JP2007254853A - 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 whitish color having a chromaticity of 90<L*<100, -10<a*<10, and -10<b*<10, 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 interference 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 90 <L * <100, 1 <10 <a * <10, −10 <b * <10 in chromaticity, white color, and formed by a 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.

  In addition, the metal oxide film-coated member has a color evaluation of 90 <L * <100 and 1 <10 <a * <10 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 the range of −10 <b * <10 and exhibiting a white 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 color tone of the base 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.

In addition, the metal oxide film in the present embodiment exhibits a white color, and the color evaluation by the L * a * b * color system (CIE color system) is 90 <L * <100, and 1 <10 <a * <. Chromaticity in the range of 10, -10 <b * <10 is preferable, and chromaticity in the range of 92 <L * <98, 15 <a * <5, -5 <b * <5 is bright white Is more preferable. The chromaticity within this range is a range that can be called white, and if it is out of this range, it is difficult to say that the white 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-grade covering member mainly including white 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 | coated 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 band as a watch exterior part in a decorative article, and an example in which a metal oxide film made of an inorganic pigment is provided on the entire surface. is there. 1A and 1B are diagrams showing a watch band as a metal oxide film covering member in Example 1, FIG. 1A is a perspective view, and FIG. 1B is a view of the watch band in FIG. It is a partial expanded sectional view. As shown in FIG. 1, a watch band 10 as a metal oxide film covering member in this embodiment is composed of a plurality of pieces. The base material 12 of the watch band 10 is made of a titanium (Ti) material, and a metal oxide film 13 having a thickness t of 0.6 μm is formed on the entire surface of the base material 12. The metal oxide film 13 is formed of an inorganic pigment which is a complex oxide having a content ratio of titanium oxide (TiO ₂ ): aluminum oxide (Al ₂ O ₃ ): 9: 1. In addition, the metal oxide film 13 has a chromaticity of L * = 95, a * = 0, b * = − 2, and the color evaluation by the L * a * b * color system (CIE color system) is vivid. Exhibits a white color. The metal oxide film 13 is formed by a high frequency sputtering method, and the formation method will be described below.

The inorganic pigment (TiO ₂ : Al ₂ O ₃ = 9: 1 complex oxide) target 6 and the base material 12 of the watch band 10 as the workpiece 8 are supplied to the chamber 5 of the vacuum apparatus shown in FIG. After being attached to the holder 9 and arranged at a distance of about 80 mm, it is evacuated to 5.0 × 10 ⁻³ Pa, then Ar gas is introduced into the vacuum chamber 5 at a flow rate of 25 cc / min, and the degree of vacuum is 0.6 Pa. Adjust to. After that, high frequency power of 2,000 w was applied to the inorganic pigment target 6 and sputtering was performed for about 1 hour. After cooling for about 20 minutes, the pressure inside the chamber 5 is changed to atmospheric pressure, and the base material 12 of the watch band 10 as the workpiece 8 is taken out. As a result, the base material 12 of the watch band 10 exhibits a uniform white color. It was confirmed that the film 13 was formed. Moreover, it was confirmed that this metal oxide film 13 is very hard and excellent in wear resistance as compared with a film using interference colors in the prior art.

  Thus, according to the present embodiment, it is possible to obtain a watch band which is excellent in decorativeness and exhibits a bright white color. 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 band piece. As described above, according to the present embodiment, a uniform and vivid white metal oxide film can be formed on the entire surface of a base material having a complicated shape such as a watch band. In addition, it is possible to obtain a watch band that has excellent decorativeness and exhibits a bright white color, and it is possible to further improve the design and color variation of the watch band.

  The metal oxide film-coated member in Example 2 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 a part of the base film. This is an example in which an object film is formed. 2A and 2B are views showing a watch case as a metal oxide film covering member in Example 2, FIG. 2A is a perspective view, and FIG. 2B is an AA cross-sectional view in FIG. It is. As shown in FIG. 2, the base material 16 of the watch case 15 as the metal oxide film covering member in the present embodiment is made of a titanium (Ti) material, and a known ion plating is used as the base film 17 on the entire surface of the base material 16. A black titanium nitride carbide (TiCN) coating is formed. The value of the thickness a of the titanium nitride carbide (TiCN) film that is the base film 17 was 1 μm.

Further, a metal oxide film 18 having a thickness b of 2 μm is formed on the surface of the base film 17 excluding portions corresponding to the upper slope and the upper surface of the foot of the watch case 15 in the base film 17. The metal oxide film 18 is formed of an inorganic pigment which is a composite oxide having a content ratio of titanium oxide (TiO ₂ ): aluminum oxide (Ai ₂ O ₃ ) of 8: 2. Further, this metal oxide film 18 has a chromaticity of L * = 90, a * = − 1, b * = 5 according to the color evaluation by the L * a * b * color system (CIE color system), Presents a bright white 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.

