JP2001301400A - Base material having hard decoration film and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate not only a damage to a decorative film but also a ruggedness on a surface of a base material. SOLUTION: The base material made of a titanium or a titanium alloy comprises an internal cured layer having a first cured layer for a solid solution of a nitrogen and an oxygen to be formed from a front surface toward an interior and a second cured layer formed from the first layer toward an interior, and a hard decorative film formed to cover the surface of the internal cured layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base material such as a camera body, a portable telephone body, a portable radio body, a video camera body, a writer body, and a personal computer body made of titanium or a titanium alloy. In particular, the present invention relates to a substrate having an internal hardened layer, a decorative hard film on the surface of the internal hardened layer, and a technique of a manufacturing method thereof.

[0002]

2. Description of the Related Art Currently, camera bodies, mobile phone bodies,
Watch case, portable radio body, video camera body,
For a lighter body, a personal computer body, and the like, a base material made of titanium or a titanium alloy is often used because of corrosion resistance and weight reduction. In addition, this material had a low hardness and was easily scratched, and the color was gray. In order to solve this problem, there is a substrate in which a hard coating such as titanium nitride is coated on a substrate surface by dry plating.

[0003]

The substrate having the hard coating has a color tone (gold) and is hardly damaged. However, this hard coating generally has
When a strong force is applied to the surface of the coating film, the coating film is not scratched, but the material is deformed and irregularities may be formed on the substrate surface. Further, when the unevenness is large, the coating may be peeled off due to the internal stress of the coating.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, not only to prevent the decorative coating from being scratched even when a strong force is applied to the coating surface, and also to prevent irregularities on the substrate surface. An object of the present invention is to provide a substrate having a hard decorative film and a method for producing the same, which can minimize peeling of the film.

[0005] A second object of the present invention is to provide a substrate having a hard decorative film made of a titanium or titanium alloy substrate having an excellent appearance quality capable of keeping the surface beautiful even when used for a long period of time, and its production. It is to provide a method.

[0006]

Means for Solving the Problems In order to achieve the above-mentioned object, a substrate having a hard coating according to the first aspect of the present invention, wherein the substrate is made of titanium or a titanium alloy, The base material is a first solid solution of nitrogen and oxygen formed at an arbitrary depth from the surface toward the inside.
And a second hardened layer formed at an arbitrary depth from the first hardened layer toward the inside, and a hard decoration coated on the surface of the inner hardened layer And a coating.

[0007] The substrate having the hard decorative coating according to the second aspect of the present invention is the substrate having the hard decorative coating according to the first aspect, wherein the internal cured layer is a first cured layer,
0.68.0 W% of nitrogen and 1.0 to 14.0 W% of oxygen are dissolved in the solid solution, and 0.5 to 14.0 W% of oxygen is dissolved in the second hardened layer. Features.

[0008] The substrate having the hard decorative coating according to the third aspect of the present invention is the substrate having the hard decorative coating according to the first aspect, wherein the internal cured layer formed on the substrate is:
A first hardened layer is formed in a range of about 1 μm from the surface to the inside, and the second hardened layer is deeper than the first hardened layer and in a range of about 20 μm from the surface to the inside. It is characterized by being formed.

Further, the base material having the hard decorative coating according to the invention of claim 4 is the base material having the hard decorative coating according to claim 1, wherein the hard decorative coating is a base material of the periodic table.
It is characterized by being a nitride, carbide, oxide, nitrocarbide or nitrocarboxylate of a, 5a or 6a group element.

[0010] The substrate having a hard decorative coating according to the invention of claim 5 is the substrate having a hard decorative coating according to claim 1, wherein the hard decorative coating is a hard carbon coating. I do.

A substrate having a hard decorative coating according to the invention of claim 6 is the substrate having a hard decorative coating according to claim 5, wherein the internal hardened layer formed on the substrate and the hard decorative coating are provided. And an intermediate layer having a two-layer structure including a lower layer mainly composed of chromium or titanium and an upper layer mainly composed of silicon or germanium.

A substrate having a hard decorative coating according to the invention of claim 7 is the substrate having a hard decorative coating according to claim 5, wherein the internal hardened layer formed on the substrate and the hard decorative coating are provided. And a lower layer mainly composed of titanium and an upper layer mainly composed of any one of tungsten, tungsten carbide, silicon carbide and titanium carbide.
It has an intermediate layer having a layer structure.

The base material having the hard decorative coating according to the invention of claim 8 is the first, fourth or fifth aspect of the present invention.
The base material having the hard decorative film according to the above, wherein the hard decorative film is formed in a range of 0.1 to 3.0 μm.

