Decorative member, its manufacturing method and decorative article

Abstract

To provide a decorative member excellent in abrasion resistance and capable of holding the sense of color derived from noble metal even when used for a long time.SOLUTION: A decorative member includes a base material and a decorative film formed on the base material. The decorative film is obtained by laminating a base layer, a control layer and a finishing layer from the base material side; the base layer includes the nitrogen carbide of metal including Ti and at least one kind selected from Nb and Ta; the finishing layer includes Au alloy; the control layer has a lamination structure including at least first and second control layers laminated from the base material side; the first control layer including Au alloy has a thickness of 0.005 μm or more and 0.016 μm or less; and the second control layer including the nitride carbide of metal including Ti and at least one kind selected from Nb and Ta has a thickness of 0.039 μm or more and 0.065 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative member, a manufacturing method thereof, and a decorative article. [Background technology]

[0002] Patent Document 1 describes a decorative member comprising a substrate and a decorative coating formed on the substrate, in which the decorative coating comprises a base layer, an adjustment layer, and a finishing layer stacked from the substrate side. The base layer is a carbide nitride layer made of a metal carbide containing at least one selected from Nb and Ta and Ti, and the finishing layer is an Au alloy layer. The adjustment layer has a layered structure in which Au alloy layers and carbide nitride layers made of a metal carbide containing at least one selected from Nb and Ta and Ti are alternately stacked. Furthermore, the publication describes that the thicknesses of the Au alloy layer and the carbide nitride layer are preferably 0.005 μm or more and 0.016 μm or less, respectively. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2020-116392 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the decorative member described in Patent Document 1 has room for improvement in terms of abrasion resistance, and there is a problem in that the color inherent to the precious metal is lost after long-term use.

[0005] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a decorative member that is excellent in abrasion resistance and that maintains the color inherent to precious metals even after long-term use. [Means for solving the problem]

[0006] The decorative member of the present invention is a decorative member comprising a substrate and a decorative coating formed on the substrate, wherein the decorative coating is formed by laminating, from the substrate side, a primer layer, an adjustment layer, and a finishing layer, wherein the primer layer comprises a metal carbide containing at least one selected from Nb and Ta and Ti, and the finishing layer comprises an Au alloy, the adjustment layer has a layered structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side, the first adjustment layer comprises an Au alloy, and the second adjustment layer comprises a metal carbide containing at least one selected from Nb and Ta and Ti, the thickness of the first adjustment layer is 0.005 μm or more and 0.016 μm or less, and the thickness of the second adjustment layer is 0.039 μm or more and 0.065 μm or less. [Effects of the Invention]

[0007] The decorative member of the present invention has excellent abrasion resistance and maintains the color inherent to the precious metal even after long-term use. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram illustrating the decorative member of the first embodiment. [Figure 2] FIG. 2 is a diagram illustrating the decorative member of the second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Modes (embodiments) for carrying out the present invention will be described in detail. The present invention is not limited to the contents described in the following embodiments. Furthermore, the components described below include those that can be easily imagined by a person skilled in the art and those that are substantially the same. Furthermore, the configurations described below can be combined as appropriate. Furthermore, various omissions, substitutions, or modifications of the configuration can be made within the scope of the gist of the present invention.

[0010] <Decorative member of embodiment> The decorative member of the embodiment includes a substrate and a decorative coating formed on the substrate. The decorative coating is formed by laminating a base layer, an adjustment layer, and a finishing layer from the substrate side. The adjustment layer has a laminated structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side. The decorative member of the embodiment will be described in more detail below.

[0011] [Embodiment 1] Fig. 1 is a diagram illustrating a decorative member of embodiment 1. That is, Fig. 1 is a schematic cross-sectional view of a decorative member 1. The decorative member of embodiment 1 includes a substrate 10 and a decorative coating 20 formed on the substrate 10. The decorative coating 20 is formed by laminating, from the substrate 10 side, a base layer 22, an adjustment layer 24, and a finishing layer 26.

[0012] [Base material] The substrate 10 is formed from, for example, metal, ceramic, or plastic. Specific examples of metals (including alloys) include stainless steel, titanium, titanium alloys, copper, copper alloys, tungsten, or hardened stainless steel, titanium, and titanium alloys. These metals can be used alone or in combination of two or more. The shape of the substrate 10 is not particularly limited.

[0013] [Base layer] The underlayer 22 contains a metal carbide containing Ti and at least one selected from Nb and Ta. The carbide containing the specific metals described above can form an underlayer 22 that exhibits a gold color similar to that of an Au alloy. Furthermore, combining Nb and / or Ta with Ti increases the film hardness of the underlayer 22, thereby improving the scratch resistance and abrasion resistance of the decorative member 1. Having an underlayer 22 that is sufficiently harder than the substrate 10 in this way increases scratch resistance, making the adjustment layer 24 and finishing layer 26 less likely to peel. Furthermore, combining Nb and / or Ta with Ti also improves the corrosion resistance of the decorative member 1.

[0014] In the above metal carbide nitrides, Nb may be used alone, Ta may be used alone, or Nb and Ta may be used in combination. Because Ta has a larger atomic weight than Nb, the use of Ta increases the film hardness, and can improve the scratch resistance and wear resistance of the decorative member 1.

[0015] In the underlayer 22, the metal carbide preferably contains 22 to 66 mass% of the at least one selected from Nb and Ta, 20 to 50 mass% of Ti, 7 to 19 mass% of nitrogen, and 4 to 15 mass% of carbon, when the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%.More preferably, in the underlayer 22, the metal carbide preferably contains 40 to 44 mass% of the at least one selected from Nb and Ta, 37 to 40 mass% of Ti, 9 to 18 mass% of nitrogen, and 5 to 7 mass% of carbon, when the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%. From the viewpoint of color tone and film hardness, it is preferable that the amounts of metal elements and nonmetal elements are within the above ranges.

[0016] From the viewpoints of color tone and film hardness, the thickness of the underlayer 22 is preferably 0.05 μm to 3 μm, more preferably 0.05 μm to 2 μm. Furthermore, if the thickness of the underlayer 22 is greater than 0.065 μm, the influence of the color of the substrate 10 can be suppressed.

[0017] From the viewpoint of scratch resistance and abrasion resistance, the film hardness of the underlayer 22 is preferably HV 1000 or more. For example, the film hardness can be adjusted to fall within the above range by appropriately changing the amount of metal elements and nonmetal elements constituting the metal carbide and the film thickness. The film hardness of the underlayer 22 is a value measured for the underlayer 22 provided on the substrate 10.

[0018] The underlayer 22 is L * a * b *In the color system, L * is between 67.03 and 71.27, * is 5.45 or more and 7.39 or less, b * is preferably 12.57 or more and 16.83 or less, or L * C * When expressed in the h color system, L * is 67.03 or more and 71.27 or less, C * is preferably 13.70 or more and 18.38 or less, and h is preferably 59.55° or more and 72.06° or less. * , a * , b * or L * , C * When h is within the above range, a gold color close to that of an Au alloy can be achieved, and by providing the adjustment layer 24 and the finishing layer 26, a more desirable gold color can be achieved. In addition, even if the decorative member 1 is worn after long-term use, discoloration can be reduced. For example, by appropriately changing the amount of metal elements and non-metal elements that make up the metal carbide and the film thickness, L * , a * , b * or L * , C * , h can be adjusted to fall within the above range. * , a * , b * is a value measured for the underlayer 22 provided on the substrate 10. * , h color range is measured a * , b * obtained from the value of a * , b * This is the color tone range that can be calculated by mathematically converting the range of

[0019] [Adjustment layer] The adjustment layer 24 has a laminated structure in which a first adjustment layer 241 and a second adjustment layer 242 are laminated from the substrate 10 side, with the first adjustment layer 241 containing an Au alloy and the second adjustment layer 242 containing a metal carbide containing Ti and at least one selected from Nb and Ta. This laminated structure allows the adjustment layer 24 to be formed with a gold color similar to that of an Au alloy. In the adjustment layer 24, the layer in contact with the base layer 22 is the first adjustment layer 241, and the layer in contact with the finishing layer 26 is the second adjustment layer 242.

[0020] Examples of the Au alloy in the first adjustment layer 241 include an Au—Ni alloy, an Au—Pt alloy, and an Au—Cu alloy. Among Au—Cu alloys, from the viewpoint of gold color, an alloy further mixed with a metal exhibiting a silver color, such as Pd, Pt, or Rh, is preferably used.

[0021] When the first adjustment layer 241 is made of an alloy containing Au, Pd, and Cu, it preferably contains 62.0 to 94.5 mass% of Au, 0.5 to 17.0 mass% of Pd, and 5.0 to 21.0 mass% of Cu, where the total of Au, Pd, and Cu is 100 mass%. When the amounts of the metal elements are within the above ranges, a more desirable gold color is exhibited.

