JP2007254851A - Metallic oxide film, and member coated with the metallic oxide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic oxide film which can be formed on the surface of a substrate having a complicated shape and presents a desired and uniform color, and to provide a member coated with the metallic oxide film. <P>SOLUTION: The metallic oxide film is made from an inorganic pigment mainly composed of a metallic oxide. The metallic oxide includes at least two metals selected from among aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), nickel (Ni), palladium (Pd), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), tungsten (W) and zinc (Zn). The metallic oxide film also presents a greenish color having a chromaticity of 30<L*<100, -60<a*<25, and -25<b*<60, by color appraisal according to an L*a*b* color system (CIE color system); and is formed with a high frequency sputtering technique. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a metal oxide film and a metal oxide film-coated member having a metal oxide film formed on a substrate, and particularly to a metal oxide film and a metal oxide film-coated member having a decorative property made of an inorganic pigment.

  The metal oxide film is used as a decorative thin film, for example, as a surface film of a decorative frame such as a frame of eyeglasses or a watch exterior part. As a thin film forming method for forming these metal oxide films on the substrate surface, an ion plating method, a vacuum heating method using a resistance heating method, a sputtering method, or the like is employed.

  Among the metal oxide films obtained by these methods, for example, by forming a titanium oxide layer having a high refractive index on the metal substrate in a film thickness range in which the interference effect acts, the chromaticity can be changed from the color of the metal substrate. A technique for providing thin films of various colors by utilizing a large change is disclosed (for example, see Patent Document 1).

  In addition, a colored hard thin film (eg, TiN) is formed on a substrate by ion plating or other vapor deposition, and then a transparent hard thin film (eg, AlN) is further laminated on the substrate as an interference film. A technique for displaying various colors by adjusting various hard film thicknesses to various film thicknesses to form an interference film is disclosed (for example, see Patent Document 2).

  Also, a titanium-aluminum alloy coating layer is formed on the entire surface of the gaming coin by ion plating or sputtering, and the coating layer is anodized to form an oxide coating layer. A technique for generating a color by the interference action of light is disclosed (for example, see Patent Document 3).

JP 7-252634 A (second page) JP-A-9-125232 (second page, FIG. 1) Japanese Patent No. 30428232 (page 4, FIG. 1)

  However, in the metal oxide film in the prior art, when a thin film is laminated on the surface of the substrate, various colors are formed by finely controlling the thickness of the thin film. It is necessary to adjust the film thickness by continuing the formation of the thin film until the desired color is observed through the viewing window of the chamber during the formation of the thin film. In order to control the film thickness more accurately, it is necessary to use a film thickness monitor. Further, the color development of the anodic oxide film also occurs due to the light interference action on the surface of the oxide film, and the thickness of the oxide film layer needs to be controlled by the anodic oxidation voltage.

  Thus, the interference color in the prior art changes even when the film thickness is slightly different. For this reason, stable color development cannot be obtained within a product, within a batch in a manufacturing process, or between batches, and when the substrate surface is uneven, differences in film thickness due to partial shapes occur even on the same product. Therefore, there is a problem that uniform color development cannot be obtained.

  An object of the present invention is to provide a metal oxide film that can be formed with a desired color and a uniform color on the surface of a substrate having a complicated surface shape, and a metal oxide film-coated member formed with the metal oxide film on a substrate. It is to provide.

  In order to achieve the above object, a metal oxide film of the present invention is a metal oxide film made of an inorganic pigment containing a metal oxide as a main component, and the metal oxide contains aluminum (Al), cobalt (Co ), Chromium (Cr), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), nickel (Ni), palladium (Pd), antimony (Sb), silicon (Si), tin (Sn) ), Titanium (Ti), Tungsten (W), Zinc (Zn), the main component is an oxide of at least two metals, and the color by the L * a * b * color system (CIE color system) Evaluation is 30 <L * <100, 1 <60 <a * <25, −25 <b * <60 in chromaticity, green color, and high frequency sputtering method. To do.

  Further, the metal oxide film is characterized in that the film thickness is in the range of 0.1 to 15.0 μm.

