JP4589772B2 - Decorative product with white coating - Google Patents

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, when the white decorative base material is stainless steel, the outermost platinum coating or platinum alloy coating is used as a catalyst in long-term use, and due to human perspiration, the base material is made of stainless steel. Slight 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 presumed to be caused by the platinum coating or platinum alloy coating acting as a catalyst on the stainless steel of the base material through sweat or the like from ultrafine pinholes that are formed 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 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, and a decorative article base material made of stainless steel, Underlayer made of titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta) formed on the surface of the substrate by dry plating. And titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide formed on the surface of the underlayer by dry plating. (NbC), and abrasion layer made of tungsten carbide (WC) or tantalum carbide (TaC), the dry plating on the surface of the resistant wear layer Ri is formed, palladium platinum comprises in the range of 30～50W% - characterized in that composed of the outermost layer Do that platinum alloy - palladium palladium alloy or platinum is contained in the range of 30～50W% .

  In addition, the decorative material base material is made of stainless steel, and the base material surface is subjected to at least one surface finish selected from a mirror surface, a satin finish, a hairline pattern, a honing pattern, a stamping pattern, and an etching pattern. ing.

The underlayer formed on the surface of the decorative article base is formed by dry plating , and has a carbon atom content of 5 to 15 atomic% titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, A metal compound film made of niobium carbide, tungsten carbide or tantalum carbide may be used. The thickness of the underlayer is preferably a film having a thickness of 0.02 to 0.2 μm.

The thickness of the wear resistant layer is 0.2 to 1.5 μm, and preferably 0.5 to 1.0 μm .

Moreover, although the thickness of outermost layer is 0.002-0.1 micrometer, Preferably it is 0.005-0.1 micrometer, More preferably, it is a film of 0.01-0.08 micrometer.

In addition, a mixed layer comprising a metal compound that forms the wear-resistant layer and an 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 forming the wear-resistant layer and a platinum-palladium alloy or a palladium-platinum 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.

Method of manufacturing a decorative article having a white coating according to the present invention, the coating having a white tone of a noble metal or a noble metal alloy in the manufacturing method of the formed ornaments by dry plating method as an outermost layer, made of stainless steel base Forming a base layer made of titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta) on the surface of the material by dry plating. And titanium carbide (TiC), chromium carbide (Cr ₃ C ₂ ), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC) on the surface of the underlayer by dry plating. , tungsten carbide (WC) or consisting of tantalum carbide (TaC) to form a wear-resistant layer, further dry the surface of the resistant wear layer Platinum by Tsu key method palladium is included in a range of 30~50W% - palladium palladium alloy or platinum is contained in the range of 30~50W% - and characterized by a step of forming an outermost layer comprising a platinum alloy To do.

  Moreover, the base material for ornaments is made of stainless steel, and the surface of the base material has at least one surface finish selected from a mirror surface, a satin finish, a hairline pattern, a honing pattern, a stamping pattern, and an etching pattern. Yes.

Further, on the surface of the base material for decorative articles, as the underlayer, from 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 atomic%. The resulting metal compound film may be formed by a dry plating method. As this underlayer, a film having a thickness of 0.02 to 0.2 μm is preferably formed by a dry plating method.

Moreover, it is preferable that the thickness of an abrasion-resistant layer is 0.2-1.5 micrometers.

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.

Further, a mixed layer comprising a metal compound that forms the wear-resistant layer and an 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.

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

  Further, it is characterized in that at least one coating different from the color tone of the color developing layer is formed on a part of the surface of the white coating having the color tone of the stainless steel made of the color developing layer by a dry plating method or a wet plating method. 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). The coating film having a color tone different from that of the coloring layer may be gold, a gold alloy not containing nickel, 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, it is preferable to form a titanium film between the color forming layer and a diamond-like carbon (DLC) film which is a film different from the color forming layer, and further form a silicon film on the surface of the titanium film.

  The outermost layer is a mixed layer composed of a metal compound forming the wear-resistant layer and a platinum-palladium alloy or a palladium-platinum alloy.

  The color developing layer is formed so that the surface hardness (Hv; micro Vickers hardness meter, 5 g load) is 700 to 2000. Further, the decorative article is a watch exterior part.

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 substrate made of stainless steel, an underlayer formed on the surface of the substrate by a dry plating method, and formed on the surface of the underlayer by a dry plating method. And the developed 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. .

[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 ornament (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 is composed of at least one plated coating formed by a dry plating method. Examples of the plating film 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 a chemical vapor deposition method (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 alloy film formed on the surface of the wear-resistant layer or a mixed layer described later by a dry plating method.

Examples of such precious metal coatings include platinum-palladium alloys or palladium-
A precious metal coating made of a platinum alloy is desirable. The brightness (whiteness) of the metal is platinum, palladium, and stainless steel in order of brightness. The platinum-palladium alloy preferably has a palladium content in the range of 30 w% to 50 w%. If the palladium content is less than 30 w%, there is a risk of nickel elution. As for the color tone, the platinum color becomes stronger and brighter than the color tone of stainless steel, so the film thickness is reduced, and the color tone of the stainless steel is brought out with the color tone of the wear-resistant layer. Moreover, when there is more palladium than 50 w%, it will become the characteristic similar to a palladium-platinum alloy. The palladium-platinum alloy preferably has a platinum content in the range of 30 to 50 w%. If the platinum content is less than 30 w%, there is a risk of nickel elution. Moreover, about the color tone, palladium color becomes strong. Moreover, when there is more palladium than 50 w%, it will become the same as the characteristic of a platinum-palladium alloy. 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 0.002 to 0.01 μm, and most 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 an 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. In addition, in the corrosion resistance test, the elution of nickel has become much smaller than before.