[0022] Carbonitrides containing the above-mentioned specific metals can form the second adjustment layer 242, which exhibits a gold color similar to that of an Au alloy. Furthermore, combining Nb and / or Ta with Ti increases the film hardness of the second adjustment layer 242, thereby improving the scratch resistance and wear resistance of the decorative member 1. Furthermore, combining Nb and / or Ta with Ti also improves the corrosion resistance of the decorative member 1.

[0023] In the above metal carbide nitrides, Nb may be used alone, Ta may be used alone, or Nb and Ta may be used in combination. Because Ta has a larger atomic weight than Nb, the use of Ta increases the film hardness, which can improve the scratch resistance and wear resistance of the decorative member 1. Furthermore, using Nb alone is preferable in terms of color brightness and material cost.

[0024] In the second adjustment layer 242, the metal carbide preferably contains 22 to 66 mass% of the at least one selected from Nb and Ta, 20 to 50 mass% of Ti, 7 to 19 mass% of nitrogen, and 4 to 15 mass% of carbon, when the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%.More preferably, in the second adjustment layer 242, the metal carbide preferably contains 40 to 44 mass% of the at least one selected from Nb and Ta, 37 to 40 mass% of Ti, 9 to 18 mass% of nitrogen, and 5 to 7 mass% of carbon, when the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%. From the viewpoint of color tone and film hardness, it is preferable that the amounts of metal elements and nonmetal elements are within the above ranges.

[0025] The thickness of the first adjusting layer 241 is 0.005 μm or more and 0.016 μm or less, and the thickness of the second adjusting layer 242 is 0.039 μm or more and 0.065 μm or less. Because the thicknesses of the first adjusting layer 241 and the second adjusting layer 242 are within these ranges, the decorative member 1 has excellent abrasion resistance and maintains the color inherent to the precious metal even after long-term use. This will be explained in detail below.

[0026] As the decorative member 1 is used, the finishing layer 26 wears, potentially revealing worn areas where the second adjusting layer 242 is exposed. However, because the thickness of the second adjusting layer 242 is 0.039 μm or greater, the second adjusting layer 242 is less likely to wear, even with extended use of the decorative member 1, and this wear is prevented. Furthermore, because the thickness of the second adjusting layer 242 is 0.065 μm or less, the worn areas reflect the reflection of the first adjusting layer 241, allowing the color inherent to the precious metal of the first adjusting layer 241 to shine through. Therefore, the worn areas where the second adjusting layer 242 is exposed are not noticeable, and changes in color tone and hues in the worn areas are kept to a minimum. In other words, even with extended use, the decorative member 1 maintains the color inherent to the precious metal, and its aesthetic appeal is less likely to deteriorate.

[0027] [Finishing layer] The finishing layer 26 contains an Au alloy. The Au alloy allows the formation of a gold-colored finishing layer 26. Examples of Au alloys include an Au-Ni alloy, an Au-Pt alloy, and an Au-Cu alloy. Among Au-Cu alloys, alloys further containing a silver-colored metal such as Pd, Pt, or Rh are preferably used in terms of the gold color.

[0028] When the above-mentioned alloy containing Au, Pd, and Cu is used for the finishing layer 26, it is preferable that the alloy contains Au in an amount of 62.0 to 94.5 mass %, Pd in ​​an amount of 0.5 to 17.0 mass %, and Cu in an amount of 5.0 to 21.0 mass %, where the total of Au, Pd, and Cu is 100 mass %. When the amounts of metal elements are within the above ranges, a more preferable gold color is exhibited.

[0029] The thickness of the finishing layer 26 is preferably 0.024 μm or more and 0.150 μm or less, and more preferably 0.024 μm or more and 0.102 μm or less. To ensure that the finishing layer 26 exhibits a desirable gold color, the thickness of the finishing layer 26 is preferably 0.024 μm or more. However, the finishing layer 26 has low hardness and is prone to scratches and wear. Therefore, considering scratch resistance, a thinner finishing layer 26 is preferable. Furthermore, forming a layer significantly thicker than 0.1 μm results in little change in color tone and increases manufacturing costs. Therefore, the thickness of the finishing layer 26 is preferably 0.150 μm or less, and more preferably 0.102 μm or less.

[0030] The film hardness of the finishing layer 26 is typically about HV 100 to 400, and preferably about HV 150 to 400. For example, the film hardness can be adjusted to fall within the above range by appropriately changing the amount of metal elements constituting the Au alloy. Note that the film hardness of the finishing layer 26 is a value measured for the finishing layer 26 provided directly on the substrate 10.

[0031] The decorative member of the first embodiment has a gold color. * a * b* In the color system, L * is between 75 and 100, a * is between 0 and 20, b * is between 5 and 25, or L * C * When expressed in the h color system, L * is between 75 and 100, C * is preferably 5 or more and 32 or less, and h is preferably 14° or more and 90° or less. * , a * , b * or L * , C * When h is within the above range, the decorative member exhibits a desirable gold color. * The color range of h is measured as above. * , b * obtained from the value of a * , b * This is the color tone range that can be calculated by mathematically converting the range of

[0032] [Embodiment 2] Figure 2 is a diagram illustrating a decorative member of embodiment 2. That is, Figure 2 is a cross-sectional schematic diagram of decorative member 2. The decorative member of embodiment 2 includes a substrate 10 and a decorative coating 20 formed on the substrate 10. The decorative coating 20 is formed by laminating, from the substrate 10 side, a base layer 22, an adjustment layer 24, and a finishing layer 26. In decorative member 2, the substrate 10, the base layer 22, and the finishing layer 26 are the same as those in embodiment 1, so their description will be omitted.

[0033] The adjustment layer 24 has a layered structure in which, from the substrate 10 side, a first adjustment layer 241, a second adjustment layer 242, a third adjustment layer 243, and a fourth adjustment layer 244 are stacked. The first adjustment layer 241 and the third adjustment layer 243 contain an Au alloy, and the second adjustment layer 242 and the fourth adjustment layer 244 contain a metal carbide containing Ti and at least one selected from Nb and Ta. This layered structure allows the adjustment layer 24 to be formed with a gold color similar to that of an Au alloy. In the adjustment layer 24, the layer in contact with the base layer 22 is the first adjustment layer 241, and the layer in contact with the finishing layer 26 is the fourth adjustment layer 244.

[0034] Examples of Au alloys that can be used in the first adjustment layer 241 and the third adjustment layer 243 include Au—Ni alloys, Au—Pt alloys, and Au—Cu alloys. Among Au—Cu alloys, from the viewpoint of golden color, alloys further mixed with silver-colored metals such as Pd, Pt, and Rh are preferably used.

[0035] When the first adjustment layer 241 and the third adjustment layer 243 each use an alloy containing Au, Pd, and Cu, the alloy preferably contains 62.0 to 94.5 mass% of Au, 0.5 to 17.0 mass% of Pd, and 5.0 to 21.0 mass% of Cu, where the total of Au, Pd, and Cu is 100 mass%. When the amounts of the metal elements are within the above ranges, a more desirable gold color is exhibited.

[0036] In the second adjusting layer 242 and the fourth adjusting layer 244, if the carbide contains the above-mentioned specific metal, the second adjusting layer 242 and the fourth adjusting layer 244 can be formed to exhibit a gold color similar to that of an Au alloy. Furthermore, by combining Nb and / or Ta with Ti, the film hardness of the second adjusting layer 242 and the fourth adjusting layer 244 increases, thereby improving the scratch resistance and wear resistance of the decorative member 2. Furthermore, by combining Nb and / or Ta with Ti, the corrosion resistance of the decorative member 2 also improves.

[0037] In the above metal carbide nitrides, Nb may be used alone, Ta may be used alone, or Nb and Ta may be used in combination. Because Ta has a larger atomic weight than Nb, the use of Ta increases the film hardness and can improve the scratch resistance and wear resistance of the decorative member 2. Furthermore, using Nb alone is preferable in terms of color brightness and material cost.

[0038] In each of the second adjustment layer 242 and the fourth adjustment layer 244, the metal nitride carbide preferably contains at least one selected from Nb and Ta in a total amount of 22% by mass to 66% by mass, at least one selected from Nb and Ta in a total amount of 20% by mass to 50% by mass, at least 7% by mass to 19% by mass, and at least 4% by mass to 15% by mass of carbon, when the total of at least one metal selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100% by mass. Furthermore, in each of the second adjustment layer 242 and the fourth adjustment layer 244, when the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%, the metal carbide more preferably contains a total of 40 to 44 mass% of at least one selected from Nb and Ta, 37 to 40 mass% of Ti, 9 to 18 mass% of nitrogen, and 5 to 7 mass% of carbon. From the viewpoints of color tone and film hardness, it is preferable that the amounts of metallic elements and non-metallic elements be within the above ranges.

