HK1063589B - Personal ornament having white coating film and process for producing the same - Google Patents
Personal ornament having white coating film and process for producing the same Download PDFInfo
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- HK1063589B HK1063589B HK04106319.7A HK04106319A HK1063589B HK 1063589 B HK1063589 B HK 1063589B HK 04106319 A HK04106319 A HK 04106319A HK 1063589 B HK1063589 B HK 1063589B
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Description
Technical Field
The present invention relates to a personal ornament (accessory) having a white coating film, and a method of manufacturing the personal ornament. More specifically, the present invention relates to a personal ornament having a hard white stainless steel colored coating film and a method for producing the same, and also relates to a personal ornament having a hard white colored platinum or platinum alloy coating film and a method for producing the same (hereinafter, "personal ornament" is simply referred to as "ornament").
Technical Field
Heretofore, many ornaments such as watches, necklaces, pendants, brooches, have been made of copper alloys for reasons of workability, material cost and others.
However, copper alloys are poor corrosion-resistant materials, and personal ornaments made of copper alloys as a base material are generally covered with a plating film formed by wet plating to prevent the base material from being corroded. Such a plating film is generally composed of an underlying nickel plating film formed by wet plating and an outermost plating film formed on the nickel plating film by wet plating. In order to make the outermost layer golden, a gold plating film is formed on the surface of the nickel plating film by wet plating. To make the outermost layer white, a platinum plating film, a platinum alloy plating film, or a rhodium plating film may be formed on the nickel plating film by wet plating. The thickness of the formed plating film is usually in the range of 1 to 5 μm.
However, the above-mentioned ornaments have a drawback of high cost due to the use of the outermost coating film containing a noble metal for corrosion resistance. Therefore, the outermost plating film of low-priced personal ornaments is generally thin and lacks long-term corrosion resistance. Further, in the production of low-priced ornaments, the noble metal plating bath solution should be strictly controlled and stored to obtain a stable thin outermost plating film, and the operator who performs plating should grasp a highly skilled plating technique to obtain a stable outermost plating film requiring a color tone. Further, it has not been possible to produce at low cost inexpensive personal ornaments having the characteristic white color of stainless steel, or having the characteristic beautiful white color of platinum or a platinum alloy.
Therefore, the present inventors have disclosed in JP-A-3-120355 (the term "JP-A" as used herein means an "unexamined Japanese patent publication") ｃA white ornament comprising ｃA base material coated on the surface with ｃA white hard coat film, the base material being further coated with ｃA platinum or platinum alloy coating film. However, the decoration does not have the characteristic white color required in the market, although it can also give a high quality image. A decorative article having a white coating and a method of making the same are disclosed in the specification of International publication WO-02/00958 of International patent application (PCT/JP01/05130) which has priority over Japanese patent application 2000-. This decorative article is inexpensive, since it is made of a low-quality metal (including an alloy) having low corrosion resistance as a base material and a white stainless steel coating film is applied to the surface thereof for imparting long-term corrosion resistance.
The metal substrate of the disclosed decorative article is coated with a white-colored stainless steel film formed by dry plating. Such ornaments are composed of a low-quality base metal such as a copper alloy, coated with a wet-plated nickel film or a dry-plated film of titanium carbide, zirconium carbide or the like as a base layer, and further coated with a stainless steel film as a surface layer.
However, such ornaments have only the outermost layer coated with a white stainless steel film without a surface coating of noble metal, and lack a large image and a high-quality image of the surface. Further, such a white coating film has a disadvantage in that the appearance quality deteriorates in a short period of time due to low hardness and low scratch resistance of the substrate or the undercoat film. Further, when a nickel plating film or a nickel alloy plating film is formed as an underlayer plating film depending on the kind of a substrate, nickel denaturation occurs, causing different rashes or eczemas, respectively.
Therefore, there is a need for a decorative article having a high quality image like a stainless steel coating film, an appearance which is not easily impaired by scratches or other causes, and which does not cause metal denaturation. There is also a need for a method of making such a decorative article.
In the above-mentioned JP-A-3-120355, TiN coating films are formed as white hard films in examples thereof. The coating film is dark gray or light gold. Therefore, the platinum coating film or the platinum alloy coating film formed on the TiN coating film is affected by the color tone of the white hard coating film (TiN coating film), and the characteristic beautiful color of platinum or platinum alloy is not generated. Further, in the case where the TiN coating film is thin, the substrate may be dented by external impact or pressure, and the platinum or platinum alloy coating film may be dented to cause defects, which is disadvantageous. The platinum coating film thickness of the article in the example of this document is 0.1 μm, which is disadvantageous in terms of cost. Further, if the platinum or platinum alloy coating film cannot be successfully formed, it is necessary to remove the platinum or platinum alloy coating film and re-form it. Aqua regia can be used to remove the membrane. Aqua regia is disadvantageous in that it can not only corrode a hard white TiN coating film but also corrode the surface of a metal substrate, which will no longer form a film.
Therefore, there is a need for a decorative article having a characteristic color of a platinum or platinum alloy coating film, excellent quality, an appearance which is not easily impaired by dishing, scratching, or other reasons, and a white coating film of low cost and high quality. There is also a need for a method of making such ornaments that removes the platinum or platinum alloy coating film without corroding the ornament substrate, underlying layer or titanium carbide layer, and regenerates the ornament by reforming the platinum or platinum alloy coating.
Object of the Invention
The present invention has been made to solve the above problems and provides a personal ornament having excellent quality, less apt to deteriorate in appearance by scratching or other causes, a white coating film having a high quality image such as a stainless steel film, and particularly not causing metal denaturation, and a method for producing the same.
The present invention has been made to solve the above problems, and provides a personal ornament having a characteristic color of platinum or a platinum alloy, excellent in quality, less likely to deteriorate in appearance due to scratches or other causes, a white coating film of high quality and low cost, and a method for manufacturing the ornament. The present invention also aims to provide a personal ornament which can remove a defective platinum or platinum alloy coating film without corroding the ornament substrate, the under layer or the titanium carbide layer and regenerate the ornament by forming again the platinum or platinum alloy coating layer, and a method of manufacturing the ornament.
Disclosure of Invention
The first personal ornament of the present invention has the outermost layer of the white coating film comprising the noble metal or noble metal alloy formed by dry plating. Such an ornament includes:
a base part of a decoration made of metal or ceramic,
a bottom layer formed on the base member,
a colored layer comprising a wear-resistant layer formed on a surface of the underlayer by dry plating and an outermost layer formed on a surface of the wear-resistant layer by dry plating;
the coloring layer is a white hard coating film with stainless steel color, and comprises a wear-resistant layer with the thickness of 0.2-1.5 μm and an outermost layer with the thickness of 0.002-0.1 μm. In the case where the outermost layer is a platinum coating film or a platinum alloy coating film, the coating film thickness is 0.002 to 0.01. mu.m.
The underlayer is preferably a non-nickel layer formed by dry plating or wet plating to prevent nickel denaturation.
The first ornament of the present invention has a mixed layer between the wear-resistant layer and the outermost layer, the mixed layer being composed of a metal compound forming the wear-resistant layer and a metal or alloy forming the outermost layer.
According to L*a*b*The color evaluation value of the colored layer in the color space (CIE colorimeter system) is preferably 70 <L*＜91，-0.1＜a*< 3.0 and 1.0 < b*Less than 5.5, preferably 75 less than L*＜85，0＜a*< 2.0 and 3.5 < b*＜5.0。
L of a colored layer formed on a decorative base article and having various finished surfaces*、a*、b*Preferably at a value of*＝±6.0，Δa*1.55 and Δ b*Range ± 2.25.
The first decorative article of the present invention may have at least one coating film formed by dry plating or wet plating and having a color different from that of the white coating film of the colored layer on a part of the surface of the white coating film of the color of stainless steel having the colored layer described above.
The coating film having a color different from that of the colored layer (hereinafter sometimes referred to as "differential coloring film") is preferably made of gold, an alloy of gold, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). The differential coloring film having a color different from that of the colored layer may have a two-layer structure, i.e., a lower layer composed of titanium nitride, zirconium nitride, or hafnium nitride and an upper layer composed of gold or an alloy of gold. The alloy of gold used for forming the differential coloring film having a color different from that of the coloring layer is preferably a non-nickel alloy to prevent nickel from being denatured.
The decoration may have a titanium coating film and a silicon coating film formed on the titanium coating film, which may be between the colored layer and the differentially colored diamond-like carbon (DLS) coating film.
The first ornament of the present invention may have an outermost layer that is a mixed layer containing a mixture of the metal compound of the above-described wear-resistant layer and at least one selected from platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof.
The surface hardness (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) of the first ornament of the present invention is preferably in the range of 700-.
The first decoration of the invention can be used for external parts of watches such as watch cases, watch bands, watch crowns (watchcrown) and back covers of watch cases.
The first personal ornament of the present invention has an outermost layer of a white coating film of a noble metal or a noble metal alloy formed by dry plating, and the process for producing the ornament comprises the steps of:
manufacturing a basic part of a decoration from metal or ceramic by means of a processing device,
forming a primer layer on the surface of the base member by dry plating or wet plating,
a colored layer having a stainless steel color is formed, that is, a wear-resistant layer is first formed of a metal compound on the underlayer by dry plating, and then, an outermost layer is formed of platinum or a platinum alloy on the wear-resistant layer by dry plating.
From the viewpoint of preventing the denaturation of nickel, the underlayer is preferably a non-nickel film formed by dry plating or wet plating.
The metallic material useful for the base part of ornaments is generally at least one metal (including alloys) selected from the following: stainless steel, titanium alloys, copper alloys, and tungsten carbide. The surface of the decorative base article may be finished in at least one of a specular surface and a patterned surface selected from the group consisting of a matte pattern, a fine grain pattern, a honing pattern, a molding pattern, and an etching pattern.
A base part for ornaments made of a ceramic material is produced by mixing 100 parts by weight of a mixture containing 3 to 7% by weight of yttrium oxide (Y)2O2) A mixture of stabilized zirconia powder of magnesium oxide (MgO) or calcium oxide (CaO) and 20-25 parts by weight of a binder is injection molded, and then mechanically rough machined, degreased, fired, ground and polished. Such a decorative base part is white.
Preferably, a surface of a decorative base member made of a metal other than copper and copper alloys or made of ceramics is coated with a primer layer containing titanium (Ti), chromium (Cr)(Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta). However, the surface of the underlayer is coated with a metal compound coating film as a wear-resistant layer, and the wear-resistant layer is made of titanium carbide (TiC), chromium carbide (Cr)3C2) In the case of zirconium carbide (ZrC), hafnium carbide (HfC), Vanadium Carbide (VC), niobium carbide (NbC), tungsten carbide (WC), or tantalum carbide (TaC), the primer layer is preferably a coating film of a metal compound formed by dry plating a metal carbide having a carbon content of 5 to 15 atomic%, such as titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide, or tantalum carbide. In this case, the coating layer of the metal carbide forming the coating film of the metal compound as the underlayer is preferably the same metal as the metal of the metal carbide forming the wear-resistant layer.
The base part of ornaments made of a metal other than copper and copper alloys or made of ceramics is preferably coated on the surface thereof with the above-mentioned primer layer by dry plating to a thickness of 0.02 to 0.2. mu.m.
The ornament base member composed of copper or copper alloy is preferably coated with a nickel coating layer as a primer layer on the surface by wet plating to a thickness of 1 to 10 μm, and may also be coated with an amorphous nickel-phosphorus alloy coating film on the nickel coating film by wet plating to a thickness of 3 to 10 μm.
However, in order to prevent the nickel from being denatured, it is preferable that the decoration base member composed of copper or copper alloy is coated on its surface with a coating film as a primer layer by wet plating, the primer layer being composed of at least one selected from the group consisting of: copper, palladium, copper-tin alloy, copper-tin-zinc alloy, and copper-tin-palladium alloy, and the thickness thereof is 2 to 9 μm.
The wear-resistant layer is preferably made of titanium carbide (TiC) or chromium carbide (Cr)3C2) A coating film of a metal compound comprising zirconium carbide (ZrC), hafnium carbide (HfCo), Vanadium Carbide (VC), niobium carbide (NbC), tungsten carbide (WC), or tantalum carbide (TaC).
The thickness of the wear-resistant layer is usually in the range of 0.2 to 1.5. mu.m, preferably 0.5 to 1.0. mu.m.
The outermost layer is preferably a coating film composed of at least one substance selected from platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof.
The outermost coating thickness is usually in the range of 0.002 to 01 μm, preferably 0.005 to 0.1 μm, more preferably 0.01 to 0.08. mu.m. However, when the outermost layer is formed of a platinum coating film or a platinum alloy coating film, the film thickness is in the range of 0.002 to 0.01. mu.m, preferably 0.005 to 0.01. mu.m.
