JP4073848B2 - Decorative product and manufacturing method thereof - Google Patents

Description

  The present invention relates to a decorative article having a multicolor coating and a method for producing the same, and more particularly, to a watch exterior part having a hard coating exhibiting a white (stainless steel) color tone and a hard laminated coating exhibiting a gold color tone. The present invention relates to a decorative article and a manufacturing method thereof.

  In recent years, ornaments such as watches have a tendency to diversify along with TPO-compliant requirements and design variations. With this trend, they have different colors such as two-tone and are highly scratch-resistant due to long-term carrying. There is a constant demand for hardened products.

  Among them, there is a demand for a decorative product having a high-quality white (stainless steel) color tone and another color tone.

  As a hard film having a white color tone, there are films formed of titanium, zirconium, hafnium, tantalum, vanadium, chromium, aluminum nitride, carbide, nitrocarbide, platinum, and a platinum alloy (for example, see Patent Document 1). Two-tone can be obtained by forming a colored coating layer on the hard film, but since the colored coating layer is directly formed on the hard film, there is a problem that the adhesion between the hard film and the colored coating layer is poor. It was.

  In addition, gold, which is a color tone combined with a white color tone, that is, a two-tone color having a white color tone and a gold color tone, is deeply popular.

  Some gold-colored coatings used for conventional ornaments have a composition comprising 80 to 95% by weight of gold, 5 to 20% by weight of nickel, and other inevitable components by a dry plating method. The gold film is used as an underlayer of at least one metal selected from titanium, tantalum, hafnium, vanadium, zirconium, nickel, and chromium, or at least one of carbides, nitrides, nitrocarbides, and alloys of the metals. Abrasion resistance and corrosion resistance can be improved by forming on the surface of the hard coating (see, for example, Patent Document 2). Since this hard film has a small color difference from the gold film, it also has a function of preventing spots caused by the wear of the gold film.

  Moreover, it can be set as the two tone of a base material and a golden film by masking on a base material, forming in order of the said hard film and a golden film, and removing masking.

  However, the golden coating itself has a low hardness, and there remains a problem such as scratches when carrying decorative items for a long time.

In addition, in the case where the base material and the gold color film are made two-tone, the hardness of the base material and the gold color film is not sufficient to be used for carrying the decorative article for a long time due to the problem of the hardness of both the base material and the gold color film.
Japanese Patent Laid-Open No. 3-120355 JP 2003-82452 A

  Therefore, there is a high-class feeling, appearance quality deterioration due to scratches and the like is difficult to occur, and it has a high-quality white layer close to a stainless steel coating, and a golden layer excellent in wear resistance, corrosion resistance and scratch resistance, Moreover, the advent of a decorative article having a multi-colored film having high adhesion between layers and a method for producing the same is desired.

Decorative article according to the present invention, stainless steel, titanium, and at least one metal or ornament base material made of an alloy selected from the group consisting of titanium alloys, titanium formed by dry plating method to the substrate surface (Ti ), Chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta), and a surface of the underlayer by dry plating. The wear-resistant layer, which is a metal compound film composed of carbide, nitride, or nitride carbide of titanium, chromium, zirconium, hafnium, vanadium, niobium, tungsten or tantalum, and the surface of the wear-resistant layer are formed by a dry plating method. platinum (Pt), palladium (Pd), the group consisting of rhodium (Rh) and these at least one alloy containing Together consist white layer selected et, coloring layer is composed of said wear-resistant layer having a thickness of 0.2 and 1.5 .mu.m, and the white layer having a thickness of 0.002～0.1Myuemu, wherein The color development layer is a coating having a stainless steel color tone , and further, at least a part of the surface of the color development layer, an intermediate layer made of gold or a gold alloy by a dry plating method, and at least a part of the surface of the intermediate layer metal nitride coating that exhibits two golden color tone Ri Do from the finish coating layer is repeatedly stacked alternately, the metal nitride film, the content of metal is 40～60Atm%, the content of nitrogen 30~50atm % Of titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN) or tantalum nitride (TaN) .