[0039] The thickness of the first adjusting layer 241 is 0.005 μm or more and 0.016 μm or less, and the thickness of the second adjusting layer 242 is 0.039 μm or more and 0.065 μm or less. The thicknesses of the third adjusting layer 243 and the fourth adjusting layer 244 are each 0.005 μm or more and 0.016 μm or less. Because the thicknesses of the first adjusting layer 241, the second adjusting layer 242, the third adjusting layer 243, and the fourth adjusting layer 244 are within the above ranges, the decorative member 2 has excellent abrasion resistance and maintains the color inherent to the precious metal even after long-term use. This will be explained in more detail below.

[0040] When the decorative member 2 is used for a short period of time, the finishing layer 26 may wear away, and shallow wear areas may appear where the fourth adjusting layer 244 is exposed. In these shallow wear areas, the fourth adjusting layer 244 is thinner, allowing the reflection of the third adjusting layer 243 to be more clearly reflected, and the color derived from the precious metal of the third adjusting layer 243 to be more clearly seen. As a result, the shallow wear areas where the fourth adjusting layer 244 is exposed are less noticeable, and changes in color tone and color appearance in the shallow wear areas are kept to a minimum. When the decorative member 2 is used for a short period of time, the color derived from the precious metal is better maintained, and aesthetics are less likely to deteriorate. Further, continued use of the decorative member 2 may cause the thin fourth adjustment layer 244 and third adjustment layer 243 to wear, potentially resulting in deep wear areas where the second adjustment layer 242 is exposed. Because the second adjustment layer 242 is 0.039 μm or thicker, it is less susceptible to wear, even with extended use of the decorative member 2, and wear is prevented. Furthermore, because the second adjustment layer 242 is 0.065 μm or thinner, even in the deep wear areas, the reflection of the first adjustment layer 241 can be reflected, allowing the color inherent to the precious metal of the first adjustment layer 241 to be seen through. Therefore, the deep wear areas where the second adjustment layer 242 is exposed are not noticeable, and changes in color tone and hues in the deep wear areas are minimized. In other words, even with extended use, the decorative member 2 maintains the color inherent to the precious metal, making it less likely to lose its aesthetic appeal. In this way, by providing the third adjustment layer 243 and the fourth adjustment layer 244, decorative member 2 has the advantage of being able to better maintain the color derived from the precious metal when used for a short period of time than decorative member 1, and of being able to more effectively prevent deterioration in aesthetic appeal.

[0041] The decorative member of the second embodiment has a gold color. * a * b * In the color system, L * is between 75 and 100, a * is between 0 and 20, b * is between 5 and 25, or L * C * When expressed in the h color system, L * is between 75 and 100, C * is preferably 5 or more and 32 or less, and h is preferably 14° or more and 90° or less. * , a * , b * or L * , C * When h is within the above range, the decorative member exhibits a desirable gold color. * The color range of h is measured as above. * , b * obtained from the value of a * , b * This is the color tone range that can be calculated by mathematically converting the range of

[0042] [Other embodiments] The decorative member may be a decorative member in which another layer is further provided between the substrate 10 and the underlayer 22 in contrast to the decorative members of the first and second embodiments.

[0043] For example, in the decorative member of such other embodiments, an adhesion layer, a hardening gradient layer, a hardening layer, a base gradient layer, a base layer, an adjustment layer, and a finishing layer are laminated in this order from the base side. Note that in the decorative member of the other embodiments, the base, the base layer, the adjustment layer, and the finishing layer are the same as those described in the first and second embodiments.

[0044] [Adhesion layer] The adhesive layer made of a metal layer has excellent adhesion to the substrate, and therefore providing the adhesive layer can improve the scratch resistance of the decorative member.

[0045] Specifically, the adhesion layer is preferably a Ti alloy layer made of a metal containing Ti and at least one selected from Nb and Ta.

[0046] In order to improve adhesion, when the total of at least one selected from Nb and Ta and Ti is taken as 100 mass%, it is preferable that the adhesion layer contains at least one selected from Nb and Ta in an amount of 25 mass% or more and 75 mass% or less, and Ti in an amount of 25 mass% or more and 75 mass% or less.

[0047] The adhesion layer is also preferably a Ti layer made of Ti that may contain oxygen. Providing a Ti layer as an adhesion layer provides high adhesion to stainless steel, ensuring high scratch resistance. The Ti layer is compatible with substrates other than stainless steel, such as SK materials and brass, and exhibits high adhesion to these substrates.

[0048] From the viewpoint of adhesion, the thickness of the adhesive layer is preferably 0.02 μm or more and 0.5 μm or less. Even if the adhesive layer is made thicker than 0.5 μm, there is no difference in adhesion and the manufacturing cost increases, so the thickness of the adhesive layer is preferably in the above range.

[0049] The adhesive layer may be a laminate of a Ti alloy layer made of a metal containing Ti and at least one selected from Nb and Ta, and a Ti layer made of Ti that may contain oxygen. In this case, it is preferable that each layer has a thickness within the above range.

[0050] The film hardness of the adhesion layer is preferably HV 200 or more and 1000 or less. Since the film hardness and the film stress (the force that tries to separate from the substrate) are proportional to each other, it is desirable that the film hardness of the adhesion layer be as low as possible. For example, the film hardness can be adjusted to the above range by appropriately changing the amount of constituent elements or the film thickness.

[0051] [Hardened gradient layer] The hardened gradient layer is a nitride layer made of a nitride of a metal containing Ti and at least one selected from Nb and Ta, and the amount of nitrogen in the hardened gradient layer changes with increasing distance from the substrate in the thickness direction of the decorative coating. From the viewpoints of film stress relaxation and maintaining film hardness, it is preferable that the amount of nitrogen increases with increasing distance from the substrate in the thickness direction of the decorative coating within a range equal to or less than the amount of nitrogen contained in the hardened layer above the hardened gradient layer.

[0052] The provision of a hardening gradient layer dramatically reduces the difference in film stress between the adhesion layer and the hardened layer, improving the adhesion of the entire decorative component and, as a result, improving its scratch resistance. The reduced stress difference also suppresses cracking. Furthermore, problems such as delamination during long-term use are dramatically improved. This structure allows for a larger hardened layer thickness. For example, even if the hardened layer is increased to 2.5 μm, making the overall thickness of the decorative coating 3.0 μm, film delamination and cracking are unlikely to occur. Furthermore, the increased composite hardness of the entire decorative component dramatically improves its scratch resistance. However, because the composite hardness of the entire decorative component is rate-determining due to the hardness of the Au alloy finishing layer, increasing the thickness of the hardened layer and the overall thickness of the decorative coating eventually leads to a plateau in scratch resistance. For this reason, it is preferable for the overall thickness of the decorative coating to be 3.0 μm or less.

[0053] The thickness of the hardening gradient layer is preferably 0.04 μm or more and 0.6 μm or less from the viewpoint of reducing the difference in membrane stress.

[0054] [Hardened layer] The hardened layer is a nitride layer made of a nitride of a metal containing Ti and at least one selected from Nb and Ta. The provision of the hardened layer increases the hardness (composite hardness) of the entire decorative member, contributing to improved scratch resistance.

[0055] In the nitrides, Nb may be used alone, Ta may be used alone, or Nb and Ta may be used in combination. Because Ta has a larger atomic weight than Nb, the use of Ta increases the film hardness, and can improve the scratch resistance and wear resistance of the decorative member.

[0056] In the hardened layer, when the total of at least one metal selected from Nb and Ta and Ti, and nitrogen is taken as 100 mass%, it is preferable that the total amount of at least one metal selected from Nb and Ta is 22 mass% to 66 mass%, Ti is 20 mass% to 55 mass%, and nitrogen is 8 mass% to 35 mass%. From the viewpoint of film hardness, it is preferable that the amounts of metal elements and non-metal elements are within the above ranges.

[0057] The thickness of the hardened layer is preferably 0.5 μm or more and 3 μm or less from the viewpoint of film hardness and abrasion resistance.

[0058] From the viewpoint of scratch resistance and wear resistance, the film hardness of the hardened layer is preferably HV 1500 or more and 3000 or less. For example, the film hardness can be adjusted to fall within the above range by appropriately changing the amount of metal elements and non-metal elements constituting the nitride and the film thickness.

[0059] [Slope base layer] The gradient base layer is a carbide nitride layer made of a metal carbide containing Ti and at least one selected from Nb and Ta, and the nitrogen and carbon contents in the carbide change with increasing distance from the substrate in the thickness direction of the decorative coating. The nitrogen and carbon contents may change continuously, such as linearly or curvedly, or discontinuously or intermittently, such as in a stepped pattern. From the viewpoints of film stress relief and maintaining film hardness, it is preferable that the nitrogen and carbon contents increase with increasing distance from the substrate in the thickness direction of the decorative coating within a range equal to or less than the nitrogen and carbon contents in the base layer above the gradient base layer.

[0060] The gradient base layer reduces the stress difference between the hardening layer and the base layer, improving adhesion of the entire decorative member and, as a result, improving scratch resistance. This structure increases the combined hardness of the entire decorative member, and also improves scratch resistance.

