Decorative member and method for manufacturing decorative member

Abstract

This decorative member has a base material and a finish layer that contains NbTiN, wherein the finish layer is superposed on the base material, satisfies, in color evaluation by the L*a*b* color system, 72.25 ≤ L* < 77.00, 2.51 ≤ a* ≤ 5.27, and 23.26 ≤ b* ≤ 24.90, and has an average surface roughness Ra of less than 4.6 nm. It is preferable that the finish layer contains Nb in an amount of 20 atom% to 30 atom% inclusive, Ti in an amount of 25 atom% to 35 atom% inclusive, and N in an amount of 45 atom% to 55 atom% inclusive when the total of a metal that is composed of Nb and Ti and N is taken as 100 atom%.

Description

Decorative member and method for manufacturing decorative member

[0001] The present invention relates to a decorative member and a method for manufacturing a decorative member.

[0002] Patent Document 1 describes a decorative member having a cherry pink color. Specifically, it is a decorative member comprising a base material and a decorative film formed on the base material, wherein the decorative film has a base layer and a finish layer laminated from the base material side, the base layer is a nitride carbide layer made of a metal nitride carbide containing at least one selected from Nb and Ta and Ti, and the finish layer is an Au alloy layer made of an alloy containing Au, a metal showing a silver color, and Cu. A decorative member is described.

[0003] International Publication No. 2017 / 170324

[0004] In recent years, there has been a demand for a decorative member having a pale yellow appearance and excellent in ease of wiping off dirt. However, such a color tone cannot be expressed by the decorative member of Patent Document 1. Therefore, an object of the present invention is to provide a decorative member having a pale yellow appearance and excellent in ease of wiping off dirt.

[0005] The decorative member of the present invention has a base material and a finish layer containing NbTiN, the finish layer is laminated on the base material, and the finish layer is L * a * b * In color evaluation by a color system, 72.25 ≦ L * < 77.00, 2.51 ≦ a * ≦ 5.27, 23.26 ≦ b * ≦ 24.90, and the average surface roughness Ra is less than 4.6 nm.

[0006] The decorative member of the present invention has a pale yellow appearance and is excellent in ease of wiping off dirt.

[0007] FIG. 1 is a schematic cross-sectional view of the decorative member of Embodiment 1. FIG. 2 shows an XPS depth profile of the decorative member of Example 1. FIG. 3 shows an XPS depth profile of the decorative member of Example 2. FIG. 4 shows an XPS depth profile of the decorative member of Example 4.

[0008] <Decorative Member of Embodiment 1>FIG. 1 is a schematic cross-sectional view of the decorative member of Embodiment 1. The decorative member 1 has a base material 10, an adhesion layer 12, and a base layer 14 including a first base layer 141, a second base layer 142, and a third base layer 143, and a finish layer 16 containing NbTiN (niobium titanium nitride). In the decorative member 1, the adhesion layer 12, the base layer 14 including the first base layer 141, the second base layer 142, and the third base layer 143, and the finish layer 16 are laminated in this order on the base material 10. In this specification, the layers laminated on the base material are also collectively referred to as a decorative film. Specifically, the adhesion layer 12, the base layer 14 (the first base layer 141, the second base layer 142, and the third base layer 143), and the finish layer 16 are also collectively referred to as a decorative film 20. The finish layer 16 satisfies 72.25 ≦ L * <77.00, 2.51 ≦ a * ≦ 5.27, 23.26 ≦ b * ≦ 24.90, and the average surface roughness Ra is less than 4.6 nm. Thus, since the decorative member 1 has a specific finish layer 16 as the outermost layer, it has a light yellow appearance and is excellent in ease of wiping off dirt. Therefore, for example, compared with the case where a TiN film is used for the decorative member, the appearance of showing a greenish color tone is suppressed, and a decorative member having better aesthetic properties can be obtained. Further, the decorative film is Ni-free, and the allergic property of the decorative member can be further reduced. In addition, the decorative film has a light yellow appearance without using a noble metal, and can contribute to, for example, SDGs Target 9, 12, etc., and cost reduction is also possible.

[0009] The base material 10 is specifically formed from metal, ceramics, or plastic. Examples of the metal (including alloys) include stainless steel, titanium, titanium alloy, copper, copper alloy, tungsten, or stainless steel, titanium, titanium alloy, etc. that have been hardened. These metals can be used alone or in combination of two or more kinds. The base material 10 is preferably formed from stainless steel or titanium. Also, the shape of the base material 10 may be appropriately adopted according to the use of the decorative member 1 and is not particularly limited.