Further, the base material having the hard decorative film according to the ninth aspect of the present invention is the base material of the first, fourth or eighth aspect.
The substrate having the hard decorative film according to the above, wherein the surface of the hard decorative film exhibits a golden color tone.

According to a tenth aspect of the present invention, there is provided a substrate having a hard decorative film according to the ninth aspect, wherein the surface of the hard decorative film has a golden color tone. And

Further, the substrate having a hard decorative coating according to the invention of claim 11 is a substrate having the hard decorative coating according to claim 1, 2 or 3, wherein the base having the hard decorative coating is provided. The material is one of a camera body, a mobile phone body, a portable radio body, a video camera body, a writer body, and a personal computer body.

In order to achieve the above-mentioned object, a method of manufacturing a substrate having a hard decorative coating according to the invention of claim 12 of the present invention comprises disposing a substrate made of titanium or a titanium alloy in a vacuum chamber. Then, a heating step of annealing treatment and a mixed gas mainly composed of nitrogen containing a small amount of oxygen component are introduced into the vacuum chamber, and the inside of the vacuum chamber is 700 to
By heating at a temperature of 800 ° C. for a predetermined time, a hardening treatment step of diffusing and solidifying nitrogen and oxygen from the surface of the titanium or titanium alloy substrate to the inside thereof, and bringing the titanium or titanium alloy substrate to room temperature A cooling step of cooling, a polishing step of polishing the surface of the base material, a cleaning step of cleaning the base material, an evacuation step of setting and evacuation of the base material in a vacuum chamber, An ion bombarding step of introducing and ionizing argon to bombard the surface of the substrate, a step of forming an intermediate layer made of metal or metal carbide by sputtering on the surface of the substrate, and argon in the vacuum chamber. Exhausting a gas containing carbon into the vacuum chamber, generating plasma in the vacuum chamber, and performing plasma CVD on the surface of the intermediate layer. Forming a tire Mondo like carbon coating, characterized in that it consists of.

According to a thirteenth aspect of the present invention, in the method of manufacturing a substrate having a hard decorative coating according to the twelfth aspect, the step of forming the intermediate layer comprises the steps of: Argon is introduced into the vacuum chamber to be ionized, and any one of silicon, tungsten, titanium carbide, silicon carbide, and chromium carbide is targeted, and any one of silicon, tungsten, titanium carbide, silicon carbide, and chromium carbide is targeted. It is characterized by one being the subject.

According to a fourteenth aspect of the present invention, in the method of manufacturing a substrate having a hard decorative film according to the twelfth aspect, the step of forming the intermediate layer includes the steps of: A first intermediate layer forming step of introducing argon into the vacuum chamber to ionize, targeting chromium or titanium, and forming a lower layer mainly composed of chromium or titanium, and subsequently, silicon or germanium is formed. A second intermediate layer forming step of forming an upper layer mainly composed of silicon or germanium as a target.

According to a fifteenth aspect of the present invention, in the method of manufacturing a substrate having a hard decorative film according to the twelfth aspect, the step of forming the intermediate layer comprises: A first intermediate layer forming step of introducing and ionizing argon into the vacuum chamber to form a lower layer mainly composed of titanium with titanium as a target, and following this step, using tungsten as a target and A second intermediate layer forming step of forming an upper layer,
It is characterized by consisting of.

In the method for producing a substrate having a hard decorative film according to the present invention, the step of forming the intermediate layer may comprise: A first intermediate layer forming step of introducing and ionizing argon into the vacuum chamber to form a titanium-targeted lower layer with titanium as a target, and subsequent to this step, including carbon in the vacuum chamber A second intermediate layer forming step of forming an upper layer mainly containing tungsten carbide or silicon carbide by introducing a gas and targeting tungsten or silicon.

In order to achieve the above-mentioned object, a method of manufacturing a substrate having a hard decorative coating according to the invention of claim 17 of the present invention comprises disposing a substrate made of titanium or a titanium alloy in a vacuum chamber. Then, a heating step of annealing treatment and a mixed gas mainly composed of nitrogen containing a small amount of oxygen component are introduced into the vacuum chamber, and the inside of the vacuum chamber is 700 to
By heating at a temperature of 800 ° C. for a predetermined time, a hardening treatment step of diffusing and solidifying nitrogen and oxygen from the surface of the titanium or titanium alloy substrate to the inside thereof, and bringing the titanium or titanium alloy substrate to room temperature A cooling step of cooling, a polishing step of polishing the surface of the base material, a cleaning step of cleaning the base material, an evacuation step of setting and evacuation of the base material in a vacuum chamber, An ion bombarding step of introducing argon to ionize and ion bombarding the surface of the base material, and applying an ion plating or sputtering treatment to the surface of the base material to form a 4
forming a hard decorative coating made of a nitride, carbide, oxide, nitrocarbide or nitrocarboxylate of a, 5a, or 6a group element.