  In the metal oxide film-coated member of the present invention, a metal oxide film is formed on at least a part of a substrate by a high-frequency sputtering method, and the metal oxide film is an inorganic pigment mainly composed of a metal oxide. A metal oxide film comprising: aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), Oxidation of at least two metals selected from nickel (Ni), palladium (Pd), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), tungsten (W), and zinc (Zn) It is characterized by having an object as a main component.

  Further, the metal oxide film-coated member is characterized in that a metal oxide film having a thickness of 0.1 to 15.0 μm is formed on at least a part of the substrate.

  The metal oxide film-coated member has a color evaluation of 30 <L * <100 and 1 <60 <a * <25 based on the L * a * b * color system (CIE color system) on at least a part of the substrate. A metal oxide film having a chromaticity in a range of −25 <b * <60 and exhibiting a greenish color is formed.

  The metal oxide film-coated member is characterized in that the base material has at least one base film, and the metal oxide film is formed on at least a part of the upper layer of the base film.

  The metal oxide film-coated member is characterized in that the base film has a base film exposed portion in which the metal oxide film is missing in part.

  Further, the metal oxide film-coated member has a base material exposed part in which a base film exposed part is missing at least partially.

  The metal oxide film-coated member is characterized in that at least one protective film is formed on the surface.

  The metal oxide film covering member has a base material of platinum (Pt), gold (Au), silver (Ag), copper (Cu), iron (Fe), zinc (Zn), titanium (Ti), aluminum. It is characterized by comprising at least one metal selected from (Al), tungsten (W), tantalum (Ta), zirconium (Zr), silicon (Si), stainless steel, brass, or an alloy.

  The metal oxide film-coated member is characterized in that the base material is made of sintered ceramics, glass, or plastic.

  The metal oxide film-coated member is characterized in that the base material is a decorative article.

  The metal oxide film-coated member is characterized in that the base material is a watch exterior part.

  In a colored thin film using interference colors in the prior art, it has been very difficult to form a film having a uniform thickness on a complex shape product. On the other hand, the present inventor has conducted extensive research and experiments to develop a film formed in a uniform color, and as a result, has found that a thin film having a uniform color can be formed by forming an inorganic pigment. It is a thing. In general, inorganic pigments are often insulators, but as a result of studying this inorganic pigment film formation method, it was found that film formation can be solved by high-frequency sputtering, and the present invention is based on this finding. It has come to be completed.

  As described above, according to the present invention, a uniform and vivid color metal oxide film can be obtained on the surface of a substrate having a concavo-convex pattern or a substrate having a complicated shape. Moreover, this metal oxide film can be formed in a necessary part on the surface of the base material, or can be formed in a pattern shape, and a metal oxide film-coated member excellent in design and color variation can be obtained.

  In addition, by forming a two-layered film of a base film and a metal oxide film on the surface of the base material, and providing a base film exposed part in which the metal oxide film is missing on a part of the base film, the design and color Variations can be further improved, and a high-grade metal oxide film-coated member can be obtained. Furthermore, by providing a transparent protective film, it is possible to prevent the metal oxide film from being peeled off and worn, and to prevent scratches caused by contact with the outside, and to obtain a metal oxide film-coated member that exhibits a more vivid color.

  The metal oxide film in the present embodiment is made of an inorganic pigment mainly composed of a metal oxide, and the metal oxide includes aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron ( Fe), magnesium (Mg), manganese (Mn), nickel (Ni), palladium (Pd), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), tungsten (W), zinc ( The main component is an oxide of at least two metals selected from Zn). Further, the metal oxide film-coated member in the present embodiment is obtained by forming the above-mentioned metal oxide film on the entire surface or a part of the substrate surface by a high frequency sputtering method.

In this method for producing a metal oxide film-coated member, an inorganic pigment target and a substrate to be processed are placed in a chamber of a vacuum apparatus, the chamber is evacuated, and a predetermined pressure (5 × 10 ⁻³ Pa or less) is obtained. After reaching Ar, an Ar gas as an inert gas is introduced into the chamber and adjusted to a set pressure (0.1 to 1.3 Pa), and then high frequency power (500 w to 2,500 w) is applied to the target. It is formed by depositing evaporated inorganic pigment particles on a substrate, and a metal oxide film having a uniform color is formed on the substrate surface regardless of the film thickness. As a result, a metal oxide film-coated member excellent in design and color variation and having a high-class feeling is realized.
In addition, the inorganic pigment target is often an insulator that is not energized, and cannot be used in a normal sputtering method in which a voltage is applied to the target.