[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, and 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 a chemical vapor deposition method (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 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.

  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 the base material layer 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 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 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 having a white color tone and a platinum-palladium alloy having 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 (heat The cathode was formed under the following film forming conditions.
<Film formation conditions>
Evaporation source: Titanium, platinum-palladium alloy (Pt: 70 w%, Pd: 30 w%)
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-palladium alloy film (outermost layer) having a white color tone of 0.006 μm in thickness (Pt: 70 w%, on the mixed plating film surface of titanium carbide and platinum-palladium alloy formed on the surface of these substrates. Pd: 30 w%) was formed by the ion plating method (hot cathode method) under the following film forming conditions to obtain a stainless steel watch case and watch band.
<Film formation conditions>
Evaporation source: Platinum-palladium alloy 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
The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the platinum-palladium alloy (including the wear resistant layer) formed on the surface of the watch case and watch band obtained as described above is 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, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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, 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 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 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 Film forming pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V

Next, a platinum-palladium alloy film (outermost layer) having a white color tone of 0.007 μm (Pt: 60 w%, Pd: 40 w%) is ion-plated on the surface of the titanium carbide plating film formed on these substrate surfaces. A stainless steel watch case and a watch band were obtained by the following film formation conditions by a coating method (hot cathode method).
<Film formation conditions>
Evaporation source: Platinum-palladium alloy 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 of platinum-palladium alloy coating (including wear-resistant layer) 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 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, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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-colored hard coating (outermost layer: platinum-palladium alloy coating) obtained in the same manner as in Example 2.
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 Film forming pressure: 0.2 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 40-50V
Filament voltage: 7V

Next, a titanium nitride plating film having a thickness of 0.6 μm and having a gold color 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 Film forming 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.
Surface hardness of platinum-palladium alloy coating (including wear-resistant layer) 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) 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. Moreover, in the corrosion resistance test, the elution of nickel was further reduced from the conventional amount.

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 (outermost layer: platinum-palladium alloy 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 to 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 2.0 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
15 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. Surface hardness of platinum-palladium alloy coating (including wear-resistant layer) 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 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. In addition, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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 (outermost layer: platinum-palladium alloy coating) obtained in the same manner as in Example 3. 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 Film forming pressure: 0.05 Pa
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: 0.2 Pa
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.

Surface hardness of platinum-palladium alloy coating (including wear-resistant layer) 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) The surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the DLC plating film 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, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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, 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 Film forming pressure: 0.665 Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V

Next, a palladium-platinum alloy coating (outermost layer) having a white color tone of 0.01 μm (Pd: 70 w%, Pt: 30 w%) is sputtered onto the surface of the zirconium carbide plating film formed on the surface of these base materials. A magnetron sputtering method was used under the following film forming conditions to obtain a stainless steel watch case and a watch band.
<Film formation conditions>
Target: Palladium-platinum alloy sputtering gas: Argon gas Deposition pressure: 0.2 Pa
Target applied power: 0.5 kW
Bias voltage (acceleration voltage): -50V
Surface hardness (Hv; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the palladium-platinum alloy coating (including the wear-resistant layer) formed on the surface 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, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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, 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 (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 Film forming pressure: 0.02 Pa
Acceleration voltage (bias voltage): Ground to -100V
Anode voltage: 60V
Filament voltage: 7V

Next, a palladium-platinum alloy film (outermost layer) (Pd: 50 w%, Pt: 50 w%) having a white color tone of 0.008 μm in thickness is formed on the surface of the titanium carbide plating film formed on the surface of these substrates. A stainless steel watch case and a watch band were obtained by the following film formation conditions by a coating method (hot cathode method).
<Film formation conditions>
Evaporation source: Palladium-platinum alloy electron gun: 10 kV, 500 mA
Gas: Argon gas deposition pressure: 0.2 Pa
Acceleration voltage (bias voltage): Ground to -50V
Anode voltage: 60V
Filament voltage: 7V
Surface hardness (HV; micro Vickers hardness meter, 5 g load, holding time 10 seconds) of the palladium-platinum alloy coating (including the wear resistant layer) formed on the surface of the watch case and 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, in the corrosion resistance test, the elution of nickel has become much smaller than before.

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.
As a comparative sample, the outermost layer of Example 1 was changed to a platinum film to make a test piece (the outermost layer of Example 1 was a platinum-palladium alloy film), and the test was performed 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 was reduced by an order of magnitude compared with the comparative example, and a very large effect was obtained. 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 a sample below is accepted.

In Examples 1 to 7, it is possible to form a plating film made of chromium, hafnium, vanadium, or niobium as the underlayer, and a plating film made of hafnium carbide, vanadium carbide, niobium carbide, or tungsten carbide as the wear resistant layer. Needless to say. 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 (2)

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 made of stainless steel is formed on the surface of the base material by a dry plating method. An underlayer made of titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta), and the surface of the underlayer by dry plating 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 tantalum carbide formed A wear-resistant layer made of (TaC) and 30-50 palladium formed on the surface of the wear-resistant layer by a dry plating method. % Of platinum is included in the range - palladium alloy or platinum palladium comprises in the range of 30～50W% - consists outermost layer consisting of platinum alloy, the wear-resistant layer and the thicknesses of 0.2 and 1.5 .mu.m 0 A decorative article having a white film , wherein a color-developing layer is composed of the outermost layer of 0.002 to 0.1 μm . A metal 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 atomic%, wherein the underlayer is formed by dry plating. 2. A decorative article having a white coating according to claim 1, which is a compound coating.