[0023] According to a eighteenth aspect of the present invention, there is provided a method of manufacturing a substrate having a hard decorative coating according to the seventeenth aspect of the present invention. The production method is characterized in that after the step of forming the hard decorative film, a step of forming a gold or gold alloy film on the surface of the hard decorative film by ion plating or sputtering.

DESCRIPTION OF THE PREFERRED EMBODIMENTS (First Embodiment for Forming Internal Hardened Layer) First, an internal hardened layer formed on a substrate made of titanium or a titanium alloy and a method for forming the same will be described. . The inner hardened layer has a first hardened layer formed at a desired depth from the surface of the base material toward the inside to dissolve nitrogen and oxygen, and an inner hardened layer at a certain depth from the first hardened layer toward the inside. And a second hardened layer formed in this manner. Reference is made to FIGS. 1 to 5 for this description.

As shown in FIG. 2, an internal hardened layer 101 is formed on the surface of a substrate 100 made of titanium or a titanium alloy. This internal hardened layer 101
It extends from the surface to a depth of approximately 20 μm. The internal hardened layer 101 is divided into a first hardened layer 102 in which nitrogen 104 and oxygen 105 are dissolved, and a second hardened layer 103 in which oxygen 105 is dissolved. The first hardened layer 102 is recognized in a region from the surface to a depth of about 1 μm, and the deeper region is the second hardened layer 103. The first hardened layer 102 in which nitrogen 104 and oxygen 105 are dissolved is particularly high in hardness and has a function of preventing the member surface from being damaged. Also, the second cured layer 10
No. 3 has a function of extending the curing range to the deep part of the member and improving the impact resistance.

As described above, the first solid solution of nitrogen and oxygen
By forming the internal hardened layer with the hardened layer of No. 1 and the second hardened layer in which oxygen was dissolved, it became possible to obtain excellent appearance quality without surface roughness and sufficient hardness. Here, the range of solid solution of nitrogen and oxygen is
The first cured layer contains 0.6 to 8.0% by weight of nitrogen;
Oxygen was 1.0-14.0% by weight. In the second cured layer, oxygen was 0.5 to 14.0% by weight. Therefore, it is preferable to dissolve as much nitrogen or oxygen as possible within the above-mentioned range where solid solution is possible. However, from the viewpoint of maintaining good appearance quality, it is necessary to select a solid solution concentration of nitrogen or oxygen within a range that does not cause surface roughness.

The first hardened layer in which nitrogen and oxygen are dissolved is preferably formed at a depth of about 1.0 μm from the surface of the member. By forming the first hardened layer at such a depth, it was possible to suppress surface roughness due to coarsening of crystal grains and to obtain sufficient surface hardness. On the other hand, the second hardened layer that dissolves oxygen is preferably formed in a region deeper than the first hardened layer to a depth of approximately 20 μm. By forming the second hardened layer at such a depth, the surface hardness can be further improved.

Next, an outline of the surface treatment apparatus used in this embodiment will be described. The surface treatment apparatus shown in FIG. 3 mainly includes a vacuum chamber 1. Inside the vacuum chamber 1, a tray 2 on which titanium or the base material 100 is placed, and a heater 3 as heating means are provided. Further, a gas introduction pipe 4 and a gas exhaust pipe 5 are connected to the vacuum chamber 1.
The gas introduction pipe 4 communicates with a gas supply source (not shown). A gas introduction valve 6 is provided at an intermediate portion of the gas introduction pipe 4.
The required gas can be introduced into the inside. On the other hand, the gas exhaust pipe 5 is in communication with the vacuum pump 7 so that the gas in the vacuum chamber 1 can be sucked and exhausted by the suction force of the vacuum pump 7. An electromagnetic valve 8 for controlling execution / stop of the vacuum suction operation is provided at an intermediate portion of the gas exhaust pipe 5. Further, an atmosphere opening pipe 9 is connected to the vacuum chamber 1, and the pressure in the vacuum chamber 1 can be set to the atmospheric pressure by opening a vent valve 10 provided at an intermediate portion of the pipe 9.