In the present invention, a mixed layer is formed between the wear-resistant layer and the outermost layer, the mixed layer containing a metal compound forming the wear-resistant layer and a metal or alloy forming the outermost layer.
The bottom layer, the wear-resistant layer, the mixed layer and the outermost layer are each preferably formed by at least one of sputtering, ion plating and arc discharge.
In the method of manufacturing the first decorative article of the present invention, at least one differential colored film having a color different from that of the colored layer is formed on a part of the surface of the white coating film composed of the colored layer having a color of stainless steel by dry plating or wet plating.
The second personal ornament (accessory) of the present invention has an outermost layer of a white decorative coating film containing a noble metal or noble metal alloy formed by dry plating. Such an ornament includes:
a base part of a decoration made of metal or ceramic,
a bottom layer formed on the base member,
a titanium carbide layer (wear-resistant layer) formed on the surface of the underlayer by dry plating,
a decorative coating layer (outermost layer) formed on the surface of the titanium carbide layer, wherein the titanium carbide layer has a thickness of 0.5 to 1.0 μm, and the decorative coating layer is a white coating film having a thickness of 0.03 to 0.06 μm.
The underlayer is preferably a non-nickel layer formed by dry plating or wet plating to prevent denaturation of nickel.
A mixed layer is formed between the titanium carbide layer and the decorative coating layer, the mixed layer being composed of titanium carbide forming the titanium carbide layer and platinum or a platinum alloy forming the decorative coating layer, and having a thickness of 0.005 to 0.1 μm.
In addition, a stainless steel coating is provided between the titanium carbide layer and the decorative coating by dry plating. This stainless steel coating protects the base article, the primer layer and the titanium carbide coating from corrosion. Therefore, if the plating with platinum or platinum alloy is not successfully performed, the formed defective platinum or platinum alloy coating film can be removed with aqua regia without corroding the underlying layer, and the platinum or platinum alloy coating film can be formed again on the surface of the stainless steel coating layer to regenerate the decoration. The thickness of the stainless steel coating is preferably in the range of 0.05-1.5. mu.m.
The stainless steel coating is preferably comprised of an austenitic stainless steel having the composition 0.01-0.12 volume percent carbon, 0.1-1.5 volume percent silicon, 1.0-2.5 volume percent manganese, 8-22 volume percent nickel, 15-26 volume percent chromium, and the balance iron. The coating film of the austenitic stainless steel is preferably formed by at least one of sputtering, ion plating and arc discharge.
According to L*a*b*The color evaluation value of the decorative coating in the color space (CIE colorimeter system) is preferably 85 < L*＜95，1.5＜a*< 4.0 and 4.5 < b*The range of less than 6.5, more preferably 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
The primer layer, the titanium carbide layer, the mixed layer and the decorative coating layer are each preferably formed by at least one of sputtering, ion plating and arc discharge.
The second decorative article of the present invention has, on a part of the surface of the decorative coating layer, at least one type of differential colored film (hereinafter, also referred to as "differential colored film") having a color different from that of the decorative coating layer, formed by dry plating or wet plating.
The differentially coloured film having a colour different from that of the decorative coating is preferably composed of gold, an alloy of gold, titanium nitride, zirconium nitride, hafnium nitride or diamond-like carbon (DLC). The differentially colored film having a color different from that of the decorative coating may have a two-layer structure, i.e., a lower layer composed of titanium nitride, zirconium nitride, or hafnium nitride, and an upper layer composed of gold or an alloy of gold. The alloy of gold used to form the differentially coloured film of a colour different from that of the decorative coating is preferably selected from non-nickel gold alloys to prevent denaturation of the nickel.
The ornament has a titanium coating film and a silicon coating film formed on the film, and has a color different from that of the decorative coating between the decorative coating and a Diamond Like Carbon (DLC) film.
The decorative coating may be a mixed layer of titanium carbide forming a titanium carbide layer and platinum or a platinum alloy.
The second ornament having a white coating film of the present invention has a decorative coating having a surface hardness (HV; Vickers hardness micro-tester, load: 5 g) in the range of 1000-2000.
The second decorative item of the invention may be a watch exterior part such as a watch case, a watch strap, a watch crown and a back cover of a watch case.
The second personal ornament of the present invention has a white decorative coating film of a noble metal or a noble metal alloy formed by dry plating, and the process for producing the ornament comprises the steps of:
manufacturing a basic part of a decoration from metal or ceramic by means of a processing device,
forming a primer layer on the surface of the base member by dry plating or wet plating,
forming a titanium carbide layer on the surface of the underlayer by dry plating,
a decorative coating layer composed of platinum or a platinum alloy is formed on the titanium carbide layer as the outermost layer by dry plating.
The base article of the garnish used in the manufacturing method may be the same as that of the first garnish of the present invention having the white coating film.
The base layer formed on the surface of the base member of the decoration may be the same as the base layer constituting the first decoration of the present invention.
In the present invention, a mixed layer is formed between the titanium carbide layer and the decorative coating layer, and the mixed layer is composed of titanium carbide forming the titanium carbide layer and platinum or a platinum alloy.
And forming a stainless steel coating between the titanium carbide layer and the decorative coating through dry plating.
In the method of manufacturing a second decorative component according to the present invention, the titanium carbide layer and/or the mixed layer are preferably formed by dry plating using methane gas.
In the method of manufacturing the second decorative article of the invention, at least one layer of a differentially colored film having a color different from that of the decorative coating is formed on a part of the surface of the white coating by dry plating or wet plating.
Further, between the decorative coating and a coating film such as Diamond (DLC) different in color from the decorative coating, a titanium coating film is formed, and a silicon coating film may also be formed thereon.
Best Mode for Carrying Out The Invention
Hereinafter, a personal ornament having a white coating film and a method for manufacturing the same according to the present invention will be described in detail.
The first personal ornament of the present invention comprises an ornament base member, a base layer preferably free of nickel, and a colored layer. The coloring layer comprises an abrasion-resistant layer and an outermost layer, or the abrasion-resistant layer, the mixed layer and the outermost layer.
The first decorative article of the present invention has at least one differential colored film having a color different from a colored layer of stainless steel on a part of the surface of a white coating film constituting the colored layer.
The second decorative article of the present invention comprises a decorative base product, a preferably nickel-free base layer, a titanium carbide layer and a decorative coating (outermost layer). A stainless steel coating may also be formed between the titanium carbide layer and the decorative coating by dry plating.
Basic product of ornament
The base article for the first and second personal ornaments each having a white coating film is made of metal or ceramic.
The metal (including alloy) specifically includes: stainless steel, titanium alloys, copper alloys, and tungsten. The metals may be used alone or in combination of two or more.
The ceramic specifically includes zirconia ceramic. Useful zirconia ceramics are stabilized zirconia containing 3-7% by weight yttria (Y2O2) or another stabilizer such as magnesia (MgO) and calcia (CaO), and are white. Specifically, the zirconia ceramic contains zirconia and a binder as main components, and the zirconia ceramic contains 20 to 25 parts by weight of the binder based on 100 parts by weight of a stabilized zirconia powder containing 3 to 7% by weight of a yttria-based stabilizer. The zirconia was white after firing. The binder is a mixture of at least two substances selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene-vinyl acetate, polybutylmethacrylate, polyacetal, wax, stearic acid, and the like.
In the present invention, zirconia ceramics having a content of yttrium oxide (yttria) -based stabilizer of 3 to 7 wt% are selected as the zirconia ceramics, and since the content of the stabilizer is less than 3 wt%, the formed zirconia ceramics have low impact strength (brittleness) and are cracked by an external impact force, while the content of the stabilizer is more than 7 wt%, the zirconia ceramics have low impact strength and are cracked by an external impact force. It is estimated that the zirconia ceramic has a crystal structure of a cubic-monoclinic mixed system with a stabilizer content in the above range, and has stable impact resistance.
The amount of the binder is 20 to 25 parts by weight based on 100 parts by weight of the powdered zirconia. Since the amount of the binder is less than 20 parts by weight, the injection-moldability of the ceramic is low and the mold cannot be completely filled, and the amount of the binder is more than 25 parts by weight, a longer time is required for removing oil stains, the productivity is lowered, and the molded product may be broken.
The metal is machined in a conventional manner to produce a decorative base part made of metal. If necessary, the decorative base article can be surface finished in at least one of a specular surface and a patterned surface selected from the group consisting of a matte pattern, a fine grain pattern, a honing pattern, a molding pattern, and an etching pattern.
A basic part of a decorative article, for example a watch case, made of ceramic is processed as follows. A material made primarily of zirconia and a binder is injection molded into the shape of a watch case to make a base part. The formed article is subjected to rough machining. And removing oil stains from the rough processed workpiece and roasting to obtain the rough workpiece of the watch shell. The rough part is further subjected to mechanical processing of grinding and polishing.
The ornaments (accessories), including parts, of the invention include watch exterior parts, such as watch case, watch band, watch crown and back cover of watch case, as well as belt loop, ring, necklace, bracelet, earring, pendant, brooch, cuff button, tie clip, bag, badge, spectacle frame, camera body and door handle.
In the present invention, before forming the primer layer on the surface, the surface of the decorative base member is preferably washed and degreased with a conventional organic solvent or the like.
Bottom layer
The underlayer of the first or second decorative article of the present invention is a plated film formed by wet plating or dry plating.
The base part of a decoration made of a metal other than copper and copper alloys, or made of ceramics, is preferably coated on the surface by dry plating with a metal underlayer containing titanium (Ti), chromium (Cr), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta). However, a metal compound coating film is applied as a wear-resistant layer on the surface of the under layer and the wear-resistant layer contains titanium carbide (TiC), chromium carbide (Cr)3C2) Zirconium carbide (ZrC), hafnium carbide (H)In the case of fC), Vanadium Carbide (VC), niobium carbide (NbC), tungsten carbide (WC) or tantalum carbide (TaC), the underlying layer is preferably a metal compound coating film formed of a metal carbide having a carbon content of 5 to 15 atomic%, such as titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide or tantalum carbide. The metal compound coating film has a carbon atom content gradually decreasing toward the surface of the decorative base member. Such a metal compound coating film is called a gradient film.
The thickness of the metal coating film and the metal compound coating film (under layer) is preferably in the range of 0.02 to 0.2. mu.m, more preferably 0.05 to 0.1. mu.m.
Dry plating includes Physical Vapor Deposition (PVD) such as sputtering, arc discharge, ion plating, and ion beam spraying, and CVD. Among them, sputtering, arc discharge and ion plating are preferable.
In the first or second decorative article of the invention, in the case where the decorative article base member is made of copper or a copper alloy, the under layer is preferably composed of a nickel coating film (thickness of 1 to 10 μm, preferably 1 to 5 μm) formed by wet plating and an amorphous nickel-phosphorus alloy coating (thickness of 3 to 10 μm, preferably 3 to 5 μm) formed thereon.
However, in the case where the base member of the ornament is made of copper or a copper alloy for the purpose of preventing nickel from being denatured, the base layer is preferably a coating film made of at least one substance selected from the group consisting of necklaces by wet plating: copper, palladium, copper-tin alloys, copper-tin-zinc alloys and copper-tin-palladium alloys, with a thickness of 2 to 9 μm, preferably 2 to 3 μm.
Coloured layer
The colored layer (color-developing layer) of the first ornament of the present invention comprises a wear-resistant layer and an outermost layer; or the abrasion resistant layer, the mixed layer and the outermost layer.
The colored layer of the second ornament of the present invention comprises a titanium carbide layer (wear-resistant layer) and a decorative coating layer (outermost layer); or a titanium carbide layer (wear layer), a stainless steel coating, and a decorative coating (outermost layer); or a titanium carbide layer (wear layer), a hybrid layer, and a decorative coating layer (outermost layer).
These layers may be formed by dry plating. The dry plating method specifically comprises: physical Vapor Deposition (PVD) such as sputtering, arc discharge, ion plating and ion beam spraying, and CVD. Among them, sputtering, arc discharge and ion plating are preferable.
[ wear-resistant layer ]
The above-mentioned wear-resistant layer is a coating film of a metal compound formed on the surface of the underlayer by dry plating.
In the first decorative article of the present invention, the wear-resistant layer is preferably made of titanium carbide (TiC) or chromium carbide (Cr)3C2) Zirconium carbide (ZrC), hafnium carbide (HfC), Vanadium Carbide (VC), niobium carbide (NbC), tungsten carbide (WC), or tantalum carbide (TaC).
In the second decorative article of the present invention, the titanium carbide layer is used as the wear-resistant layer, and the metal compound coating film for the wear-resistant layer is a titanium carbide coating film.
The thickness of the wear resistant layer is 0.2-1.5 μm, preferably 0.5-1.0. mu.m.