[0061] The thickness of the underlying gradient layer is preferably 0.02 μm or more and 0.5 μm or less from the viewpoint of reducing the difference in film stress.

[0062] Furthermore, decorative members of other embodiments may be decorative members that do not have at least one of the above-mentioned adhesion layer, hardening gradient layer, hardening layer, and base gradient layer. More specifically, examples include embodiments having the following layered configurations. Base material / adhesion layer / hardening layer / undercoat gradient layer / undercoat layer / adjustment layer / finishing layer Base material / adhesion layer / hardening gradient layer / hardening layer / priming layer / adjustment layer / finishing layer Base material / adhesion layer / hardening layer / priming layer / adjustment layer / finishing layer Base material / adhesion layer / primer layer / adjustment layer / finishing layer Base material / hardening layer / undercoat gradient layer / undercoat layer / adjustment layer / finishing layer Base material / hardening layer / priming layer / adjustment layer / finishing layer

[0063] In other embodiments of the decorative member, one or more adhesion layers may be laminated. The same applies to the hardening gradient layer, the hardening layer, and the base gradient layer. Furthermore, other layers may be formed between the substrate and the base layer as long as the effects of the present invention are not impaired.

[0064] The decorative members of the other embodiments described above all have the specific adjustment layer, and therefore have excellent abrasion resistance, and retain the color inherent to the precious metal even after long-term use.

[0065] In addition, the decorative members of the other embodiments are all gold in color. * a * b * In the color system, L * is between 75 and 100, a * is between 0 and 20, b * is between 5 and 25, or L * C * When expressed in the h color system, L * is between 75 and 100, C * is preferably 5 or more and 32 or less, and h is preferably 14° or more and 90° or less. * , a * , b * or L * , C * When h is within the above range, the decorative member exhibits a more desirable gold color. * The color range of h is measured as above. * , b * obtained from the value of a * , b * This is the color tone range that can be calculated by mathematically converting the range of

[0066] The amount of elements in each layer, the thickness of each layer, the color tone of each layer, and the color tone of the entire decorative member can be determined by the methods described in the examples.

[0067] <Method of manufacturing decorative member according to the embodiment> The method for manufacturing a decorative member according to the embodiment is a method for manufacturing a decorative member including a substrate and a decorative coating formed on the substrate. The decorative coating is formed by laminating a base layer, an adjustment layer, and a finishing layer from the substrate side. The adjustment layer has a laminated structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side. The method for manufacturing a decorative member according to the embodiment will be described in more detail below.

[0068] [Embodiment 1] The method for manufacturing a decorative member of embodiment 1 produces the decorative member of embodiment 1 described above. That is, it is a method for manufacturing a decorative member 1 that includes a substrate 10 and a decorative coating 20 formed on the substrate 10. The decorative coating 20 is formed by laminating, from the substrate 10 side, a base layer 22, an adjusting layer 24, and a finishing layer 26. Here, the adjusting layer 24 has a layered structure in which, from the substrate 10 side, a first adjusting layer 241 and a second adjusting layer 242 are laminated.

[0069] First, in the underlayer lamination step, the underlayer 22 containing a carbide of a metal containing Ti and at least one selected from Nb and Ta is laminated on the substrate 10.

[0070] In the underlayer deposition process, a reactive sputtering method is preferably used. The reactive sputtering method involves introducing a reactive gas together with an inert gas, and forming a reaction compound coating between the target constituent atoms and the non-metallic elements of the reactive gas on the substrate. In the underlayer deposition process, the target (raw metal) is preferably an alloy of Nb and / or Ta and Ti, more specifically, a sintered body of an alloy of the above metals. In the sintered body, the type and proportion of metals can be appropriately selected to obtain the desired underlayer. Examples of reactive gases used include carbon-containing gases such as methane gas and acetylene gas, and nitrogen-containing gases such as nitrogen gas and ammonia. Examples of inert gases include Ar gas, Kr gas, and Xe gas. The amounts of metal elements and non-metallic elements in the reaction compound can be adjusted by appropriately changing the applied voltage, the type and proportion of target constituent atoms, and the selection and amount of reactive gas.

[0071] Next, in the adjustment layer lamination process, a first adjustment layer 241 containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the base layer 22 laminated in the base layer lamination process, and a second adjustment layer 242 containing a metal nitride carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less is laminated on the first adjustment layer 241.

[0072] Sputtering is preferably used to deposit the first adjustment layer 241. Sputtering involves applying a high DC or AC voltage between a substrate and a target consisting of the constituent atoms of the coating while introducing an inert gas into a vacuum-evacuated chamber. Ionized Ar ions collide with the target, causing the target material to be ejected and deposited on the substrate. The target (raw metal) used to deposit the first adjustment layer 241 is an Au alloy, preferably an alloy combining Au, Pd, and Cu. More specifically, a sintered body of the alloy of the above metals. The type and proportion of metals in the sintered body can be selected as appropriate to obtain the desired finish layer. Examples of inert gases used include Ar gas, Kr gas, and Xe gas. The amount of metal elements in the Au alloy can be adjusted by appropriately changing the applied voltage, the proportion of the target constituent atoms, and other parameters. The thickness of the first adjustment layer 241 can be adjusted within the above range by appropriately changing the deposition time.

[0073] The second adjusting layer 242 can be deposited in the same manner as the base layer deposition step. The thickness of the second adjusting layer 242 can be adjusted to fall within the above range by appropriately changing the film formation time.

[0074] Next, in the finishing layer lamination step, a finishing layer 26 containing an Au alloy is laminated on the second adjustment layer 242 laminated in the adjustment layer lamination step. The finishing layer lamination step can be performed in the same manner as the lamination of the first adjustment layer 241.

[0075] [Embodiment 2] The decorative member of the second embodiment described above can be obtained by the method for manufacturing a decorative member. Specifically, this is a method for manufacturing a decorative member 2 that includes a substrate 10 and a decorative coating 20 formed on the substrate 10. The decorative coating 20 is formed by laminating, from the substrate 10 side, a base layer 22, an adjusting layer 24, and a finishing layer 26. Here, the adjusting layer 24 has a layered structure in which, from the substrate 10 side, a first adjusting layer 241 and a second adjusting layer 242 are laminated, as well as a third adjusting layer 243 and a fourth adjusting layer 244. The base layer laminating step and the finishing layer laminating step are the same as those in the first embodiment, and therefore will not be described here.

[0076] In the adjustment layer lamination step, a first adjustment layer 241 containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the base layer 22 laminated in the base layer lamination step, and a second adjustment layer 242 containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less is laminated on the first adjustment layer 241. Furthermore, a third adjustment layer 243 containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the second adjustment layer 242, and a fourth adjustment layer 244 containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the third adjustment layer 243.

[0077] The lamination of the first adjusting layer 241 and the lamination of the second adjusting layer 242 can be performed in the same manner as the lamination of the first adjusting layer 241 and the lamination of the second adjusting layer 242 in the first embodiment.

[0078] Subsequently, the third adjusting layer 243 can be deposited in the same manner as the first adjusting layer 241. The fourth adjusting layer 244 can be deposited in the same manner as the second adjusting layer 242. However, by appropriately changing the deposition time, the thickness of the second adjusting layer 242 is adjusted to fall within the above range.

[0079] In the finishing layer laminating step, a finishing layer 26 containing an Au alloy is laminated on the fourth adjustment layer 244 laminated in the adjusting layer laminating step.

[0080] [Other embodiments] The manufacturing method of the other embodiment can produce the decorative member of the other embodiment described above, i.e., a manufacturing method of a decorative member in which the other layer described above is further provided between the substrate 10 and the underlayer 22.

[0081] For example, in the manufacturing method of other embodiments, the adhesion layer laminating step, hardening gradient layer laminating step, hardening layer laminating step, base gradient layer laminating step, base layer laminating step, adjustment layer laminating step, and finishing layer laminating step are performed in this order. In the manufacturing methods of other embodiments, the base layer laminating step, adjustment layer laminating step, and finishing layer laminating step are the same as those described in embodiments 1 and 2. The adhesion layer laminating step, hardening gradient layer laminating step, hardening layer laminating step, and base gradient layer laminating step can be appropriately performed by a sputtering method such as reactive sputtering, or a dry plating method such as ion plating or arc ion plating.

[0082] Furthermore, in other embodiments of the manufacturing method, decorative components are manufactured that do not have at least one of the above-mentioned adhesion layer, hardened gradient layer, hardened layer, and base gradient layer, so that at least one of the adhesion layer lamination process, hardened gradient layer lamination process, hardened layer lamination process, and base gradient layer lamination process can be omitted as appropriate.

[0083] <Decorative article of the embodiment> The decorative article of the embodiment includes the decorative member described above. Specific examples of the decorative article of the embodiment include eyeglasses including components such as eyeglass frames; accessories such as necklaces, earrings, pierced earrings, rings, pendants, brooches, and bracelets; watches including components such as watch cases, watch bands, bezels, crowns, and clasps; and sporting goods. These decorative articles may be partially or entirely composed of the decorative member described above, and can be manufactured using the decorative member described above by known methods.