Next, the surface treatment method will be described. The surface treatment method according to this embodiment includes the following steps. (1) A heating step of arranging titanium or the base material 100 in a vacuum chamber and heating and annealing. (2) After the heating step, a mixed gas mainly composed of nitrogen containing a trace amount of an oxygen component is introduced into the vacuum chamber, and the inside of the vacuum chamber 1 is heated at a temperature of 700 to 800 ° C. for a predetermined time under a predetermined reduced pressure. A curing process in which nitrogen and oxygen are diffused and solid-solved from the surface of the substrate 100 to the inside by heating; (3) A cooling step of cooling the substrate 100 to room temperature after the curing step.

The heating step is a step in which the base material 100 is heated and annealed for the purpose of relaxing a work strain layer generated on the surface of the base material 100 by hot forging or subsequent polishing. . The processing strain layer generated by the polishing process is
The stress during the polishing process remains as lattice strain, and is in an amorphous phase or in a state in which crystallinity is reduced. When the next hardening process is performed on the polished base material 100 without performing the annealing process, in the same hardening process, diffusion and solid solution of nitrogen and oxygen are performed while relaxing the work strain layer. Will progress.

As a result, the amount of reaction between nitrogen and oxygen on the surface of the substrate 100 increases, the amount of diffusion and solid solution into the inside decreases, and nitrides and oxides as coloring substances are formed near the surface. You. The formation of these coloring substances is not preferable because it deteriorates the appearance quality. For this reason, in the present embodiment, a heating step is inserted before the curing step to remove processing strain in advance, thereby promoting solid solution of nitrogen and oxygen in the curing step. This heating step is preferably performed under reduced pressure in which the inside of the vacuum chamber is evacuated. Alternatively, it is preferable that the evacuation is performed under a reduced pressure in which an inert gas is introduced into the vacuum chamber after evacuating the vacuum chamber. By performing the heating process in such an atmosphere, the base material becomes a nitrogen and oxygen component (introduced in the curing process).
Reaction with other impurities can be prevented.

Next, in a curing treatment step, a mixed gas mainly composed of nitrogen containing a trace amount of an oxygen component is introduced into the vacuum chamber,
Nitrogen and oxygen are diffused and solid-solved from the surface of the substrate 100 to the inside. By this curing treatment step, a first cured layer in which nitrogen and oxygen are dissolved in a solid solution is formed near the surface of the substrate 100, and a second cured layer in which oxygen is dissolved in the substrate 100 in the depth direction is formed. Is formed. Various gases containing oxygen can be used as the trace oxygen component contained in the mixed gas. For example, oxygen gas, hydrogen gas, water vapor, ethyl alcohol, methyl alcohol, and the like are examples of the oxygen component. Further, a carbon dioxide gas or a carbon monoxide gas may be contained together with the water vapor.

In the curing step, the base material 100
On the other hand, nitrogen and a trace amount of oxygen components must be diffused and dissolved into the inside of the substrate 100 without forming a compound. For that purpose, the processing temperature in the same step is important. Therefore, in order to obtain this optimum processing temperature, JIS
A surface treatment based on the method of the present invention was performed by changing a treatment temperature in a range of 630 to 830 ° C. by using a titanium second material having a mirror surface appearance defined by the standard as a member to be treated. As a mixed gas mainly composed of nitrogen containing a small amount of oxygen component, 9
A mixed gas in which 2000 ppm (0.2%) of oxygen and 4000 ppm (0.4%) of hydrogen were added to 9.4% of nitrogen was used. The inside of the vacuum chamber was kept under reduced pressure, and a heat treatment was performed for 5 hours.

FIG. 1 shows the result of measuring the Vickers hardness of the member to be processed after the curing treatment. As is clear from the figure, when the treatment temperature was lower than 700 ° C., the Vickers hardness became Hv = 750 or less, and a sufficient curing treatment was not performed. This means that at a processing temperature lower than 700 ° C., nitrogen and oxygen diffuse sufficiently into the member to be processed,
This is because the first hardened layer and the second hardened layer are not properly formed because they do not form a solid solution. On the other hand, when the processing temperature is 8
When the temperature is higher than 00 ° C., the diffusion and solid solution rates of nitrogen and oxygen in the member to be processed are high, and a hardened layer can be obtained in a deep region. For this reason, Vickers hardness became Hv = 1100 or more.

However, when the processing temperature exceeds 800 ° C.,
It has been found that the crystal grains of the member to be processed are coarsened and surface roughness occurs. Therefore, when the processing temperature exceeds 800 ° C., good appearance quality cannot be maintained. In this case, since surface roughness occurs, it is necessary to insert surface polishing or the like in a subsequent process. Based on the above results, 700-800
The curing process was performed within the temperature range of ° C.
The concentration of the oxygen component in the nitrogen-based mixed gas described above may be arbitrary, but preferably the concentration of the oxygen component is adjusted to 100 to 30,000 ppm with respect to nitrogen. That is, when the concentration of the oxygen component is less than 100 ppm (0.01%), the solid solution of oxygen is not sufficiently performed. On the other hand, when the concentration of the oxygen component exceeds 30,000 ppm (3%), the oxide A layer may be formed and surface roughness may occur.

