JP7707032B2 - Decorative member, watch, and method for manufacturing decorative member - Google Patents

Description

The present invention relates to a decorative member, a watch, and a method for manufacturing a decorative member.

Patent Document 1 describes an ornamental article having a substrate and a black hard coating made of diamond-like carbon (hereinafter referred to as DLC) formed on the substrate. Specifically, the black hard coating includes a gradient layer made of DLC, and the hydrogen content in the gradient layer increases with increasing distance from the substrate.

JP 2018-53365 A

The decorative article in Patent Document 1 has excellent performance of the black hard coating, such as hardness and friction coefficient, but has the problem that it cannot express external colors other than black.

The object of the present invention is to provide a decorative member that has excellent hardness and friction coefficient, as well as a blue exterior color.

The decorative member of the present invention is a decorative member in which a first adhesion layer, a second adhesion layer, a hard layer, and an outermost layer are laminated in this order on a base material, the first adhesion layer containing at least one element selected from Ti and Cr, the second adhesion layer containing at least one element selected from Si and Ge, the hard layer containing DLC and having a thickness of 0.4 μm or more and 1.2 μm or less, the outermost layer containing DLC, the hard layer formed on a laminate in which the base material, the first adhesion layer, and the second adhesion layer are laminated in this order has an L ^* value of 48 or more and 49 or less in the L ^* a ^* b ^* color system (CIE 1976), an a ^* value of 0 or more and 0.1 or less, and a b ^* value of 1.5 or more and 1.7 or less, the outermost layer which is the outermost surface of the decorative member has an L ^{* value of 30 or more and 31 or less in the L* a *} b ^* color system (CIE 1976), and The ^a* value is 1.1 or more and 1.7 or less, and the b ^* value is -11 or more and -9 or less.

The decorative member of the present invention has excellent hardness and coefficient of friction, and has a blue appearance color.

FIG. 1 is a diagram for explaining a decorative member according to an embodiment. FIG. 2 is a diagram for explaining a decorative member according to a reference example. FIG. 3 shows the results of SEM observation of the hard layer 14 of the decorative member obtained in the reference example. FIG. 4 shows the results of SEM observation of the outermost layer 15 of the decorative member obtained in the example. FIG. 5 is a diagram showing an XPS spectrum measured on the hard layer 14 of the decorative member obtained in the reference example. FIG. 6 is a diagram showing an XPS spectrum measured on the outermost layer 15 of the decorative member obtained in the example.

The following provides a detailed description of the form (embodiment) for carrying out the present invention. The present invention is not limited to the contents described in the following embodiment. The components described below include those that a person skilled in the art can easily imagine and those that are substantially the same. Furthermore, the configurations described below can be combined as appropriate. Various omissions, substitutions, or modifications of the configuration can be made without departing from the spirit of the present invention.

<Decorative member according to the embodiment>
Fig. 1 is a diagram for explaining a decorative member according to an embodiment. Fig. 1 is a schematic cross-sectional view of a decorative member 10. In the decorative member 10, a first adhesive layer 12, a second adhesive layer 13, a hard layer 14, and an outermost layer 15 are laminated in this order on a base material 11.

The substrate 11 is a substrate formed from a 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. In addition, there are no limitations on the shape of the substrate.

The first adhesion layer 12 contains at least one element selected from Ti and Cr. The provision of the first adhesion layer 12 can improve adhesion between the substrate 11 and the layer laminated on the first adhesion layer 12. From the viewpoint of adhesion, the thickness of the first adhesion layer 12 is preferably 0.1 μm or more and 0.2 μm or less.

The second adhesion layer 13 contains at least one element selected from Si and Ge. The presence of the second adhesion layer 13 can improve adhesion between the first adhesion layer 12 and the layer containing DLC that is laminated on the second adhesion layer 13.