[ stainless Steel coating ]
A stainless steel layer may be provided to constitute a second decoration of the invention. The stainless steel layer is formed between the titanium carbide layer and the decorative coating layer, and the reproducibility of the garnish can be enhanced. It was found that when the decorative coating could not be successfully formed (the formed decorative coating was irregular, etc.), the formed defective decorative coating was removed using aqua regia. Aqua regia not only removes the decorative coating, but also corrodes the titanium carbide layer, the bottom layer and the surface of the basic part of the ornament, and the regeneration of the ornament cannot be carried out. Providing a stainless steel coating solves this problem. The stainless steel coating protects the titanium carbide layer, the bottom layer and the surface of the basic article of decoration from corrosion when the decorative coating is removed with aqua regia. Therefore, it is possible to remove the decorative coating having the defect with aqua regia and to form the decorative coating again on the surface of the stainless steel coating film, so that the decorative article having the defective decorative coating can be regenerated.
The thickness of the stainless steel coating formed by sputtering dry plating is in the range of 0.05-1.5 μm. The stainless steel coating is preferably composed of an austenitic stainless steel having a composition of 0.01-0.12 vol.% carbon, 0.1-1.5 vol.% silicon, 1.0-2.5 vol.% manganese, 8-22 vol.% nickel, 15-26 vol.% chromium, and the balance iron.
[ outermost layer ]
The outermost layer of the first decorative article of the invention is a coating film composed of a noble metal (including an alloy thereof) formed by dry plating on the surface of the wear-resistant layer or the surface of the mixed layer described below.
Such a noble metal coating film is formed of at least one noble metal selected from platinum (Pt), palladium (Pd), rhodium (Rh), and alloys thereof.
The first ornament uses a mixed layer described below as the outermost layer.
The thickness of the outermost layer is 0.002 to 0.1. mu.m, preferably 0.005 to 0.1. mu.m, more preferably 0.01 to 0.08. mu.m. However, in the case where the outermost layer is composed of a platinum coating film or a platinum alloy coating film, the film thickness is 0.002 to 0.01. mu.m, preferably 0.05 to 0.08. mu.m.
The decorative coating layer as the outermost layer of the second decorative article of the invention is a coating film of platinum or a platinum alloy as a noble metal formed on the surface of a titanium carbide layer (wear-resistant layer) which has been formed by dry plating, or the surface of a mixed layer described below, by dry plating.
The decorative coating of the second garnish may be a mixed layer (a mixed layer composed of titanium carbide forming a titanium carbide layer and platinum or a platinum alloy) described below.
The thickness of the decorative coating is 0.02 to 0.1. mu.m, preferably 0.03 to 0.06. mu.m.
Preferably, the alloy forming the outermost layer of the decorative coating is a non-nickel alloy.
[ Mixed layer ]
The first decorative article of the present invention may have a mixed layer formed between the wear-resistant layer and the outermost layer, if necessary. The mixed layer may be a coating film formed by dry plating.
Such a coating film is composed of a metal compound (e.g., titanium carbide) forming a wear-resistant layer and a metal or alloy (e.g., platinum or a platinum alloy) forming an outermost layer. The thickness of the mixed layer is generally 0.005 to 0.1. mu.m, preferably 0.01 to 0.08. mu.m. The hybrid layer may provide greater adhesion between the abrasion resistant layer and the outermost layer.
A color evaluation value of a colored layer comprising the abrasion-resistant layer and the outermost layer, or the colored layer comprising the abrasion-resistant layer, the mixed layer and the outermost layer*a*b*The color space (CIE colorimeter system) is preferably 70 < L*＜91，-0.1＜a*< 3.0 and 1.0 < b*Less than 5.5, preferably 70 < L*＜85，0＜a*< 2.0 and 3.5 < b*＜5.0。
The color evaluation values of the colored layer formed on the mirror-finished ornament base and the colored layer formed on the fine-grain finished (fine-grain pattern) ornament base are determined in accordance with L*a*b*The color space (CIE colorimeter system) is preferably more than 85L*＜90，0＜a*< 2.0 and 3.5 < b*In the range < 5.5, and at 75 < L*＜85，0＜a*< 2.0 and 3.5 < b*The range of < 5.0.
L of a colored layer formed on a decorative base article and having various finished surfaces*、a*、b*Preferably at a value of*＝±6.0，Δa*1.55 and Δ b*Range ± 2.25.
The surface hardness (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) of the colored layer is preferably in the range of 700-.
The first decorative article of the present invention has excellent quality due to the presence of at least the wear-resistant layer having a thickness of 0.2 to 1.5 μm and the outermost layer of noble metal having a thickness of 0.002 to 0.1 μm on the surface of the under layer, has a very small possibility that the appearance quality is damaged by scratching or other reasons, and has a white coating film having an appearance like a stainless steel coating film.
The second decorative article of the present invention may optionally have a mixed layer between the titanium carbide layer and the decorative coating. The mixed layer may be formed by dry plating.
This coating film is composed of titanium carbide forming a titanium carbide layer and platinum or a platinum alloy forming a decorative coating layer. The thickness of the mixed layer is generally 0.005 to 0.04. mu.m, preferably 0.008 to 0.03. mu.m. The hybrid layer provides greater adhesion between the titanium carbide layer and the decorative coating.
A coloring layer comprising a titanium carbide layer and a decorative coating layer, or a coloring layer comprising a titanium carbide layer, a mixed layer and a decorative coating layer, the color evaluation value of which is in accordance with L*a*b*The color space (CIE colorimeter system) is preferably more than 85 < L*＜90，1.5＜a*< 4.0 and 4.5 < b*The range of less than 6.5, more preferably 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
The color evaluation values of the colored layer formed on the mirror-finished ornament base and the colored layer formed on the fine-grain-finished (fine grain pattern) ornament base were determined in accordance with L*a*b*Color space (CIE chromaticity system) of 85 < L*＜90，0＜a*< 2.0 and 3.5 < b*In the range < 5.0, and at 75 < L*＜85，0＜a*< 2.0 and 3.5 < b*The range of < 5.0.
L of a colored layer formed on a decorative base article and having various finished surfaces*、a*、b*Preferably at a value of*＝±6.0，Δa*1.55 and Δ b*Range ± 2.25.
A surface layer comprising a titanium carbide layer and a decorative coating; or the surface layer comprising the titanium carbide layer, the mixed layer and the decorative coating layer has a surface hardness (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) preferably in the range of 700-.
Since at least a titanium carbide coating layer having a thickness of 0.5 to 1.0 μm and a decorative coating layer having a thickness of 0.03 to 0.06 μm on the surface of the under layer are present, the second decorative article of the present invention has a very small possibility that the appearance quality is impaired by scratches or other causes, and has a white coating film of excellent quality.
Additional coating film on the colored film
The first ornament of the present invention has at least one other film (differential coloring film) on a part of the white coating film having a color of stainless steel, formed by dry plating or wet plating, which is different from the color of the coloring layer.
The second decorative article of the present invention has at least one other film (differential coloring film) formed by dry plating or wet plating on a part of the surface of a white coating film having a color of platinum or a platinum alloy, the color being different from that of the coloring layer.
The differentially colored film is preferably composed of gold, an alloy of gold (preferably a gold alloy other than nickel), titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon (DLC). This coating film is visible and is the outermost coloured layer. Therefore, the decoration of the present invention includes two-tone decorations and the like.
The thickness of the differentially colored film for plating is preferably 0.1 to 1.0. mu.m, more preferably 0.2 to 0.5. mu.m.
The differentially colored film may have a two-layer structure including a base layer of titanium nitride, zirconium nitride or hafnium nitride and an upper layer of gold or a gold alloy (preferably a gold alloy other than nickel; e.g., a gold-iron alloy). In this structure, the thickness of the lower layer is generally 0.2 to 1.5. mu.m, preferably 0.5 to 1.0. mu.m, and the thickness of the upper layer is generally 0.03 to 0.2. mu.m, preferably 0.05 to 0.1. mu.m.
The differential coloring film may have a three-layer structure including a base layer of titanium, an intermediate layer of titanium nitride, zirconium nitride or hafnium nitride, and an upper layer of gold or a gold alloy (preferably a gold alloy other than nickel). In this structure, the thickness of the lower layer is generally 0.02 to 1.0. mu.m, preferably 0.03 to 0.8. mu.m, the thickness of the intermediate layer is generally 0.2 to 1.5. mu.m, preferably 0.5 to 1.0. mu.m, and the thickness of the upper layer is generally 0.03 to 0.2. mu.m, preferably 0.05 to 0.1. mu.m.
Further, such a differential colored film includes a titanium coating film, a silicon coating film, and a diamond-like carbon (DLC) coating film formed in this order on a part of the surface of the colored layer. In this structure, the thickness of the lower layer is generally 0.05 to 0.3. mu.m, preferably 0.08 to 0.2. mu.m, the thickness of the intermediate layer is generally 0.05 to 0.3. mu.m, preferably 0.08 to 0.2. mu.m, and the thickness of the upper layer is generally 0.5 to 3.0. mu.m, preferably 0.8 to 1.5. mu.m.
The layers constituting the above single-layer structure, two-layer structure and three-layer structure are generally formed by a dry plating method. Dry plating methods specifically include Physical Vapor Deposition (PVD) such as sputtering, arc discharge, ion plating, and ion beam spraying; and CVD. Among them, sputtering, arc discharge and ion plating are preferable.
The differential coloring layer film may have a two-layer structure including a lower layer composed of a strike plated film of gold formed by wet plating and an upper layer composed of gold or an alloy of gold (preferably a gold alloy coating film other than nickel) formed by wet plating. In this structure, the thickness of the lower layer is generally 0.05 to 0.2. mu.m, preferably 0.05 to 0.1. mu.m, and the thickness of the upper layer is generally 1.0 to 10 μm, preferably 1.0 to 3.0. mu.m.
For example, such a decorative article having a differentially colored coating film on a portion of the surface of the colored layer can be produced by the following method.
First, a primer layer is formed on the surface of the decoration base member. The colored layer is formed on the surface of the base layer. A part of the surface of the colored layer is subjected to a masking treatment. The surface of the colored layer and the surface of the mask are covered with a plating film having a color different from that of the colored layer by dry plating or wet plating. Thereafter, the mask is removed together with the plating film formed thereon. The steps of masking, plating, and removing the mask are performed at least once. Thus, the outermost coating film having two or more tones, i.e., a white coating film having a stainless steel color or a white coating film having a platinum or platinum alloy color, and at least one differential coloring plating film are produced.
Effects of the invention
The decorative article of the present invention has excellent quality, high scratch resistance, no damage in appearance due to scratches or other causes, and has a white coating film with a high quality image like a stainless steel image (image). The invention also provides a method of making such an ornamental article. Another decorative article of the present invention does not cause denaturation of nickel metal and has excellent quality, high scratch resistance, no deterioration in appearance due to scratches or other causes, and a white coating film of high quality image like that of stainless steel. The invention also provides a method of making such an ornamental article.
The present invention also provides a decorative article having excellent quality of a characteristic color of platinum or a platinum alloy, high hardness, no deterioration in appearance due to dents, scratches or other causes, and a white coating film of excellent quality, which can be produced at low cost. Methods of making such ornaments are also provided. The ornament of the present invention has a stainless steel coating between the titanium layer and the decorative coating. When it is found that the formed platinum or platinum alloy coating film has defects like color irregularities, the film can be regenerated by removing the platinum or platinum alloy coating film using aqua regia without causing corrosion of the ornament base, the under layer and the titanium carbide layer, and forming an additional platinum or platinum alloy coating film after the film is removed. Methods of making such ornaments are also provided.
Examples
The invention is illustrated with reference to the following examples, which are not to be construed as limiting the invention.
Example A1
Basic parts of watch cases and watch bands were manufactured from stainless steel (SUS316L) by machining, and these basic parts were washed with an organic solvent and cleaned of oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium plating film (primer layer) was formed on the surface of the base member by ion plating (hot cathode method) under the following film forming conditions to a thickness of 0.05. mu.m.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the plated titanium carbide film formed on the base member, a white mixed film (mixed layer) of titanium carbide and platinum was formed by ion plating (hot cathode method) in a thickness of 0.05 μm under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium, platinum
An electron gun: 10kV, 300mA (source: titanium)
10kV, 500mA (source: platinum)
Gas: methane gas
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the mixed plating film of titanium carbide and platinum on the base article, a white coating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following conditions, to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1400 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). Watch cases and watch bands have a white coating film formed on a platinum coating film, have high scratch resistance, and give high-quality images similar to those of a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A2
Basic parts of watch cases and watch bands are manufactured from brass (copper alloy) by machining, and these basic parts are washed with an organic solvent and cleaned from oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
The above base member was immersed in a plating bath solution having the following composition and subjected to electroplating under the plating conditions listed below to form a copper-tin alloy plating film (primer layer 1) having a thickness of 2 μm on the surface of the base member. The formed plating film was washed with water.