  The thickness of the metal oxide film is preferably in the range of 0.1 to 15.0 μm, and more preferably in the range of 0.3 to 1.5 μm. When the film thickness is smaller than 0.1 μm, it is not preferable because the base color is transmitted and the color of the coating itself cannot be obtained. On the other hand, when the film thickness is larger than 15.0 μm, the surface roughness increases as a characteristic of the film forming method, resulting in a blackish color development, and the film stress increases, so that the film is easily peeled off.

  Further, the metal oxide film in the present embodiment exhibits a green color, and the color evaluation by the L * a * b * color system (CIE color system) is 30 <L * <100, and 1 <60 <a * <. Chromaticity in the range of 25, -25 <b * <60 is preferable, and chromaticity in the range of 35 <L * <45, 25 <a * <-15, 0 <b * <10 is a bright green color. Is more preferable. The chromaticity in this range is a range that can be referred to as green, and if it is outside this range, it is difficult to say that the green color is practically beautiful, so the commercial value is lowered.

The L * a * b * color system (CIE color system) is a color coordinate used in the International Lighting Commission and represents the following sensory chromaticity.
L *: Black ← Minus (−) side, plus (+) side → White a *: Green ← Minus (−) side, plus (+) side → Red b *: Blue ← Minus (−) side, plus (+ ) Side → yellow

  It is also possible to form a two-layered film of a base film and a metal oxide film on the substrate surface, and to provide a base film exposed portion where the metal oxide film is missing in a part of the base film. This undercoating film may be formed by either wet plating or dry plating, and by using a color different from that of the metal oxide film, a so-called two-tone color is realized by combining the undercoating film exposed portion and the metal oxide film. It is possible. As a result, the design and color variation can be further improved, and a high-quality coating member mainly made of green can be obtained. Furthermore, the base-material exposed part lacked in a part of base film exposed part can also be provided, and a multicolor combination is possible, and what is called multicolor is also realizable.

  Furthermore, a transparent protective film can be provided on the surface of the metal oxide film-covered member, that is, at least a part of the base material exposed part, the base film exposed part, or the metal oxide film. As a result, peeling and abrasion of the metal oxide film and the base film can be prevented, and scratches caused by contact with the outside can be prevented. Moreover, the metal oxide film coating | coated member which exhibits a more vivid color can be obtained rather than providing a transparent protective film on the surface.

  Moreover, as a base material in this embodiment, platinum (Pt), gold (Au), silver (Ag), copper (Cu), iron (Fe), zinc (Zn), titanium (Ti), aluminum (Al) Various metals such as tungsten (W), tantalum (Ta), zirconium (Zr), silicon (Si), stainless steel, brass, or alloys can be used. Furthermore, various materials such as sintered ceramics, glass or plastic can be used. As a result, the metal oxide film-coated member in this embodiment can be applied to many products such as tableware, toys, figurines, etc., but exhibits an excellent effect when applied to decorative items, particularly watch exterior parts. It is.

  FIGS. 1 to 3 are diagrams showing metal oxide film-coated members in Examples 1 to 3 of the present invention. FIGS. 4 and 5 show formation of a metal oxide film on a substrate in each example of the present invention. It is a figure which shows the vacuum apparatus for obtaining a metal oxide film coating member. Hereinafter, specific examples of the metal oxide film and the metal oxide film-coated member of the present invention will be described with reference to FIGS.

  The metal oxide film-coated member in Example 1 is an example of a watch case in a watch exterior product. A base film is formed on the entire outer surface of the watch case, and a metal oxide is formed on the entire surface of the base film. This is an example in which a film is formed. 1A and 1B are views showing a watch case as a metal oxide film covering member in Example 1, FIG. 1A is a perspective view, and FIG. 1B is a partially enlarged view of the watch case in FIG. It is sectional drawing. As shown in FIG. 1, the base material 11 of the watch case 10 as a metal oxide film covering member in the present embodiment is made of a brass material, and nickel / chromium (Ni) by wet plating is formed on the entire surface of the base material 11 as a base film 13. -Cr) is plated. The undercoat 13 is composed of a nickel layer 12a having a thickness a of 2 μm and a chromium layer 12b having a thickness b of 1 μm formed thereon, and the thickness of the undercoat 13 is 3 μm. Further, a metal oxide film 14 having a thickness c of 0.5 μm is formed on the upper layer of the base film 13.

