mu] m. The color evaluation of the coloring layer by L *, a *, b * display system (CIE surface system) is 70 <L * <91, −0.1 <a * <3.0, 1.0 <b * <. It is 5.5, The decorative article which has a white film in any one of Claim 1, 12-14 characterized by the above-mentioned. 2. The underlayer, the wear-resistant layer, the mixed layer, and the outermost layer are formed by at least one of a sputtering method, an ion plating method, and an arc method. The ornament which has a white film in any one of Claims 8-17. A portion of the surface of the white coating film having a stainless steel color tone formed of the coloring layer has at least one coating film formed by a dry plating method or a wet plating method and having a color tone different from that of the coloring layer. A decorative article having a white coating according to any one of claims 1, 16, or 17. The decorative article having a white coating film according to claim 19, wherein the coating film having a color tone different from that of the coloring layer is made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). The white coating film according to claim 19, wherein the coating film different from the coloring layer has a two-layer structure of a lower layer made of titanium nitride, zirconium nitride or hafnium nitride and an upper layer made of gold or a gold alloy. Having ornaments. A titanium coating and a silicon coating formed on the surface of the titanium coating are provided between the coloring coating and a diamond-like carbon (DLC) coating that is a coating different from the coloring coating. Item 21. A decorative article having a white coating according to item 19 or 20. The outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and platinum (Pt), palladium (Pd) or rhodium (Rh). A decorative article having a white coating according to any one of the above. The outermost layer is a mixed layer made of a metal compound that forms the wear-resistant layer and a platinum alloy, a palladium alloy, or a rhodium alloy. A decorative product with a white coating. 25. A decorative article having a white coating according to claim 1, wherein the color developing layer has a surface hardness (Hv; micro Vickers hardness tester, 5 g load) of 700 to 2,000. . 26. The decorative article having a white coating according to claim 1, wherein the decorative article is a watch exterior part. In a method for manufacturing a decorative article in which a coating having a white color tone made of a noble metal or a noble metal alloy is formed by a dry plating method as an outermost layer, a base material for a decorative article is manufactured by various processing means using a material made of stainless steel. A step of forming a barrier layer on the surface of the substrate by a wet plating method, a step of forming an underlayer on the surface of the barrier layer by a dry plating method, and a metal compound by a dry plating method on the surface of the underlayer And forming a hard coloring layer having a stainless steel color by forming an outermost layer made of platinum or a platinum alloy by a dry plating method on the surface of the wear-resistant layer. A method for producing a decorative article having a white coating characterized by the above. 28. The decorative article having a white coating according to claim 27, wherein a strike plating coating layer made of gold or a gold alloy is formed between the substrate surface made of stainless steel and the barrier layer by a wet plating method. Production method. 29. The method for producing a decorative article having a white coating according to claim 28, wherein a coating having a thickness of 0.05 to 0.3 [mu] m is formed on the surface of the substrate as a strike plating coating by a wet plating method. 28. The decoration having a white coating according to claim 27, wherein a coating made of rhodium (Rh), gold (Au) or chromium (Cr) is formed on the surface of the base material by a wet plating method as the barrier layer. Product manufacturing method. 28. A film made of at least one of a rhodium alloy, a palladium alloy, a platinum alloy, a copper alloy, and a gold alloy is formed as a barrier layer on the surface of the base material by a wet plating method. A method for producing a decorative article having a white coating. 32. The decorative article having a white coating according to claim 27, 30 or 31, wherein a coating having a thickness of 0.3 to 3 [mu] m is formed on the surface of the substrate as the barrier layer by a wet plating method. Manufacturing method. Titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta) 28. The method for producing a decorative article having a white coating film according to claim 27, wherein the coating film is formed by a dry plating method. Titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or carbonized carbon having a carbon atom content of 5 to 15 atomic% on the surface of the barrier layer of the decorative article substrate. 