Although the degree of pressure reduction in the above-mentioned curing step may be arbitrarily determined, the pressure in the vacuum chamber is preferably adjusted within the range of 0.01 to 10 Torr. Further, as the trace amount of oxygen component contained in the mixed gas used in the curing process, various gases containing oxygen can be used. For example, oxygen gas, hydrogen gas, water vapor, and alcohol gas such as ethyl alcohol and methyl alcohol are examples of the oxygen component. Further, a carbon dioxide gas or a carbon monoxide gas may be contained together with the water vapor.

Next, the cooling process will be described. The cooling step aims to quickly lower the temperature of the base material 100 after the curing step to room temperature. This cooling step
It is preferable not to carry out the treatment in the same gas atmosphere as the curing treatment step. When the cooling step is performed in the same gas atmosphere as the hardening step, nitrides and oxides are formed on the surface of the base material 100, and there is a possibility that the appearance quality may be deteriorated. Therefore, this cooling step is preferably performed in an atmosphere of an inert gas such as argon or helium. That is, in the cooling step, the inside of the vacuum chamber is evacuated to a high vacuum to remove a nitrogen-based mixed gas containing a trace amount of an oxygen component, and then cooled to room temperature under a reduced pressure in which an inert gas is introduced into the vacuum chamber. Is preferred. The cooling step may be performed under a vacuum atmosphere.

Hereinafter, specific treatment conditions of the surface treatment method according to the present embodiment will be described. First, as a base material (member to be processed), a base material was manufactured by processing a titanium type 2 material defined by JIS standards into a desired shape by hot forging, cold forging, or a combination of both. If the shape of the base material 100 is difficult to obtain by forging, cutting may be performed. Next, the base material 100 was polished by buffing, so that the surface of the base material was mirror-finished.

Next, using the surface treatment apparatus shown in FIG.
The surface hardening treatment of the substrate 100 was performed. First, the inside of the vacuum chamber 1 of the surface treatment apparatus is evacuated to a high pressure of 1 × 10 ⁻⁵ Torr or less through a gas exhaust pipe 5 to eliminate the influence of the residual gas atmosphere.
Heat 00 at a temperature of 650-830 ° C. The heating state is maintained for 30 minutes, and the base material 100 is annealed (heating step).

Next, a mixed gas obtained by adding 5000 ppm (0.5%) of oxygen to 99.5% of nitrogen is introduced as a reaction gas from the gas introduction pipe 4. And vacuum chamber 1
Is adjusted to 0.2 Torr, and heating is performed for 5 hours while substantially maintaining the temperature (650-830 ° C.) at the time of annealing. By this curing treatment step, the nitrogen 104 and oxygen 105 are adsorbed and diffused on the surface of the base material 100, and the nitrogen 104 and oxygen 105 are solid-dissolved from the surface of the base material 100 to the inside, so that the first cured layer 102 Then, an internal cured layer 101 composed of the second cured layer 103 is formed (see FIG. 2). (Curing treatment step). Thereafter, the supply of the mixed gas was stopped, and the mixture was cooled to room temperature while evacuating (cooling step).

Next, a plurality of results obtained by changing the processing temperature in the heating step and the curing step are compared. As the base material (member to be processed), a material having a mirror-like appearance made of a titanium second class material defined by JIS standards was used. The heating step and the curing treatment step were performed with the treatment temperature varied in a temperature range of 650 to 830 ° C. Thereafter, the hardness, the diffusion depth and concentration of nitrogen and oxygen, the surface roughness, and the size of crystal grains in the surface texture were measured and evaluated. Hardness was measured with a Vickers hardness tester and 1.0 μm from the surface.
A hardness Hv = 750 or more at a depth of m was regarded as acceptable. The diffusion depth and concentration of nitrogen and oxygen were measured by a secondary ion mass spectrometer (SIMS). As for the surface roughness, the average surface roughness Ra was measured using a surface roughness meter, and a value of 0.4 μm or less was regarded as acceptable. Regarding the size of the crystal grains Rc, the crystal structure of the surface was measured with an electron microscope, and those having a size in the range of 20 to 65 μm were accepted. Table 1 shows the measurement results.

