JP3512597B2 - Decorative material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative member coated with a hard carbon film, and more particularly to an improvement of a decorative member such as a watch case, a band outer part, a necklace, a pierced earring, an eyeglass frame, and a fishing tackle.

[0002]

2. Description of the Related Art Conventional decorative members are used by processing natural minerals. However, if the human body touches the decorative member directly, and sweat or the like is exposed, or if it is exposed to seawater or rain, it will be corrosion-resistant, or will be cracked or chipped by an external impact. There is a problem.

In order to solve such problems, recently, colored ceramics such as zirconia and alumina having excellent corrosion resistance and scratch resistance, WC, TiC, T
A technology of using a sintered alloy having a gold color or a silver color such as iN has been developed.

[0004]

However, the above-mentioned colored ceramics and sintered alloys have a problem that even if they exhibit a color peculiar to the material, they are monochromatic and lack decorativeness. So, to further enhance the decorativeness,
Partial coatings or combinations of pears and mirrors have been used, but the decorative effect has not been improved to a satisfactory degree, and the manufacturing cost has increased.

On the other hand, there has been proposed a technique of coating a diamond film on a substrate such as a ceramic or a sintered alloy by a thin film forming method such as a thermal CVD method, a microwave CVD method, and an arc plasma jet method. This film has a high-purity diamond structure in which carbon atoms are bonded by SP ³ hybridization, and excellent wear resistance can be achieved due to the large diamond crystal grains (size of several μm or more). On the other hand, the surface is uneven (Rmax> 1 μm).
m) In addition, since a large amount of voids were present, light was scattered on the surface, whereby interference colors such as shining seven colors were not generated, and the decorativeness was still poor.

Further, the diamond film needs to be mirror-finished for decoration by forming irregular surface textures by large crystal grains. However, since the film itself is very high in hardness and high in strength, the surface processing is difficult. There is also a problem that it is difficult.

Further, since many voids are present in the film, when exposed to sweat or seawater for a long time, metal components in the base are eluted, and allergy such as inflammation of the skin due to contact with the skin has occurred. Was.

In view of the above circumstances, the present inventor has made intensive studies and found that the diamond crystal grains in the film were reduced to form a dense hard carbon film, and that the thickness of the film was defined. It has been found that decorative properties that shine in seven colors can be obtained while having the color tone of the substrate.

Accordingly, the present invention has been accomplished based on the above findings, and an object of the present invention is to provide a decorative member which exhibits a color tone peculiar to a substrate and shines in seven colors.

It is another object of the present invention to provide a decorative member which is excellent in abrasion resistance, has high hardness to prevent scratches, and eliminates allergic reaction to a human body.

It is still another object of the present invention to provide a decorative member that requires no or less surface processing and that has a reduced manufacturing cost.

[0012]

According to the present invention, there is provided a decorative member comprising:
A hard phase mainly composed of C, TiCN, TiN, and TiC is combined with a binder phase composed of an iron group metal such as Ni or Co by 1 to 2 times.
Cemented carbide containing about 0% by weight, TiC-based cermet,
On a sintered substrate composed of a TiCN-based cermet and a TiN-based cermet, a wavelength of 1500 in Raman spectrum
± 60 cm ^-1 and 1160 ± 40 cm ^-1 and wavelength 134
Having each peak of 0 ± 40 cm ⁻¹ and 116
Assuming that the highest peak intensity among peaks existing at 0 ± 40 cm ⁻¹ is H ₁ and the highest intensity peak among 1340 ± 40 cm ⁻¹ is H ₂ , H ₁ / H ₂ The peak intensity ratio represented by
1, a hard carbon film having a density of 3.1 g / cm ³ or more, a diamond precursor, a diamond crystal having an average crystal grain size of 1 μm or less, and an amorphous carbon phase, and having a surface roughness of Ra 0.05 μm or less. .15-2.
It is characterized by being coated with a thickness of 0 μm.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Configuration of Decorative Member The decorative member of the present invention will be described in detail with reference to FIGS. 1 and 2 are cross-sectional views of the decorative member of the present invention. FIGS. 3 and 4 are examples of application of the decorative member of the present invention.
Is a watch case.