Specifically, the second adhesion layer 13 may contain at least one element selected from Si and Ge. For example, the second adhesion layer 13 may be formed of one of Si and Ge, or may be formed of Si and Ge. Furthermore, the second adhesion layer 13 may contain a nitride, carbide, or carbonitride of at least one element selected from Si and Ge. Examples of nitrides, carbides, and carbonitrides include SiN, SiC, SiCN, GeN, GeC, and GeCN.

From the viewpoint of adhesion, the thickness of the second adhesion layer 13 is preferably 0.1 μm or more and 0.2 μm or less.

The hard layer 14 includes DLC. DLC includes carbon and hydrogen, and has an amorphous structure in which carbon having ^sp3 bonds corresponding to the diamond structure and carbon having ^sp2 bonds corresponding to the graphite structure are randomly mixed.

The hard layer 14 has a thickness of 0.4 μm or more and 1.2 μm or less. If the thickness is within this range, it can exhibit the performance (suitable hardness and friction coefficient, etc.) of a DLC layer described below, and is also preferable in that it can exhibit the black color described below.

The hard layer 14 has an L ^* value of 48 to 49 in the L ^* a ^* b ^* color system (CIE 1976), an a ^* value of 0 to 0.1, and a b ^* value of 1.5 to 1.7. Here, the L ^* value, a ^* value, and b ^* value are values obtained for the hard layer 14 formed on the laminate in which the substrate 11, the first adhesive layer 12, and the second adhesive layer 13 are laminated in this order. When the L ^* value, a ^* value, and b ^* value are in the above ranges, the color is black. In this specification, the term "black" also includes dark gray.

The hard layer 14 has a high hardness, and typically has a Vickers hardness HV of 1800 or more and 2200 or less. Here, the Vickers hardness HV is a value obtained for the hard layer 14 formed on a laminate in which the substrate 11, the first adhesive layer 12, and the second adhesive layer 13 are laminated in this order. Specifically, the Vickers hardness is measured using a microindentation hardness tester (manufactured by FISCHER, HM2000XYp) by applying a Vickers indenter to the sample surface with a load of 5 mN, holding the load for 10 seconds, and then removing the load, and calculating the Vickers hardness from the depth of the inserted Vickers indenter.

The hard layer 14 has a low coefficient of friction, and typically has a coefficient of friction (JIS R 1613) of 0.12 or more and 0.15 or less. Here, the coefficient of friction is a value determined for the hard layer 14 formed on a laminate in which the substrate 11, the first adhesive layer 12, and the second adhesive layer 13 are laminated in this order.

The hard layer 14 also has excellent abrasion resistance.

The outermost layer 15 contains DLC.

The outermost layer 15 preferably has a thickness of 0.05 μm or more and 0.07 μm or less. If the thickness is in this range, as described below, the decorative member 10 can exhibit excellent hardness and friction coefficient, and is also preferable in that the decorative member 10 can exhibit a blue color.

The outermost layer 15 has an L ^* value of 30 to 31 in the L ^* a ^* b ^* color system (CIE 1976), an a ^* value of 1.1 to 1.7, and a b ^{* value} of -11 to -9. Here, the L ^* value, a ^* value, and b ^* value are values obtained for the outermost layer 15 on the outermost surface of the decorative member 10. In other words, they are values obtained for the outermost layer 15 formed on a laminate in which the substrate 11, the first adhesive layer 12, the second adhesive layer 13, and the hard layer 14 are laminated in this order. When the L ^* value, a ^* value, and b ^* value are in the above ranges, the color blue is indicated. In this specification, the "blue" specifically means a blackish blue or a dark navy blue.

The outermost layer 15 also maintains the excellent hardness and friction coefficient of the hard layer 14, and typically has a numerical range of Vickers hardness HV and friction coefficient that is similar to that of the hard layer 14. Here, the Vickers hardness HV and friction coefficient are values obtained for the outermost layer 15 that is the outermost layer of the decorative member 10. In other words, they are values obtained for the outermost layer 15 formed on a laminate in which the base material 11, the first adhesion layer 12, the second adhesion layer 13, and the hard layer 14 are laminated in this order. Furthermore, the outermost layer 15 also has excellent abrasion resistance.