[0010] The adhesion layer 12 is laminated on the substrate 10 and contains, for example, Ti or TiN. The adhesion layer 12 can improve the adhesion between the substrate 10 and the decorative film 20. The TiN contained in the adhesion layer 12 may contain Ti in an amount greater than 80 atomic% and less than 100 atomic% and N in an amount greater than 0 atomic% and less than 20 atomic% when the total of Ti and N is 100 atomic%. Furthermore, from the viewpoint of adhesion, it is preferable that the TiN contained in the adhesion layer 12 contains Ti in an amount of 95 atomic% or more and less than 100 atomic% and N in an amount greater than 0 atomic% and 5 atomic% or less when the total of Ti and N is 100 atomic%. From the viewpoint of adhesion, the thickness of the adhesion layer 12 is preferably 0.1 μm or more and 0.5 μm or less.

[0011] The base layer 14 consists of three layers: a first base layer 141, a second base layer 142, and a third base layer 143. The first base layer 141 is laminated on the adhesion layer 12, the second base layer 142 is laminated on the first base layer 141, and the third base layer 143 is laminated on the second base layer 142. The first base layer 141, the second base layer 142, and the third base layer 143 contain NbTiN. The N content in the base layer 14 is preferably less than or equal to the N content in the finishing layer 16, which will be described later. That is, the N content in the base layer 14 is preferably the same as the N content in the finishing layer 16, or less than the N content in the finishing layer 16. Specifically, it is preferable to set the N content in the third base layer 143 to be less than or equal to the N content in the finishing layer 16, the N content in the second base layer 142 to be less than the N content in the third base layer 143, and the N content in the first base layer 141 to be less than the N content in the second base layer 142. By providing such a base layer 14, the N content in the decorative coating 20 can be increased in stages from the substrate 10 side toward the surface, improving the adhesion between the substrate 10 and the decorative coating 20. In other words, film stress can be relieved and the occurrence of cracks can be suppressed. In addition, by providing the base layer 14, the thickness of the decorative coating 20 can be increased, improving its hardness and abrasion resistance. Furthermore, by providing the base layer 14, the color tone can be brought closer to that of the finishing layer 16.

[0012] More specifically, the NbTiN contained in the first sublayer 141 preferably contains Nb in an amount of 30 to 35 atomic percent, Ti in an amount of 45 to 50 atomic percent, and N in an amount of 15 to 25 atomic percent, when the total amount of Nb, Ti, and N is 100 atomic percent. Furthermore, the NbTiN contained in the second sublayer 142 preferably contains Nb in an amount of 29 to 31 atomic percent, Ti in an amount of 30 to 35 atomic percent, and N in an amount of 36 to 41 atomic percent, when the total amount of Nb, Ti, and N is 100 atomic percent. Furthermore, the NbTiN contained in the third base layer 143 preferably contains 20 to 30 atomic percent of Nb, 25 to 35 atomic percent of Ti, and 45 to 55 atomic percent of N, when the total of Nb, Ti, and N is set to 100 atomic percent. Thus, it is desirable that the third base layer 143 has similar concentrations of Nb, Ti, and N as described later in the finishing layer 16. For example, if the N content of the third base layer 143 is greater than the N content of the finishing layer 16, the film stress will increase, and there is a risk of cracking in the film. On the other hand, if the N content of the third base layer 143 is less than the N content of the second base layer 142, the hardness of the third base layer 143 may decrease. This may reduce the overall hardness of the decorative coating 20, and consequently, it may not be possible to sufficiently suppress the occurrence of scratches on the decorative member 1. To address these concerns, the N content of the third base layer 143 is preferably within the above range. Furthermore, from the viewpoint of membrane stress relaxation, it is most preferable that the N content in the base layer 14 is smaller than the N content in the finishing layer 16. Specifically, it is most preferable to make the N content in the third base layer 143 smaller than the N content in the finishing layer 16, the N content in the second base layer 142 smaller than the N content in the third base layer 143, and the N content in the first base layer 141 smaller than the N content in the second base layer 142.

[0013] The sum of the thicknesses of the first sublayer 141, the second sublayer 142, and the third sublayer 143 is preferably 0.6 μm or more and 1.1 μm or less, from the viewpoint of hardness and abrasion resistance.