Copper-tin plating
< plating bath solution composition >
Copper cyanide 15 g/l (calculated as copper)
Sodium stannate 15 g/l (calculated as stannum)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 30 g/l
Whitening agent 10 ml/l
< plating conditions >
pH 12.5(50℃)
The temperature of the solution is 50 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-mentioned base member coated with the copper-tin alloy plating film was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a copper-tin-zinc alloy plating film (primer layer 2) having a thickness of 2 μm on each surface of the copper-tin alloy plating film. The formed plating film was washed with water.
Copper-tin-zinc alloy plating
< plating bath solution composition >
Copper cyanide 8.5 g/l (in terms of copper)
34.0 g/l sodium stannate (calculated as tin)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 50 g/l
Whitening agent 15 ml/l
Whitening agent 25 ml/l
< plating conditions >
pH 13.0(50℃)
The temperature of the solution is 60 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-mentioned base member coated with the copper-tin-zinc alloy plating film was immersed in a plating bath solution having the following composition, and strike plating was carried out under the plating conditions listed below to form a palladium strike plating film (base layer 3) having a thickness of 0.5 μm on the copper-tin-zinc plating film. The formed plating film was washed with water.
Palladium strike electroplating
< plating bath solution composition >
Pure palladium 1-3 g/l
< electroplating Condition >
pH 8
The temperature of the solution was 32 deg.C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a tantalum coating film (underlayer 4) was formed on the palladium strike electroplated coating surface to a thickness of 0.05 μm by a sputtering magnetron sputtering system under the following film formation conditions.
< film Forming conditions >
Target: tantalum
Sputtering gas: argon gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Acceleration voltage (bias): -50V
On each surface of the tantalum plated film formed on the base article, a white tantalum carbide coating film (abrasion resistant layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: tantalum
Sputtering gas: methane-argon gas mixture
Film forming pressure: 0.665Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Finally, on the surface of the tantalum carbide coating film formed on the base member, a white palladium coating film (outermost layer) having a thickness of 0.005 μm was formed by sputtering (magnetron sputtering system) under the following conditions to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
Target: palladium (II)
Sputtering gas: argon gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A3
Basic parts of watch cases and watch bands were manufactured from stainless steel (SUS316L) by machining, and these basic parts were washed with an organic solvent and cleaned of oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, by ion plating (hot cathode method), a titanium plating film (primer layer) having a thickness of 0.05 μm was formed on each surface of the base member under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium plating film formed on the base article, a white titanium carbide plating film (wear-resistant layer) having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide plating film formed on the base article, a white platinum coating film (outermost layer) was formed in a thickness of 0.005 μm by ion plating (hot cathode method) under the following conditions to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the watch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film formed on a wristwatch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A4
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example a3, a coating film (differential coloring film) of a color different from that of the hard film was formed by dry plating.
Specifically, a titanium plating film having a thickness of 0.05 μm was formed on the surface of the hard coat film by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium plating film, a gold-colored titanium nitride plating film having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-nitrogen mixture
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium nitride plating film, a gold-iron alloy plating film having a thickness of 0.1 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: gold-iron alloy
An electron gun: 8kV and 500mA
Gas: argon gas
Film forming pressure: 0.26Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 10-30V
Filament voltage: 7V
A part of the gold-iron alloy plating film is subjected to a masking treatment (with an epoxy resist as a masking material). The gold-iron alloy plating film, the titanium nitride plating film and the titanium plating film are successively removed by an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had two color tones of outermost coating films having a hard coating film of stainless steel color and a gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film is a solution containing cyanide as a main component and an additional oxidizing agent. The etching solution for titanium nitride plating film and titanium plating film is a solution containing nitric acid as a main component and additionally ammonium fluoride. The mask stripping solution used was dichloromethane.
The platinum coating film formed on the surface of the watch case and the watch band as described above had a surface hardness of 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) and the gold-iron alloy plating film had a surface hardness of 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film formed on a wristwatch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the outermost layer (white coating film) constituting the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A5
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example a3, a coating film (differential coloring film) of a color different from that of the hard film was formed by wet plating.
Specifically, the base member having the hard coating film is subjected to pretreatment of electrolytic degreasing, neutralization and water washing cleaning.
The base article coated with the hard film was subjected to electroplating in a plating bath solution having the following composition under the electroplating conditions listed below. A0.1 μm thick gold film was formed by strike plating on the surface of the hard coat film. The formed plating film was washed with water.
Gold strike electroplating
< plating bath solution composition >
Gold 3-5 g/l
Sulfuric acid 10 g/l
< plating conditions >
pH 0.3≤pH＜1
The temperature of the solution is 25 DEG C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base article having the strike-plated gold film was plated in a plating bath solution having the following composition under the plating conditions listed below. A gold-iron alloy plating film with a thickness of 2.0 μm is formed on the surface of the gold film subjected to strike electroplating. The formed plating film was washed with water.
Gold-iron alloy plating
< plating bath solution composition >
Potassium cyanide 8.7 g/l (metals 5.0 g/l)
Ferric chloride 2.7 g/l (Metal 1.0 g/l)
Citric acid 150 g/l or more
Sodium citrate 150 g/l or more
Whitening agent 10 ml/l
< plating conditions >
pH 3.5-3.7
Bath temperature is 37-40 deg.C
Current density (Dk) 1.0-1.5A/dm2
Be (Baume specific gravity) 20
And carrying out local mask treatment on the gold-iron alloy coating. The gold-iron alloy plating film and the strike-plated gold film are successively removed by an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had two color tones of outermost coating films having a hard coating film of stainless steel color and a gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film is a solution containing cyanide as a main component and an additional oxidizing agent. The mask stripping solution used was dichloromethane.
The platinum coating film formed on the surface of the watch case and the watch band as described above had a surface hardness of 1100 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) and the gold-iron alloy plating film had a surface hardness of 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film formed on a wristwatch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the outermost layer (white coating film) constituting the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A6
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example a3, a coating film (differential coloring film) of a color different from that of the hard film was formed by dry plating.
Specifically, a mask material (epoxy resist) is applied on a part of the hard film surface and dried. On the surface of the hard film and the surface of the mask material, a titanium plating film having a thickness of 0.05 μm was formed by sputtering (magnetron sputtering system) under the following film formation conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: argon gas
Film forming pressure: 0.02Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
On the titanium plating film surface, a silicon plating film of 0.1 μm thickness was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: silicon
Sputtering gas: argon gas
Film forming pressure: 0.05Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
Then, on the surface of the silicon plating film, a black diamond-like carbon (DLC) plating film of 0.1 μm thickness was formed by plasma CVD (chemical vapor deposition) under the following conditions.
< film Forming conditions >
Gas: benzene and its derivatives
Film forming pressure: 0.2Pa
Filament current: 20A
Anode current: 2.0A
Cathode voltage (acceleration voltage): -1.0 to-5.0V
Finally, the mask material was etched with methylene chloride, and the titanium plating film, the silicon plating film, and the DCL plating film formed on the mask were peeled off (lift off). As a result, the obtained wristwatch case and watch band each had an outermost coating film of two tones.
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds), and the surface hardness of the DLC plating film was 1800 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of outermost layer (white coating film) constituting the colored layer of 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A7
Basic parts of watch cases and watch bands were made of titanium by machining, and these basic parts were washed with an organic solvent and cleaned from oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a zirconium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by sputtering (magnetron system) under the following film forming conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: argon gas
Film forming pressure: 0.5Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the zirconium coated film on the base article, a white zirconium carbide coating film (wear-resistant layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: methane-argon gas mixture
Film forming pressure: 0.665Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Finally, on the surface of the zirconium carbide coating film formed on the base article, a white platinum coating film (outermost layer) having a thickness of 0.005 μm was formed by sputtering (magnetron sputtering system) under the following conditions, to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum (II)
Sputtering gas: argon gas
Film forming pressure: 0.2Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example A8
The zirconia ceramics are formed into the shape of a wristwatch case and a watch band, basic parts of the wristwatch case and the watch band are manufactured, the basic parts are washed, and oil stains are removed with an organic solvent. (the method of manufacturing a basic part such as a watch case is described in detail in Japanese patent application laid-open No. 2001 & 333236 (application No. 10/30 2001), filed by the present inventor (paragraphs: [0032] - [0036 ])). At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, by ion plating (hot cathode method), a chromium plating film (primer layer) having a thickness of 0.05 μm was formed on each surface of the base member under the following film formation conditions.
< film Forming conditions >
An evaporation source: chromium (III)
An electron gun: 10kV and 300mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the chromium plating film formed on the base article, a chromium carbide plating film (wear-resistant layer) having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: chromium (III)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the chromium carbide plating film of the base member, a white palladium plating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following film forming conditions, to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: palladium (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and4.0＜b*＜5.0。
example A9
Basic parts of watch cases and watch bands were manufactured from stainless steel (SUS316L) by machining, and these basic parts were washed with an organic solvent and cleaned of oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium carbide plating film (primer layer) having a thickness of 0.05 μm and a concentration gradient structure of 5 to 15 atomic% of carbon content was formed on each surface of the base member by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-methane mixture
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium carbide coating film as the base layer formed on the base member, a white titanium carbide coating film (abrasion resistant layer) having a thickness of 0.6 μm and a carbon content of 40. + -.10 atomic% was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide coating film of the base article, a white platinum coating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following film forming conditions, to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
The watch case and watch band obtained above, and the watch case and watch band obtained in example A3 were subjected to a scratch resistance test to compare the adhesion of the film to the base article. Scratch tests were carried out using a surface tester [ HEIDON (model 14) ].
The sample of the decoration device part of example a3 was produced to have a base layer made of a titanium plating film and a white titanium carbide plating film (abrasion resistant layer) having a carbon content of 40 ± 10 atomic%. In addition, another sample of the decorative component of example A9 was produced, which had a base layer composed of a titanium carbide coating film having a carbon content of 5 to 15 at% and a white titanium carbide coating film (abrasion resistant layer) having a carbon content of 40. + -.10 at%. The adhesion (critical load, described below) of the coating films of these decorative part samples was measured.
In the measurement, the tip angle of the diamond pressure head is 90 degrees, and the curvature radius of the top is 50 μm; the scratching speed is 30 mm/min; the scratch load is increased from 50gf to 300gf at 50gf intervals.
For the test results, the scratch resistance rapidly changes under a certain scratch load from the viewpoint of the scratch load and the resistance after scratch. This is assumed to be because the scratch resistance increases linearly with increasing load up to the critical load, and when the load exceeds the critical load, the coating film formed on the base article may crack, flaking off. The resulting cracks and chip peelings cause a sudden increase in scratch resistance, resulting in an increase in the coefficient of friction. From this critical load, the adhesion of the coating film to the base article was evaluated. At the point of sudden change in scratch resistance, the surface condition was observed with an optical microscope to evaluate the adhesive strength.
The sample of example A3 exhibited chip delamination at 200gf scratch load, while the sample of example a9 exhibited chip delamination at 250gf load. That is, the critical load was 200gf in example A3 and 250gf in example A9. This means that the coating film of the decorative component of example a9 had 25% greater adhesion than that of example A3.
In the above examples a1-a9, generally, a decoration base member made of tungsten carbide; the bottom layer is formed by a plating film formed by chromium, hafnium, vanadium or niobium; the wear-resistant layer is formed by a coating film formed by hafnium carbide, vanadium carbide, niobium carbide or tungsten carbide; and the outermost layer is composed of a rhodium coating film, a rhodium alloy coating film, a palladium alloy coating film, or a platinum alloy coating film. In examples A1-A9, watch cases and watch bands were produced. However, the method of example A1-A9 can of course be applied to other accessories, such as necklaces, pendants and brooches.
Example B1
A base member of a wristwatch case and a watch band was made of stainless steel (SUS316L) by machining, and the surface of the base member was finished in a fine grain pattern, and the base member was washed with an organic solvent and cleaned of oil stains.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium plating film formed on the base article, a white plating film (wear-resistant layer) of titanium carbide having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane gas
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage 7V
On each surface of the titanium carbide coating film on the base member, a white mixed coating film (mixed layer) of titanium carbide and platinum was formed by ion plating (hot cathode method) in a thickness of 0.05 μm under the following conditions.