In the decorative member 1 shown in FIG. 1, reference numeral 2 denotes a substrate on which a film is applied as the sintered substrate, and reference numeral 3 denotes a hard carbon film.
Further, in the decorative member 4 of FIG. 2, a partial region of the hard carbon film 3, that is, a layer region including a contact surface with the substrate 2 is configured as a contact region 5 with the substrate 2.

The base 2 is made of a sintered alloy or ceramics. This sintered alloy has a hard phase mainly composed of WC, TiCN, TiN and TiC and a binder phase composed of an iron group metal such as Ni or Co. Cemented carbide containing about 20% by weight,
TiC-based cermet, TiCN-based cermet, and TiN-based cermet.

The hard carbon film 3 is formed by placing the substrate 2 in a reaction apparatus and using a thermal CVD method, a microwave CVD method, an electron cyclotron resonance plasma CVD method or the like. The CVD method (ECR plasma CVD method) is preferable.

The hard carbon film 3 is made of diamond.
± 40 cm ⁻¹ , 1340 ± 40 cm ⁻¹ and 1500 ±
There are three peaks at 60 cm ^-1 . 1160 ± 40c
The peak at m ^-1 indicates a diamond precursor or polyene structure, and is a very fine crystal. Also, 1340
The peak at ± 40 cm ⁻¹ indicates a diamond crystal at 1500
The peak at ± 60 cm ^-1 indicates an amorphous carbon phase.

The hard carbon film 3 is composed of an ultrafine diamond precursor (or polyene structure), a diamond crystal and an amorphous carbon phase as described above, and has a density of 3.1 g / cm ³ or more due to the composite composition thereof. A good film is obtained.

Such diamond crystals are extremely fine, and these fine crystals enter the amorphous carbon phase to form a highly dense film having almost no voids. The average crystal grain size of the fine crystals was measured using a transmission electron microscope (TEM).
For example, it is about 40 nm.

As described above, since the phase of the diamond precursor is present together with the amorphous carbon phase in a small amount, the compressive stress remaining in the film is reduced despite the complete dense film, and there is no distortion of the film. Adhesion is ensured. Although the reason for the decrease in internal stress cannot be escaped from the range of inference, it is considered that some stress relaxation mechanism acts.

The composition of the hard carbon film 3 is related to the density, and it was confirmed that the main component was crystalline by performing a flotation method and a density measurement using fluorescent X-rays. That is, the density of the diamond crystal is 3.52 g / cm ³ , and the density of the diamond precursor (or polyene structure) phase and the amorphous carbon phase is 1.8 g / cm ³ or less. By setting the density of the film 3 to 3.1 g / cm ³ or more, 76% or more of diamond crystals are present in the film. Further, the film density is 3.3 to 3.4 g / c.
In the case of m ^3, the diamond crystals at least 89 to 93% is present in the film.

Further, the hard carbon film 3 does not show surface irregularities caused by a relatively large diamond crystal as in the prior art, and is excellent in flatness. Therefore, it is not necessary to flatten the surface, and mirror finishing can be performed. Even if it does, it can be easily processed in a short time. Incidentally, the surface roughness Ra of the hard carbon film 3 became 0.05 μm or less. Moreover, the hardness Hv of the hard carbon film 3 is 8000 kgf / mm.
² or more. Note that a smooth surface can be obtained for a film containing only the amorphous carbon phase, but 3000 kg
The hardness is f / mm ² or less, the compressive stress in the film is large, and peeling, wrinkling, and floating of the film are observed.

The contact region 5 of the decorative member 4 shown in FIG. 2 is composed of at least a composite of diamond and metal carbide. In the case of this composition, the adhesion is improved for the following reasons. In other words, atoms are bonded by interposing electrons, but a covalent bond, in which electrons are shared by both atoms, generally has a stronger binding force than an ionic bond, and diamond has a stronger binding force, particularly in diamond. Therefore, in order to improve the adhesion strength between the diamond film and the different compound, it is preferable to interpose a covalent compound having a similar bonding mode between the two. Therefore, a compound containing carbon, which is a diamond component, is better in terms of consistency, and a metal carbide is preferably used. The metal carbide includes silicon carbide and boron carbide as a covalent carbide, and silicon carbide is particularly desirable. In addition, the diamond and the metal carbide are not separated from each other, but have a structure in which the metal carbide surrounds the diamond (a structure in which diamonds are distributed in an island shape). improves.