[0041]

[Table 1]

In Table 1, Sample Nos. S1 to S4 are base materials obtained by changing the processing temperature in the heating step and the curing step. The sample number Sc is an untreated pure titanium base material. As shown in Table 1, sample number S
1 (treatment temperature of 650 ° C.) shows that the average surface roughness Ra and the crystal grain size Rc after the surface treatment are as good as the untreated pure titanium base material (sample No. Sc). I was holding. However, the hardness at a depth of 1.0 μm from the surface showed a low value of Hv = 380. Therefore, the nitrogen content at the same depth is 0.05% by weight.
And contains almost no nitrogen. That is, it is understood that the first cured layer 102 shown in FIG. 2 is not formed. Further, the oxygen content at a depth of 20 μm from the surface is also 0.01% by weight, which indicates that the second hardened layer 103 is not formed.

Sample No. S4 (processing temperature: 830 ° C.) has a hardness Hv = 1320 at a depth of 1.0 μm from the surface.
However, the average surface roughness was as large as Ra = 1.0 μm, and the crystal grains were also coarsened to Rc = 80 to 200 μm, and the surface roughness was remarkably recognized. For use as a substrate, the degree of such surface roughness is outside the allowable range.
On the other hand, in sample numbers S2 and S3, the hardness at a depth of 1.0 μm from the surface was Hv = 820 to 935.
And a sufficiently high value, and the average surface roughness Ra = 0.2
5 to 0.3 μm, crystal grain size Rc = 30 to 60 μm
In this case, the same good appearance quality as that of the untreated pure titanium base material (sample No. Sc) was maintained.

Sample Nos. S2 and S3 contain 0.6 to 8.0% by weight (specifically, 0.8 to 1.6% by weight) of nitrogen at a depth from the surface to 1.0 μm, and 1.0
2 to 14.0% by weight (specifically, 1.7 to 2.6% by weight).
It can be seen that the cured layer 102 is formed. Further, oxygen at a depth of 20 μm from the surface contains 0.5 to 14.0% by weight (specifically, 0.7 to 1.0% by weight). It can be seen that the cured layer 103 is also formed. FIG. 4 is a diagram showing the results of measuring the nitrogen content and the oxygen content with respect to the depth from the surface. As a measurement object, the base material of sample number S2 was used.

As can be seen from the figure, the base material of the sample No. S2 subjected to the surface hardening treatment in this embodiment has a depth of 1 mm from the surface.
It can be seen that a large amount of nitrogen and oxygen are dissolved in a region up to μm, and a large amount of oxygen is dissolved in a deeper region. Thus, a substrate having an internal cured layer could be obtained. The substrates of Sample Nos. S2 and S3 maintained the same mirror quality as the substrate before the surface hardening treatment.

Next, the substrate provided with the internal cured layer was further polished by barrel polishing. The polishing method is described below. First, a substrate is placed in a barrel layer of a centrifugal barrel polishing machine. Next, walnut chips and an alumina-based abrasive are put into the barrel layer as a polishing medium. Then, barrel polishing is performed for about 10 hours to remove a 0.7 μm portion from the surface of the hard layer formed on the surface of the base material. As a result, fine strains on the surface of the substrate were removed, and the surface of the substrate was further smoothed and uniformized. Thus, a substrate having a mirror surface emitting a more uniform silver-white luster was obtained. Therefore, such barrel polishing is important in order to improve the beauty of the mirror surface of the base material and enhance the decorative value.

Although barrel polishing is used in the above embodiment, a known mechanical polishing means such as buff polishing or a combination of barrel polishing and buff polishing may be used as the polishing means. Further, if the surface of the first hardened layer is polished too deeply toward the inside, a region having a low nitrogen and oxygen content, particularly a low nitrogen content, will be exposed on the surface. In other words, the lower the hardness, the more exposed the region with lower hardness, and the lower the surface hardness of the substrate.
Conversely, if the polishing depth is shallow, a beautiful mirror surface cannot be obtained. Therefore, the polishing depth is set to 0.1 to 3.0 μm from the surface of the first hardened layer. Preferably,
0.2-2.0 μm, more preferably 0.5-1.
0 μm. By setting the polishing depth within the above range, a smooth mirror surface can be obtained while maintaining the surface hardness of the base material at a level that can withstand practical use. For more information,
It is sufficient that the polished base material has a hardness of 500 to 800 Hv under a load of 100 g.

The above-described surface hardening treatment has a shorter processing time and higher productivity than conventional hardening treatments such as ion implantation, ion nitriding, and carburizing. In addition, since the base material that has undergone the above-described surface hardening treatment has a hardened layer reaching a region as deep as 20 μm from its surface, it is not damaged even when used for a long time. In particular, since a mirror surface emitting uniform gloss can be provided by barrel polishing, decorative value can be enhanced.