< film Forming conditions >
An evaporation source: titanium, platinum
An electron gun: 10kV, 300mA (source: titanium)
10kV, 500mA (source: platinum)
Gas: methane
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the mixed plating film of titanium carbide and platinum on the base member, a white platinum plating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following conditions, to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1400 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 75 & lt L*＜85，0＜a*< 2.0 and 3.5 < b*＜5.0。
Example B2
The basic parts of watch cases and watch bands are produced from titanium by machining and honing-finishing, which are cleaned and freed from oil stains with organic solvents.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a zirconium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by sputtering (magnetron system) under the following film forming conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: argon gas
Film forming pressure: 0.5Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the zirconium coated film on the base article, a white zirconium carbide coating film (wear-resistant layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: methane
Film forming pressure: 0.665Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Finally, on the surface of the zirconium carbide coating film formed on the base article, a white platinum coating film (outermost layer) having a thickness of 0.005 μm was formed by sputtering (magnetron sputtering system) under the following conditions, to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum (II)
Sputtering gas: argon gas
Film forming pressure: 0.2Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 70 & lt L*＜82，0＜a*< 2.0 and 3.0 < b*＜4.5。
Example B3
Basic parts of watch cases and watch bands are manufactured from brass (copper alloy) by machining, and these basic parts are washed with an organic solvent and cleaned from oil stains. Meanwhile, the surface of the basic part is finished in a mirror surface state and a fine grain mode through mechanical processing.
The above base member was immersed in a plating bath solution having the following composition and subjected to electroplating under the plating conditions listed below to form a copper-tin alloy plating film (primer layer 1) having a thickness of 2 μm on the surface of the base member. The formed plating film was washed with water.
Copper-tin plating
< plating bath solution composition >
Copper cyanide 15 g/l (calculated as copper)
Sodium stannate 15 g/l (calculated as stannum)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 30 g/l
Whitening agent 10 ml/l
< plating conditions >
pH 12.5(50℃)
The temperature of the solution is 50 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-described base article coated with the copper-tin alloy plating film was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a copper-tin-zinc alloy plating film (primer layer 2) having a thickness of 2 μm on each surface of the copper-tin alloy. The formed plating film was washed with water.
Copper-tin-zinc alloy plating
< plating bath solution composition >
Copper cyanide 8.5 g/l (in terms of copper)
34.0 g/l sodium stannate (calculated as tin)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 50 g/l
Whitening agent 15 ml/l
Whitening agent 25 ml/l
< plating conditions >
pH 13.0(50℃)
The temperature of the solution is 60 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-mentioned base member coated with the copper-tin-zinc alloy plating film was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a palladium strike plating film (base layer 3) having a thickness of 0.5 μm on the copper-tin-zinc plating film. The formed plating film was washed with water.
Palladium strike electroplating
< plating bath solution composition >
Pure palladium 1-3 g/l
< electroplating Condition >
pH 8
The temperature of the solution was 32 deg.C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a tantalum coating film (underlayer 4) was formed on the palladium strike plating coating surface to a thickness of 0.05 μm by sputtering (magnetron system) under the following film formation conditions.
< film Forming conditions >
Target: tantalum
Sputtering gas: argon gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the tantalum-coated film on the base article, a white tantalum carbide coating film (abrasion-resistant layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: tantalum
Sputtering gas: methane-argon gas mixture
Film forming pressure: 0.665Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Finally, on the tantalum carbide coating film formed on the base member, a white palladium coating film (outermost layer) of 0.005 μm thickness was formed by sputtering (magnetron sputtering system) under the following conditions to obtain a stainless steel-colored wristwatch case and watch band.
< film Forming conditions >
Target: palladium (II)
Sputtering gas: argon gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 75 & lt L*＜90，0＜a*< 2.0 and 3.5 < b*＜5.0。
Example B4
A base member of a wristwatch case and a watch band was manufactured from stainless steel (SUS316L) by machining, and surface-finished in a mirror-like state, and the base member was washed with an organic solvent and cleaned of oil stains.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, passing; ion plating (hot cathode method), under the following film formation conditions, titanium plating films (primer layers) having a thickness of 0.05 μm were formed on the respective surfaces of the base member.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium plating film formed on the base member, a white plating film (wear-resistant layer) of white titanium carbide having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide coating film on the base member, a white platinum coating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following conditions to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 85 < L*＜90，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example B5
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example B4, a coating film (differential coloring film) of a color different from that of the hard film was formed by dry plating.
Specifically, a titanium plating film having a thickness of 0.05 μm was formed on the surface of the hard coat film by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium plating film, a gold-colored titanium nitride plating film having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-nitrogen mixture
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium nitride plated film, a gold-colored gold-iron alloy plated film having a thickness of 0.1 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: gold-iron alloy
An electron gun: 8kV and 500mA
Gas: argon gas
Film forming pressure: 0.26Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 10-30V
Filament voltage: 7V
A part of the gold-iron alloy plating film was subjected to masking treatment (with an epoxy resist as a masking material). The gold-iron alloy plating film, the titanium nitride plating film and the titanium plating film are successively removed by an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had two color tones of outermost coating films having a hard coating film of stainless steel color and a gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film is a solution containing cyanide as a main component and an additional oxidizing agent. The etching solution for the titanium nitride plating film and the titanium plating film is a solution containing nitric acid as a main component and additionally ammonium fluoride. The mask stripping solution used was dichloromethane.
The platinum coating film formed on the surface of the watch case and the watch band as described above had a surface hardness of 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) and the gold-iron alloy plating film had a surface hardness of 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the outermost layer (white coating film) constituting the colored layer of 85 < L*＜90，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example B6
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example B4, a coating film (differential coloring film) of a color different from that of the hard film was formed by dry plating.
Specifically, the base member having the hard coating film is subjected to pretreatment of electrolytic degreasing, neutralization and water washing cleaning.
The base article coated with the hard film was subjected to electroplating in a plating bath solution having the following composition under the electroplating conditions listed below. A strike-plated gold film of 0.1 μm thickness was formed on the surface of the hard coat film. The formed plating film was washed with water.
Gold strike electroplating
< plating bath solution composition >
Gold 3-5 g/l
Sulfuric acid 10 g/l
< electroplating Condition >
pH 0.3≤pH＜1
The temperature of the solution is 25 DEG C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base article having the strike-plated gold film was plated in a plating bath solution having the following composition under the plating conditions listed below. A gold-iron alloy plating film having a thickness of 2.0 μm was formed on the surface of the gold film subjected to the strike plating. The formed plating film was washed with water.
Gold-iron alloy plating
< plating bath solution composition >
Potassium cyanide 8.7 g/l (metals 5.0 g/l)
Ferric chloride 2.7 g/l (Metal 1.0 g/l)
Citric acid 150 g/l or more
Sodium citrate 150 g/l or more
Whitening agent 10 ml/l
< plating conditions >
pH 3.5-3.7
Bath temperature is 37-40 deg.C
Current density (Dk) 1.0-1.5A/dm2
Be (Bomei specific gravity) 20
And carrying out local mask treatment on the gold-iron alloy coating. The gold-iron alloy plating film and the strike-plated gold film are successively removed by an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had two color tones of outermost coating films having a hard coating film of stainless steel color and a gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film and removing the gold film of the strike plating is a solution containing cyanide as a main component and an additional oxidizing agent. The mask stripping solution used was dichloromethane.
The platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above had a surface hardness of 1100 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) and the gold-iron alloy plating film had a surface hardness of 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the outermost layer (white coating film) constituting the colored layer is 82 < L*＜85，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example B7
On a part of the surface of a hard film (platinum coating film) of a stainless steel color formed in the same manner as in example B4, a coating film (differential coloring film) of a color different from that of the hard film was formed by dry plating.
Specifically, a mask material (epoxy resist) is applied on a part of the hard film surface and dried. On the surface of the hard film and the surface of the mask material, a titanium plating film having a thickness of 0.05 μm was formed by sputtering (magnetron sputtering system) under the following film formation conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: argon gas
Film forming pressure: 0.02Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
On the titanium plating film surface, a silicon plating film of 0.1 μm thickness was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: silicon
Sputtering gas: argon gas
Film forming pressure: 0.05Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
Then, on the surface of the silicon plating film, a black diamond-like carbon (DLC) plating film was formed by plasma CVD (chemical vapor deposition) under the following film formation conditions in a thickness of 0.1 μm.
< film Forming conditions >
Gas: benzene and its derivatives
Film forming pressure: 0.2Pa
Filament voltage: 20A
Anode current: 2.0A
Cathode voltage (acceleration voltage): -1.0 to-5.0V
Finally, the mask material was etched with methylene chloride, and the titanium plating film, the silicon plating film, and the DCL plating film formed on the mask were peeled off (lift off). As a result, the obtained wristwatch case and watch band each had an outermost coating film of two tones.
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds), and the surface hardness of the DLC plating film was 1800 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the outermost layer (white coating film) constituting the colored layer of 85 < L*＜90，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example B8
The zirconia ceramics are formed into the shape of a wristwatch case and a watch band, basic parts of the wristwatch case and the watch band are manufactured, and the basic parts are washed with an organic solvent and cleaned of oil stains. A method for manufacturing a basic part such as a watch case is described in Japanese patent application publication 2001-333236 (application 10/30/2001), filed by the present inventor (paragraphs: [0032] -0036[ ]), specifically described). At the same time, the surface of the base piece is finished to a mirror surface state.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, by ion plating (hot cathode method), a chromium plating film (primer layer) having a thickness of 0.05 μm was formed on each surface of the base member under the following film formation conditions.
< film Forming conditions >
An evaporation source: chromium (III)
An electron gun: 10kV and 300mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the chromium plating film formed on the base article, a white chromium carbide plating film (wear-resistant layer) having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: chromium (III)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the chromium carbide plating film of the base article, a white palladium plating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following film formation conditions to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: palladium (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the palladium coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 85 < L*＜90，0＜a*< 2.0 and 4.0 < b*＜5.0。
Example B9
Basic parts of watch cases and watch bands were manufactured from stainless steel (SUS316L) by machining and mirror finishing, and these basic parts were washed with an organic solvent and cleaned of oil stains. At the same time, the surface of the base piece is finished in a fine grain pattern by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium carbide plating film (primer layer) having a thickness of 0.05 μm and a concentration gradient structure having a carbon content of 5 to 15 atomic% was formed on each surface of the base member by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-methane mixture
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium carbide coating film formed as the base layer on the base member, a white titanium carbide coating film (abrasion resistant layer) having a thickness of 0.6 μm and a carbon content of 40. + -.10 at% was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide coating film of the base article, a white platinum coating film (outermost layer) having a thickness of 0.005 μm was formed by ion plating (hot cathode method) under the following film forming conditions to obtain a stainless-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 85 < L*＜90，0＜a*< 2.0 and 4.0 < b*＜5.0。
The watch case and watch band obtained above, and the watch case and watch band obtained in example B4 were subjected to a scratch resistance test in the same manner as for plastic A9 to compare the adhesion of the film to the base article.
A sample of the decoration device part of example B4 was produced to have a base layer made of a titanium plating film and a white titanium carbide plating film (abrasion resistant layer) having a carbon content of 40. + -.10 atomic%. In addition, another sample of the decorative component of example B9 was produced having a primer layer composed of a titanium carbide coating film having a carbon content of 5 to 15 at% and a white titanium carbide coating film (abrasion resistant layer) having a carbon content of 40. + -.10 at%. The adhesion (critical load) of the coating film of these decorative component samples was measured.
The sample of example B4 exhibited chip delamination at 200gf scratch load, while the sample of example B9 exhibited chip delamination at 250gf load. That is, the critical load in example B4 was 200gf, and the critical load in example B9 was 250 gf. This means that the coating film of the decorative component of example B9 had 25% greater adhesion than that of example B4.
In the above examples B1-B9, generally, the decoration base member is made of tungsten carbide; the bottom layer is formed by a plating film formed by chromium, hafnium, vanadium or niobium; the wear-resistant layer is formed by a coating film formed by hafnium carbide, vanadium carbide, niobium carbide or tungsten carbide; and the outermost layer is composed of a rhodium coating film, a rhodium alloy coating film, a palladium alloy coating film, or a platinum alloy coating film. In examples B1-B9, watch cases and watch bands were produced. However, the method of examples B1-B9 can of course be applied to other accessories, such as necklaces, pendants and brooches.
Example C1
The basic parts of watch cases and watch bands were manufactured from stainless steel (SUS316L) by machining, and the basic parts were washed with an organic solvent and cleaned of oil stains. At the same time, the surface of the base piece is finished by machining a mirror surface.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium plating film formed on the base article, a white plating film (titanium carbide layer) of titanium carbide having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane gas
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide coating film on the base member, a white mixed coating film (mixed layer) of titanium carbide and platinum was formed by ion plating (hot cathode method) in a thickness of 0.02 μm under the following conditions.