[0014] Furthermore, regarding the sub-layer 14, which includes the first sub-layer 141, the second sub-layer 142, and the third sub-layer 143, L * a * b * L in color evaluation using color systems * a * , b * The range of values ​​may differ from that of the finishing layer 16. For example, L * It is small and dark, a * The surface may be large and have a strong reddish tint, and it does not have to exhibit the pale yellow color of the finishing layer 16. Furthermore, the average roughness Ra of the base layer 14, which includes the first base layer 141, the second base layer 142, and the third base layer 143, may differ from that of the finishing layer 16. For example, Ra may be 4.6 nm or greater.

[0015] The finishing layer 16 is laminated on the base layer 14 (specifically the third base layer 143) and contains NbTiN. The finishing layer 16 is L * a * b * In color evaluation using the CIE color system, 72.25 ≤ L * <77.00, 2.51 ≤ a * ≤5.27, 23.26 ≤b * ≤ 24.90. Also, 74.01 ≤ L * <76.27, 3.06 ≤ a * ≤4.21, 24.34 ≤b * It is preferable that the value is ≤24.90. Therefore, the decorative member 1 is pale yellow (specifically, an antique-style pale yellow). Also, L * C * In color evaluation using the h color system, 23.29 ≤ C * Preferably, ≤25.19 and 77.37 ≤ h ≤ 83.85. From the viewpoint of a preferred pale yellow color, 24.53 ≤ C * It is more desirable that ≤ 25.19, and even more desirable that 80.20 ≤ h ≤ 82.83. Note that L * a * b * The color system was standardized by the International Commission on Illumination (CIE) in 1976. Furthermore, in this specification, the L of the finishing layer 16 * a* , b * , C * ,h is a value obtained for the finishing layer 16 present on the outermost surface when the decorative member 1 was manufactured.

[0016] The finishing layer 16 has an average roughness Ra of less than 4.6 nm, preferably 3.8 nm or less. When the average roughness is within the above range, the material exhibits excellent dirt-wiping properties, which are essential characteristics for decorative members.

[0017] From the viewpoint of color tone and average roughness, the finishing layer 16 preferably contains Nb in amounts of 20 to 30 atomic percent, Ti in amounts of 25 to 35 atomic percent, and N in amounts of 45 to 55 atomic percent, when the total amount of metals consisting of Nb and Ti and N is 100 atomic percent.

[0018] The thickness of the finishing layer 16 is preferably 0.1 μm or more from the viewpoint of hardness and abrasion resistance. A thickness of 0.09 μm or more has the advantage of preventing the substrate from showing through, making it less susceptible to the influence of the substrate, and allowing it to exhibit a desirable pale yellow color. Furthermore, the thickness of the finishing layer 16 is preferably 0.2 μm or less from the viewpoint of color tone and average roughness. Moreover, the thickness of the finishing layer 16 is more preferably less than 0.2 μm from the viewpoint of average roughness.

[0019] In the decorative member 1, the thickness of the decorative coating 20 is preferably 0.8 μm or more and 1.5 μm or less from the viewpoint of hardness and wear resistance. Furthermore, the decorative member 1 is preferably hardened to 1000 HV or more from the viewpoint of wear resistance.

[0020] <Method for Manufacturing Decorative Members of Embodiment 1> The method for manufacturing decorative members of Embodiment 1 includes an adhesion layer lamination step, a base layer lamination step, and a finishing layer lamination step. As long as the above-mentioned adhesion layer 12, the first base layer 141, the second base layer 142, and the third base layer 143 as base layers 14, and the finishing layer 16 can be laminated on the substrate 10, the method is not particularly limited, but it can be suitably manufactured by a sputtering method such as reactive sputtering. In the sputtering method, a high voltage of DC or AC is applied between the substrate and a target consisting of constituent atoms of the coating while introducing an inert gas such as argon gas into a chamber that has been evacuated to a vacuum, causing ionized Ar to collide with the target, and the ejected target material is formed on the substrate. In the reactive sputtering method, a reaction gas is introduced together with an inert gas such as argon gas, and a reaction compound coating of target constituent atoms and nonmetallic elements constituting the reaction gas is formed on the substrate.

[0021] The adhesion layer lamination process can be carried out by sputtering. For example, using Ti as the target and argon gas as the inert gas, an adhesion layer 12 containing Ti is laminated onto the substrate 10. Alternatively, TiN containing N in the aforementioned amounts may be laminated as the adhesion layer 12.