In the above-mentioned curing process, the same result was obtained even when the following mixed gas was selected as a nitrogen-based reaction gas containing a trace amount of oxygen component to be introduced into the vacuum chamber 1. The measurement results are shown below. First,
3000 ppm in 99.7% nitrogen as mixed gas
Table 2 shows the measurement results when a mixed gas to which (0.3%) water vapor was added was selected.

[0050]

[Table 2]

In Table 2, Sample Nos. S5 to S8 are base materials obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 2, sample number S5
(Treatment temperature 650 ° C.) is the average surface roughness R after the surface treatment.
As for a and the crystal grain size Rc, both had good appearance quality equivalent to that of the untreated pure titanium base material (sample No. Sc). However, the hardness at a depth of 1.0 μm from the surface showed a low value of Hv = 405. Therefore, the nitrogen content at the same depth is 0.06% by weight, and contains almost no nitrogen. That is, FIG.
It can be seen that the first cured layer 102 shown in FIG. Further, the oxygen content at a depth of 20 μm from the surface is also 0.01% by weight, which indicates that the second hardened layer 103 is not formed.

Sample number S8 (processing temperature: 830 ° C.) has a hardness Hv = 1400 at a depth of 1.0 μm from the surface.
However, the average surface roughness was as large as Ra = 1.2 μm, and the crystal grains were coarsened to Rc = 80 to 250 μm, and the surface roughness was remarkably recognized. In order to use the substrate for decorative articles, the degree of such surface roughness is out of an allowable range. On the other hand, in sample numbers S6 and S7, the hardness at a depth of 1.0 μm from the surface was Hv = 820-9.
40 and a sufficiently high value, and the average surface roughness Ra =
0.25 to 0.3 μm, crystal grain size Rc = 30 to 6
At 0 μm, a good appearance quality equivalent to that of the untreated pure titanium base material (sample number Sc) and the untreated pure titanium was retained.

Sample Nos. S6 and S7 contain 0.6 to 8.0% by weight (specifically, 0.9 to 1.6% by weight) of nitrogen at a depth from the surface to 1.0 μm, and 1.0
2 to 14.0% by weight (specifically, 2.0 to 2.5% by weight).
It can be seen that the cured layer 102 is formed. Further, oxygen at a depth of 20 μm from the surface contains 0.5 to 14.0% by weight (specifically, 0.8 to 1.2% by weight), and the second layer shown in FIG. It can be seen that the cured layer 103 is also formed. FIG. 5 is a diagram showing the results of measuring the nitrogen content and the oxygen content with respect to the depth from the surface. The measurement object used was the substrate of sample number S6. As is clear from the figure, the base material of Sample No. S6 subjected to the surface hardening treatment in this example has a large amount of nitrogen and oxygen dissolved in a region from the surface to a depth of 1.0 μm, and further deeper. It can be seen that a large amount of oxygen is dissolved in the region.

Next, as a mixed gas, 99.4% of nitrogen and 2000 ppm (0.2%) of oxygen, and 4000 ppm of oxygen.
Table 3 shows the measurement results when a mixed gas to which ppm (0.4%) of hydrogen was added was selected.

[0055]

[Table 3]

In Table 3, sample numbers S9 to S12
This is a substrate obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 3, sample number S
9 (treatment temperature of 650 ° C.) shows that the average surface roughness Ra and the crystal grain size Rc after the surface treatment are as good as the untreated pure titanium base material (sample number Sc). I was holding. However, the hardness at a depth of 1.0 μm from the surface showed a low value of Hv = 370. Sample number S12 (processing temperature 830 ° C.) is 1.0
Although the hardness at a depth of μm is as high as Hv = 1300, the average surface roughness is as large as Ra = 1.1 μm, and the crystal grains are also coarsened to Rc = 80 to 200 μm, and the surface roughness is remarkably recognized. Was done. To use the base material for decoration,
The degree of such surface roughness is outside the allowable range. On the other hand, in sample numbers S10 and S11, the hardness at a depth of 1.0 μm from the surface was Hv = 810 to 920.
And a sufficiently high value, and the average surface roughness Ra = 0.2
5 to 0.3 μm, crystal grain size Rc = 30 to 60 μm
In this case, the same good appearance quality as that of the untreated pure titanium base material (sample No. Sc) was maintained.