< film Forming conditions >
An evaporation source: titanium, platinum
An electron gun: 10kV, 300mA (source: titanium)
10kV, 500mA (source: platinum)
Gas: methane gas
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the mixed plating film of titanium carbide and platinum on the base article, a white platinum plating film (decorative coating) was formed by ion plating (hot cathode method) to a thickness of 0.05 μm under the following conditions to obtain a platinum-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1400 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A watch case and a watch band having a white coating film formed on a platinum coating film, having high scratch resistance, and capable of giving a high-quality platinum tone.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of the colored layer is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C2
A basic member of a wristwatch case and a wristwatch band as a personal ornament, which is made of titanium by machining, is washed with an organic solvent and is free from oil stains. Simultaneously, the surface of the basic part is mirror finished by machining.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a zirconium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by sputtering (magnetron system) under the following film forming conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: argon gas
Film forming pressure: 0.5Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the zirconium coated film on the base article, a white titanium carbide coating film (titanium carbide layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: methane gas
Film forming pressure: 0.6Pa
Power applied to the target: 0.5kW
Acceleration voltage (bias): -50V
On each surface of the titanium carbide coating film formed on the base member, a white stainless steel coating film (stainless steel coating) having a thickness of 0.2 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: austenitic stainless steel SUS304
Sputtering gas: argon gas
Film forming pressure: 0.2-0.9Pa
Power applied to the target: 0.4-0.5kW
Bias voltage (acceleration voltage): grounded to-300V
Finally, on the surface of the stainless steel plated film formed on the base member, a white platinum plated film (decorative coating) was formed in a thickness of 0.05 μm by sputtering (magnetron sputtering system) under the following conditions to obtain a platinum-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum (II)
Sputtering gas: argon gas
Film forming pressure: 0.2Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C3
Basic parts of watch cases and watch bands are manufactured from brass (copper alloy) by machining, and these basic parts are washed with an organic solvent and cleaned from oil stains. Simultaneously, the surface of the basic part is mirror finished by machining.
The above base member was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a copper-tin alloy plated film (underlayer 1) having a thickness of 2 μm on the surface of the base member. The formed plating film was washed with water.
Copper-tin plating
< plating bath solution composition >
Copper cyanide 15 g/l (calculated as copper)
Sodium stannate 15 g/l (calculated as stannum)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 30 g/l
Whitening agent 10 ml/l
< plating conditions >
pH 12.5(50℃)
The temperature of the solution is 50 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-mentioned base article coated with the copper-tin alloy plating film was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a copper-tin-zinc alloy plating film (primer layer 2) having a thickness of 2 μm on each surface of the copper-tin alloy coating film. The formed plating film was washed with water.
Copper-tin-zinc alloy plating
< plating bath solution composition >
Copper cyanide 8.5 g/l (in terms of copper)
34.0 g/l sodium stannate (calculated as tin)
Zinc cyanide 1 g/l (calculated as zinc)
KOH 20 g/l
KCN (free) 50 g/l
Whitening agent 15 ml/l
Whitening agent 25 ml/l
< plating conditions >
pH 13.0(50℃)
The temperature of the solution is 60 DEG C
Current density (Dk) 2A/dm2
Film formation speed of 3min/1 μm
The above-mentioned base member coated with the copper-tin-zinc alloy plating film was immersed in a plating bath solution having the following composition, and subjected to electroplating under the plating conditions listed below to form a palladium strike plating film (underlayer 3) having a thickness of 0.5 μm on the surface of the copper-tin-zinc plating film. The formed plating film was washed with water.
Palladium strike electroplating
< plating bath solution composition >
Pure palladium 1-3 g/l
< electroplating Condition >
pH 8
The temperature of the solution was 32 deg.C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a tantalum coating film (underlayer 4) was formed on the palladium strike plating coating surface to a thickness of 0.05 μm by sputtering (magnetron system) under the following film formation conditions.
< film Forming conditions >
Target: tantalum
Sputtering gas: argon gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the tantalum plating film formed on the base article, a white titanium carbide coating film (titanium carbide layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: methane-argon gas mixture
Film forming pressure: 0.6Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Finally, on the surface of the titanium carbide coating film formed on the base article, a white platinum alloy coating film (decorative coating) having a thickness of 0.05 μm was formed by sputtering (magnetron sputtering system) under the following conditions, to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum alloy
Sputtering gas: argon gas
Film forming pressure: 0.6Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the platinum alloy coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum alloy color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C4
Zirconia ceramics are formed into the shapes of a wristwatch case and a watch band, basic articles of a wristwatch case and a watch band as personal ornaments are manufactured, and these basic articles are washed with an organic solvent and oil stains are removed. (the method of manufacturing a base member such as a watch case is described in detail in Japanese patent application laid-open No. 2001-333236 (application No. 10/30 2001), filed by the present inventor (paragraphs: [0032] -0036 ])). At the same time, the surface of the base piece is finished by machining a mirror surface.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
On the surface of the base member, a chromium plating film (underlayer) was formed in a thickness of 0.05 μm by sputtering (magnetron system) under the following film forming conditions.
< film Forming conditions >
Target: chromium (III)
Sputtering gas: methane gas
Film forming pressure: 0.4Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
Under the following conditions, a white titanium carbide coating film (titanium carbide layer) having a thickness of 0.6 μm was formed on the surface of the chromium coating film formed on the base member by sputtering (magnetron system).
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: methane gas
Film forming pressure: 0.6Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
On each surface of the titanium carbide coating film formed on the base member, a white stainless steel coating film (stainless steel coating) having a thickness of 0.2 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: austenitic stainless steel (SUS304)
Sputtering gas: argon gas
Film forming pressure: 0.2-0.9Pa
Power applied to the target: 0.4-0.5kW
Bias voltage (acceleration voltage): grounded to-300V
Finally, on the stainless steel-coated surface formed on the base member, a white platinum coating (decorative coating) was formed in a thickness of 0.05 μm by sputtering (magnetron sputtering system) under the following conditions to obtain a platinum-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum (II)
Sputtering gas: argon gas
Film forming pressure: 0.2Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the wristwatch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C5
Basic members of a wristwatch case and a watch band for personal ornaments are manufactured from stainless steel (SUS316L) by machining, and these basic members are washed with an organic solvent and removed of oil stains. At the same time, the surface of the base piece is finished with a mirror surface by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium plating film (primer layer) was formed on each surface of the base member by ion plating (hot cathode method) under the following film forming conditions to a thickness of 0.05 μm.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium plating film formed on the base article, a white titanium carbide plating film (wear-resistant layer) having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide plating film formed on the base article, a white platinum plating film (decorative coating) having a thickness of 0.05 μm was formed by ion plating (hot cathode method) under the following conditions to obtain a stainless-steel-colored wristwatch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the watch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C6
On a part of the surface of the platinum coating film (decorative coating film) formed in the same manner as in example C5, a plated film (differential colored film) having a color different from that of the film was formed by dry plating.
Specifically, a titanium plating film having a thickness of 0.05 μm was formed on the surface of the coating film by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium plating film, a gold-colored titanium nitride plating film having a thickness of 0.6 μm was formed by ion plating (hot cathode method) under the following film formation conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-nitrogen mixture
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 40-50V
Filament voltage: 7V
On the surface of the titanium nitride plated film, a gold-colored gold-iron alloy plated film having a thickness of 0.1 μm was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: gold-iron alloy
An electron gun: 8kV and 500mA
Gas: argon gas
Film forming pressure: 0.26Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 10-30V
Filament voltage: 7V
A part of the gold-iron alloy plating film was subjected to masking treatment (with an epoxy resist as a masking material). The gold-iron alloy plating film, the titanium nitride plating film and the titanium plating film are successively removed by an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had outermost coating films of two tones, the coating films having a platinum-colored coating film and a gold-colored gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film is a solution containing cyanide as a main component and an additional oxidizing agent. The etching solution for the titanium nitride plating film and the titanium plating film is a solution containing nitric acid as a main component and additionally ammonium fluoride. The mask stripping solution used was dichloromethane.
The platinum coating film formed on the surface of the watch case and the watch band as described above had a surface hardness of 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds) and the gold-iron alloy plating film had a surface hardness of 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C7
On a part of the surface of the platinum coating film (decorative coating film) formed in the same manner as in example C5, a plating film (differential coloring film) having a color different from that of the film was formed by wet plating.
Specifically, the base article having the coating film thereon is subjected to pretreatment of electrolytic degreasing, neutralization and water washing cleaning.
The base article of the coated film was plated in a plating bath solution having the following composition under the plating conditions listed below. A strike-plated gold film of 0.1 μm thickness was formed on the surface of the base member. The formed plating film was washed with water.
Gold strike electroplating
< plating bath solution composition >
Gold 3-5 g/l
Sulfuric acid 10 g/l
< electroplating Condition >
pH 0.3≤pH＜1
The temperature of the solution is 25 DEG C
Current density (Dk) 3-5A/dm2
The time is 30 seconds
The base article having the strike-plated gold film was plated in a plating bath solution having the following composition under the plating conditions listed below. A gold-iron alloy plating film having a thickness of 2.0 μm was formed on the surface of the gold film subjected to the strike plating. The formed plating film was washed with water.
Gold-iron alloy plating
< plating bath solution composition >
Potassium cyanide 8.7 g/l (metals 5.0 g/l)
Ferric chloride 2.7 g/l (Metal 1.0 g/l)
Citric acid 150 g/l or more
Sodium citrate 150 g/l or more
Whitening agent 10 ml/l
< plating conditions >
pH 3.5-3.7
Bath temperature is 37-40 deg.C
Current density (Dk) 1.0-1.5A/dm2
Be (Bomei specific gravity) 20
And carrying out local mask treatment on the gold-iron alloy coating. The gold film electroplated by the strike of the gold-iron alloy coating is successively removed by means of an etching solution. Finally, the mask is removed. Thus, a wristwatch case and a watch band were obtained which had two color tones of outermost coating films having a hard coating film of stainless steel color and a gold-iron alloy plating film.
The etching solution (stripping liquid) for removing the gold-iron alloy plating film and removing the gold film of the strike plating is a solution containing cyanide as a main component and an additional oxidizing agent. The mask stripping solution used was dichloromethane.
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the watch band as described above was 1100 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds), and the surface hardness of the gold-iron alloy plating film was 120 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C8
On a part of the surface of the platinum coating film (decorative coating film) formed in the same manner as in example B4, a plating film (differential coloring film) having a color different from that of the hard film was formed by dry plating.
Specifically, a masking material (epoxy resist) is applied on a part of the surface of the coating film and dried. On the surface of the coating film and the surface of the mask material, a titanium plating film of 0.05 μm thickness was formed by sputtering (magnetron sputtering system) under the following film formation conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: argon gas
Film forming pressure: 0.02Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
On the titanium plating film surface, a silicon plating film of 0.1 μm thickness was formed by sputtering (magnetron sputtering system) under the following film formation conditions.
< film Forming conditions >
Target: silicon
Sputtering gas: argon gas
Film forming pressure: 0.05Pa
Power applied to the target: 0.3-0.5kW
Bias voltage (acceleration voltage): -50 to-100V
Then, on the surface of the silicon plating film, a black diamond-like carbon (DLC) plating film was formed by plasma CVD (chemical vapor deposition) under the following film formation conditions in a thickness of 0.1 μm.
< film Forming conditions >
Gas: benzene and its derivatives
Film forming pressure: 0.2Pa
Filament voltage: 20A
Anode current: 2.0A
Cathode voltage (acceleration voltage): -1.0 to-5.0V
Finally, the mask material was etched with methylene chloride, and the titanium plating film, the silicon plating film, and the DCL plating film formed on the mask were peeled off (lift off). As a result, the obtained watch case and watch band each had a decorative coating film of two tones.
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the watch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds), and the surface hardness of the DLC plating film was 1800 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), the color evaluation value of the decorative coating is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C9
A basic member of a watch case and a watch band as a personal ornament is produced from titanium by machining, and the basic member is washed with an organic solvent and is cleaned from oil stains. At the same time, the surface of the base piece is finished by machining a mirror surface.
The base part is placed in a sputtering apparatus and the surface of the base part is cleaned by bombardment under an argon atmosphere.
Then, a zirconium plating film (primer layer) having a thickness of 0.05 μm was formed on the surface of the base member by sputtering (magnetron system) under the following film forming conditions.
< film Forming conditions >
Target: zirconium
Sputtering gas: argon gas
Film forming pressure: 0.5Pa
Power applied to the target: 0.5kW
Acceleration voltage (bias): -50V
On each surface of the zirconium coated film on the base article, a white titanium carbide coating film (titanium carbide layer) having a thickness of 0.6 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: titanium (IV)
Sputtering gas: methane-argon mixture
Film forming pressure: 0.6Pa
Power applied to the target: 0.5kW
Acceleration voltage (bias): -50V
Then, on each surface of the titanium carbide coating film formed on the base member, a white stainless steel coating film (stainless steel coating) having a thickness of 0.2 μm was formed by sputtering (magnetron sputtering system) under the following conditions.
< film Forming conditions >
Target: austenitic stainless steel SUS304
Sputtering gas: argon gas
Film forming pressure: 0.2-0.9Pa
Power applied to the target: 0.4-0.5kW
Bias voltage (acceleration voltage): grounded to-300V
Finally, on the surface of the stainless steel plated film formed on the base article, a white platinum coating film (decorative coating) was formed in a thickness of 0.005 μm by sputtering (magnetron sputtering system) under the following conditions to obtain a platinum-colored wristwatch case and watch band.