[0022] The underlayer lamination process (first underlayer lamination process, second underlayer lamination process, and third underlayer lamination process) can be carried out by reactive sputtering. Specifically, the first underlayer lamination process, the second underlayer lamination process, and the third underlayer lamination process are carried out in this order, and the first underlayer 141, second underlayer 142, and third underlayer 143 containing NbTiN are laminated on the adhesion layer 12 in this order. For example, in each process, an NbTi alloy is used as the target, argon gas as the inert gas, and nitrogen gas as the reactive gas to laminate the underlayer 14 (first underlayer 141, second underlayer 142, and third underlayer 143) containing NbTiN on the adhesion layer 12. The first, second, and third base layer lamination processes can be carried out by appropriately setting the nitrogen gas flow rate, inert gas flow rate, film deposition rate, and total pressure in the chamber, respectively. The Nb and Ti content in the first, second, and third base layer 143 can be adjusted by appropriately changing the proportion of target constituent atoms. The N content in the first, second, and third base layer 143 can be adjusted by appropriately changing the nitrogen gas flow rate. Furthermore, in the third base layer lamination process, it is preferable to set the film deposition rate to be greater than 0.01 μm / min and less than 0.02 μm / min.

[0023] The finishing layer lamination process can be carried out by reactive sputtering. For example, using an NbTi alloy as the target, argon gas as the inert gas, and nitrogen gas as the reactive gas, a finishing layer 16 containing NbTiN is laminated on the base layer 14 (specifically, the third base layer 143). The finishing layer lamination process can be carried out by appropriately setting the nitrogen gas flow rate, the inert gas flow rate, the film deposition rate, and the total pressure in the chamber. Furthermore, in the finishing layer lamination process, the nitrogen gas flow rate ratio (nitrogen gas flow rate / (nitrogen gas flow rate + inert gas flow rate)) is set to 0.30 or more and 0.41 or less, and the film deposition rate is set to less than 0.02 μm / min. This results in L * a * , b * , C *A finishing layer 16 can be laminated in which the value of h and the average roughness Ra are within the above range. If the film deposition rate is too high than 0.02 μm / min, there is a concern that the average roughness will be high. The film deposition rate can be adjusted by appropriately changing conditions such as the voltage applied to the target or the surface area of ​​the target. The content of Nb and Ti in the finishing layer 16 can be adjusted by appropriately changing the proportion of constituent atoms of the target. The content of N in the finishing layer 16 can be adjusted by appropriately changing the flow rate of nitrogen gas. In addition, in the finishing layer lamination process, it is preferable to set the total pressure in the chamber to 0.088 Pa or more and 0.100 Pa or less.

[0024] Furthermore, in the adhesion layer lamination process, the underlayer lamination process, and the finishing layer lamination process, the film thickness can be adjusted by appropriately changing the film formation time so that it falls within the range described above.

[0025] <Modified Decorative Member> In Embodiment 1, the decorative member has an adhesive layer 12, a base layer 14 consisting of a first base layer 141, a second base layer 142, and a third base layer 143, and a finishing layer 16, all laminated on a base material 10 in this order. However, it is not limited to this, and as shown in the modified example below, the above-mentioned finishing layer (containing NbTiN, L) is laminated on the base material. * a * , b * If a finishing layer (with a value and average roughness Ra within the above-mentioned range) is laminated, it will have a pale yellow appearance and exhibit the effect of being easy to wipe off dirt. Regarding the modified form, the same points as in Embodiment 1 will be omitted from the explanation, and only the differences from Embodiment 1 will be described.

[0026] The decorative member comprises a base material and a finishing layer containing NbTiN, and the finishing layer may be laminated on the base material (Decorative member of Modified Example 1). In addition, in the decorative member of Modified Example 1, the above-mentioned adhesion layer may be provided between the base material and the finishing layer from the viewpoint of improving the adhesion between the base material and the decorative coating.