The underlayer formed on the decorative article base material is a carbide of titanium, chromium, zirconium, hafnium, vanadium, niobium or tantalum formed by a dry plating method (carbon atom content is 5 to 15 atomic%). ), A metal compound film made of nitride or nitride carbide .

The underlayer is a film having a thickness of 0.02 to 0.2 μm formed by a dry plating method .

The white layer has a thickness of 0.01 to 0.08 μm .

The color developing layer has a surface hardness (HV; micro Vickers hardness meter, 5 g load) of 700 to 2000 .

The lamination period (λ) of the metal nitride film exhibiting the golden color tone is 20 to 40 nm.
And the film thickness of the whole laminated | stacked film is 0.1-3.0 micrometers , It is characterized by the above-mentioned.

Further, the finish coating layer is composed of the metal nitride coating and a gold coating made of gold or a gold alloy having a thickness of 0.005 to 0.1 μm formed on the coating surface .

In addition, the method for manufacturing a decorative article according to the present invention uses a material made of at least one metal or alloy selected from stainless steel, titanium, and a titanium alloy, and titanium (Ti ), Chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta), and forming a base layer on the surface of the base layer. A wear-resistant layer, which is a metal compound film made of carbide, nitride, or nitrided carbide of titanium, chromium, zirconium, hafnium, vanadium, niobium, tungsten or tantalum, is formed by a dry plating method. Whether platinum (Pt), palladium (Pd), rhodium (Rh), or an alloy containing at least one of these by plating Forming a white color layer having a stainless steel color tone by forming a white layer selected from the group consisting of: and forming an intermediate layer made of gold or a gold alloy on at least a part of the surface of the color development layer by a dry plating method Then, at least a part of the surface of the intermediate layer exhibits at least two kinds of gold color tones in a dry plating apparatus in a nitrogen gas atmosphere, the metal content is 40 to 60 atm%, and the nitrogen content is 30 to 30%. A metal nitride film of titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN) or tantalum nitride (TaN), which is 50 atm%, is alternately and repeatedly laminated to form a finished film layer. It is characterized by that.

  According to the present invention, there is a high-class feeling, it is hard and excellent in scratch resistance, appearance quality deterioration due to scratches and the like is unlikely to occur, and it is close to a stainless steel film, and has a high-quality white coating and a high surface hardness, It is possible to provide a decorative article having both a scratch resistance and a gold film having excellent wear resistance and corrosion resistance, and a method for producing the same.

  Hereinafter, a decorative article having a multicolored coating and a method for producing the same according to the present invention will be described in detail.

A decorative article having a multi-colored 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 a white layer, or an abrasion resistant layer, a first mixed layer, and a white layer. Further, a finish coating layer composed of an intermediate layer and a metal nitride coating is provided on the surface of the coloring layer. Furthermore, you may have a layer which consists of a golden film, a 2nd mixed layer, and a metal nitride film as finishing film layers other than a metal nitride film.
(Base material for decorative products)
The ornamental base material used in the ornamental article having the multicolored coating according to the present invention is a substrate formed from metal or ceramics.

  The base material for ornaments used in the present invention is usually selected from stainless steel, titanium, titanium alloy, copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium alloy, tungsten carbide and tantalum carbide. At least one metal or alloy.

It is made of zirconium ceramics, and its composition is stabilized zirconia containing 3 to 7% by weight of a stabilizing material of yttrium oxide (Y ₂ O ₂ ), magnesium oxide (MgO) or calcium oxide (CaO), and exhibits a white color tone. The base material etc. which are used are used.

  The zirconia ceramic contains 20 to 25 parts by weight of a binder with respect to 100 parts by weight of stabilized zirconia powder containing zirconia and a binder as main components and containing 3 to 7% by weight of a stabilizer such as yttrium oxide, and fired. Later, white tone is exhibited. 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. It is because it becomes easy to generate | occur | produce. 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.

  A base material for decorative articles made of a metal or an alloy is prepared from the above metal or alloy by a conventionally known machining or surface finishing process, and the surface of the base material is at least a mirror surface, a satin finish, a hairline pattern, a honing pattern, a stamping pattern or the like. It has an etching pattern and these two or more patterns.