< film Forming conditions >
Target: platinum (II)
Sputtering gas: argon gas
Film forming pressure: 0.2Pa
Power applied to the target: 0.5kW
Bias voltage (acceleration voltage): -50V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the watch band as described above was 1300 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality platinum color.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
Example C10
Basic members of watch cases and watch bands as personal ornaments are manufactured from stainless steel (SUS316L) by machining, and these basic members are washed with an organic solvent and removed of oil stains. Simultaneously, the surface of the basic part is mirror finished by machining.
The base piece was placed in an ion plating apparatus and the surface of the base piece was cleaned by bombardment under an argon atmosphere.
Then, a titanium carbide plating film (undercoat layer) having a concentration gradient structure with a carbon content of 5 to 15 atomic% was formed on each surface of the base member by ion plating (hot cathode method) under the following film formation conditions to a thickness of 0.05 μm.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV, 200 and 500mA
Gas: argon-methane gas mixture
Film forming pressure: 0.004-0.009Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 50V
Filament voltage: 7V
On each surface of the titanium carbide coating film as the underlayer formed on the base article, a white titanium carbide coating film (titanium carbide layer) having a thickness of 0.6 μm and a carbon content of 40. + -. 10 atomic% was formed by ion plating (hot cathode method) under the following film forming conditions.
< film Forming conditions >
An evaporation source: titanium (IV)
An electron gun: 10kV and 300mA
Gas: methane-argon mixture
Film forming pressure: 0.02Pa
Acceleration voltage (bias): grounded to-100V
Anode voltage: 60V
Filament voltage: 7V
On each surface of the titanium carbide coating film of the base article, a white platinum coating film (decorative coating) having a thickness of 0.05 μm was formed by ion plating (hot cathode method) under the following film forming conditions to obtain a platinum-colored watch case and watch band.
< film Forming conditions >
An evaporation source: platinum (II)
An electron gun: 10kV and 500mA
Gas: argon gas
Film forming pressure: 0.2Pa
Acceleration voltage (bias): grounded to-50V
Anode voltage: 60V
Filament voltage: 7V
The surface hardness of the platinum coating film formed on the surface of the wristwatch case and the watch band as described above was 1200 (HV; Vickers hardness micro-tester, load: 5 g, retention time: 10 seconds). A white coating film on a watch case and a watch band has high scratch resistance and gives a high-quality image similar to a stainless steel coating film.
According to L*a*b*Color space (CIE colorimeter system), color evaluation value of decorative coating (white coating film) is 88 < L*＜92，1.8＜a*< 2.5 and 5.0 < b*＜5.5。
The above-obtained wristwatch case and watch band, and the wristwatch case and watch band obtained in example C5 were subjected to a scratch resistance test in the same manner as in example A9 to compare the adhesion of the film to the base article.
A sample of the decorative component of example C5 was prepared having a base layer composed of a titanium plating film and a white titanium carbide plating film (abrasion resistant layer) having a carbon content of 40. + -. 10 atomic%. In addition, another sample of the decorative component of example C10 was produced which had a primer layer composed of a titanium carbide coating film having a carbon content of 5 to 15 at% and a white titanium carbide coating film (abrasion resistant layer) having a carbon content of 40. + -.10 at%. The adhesion (critical load) of the coating films of these decorative parts was measured.
The sample of example C5 exhibited chip delamination at 200gf scratch load, while example C10 exhibited chip delamination at 250gf load. That is, the critical load was 200gf in example C5 and 250gf in example C10. This means that the coating film of the decorative component of example C10 had 25% greater adhesion than that of example C5.
In the above examples C1-C10, generally, the decoration base member is made of tungsten carbide; the bottom layer is formed by a plating film formed by chromium, hafnium, vanadium or niobium; in examples C1-C10, watch cases and watch bands were produced. However, the method of examples C1-C10 can of course be applied to other accessories, such as necklaces, pendants and brooches.
Claims (102)
1. A personal ornament having a white coating film formed by dry plating as an outermost layer, the coating film comprising a noble metal or an alloy of a noble metal, the ornament comprising:
a basic part of a decoration made of metal or ceramic,
a base layer formed on the base member,
a colored layer including a wear-resistant layer formed on a surface of the underlayer by dry plating and an outermost layer formed on a surface of the wear-resistant layer by dry plating or wet plating;
the coloring layer is a white hard coating film with stainless steel color, and comprises a wear-resistant layer with the thickness of 0.2-1.5 μm and an outermost layer with the thickness of 0.002-0.1 μm.
2. The decorative article of claim 1, wherein said base layer is a nickel-free layer formed by dry plating.
3. The decorative article of claim 1, wherein the base member of the decorative article is comprised of at least one metal selected from the group consisting of stainless steel, titanium alloys, copper alloys, and tungsten carbide.
4. The ornament according to claim 1, wherein a base member of the ornament is composed of at least one metal selected from the group consisting of stainless steel, titanium alloy, copper alloy and tungsten carbide, and a surface of the base member is finished in at least one state selected from the group consisting of a mirror surface, a matte pattern, a fine grain pattern, a honing pattern, a molding pattern and an etching pattern.
5. The decorative article of claim 1, wherein the base article of the decorative article comprises a zirconia ceramic, the ceramic being white stabilized zirconia containing 3 to 7 weight percent Y2O2MgO or CaO as a stabilizer.
6. The decorative article of claim 1, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of ceramics, and the primer layer on the surface of the base member is formed of titanium, chromium, zirconium, hafnium, vanadium, niobium, or tantalum by a dry plating method.
7. The decorative article of claim 1, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of a ceramic, and the primer layer on the surface of the base member is a coating film of a metal compound consisting of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide, or tantalum carbide by dry plating, and has a carbon atom content of 5 to 15 atomic%.
8. The decorative article of claim 1, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of ceramics, and the base layer is a coating film of 0.02 to 0.2 μm thickness formed by dry plating.
9. The decorative article according to claim 3, wherein the base member of the decorative article is made of copper or a copper alloy, and the primer layer is composed of a 1-10 μm thick nickel coating film formed on the surface of the base member by wet plating and a 3-10 μm thick amorphous nickel-phosphorus alloy coating film formed on the surface of the nickel coating film by wet plating.
10. The decorative article of claim 3, wherein the base member of the decorative article is made of copper or a copper alloy, and the base layer is a 2-9 μm thick coating film formed by a wet plating method from at least one material selected from the group consisting of copper, palladium, a copper-tin alloy, a copper-tin-zinc alloy, and a copper-tin-palladium alloy.
11. The ornament according to claim 1, wherein said wear-resistant layer is a metal compound coating film composed of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide, or tantalum carbide.
12. The decorative article of claim 1, wherein said wear layer has a thickness in the range of 0.5-1.0 μm.
13. The ornament according to claim 1 wherein the outermost layer is a coating film made of at least one material selected from the group consisting of platinum, palladium, rhodium and alloys thereof.
14. The decorative article of claim 1, wherein said outermost layer has a thickness in the range of 0.01-0.08 μm.
15. The ornament of claim 1 wherein there is a mixed layer between the wear layer and the outermost layer, the layer being composed of a metal compound forming the wear layer and a metal or alloy forming the outermost layer.
16. The decorative article of claim 15, wherein the thickness of said mixed layer is in the range of 0.005-0.1 μm.
17. The decoration of claim 1, wherein in accordance with L*a*b*Color space, CIE colorimeter system, and color evaluation value of the colored layer of 70 & lt L*＜91，-0.1＜a*< 3.0 and 1.0 < b*The range of < 5.5.
18. The ornament of claim 1 wherein L of the colored layers formed on different finished surfaces of the base article of the ornament is L*、a*、b*At a value of Δ L*＝±6.0，Δa*1.55 and Δ b*Range ± 2.25.
19. The decorative article of claim 1 or 15, wherein the underlayer, the wear layer, the mixed layer, and the outermost layer are each formed by at least one of a sputtering method, an ion plating method, and an arc discharge method.
20. The ornament according to claim 1, wherein at least one differentially colored film having a color different from that of the white coating film is formed on a part of the surface of the white coating film having a color of stainless steel by dry plating or wet plating.
21. The ornament of claim 20 wherein the differential coloring film having a color different from the color of the coloring layer is made of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
22. The ornament of claim 20 wherein the differential coloring film having a color different from the color of the coloring layer is made of gold, nickel-free gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
23. The ornament according to claim 20 wherein the differential colored film having a color different from that of the colored layer has a two-layer structure consisting of a lower layer of titanium nitride, zirconium nitride or hafnium nitride and an upper layer of gold or a gold alloy.
24. The ornament of claim 20 wherein the differential colored film having a color different from that of the colored layer has a two-layer structure consisting of a lower layer of titanium nitride, hafnium nitride or hafnium nitride and an upper layer of gold or nickel-free gold alloy.
25. The ornament as claimed in claim 21, wherein a titanium coating film and a silicon coating film formed on the titanium film are provided between the coloring layer and the differentially colored diamond-like carbon, DLC, coating film of a color different from that of the coloring layer.
26. The ornament according to claim 1 wherein the outermost layer is a mixed layer composed of a mixture of a metal compound forming the wear-resistant layer and at least one material selected from the group consisting of platinum, palladium, rhodium and alloys thereof.
27. The ornament according to claim 1, wherein the colored layer has a surface hardness, HV; vickers hardness tester, load: 5 g, retention time: 10 seconds, 700 and 2000 seconds.
28. The decoration of claim 1, wherein said decoration is an exterior component of a watch.
29. A personal ornament as claimed in claim 1, wherein the wear layer is a titanium carbide layer having a thickness of 0.5 to 1.0 μm; the outermost layer is a decorative coating which is a white coating film made of platinum or a platinum alloy and has a thickness of 0.03 to 0.06 μm.
30. The decorative article of claim 29, wherein the base member of the decorative article is comprised of at least one metal selected from the group consisting of stainless steel, titanium alloys, copper alloys, and tungsten carbide.
31. The decorative article of claim 29, wherein the base member of the decorative article is comprised of a zirconia ceramic, the ceramic being white stabilized zirconia containing 3 to 7 weight percent Y2O2MgO or CaO.
32. The decorative article of claim 29, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of ceramic, and the primer layer on the surface of the base member is formed of titanium, chromium, zirconium, hafnium, vanadium, niobium, or tantalum by a dry plating method.
33. The decorative article of claim 29, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of a ceramic, and the primer layer on the surface of the base member is a metal compound coating film formed by dry plating 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 at%.
34. The decorative article of claim 29, wherein the base member of the decorative article is made of a metal other than copper and copper alloys, or is made of ceramic, and the base layer is a coating film of 0.02 to 0.2 μm thickness formed by dry plating.
35. The decorative article of claim 30, wherein the base article of the decorative article is composed of copper or a copper alloy, and the primer layer is composed of a 1-10 μm thick nickel coating film formed on the surface of the base article by wet plating and a 3-10 μm thick amorphous nickel-phosphorus alloy coating film formed on the surface of the nickel coating film by wet plating.
36. The decorative article of claim 30, wherein the base member of the decorative article is made of copper or a copper alloy, and the base layer is a 2-9 μm thick coating film formed by a wet plating method from at least one material selected from the group consisting of copper, palladium, a copper-tin alloy, a copper-tin-zinc alloy, and a copper-tin-palladium alloy.
37. An ornamental article according to claim 29, wherein a mixed layer is provided between the titanium carbide layer and the decorative coating, the mixed layer being composed of titanium carbide forming the titanium carbide layer and platinum or a platinum alloy forming the decorative coating, and having a thickness in the range of 0.005 to 0.1 μm.
38. The decorative article of claim 29, wherein between the titanium carbide layer and the decorative coating there is a stainless steel coating layer formed by dry plating to a thickness of 0.05-1.5 μm.
39. The decorative article of claim 38, wherein said stainless steel coating is comprised of an austenitic stainless steel having the composition 0.01-0.12 volume percent carbon, 0.1-1.5 volume percent silicon, 1.0-2.5 volume percent manganese, 8-22 volume percent nickel, 15-26 volume percent chromium, and the balance iron
40. The decoration of claim 29, wherein L is*a*b*Color space, CIE colorimeter system, and decorative coating color evaluation value of 85 & lt L*＜95，1.5＜a*< 4.0 and 4.5 < b*The range of < 6.5.
41. The decorative article of claim 29, wherein the underlayer, titanium carbide layer, hybrid layer, and decorative coating are each formed by at least one of sputtering, ion plating, and arc discharge.
42. The decorative article of claim 29, wherein at least one differentially colored film having a color different from the color of the decorative coating is formed on a portion of the surface of the decorative coating by dry plating or wet plating.