[0027] The decorative member comprises a base material, a different underlayer than that of Embodiment 1, and a finishing layer containing NbTiN, and the underlayer and finishing layer may be laminated on the base material in this order (Decorative member of Modification 2). The underlayer is not particularly limited as long as it is a layer that can increase the thickness of the decorative coating and contribute to improving hardness and abrasion resistance. For example, the underlayer preferably contains NbTiN from the viewpoint of adhesion between the base material and the decorative coating and color tone. When the underlayer contains NbTiN, from the viewpoint of relaxing film stress and suppressing crack occurrence, the N content in the underlayer is preferably less than or equal to the N content in the finishing layer, and more preferably less than the N content in the finishing layer. Specifically, in the underlayer 14 described above, a configuration is given in which at least one layer is omitted from the first underlayer 141, the second underlayer 142, and the third underlayer 143. With such a configuration, the N content in the decorative coating increases stepwise from the base material side toward the surface. Therefore, film stress can be relieved and crack occurrence can be suppressed. In these cases, the thicknesses of the first underlayer 141, the second underlayer 142, and the third underlayer 143 can be appropriately set from the viewpoint of hardness and wear resistance. In addition, one gradient layer may be provided as the underlayer, which contains NbTiN and in which the N content in NbTiN increases continuously from the base material side to the finish layer side. In the decorative member of the modified example 2, the above-mentioned adhesion layer may be provided between the base material and the underlayer from the viewpoint of improving the adhesion between the base material and the decorative coating.

[0028] In addition, the decorative member of Embodiment 1 may be configured in which the adhesion layer is omitted. In other words, the base material 10 may be configured in which a first base layer 141, a second base layer 142, and a third base layer 143, and a finishing layer 16 are laminated in this order as the base layer 14. Furthermore, as long as it does not hinder the objective of the present invention, layers other than those described above may be provided between the base material and the finishing layer.

[0029] The modified decorative member can be manufactured by performing an adhesion layer lamination process, a base layer lamination process, and a finish layer lamination process as appropriate to achieve the desired configuration. Each of these processes can be carried out in the same manner as described in the manufacturing method of the decorative member of Embodiment 1. If the base layer is a sloped layer, the layer can be formed by increasing the amount of nitrogen gas or decreasing the NbTi film deposition rate in order to increase the N content in NbTiN from the substrate side to the finish layer side.

[0030] <Decorative items including decorative members> The decorative members of the embodiments and modified examples can be used in decorative items. Examples of decorative items including the above decorative members include eyeglasses including components such as eyeglass frames; accessories such as necklaces, earrings, piercings, rings, pendants, brooches, and bracelets; watches including components such as watch cases and watch bands (e.g., wristwatches, desk clocks, wall clocks, pocket watches); parts used in watches such as hands and dials; and sports equipment. These decorative items may be composed of part of the above decorative members or entirely of the above decorative members, and can be manufactured using the above decorative members by known methods.

[0031] The watch may be a light-powered watch, a thermoelectric watch, a radio-controlled self-correcting watch, a mechanical watch, or a general electronic watch. Wristwatches, in particular, are an example of decorative items that can accumulate dirt through use. By using the decorative components of the embodiments and modifications in a wristwatch, a watch can be obtained that has a pale yellow color (specifically, an antique-style pale yellow) and is easy to wipe clean of any dirt that accumulates on it. Furthermore, the above watch can maintain a very clean appearance.

[0032] [Examples] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. [Example 1] A decorative member of Embodiment 1 was manufactured (Figure 1). SUS316L material as defined in JIS was used as the base material 10. First, in the adhesion layer lamination process, an adhesion layer 12 (thickness 0.2 to 0.3 μm) containing Ti was laminated on the base material 10 by sputtering. Here, Ti was used as the target and argon gas as the inert gas. Next, in the underlayer lamination process (first underlayer lamination process, second underlayer lamination process, and third underlayer lamination process), a first underlayer 141 (thickness 0.1 to 0.3 μm), a second underlayer 142 (thickness 0.2 to 0.4 μm), and a third underlayer 143 (thickness 0.2 to 0.4 μm) containing NbTiN were laminated on the adhesion layer 12 in this order by reactive sputtering. Here, an NbTi alloy containing constituent atoms in a predetermined proportion was used as the target, argon gas as the inert gas, and nitrogen gas as the reaction gas. In the first, second, and third base layer lamination processes, the nitrogen gas flow rate, argon gas flow rate, deposition rate, and total pressure in the chamber were set appropriately. In the third base layer lamination process, the deposition rate was set to be greater than 0.01 μm / min and less than 0.02 μm / min. Next, in the finishing layer lamination process, a finishing layer 16 (approximately 0.1 μm thick) containing NbTiN was laminated on the third base layer 143 by reactive sputtering. Here, an NbTi alloy containing constituent atoms in a predetermined proportion was used as the target, argon gas as the inert gas, and nitrogen gas as the reaction gas. Furthermore, the finishing layer lamination process was carried out by setting the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, film deposition rate, total pressure in the chamber, and bias voltage as shown in Table 1. In this way, the decorative member of Example 1 was obtained.

