JP2007162141A - Accessory having white coating film and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an accessory which shows a sense of quality, has excellent scratch resistance, hardly degrades appearance quality due to a damage or the like, and has a white coating film showing a sense of quality like a coating film of stainless steel. <P>SOLUTION: The accessory having the white coating film has the outermost coating layer which is made from a precious metal or a precious metal alloy, shows a white color tone and is formed by a dry plating method, and comprises: a base material for the accessory made from a metal or a ceramic; an underlayer formed on the surface of the base material; and a coloring layer consisting of an abrasion-resistant layer formed on the surface of the underlayer by a dry plating method, and the outermost layer formed on the surface of the abrasion-resistant layer by a dry plating method. The coloring layer is the hard white coating film which shows a color tone of stainless steel and is formed of the abrasion-resistant layer with a thickness of 0.2 to 1.5 μm and the outermost layer with a thickness of 0.002 to 0.1 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative article having a white coating and a method for producing the same, and more particularly to a decorative article having a hard, stainless steel color 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 prepared using this copper alloy as a raw material has poor corrosion resistance, a plating film is applied to the surface of the base material 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. When the outermost layer 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 a palladium plating film, a palladium alloy plating film or a rhodium plating film. Etc. are 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. Further, 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, as a white jewelry, in Japanese Patent Application Laid-Open No. 3-120355, a white jewelry in which a metal base material surface is coated with a white hard film and a platinum or platinum alloy film formed on the film surface. Disclosed. However, the white film formed on such a jewelry can provide a high-class feeling, but the white tone specific to stainless steel required in the market cannot be obtained. In addition, as a decorative article having a white coating, in the specification of Japanese Patent Application No. 2000-192077 (filed on June 27, 2000, unpublished), on the surface of a decorative article made of metal (including an alloy), particularly a metal having poor corrosion resistance. A low-cost decorative article having a white-colored stainless steel coating that is inexpensive and excellent in long-term corrosion resistance, and a method for producing the same are disclosed.

  The disclosed content is a decorative article in which the surface of a decorative substrate made of metal is coated with a stainless steel film having a white color tone by a dry plating method. In addition, a decorative substrate made of a copper alloy or the like that is inferior in functional quality such as corrosion resistance is coated with a nickel plating film by a wet plating method as a base plating film, or by titanium plating, zirconium carbide, etc. by a dry plating method Then, the surface of the base plating film is coated with a stainless steel film by a dry plating method.

  However, since the white film formed on such a decorative article is simply formed with a stainless steel film on the outermost layer, that is, the noble metal film is not formed on the outermost layer, the decorative article lacks a profound feeling, The surface quality was high-quality. In addition, depending on the type of base material for decorative goods and the type of the base plating film, there is a problem that the hardness is low, scratches are easily generated, and the appearance quality is deteriorated in a short time.

Accordingly, there is a demand for the appearance of a decorative article having a high-quality white film having a high-class feeling close to that of a stainless steel film and a method for producing the same, which has a high-quality feeling and hardly deteriorates in appearance quality due to scratches and the like.
Japanese Patent Laid-Open No. 3-120355

  The present invention is intended to solve the above-described problem, and has a high-grade feeling, appearance quality deterioration due to scratches and the like hardly occurs, and a decorative article having a high-grade white coating close to a stainless steel coating And it aims at providing the manufacturing method.

A decorative article having a white coating according to the present invention is:
In a decorative article in which a 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,
A decorative substrate made of metal or ceramics;
An underlayer formed on the surface of the substrate;
A wear-resistant layer formed on the surface of the underlayer by a dry plating method, and a coloring layer consisting of an outermost layer formed on the surface of the wear-resistant layer by a dry plating method,
The color-developing layer is a hard white film having a stainless steel color tone and comprising 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. However, when the outermost layer is a platinum film or a platinum alloy film, the thickness of the film is 0.002 to 0.01 μm.

The metal used as the material for the decorative article base material is usually made of at least one metal (including an alloy) selected from the group consisting of stainless steel, titanium, titanium alloy, copper, copper alloy, and tungsten carbide.
The ceramic material used as the base material for the decorative article is usually made of zirconia ceramics, and contains a stabilizer having a composition of yttrium oxide (Y ₂ O ₂ ), magnesium oxide (MgO) or calcium oxide (CaO). Stabilized zirconia containing 3 to 7% by weight, which exhibits a white color tone.