In this way, the decorative member 10 uses a two-layer structure of the hard layer 14 and the outermost layer 15 as the DLC layer, which gives it excellent hardness and friction coefficient, and also allows it to express a blue appearance color. In other words, the decorative member 10 is both durable and aesthetically pleasing.

This is believed to be because the structurally changed outermost layer 15 has the same ^sp3 ratio (( ^sp3 /( ^sp3 + ^sp2 )) as the hard layer 14, and therefore is able to maintain an excellent hardness of at least HV1400 or more. Also, since the outermost layer 15 has a greater amount of hydrogen than the hard layer 14, it is believed that the color becomes lighter (closer to transparent) and thin film interference occurs. This is believed to be why the blue appearance color can be expressed.

The decorative member 10 also has an excellent luster. This is believed to be because the particle size of the DLC contained in the outermost layer 15 is smaller than the particle size of the DLC contained in the hard layer 14. Furthermore, the two-layer structure of the hard layer 14 and the outermost layer 15 of the decorative member 10 improves fingerprint resistance, corrosion resistance, and weather resistance, and the two-layer structure can also be used as a barrier film.

<Method of manufacturing decorative member according to embodiment>
The method for producing a decorative member according to the embodiment is the method for producing a decorative member described above, that is, a method for producing a decorative member 10 in which a first adhesion layer 12, a second adhesion layer 13, a hard layer 14 and an outermost layer 15 are laminated in this order on a substrate 11. The method for producing a decorative member according to the embodiment includes a first adhesion layer forming step, a second adhesion layer forming step, a hard layer forming step and an outermost layer forming step.

The first adhesion layer forming process is a process of forming a first adhesion layer 12 containing at least one element selected from Ti and Cr on the substrate 11. The second adhesion layer forming process is a process of forming a second adhesion layer 13 containing at least one element selected from Si and Ge on the first adhesion layer 12 formed in the first adhesion layer forming process. Specifically, these processes can be performed by a sputtering method, an arc ion plating method, or an ion plating method.

The hard layer forming process is a process in which a hard layer 14 containing DLC is formed on the second adhesive layer 13 formed in the second adhesive layer forming process by applying a negative bias voltage of 2 kV or more and 5 kV or less, more preferably 3.5 kV, to the substrate 11 on which the first adhesive layer 12 and the second adhesive layer 13 are formed by the plasma CVD method.

Specifically, in the hard layer formation process, a voltage in the above range is applied to the substrate 11, which is set in a vacuum device and on which the second adhesive layer 13 has been formed. This converts the gas containing the raw material into plasma, and the raw material is deposited on the substrate to form the hard layer 14. As the gas containing the raw material, a hydrocarbon gas such as methane, acetylene, or benzene is preferably used. This allows the formation of a layer containing DLC that contains carbon and hydrogen.

By appropriately adjusting the time for applying the voltage (film formation time), the hard layer 14 having a thickness in the above-mentioned specific range can be formed. The film formation time is, for example, 60 minutes or more and 120 minutes or less. Furthermore, by applying a voltage in the above-mentioned specific range during the above-mentioned appropriately adjusted film formation time, the L ^* value, a ^* value, and b ^* value can be adjusted to the above-mentioned range. That is, a hard layer 14 exhibiting black color can be formed. Furthermore, by applying a voltage in the above-mentioned specific range during the above-mentioned appropriately adjusted film formation time, the hard layer 14 having a suitable hardness and friction coefficient can be formed.

The outermost layer forming process is a process in which an outermost layer 15 containing DLC is formed on the hard layer 14 formed in the hard layer forming process by applying a negative bias voltage of 0.05 kV or more and 0.4 kV or less to the substrate 11 on which the first adhesive layer 12, the second adhesive layer 13 and the hard layer 14 are formed by the plasma CVD method.