  Further, a decorative material base material made of ceramics, for example, a watch case base material, is formed after a molded body having a watch case shape is formed by injection molding using a material mainly composed of zirconia and a binder. The body is rough processed by machining, and the rough processed compact is degreased and fired to make a rough base material for the watch case, and then the rough base material is manufactured by machining such as grinding and polishing. The

  Examples of the ornaments (including accessories) (including parts) in the present invention 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 stoppers, badges, medals, eyeglass frames, camera bodies, door knobs and the like.

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 multicolor coating according to the present invention is composed of at least one plating 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.

  In addition, a metal compound film made of carbide, nitride, or nitride carbide of titanium, chromium, zirconium, hafnium, vanadium, niobium, tungsten, or tantalum is desirable. In particular, when forming the carbide, from the viewpoint of further improving the adhesion between the base material and the wear-resistant layer, the underlayer is formed by a dry plating method and has a carbon atom content of 5 to 15 atomic%. A metal compound film made of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or tantalum carbide 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 the multicolor coating according to the present invention, when the decorative base 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 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 a zinc alloy and a copper-tin-palladium alloy.
(Coloring layer)
The coloring layer constituting the decorative article having the multicolor coating according to the present invention is composed of an abrasion resistant layer and a white layer, or an abrasion resistant layer, a first mixed layer and a white 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.

As such a metal compound film, a metal compound film made of a carbide, nitride, or nitride carbide of titanium, chromium, zirconium, hafnium, vanadium, niobium, tungsten or tantalum is desirable.

  The wear-resistant layer has a thickness of 0.2 to 1.5 μm, preferably 0.5 to 1.0 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.
(White layer)
The white layer is made of a film of a noble metal (including an alloy) formed by a dry plating method on the surface of the wear-resistant layer or the first mixed layer described later.

As such a noble metal coating, a noble metal coating consisting of at least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh) and an alloy containing at least one of these is desirable.
Moreover, in this invention, the 1st mixed layer mentioned later can be made into a white layer.

  The thickness of the white 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 white layer, the thickness of the film is 0.002 to 0.01 μm, preferably 0.005 to 0.08 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. (First mixed layer)
In the present invention, the first mixed layer that may be formed between the wear-resistant layer and the white layer as necessary is a film formed by a dry plating method.

  This coating consists of a metal compound (for example, titanium carbide) that forms a wear-resistant layer and a metal or alloy (for example, platinum, platinum alloy) that forms a white 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 white layer can be further strengthened.

  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.

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 white layer or the abrasion resistant layer, the first mixed layer and the white layer as described above 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 ornaments which gave the mirror surface finish, and the coloring layer formed on the base material for ornaments which gave the 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 coloring layer is usually 700 to 2000, preferably 1000 to 2000.

In the present invention, there is a sense of quality by forming a white layer comprising 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, Appearance quality degradation due to scratches and the like is unlikely to occur, and a high-quality decorative article close to a stainless steel coating can be obtained.
(Middle layer)
The intermediate layer used in the present invention is composed of at least one plating film formed by a dry plating method. The adhesion between the color forming layer and the finished coating layer can be improved by the intermediate layer.

  As the intermediate layer, gold or a gold alloy is desirable.

Specifically, the dry plating method is preferably a sputtering method, an ion plating method, or an arc ion plating method.
(Finish coating layer)
In the metal nitride film formed as the finish film layer according to the present invention, metal nitride films exhibiting at least two kinds of gold color tones are alternately and repeatedly laminated.

  Examples of the metal nitride forming the metal nitride coating include titanium nitride (TiN), zirconium nitride (ZrN), and hafnium nitride having a metal content of 40 to 60 atm% and a nitrogen content of 30 to 50 atm%. (HfN) or tantalum nitride (TaN) is desirable. When the nitrogen content is within the above range, the nitride film exhibits a golden color tone and is hard.

  The metal nitride film is preferably a metal nitride film in which the above-mentioned film made of titanium nitride and the above-mentioned film made of zirconium nitride, hafnium nitride or tantalum nitride are alternately and repeatedly laminated.