In the decorative article having a white coating according to the present invention, when the decorative article base material is made of a metal other than copper and a copper alloy, or a ceramic, the base layer formed on the surface of the base material is dry-plated. It is desirable that the coating is made of titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), or tantalum (Ta). Further, 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) as an abrasion resistant layer, When forming a metal compound film made of tungsten carbide (WC) or tantalum carbide (TaC), the base layer is formed by a dry plating method from the viewpoint of further improving the adhesion between the base material and the wear-resistant layer. Further, 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 the case where the decorative article base material is made of a metal other than copper and a copper alloy, or ceramics, the base layer is preferably a film having a thickness of 0.02 to 0.2 μm formed by a dry plating method.
Moreover, in the decorative article having a white film according to the present invention, when the decorative article base material is made of copper or a copper alloy, the base layer is formed on the surface of the base material by a wet plating method. It is preferably composed of a 10 μm nickel coating and an amorphous nickel-phosphorus alloy coating having a thickness of 3 to 10 μm formed on the surface of the nickel coating by a wet plating method.

From the viewpoint of preventing nickel allergy, when the decorative article base material is made of copper or a copper alloy, the base layer is formed by wet plating, copper, palladium, copper-tin alloy, copper- It is preferable that the coating film has a thickness of 2 to 9 μm and comprises at least one selected from the group consisting of a tin-zinc alloy and copper-tin-palladium.
The wear-resistant layer includes titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide (WC). Alternatively, a metal compound film made of 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.
The outermost layer is preferably a film made of at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof.

The outermost layer has a thickness of 0.002 to 0.1 μm, preferably 0.005 to 0.1 μm, and more preferably 0.01 to 0.08 μm.
The decorative article having a white coating according to the present invention is a mixed layer comprising a metal compound forming the wear-resistant layer and a metal or alloy forming the outermost layer between the wear-resistant layer and the outermost layer. You may have.

The color evaluation by L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
It is desirable that 70 <L * <91, −0.1 <a * <3.0, and 1.0 <b * <5.5.
The underlayer, the wear-resistant layer, the mixed layer, and the outermost layer are preferably formed by at least one of a sputtering method, an ion plating method, and an arc method.

The decorative article having a white coating according to the present invention is formed on a part of the surface of the white coating having a stainless steel color tone formed of the color developing layer, and is formed at least different from the color tone of the color developing layer formed by a dry plating method or a wet plating method. You may have one film.
The coating different from the color tone of the coloring layer is preferably made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). 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.

Further, this decorative article has a titanium coating and a silicon coating formed on the surface of the titanium coating between the coloring layer and a diamond-like carbon (DLC) coating which is a coating different from the coloring layer. May be.
In the decorative article having a white coating according to the present invention, the outermost layer includes a metal compound that forms the wear-resistant layer, platinum (Pt), palladium (Pd), rhodium (Rh), and an alloy thereof. It may be a mixed layer composed of at least one selected.

In the decorative article having a white coating according to the present invention, 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.
The ornament having the white coating according to the present invention may be a watch exterior part.
The method for producing a decorative article having a white coating according to the present invention is as follows.
In the method of 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,
Using a material made of metal or ceramics to produce a base material for decorative goods by various processing means;
Forming a base layer on the substrate surface by a dry plating method or a wet plating method;
By forming a wear resistant layer made of a metal compound on the surface of the underlayer by a dry plating method, and further forming an outermost layer made of platinum or a platinum alloy on the surface of the wear resistant layer by a dry plating method, And a step of obtaining a hard coloring layer having the above.

The metal used as the material for the decorative article base material is usually made of at least one metal selected from the group consisting of stainless steel, titanium, titanium alloy, copper, copper alloy, and tungsten carbide.
When the material for the decorative article is ceramic, the stabilized zirconia powder containing 3 to 7% by weight of a stabilizer of yttrium oxide (Y ₂ O ₂ ), magnesium oxide (MgO) or calcium oxide (CaO). A material containing 20 to 25 parts by weight of a binder with respect to 100 parts by weight is formed by injection molding, and then formed by roughing, degreasing, firing, grinding and polishing processes by machining, and exhibits a white color tone. Yes.

  When the base material for decorative articles is made of a metal other than copper and copper alloy, or ceramics, titanium (Ti), chromium (Cr), zirconium (Zr), hafnium ( It is desirable to form a film made of Hf), vanadium (V), niobium (Nb), or tantalum (Ta) by a dry plating method.