[0033] [Examples 2, 4, and 5] Except that the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, film deposition rate, total pressure in the chamber, and bias voltage were set as shown in Table 1 during the finishing layer lamination process, decorative members for Examples 2, 4, and 5 were obtained in the same manner as in Example 1.

[0034] [Example 3] In the finishing layer lamination process, the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, deposition rate, total pressure in the chamber, and bias voltage were set as shown in Table 1, and the deposition time was adjusted so that the thickness of each layer was approximately 0.7 times that of Example 1. Except for these differences, the decorative member of Example 3 was obtained in the same manner as in Example 1.

[0035] [Comparative Example 1, Comparative Example 5] SUS316L material as specified in JIS was used as the base material. First, in the adhesion layer lamination process, an adhesion layer (thickness 0.2 to 0.3 μm) containing Ti was laminated on the base material by sputtering. Here, Ti was used as the target and argon gas as the inert gas. Next, in the underlayer lamination process (first underlayer lamination process, second underlayer lamination process, and third underlayer lamination process), a first underlayer (thickness 0.1 to 0.3 μm), a second underlayer (thickness 0.1 to 0.3 μm), and a third underlayer (thickness 0.1 to 0.3 μm) containing NbTiN were laminated on the adhesion layer in this order by reactive sputtering. Here, an NbTi alloy containing constituent atoms in a predetermined proportion was used as the target, argon gas as the inert gas, and nitrogen gas as the reaction gas. In the first, second, and third base layer lamination processes, the nitrogen gas flow rate, argon gas flow rate, deposition rate, and total pressure in the chamber were set appropriately. In the third base layer lamination process, the deposition rate was set to be greater than 0.01 μm / min and less than 0.03 μm / min. Next, in the finishing layer lamination process, a finishing layer (thickness 0.3 to 0.4 μm) containing NbTiN was laminated on the third base layer by reactive sputtering. Here, an NbTi alloy containing constituent atoms in a predetermined proportion was used as the target, argon gas as the inert gas, and nitrogen gas as the reactive gas. Furthermore, in the finishing layer lamination process, the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, deposition rate, total pressure in the chamber, and bias voltage were set as shown in Table 1. The film deposition rate of the finishing layer was adjusted to approximately twice that of Example 1 (0.02 μm / min) to obtain the decorative members of Comparative Example 1 and Comparative Example 5. In this way, the decorative members of Comparative Example 1 and Comparative Example 5 were obtained.

[0036] [Comparative Examples 2 and 3] In the finishing layer lamination process, the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, film deposition rate, total pressure in the chamber, and bias voltage were set as shown in Table 1, otherwise the decorative members of Comparative Examples 2 and 3 were obtained in the same manner as in Example 1.

[0037] [Comparative Example 4] In the finishing layer lamination process, the nitrogen gas flow rate, argon gas flow rate, flow rate ratio, film deposition rate, total pressure in the chamber, and bias voltage were set as shown in Table 1, and the film deposition time was adjusted so that the thickness of the finishing layer and the thickness of the third underlayer were each about 1.5 times that of Example 1. Otherwise, the decorative member of Comparative Example 4 was obtained in the same manner as in Example 1.