In the decorative members 1 and 4 having the above-described structure, the hard carbon film 3 is formed to have a thickness of 0.15 to 2.0 μm, preferably 0.3 to 1.0 μm, so that the incident natural light Arrives at the base 2, the reflected light and the incident light interfere,
This makes it glow in seven colors. When the thickness is reduced to this level, the unique color tone of the base 2 can be seen from the outside, and the decorativeness is further improved by the color tone and the interference light. When the thickness of the hard carbon film 3 exceeds 2.0 μm,
Such interference light does not sufficiently appear, and is 0.15 μm
If it is less than this, a dense film cannot be obtained. In using such a substrate 2, it is preferable that the reflectance to natural light be at least 50% or more.

The film forming means and said hard carbon film 3 is formed by a plasma CVD method or a thermal filament CVD method, especially ECR plasma CVD method is preferred. That is, according to the ECR plasma CVD method in which a magnetic field is further applied to the plasma generation region in the plasma CVD method, low pressure (1 to
A high-density plasma can be obtained at a gas pressure of rr or less, and the plasma can be uniformly generated in a wide area. As a result, a uniform film is formed in an area about 10 times as large as that of a normal plasma CVD method. Can be formed.

On the other hand, the microwave CVD method has a small coating area due to a small plasma generation area and usually has a diameter of about 20 mm, and its application as a processing member is limited. In addition, if the pressure is too high or the plasma density is too low, if the substrate has a complicated structure or a substrate having a curved structure, a uniform plasma suitable for such a structure cannot be obtained. The film thickness distribution tends to be non-uniform.

On the other hand, in the hot filament CVD method, the filament is easily cut, and it is necessary to set the filament in accordance with the shape of the substrate in order to control the variation in the film thickness. Therefore, the apparatus lacks versatility.

Hereinafter, the ECR plasma CVD method will be described in detail. When a reaction gas is introduced into a reaction furnace in which a substrate having a predetermined shape is installed, a microwave of 2.45 GHz is introduced at the same time, and a magnetic field of 875 Gauss or more is applied, the electron cyclone frequency f = eB / 2πm ( However,
Cyclone motion occurs based on (m: electron mass, e = electron charge, B: magnetic flux density). When this frequency coincides with the microwave frequency (2.45 GHz), resonance occurs, and electrons are remarkably absorbed by the microwave energy, accelerated, and collide with neutral molecules, thereby causing ionization.
As a result, high-density plasma is generated. The substrate temperature was 150 to 1000 ° C., and the furnace pressure was 1 × 10 ^{−2 to} 1 t.
orr.

According to this method, the constituents of the hard carbon film and the like are changed by changing the substrate temperature, the furnace pressure and the reaction gas concentration during the film formation. Specifically, as the pressure in the furnace increases, the plasma region becomes smaller and the growth rate of the film decreases, but on the other hand, the crystallinity improves. On the other hand, when the reaction gas concentration increases, the particle size of the film decreases,
Crystallinity deteriorates.

As a raw material gas, a hydrogen gas and a carbon-containing gas are used. This carbon-containing gas includes, for example, alkanes such as methane, ethane, and propane, ethylene, propylene,
Alkenes, acetylenes, aromatic hydrocarbons such as benzene, cycloparaffins such as cyclopropane, and cycloolefins such as cyclopentene.
Also, oxygen-containing carbon compounds such as carbon monoxide, carbon dioxide, methyl alcohol and acetone, and nitrogen-containing carbon compounds such as mono (di, tri) methylamine and mono (di, tri) ethylamine are used as carbon source gases. You may. And
These various gases are used alone or in combination.

Further, in order to form the adhesion region 5 for further improving the adhesion, if necessary, a diamond nucleus generation treatment (once a single crystal of diamond is grown on the substrate in a dot-like manner) is carried out. As the gas, a hydrogen gas, a carbon-containing gas and a silicon-containing gas are introduced. Examples of the silicon-containing gas include halides such as silicon tetrafluoride, silicon tetrachloride, and silicon tetrabromide, oxides such as silicon dioxide, and mono (di, tri, tetra, penta) silane, mono, (di, There are silane compounds such as tri (tetra) methylsilane and silanol compounds such as silanol such as trimethylsilanol. These may be used alone or in combination.