When the base material for ornaments is made of a metal other than copper and copper alloy, or ceramics, a film having a thickness of 0.02 to 0.2 μm is formed on the surface of the base material as the base layer by a dry plating method. Is desirable.
When the decorative article base material is made of copper or a copper alloy, a nickel film having a thickness of 1 to 10 μm is formed on the surface of the base material as a base layer by a wet plating method. It is preferable to form a 10 μm amorphous nickel-phosphorus alloy film by a wet plating method.

  Further, from the viewpoint of preventing nickel allergy, when the decorative article base material is made of copper or a copper alloy, copper, palladium, copper-tin alloy, copper-tin are used as the base layer on the surface of the base material. -It is preferable to form a 2-9 micrometer-thick film which consists of at least 1 chosen from the group which consists of a zinc alloy and copper-tin-palladium by a wet plating method.

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

The outermost layer is preferably a film made of at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof.
The thickness of the outermost layer is usually 0.002 to 0.1 μm, preferably 0.005 to 0.1 μm, and more preferably 0.01 to 0.08 μm. However, when the outermost layer is a platinum film or a platinum alloy film, the thickness of the film is 0.002 to 0.01 μm, preferably 0.005 to 0.01 μm.

In the present invention, a mixed layer comprising a metal compound that forms the wear-resistant layer and a metal or alloy that forms the outermost layer may be formed between the wear-resistant layer and the outermost layer.
In the method for producing a decorative article having a white coating according to the present invention, the color evaluation of the coloring layer by L *, a *, b * display system (CIE surface system)
It is desirable that 70 <L * <91, −0.1 <a * <3.0, and 1.0 <b * <5.5. Among these, it is preferable that 75 <L * <85, 0 <a * <2.0, and 3.5 <b * <5.0.

The underlayer, the wear-resistant layer, the mixed layer, and the outermost layer are preferably formed by at least one of a sputtering method, an ion plating method, and an arc method.
In the method for producing a 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 applied to a part of the surface of the white coating having the stainless steel color tone composed of the coloring layer by a dry plating method or a wet method. It can be formed by a plating method.

  The coating different from the color tone of the coloring layer is preferably made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). In addition, as the 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.

Furthermore, a titanium film may be formed between the coloring layer and a diamond-like carbon (DLC) film that is a film different from the coloring layer, and a silicon film may be formed on the surface of the titanium film.
The outermost layer is a mixed layer comprising a metal compound forming the wear-resistant layer and at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof. Also good.

In the decorative product obtained by the method for manufacturing a decorative product having a white coating according to the present invention, 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 it is 1000-2000.
The ornament obtained by the method for producing an ornament having a white coating according to the present invention may be a watch exterior part.

  According to the present invention, a decorative article having a high-class white coating that has a high-class feeling, is hard and excellent in scratch resistance, hardly deteriorates in appearance quality due to scratches, and is close to a stainless steel coating, and its A manufacturing method 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 composed of a decorative article base material, a base layer, and a coloring layer. 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. .
Decorative article base material The decorative article base material used in a decorative article having a white coating according to the present invention is a base material formed of metal or ceramics.

Specific examples of the metals (including alloys) include stainless steel, titanium, titanium alloys, copper, copper alloys, and tungsten. These metals can be used alone or in combination of two or more.
Specific examples of the ceramics include zirconia ceramics. This zirconia ceramic is a stabilized zirconia having a composition of 3 to 7% by weight of yttrium oxide (Y ₂ O ₂ ) or another stabilizer (for example, magnesium oxide (MgO), calcium oxide (CaO)), and has a white color tone. Presents. More specifically, this zirconia ceramic is composed of zirconia and a binder as main components, and 20 to 25 binders per 100 parts by weight of stabilized zirconia powder containing 3 to 7% by weight of a stabilizer such as yttrium oxide. It contains parts by weight and exhibits a white color tone after firing. As the binder, for example, a mixture of at least two selected from the group consisting of polyethylene, polypropylene, polystyrene, ethylene vinyl acetate, butyl methacrylate, polyacetal, wax and stearic acid is preferable.