Specifically, in the outermost layer forming process, a voltage in the above range is applied to the substrate 11, which is set in a vacuum device and on which the hard layer 14 has been formed. This converts the gas containing the raw material into plasma, and the raw material is deposited on the substrate to form the outermost layer 15. The gas containing the raw material is preferably the same as that used in the hard layer forming process. This allows the formation of a layer containing DLC that contains carbon and hydrogen.

By appropriately adjusting the time for applying the voltage (film formation time), the outermost layer 15 having a thickness in the above-mentioned specific range can be formed. The film formation time is, for example, 7 minutes or more and 11 minutes or less. Furthermore, by applying a voltage in the above-mentioned specific range during the above-mentioned appropriately adjusted film formation time, the L ^* value, a ^* value, and b ^* value can be adjusted to the above-mentioned range. That is, the outermost layer 15 exhibiting a blue color can be formed. Furthermore, by applying a voltage in the above-mentioned specific range during the above-mentioned appropriately adjusted film formation time, the outermost layer 15 in which suitable hardness and friction coefficient are maintained can be formed.

<Modification>
In the decorative member according to the embodiment, a gradient layer containing DLC may be provided between the hard layer 14 and the outermost layer 15. In the gradient layer, for example, the hydrogen content or the ^sp3 ratio varies in the thickness direction. The provision of the gradient layer can improve color reproducibility. This modification can be produced by providing a gradient layer formation process between the hard layer formation process and the outermost layer formation process. The gradient layer can be formed by gradually changing the negative bias voltage from the start to the end of its formation.

<Watch according to the embodiment>
The timepiece according to the embodiment includes the decorative member described above. At least a portion of the timepiece according to the embodiment is composed of the decorative member described above. The timepiece may be any of a wristwatch, a table clock, and a wall clock. The timepiece may be any of a light-powered timepiece, a heat-powered timepiece, a radio-controlled self-correcting timepiece, a mechanical timepiece, and a general electronic timepiece. Such a timepiece is manufactured by a known method using the decorative member described above. Wristwatches in particular tend to be easily scratched by rubbing against a shirt or by colliding with a desk, a wall, and the like. Since the timepiece according to the embodiment includes the decorative member described above, it has excellent durability and can maintain its blue color tone and appearance in a very beautiful condition.
The decorative member described above may be included in an ornament other than a watch. Examples of such ornaments include necklaces, pendants, brooches, and glasses. These may be partially or entirely composed of the decorative member described above. Since the ornament contains the decorative member described above, it has excellent durability and can maintain its blue color and appearance in a very beautiful condition.