This metal oxide film 14 is an inorganic composite oxide having a content ratio of 2: 1: 4: 3 of cobalt oxide (CoO): zinc oxide (ZnO): nickel oxide (NiO): titanium oxide (TiO ₂ ). It is formed from a pigment. In addition, the metal oxide film 13 has a chromaticity of L * = 33, a * = − 20, b * = 8, and the color evaluation by the L * a * b * color system (CIE color system) is vivid. Presents a greenish color. The metal oxide film 14 is formed by a high frequency sputtering method, and the formation method will be described below.

An inorganic pigment (CoO: ZnO: NiO: TiO ₂ = 2: 1: 4: 3 composite oxide) target 6 and an undercoating film 13 are formed on the entire surface of the object 8 as an object to be processed 8 into the chamber 5 of the vacuum apparatus shown in FIG. Attach the watch case base 11 with nickel-chromium (Ni—Cr) plating by wet plating to the base holder 9 and place it at a distance of about 80 mm, then up to 5.0 × 10 ⁻³ Pa After exhausting, Ar gas is introduced into the vacuum chamber 5 at a flow rate of 25 cc / min, and the degree of vacuum is adjusted to 0.6 Pa. After that, high frequency power of 2,000 w was applied to the inorganic pigment target 6 and sputtering was performed for about 60 minutes. After cooling for about 20 minutes, the inside of the chamber 5 was brought to atmospheric pressure, and the watch case base 11 as the workpiece 8 was taken out. It was confirmed that the material film 14 was formed. Moreover, it was confirmed that this metal oxide film 14 is very hard and excellent in wear resistance as compared with a film using interference colors in the prior art.

The vacuum apparatus shown in FIG. 5 includes a rotation mechanism 7 and is attached to the substrate holder 9 so that the substrate holder 9 rotates and the workpiece 8 itself also rotates. Therefore, a metal oxide film can be formed on the entire surface of the watch case.
As described above, according to the present embodiment, it is possible to obtain a watch case having a bright green color with excellent decorativeness. In addition, a uniform and vivid green-based metal oxide film can be formed on the entire surface of a base material having a complicated shape such as a watch case.

  The metal oxide film covering member in Example 2 is an example of a gaming coin, and is an example in which a metal oxide film is formed on one surface of the coin. 2A and 2B are diagrams showing a gaming coin as a metal oxide film covering member in Example 2, FIG. 2A is a perspective view, and FIG. 2B is a cross-sectional view taken along line AA in FIG. FIG. As shown in FIG. 2, the base material 16 of the gaming coin 15 as the metal oxide film covering member in the present embodiment is made of an austenitic stainless material, and the entire surface of one surface 16a of the base material 16 has a film thickness t. A metal oxide film 18 having a value of 1.0 μm is formed.

The metal oxide film 18 is an inorganic composite oxide having a content ratio of cobalt oxide (CoO): zinc oxide (ZnO): nickel oxide (NiO): titanium oxide (TiO ₂ ) of 1: 2: 4: 3. It is formed from a pigment. Further, this metal oxide film 18 has a chromaticity of L * = 45, a * = − 18, b * = 5 according to the color evaluation by the L * a * b * color system (CIE color system), Presents a vivid greenish color. This metal oxide film 18 is formed by the high frequency sputtering method as in the first embodiment. The formation method will be described below.