  In the present invention, the reason for selecting zirconia ceramics containing 3 to 7% by weight of a stabilizer such as yttrium oxide (yttria) is that if the stabilizer such as yttria is less than 3% by weight, the impact resistance of the molded zirconia ceramics The resistance decreases (becomes brittle), and it is easy for cracks to occur due to external impact, and even if the stabilizer exceeds 7% by weight, impact resistance decreases, and cracks occur due to external impact. This is because it becomes easy to occur. When the stabilizer is within the above range, the crystal structure of zirconia ceramics is a two-phase mixed structure of cubic and monoclinic crystals, so that the impact resistance is considered to be stable.

  In addition, the binder content is set to 20 to 25 parts by weight with respect to 100 parts by weight of zirconia powder. When the binder is less than 20 parts by weight, the injection molding becomes worse and the material is completely filled in the mold. This is because if the amount is more than 25 parts by weight, the degreasing process takes time and the mass productivity is deteriorated, and the molded shape is easily broken.

The base material for decorative articles made of metal is prepared from the above-described 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.
Further, a decorative article base material made of ceramics, for example, a watch case base material, is made by forming a molded article having a watch case shape by injection molding using a material mainly composed of zirconia and a binder. It is manufactured by roughing by machining, further degreasing and firing the roughened molded body to make a rough base material for a watch case, and then machining the rough base material by grinding and polishing. .

  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, it is preferable to wash and degrease the surface of the decorative article substrate in advance with a conventionally known organic solvent or the like before forming the base layer on the surface of the decorative article substrate.
Underlayer The underlayer constituting the decorative article having a white coating according to the present invention comprises at least one plated coating formed by a wet plating method and / or a dry plating method.

  When the base material for decoration is made of a metal other than copper and copper alloy, or ceramics, the underlying layer formed on the surface of the base material is titanium (Ti) or chromium (Cr) formed by a dry plating method. A metal coating made of zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta) is desirable.

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.

The thickness of these metal coating and metal compound coating (underlayer) is preferably 0.02 to 0.2 μm, and particularly preferably 0.05 to 0.1 μm.
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.

  Moreover, in the decorative article having a white coating according to the present invention, when the decorative article base material is made of copper or a copper alloy, the base layer has a thickness of 1 to 10 μm formed on the surface of the base material by a wet plating method, Preferably, it is composed of a nickel film having a thickness of 1 to 5 μm and an amorphous nickel-phosphorus alloy film having a thickness of 3 to 10 μm, preferably 3 to 5 μm, formed on the surface of the nickel film by a wet plating method.

  From the viewpoint of preventing nickel allergy, when the decorative article base is made of copper or a copper alloy, the base layer is formed by wet plating, copper, palladium, copper-tin alloy, copper-tin- It is preferable that the coating film has a thickness of 2 to 9 [mu] m, preferably 2 to 3 [mu] m, made of at least one selected from the group consisting of zinc alloys and copper-tin-palladium alloys.

Color-forming layer The color-forming layer constituting the decorative article having a 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 at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh) and alloys thereof 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 as follows.
It is desirable that 70 <L * <91, −0.1 <a * <3.0, and 1.0 <b * <5.5. 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 table system) color evaluation,
85 <L * <90, 0 <a * <2.0, 3.5 <b * <5.0,
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.

Moreover, 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 The decorative article having the white coating according to the present invention has a dry plating method or at least one coating different from the coloring 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. It may be formed by a wet plating method.
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 prepared, for example, by the following method.
First, a base layer is formed on the surface of the base material for decorative goods, and after forming the coloring layer on the surface of the base layer, a masking process is applied to a part of the surface of the coloring layer, and the coloring layer and the mask surface are colored. A white coating film having a stainless steel color tone is formed by forming a plating film having a color tone different from that of the layer by a dry plating method or a wet plating method, and then performing a process of removing the mask and the plating film on the mask at least once. An outermost layer film having two or more color tones, which is composed of this white film and at least one plating film having a different color tone, can be obtained.

[Example]
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, 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 base materials 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
Next, a mixed plating film (mixed layer) of titanium carbide and platinum having a white color tone with a thickness of 0.05 μm is applied to 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 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 formed on the surfaces 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

First, a wristwatch case base material and a wristwatch band base material obtained by machining brass (copper alloy) were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining.
Subsequently, these base materials were attached in a sputtering apparatus, and the surface of the base material was bombard cleaned in an argon atmosphere.