[0084] The timepiece may be a photovoltaic timepiece, a heat-powered timepiece, a radio wave-receiving self-correcting timepiece, a mechanical timepiece, or a general electronic timepiece. Wristwatches are particularly an example of decorative items that are easily scratched by rubbing against a shirt or hitting a desk, wall, etc. Because the timepiece is manufactured using the decorative member described above, it has excellent abrasion resistance and can maintain its color and appearance in a very beautiful condition even after long-term use.

[0085] Based on the above, the present invention relates to the following. [1] A decorative member comprising a substrate and a decorative coating formed on the substrate, wherein the decorative coating is formed by laminating, from the substrate side, a base layer, an adjustment layer, and a finishing layer, wherein the base layer contains a metal carbide containing at least one selected from Nb and Ta and Ti, and the finishing layer contains an Au alloy, the adjustment layer has a layered structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side, the first adjustment layer contains an Au alloy, and the second adjustment layer contains a metal carbide containing at least one selected from Nb and Ta and Ti, the thickness of the first adjustment layer is 0.005 μm or more and 0.016 μm or less, and the thickness of the second adjustment layer is 0.039 μm or more and 0.065 μm or less. The decorative member has excellent abrasion resistance and retains the color inherent to the precious metal even after long-term use. [2] The decorative member according to claim 1, wherein the adjustment layer has a laminated structure in which, from the base material side, in addition to the first adjustment layer and the second adjustment layer, a third adjustment layer and a fourth adjustment layer are laminated, the third adjustment layer contains an Au alloy, and the fourth adjustment layer contains a metal carbide containing at least one selected from Nb and Ta and Ti, and the thicknesses of the third adjustment layer and the fourth adjustment layer are each 0.005 μm or more and 0.016 μm or less. By providing the third and fourth adjustment layers, the decorative member described above has the advantage of being able to better maintain the color inherent in the precious metal when used for a short period of time, and of further preventing deterioration in aesthetic appeal. [3] The decorative member is L * a * b * In the color system, L * is between 75 and 100, a* is between 0 and 20, b * is between 5 and 25, or L * C * In the h color system, it is L * is between 75 and 100, C * The decorative member according to [1] or [2], wherein is 5 or more and 32 or less, and h is 14° or more and 90° or less. L * , a * , b * or L * , C * When h is within the above range, the decorative member exhibits a desirable gold color. [4] The decorative member according to [1], wherein in each of the base layer and the second adjustment layer, the metal carbide contains at least one selected from Nb and Ta in a total amount of 22% by mass to 66% by mass, 20% by mass to 50% by mass, Ti in a total amount of 20% by mass to 50% by mass, nitrogen in a total amount of 7% by mass to 19% by mass, and carbon in a total amount of 4% by mass to 15% by mass, where the total of the metals consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100% by mass. [5] The decorative member according to [2], wherein in each of the base layer, the second adjustment layer and the fourth adjustment layer, the metal carbide contains at least one selected from Nb and Ta in a total amount of 22% by mass to 66% by mass, 20% by mass to 50% by mass, Ti in a total amount of 7% by mass to 19% by mass, and carbon in a total amount of 4% by mass to 15% by mass, where the total of metals consisting of at least one selected from Nb and Ta and Ti, nitrogen and carbon is taken as 100% by mass. From the viewpoint of color tone, it is preferable that the amounts of metal elements and nonmetal elements are within the above ranges. [6] In the decorative member according to [1], in each of the finishing layer and the first adjusting layer, the Au alloy is an alloy containing Au, Cu, and Pd, and contains Au in an amount of 62.0% by mass to 94.5% by mass, Pd in ​​an amount of 0.5% by mass to 17.0% by mass, and Cu in an amount of 5.0% by mass to 21.0% by mass, where the total of Au, Pd, and Cu is 100% by mass. [7] In the decorative member according to [2], in each of the finishing layer, the first adjustment layer, and the third adjustment layer, the Au alloy is an alloy containing Au, Pd, and Cu, and contains Au in an amount of 62.0% by mass to 94.5% by mass, Pd in ​​an amount of 0.5% by mass to 17.0% by mass, and Cu in an amount of 5.0% by mass to 21.0% by mass, when the total of Au, Pd, and Cu is 100% by mass. When the amount of the metal element is within the above range, a more desirable gold color is exhibited. [8] The above-mentioned underlayer is L * a * b * In the color system, L * is between 67.03 and 71.27, * is 5.45 or more and 7.39 or less, b * is 12.57 or more and 16.83 or less, or L * C * When expressed in the h color system, L * is 67.03 or more and 71.27 or less, C * The decorative member according to [1] or [2], wherein is 13.70 or more and 18.38 or less, and h is 59.55° or more and 72.06° or less. L * , a * , b * or L * , C * When h is within the above range, a gold color close to that of an Au alloy can be achieved, and by providing the adjustment layer 24 and the finishing layer 26, a more desirable gold color can be achieved. [9] A method for manufacturing a decorative member including a substrate and a decorative coating formed on the substrate, wherein the decorative coating is formed by laminating a base layer, an adjustment layer, and a finishing layer from the substrate side, and the adjustment layer has a layered structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side, the method comprising: a base layer laminating step of laminating the base layer containing a carbide of a metal containing at least one selected from Nb and Ta and Ti on the base layer laminated in the base layer laminating step; A method for manufacturing a decorative member, comprising: an adjustment layer lamination step of laminating a first adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less; and laminating a second adjustment layer on the first adjustment layer, the second adjustment layer containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less; and a finishing layer lamination step of laminating a finishing layer containing an Au alloy on the second adjustment layer laminated in the adjustment layer lamination step. The above-mentioned manufacturing method provides a decorative member that is excellent in abrasion resistance and maintains the color inherent to the precious metal even after long-term use.

[10] The adjustment layer has a laminated structure in which, from the substrate side, a third adjustment layer and a fourth adjustment layer are laminated in addition to the first adjustment layer and the second adjustment layer, and the adjustment layer laminating step includes laminating the first adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less on the underlayer laminated in the underlayer laminating step, and laminating the second adjustment layer containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less on the first adjustment layer, and the third adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the second adjustment layer, and the fourth adjustment layer containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.005 μm or more and 0.016 μm or less is laminated on the third adjustment layer; and the finishing layer lamination step is a step of laminating the finishing layer containing an Au alloy on the fourth adjustment layer laminated in the adjustment layer lamination step. The above-described manufacturing method makes it possible to obtain a decorative member that can better maintain the color inherent to the precious metal and that can further prevent deterioration in aesthetics even when used for a short period of time.

[11] A decorative article comprising the decorative member according to [1] or [2]. The decorative article has excellent abrasion resistance and can maintain its color and appearance in a very beautiful state even after long-term use.

[0086] [Example] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0087] [Evaluation method] (color tone) The color tone was measured using KONICA MINOLTA CM-2600d and CM-700d (in accordance with JIS Z 8722 Condition C, ISO 7724 / 1, CIE No. 15, and ASTM E 1164). Specifically, the color tone was measured using the SCI method under a light source of D65. * a * b * Color space L * , a * , b * More specifically, the CIE standard illuminant D65 was used as the measurement light source, the viewing angle was set to 10°, and the specular reflection light processing was set to the SCI method. * a * b * Color space L * , a * , b * was measured.

[0088] (composition ratio) The composition ratio of the film was measured by energy dispersive X-ray spectroscopy (EDS) using a JEOL JCM-6000PLUS. Specifically, Nb, Ti, C, and N were measured at an accelerating voltage of 15 kV, and Au, Cu, and Pd were measured at an accelerating voltage of 5 kV.

[0089] (film thickness) The film thickness of each layer was measured by observing the cross section of the film in the direction perpendicular to the substrate with a scanning electron microscope (SEM) using a Gemini 300 manufactured by ZEISS. The cross-section was processed using a cross-section polisher (CP) and a focused ion beam (FIB) processing system.