An inorganic pigment (CoO: ZnO: NiO: TiO ₂ = 1: 2: 4: 3 complex oxide) target 2 and a base material 16 of gaming coins as an object to be processed 3 are fed into the chamber 1 of the vacuum apparatus shown in FIG. Was attached to the substrate holder 3 and arranged at a distance of about 80 mm. At this time, one surface 16a of the base 16 of the gaming coin was disposed so as to face the target 2, and masking was performed on the surface other than the one surface 16a. Thereafter, the gas is exhausted to 5.0 × 10 ⁻³ Pa, and then Ar gas is introduced into the vacuum chamber 1 at a flow rate of 25 cc / min to adjust the degree of vacuum to 0.6 Pa. Thereafter, a high frequency power of 2,000 w was applied to the inorganic pigment target 2 and sputtering was performed for about 90 minutes. After cooling for about 20 minutes, the inside of the chamber 1 is brought to atmospheric pressure, and the base material 16 of the gaming coin as the object to be processed 3 is taken out. As a result, a metal oxide exhibiting a uniform green color on one surface 16a of the base material 16 is obtained. It was confirmed that the film 18 was formed. Further, it was confirmed that this metal oxide film 18 was very hard and excellent in wear resistance as compared with the film using the interference color in the prior art as in Example 1.

  As described above, according to the present embodiment, a metal oxide film can be formed on a necessary portion of the surface of the base material, and therefore, a surface-shaped base material having a concavo-convex pattern or a base having a complicated shape like a game coin. A uniform and vivid green metal oxide film can be formed on one surface of the material. In addition, a so-called two-tone color can be realized by combining a metal oxide film exhibiting green, which is one surface of a gaming coin, and a metal surface made of austenitic stainless steel, which is a base material exposed portion, as the other surface. . As a result, the design and color variation can be further improved.

The metal oxide film covering member in Example 3 is an example of an eyeglass frame, in which a metal oxide film made of an inorganic pigment is provided on the entire surface, and then a transparent protective film is provided on the entire surface of the eyeglass frame. It is. 3 is a view showing a spectacle frame as a metal oxide film covering member in Example 3, FIG. 3 (a) is a perspective view, and FIG. 3 (b) is a partially enlarged sectional view in FIG. 3 (a). is there. As shown in FIG. 3, the base material 21 of the spectacle frame 20 as a metal oxide film covering member in the present embodiment is made of a titanium (Ti) material, and the value of the film thickness c is 0.4 μm on the entire surface of the base material 21. The metal oxide film 22 is formed. This metal oxide coating 22 is
It is formed from an inorganic pigment which is a complex oxide having a content ratio of cobalt oxide (CoO): zinc oxide (ZnO): nickel oxide (NiO): titanium oxide (TiO ₂ ) of 2: 2: 3: 3. In addition, the metal oxide film 22 has a chromaticity of L * = 40, a * = − 25, b * = 0 and color evaluation based on the L * a * b * color system (CIE color system). Presents a greenish color. The metal oxide film 22 is formed by a high frequency sputtering method, and the formation method will be described below.

The inorganic pigment (CoO: ZnO: NiO: TiO ₂ = 2: 2: 3: 3 composite oxide) target 6 and the base material of the spectacle frame 20 as the workpiece 8 are placed in the chamber 5 of the vacuum apparatus shown in FIG. 21 is attached to the substrate holder 9 and arranged at a distance of about 80 mm, and then evacuated to 5.0 × 10 ⁻³ Pa. Thereafter, Ar gas is introduced into the vacuum chamber 1 at a flow rate of 25 cc / min, and the degree of vacuum is increased. Is adjusted to 0.6 Pa. Thereafter, a high frequency power of 2,000 w was applied to the inorganic pigment target 6 and sputtering was performed for about 30 minutes. After cooling for about 20 minutes, the pressure inside the chamber 5 is changed to atmospheric pressure, and the base material 21 of the spectacle frame 20 as the object to be processed 8 is taken out. It was confirmed that the film 22 was formed. Further, it was confirmed that the metal oxide film 22 was very hard and excellent in wear resistance as compared with the film using the interference color in the prior art as in Example 1.

Next, the first agent and the second agent of the two-component urethane paint were mixed on the entire surface of the metal oxide film 22 formed on the entire surface of the base material 21 of the spectacle frame and applied by spraying or the like. Thereafter, it was heated and held at 70 ° C. for 60 minutes to cure, and a transparent protective film 23 was formed.
As described above, according to the present embodiment, a uniform and vivid green-based metal oxide film can be formed on the entire surface of a base material having a complicated shape such as a spectacle frame. Further, by providing a transparent protective film 23 on the entire surface of the metal oxide film 22 formed on the surface of the spectacle frame 20, the metal oxide film 22 is prevented from being peeled off or worn, and scratches caused by contact with the outside are prevented. Can be prevented. In addition, a spectacle frame exhibiting a brighter green color can be obtained by the action of the transparent protective film 23.