Next, these substrates are immersed in a plating solution having the following composition, and electroplated under the following plating conditions to form a copper-tin alloy plating film (underlayer 1) having a thickness of 2 μm on the substrate surface. , Washed with water.
<Copper-tin alloy plating>
<Composition of plating solution>
Copper cyanide 15g / l (in terms of copper)
Sodium stannate 15g / l (tin equivalent)
Zinc cyanide 1g / l (Zinc conversion)
KOH 20g / l
KCN (free) 30g / l
Brightener 10ml / l
<Plating conditions>
pH 12.5 (at 50 ° C)
Liquid temperature 50 ℃
Current density (Dk) 2A / dm ²
Deposition rate 3 min / 1 μm
Next, the substrate having these copper-tin alloy plating films is dipped in a plating solution having the following composition, electroplated under the following plating conditions, and a 2 μm thick copper-tin-zinc alloy plating film (underlayer) 2) was formed on the surface of the copper-tin alloy plating film and washed with water.
<Copper-tin-zinc alloy plating>
<Composition of plating solution>
Copper cyanide 8.5g / l (in terms of copper)
Sodium stannate 34.0g / l (tin equivalent)
Zinc cyanide 1g / l (Zinc conversion)
KOH 20g / l
KCN (free) 50g / l
Brightener 1 5ml / l
Brightener 2 5ml / l
<Plating conditions>
pH 13.0 (at 50 ° C)
Liquid temperature 60 ℃
Current density (Dk) 2A / dm ²
Deposition rate 3 min / 1 μm
Next, a substrate having these copper-tin-zinc alloy plating films is dipped in a plating solution having the following composition and electroplated under the following plating conditions to form a palladium strike plating film (underlayer) having a thickness of 0.5 μm. 3) was formed on the surface of the copper-tin-zinc alloy plating film and washed with water.
<Palladium strike plating>
<Composition of plating solution>
Pure palladium 1-3g / l
<Plating conditions>
pH 8
Liquid temperature 32 ℃
Current density (Dk) 3-5 A / dm ²
Time 30 seconds Next, these substrates were mounted in a sputtering apparatus, and the substrate surface was bombarded cleaned in an argon atmosphere.

Next, a 0.05-μm-thick tantalum film (underlayer 4) was formed on the surface of the palladium strike plating film formed on the surface of the base material by the sputtering method (magnetron sputtering method) under the following film formation conditions.
<Film formation conditions>
Target: Tantalum Sputtering gas: Argon gas Deposition pressure: 0.4 Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V
Next, a tantalum 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 tantalum plating film formed on the surface of the base material by a sputtering method (magnetron sputtering method) under the following film formation conditions. Formed.
<Film formation conditions>
Target: Tantalum 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
Next, a palladium film (outermost layer) having a white color tone of 0.005 μm in thickness is formed on the surface of the tantalum carbide plating film formed on these substrate surfaces by sputtering (magnetron sputtering method) under the following film formation conditions. Got stainless steel color watch case and watch band.
<Film formation conditions>
Target: Palladium Sputtering gas: Argon gas Deposition pressure: 0.4 Pa
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 palladium coating formed on the surfaces of the watch case and watch band obtained as described above was 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

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, 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 base materials 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 film formed on the surfaces of the watch case and the watch band obtained as described above was 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

A plating film having a color tone different from that of the hard film was formed on a part of the surface of the stainless steel-colored hard film (platinum film) obtained in the same manner as in Example 3 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: 0.26Pa
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 formed on the surface of the watch case and watch band obtained as described above is 1200, and gold-iron The surface hardness (HV; micro Vickers hardness tester, 5 g load, holding time 10 seconds) of the 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.

In addition, the color evaluation by the L *, a *, b * display system (CIE surface system) of the outermost layer (white film) constituting the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

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 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 plating film having a thickness of 2.0 μm. It was formed on the surface of the plating film and washed with water.
《Gold-iron alloy plating》
<Composition of plating solution>
Potassium cyanide 8.7 g / l (metal 5.0 g / l)
Iron chloride 2.7g / l (metal 1.0g / l)
Citric acid 150 g / l or more Sodium citrate 150 g / l or more Brightener 10 ml / l
<Plating conditions>
pH 3.5-3.7
Bath temperature 37-40 ° C
Current density (Dk) 1.0 to 1.5 A / dm ²
Be (Baume specific gravity) 20
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.
Surface hardness of the platinum film formed on the surface of the watch case and watch band obtained as described above (HV; micro Vickers hardness meter, 5 g load, holding time 10 seconds)
Was 1100, and the surface hardness (HV; micro Vickers hardness meter, 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.