[0090] [Experimental Example 1] Preferred color range of the base layer To determine the preferred color range of the underlayer, first, a sample in which only the underlayer was formed as a single layer (Experimental Example 1-1) and a sample in which a finish layer of a reference color was formed (Experimental Example 1-2) were prepared. The sample of Experimental Example 1-1 was prepared as follows. The sputtering target used was a sintered body with an alloy composition of 50 mass % Ti and 50 mass % Nb. SUS316L material was used for the substrate 10. A 0.15 μm underlayer made of NbTiCN was formed on the substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of 95 mL / min of argon gas, 51.9 mL / min of nitrogen gas, and 50 mL / min of methane gas. Furthermore, as shown in Tables 1 and 2 below, samples with similar underlayers were prepared by changing the amount of nitrogen gas or methane gas. The sample of Experimental Example 1-2 was fabricated as follows. The sputtering target used was a sintered body of Au 83.7% by mass, Cu 15.6% by mass, and Pd 0.7% by mass. SUS316L material was used for the substrate 10. A finishing layer of 0.1 μm was formed on the underlayer of the sample of Experimental Example 1-1 using a sputtering target of Au 83.7% by mass, Cu 15.6% by mass, and Pd 0.7% by mass in an argon gas atmosphere of 180 mL / min. Next, the surface color tone of the sample of Experimental Example 1-1 was compared visually with the surface color tone of the sample of Experimental Example 1-2, and the samples that were relatively similar in color were evaluated as ○, those that were different in color as △, and those that were significantly different in color as ×. Then, the L of each of the base layer (sample of Experimental Example 1-1) and the finishing layer (sample of Experimental Example 1-2) * , a * , b * The color of the sample in Experimental Example 1-2 was L * = 84.46, a * =9.95, b *Next, the difference in color tone between the sample of Experimental Example 1-1 and the sample of Experimental Example 1-2 was measured using ΔL * , Δa * , Δb * The results of visual evaluation were numerically supported. * is the L of the reference color * and the comparison L * is the difference between Δa * , Δb * The same is true for ΔL * The larger the difference in brightness, the greater the difference in brightness. * , Δb * The larger the difference, the greater the difference in hue and saturation. By the way, a common value for evaluating color difference is ΔE * ab, but when evaluating the color difference between precious metal colors and non-precious metal colors as mentioned above, L * The difference is a * , b * It becomes larger than the difference between ΔE * The value of ab is L * Therefore, in this specification, only when examining the preferred color tone range of the base layer, the hue and saturation of the base layer cannot be evaluated correctly because the difference in ΔE * Not ab, but ΔL * , Δa * , Δb * The evaluation was carried out. Visual results and ΔL * , Δa * , Δb * Based on the results of the above, the final desired L of the base layer was determined. * a * b * The preferred color range of the underlayer was determined as L * C * C when expressed in the h color system * , the value of h is the actual measured value a * , b * The color is calculated from the color range determined based on the above. The results of investigating the color tone range of the primer layer are shown in Tables 1 and 2. Table 1 shows the results of investigating the color tone range of the primer layer as the carbonization amount of the primer layer increases, and Table 2 shows the results of investigating the color tone range of the primer layer as the nitride amount of the primer layer increases. * , a * , b * is the value measured by CM-700d.

[0091] [Table 1]

[0092] [Table 2]

[0093] From the color judgment results in Tables 1 and 2, the preferred color range for the base layer is L * a * b * In the color system, L * is between 67.03 and 71.27, * is 5.45 or more and 7.39 or less, b * is determined to be between 12.57 and 16.83, and L * C * In the h color system, it is 67.03 or more and 71.27 or less, C * was between 13.70 and 18.38, and h was between 59.55° and 72.06°.

[0094] From a color perspective, it is preferable to form the adjustment layers (specifically, the second and fourth adjustment layers) under the same gas conditions as the underlayer. In other words, it is preferable to form the adjustment layers under the same gas conditions as the underlayer so that, when formed thick, they exhibit the same color range as the underlayer. Furthermore, because of their thinness, the adjustment layers always reflect the underlayer, acting like a translucent colored sheet. Therefore, it is not possible to evaluate the color of the adjustment layer alone. However, if the gas conditions used to form the adjustment layer are significantly different from those used to form the underlayer, a noticeable color difference may occur during wear. Therefore, it is preferable to form the adjustment layers under the same conditions as the underlayer.

[0095] [Experimental Example 2] Preferred color range for the finishing layer To determine the color tone range of the finish layer, first, various samples with different finish layer thicknesses were prepared. The sample of Experimental Example 2 was prepared as follows. The sputtering targets used were a sintered body having an alloy composition of 50 mass % Ti, 50 mass % Nb, and a sintered body having 83.7 mass % Au, 15.6 mass % Cu, and 0.7 mass % Pd. The membrane structure of Experimental Example 2 is shown in FIG. The substrate 10 was made of SUS316L material. First, underlayer 22 made of NbTiCN was formed to a thickness of 0.15 μm on substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of 95 mL / min argon gas, 51.9 mL / min nitrogen gas, and 50 mL / min methane gas. Next, in an argon gas atmosphere at 180 mL / min, a first adjustment layer 241 made of AuCuPd was formed to a thickness of 0.01 μm on the underlayer 22 using a sputtering target of Au 83.7 mass % Cu 15.6 mass % Pd 0.7 mass %. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of 50 mass% Ti and 50 mass% Nb was used to form a second adjustment layer 242 made of NbTiCN on the first adjustment layer 241 to a thickness of 0.039 μm or more and 0.065 μm or less. Next, in an argon gas atmosphere at 180 mL / min, a sputtering target of Au83.7 mass % Cu15.6 mass % Pd0.7 mass % was used to form a third adjusting layer 243 of AuCuPd to a thickness of 0.01 μm on the second adjusting layer 242. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a fourth adjustment layer 244 made of NbTiCN was formed to a thickness of 0.015 μm on the third adjustment layer 243 using a sputtering target of 50 mass % Ti and 50 mass % Nb. Finally, a finishing layer 26 made of AuCuPd was formed to a thickness of 0.015 μm on the fourth adjusting layer 244 using a sputtering target of Au 83.7 mass %, Cu 15.6 mass % and Pd 0.7 mass % in an argon gas atmosphere at 180 mL / min. Furthermore, as shown in Table 3 below, samples were prepared in which the thickness of the finishing layer 26 was changed and in which the underlayer, adjustment layer, and finishing layer were formed in the same manner. The surface color tone of the sample of Experimental Example 2 was measured. The results are shown in Table 3. * , a * , b * is the value measured by CM-2600d.

[0096] [Table 3]

[0097] It is believed that if the thickness of the finishing layer is less than 0.024 μm, the finishing layer will not tend to exhibit the desired gold color. Furthermore, even if the thickness of the finishing layer is made thicker than 0.1 μm, the change in color tone is thought to be small. Therefore, from the results of Table 3, it can be seen that the most desirable color tone range for the finishing layer is L * a * b * In the color system, L * is between 82.33 and 100, a * is 9.70 or more and 12.16 or less, b * is determined to be between 14.82 and 19.36, and L * C * When expressed in the h color system, L * is 82.33 or more and 100 or less, C * was between 17.71 and 22.86, and h was between 50.63° and 63.39°.

[0098] [Example 1] The production of Example 1 was carried out by reactive sputtering. The sputtering targets used were a sintered body having an alloy composition of 50 mass % Ti, 50 mass % Nb, and a sintered body having 83.7 mass % Au, 15.6 mass % Cu, and 0.7 mass % Pd. The membrane structure of Example 1 is shown in FIG. The substrate 10 was made of SUS316L material. First, underlayer 22 made of NbTiCN was formed to a thickness of 0.15 μm on substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min. Next, in an argon gas atmosphere at 180 mL / min, a sputtering target of Au83.7 mass % Cu15.6 mass % Pd0.7 mass % was used to form a first adjustment layer 241 made of AuCuPd to a thickness of 0.01 μm on the underlayer 22. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of 50 mass% Ti and 50 mass% Nb was used to form a second adjustment layer 242 made of NbTiCN to a thickness of 0.039 μm on the first adjustment layer 241. Finally, a finishing layer 26 made of AuCuPd was formed to a thickness of 0.03 μm on the second adjusting layer 242 using a sputtering target of Au 83.7 mass %, Cu 15.6 mass % and Pd 0.7 mass % in an argon gas atmosphere at 180 mL / min. Furthermore, as shown in Table 4 below, samples of Example 1 were also produced in the same manner when the thickness of the second adjustment layer 242 was changed to 0.042 μm and 0.065 μm.

[0099] [Example 2] The production of Example 2 was carried out by reactive sputtering. The sputtering targets used were a sintered body having an alloy composition of 50 mass % Ti, 50 mass % Nb, and a sintered body having 83.7 mass % Au, 15.6 mass % Cu, and 0.7 mass % Pd. The membrane structure of Example 2 is shown in FIG. The substrate 10 was made of SUS316L material. First, underlayer 22 made of NbTiCN was formed to a thickness of 0.15 μm on substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min. Next, in an argon gas atmosphere at 180 mL / min, a first adjusting layer 241 made of AuCuPd was formed to a thickness of 0.01 μm on the underlayer 22 using a sputtering target of Au 83.7 mass %, Cu 15.6 mass % and Pd 0.7 mass %. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of 50 mass% Ti and 50 mass% Nb was used to form a second adjustment layer 242 made of NbTiCN on the first adjustment layer 241 to a thickness in the range of 0.039 μm or more and 0.065 μm or less. Next, in an argon gas atmosphere at 180 mL / min, a sputtering target of Au83.7 mass % Cu15.6 mass % Pd0.7 mass % was used to form a third adjusting layer 243 made of AuCuPd to a thickness of 0.01 μm on the second adjusting layer 242. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of 50 mass% Ti and 50 mass% Nb was used to form a fourth adjustment layer 244 made of NbTiCN to a thickness of 0.01 μm on the third adjustment layer 243. Finally, in an argon gas atmosphere at 180 mL / min, a finishing layer 26 made of AuCuPd was formed to a thickness of 0.03 μm on the second adjusting layer 242 using a sputtering target of Au 83.7 mass % Cu 15.6 mass % Pd 0.7 mass %.