Inorganic vacuum (a composite oxide of TiO ₂ : Al ₂ O ₃ = 8: 2) target 2 is applied to the chamber 1 of the vacuum apparatus shown in FIG. A watch case base 16 on which a black titanium nitride (TiCN) film was formed was attached to the base holder 4 and arranged at a distance of about 80 mm. At this time, the upper surface side of the watch case 15 was disposed so as to face the target 6, and masking was performed on the upper slope of the watch case 15 and the surface corresponding to the upper surface of the foot, which become the base coat exposed portion 17 a. Then, it exhausts to 5.0x10 < ^-3 > Pa, Ar gas is introduce | transduced in the vacuum chamber 5 by the flow volume of 25 cc / min after that, and a vacuum degree is adjusted to 0.6 Pa. Thereafter, high frequency power of 2,000 w was applied to the inorganic pigment target 2 and sputtering was performed for about 120 minutes. After cooling for about 20 minutes, the inside of the chamber 1 is brought to atmospheric pressure, and the watch case base 16 as the workpiece 3 is taken out. As a result, the surface of the base coat 17 excluding the base coat exposed portion 17a of the watch case 15 is uniform. It was confirmed that a white metal oxide 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 part of the surface of the base material, so that a uniform and bright white metal oxide film is formed on a part of the base material of the watch case. can do. In addition, a so-called two-tone watch case can be obtained by combining a black and white metal oxide film with a titanium nitrocarbide (TiCN) film that is an exposed part of the base film. As a result, a watch case excellent in decorativeness, design and color variation can be obtained.

  The metal oxide film-coated member in Example 3 is an example of a pointer for displaying the time in a watch exterior product, and a base film is formed on the entire surface, and a part of the base film is formed. This is an example in which a metal oxide film is formed and a protective film is further provided on the surface of the metal oxide film. FIG. 3 is a view showing a timepiece hand as a metal oxide film-coated member in Example 3, FIG. 3 (a) is an hour hand 20a, FIG. 3 (b) is a minute hand 20b, and FIG. 3 (c) is a second hand. FIG. 3D is a cross-sectional view of the hour hand 20a in FIG. In this embodiment, the hour hand 20a shown in FIGS. 3A and 3D in the pointer will be described as an example.

As shown in FIGS. 3A and 3D, the base 21 of the hour hand 20a for a watch as the metal oxide coating covering member in the present embodiment is made of a brass material, and the entire surface of the base 21 is covered. The base coating 22 is nickel (Ni) plated by wet plating. The value of the thickness c of the nickel layer as the undercoat 22 is 2 μm. Further, a metal oxide film 23 having a film thickness d of 0.5 μm is formed on the base film upper surface portion 22 a corresponding to the upper surface side of the hour hand 20 a in the base film 22. This metal oxide film 23 is formed of an inorganic pigment which is a complex oxide having a content ratio of titanium oxide (TiO ₂ ): aluminum oxide (Al ₂ O ₃ ) of 9: 1. Further, this metal oxide film 23 has a chromaticity of L * = 100, a * = − 3, b * = 1 according to an L * a * b * color system (CIE color system). Presents a bright white color. This metal oxide film 23 is formed by the high frequency sputtering method as in the first embodiment. The formation method will be described below.

The inorganic pigment (TiO ₂ : Al ₂ O ₃ = 9: 1 complex oxide) target 2 is placed in the chamber 1 of the vacuum apparatus shown in FIG. The substrate 21 of the hour hand that is plated with (Ni) was attached to the substrate holder 4 and arranged at a distance of about 80 mm. At this time, the undercoat upper surface portion 22a corresponding to the upper surface side of the hour hand 20a was arranged so as to face the target 6, and the surface other than the undercoat upper surface portion 22a was masked. Then, it exhausts to 5.0x10 < ^-3 > Pa, Ar gas is introduce | transduced in the vacuum chamber 5 by the flow volume of 25 cc / min after that, and a vacuum degree is adjusted to 0.6 Pa. Thereafter, high frequency power of 2,000 w was applied to the inorganic pigment target 2 and sputtering was performed for about 30 minutes. After cooling for about 20 minutes, the pressure inside the chamber 1 is changed to atmospheric pressure, and the hour hand base material 21 as the workpiece 3 is taken out. It was confirmed that the metal oxide film 23 was formed. Further, it was confirmed that this metal oxide film 23 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, a first agent and a second agent of a two-component urethane paint were mixed on the surface of the metal oxide film 23 corresponding to the upper surface of the base 21 of the hour hand 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 24 was formed.

  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, so that a uniform and bright white metal oxide film 23 is formed on the upper surface of the hour hand 20a for a watch. can do. Moreover, the hour hand 20a for timepieces which exhibits a more vivid white can be obtained by providing the transparent protective film 24 on the metal oxide film 23 formed on the upper surface of the hour hand 20a. As a result, it is possible to obtain timepiece hands that have excellent decorativeness and exhibit a bright white color, and it is possible to further improve the design and color variations of the timepiece hands.

In the present embodiment, an example in which a single oxide film is formed has been described, but the present invention is not limited to this, and a plurality of oxide films can be formed.
In the present embodiment, an example in which titanium oxide (TiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) are formed as oxide films has been described. However, the present invention is not limited to this, and oxide films of other substances are used. Can be formed.

FIGS. 1A and 1B show a timepiece band as a metal oxide film-coated member in Example 1 of the present invention, FIG. 1A being a perspective view, and FIG. 1B being a portion of the timepiece band in FIG. It is an expanded sectional view. It is a figure which shows the timepiece case 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). is there. FIGS. 3A, 3B, and 3C are perspective views showing an hour hand, a minute hand, and a second hand, respectively, according to a third embodiment of the present invention. FIG. FIG. 3D is a cross-sectional view of the hour hand taken along the line B-B in FIG. 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 Rotation mechanism 10 Watch band 12 Watch band base material 13 Metal oxide film 15 Watch case 16 Watch case base Material 17 Base coating 17a Base coating exposed portion 18 Metal oxide coating 20a Clock hour hand 20b Clock minute hand 20c Clock second hand 21 Hour hand base material 22 Base coating 22a Base coating upper surface 23 Metal oxide coating 24 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 90 <L * <100, and 1 <10 <a * <10. A metal oxide film having a chromaticity in a range of −10 <b * <10 and exhibiting a white 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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