In addition, the color evaluation by the L *, a *, b * display system (CIE surface system) of the outermost layer (white film) constituting the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

A plating film having a color tone different from that of the hard film was formed on a part of the surface of the stainless steel-colored hard film (platinum film) obtained in the same manner as in Example 3 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 etched with methylene chloride, and the titanium plating film, the silicon plating film and the 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 film formed on the surface of the watch case and the watch band obtained as described above is 1200, and the DLC plating film The surface hardness (HV; micro Vickers hardness meter, 5 g load, holding time 10 seconds) was 1800. 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 by the L *, a *, b * display system (CIE surface system) of the outermost layer (white film) constituting the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

First, a wristwatch case base material and a wristwatch band base material obtained by machining titanium were washed and degreased with an organic solvent. In addition, the surface of these base materials was made into the hairline finish by machining.
Subsequently, these base materials were attached in a sputtering apparatus, and the surface of the base material was bombard 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 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
Next, a platinum coating (outermost layer) having a white color tone with a thickness of 0.005 μm is formed on the surface of these substrate surfaces by the sputtering method (magnetron sputtering method) under the following film formation conditions. Got stainless steel color 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 film formed on the surfaces of the watch case and watch band obtained as described above was 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

  First, a wristwatch case base material and a wristwatch band base material obtained by molding or processing the shape of a wristwatch case and a wristwatch band prepared using zirconia ceramics were washed and degreased with an organic solvent. (For the manufacturing method of these base materials, for example, watch cases, the specification [0032] to [0036] according to Japanese Patent Application No. 2001-333236, filed on October 30, 2001 by the applicant of the present application, Specifically, the surfaces of these substrates were hairlined by machining.

Next, these substrates were mounted in an ion plating apparatus, and the substrate surface was bombard cleaned in an argon atmosphere.
Next, a chromium plating film (underlayer) having a thickness of 0.05 μm was formed on the surface of these base materials by the ion plating method (hot cathode method) under the following film forming conditions.
<Film formation conditions>
Evaporation source: Chrome Electron gun: 10 kV, 300 mA
Gas: Argon gas Deposition pressure: 0.004 to 0.009 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V
Subsequently, a chromium carbide plating film (abrasion resistant layer) having a thickness of 0.6 μm is formed on the surface of the chromium plating film formed on the surface of the substrate by the ion plating method (hot cathode method) as described below. Formed under conditions.
<Film formation conditions>
Evaporation source: Chrome 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 palladium coating (outermost layer) having a white color tone with a thickness of 0.005 μm is formed on the surface of the chromium carbide plating coating formed on these substrate surfaces 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: Palladium 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 palladium coating formed on the surfaces of the watch case and watch band obtained as described above was 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.

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, these substrates were mounted in an ion plating apparatus, and the substrate surface was bombard cleaned in an argon atmosphere.

Next, a titanium carbide plating film (undercoat layer) 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 these base materials by the ion plating method (hot cathode method) as follows. The film was formed under film 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 formed on the surfaces of the watch case and the watch band obtained as described above was 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 by the L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
82 <L * <85, 0 <a * <2.0, 4.0 <b * <5.0
Met.
Further, the wristwatch case and wristband obtained as described above and the wristwatch case and wristband obtained in Example 3 were each subjected to a scratch test to compare the adhesion of the coating to the base material. The measuring instrument used for the scratch test is a HEIDON-14 type surface property measuring instrument.

  Hereinafter, a decorative part sample of Example 3 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 9 having a base layer composed of a 15 atom% titanium carbide 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 atom% 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 3, chipping peeling occurred when the scratch load was 200 gr. On the other hand, in Example 9, chipping peeling occurred when the scratch load was 250 gf. That is, the critical load in Example 3 was 200 gf, and the critical load in Example 9 was 250 gf. From this, it is understood that the decorative part of Example 9 has a coating adhesion strength of 25% higher than that of the decorative part of Example 3.

  In Examples 1 to 9 above, tungsten carbide as a decorative substrate, a plating film made of chromium, hafnium, vanadium, or niobium as an underlayer, hafnium carbide, vanadium carbide, niobium carbide, or carbonized as an abrasion resistant layer Needless to say, a plating film made of tungsten 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 1-9, watch cases and wristbands are manufactured. Needless to say, the techniques described in Examples 1-9 can also be applied to ornaments such as necklaces, pendants, brooches and the like. .