In this embodiment, although the example which formed the oxide film of one layer was demonstrated, it is not limited to this, A multiple layer oxide film can be formed.
In the present embodiment, cobalt oxide (CoO), zinc oxide (ZnO), nickel oxide (NiO), and titanium oxide (TiO ₂ ) are formed as oxide films. However, the present invention is not limited thereto. Instead, an oxide film of another substance can be formed.

It is a figure which shows the timepiece case as a metal oxide film coating | coated member in Example 1 of this invention, Fig.1 (a) is a perspective view, FIG.1 (b) is the elements on larger scale of the timepiece case in Fig.1 (a). It is. It is a figure which shows the coin for game as a metal oxide film coating | coated member in Example 2 of this invention, Fig.2 (a) is a perspective view, FIG.2 (b) is AA sectional drawing in Fig.2 (a). It is. It is a figure which shows the spectacles frame as a metal oxide film coating | coated member in Example 3 of this invention, Fig.3 (a) is a perspective view, FIG.3 (b) is the elements on larger scale of the spectacles frame in Fig.3 (a). It is. It is a simulation cross section which shows the principal part of the vacuum apparatus which forms a metal oxide film in a base material in the Example of this invention. It is a simulation cross section which shows the principal part of the other vacuum apparatus which forms a metal oxide film in a base material in the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 5 Vacuum apparatus 2, 6 Inorganic pigment target 3, 9 Base material holder 4, 8 To-be-processed object 7 Rotating mechanism 10 Watch case 11 Watch case base material 12a Nickel layer 12b Chromium layer 13 Base film 14 Metal oxide film 15 Game Coin 16 Game Coin Base 16a One Surface 18 Metal Oxide Film 20 Glass Frame 21 Glass Frame Base 22 Metal Oxide Film 23 Transparent Protective Film

Claims (11)

  A metal oxide film composed of an inorganic pigment containing a metal oxide as a main component, wherein the metal oxide is aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe) , Magnesium (Mg), manganese (Mn), nickel (Ni), palladium (Pd), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), tungsten (W), zinc (Zn) The main component is an oxide of at least two metals selected from among the above, and the color evaluation by the L * a * b * color system (CIE color system) is 30 <L * <100, and 1 <60 <a * <25. A metal oxide film having a chromaticity in the range of −25 <b * <60 and exhibiting a greenish color and formed by a high-frequency sputtering method.   2. The metal oxide film according to claim 1, wherein the metal oxide film is formed in a range of 0.1 to 15.0 [mu] m.   A metal oxide film-coated member, wherein the metal oxide film according to claim 1 or 2 is formed on at least a part of a substrate.   4. The metal oxide film coating according to claim 3, wherein the base material has at least one undercoat film, and the metal oxide film is formed on at least a part of an upper layer of the undercoat film. Element.   The metal oxide film-coated member according to claim 4, wherein the base film has a base film exposed portion in which the metal oxide film is missing in a part thereof.   The metal oxide film-coated member according to claim 5, wherein the base film exposed part has a base material exposed part that is missing at least in part.   The metal oxide film-coated member according to any one of claims 3 to 6, wherein a protective film of at least one layer is formed on the surface.   The base material is platinum (Pt), gold (Au), silver (Ag), copper (Cu), iron (Fe), zinc (Zn), titanium (Ti), aluminum (Al), tungsten (W), 8. The method according to claim 3, comprising at least one metal selected from tantalum (Ta), zirconium (Zr), silicon (Si), stainless steel, and brass, or an alloy. The metal oxide film covering member as described.   The metal oxide film-coated member according to any one of claims 3 to 7, wherein the base material is made of sintered ceramics, glass, or plastic.   The metal oxide film-coated member according to any one of claims 3 to 9, wherein the base material is a decorative article. The metal oxide film-coated member according to any one of claims 3 to 10, wherein the base material is a watch exterior part.

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