43. The decorative article of claim 29, wherein the differentially colored film having a color different from the color of the decorative coating comprises gold, an alloy of gold, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
44. The decorative article of claim 29, wherein the differentially colored film having a color different from the color of the decorative coating has a two-layer structure consisting of a lower layer of titanium nitride, hafnium nitride, or hafnium nitride and an upper layer of gold or a gold alloy.
45. The decorative article of claim 43, wherein a titanium coating film and a silicon coating film formed on the titanium film are provided between the colored layer and the differentially colored diamond-like carbon, DLC, coating film having a color different from that of the decorative coating.
46. The decorative article of claim 29, wherein said decorative coating is a hybrid layer comprised of a mixture of titanium carbide forming a titanium carbide layer and platinum or a platinum alloy.
47. The decorative article of claim 29, wherein the colored layer has a surface hardness, HV; vickers hardness micro-tester, load: 5 g, retention time: 10 seconds, 1000-.
48. The decorative article of claim 29, wherein said decorative article is an exterior component of a watch.
49. A method of making a personal ornament as claimed in claim 1, comprising the steps of:
manufacturing a basic part of a decoration from metal or ceramic by means of a processing device,
forming a primer layer on the surface of the base member by dry plating or wet plating,
a colored layer having a stainless steel color is formed, that is, a wear-resistant layer is first formed of a metal compound on the underlayer by dry plating, and then, an outermost layer is formed of platinum or a platinum alloy on the wear-resistant layer by dry plating.
50. The method of claim 49 wherein said primer layer is a nickel-free layer formed by dry or wet plating.
51. The method of claim 49 wherein the base article of the decoration comprises at least one metal selected from the group consisting of stainless steel, titanium alloys, copper alloys, and tungsten carbide.
52. The method of claim 49, wherein the base member of the decorative article is composed of at least one metal selected from the group consisting of stainless steel, titanium alloy, copper alloy and tungsten carbide, and the surface of the base member is finished in at least one state selected from the group consisting of mirror surface, matte pattern, fine grain pattern, honing pattern, molding pattern and etching pattern.
53. The method of claim 49, wherein the decorative base piece is made by the steps of: 100 parts by weight of a stabilizer containing 3-7 wt% of Y2O2A mixture of a stable zirconia powder of MgO or CaO and 20-25 parts by weight of a binder, and subjecting the formed product to mechanical rough machining, oil stain removal, firing, grinding and polishing.
54. The method of claim 49 wherein the base member of the decorative article is comprised of a metal other than copper and copper alloys or is comprised of a ceramic and the primer layer on the surface of the base member is formed of titanium, chromium, zirconium, hafnium, vanadium, niobium or tantalum by dry plating.
55. The method of claim 49 wherein the base article of the decorative article is composed of a metal other than copper and copper alloys or is composed of a ceramic, and the primer layer on the surface of the base article is a coating film of a metal compound formed by dry plating 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 at%.
56. A method according to claim 49, wherein the base piece of the decorative article is made of a metal other than copper and copper alloys, or is made of ceramic, and the base layer is formed by dry plating to a thickness of 0.02 to 0.2 μm.
57. A method according to claim 51, wherein the base article of the decorative article is made of copper or a copper alloy, and the primer layer is composed of a nickel coating film of 1 to 10 μm thickness formed on the surface of the base article by wet plating and a coating film of an amorphous nickel-phosphorus alloy of 3 to 10 μm thickness formed on the surface of the nickel coating film by wet plating.
58. A method according to claim 51, wherein the base member of the decorative article is composed of copper or a copper alloy, and the primer layer is composed of at least one material selected from the group consisting of copper, palladium, a copper-tin alloy, a copper-tin-zinc alloy and a copper-tin-palladium alloy by a wet plating method and has a thickness of 2 to 9 μm.
59. The method of claim 49 wherein said wear resistant layer is a metal compound coating film comprised of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tungsten carbide, or tantalum carbide.
60. A method according to claim 49, wherein the wear resistant layer has a thickness in the range of 0.2 to 1.5 μm.
61. A method according to any one of claims 49 to 60, wherein the outermost layer is a coating film of at least one material selected from platinum, palladium, rhodium and alloys thereof.
62. A method according to claim 49, wherein the outermost layer is formed to have a coating thickness of 0.002 to 0.1 μm.
63. A method according to claim 49, wherein between the wear resistant layer and the outermost layer, a mixed layer is provided consisting of a metal compound forming the wear resistant layer and a metal or alloy forming the outermost layer.
64. The method of claim 49 in terms of L*a*b*Color space, CIE colorimeter system, and color evaluation value of the colored layer of 70＜L*＜91，-0.1＜a*< 3.0 and 1.0 < b*The range of < 5.5.
65. A method as claimed in claim 49, characterized in that the L of the coloured layers formed on the different finished surfaces of the basic article of decoration*、a*、b*At a value of Δ L*＝±6.0，Δa*1.55 and Δ b*Range ± 2.25.
66. The method of claim 49, wherein the underlayer, the wear layer, the hybrid layer, and the outermost layer are each formed by at least one of a sputtering method, an ion plating method, and an arc discharge method.
67. The method according to claim 49, wherein at least one differentially colored film having a color different from that of the white coating film is formed on a part of the surface of the white coating film having a color of stainless steel by dry plating or wet plating.
68. The method of claim 67, wherein the differential coloring film having a color different from that of the colored layer is composed of gold, gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
69. The method of claim 67, wherein said differential coloring film having a color different from that of the colored layer is composed of gold, a nickel-free gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
70. The method according to claim 67, wherein the differential coloring film having a color different from that of the coloring layer has a two-layer structure consisting of a lower layer composed of titanium nitride, zirconium nitride, or hafnium nitride and an upper layer composed of gold or a gold alloy.
71. The method according to claim 67, wherein the differential coloring film having a color different from that of the coloring layer has a two-layer structure consisting of a lower layer composed of titanium nitride, zirconium nitride, or hafnium nitride and an upper layer composed of gold or a nickel-free gold alloy.
72. The method of claim 68, wherein a titanium coating film and a silicon coating film formed on the titanium coating film are provided between the colored layer and the differentially colored diamond-like carbon, DLC, coating film of a color different from that of the colored layer.
73. The method of claim 49, wherein the outermost layer is a mixed layer composed of a mixture of a metal compound forming the wear-resistant layer and at least one material selected from the group consisting of platinum, palladium, rhodium and alloys thereof.
74. The method of claim 49 wherein the colored layer has a surface hardness, HV; vickers hardness tester, load: 5 g, retention time: 10 seconds, 700 and 2000 seconds.
75. A method according to any of claims 49-74, wherein the decorative item is an exterior part of a watch.
76. A method according to claim 49, wherein the wear layer is formed of titanium carbide and the outermost layer is a decorative coating formed of platinum or a platinum alloy.
77. A method according to claim 76, wherein the base piece of the decorative article is formed from at least one metal selected from stainless steel, titanium alloys, copper alloys and tungsten carbide.
78. The decorative article of claim 76, wherein said decorative article base member is made by the steps of: prepared from 100 weight parts of a composition containing 3-7 wt.% of Y2O2A mixture of stabilized zirconia powder with MgO or calcium oxide as a stabilizer and 20-25 parts by weight of a binder is formed, and the formed product is subjected to mechanical processing roughening, oil stain removal, firing, grinding and finishing.
79. The method of claim 76 wherein the base member of the decorative article is comprised of ceramic or other metal other than copper and copper alloys and the primer layer on the surface of the base member is formed by dry plating from titanium, chromium, zirconium, hafnium, vanadium, niobium or tantalum.
80. The method of claim 76 wherein the base article of the decorative article is comprised of ceramic or other metal other than copper and copper alloys and the primer layer on the surface of the base article is a metal compound coating film formed by dry plating of titanium carbide, chromium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide or tantalum carbide having a carbon atom content of 5 to 15 at%.
81. A method according to claim 76, wherein the base piece of the decorative article is made of a metal other than copper and copper alloys, or is made of a ceramic, and the base layer is formed by dry plating to a thickness of 0.02 to 0.2 μm.
82. A method according to claim 77, wherein the base member of the decorative article is made of copper or a copper alloy, and the primer layer is composed of a 1-10 μm thick nickel coating film formed by wet plating and a 3-10 μm thick coating film of an amorphous nickel-phosphorus alloy formed on the surface of the nickel coating film by wet plating.
83. A method according to claim 77, wherein the base member of the decorative article is composed of copper or a copper alloy, and the primer layer is composed of at least one material selected from the group consisting of copper, palladium, a copper-tin alloy, a copper-tin-zinc alloy and a copper-tin-palladium alloy by a wet plating method and has a thickness of 2 to 9 μm.
84. A method according to claim 76, wherein between the titanium carbide layer and the decorative coating, a hybrid layer of titanium carbide forming the titanium carbide layer and platinum or a platinum alloy forming the decorative coating is provided.
85. The method of claim 76, wherein the stainless steel coating is formed between the titanium carbide layer and the decorative coating by dry plating to a thickness of 0.05-1.5 μm.
86. The method of claim 85 wherein the stainless steel coating is comprised of an austenitic stainless steel having a composition of 0.01-0.12 vol.% carbon, 0.1-1.5 vol.% silicon, 1.0-2.5 vol.% manganese, 8-22 vol.% nickel, 15-26 vol.% chromium, and the balance iron, and is formed by at least one of sputtering, ion plating, and arc discharge.
87. The method of claim 76, in accordance with L*a*b*Color space, CIE colorimeter system, the color evaluation value of the decorative coating is more than 85 < L*＜95，1.5＜a*< 4.0 and 4.5 < b*The range of < 6.5.
88. The method of claim 76, wherein the underlayer, the titanium carbide layer, the intermixed layer, and the decorative coating are each formed by at least one of sputtering, ion plating, and arc discharge.
89. The method of claim 76, wherein the titanium carbide layer and/or intermixed layer is formed by dry plating using methane gas.
90. The method of claim 76, wherein at least one differentially colored film having a color different from the color of the decorative coating is formed on a portion of the surface of the decorative coating by dry plating or wet plating.
91. The method of claim 90 wherein said differentially colored film having a color different from the color of the decorative coating is comprised of gold, a gold alloy, titanium nitride, zirconium nitride, hafnium nitride, or diamond-like carbon, DLC.
92. The method of claim 90 wherein the differentially colored film having a color different from the color of the decorative coating has a two-layer structure comprising a lower layer of titanium nitride, zirconium nitride or hafnium nitride and an upper layer of gold or a gold alloy.
93. The method of claim 91 having a titanium coating film and a silicon coating film formed on the titanium coating film between the decorative coating and the differentially colored diamond-like carbon, DLC, coating films of a color different from that of the decorative coating.
94. A method according to claim 76, wherein the decorative coating is a hybrid layer of a mixture of titanium carbide and platinum or a platinum alloy forming a titanium carbide layer.
95. The method of claim 76, wherein the colored layer has a surface hardness, HV; vickers hardness micro-tester, load: 5 g, retention time: 10 seconds, 1000-.
96. A method according to claim 76, wherein the decorative article is an exterior component of a watch.
97. The method of claim 43, wherein the underlayer, the wear layer, the hybrid layer, and the outermost layer are each formed by at least one of sputtering, ion plating, and arc discharge. 98. The method of claim 49 wherein a titanium coating film and a silicon coating film formed on the titanium film are provided between the colored layer and the differentially colored diamond-like carbon, DLC, coating film of a color different from that of the colored layer.
99. The method of claim 64, wherein the primer layer, wear layer, hybrid layer, and decorative coating are each formed by at least one of sputtering, ion plating, and arc discharge.
100. The method of claim 84, wherein the primer layer, wear layer, hybrid layer, and decorative coating are each formed by at least one of sputtering, ion plating, and arc discharge.
101. The method of claim 84, wherein said titanium carbide layer and/or intermixed layer is formed by dry plating using methane gas.
102. The method of claim 91 wherein a titanium coating film and a silicon coating film formed on the titanium film are provided between the colored layer and the differentially colored diamond-like carbon, DLC, coating film of a color different from that of the colored layer.
103. The method of claim 22, wherein a titanium coating film and a silicon coating film formed on the titanium film are provided between the colored layer and a differentially colored diamond-like carbon (DLC) coating film having a color different from that of the colored layer.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP400629/2001 | 2001-12-28 | ||
| JP2001400629 | 2001-12-28 | ||
| JP2002001953 | 2002-01-09 | ||
| JP1953/2002 | 2002-01-09 | ||
| JP2002148793 | 2002-05-23 | ||
| JP148793/2002 | 2002-05-23 | ||
| PCT/JP2002/013661 WO2003056966A1 (en) | 2001-12-28 | 2002-12-26 | Decorative article having white coating and method for manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1063589A1 HK1063589A1 (en) | 2005-01-07 |
| HK1063589B true HK1063589B (en) | 2005-11-18 |
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