Claims (45)

In a decorative article in which a 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,
A decorative substrate made of metal or ceramics;
An underlayer formed on the surface of the substrate;
A wear-resistant layer formed on the surface of the underlayer by a dry plating method, and a coloring layer consisting of an outermost layer formed on the surface of the wear-resistant layer by a dry plating method,
The white color layer is a hard white film having a stainless steel color tone, comprising 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 with a coating.   2. The white coating film according to claim 1, wherein the decorative article base material is made of at least one metal selected from the group consisting of stainless steel, titanium, a titanium alloy, copper, a copper alloy, and tungsten carbide. Having ornaments. Stabilized zirconia in which the decorative article base material is made of zirconia ceramics and the composition thereof contains 3 to 7% by weight of a stabilizer of yttrium oxide (Y ₂ O ₂ ), magnesium oxide (MgO) or calcium oxide (CaO). The decorative article having a white coating according to claim 1, wherein the decorative article has a white color tone.   The decorative article base material is made of a metal other than copper and copper alloy, or ceramics, and the base layer formed on the base material surface is formed by dry plating, titanium (Ti), chromium ( The white film according to any one of claims 1 to 3, wherein the white film is made of Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), or tantalum (Ta). With ornaments.   The decorative article base material is made of a metal other than copper and copper alloy, or ceramics, and the base layer formed on the base material surface is formed by a dry plating method, and has a carbon atom content of 5 to 5. 5. The metal compound film comprising 15 atom% titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide, or tantalum carbide, according to claim 1. Ornaments.   The ornamental base material is made of a metal other than copper and copper alloy, or ceramics, and the underlayer is a film having a thickness of 0.02 to 0.2 μm formed by a dry plating method. The ornament which has a white film in any one of Claims 1-4.   The decorative article base material is made of copper or a copper alloy, and the base layer is formed on the surface of the base material by a wet plating method. The nickel coating has a thickness of 1 to 10 μm, and the nickel coating surface is wet-plated. The decorative article having a white coating according to claim 1 or 2, comprising an amorphous nickel-phosphorus alloy coating having a thickness of 3 to 10 µm formed by a method.   Copper, palladium, copper-tin alloy, copper-tin-zinc alloy, and copper-tin-, wherein the decorative article base material is made of copper or a copper alloy, and the base layer is formed by a wet plating method. The decorative article having a white coating according to claim 1 or 2, wherein the decorative article is a coating having a thickness of 2 to 9 µm and comprising at least one selected from the group consisting of palladium. 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).
The decorative article having a white coating film according to any one of claims 1 to 8, which is a metal compound coating film made of tungsten carbide (WC) or tantalum carbide (TaC).   The decorative article having a white coating film according to any one of claims 1 to 9, wherein the wear-resistant layer has a thickness of 0.5 to 1.0 µm.   11. The outermost layer is a film made of at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof. A decorative article having the white coating described in 1.   The thickness of the said outermost layer is 0.01-0.08 micrometer, The ornament which has a white film in any one of Claims 1-11 characterized by the above-mentioned.   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 ornament which has a white film in any one of 1-12.   The decorative article having a white coating film according to any one of claims 1 to 13, wherein the mixed layer has a thickness of 0.005 to 0.1 µm. The color evaluation by L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
The white color according to claim 1, wherein 70 <L * <91, −0.1 <a * <3.0, 1.0 <b * <5.5. A decorative article with a coating.   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. 4. A decorative article having a white film according to any one of 4 to 15.   A part of the surface of the white coating film having a stainless steel color tone composed 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. The ornament which has a white film in any one of Claims 1-14.   18. The decorative article having a white coating according to claim 17, wherein the coating 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 17, 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. With 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 19. A decorative article having a white coating according to Item 17 or 18.   The outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof. The ornament which has a white film in any one of Claims 1-10, 12-15, and 17-20 characterized by these. The color developing layer has a surface hardness (HV; micro Vickers hardness meter, 5 g load) of 700-2.
The decorative article having a white film according to any one of claims 1 to 21, wherein the decorative article is 000.   23. The decorative article having a white coating according to claim 1, wherein the decorative article is a watch exterior part. In the method of 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,
Using a material made of metal or ceramics to produce a base material for decorative goods by various processing means;