Based on the above, the present invention relates to the following.
[1] A decorative member in which a first adhesive layer, a second adhesive layer, a hard layer, and an outermost layer are laminated in this order on a substrate, the first adhesive layer containing at least one element selected from Ti and Cr, the second adhesive layer containing at least one element selected from Si and Ge, the hard layer containing DLC and having a thickness of 0.4 μm to 1.2 μm, the outermost layer containing DLC, the hard layer formed on the laminate in which the substrate, the first adhesive layer, and the second adhesive layer are laminated in this order has an L ^* value of 48 to 49 in the L ^* a ^* b ^* color system (CIE 1976), an a* value of 0 to 0.1, and a b ^* value of 1.5 to 1.7, and the outermost layer on the outermost surface of the decorative member has an L ^* value of 48 to 49 in the L ^* a ^* b ^* color system (CIE 1976). A decorative member having an ^a* value of 30 or greater and 31 or less, an a ^* value of 1.1 or greater and 1.7 or less, and a b ^* value of -11 or greater and -9 or less.
[2] The decorative member according to [1], wherein the outermost layer has a thickness of 0.05 μm or more and 0.07 μm or less.
The decorative member according to the above [1] or [2] has excellent hardness and friction coefficient, and has a blue appearance color.
[3] A watch comprising the decorative member according to [1] or [2].
The above watch is highly durable and maintains its blue color and appearance in very good condition.
[4] A method for producing a decorative member in which a first adhesion layer, a second adhesion layer, a hard layer and an outermost layer are laminated in this order on a substrate, the method comprising the steps of: forming, on the substrate, the first adhesion layer containing at least one element selected from Ti and Cr; forming, on the first adhesion layer formed in the first adhesion layer forming step, the second adhesion layer containing at least one element selected from Si and Ge; and applying a voltage of 2 kV or more to the substrate on which the first adhesion layer and the second adhesion layer have been formed by plasma CVD on the second adhesion layer formed in the second adhesion layer forming step. and a surface layer forming step of forming the surface layer containing DLC on the hard layer formed in the hard layer forming step while applying a negative bias voltage of 0.05 kV to 0.4 kV to the substrate on which the first adhesive layer, the second adhesive layer and the hard layer are formed by a plasma CVD method. The hard layer has a thickness of 0.4 μm to 1.2 μm. The hard layer formed on the laminate in which the substrate, the first adhesive layer and the second adhesive layer are laminated in this order has a thickness of 0.4 μm to 1.2 μm. ^a* a ^* b ^* color system (CIE 1976) having an L ^* value of 48 to 49, an a ^* value of 0 to 0.1, and a b ^* value of 1.5 to 1.7, and for the outermost layer at the outermost surface of the decorative member, an L ^* value of 30 to 31, an a* value of 1.1 to 1.7, and a b ^* value of -11 to -9, in the L ^* a ^* b ^* color system (CIE ¹⁹⁷⁶ ).
According to the above-mentioned method for producing a decorative member, a decorative member having excellent hardness and friction coefficient as well as a blue appearance color can be obtained.

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

[Reference example]
Fig. 2 is a diagram for explaining a decorative member of a reference example. Fig. 2 is a schematic cross-sectional view of a decorative member 20. In the decorative member 20, a first adhesive layer 12 (Ti layer), a second adhesive layer 13 (Si layer), and a hard layer 14 (DLC layer) were formed on a base material 11 (SUS substrate).
In the first adhesion layer forming step, a Ti layer having a thickness of 0.2 μm was formed on the SUS substrate by a sputtering method, and in the second adhesion layer forming step, a Si layer having a thickness of 0.2 μm was formed on the Ti layer by a sputtering method.
In the hard layer forming process, a hard layer 14 containing DLC was formed on the Si layer by plasma CVD. Specifically, a substrate on which the Si layer was formed was placed in a vacuum device, and benzene was introduced into the vacuum device as a raw material gas in addition to Ar gas as an inert gas. The pressure inside the device was kept at 0.3 Pa, and benzene was decomposed by plasma CVD to form a DLC layer (hard layer 14) on the Si layer. From the start of film formation to the end of film formation, the negative bias voltage was kept constant at 3.5 kV. In addition, the film formation time in the outermost layer forming process was 90 minutes. In this way, the decorative member 20 was produced.

[Example]
In the example, a decorative member 10 shown in Fig. 1 was produced. That is, a first adhesive layer 12 (Ti layer), a second adhesive layer 13 (Si layer), a hard layer 14 (DLC layer), and an outermost layer 15 (DLC layer) were produced on a base material 11 (SUS substrate).
The hard layer forming process was carried out in the same manner as in the reference example. Next, in the outermost layer forming process, the outermost layer 15 containing DLC was formed on the hard layer 14 by the plasma CVD method. Specifically, in the outermost layer forming process, the substrate on which the hard layer 14 was formed and disposed in the vacuum device was used as it was. In addition, following the hard layer forming process, benzene was introduced as a raw material gas in addition to Ar gas as an inert gas into the vacuum device, and the pressure inside the device was kept at 0.4 Pa. Then, similar to the hard layer forming process, benzene was decomposed by the plasma CVD method to form a DLC layer (outermost layer 15) on the hard layer 14. The negative voltage applied to the substrate in the hard layer forming process was switched to the negative voltage applied to the substrate in the outermost layer forming process instantly, and the negative bias voltage was constant at 0.1 kV from the start of film formation to the end of film formation. In addition, the film formation time in the outermost layer forming process was 10 minutes. In this manner, the decorative member 10 was produced.