[0100] [Comparative Example 1] The production of Comparative Example 1 was carried out by reactive sputtering. The sputtering targets used were a sintered body having an alloy composition of 50 mass % Ti, 50 mass % Nb, and a sintered body having 83.7 mass % Au, 15.6 mass % Cu, and 0.7 mass % Pd. The membrane structure of Comparative Example 1 is shown in FIG. The substrate 10 was made of SUS316L material. First, underlayer 22 made of NbTiCN was formed to a thickness of 0.15 μm on substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min. Next, in an argon gas atmosphere at 180 mL / min, a first adjusting layer 241 made of AuCuPd was formed to a thickness of 0.01 μm on the underlayer 22 using a sputtering target of Au 83.7 mass %, Cu 15.6 mass % and Pd 0.7 mass %. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of 50 mass % Ti and 50 mass % Nb was used to form a second adjustment layer 242 made of NbTiCN on the first adjustment layer 241 to a thickness of less than 0.039 μm. Specifically, the second adjustment layer 242 was formed to a thickness of 0.013 μm. Finally, in an argon gas atmosphere at 180 mL / min, a finishing layer 26 made of AuCuPd was formed to a thickness of 0.03 μm on the second adjusting layer 242 using a sputtering target of Au 83.7 mass % Cu 15.6 mass % Pd 0.7 mass %. Furthermore, as shown in Table 4 below, samples of Comparative Example 1 were also produced in the same manner when the thickness of the second adjustment layer 242 was changed to 0.027 μm and 0.036 μm.

[0101] Comparative Example 2 The production of Comparative Example 2 was carried out by reactive sputtering. The sputtering targets used were a sintered body having an alloy composition of 50 mass % Ti, 50 mass % Nb, and a sintered body having 83.7 mass % Au, 15.6 mass % Cu, and 0.7 mass % Pd. The membrane structure of Comparative Example 2 is shown in FIG. The substrate 10 was made of SUS316L material. First, underlayer 22 made of NbTiCN was formed to a thickness of 0.15 μm on substrate 10 using a sputtering target of 50 mass % Ti and 50 mass % Nb in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min. Next, in an argon gas atmosphere at 180 mL / min, a first adjusting layer 241 made of AuCuPd was formed to a thickness of 0.01 μm on the underlayer 22 using a sputtering target of Au 83.7 mass %, Cu 15.6 mass % and Pd 0.7 mass %. Next, in an atmosphere of argon gas 95 mL / min, nitrogen gas 51.9 mL / min, and methane gas 50 mL / min, a sputtering target of Ti 50 mass % and Nb 50 mass % was used to form second adjustment layer 242 made of NbTiCN on first adjustment layer 241 to a thickness of more than 0.065 μm. Specifically, the second adjustment layer 242 was formed to a thickness of 0.074 μm. Finally, in an argon gas atmosphere at 180 mL / min, a finishing layer 26 made of AuCuPd was formed to a thickness of 0.03 μm on the second adjusting layer 242 using a sputtering target of Au 83.7 mass % Cu 15.6 mass % Pd 0.7 mass %. Furthermore, as shown in Table 4 below, a sample of Comparative Example 1 was similarly produced in the case where the thickness of the second adjustment layer 242 was changed to 0.081 μm.

[0102] [Consideration of the thickness of the second adjustment layer] The thickness range of the second adjustment layer was evaluated from two perspectives: wear resistance with long-term use and the color sensation derived from precious metals with long-term use, and the thickness range that has wear resistance with long-term use and still allows the color sensation derived from precious metals to be felt even after long-term use was investigated. The evaluation of abrasion resistance due to long-term use and the evaluation of color appearance due to precious metals due to long-term use will be described in detail below.

[0103] (Wear resistance over long-term use) First, the plate-shaped samples prepared in Example 1, Comparative Example 1, and Comparative Example 2 were subjected to cloth buffing using a router to abrade a portion of the sample surface. Specifically, different positions on each sample were abraded under two conditions: 6,000 rpm, 100 g load, and 60 seconds of processing time (light abrasion test), and 30,000 rpm, 100 g load, and 120 seconds of processing time (severe abrasion test). Furthermore, a light abrasion test showed that only the finish layer was worn away, simulating the abrasion that occurs with short-term use. Furthermore, rigorous abrasion resistance tests have shown that not only the finishing layer but also the thinner layers below it can be worn away, making it possible to reproduce the wear that would occur in actual long-term use. In order to evaluate the abrasion resistance during long-term use, the sample surface after a light abrasion test and the sample surface after a severe abrasion test were measured by the above-mentioned color tone measurement method. * , a * , b * Measure the ΔE between the colors. * I looked up ab. Here, ΔE * ab means L * , a * , b * represents the distance between two points in a three-dimensional orthogonal coordinate system with the axis, and ΔE * The larger the value of ab, the more the hue being compared differs from the reference hue. If the second adjusting layer is thin, the finishing layer, the second adjusting layer, and the first adjusting layer will be worn away when subjected to a severe abrasion test, resulting in a color difference ΔE between the surface color and the surface of a sample that has been abraded in a light abrasion test. * ab becomes relatively large. Conversely, if the second adjustment layer is thick, even if it is worn in a severe abrasion test, the color tone of the sample surface will remain almost the same as that of the sample worn in a light abrasion test, so ΔE * The value of ab becomes smaller, which means that the second adjustment layer is resistant to wear. Various samples with different thicknesses of the second adjustment layer were prepared, and ΔE *The thickness of the second adjusting layer at which the value of ab becomes small was investigated, and it was determined that if the thickness was thicker than this, the layer had sufficient wear resistance for long-term use. As a double check, the surface of samples that had been abraded in a rigorous abrasion test was measured for Au, Cu, and Pd, which are constituent elements of the first adjusting layer, using the elemental content measurement method described above. Based on these results, we determined whether various samples with different second adjusting layer thicknesses could withstand wear associated with long-term use. That is, if the constituent elements of the first adjusting layer, Au, Cu, and Pd, could not be measured sufficiently, we determined that the second adjusting layer directly above the first adjusting layer had also worn away. (Note: If the second adjusting layer is too thin, it is thought that the first adjusting layer will wear away along with the second adjusting layer in a rigorous abrasion test, making it impossible to detect elements such as Au that make up the first adjusting layer. On the other hand, if the second adjusting layer is thick enough, the second adjusting layer and the first adjusting layer will remain unabraded even in a rigorous abrasion test, and it is thought that the elements such as Au that make up the first adjusting layer will be detectable.)

[0104] (Color derived from precious metals due to long-term use) First, among the samples abraded under the above-mentioned processing conditions (severe abrasion test) of 30,000 rpm, 100 g load, and processing time of 120 seconds, the samples that were judged to have abrasion resistance due to long-term use were measured by the above-mentioned color measurement method, and the color difference ΔE between the color tone of the abraded surface (surface of the second adjusting layer) of the sample was measured by the above-mentioned color tone measurement method, and the color tone of the abraded surface (surface of the base layer and residues of precious metal elements originating from the first adjusting layer that were present on the surface of the base layer) of a sample that did not have abrasion resistance due to long-term use and in which the base layer was completely exposed was measured. * The values ​​ab were calculated to evaluate whether the sample had a color appearance derived from precious metals that would occur with long-term use. Specifically, the sample for comparison was the sample in Comparative Example 1 in which the second adjustment layer 242 was formed to a thickness of 0.027 μm. That is, various samples with different film thicknesses of the second adjusting layer were prepared, and ΔE * The thickness of the second adjustment layer at which the value of ab converges to 0 is examined, and ΔE * When the value of ab is sufficiently larger than 0, it is determined that the color originating from the first adjustment layer (noble metal) is visible through the second adjustment layer. Here, the reason why we chose the surface color of the polished part of the sample where the base layer was definitely exposed through a rigorous abrasion test as the comparison subject for the color tone, rather than the surface color tone of a sample where only the base layer was formed, is that the surface exposed through a rigorous abrasion test, in all samples, had residues of precious metal elements from the precious metal layer that was directly above it, and exhibited a color tone that was slightly different from that of a simple base layer, and if a simple base layer were chosen as the comparison subject, ΔE * The value of ab does not converge to 0, and ΔE * This is because ab will no longer be able to make a correct judgment. Next, samples in which the color originating from the precious metal could actually be visually identified were evaluated as ◯, samples in which the color originating from the precious metal could hardly be identified as △, and samples in which the color originating from the precious metal could not be identified as ×. Finally, the ΔE * Based on the ab values ​​and the results of the visual evaluation, samples in which the color derived from the precious metal could be identified were evaluated as ○, samples in which the color was almost indistinguishable were evaluated as △, and samples in which the color was not discernible were evaluated as × (Table 4, overall evaluation). Table 4 shows the results of an investigation into the thickness range of the second adjusting layer based on two viewpoints: wear resistance with long-term use and the color appearance derived from precious metals with long-term use. The processing conditions (0), (1), and (2) in the table indicate (0): unprocessed, (1): 6000 rpm, 100 g load, processing time 60 seconds (light wear test), and (2): 30000 rpm, 100 g load, processing time 120 seconds (severe wear test). Note that the L in Table 4 * , a * , b * is the value measured by CM-700d.