  Such a metal nitride film can obtain a hard metal nitride film by alternately and repeatedly laminating at least two kinds of metal nitride films described above. In particular, a metal nitride film having high hardness and excellent scratch resistance can be obtained by stacking the layers at a certain period. The reason why this metal nitride film is high in hardness and excellent in scratch resistance is not clear, but it is presumed that high surface hardness can be obtained because of the large internal stress accumulation effect in the laminated film.

  In the present invention, the lamination period (λ) of the metal nitride film is 10 to 50 nm, preferably 20 to 40 nm, and the film thickness of the whole laminated film is 0.1 to 3.0 μm, preferably 0.5. It is desirable that it is -2.0 micrometers. Here, the lamination period (λ) is, for example, the thickness of the first metal nitride film and the thickness of the second metal nitride film when two types of metal nitride films are repeatedly laminated. Refers to the total film thickness.

  The thickness of each film constituting the metal nitride film is usually in the range of 10 to 50 nm.

  Each layer of such a metal nitride film is preferably formed by at least one dry plating method selected from a sputtering method, an ion plating method, and an arc type ion plating method. Of these, the sputtering method and the arc type ion plating method are preferable. From the viewpoint of productivity, it is preferable to form a metal nitride film by one kind of dry plating method.

  In the present invention, the Vickers hardness (HV) on the surface of the decorative article base material or the surface of the metal nitride film formed on the surface of the intermediate layer depends on the type of the decorative article base material, and the type and thickness of the intermediate layer. Although it is different, the decorative article according to the present invention has a Vickers hardness (HV) of 3000 or more measured using an ultra micro indentation hardness tester (Vickers indenter, load 5 mN, holding time 10 seconds). Desirable in terms of scratch resistance.

  The metal nitride coating according to the present invention enables the production of a decorative article having excellent wear resistance, corrosion resistance and scratch resistance, and wear resistance, corrosion resistance and scratch resistance even when tungsten carbide or tantalum carbide is used as a substrate. It is possible to produce decorative products that are superior in strength and that are tough and will not crack even if accidentally dropped.

In the metal nitride film according to the present invention, since the kind, film thickness, combination, and the like of the metal nitride film can be variously changed, there are many variations in golden color tone.
(Second mixed layer)
In the present invention, the metal nitride forming the metal nitride coating and the gold or gold forming the gold coating are formed between the metal nitride coating formed as the finish coating layer and a gold coating described later, if necessary. A second mixed layer made of an alloy can be formed. This second mixed layer is intended to be adjusted to the same color tone as that of the gold coating. For example, even if the gold film wears over time and the second mixed layer appears on the surface of the decorative article, if the color of the second mixed layer is the same as that of the gold film, the decorative article is used for a long time. Can be used. Further, by providing such a second mixed layer, it can be expected that the adhesion between the metal nitride film and the gold film is further improved.

  The second mixed layer is formed by a sputtering method, an ion plating method, or an arc type ion plating method.

The thickness of this mixed layer is 0.005 to 0.1 μm, preferably 0.01 to 0.08 μm.
(Golden film)
The metal nitride film in the present invention, and further the gold film that may constitute the finish film layer together with the second mixed layer, is formed on the metal nitride film or the second mixed layer by a dry plating method. It is a film having a golden color tone made of gold or a gold alloy.

It is desirable from the viewpoint of cost that the golden coating is a hard coating having a thickness of 0.005 to 0.1 μm, preferably 0.05 to 0.1 μm.
Examples of the gold alloy include Al, Si, V, Cr, Ti, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Pb, Ag, Sn, Hf, Tf, An Au alloy containing at least one selected from W and Pt can be used.

  From the viewpoint of preventing nickel allergy, it is preferable to form a nickel-less coating.

  Further, the color tone of the surface of the metal nitride film or the second mixed layer formed immediately below the gold film is preferably matched to the gold color tone of the gold film.

  As the dry plating method, a sputtering method, an ion plating method and an arc type ion plating method are desirable.