28. The method for producing a decorative article having a white film according to claim 27, wherein the metal compound film made of tantalum is formed by a dry plating method. 35, 34 or 34, wherein a film having a thickness of 0.02 to 0.2 μm is formed on the surface of the barrier layer of the decorative article base material by a dry plating method as the underlayer. The manufacturing method of the ornament which has a white film of description. Titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC) as the wear-resistant layer on the surface of the base layer for the decorative article base material 28. The decorative article having a white coating according to claim 27, wherein a coating comprising a metal compound coating comprising niobium carbide (NbC), tungsten carbide (WC), or tantalum carbide (TaC) is formed by a dry plating method. Production method. 37. The white color according to claim 27 or 36, wherein a film having a thickness of 0.2 to 1.5 [mu] m is formed as a wear-resistant layer on the surface of the base layer of the decorative article base material by a dry plating method. A method for producing a decorative article having a coating. 28. A coating made of platinum (Pt), palladium (Pd) or rhodium (Rh) is formed on the surface of the wear-resistant layer of the decorative article base material by a dry plating method as the outermost layer. The manufacturing method of the ornament which has a white film of description. 28. The white coating according to claim 27, wherein a coating made of a platinum alloy, a palladium alloy or a rhodium alloy is formed on the surface of the wear-resistant layer of the decorative article base material by a dry plating method as the outermost layer. A method for manufacturing ornaments. The coating film having a thickness of 0.002 to 0.1 µm is formed as the outermost layer on the surface of the wear-resistant layer of the decorative article base material by a dry plating method. 39. A method for producing a decorative article having a white coating according to 39. The mixed layer comprising a metal compound that forms the wear-resistant layer and a metal or an alloy that forms the outermost layer is formed between the wear-resistant layer and the outermost layer. The manufacturing method of the ornament which has a white film in any one of Claims 36-40. The color evaluation of the coloring layer by L *, a *, b * display system (CIE surface system) is 70 <L * <91, −0.1 <a * <3.0, 1.0 <b * <. It is 5.5, The manufacturing method of the ornament which has a white film in any one of Claim 27 and Claim 38-41 characterized by the above-mentioned. The underlayer, the wear-resistant layer, the mixed layer, and the outermost layer are formed by at least one of a sputtering method, an ion plating method, and an arc method. The manufacturing method of the ornament which has a white film in any one of -41. 43. The method according to claim 42, wherein at least one coating different from the color tone of the coloring layer is formed on a part of the surface of the white coating having the color tone of the stainless steel made of the coloring layer by a dry plating method or a wet plating method. Item 44. A method for producing a decorative article having a white coating according to Item 43. 45. The manufacture of a decorative article having a white coating according to claim 44, wherein the coating different from the color tone of the coloring layer is made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride or diamond-like carbon (DLC). Method. 45. The white coating film according to claim 44, wherein a coating film having a two-layer structure of a lower layer made of titanium nitride, zirconium nitride or hafnium nitride and an upper layer made of gold or a gold alloy is formed as a coating different from the coloring layer. A method for producing a decorative article having 45. A titanium coating is formed between the coloring layer and a diamond-like carbon (DLC) coating, which is a coating different from the coloring layer, and a silicon coating is further formed on the surface of the titanium coating. Or the manufacturing method of the ornament which has a white film of 45. The outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and platinum (Pt), palladium (Pd), or rhodium (Rh). 47. A method for producing a decorative article having a white coating according to any one of 47. 48. The outermost layer is a mixed layer made of a metal compound forming the wear-resistant layer and a platinum alloy, a palladium alloy, or a rhodium alloy. A method for producing a decorative article having a white coating. The method for producing a decorative article having a white coating according to any one of claims 27 to 49, wherein the color developing layer has a surface hardness (Hv; micro Vickers hardness meter, 5 g load) of 700 to 2,000. 51. The method for manufacturing a decorative article having a white coating according to claim 27, wherein the decorative article is a watch exterior part.