According to the decorative member 1 thus obtained, the hard carbon film 3 is mainly composed of diamond having a fine grain structure, is dense, has no void defects on the film surface and inside, and has excellent smoothness. I have. Therefore, when the surface of the member that touches the human skin is coated with the hard carbon film 3, high corrosion resistance is obtained. In particular, the occurrence of local corrosion on voids or the like due to sweat or acid rain is prevented. When the adhesion region 5 is provided on the base 2, the adhesion of the hard carbon film 3 can be further enhanced, and the hard carbon film 3 is not peeled off. Moreover, FIG.
A smooth and dense film could be formed on the surface of a substrate of any shape, such as a band piece, a substrate having a complicated structure, such as a watch case of FIG. 4, and a substrate having a curved surface structure.

[0033]

Next, an embodiment of the present invention will be described. In a furnace of an ECR plasma CVD apparatus, a cemented carbide (80
% WC-10% by weight Co-10% by weight Ni), Ti
C-based cermet (80% by weight TiC-15% by weight Cr ₂
C ₂ -5 wt% Ni) or TiN-based cermet (85 wt% TiN-15 wt% Ni)
ml container was set up.

Then, H ₂ gas is introduced at a flow rate of 97 sccm, CH ₄ gas is introduced at a flow rate of 3 sccm, the gas concentration is set to 1%, the substrate temperature is set to 650 ° C., the furnace pressure is set to 0.1 torr, and plasma is applied for 1.5 hours. To generate diamond nuclei, and thereafter, H ₂ gas, CH _2
4 gas and Si (CH ₃ ) ₄ gas at 297
Introduced at a flow rate of sccm, 3 sccm, 0.3 sccm, and applied a magnetic field of a maximum of 2 kGauss by ECR plasma CVD under the conditions of a gas concentration of 1%, a substrate temperature of 650 ° C., and a furnace pressure of 0.5 torr. Film was formed for 12 hours under the condition of microwave power of 3.0 KW.
An adhesion region 5 having an average film thickness of 0.5 μm in which diamond and silicon carbide were mixed was formed on the inner surface of the container.

Next, H ₂ gas, CH ₄ gas, and CO ₂ gas having a purity of 99.9% or more were introduced onto the contact region 5 at flow rates of 210 sccm, 30 sccm, and 60 sccm, respectively, and a gas concentration of 30% At a temperature of 650 ° C. and a furnace pressure of 0.1 torr or 0.01 torr, a film was similarly formed with a thickness of 0.5 μm.

The Raman spectrum of the hard carbon film 3 (thickness: 1 μm) was measured, and the results shown in FIG. 3 were obtained. As is clear from the figure, peaks at wavelengths of 1500 ± 60 cm ⁻¹ , 1160 ± 40 cm ^−1, and 1340 ± 40 cm ⁻¹ were confirmed. Also,
When the density of the film was measured by the floating and sedimentation method using an aqueous solution of thallium formate, when the pressure in the furnace was 0.1 torr, 3.
3.2 g at 3 g / cm ³ and 0.01 torr
g / cm ³ .

In the hard carbon film 3 having the above structure,
When the color tone and the film pressure strength were measured while changing the film thickness as shown in Table 1, the results shown in the table were obtained.

[0038]

[Table 1]

As for the color tone, the color tone peculiar to the substrate is shown.
Furthermore, the state that has become shining in seven colors is classified, and
In the case of the best color state, ○ is a color state in which the color is slightly shining, whereas △ is a case where almost no interference light is generated, and X is a case where it is almost black.

The film pressure strength was evaluated based on the adhesion strength by an indenter, and was classified into four types according to the film peeling start load.
○○ If it is not peeling any even with a load of 50kgf / cm ² or more ,, ○ is 10kgf / cm ² or more, 50
When peeled off with a load of less than kgf / cm ² , △ is 1k
When the film was peeled off with a load of gf / cm ² or more and less than 10 kgf / cm ² , X was obtained when the film was peeled off with a load of 1 kgf / cm ² or less.

As is clear from Table 1, the sample N of the present invention
o. With regard to 2 to 6, both the color tone and the film pressure strength were good. Sample No. For No. 1, both the color tone and the film pressure strength were good, but the thickness of the carbon film was extremely thin, so that the film was dense.