<Evaluation method>
[Color tone]
The L ^{* ,} a ^* and b* values in the L*a ^* b ^* color system (CIE 1976) were determined for the hard layer 14 of the decorative member obtained in the Reference Example and the outermost layer 15 of the decorative member obtained in ^the Example. Specifically, a spectrophotometer (CM-2600d, manufactured by Konica Minolta, Inc.) was used to measure the values, with a D65 light source and a viewing angle of 10°.
[Particle size]
The surface of the hard layer 14 of the decorative member obtained in the reference example and the surface of the outermost layer 15 of the decorative member obtained in the example were observed by SEM. Specifically, the observation was performed using a Carl Zeiss Gemini 300 at a sample incidence voltage of 5 kV, WD of 6 mm, and a magnification of 50,000 times. From this, the particle size range was obtained.
[Hydrogen content]
The hydrogen content of the hard layer 14 of the decorative member obtained in the Reference Example and the outermost layer 15 of the decorative member obtained in the Example was measured by RBS-ERDA Rutherford Backscattering Spectrometry-Elastic Recoil Detection Analysis using a Pelletron 3SDH manufactured by National Electrostatics Corporation.
[sp ³ ratio (sp ³ /(sp ³ +sp ² ))]
XPS C1s spectra were obtained for the hard layer 14 of the decorative member obtained in the Reference Example and the outermost layer 15 of the decorative member obtained in the Example. Specifically, an XPS X-ray photoelectron spectrometer (Nexsa, manufactured by Thermo Fisher Scientific) was used to perform waveform separation of the narrow spectrum of C (carbon) to measure the ratio of ^sp3 and ^sp2 .
[Hardness]
The hardness was measured for the hard layer 14 of the decorative member obtained in the reference example and the outermost layer 15 of the decorative member obtained in the example. Specifically, the Vickers hardness HV was measured using a microindentation hardness tester (HM2000XYp, manufactured by FISCHER). A Vickers indenter was used as the measuring probe, and a load of 5 mN was held for 10 seconds, after which the load was removed, and the hardness was calculated from the depth of the Vickers indenter inserted.
[Coefficient of friction]
The friction coefficient (JIS R 1613) was determined for the hard layer 14 of the decorative member obtained in the Reference Example and the outermost layer 15 of the decorative member obtained in the Example. Specifically, a ball-on-disk test was performed using a multi-function friction tester (UMT Tribo Lab, manufactured by Bruker) under the conditions of a load of 5 N, a linear velocity of 0.1 m/s, a sliding radius of 5 mm, and a sliding distance of 1000 m. A SUS304 ball with a diameter of 5 mm was used on the ball side, and a film of the target DLC was formed on SUS316L on the disk side.

<Evaluation Results>
Fig. 3 is a diagram showing the results of SEM observation of the hard layer 14 of the decorative member obtained in the reference example. Fig. 4 is a diagram showing the results of SEM observation of the outermost layer 15 of the decorative member obtained in the example.
Fig. 5 shows an XPS spectrum measured for the hard layer 14 of the decorative member obtained in the reference example. Fig. 6 shows an XPS spectrum measured for the outermost layer 15 of the decorative member obtained in the example.
The evaluation results are shown in Table 1.