[0105] [Table 4]

[0106] From Table 4, it was determined that the film thickness range in which the film has wear resistance for long-term use and allows the color derived from the precious metal to be felt even after long-term use is 0.039 μm or more and 0.065 μm (sample of Example 1). As a result, when a decorative member is formed within the above-mentioned film thickness range, it is possible to obtain a decorative member that is less susceptible to discoloration due to wear over long-term use.

[0107] [Consideration of a more preferable membrane structure] Regarding a more preferable film structure, the samples prepared in Examples 1 and 2 were evaluated from two perspectives: discoloration due to wear associated with short-term use and discoloration due to wear associated with long-term use. A film structure was considered that would not only be less susceptible to discoloration due to wear associated with long-term use, but also less susceptible to discoloration due to wear associated with short-term use.

[0108] (Discoloration due to wear and tear from short-term use) For the samples prepared in Examples 1 and 2, first, a part of the sample surface was polished under conditions of 6000 rpm, 100 g load, and processing time of 60 seconds (light abrasion test). Next, the L of the worn and untreated surfaces of the sample was measured. * , a * , b * The difference in color between the abraded surface and the unprocessed surface is measured by the color measurement method described above, and ΔE * The discoloration due to wear over a short period of use was evaluated using numerical values ​​ab.

[0109] (Discoloration due to wear and tear over time) First, the sample surface was polished with a cloth buff using a router to wear off a portion of the surface. Specifically, the polishing was performed under the conditions of 30,000 rpm, 100 g load, and 120 seconds processing time (severe wear test). Next, the L of the worn and untreated surfaces of the sample was measured. * , a * , b * The difference in color between the abraded surface and the unprocessed surface is measured by the color measurement method described above, and ΔE * The discoloration due to wear over long-term use was evaluated using numerical values ​​ab. Table 5 shows the results of evaluating discoloration due to wear over long-term use and discoloration due to wear over short-term use. The processing conditions (0), (1), and (2) in the table indicate (0): unprocessed, (1): 6000 rpm, 100 g load, and processing time of 60 seconds (light abrasion test), and (2): 30000 rpm, 100 g load, and processing time of 120 seconds (severe abrasion test). * , a * , b * is the value measured by CM-2600d. [Table 5]

[0110] The results in Table 5 show that, with regard to discoloration due to wear over long-term use, both Examples 1 and 2 are at the same level, but with regard to discoloration due to wear over short-term use, Example 2 is less likely to be discolored than Example 1. Therefore, it was determined that the membrane structure of Example 2 was more preferable. [Explanation of symbols]

[0111] 1 decorative member, 2 decorative member, 10 substrate, 20 decorative coating, 22 base layer, 24 adjustment layer, 241 first adjustment layer, 242 second adjustment layer, 243 third adjustment layer, 244 fourth adjustment layer, 26 finishing layer

Claims

1. A decorative member comprising a substrate and a decorative coating formed on the substrate, The decorative coating is formed by laminating, from the substrate side, a base layer, an adjustment layer, and a finishing layer, the underlayer contains a metal carbide containing Ti and at least one selected from Nb and Ta, the finishing layer comprises an Au alloy; the adjustment layer has a laminated structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side, the first adjustment layer contains an Au alloy, and the second adjustment layer contains a metal carbide containing at least one selected from Nb and Ta and Ti; the thickness of the first adjustment layer is 0.005 μm or more and 0.016 μm or less, and the thickness of the second adjustment layer is 0.039 μm or more and 0.065 μm or less; Decorative material.

2. the adjustment layer has a laminated structure in which, from the base side, the first adjustment layer, the second adjustment layer, a third adjustment layer, and a fourth adjustment layer are laminated, the third adjustment layer contains an Au alloy, and the fourth adjustment layer contains a metal carbide containing at least one selected from Nb and Ta and Ti; the third adjustment layer and the fourth adjustment layer each have a thickness of 0.005 μm or more and 0.016 μm or less; The decorative member according to claim 1 .

3. The decorative member is L * a * b * In the color system, L * is 75 or more and 100 or less, a * is 0 to 20, b * is 5 or more and 25 or less, or L * C * When expressed in the h color system, L * is between 75 and 100, C * is 5 or more and 32 or less, and h is 14° or more and 90° or less, The decorative member according to claim 1 or 2.

4. In each of the underlayer and the second adjustment layer, the metal carbide contains, when the total of the metal consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%, the at least one selected from Nb and Ta in an amount of 22 mass% to 66 mass% in total, the Ti in an amount of 20 mass% to 50 mass% in total, the nitrogen in an amount of 7 mass% to 19 mass% in total, and the carbon in an amount of 4 mass% to 15 mass% in total. The decorative member according to claim 1 .

5. In each of the underlayer, the second adjustment layer, and the fourth adjustment layer, the metal carbide contains, when the total of the metal consisting of at least one selected from Nb and Ta and Ti, nitrogen, and carbon is taken as 100 mass%, at least one selected from Nb and Ta in an amount of 22 mass% to 66 mass% in total, Ti in an amount of 20 mass% to 50 mass% in total, nitrogen in an amount of 7 mass% to 19 mass% in total, and carbon in an amount of 4 mass% to 15 mass% in total. The decorative member according to claim 2 .

6. In each of the finishing layer and the first adjustment layer, the Au alloy is an alloy containing Au, Cu, and Pd, and when the total of Au, Pd, and Cu is 100 mass%, the Au alloy contains 62.0 mass% to 94.5 mass%, Pd contains 0.5 mass% to 17.0 mass%, and Cu contains 5.0 mass% to 21.0 mass%, The decorative member according to claim 1 .

7. In each of the finishing layer, the first adjustment layer, and the third adjustment layer, the Au alloy is an alloy containing Au, Pd, and Cu, and contains Au in an amount of 62.0 mass% to 94.5 mass%; Pd in ​​an amount of 0.5 mass% to 17.0 mass%; and Cu in an amount of 5.0 mass% to 21.0 mass% when the total of Au, Pd, and Cu is 100 mass%. The decorative member according to claim 2 .

8. The underlayer is L * a * b * In the color system, L * is 67.03 or more and 71.27 or less, a * is 5.45 or more and 7.39 or less, b * is 12.57 or more and 16.83 or less, or L * C * When expressed in the h color system, L * is 67.03 or more and 71.27 or less, C * is 13.70 or more and 18.38 or less, and h is 59.55° or more and 72.06° or less, The decorative member according to claim 1 or 2.

9. A method for manufacturing a decorative member including a substrate and a decorative coating formed on the substrate, comprising: The decorative coating is formed by laminating, from the substrate side, a base layer, an adjustment layer, and a finishing layer, the adjustment layer has a laminated structure in which at least a first adjustment layer and a second adjustment layer are laminated from the substrate side, a base layer laminating step of laminating the base layer containing a carbide of a metal including at least one selected from Nb and Ta and Ti on the base material; an adjustment layer lamination step of laminating the first adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less on the underlayer laminated in the underlayer lamination step, and laminating the second adjustment layer containing a carbide of a metal containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less on the first adjustment layer; a finishing layer lamination step of laminating the finishing layer containing an Au alloy on the second adjustment layer laminated in the adjustment layer lamination step, A method for manufacturing a decorative member.

10. the adjustment layer has a laminated structure in which, in addition to the first adjustment layer and the second adjustment layer, a third adjustment layer and a fourth adjustment layer are laminated from the substrate side; the adjustment layer laminating step is a step of laminating the first adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less on the underlayer laminated in the underlayer laminating step, laminating the second adjustment layer containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.039 μm or more and 0.065 μm or less on the first adjustment layer, further laminating the third adjustment layer containing an Au alloy and having a thickness of 0.005 μm or more and 0.016 μm or less on the second adjustment layer, and laminating the fourth adjustment layer containing a metal carbide containing at least one selected from Nb and Ta and Ti and having a thickness of 0.005 μm or more and 0.016 μm or less on the third adjustment layer, The finishing layer laminating step is a step of laminating the finishing layer containing an Au alloy on the fourth adjustment layer laminated in the adjustment layer laminating step. The method for manufacturing a decorative member according to claim 9.

11. A decorative article comprising the decorative member according to claim 1 or 2.

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