FIG. 5 shows a Raman spectrum chart for the hard carbon film 3 according to the present invention. In FIG. 5, peaks at wavelengths of 1500 ± 60 cm ⁻¹ , 1160 ± 40 cm ⁻¹ and 1340 ± 40 cm ⁻¹ are present. I understand. Therefore, the peak intensity at 1160 ± 40 cm ⁻¹ is 11
Pull the hatched between positions 00cm ^-1 and 1700 cm ^-1, which as a baseline, there the highest peak intensity of the intensity of the peaks present in 1160 ± 40 cm ^-1 in H _1, 1340 ± 40cm ^-1 When the highest peak intensity among the peaks is H ₂ , H ₁ /
Peak intensity ratio represented with H ₂ is 0.05 or more, preferably better to 0.2-1.0.

That is, when the peak intensity ratio is less than 0.05, diamond crystal grains grow too large, voids are generated in the film, or the surface roughness of the film becomes large. Corrosion easily progresses.
On the other hand, if the peak intensity ratio is too large, the ratio of diamond crystals decreases, resulting in a decrease in film strength. . This H ₁
The peak intensity ratio represented by / H ₂ is preferably 1.0 or less.

In this Raman spectroscopy spectrum, a peak is located at 1500 ± 60 cm ⁻¹ , and when the highest peak intensity among peaks in the region is H ₃ , H ₁ <H ₂ <H ₃ It is desirable that the above relationship be satisfied. This peak indicates the amorphous carbon phase existing between the diamond crystals. However, when the intensity of H ₃ is low, and when H ₁ > H ₃ or H ₂ > H ₃ , the denseness of the film is reduced and the allergic source This is because the metal is eluted.

Incidentally, 1340 ± 40 by Raman spectroscopy.
The reason ^why cm ⁻¹ is hard to be confirmed is due to the size effect (the peak becomes difficult to appear as the crystal size decreases) and the fact that the sensitivity to the amorphous carbon phase is much higher than that of diamond.

[0046]

As described above, according to the decorative member of the present invention, the wavelength of 150 nm in the Raman spectrum is provided on the substrate.
0 ± 60cm ^-1 and 1160 ± 40cm ^-1 and wavelength 1340
Each having a peak of ± 40 cm ^-1 and a density of 3.1 g / cm ³
By coating the above hard carbon film with a thickness of 0.15 to 2.0 μm, it shows a unique color tone of the base, and further shines in seven colors, watch exterior parts, necklaces, piercings, eyeglass frames, fishing gear, buttons, A decorative member such as a broach could be provided.

According to the present invention, the abrasion resistance is excellent.
A low-cost decorative member that has high hardness that is resistant to scratching, that eliminates allergic reactions to the human body, and that does not require or reduce surface processing can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative member of the present invention.

FIG. 2 is a sectional view of another decorative member of the present invention.

FIG. 3 is a perspective view of a band piece as a decorative member of the present invention.

FIG. 4 is a perspective view of a watch case as a decorative member of the present invention.

FIG. 5 is a Raman spectrum chart of a hard carbon film according to the present invention.

[Explanation of symbols] 1, 4 decorative members 2 Substrate 3 Hard carbon film 5 Adhesion area

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A44C 5/00-5 / 24,25 / 00 C23C 16/26

Claims (1)

(57) [Claims] 1. Mainly WC, TiCN, TiN, TiC
Made of iron group metals such as Ni and Co
Cemented carbide containing about 1 to 20% by weight of binder phase, TiC
Base cermet, TiCN base cermet, TiN base cermet
Yes Then Tomo each peak of Tsu in the Raman spectrum on the substrate made of a preparative wavelength 1500 ± 60cm ^-1 1160 ± 40cm ^-1 and a wavelength 1340 ± 40 cm ^-1
Of the peaks existing at 1160 ± 40 cm ⁻¹
The high strength peak intensity _H 1, 1340 ± 40cm
Peak intensity of the highest intensity among peaks existing at ^-1
When was the _{H 2,} the peak represented by H 1 / _{H 2} Strength
The ratio is 0.2 to 1, the density is 3.1 g / cm ³ or more ,
Diamond precursor, diamond with an average crystal grain size of 1 μm or less
Consisting of Mondo crystal and amorphous carbon phase,
A decorative member formed by coating a hard carbon film having a surface roughness of Ra 0.05 μm or less with a thickness of 0.15 to 2.0 μm.