Forming a base layer on the substrate surface by a dry plating method or a wet plating method;
By forming a wear resistant layer made of a metal compound on the surface of the underlayer by a dry plating method, and further forming an outermost layer made of platinum or a platinum alloy on the surface of the wear resistant layer by a dry plating method, A method for producing a decorative article having a white coating, comprising the step of:   The white coating film according to claim 24, wherein the decorative article base material is made of at least one metal selected from the group consisting of stainless steel, titanium, titanium alloy, copper, copper alloy, and tungsten carbide. A method for manufacturing a decorative article. A binder for 100 parts by weight of stabilized zirconia powder containing 3 to 7% by weight of a stabilizer of yttrium oxide (Y ₂ O ₂ ), magnesium oxide (MgO) or calcium oxide (CaO). A material containing 20 to 25 parts by weight is formed by injection molding, and thereafter formed by machining, roughing, degreasing, firing, grinding and polishing steps, and exhibits a white color tone. 25. A method for producing a decorative article having the white coating according to 24.   On the surface of a decorative substrate made of a metal other than copper and copper alloy, or ceramics, as the underlayer, titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), 27. The method for producing a decorative article having a white film according to claim 24, wherein the film made of niobium (Nb) or tantalum (Ta) is formed by a dry plating method.   Titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide having a carbon atom content of 5 to 15 atomic% on the surface of the decorative substrate made of a metal other than copper and copper alloy, or ceramics. The method according to any one of claims 24 to 27, wherein the metal compound film made of niobium carbide, tungsten carbide or tantalum carbide is formed by a dry plating method.   25. A film having a thickness of 0.02 to 0.2 μm is formed as a base layer on a surface of a base material for decorative articles made of a metal other than copper and copper alloy, or ceramics by a dry plating method. The manufacturing method of the ornament which has a white film in any one of -27.   A nickel coating having a thickness of 1 to 10 μm is formed as a base layer on the surface of a decorative article substrate made of copper or a copper alloy by a wet plating method, and an amorphous nickel-phosphorous alloy having a thickness of 3 to 10 μm is formed on the surface of the nickel coating. The method for producing a decorative article having a white coating according to claim 24 or 25, wherein the coating is formed by a wet plating method. From the at least one selected from the group consisting of copper, palladium, copper-tin alloy, copper-tin-zinc alloy and copper-tin-palladium as the base layer on the surface of the decorative article substrate made of copper or copper alloy The method for producing a decorative article having a white coating according to claim 24 or 25, wherein the coating having a thickness of 2 to 9 µm is formed by a wet plating method. The wear-resistant layer comprises titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tungsten carbide (WC). The method for producing a decorative article having a white film according to any one of claims 24 to 31, wherein the metal compound film is made of tantalum carbide (TaC).   The method for producing a decorative article having a white coating according to any one of claims 24 to 32, wherein the wear-resistant layer has a thickness of 0.2 to 1.5 µm.   34. The film according to claim 24, wherein the outermost layer is a coating made of at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof. The manufacturing method of the ornament which has a white film of description.   The method for producing a decorative article having a white coating according to any one of claims 24 to 34, wherein the outermost layer has a thickness of 0.002 to 0.1 µm.   25. 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. 35. A method for producing a decorative article having a white coating according to any one of 35. The color evaluation by L *, a *, b * display system (CIE surface system) of the coloring layer is as follows:
The white coating film according to any one of claims 24 to 36, wherein 70 <L * <91, -0.1 <a * <3.0, and 1.0 <b * <5.5. A method for manufacturing a decorative article.   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.   37. The method according to claim 24, 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. The manufacturing method of the ornament which has a white film in any one of.   40. The decorative article having a white coating according to claim 39, wherein the coating 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). Production method.   40. The white film according to claim 39, wherein a 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 film different from the coloring layer. A method for producing a decorative article having a coating.   40. 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 40.   The outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof. The method for producing a decorative article having a white coating according to any one of claims 24 to 33, 35, 37, and 39 to 42.   44. The method for producing a decorative article having a white film according to any one of claims 24 to 43, wherein the color developing layer has a surface hardness (HV; micro Vickers hardness meter, 5 g load) of 700 to 2000.   45. The method for producing a decorative article having a white coating according to any one of claims 24 to 44, wherein the decorative article is a watch exterior part.