  As a decorative article according to the present invention, a Vickers hardness (HV) measured using an ultra-fine indentation hardness tester (Vickers indenter, load 5 mN, holding time 10 seconds) is 3000 or more, preferably 3500 to 5000, More preferably, it is 4000 to 5000 from the viewpoint of scratch resistance.

  A decorative article having such a golden-colored coating on a part of the surface of the color-developing layer can be prepared, for example, by the following method.

First, a base layer is formed on the surface of the decorative article substrate, and after the color forming layer is formed on the surface of the base layer, an intermediate layer and a finish coating layer are formed on at least a part of the surface of the color forming layer. After that, a part of the finished coating layer is masked with petroleum resin, etc., soaked in the first stripping solution to strip the finishing coating layer, and then soaked in the second stripping solution to cover the intermediate layer. Peel off. Then, a multicolored film can be obtained by immersing in a third stripping solution to peel off the mask, washing and drying. When the finish coating layer is peeled off, it is possible to prevent the coloring layer from being damaged by providing the intermediate layer.

  Further, a decorative product having a multicolor coating according to the present invention in which at least a gold coating is further formed on the metal nitride coating has a high surface hardness, excellent scratch resistance, and wear resistance and corrosion resistance. Is excellent.

  Furthermore, the decorative article having the multi-colored coating according to the present invention using tungsten carbide or tantalum carbide as the base material has the above-mentioned metal nitride coating, so it is tough and will not crack even if dropped accidentally. Moreover, it is excellent in wear resistance, corrosion resistance and scratch resistance.

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

  First, a mirror-finished watch base material and watch band base material obtained by machining stainless steel (SUS316L) were washed and degreased with an organic solvent.

  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 (first mixed layer) of titanium carbide and platinum having a white color tone of 0.05 μm in thickness is formed on the surface of the titanium carbide plating film formed on the surface of these substrates by an ion plating method (hot cathode). Method) 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 (white 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 an ion plating method (hot cathode method) as follows. 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 were excellent in scratch resistance, and were formed with a high-quality white coating close to a stainless steel coating.

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.

Next, the watch case and the watch band were attached to a sputtering apparatus, and a gold alloy film (intermediate layer) having a thickness of 0.1 μm was formed on the surface of the white layer in an argon atmosphere by sputtering under the following film forming conditions.
<Film formation conditions>
Target: Gold alloy (96.3% by weight of gold, 3.7% by weight of iron)
Sputtering power supply: 0.4 kW
Gas: Argon gas Deposition pressure: 0.16 Pa
Acceleration voltage (bias voltage): Ground to -200V
Subsequently, these base materials were attached in a sputtering apparatus, and a titanium film having a thickness of 0.05 μm was formed on the surface of the intermediate layer in an argon atmosphere by the sputtering method under the following film forming conditions.
<Film formation conditions>
Target: Titanium Sputtering supply power: 0.8kW
Sputtering gas: Argon gas Deposition pressure: 0.16 Pa
Bias voltage: Grand to -200V
Next, a titanium nitride film and a zirconium nitride film exhibiting a gold color are formed on the surface of the formed titanium film in this sputtering apparatus in a mixed gas atmosphere of argon gas and nitrogen gas in this order by the sputtering method. A metal nitride film (finished film layer) having a lamination period (λ) of 21 nm and a film thickness of the entire laminated film of 0.68 μm was formed by alternately laminating under conditions.
<Film formation conditions>
Target: Titanium, zirconium Sputtering power supply: 0.8kW
Sputtering gas: Mixed gas of argon gas and nitrogen gas Film forming pressure: 0.16 Pa
Bias voltage: Grand to -200V
The metal nitride film obtained as described above had 60 layers, and the outermost layer film was a zirconium nitride film.