Reference Signs List 10, 20 Decorative member 11 Substrate 12 First adhesive layer 13 Second adhesive layer 14 Hard layer 15 Outermost layer

Claims (5)

A decorative member comprising a substrate, a first adhesive layer, a second adhesive layer, a hard layer and an outermost layer laminated in this order on the substrate,
The first adhesion layer contains at least one element selected from Ti and Cr,
the second adhesion layer contains at least one element selected from Si and Ge;
The hard layer contains diamond-like carbon having a hydrogen content of 15 at% or more and 25 at% or less , and has a thickness of 0.4 μm or more and 1.2 μm or less;
the outermost layer contains diamond-like carbon having a hydrogen content of 35 at % or more and 45 at % or less ,
the hard layer formed on the laminate in which the base material, the first adhesive layer and the second adhesive layer are laminated in this order has an L* value of 48 to 49 inclusive, an a* value of 0 to 0.1 inclusive, and a b* value of 1.5 to 1.7 inclusive in the L*a*b* color system (CIE 1976);
A decorative member, wherein the outermost layer of the decorative member has an L* value of 30 or more and 31 or less, an a* value of 1.1 or more and 1.7 or less, and a b* value of -11 or more and -9 or less in the L*a*b* color system (CIE 1976). The decorative member according to claim 1 , wherein the outermost layer has a thickness of 0.05 μm or more and 0.07 μm or less. A watch comprising the decorative member according to claim 1 or 2. A method for producing a decorative member in which a first adhesive layer, a second adhesive layer, a hard layer, and an outermost layer are laminated in this order on a substrate,
a first adhesion layer forming step of forming the first adhesion layer containing at least one element selected from Ti and Cr on the base material;
a second adhesion layer forming step of forming the second adhesion layer containing at least one element selected from Si and Ge on the first adhesion layer formed in the first adhesion layer forming step;
a hard layer forming step of forming the hard layer containing diamond-like carbon on the second adhesive layer formed in the second adhesive layer forming step by a plasma CVD method while applying a negative bias voltage of 2 kV to 5 kV to the base material on which the first adhesive layer and the second adhesive layer are formed;
and a surface layer forming step of forming the surface layer containing diamond-like carbon on the hard layer formed in the hard layer forming step while applying a negative bias voltage of 0.05 kV or more and 0.4 kV or less to the base material on which the first adhesive layer, the second adhesive layer and the hard layer are formed by a plasma CVD method,
The hard layer has a thickness of 0.4 μm or more and 1.2 μm or less,
the hard layer formed on the laminate in which the base material, the first adhesive layer and the second adhesive layer are laminated in this order has an L ^* value of 48 to 49 inclusive, an a ^* value of 0 to 0.1 inclusive, and a b ^* value of 1.5 to 1.7 inclusive in the L ^* a ^* b ^* color system (CIE 1976);
A method for manufacturing a decorative member, wherein the outermost layer on the outermost surface of the decorative member has an L ^* value of 30 to 31, an a ^* value of 1.1 to 1.7, and ^{a b *} value of -11 to -9 in the L ^* a*b* color system (CIE 1976). A decorative member comprising a substrate, a first adhesive layer, a second adhesive layer, a hard layer and an outermost layer laminated in this order on the substrate,
The first adhesion layer contains at least one element selected from Ti and Cr,
the second adhesion layer contains at least one element selected from Si and Ge;
The hard layer is sp ³ Ratio (sp ³ /(sp ³ +sp ² )) contains 28% or more and 35% or less of diamond-like carbon, and has a thickness of 0.4 μm or more and 1.2 μm or less;
The outermost layer is sp ³ Ratio (sp ³ /(sp ³ +sp ² )) contains diamond-like carbon in an amount of 29% or more and 36% or less,
the hard layer formed on the laminate in which the base material, the first adhesive layer and the second adhesive layer are laminated in this order has an L* value of 48 to 49 inclusive, an a* value of 0 to 0.1 inclusive, and a b* value of 1.5 to 1.7 inclusive in the L*a*b* color system (CIE 1976);
The outermost layer of the decorative member has an L* value of 30 or more and 31 or less, an a* value of 1.1 or more and 1.7 or less, and a b* value of -11 or more and -9 or less in the L*a*b* color system (CIE 1976).
Decorative materials.

Images