[0038] [Measurement Method and Measurement Results] <Composition Ratio> The composition ratio of each layer was obtained based on the composition profile (depth profile) of the film cross-section obtained with a Nexsa X-ray photoelectron spectrometer (XPS) manufactured by Thermo Fisher Scientific. At this time, the XPS irradiation X-ray source was AlKα, the acceleration voltage was 3 keV, and the electron beam was irradiated onto the sample surface, and the depth profile was measured while etching the sample surface with an Ar ion gun. Figures 2 to 4 show the XPS depth profiles for the decorative members of Examples 1, 2, and 4. In all of the decorative members of Examples 1, 2, and 4, the content of Nb, Ti, and N in the third base layer 143 and the finishing layer 16 was about the same. In addition, in the decorative member of Example 1, the adhesion layer 12 contained Ti in an amount of 95 atomic% to 100 atomic%, and N in an amount of 0 atomic% to 5 atomic%, when the total of Ti and N was set to 100 atomic%, respectively. Regarding the first sublayer 141, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 30 to 35 atomic%, Ti in an amount of 45 to 50 atomic%, and N in an amount of 15 to 25 atomic%. Regarding the second sublayer 142, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 29 to 31 atomic%, Ti in an amount of 30 to 35 atomic%, and N in an amount of 36 to 41 atomic%. Regarding the third sublayer 143 and the finishing layer 16, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 22 to 25 atomic%, Ti in an amount of 25 to 30 atomic%, and N in an amount of 48 to 52 atomic%. Furthermore, in the decorative member of Example 2, the adhesion layer 12 contained Ti in an amount of 98 to 100 atomic percent and N in an amount of 0 to 2 atomic percent, when the total amount of Ti and N was set to 100 atomic percent. The first underlayer 141 contained Nb in an amount of 30 to 35 atomic percent, Ti in an amount of 45 to 50 atomic percent, and N in an amount of 15 to 25 atomic percent, when the total amount of Nb, Ti, and N was set to 100 atomic percent.Regarding the second underlayer 142, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 29 atomic% to 31 atomic%, Ti in an amount of 30 atomic% to 35 atomic%, and N in an amount of 36 atomic% to 41 atomic%. Regarding the third underlayer 143 and the finishing layer 16, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 22 atomic% to 25 atomic%, Ti in an amount of 25 atomic% to 30 atomic%, and N in an amount of 48 atomic% to 52 atomic%. Furthermore, in the decorative member of Example 4, regarding the adhesion layer 12, when the total of Ti and N is set to 100 atomic%, it contained Ti in an amount of 95 atomic% to 98 atomic%, and N in an amount of 2 atomic% to 5 atomic%. Regarding the first sublayer 141, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 30 to 35 atomic%, Ti in an amount of 45 to 50 atomic%, and N in an amount of 15 to 25 atomic%. Regarding the second sublayer 142, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 29 to 31 atomic%, Ti in an amount of 30 to 35 atomic%, and N in an amount of 36 to 41 atomic%. Regarding the third sublayer 143 and the finishing layer 16, when the total of Nb, Ti, and N is set to 100 atomic%, it contained Nb in an amount of 22 to 25 atomic%, Ti in an amount of 25 to 30 atomic%, and N in an amount of 48 to 52 atomic%.

[0039] <Film Thickness> The film thickness of the finishing layer was obtained based on SEM images of the film cross-section obtained with a scanning electron microscope (SEM) of a ZEISS Gemini300. The film cross-section was processed using a cross-section polisher (CP) and an integrated ion beam (FIB) system. The total film thickness was measured with a micro-shape measuring instrument, an ET200 manufactured by Kosaka Laboratory. The film thickness of the finishing layer and the total film thickness (film thickness of the decorative coating) measured as described above are shown in Table 2.

[0040] <L * a * b * Color system and L * C *h Color evaluation using a color system > Measurements were taken using a CM-26d spectrophotometer manufactured by Konica Minolta. Specifically, using a light source D65, L * a * b * Color system L * a * , b * And, L * C * h Color system C * L was measured as described above. * a * , b * , C * Table 2 shows the values ​​for h.

[0041] <Average Roughness Ra> The average roughness Ra was measured using a scanning probe microscope, SPI3800N, manufactured by SII, in dynamic force mode (DFM), in accordance with surface roughness JIS B 0601:2001. The average roughness Ra measured as described above is shown in Table 2.

[0042] [Evaluation Method and Results] The color tone is L * a * b * In color evaluation using a color system, 74.01 ≤ L * ≤76.27, 3.06 ≤a * ≤4.21, 24.34 ≤b * ◎ indicates ≤24.90, and L indicates 72.25 ≤L. * <77.00, 2.51 ≤ a * ≤5.27, 23.26 ≤b * A score of ○ was given if the value was ≤24.90. All other cases were marked with ×. For wipeability, a score of ◎ was given if the average roughness Ra was 3.8 nm or less, and ○ was given if it was greater than 3.8 nm but less than 4.6 nm. Conversely, a score of × was given if it was 4.6 nm or greater. For the overall evaluation, a score of ◎ was given if both the color tone and wipeability were ◎. Additionally, a score of ○ was given if the color tone was ◎ and the wipeability was ○, if the color tone was ○ and the wipeability was ◎, or if both the color tone and wipeability were ○. Conversely, a score of × was given if either the color tone or the wipeability was ×. The evaluation results described above are shown in Table 2.