Next, for two-tone processing, masking is performed using petroleum-based resin at desired positions of the watch case and the watch band, and then the first stripping solution (HF: 10% by volume, HNO ₃ : 30% by volume, Water: 60% by volume) is used to peel the finished coating layer (required time 30-180 seconds). After washing with running water, the intermediate layer is peeled using a second stripping solution (KCN: 5% by volume, NaOH: 20% by volume, water 75% by volume) (conditions: 40 ° C., 5 minutes). After washing with running water, the mask is peeled off using methylene chloride, which is the third stripping solution, washed with alcohol and running water, and then dried to provide a two-tone watch case that has both a white (stainless steel) color tone and a gold color tone. And it becomes a watch band.

  The surface hardness of the finish film layer formed on the surface of the wristwatch case and wristband obtained as described above is HV4110 measured with a Fischer hardness meter (Fischer, Vickers indenter, load 5 mN, holding time 10 seconds). Indicated. The number of test samples was 5, and the numerical value of the surface hardness was represented by its average value.

Further, the obtained watch case and watch band were subjected to a corrosion resistance test and a wear test according to the following methods.
(1) Corrosion resistance test The corrosion resistance test was performed according to JIS H8502 (CASS test). The test time was 96 hours, and the corrosion resistance evaluation of the test surface was accepted when the rating number was 9.8 or more according to the rating number standard chart. As a result of the corrosion resistance test in Example 1, the rating number was 9.8 or more, that is, passed.
(2) Abrasion test The test piece on which the film is formed is fixed to the opening of the test piece mounting base with the test piece pressing plate and the test piece pressing screw with the film forming surface side facing down. Then, abrasive paper is affixed to the wear ring. An upward load is applied to the wear ring so as to press the abrasive paper against the test piece by a balance mechanism.

  Then, the test piece mounting base is reciprocated by a mechanism that converts the rotational movement of the motor into a reciprocating motion, and the wear wheel is rotated in the direction of the arrow by an angle of 0.9 ° for each reciprocation of the test piece mounting base. The rotation always brings the specimen into contact with a new, unworn area of the abrasive paper affixed to the wear wheel. The number of reciprocations of the specimen mounting base can be automatically set, and the wear tester automatically stops at the set number of times.

Further, as the abrasive paper to be attached to the wear ring, a wrapping film (with Al ₂ O ₃ particles having a particle diameter of 12 μm on the film surface) is used, and the contact load between this abrasive paper and the test piece is 500 g. The wear test was performed on the condition that the number of reciprocating motions of the mounting base was 100 times. Test conditions are shown below.

A coating of the present invention is formed on a test piece (SUS304) and a conventional gold coating layer mainly composed of titanium nitride is formed by ion plating, and then gold or a gold alloy is formed on this layer. A comparative test using a wear tester was performed on a test piece (SUS304) having a coating structure similar to that of an exterior part in which a gold coating layer as a main component was formed by an ion plating method.
<Test conditions>
Abrasion tester: Suga Test Instruments Co., Ltd.
NUS-ISO-2
Abrasive paper: Wrapping film Al ₂ O _{3 with} a particle diameter of 12 μm, # 1200
Contact load: 500g
Number of reciprocating motions: 100 times As a result of the abrasion test, the product of the present invention had no change in the surface state of both the coloring layer and the finished coating layer. In other words, it was a pass. On the other hand, in the conventional product, the gold alloy of the outermost layer was taken off, and countless scratches entered the gold-colored coating layer of titanium nitride.

  In Example 1, the intermediate layer and the finish coating layer were formed in this order on the surface of the color developing layer. However, the base layer and the finish coating layer were formed in this order on the substrate, and the intermediate layer and the color developing on the surface. Needless to say, there is no problem even if the layers are formed, that is, the layers of gold and white are interchanged.

  Also, there is no problem in forming colors other than white and gold by changing the thicknesses of the white layer and the finish coating layer, and further adding other colors to the white and gold.

  In Example 1 above, the masking treatment was performed after each layer was formed, but masking was performed after the white layer was formed, and then there was no problem even if the intermediate layer and the finish coating layer were formed and the mask was peeled off. Can be easily imagined. This method is as follows.

  The process of forming a resin mask on a part of the surface of the color development layer, the process of forming an intermediate layer and a finish film layer or a finish film layer, and detaching the resin mask and the film on the resin mask by immersing the decorative article in a peeling solution And a step of washing and drying the decorative article.

Furthermore, in Example 1, a watch case and a watch band are manufactured. Needless to say, the technique described in Example 1 can also be applied to decorative items such as a necklace, a pendant, and a brooch.

Claims (8)

A base material for ornaments made of at least one metal or alloy selected from stainless steel, titanium, and titanium alloy, and titanium (Ti), chromium (Cr), zirconium formed on the surface of the base material by a dry plating method (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or a tantalum (Ta) coating layer, and titanium, chromium, zirconium formed on the surface of the base layer by a dry plating method , Hafnium, vanadium, niobium, tungsten or tantalum carbide, nitride, a wear resistant layer which is a metal compound film made of nitride carbide, and platinum (Pt), palladium ( pd), Toka white layer is selected from the group consisting of rhodium (Rh) and these at least one alloy containing Together constitute, the coloring layer, and the wear-resistant layer having a thickness of 0.2 and 1.5 .mu.m, is composed of said white layer having a thickness of 0.002～0.1Myuemu, the coloring layer stainless steel color tone a coating having further at least a portion of the surface of the coloring layer exhibits an intermediate layer made of gold or gold alloy by a dry plating method, at least two golden color on at least part of the surface of the intermediate layer Ri Do from the finishing coat layer metal nitride film are repeatedly alternately laminated, the metal nitride film, the content of metal is 40～60Atm%, the content of nitrogen is 30～50Atm%, titanium nitride ( A decorative article characterized by being one of TiN), zirconium nitride (ZrN), hafnium nitride (HfN), and tantalum nitride (TaN) . The underlayer formed on the decorative article base material is formed by dry plating, titanium, chromium, zirconium, hafnium, vanadium, niobium or tantalum carbide (carbon atom content is 5 to 15 atomic%), 2. The decorative article according to claim 1, wherein the decorative article is a metal compound film made of nitride or carbonitride . The decorative article according to claim 1 or 2 , wherein the underlayer is a film having a thickness of 0.02 to 0.2 µm formed by a dry plating method . The decorative article according to claim 1 , wherein the white layer has a thickness of 0.01 to 0.08 μm . The decorative article according to claim 1 , wherein the color development layer has a surface hardness (HV; micro Vickers hardness meter, 5 g load) of 700 to 2,000 . Claim 1 lamination period of the metal nitride film exhibiting the golden tone (lambda) is 20 to 40 nm, and the total thickness of the laminated film is characterized in that it is a 0.1~3.0μm Ornaments listed in The finishing coating layer, and said metal nitride film, according to claim 1, characterized in that it consists of a golden coating consisting of gold or a gold alloy 0.005~0.1μm thickness formed on the coating film surface Ornaments . Using a material made of at least one metal or alloy selected from stainless steel, titanium, and titanium alloy, titanium (Ti), chromium (Cr), zirconium (Zr), hafnium is formed on the surface of the base material by a dry plating method. (Hf), vanadium (V), niobium (Nb), or a tantalum (Ta) coating layer is formed, and the surface of the underlayer is dry-plated by titanium, chromium, zirconium, hafnium, vanadium. Forming a wear-resistant layer that is a metal compound film made of carbide, nitride, or nitride carbide of niobium, tungsten, or tantalum, and further, platinum (Pt), palladium (Pd), Forming a white layer selected from the group consisting of rhodium (Rh) and an alloy containing at least one of them; A step of obtaining a coloring layer having a stainless steel color tone, and forming an intermediate layer made of gold or a gold alloy by a dry plating method on at least a part of the surface of the coloring layer, and at least a part of the surface of the intermediate layer In addition, titanium nitride (TiN) having a metal content of 40 to 60 atm% and a nitrogen content of 30 to 50 atm% exhibiting at least two kinds of gold color tones in a dry plating apparatus in a nitrogen gas atmosphere, A method for manufacturing a decorative article, characterized in that a metal nitride film made of zirconium nitride (ZrN), hafnium nitride (HfN), or tantalum nitride (TaN) is alternately and repeatedly laminated to form a finished film layer.