[0043]

[0044]

[0045] In Examples 1 to 5, the ratio of N is the same in the third base layer and the finishing layer, but the value in the third base layer may be between the values ​​in the finishing layer and the second finishing layer. Such decorative members are more preferable when considering film stress relaxation. Furthermore, it is believed that if such decorative members are manufactured, the same evaluation results for color tone and wipeability will be obtained as in Examples 1 to 5. Also, whether the base layer is composed of one layer or multiple layers, if a decorative member is manufactured with a base layer having a lower N content than the finishing layer, it is believed that the same evaluation results for color tone and wipeability will be obtained as in Examples 1 to 5.

[0046] Based on the above, the present invention relates to the following: [1] A base material and a finishing layer containing NbTiN, wherein the finishing layer is laminated on the base material, and the finishing layer is L * a * b * In color evaluation using a color system, 72.25 ≤ L * <77.00, 2.51 ≤ a * ≤5.27, 23.26 ≤b *[1] A decorative member having a surface roughness Ra of less than 4.6 nm and a coefficient of gravity of ≤24.90. [2] The decorative member according to [1], wherein the finishing layer comprises a metal consisting of Nb and Ti, and when the total amount of N is 100 atomic%, Nb is 20 atomic% to 30 atomic%, Ti is 25 atomic% to 35 atomic%, and N is 45 atomic% to 55 atomic%. [3] The decorative member according to [1] or [2], further comprising a base layer containing NbTiN, wherein the base layer is laminated between the substrate and the finishing layer, and the N content in the base layer is less than or equal to the N content in the finishing layer. [4] The decorative member according to [1] or [2], further comprising an adhesive layer containing Ti, wherein the adhesive layer is laminated between the substrate and the finishing layer. [5] The process includes a finishing layer lamination step of laminating a finishing layer containing NbTiN on a substrate by reactive sputtering, wherein the finishing layer lamination step is performed with a nitrogen gas flow rate ratio (nitrogen gas flow rate / (nitrogen gas flow rate + inert gas flow rate)) of 0.30 or more and 0.41 or less, and a film deposition rate of less than 0.02 μm / min, and the finishing layer is L * a * b * In color evaluation using a color system, 72.25 ≤ L * <77.00, 2.51 ≤ a * ≤5.27, 23.26 ≤b * A method for manufacturing a decorative member, wherein the coefficient of roughness is ≤24.90 and the average surface roughness Ra is less than 4.6 nm.

[0047] 1 Decorative component 10 Base material 12 Adhesion layer 14 Underlayer 141 First underlayer 142 Second underlayer 143 Third underlayer 16 Finishing layer 20 Decorative coating

Claims

1. The material comprises a base material and a finishing layer containing NbTiN, wherein the finishing layer is laminated on the base material, and the finishing layer is L * a * b * In color evaluation using a color system, 72.25 ≤ L * <77.00, 2.51 ≤ a * ≤5.27, 23.26 ≤b * A decorative member having a surface roughness Ra of less than 4.6 nm and a coefficient of measurement of ≤24.

90.

2. The decorative member according to claim 1, wherein the finishing layer contains Nb in amounts of 20 atomic% to 30 atomic%, Ti in amounts of 25 atomic% to 35 atomic%, and N in amounts of 45 atomic% to 55 atomic%, when the total amount of metals consisting of Nb and Ti and N is 100 atomic%.

3. The decorative member according to claim 1 or 2, further comprising a base layer containing NbTiN, wherein the base layer is laminated between the substrate and the finishing layer, and the N content in the base layer is less than or equal to the N content in the finishing layer.

4. The decorative member according to claim 1 or 2, further comprising an adhesive layer containing Ti, wherein the adhesive layer is laminated between the substrate and the finishing layer.

5. A finishing layer laminating step of laminating a finishing layer containing NbTiN on a substrate by a reactive sputtering method, wherein the finishing layer laminating step sets the flow rate ratio of nitrogen gas (flow rate of nitrogen gas / (flow rate of nitrogen gas + flow rate of inert gas)) to 0.30 or more and 0.41 or less, and sets the film formation rate to less than 0.02 μm / min to laminate the finishing layer, and the finishing layer is L * a * b * In color evaluation by a color system, 72.25 ≤ L * <77.00, 2.51 ≤ a * ≤ 5.27, 23.26 ≤ b * ≤ 24.90, and the average surface roughness Ra is less than 4.6 nm. A method for manufacturing a decorative member.

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