From the results, it was found that the sample numbers S11 and S1
2 has a depth of 0.6 to 1.0 μm from the surface, similarly to the base materials of sample numbers S2 and S3 in the above-described embodiment.
It can be easily estimated that the first cured layer 102 shown in FIG. 2 is formed, containing 8.0% by weight of nitrogen and 1.0 to 14.0% by weight of oxygen. Further, it can be easily inferred that 0.5 to 14.0% by weight of oxygen is contained at a depth from the surface to 20 μm, and the second hardened layer 103 shown in FIG. 2 is formed.

Next, as a mixed gas, 2500 ppm (0.25%) water vapor in 99.7% nitrogen, and 50 ppm
Table 4 shows the measurement results when a mixed gas to which 0 ppm (0.05%) of carbon dioxide was added was selected.

[0059]

[Table 4]

In Table 4, sample numbers S13 to S16
Is a substrate obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 4, the sample No. S13 (processing temperature 650 ° C.) shows that the average surface roughness Ra after the surface treatment and the crystal grain size Rc are both untreated pure titanium substrates (sample No. Good appearance quality equivalent to that of Sc) was maintained. However, from the surface 1.0
The hardness at a depth of μm showed a low value of Hv = 340. Sample No. S16 (processing temperature of 830 ° C.) has a high hardness of Hv = 1240 at a depth of 1.0 μm from the surface, but has a large average surface roughness of Ra = 1.0 μm and a crystal grain of Rc = 80. Coarsened to ~ 200 μm,
Surface roughness was remarkably observed. In order to use the substrate for decorative articles, the degree of such surface roughness is out of an allowable range.
On the other hand, in sample numbers S14 and S15, the hardness at a depth of 1.0 μm from the surface was Hv = 800 to 85.
0 and a sufficiently high value, and the average surface roughness Ra = 0.
25 to 0.3 μm, crystal grain size Rc = 30 to 60 μm
m, a good appearance quality equivalent to that of the untreated pure titanium base material (sample No. Sc) was retained.

From the results, it was found that the sample numbers S14 and S1
5 are sample numbers S2 and S3 in Example 1 shown above.
As in the case of the base material, a depth of 0.6
~ 8.0 wt% nitrogen, and 1.0-14.0 wt%
Can be easily estimated that the first cured layer 102 shown in FIG. 2 is formed. Furthermore, 0.5-14.0 at a depth of 20 μm from the surface.
It can easily be inferred that it contains oxygen by weight and forms the second cured layer 103 shown in FIG.

Next, Table 5 shows the measurement results when a mixed gas obtained by adding 7000 ppm (0.3%) of ethyl alcohol gas to 99.3% of nitrogen was selected as the mixed gas.
Shown in

[0063]

[Table 5]

In Table 5, sample numbers S17 to S20
Is a substrate obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 5, the sample No. S17 (treatment temperature 650 ° C.) shows that the average surface roughness Ra after the surface treatment and the crystal grain size Rc are both untreated pure titanium substrates (sample number Good appearance quality equivalent to that of Sc) was maintained. However, from the surface 1.0
The hardness at a depth of μm showed a low value of Hv = 330.

The sample number S20 (processing temperature 830 ° C.)
The hardness at a depth of 1.0 μm from the surface is Hv = 120.
Although it was as high as 0, the average surface roughness was as large as Ra = 1.0 μm, and the crystal grains were also coarsened to Rc = 80 to 180 μm, and the surface roughness was remarkably recognized. In order to use the substrate for decorative articles, the degree of such surface roughness is out of an allowable range. In contrast, sample numbers S18 and S19
Has a hardness of Hv = 7 at a depth of 1.0 μm from the surface.
80 to 830, a sufficiently high value, average surface roughness Ra = 0.25 to 0.3 μm, and crystal grain size Rc = 3
0 to 55 μm, untreated pure titanium substrate (sample number S
The same good appearance quality as in c) was maintained.

From the results, it was found that the sample numbers S18 and S1
9 is the sample number S2, S3 in Example 1 shown above.
As in the case of the base material, a depth of 0.6
~ 8.0 wt% nitrogen, and 1.0-14.0 wt%
Can be easily estimated that the first cured layer 102 shown in FIG. 2 is formed. Furthermore, 0.5-14.0 at a depth of 20 μm from the surface.
It can easily be inferred that it contains oxygen by weight and forms the second cured layer 103 shown in FIG.

In the above-described embodiment, after the heating step is evacuated to a high vacuum, annealing is performed by heating in a vacuum atmosphere. However, the heating step is not limited to the vacuum atmosphere. May be carried out in an inert gas atmosphere. However, also in this case, it is preferable that the inside of the vacuum chamber be in a reduced pressure state.

In the above-described embodiment, the cooling step is performed while evacuating the vacuum. However, the cooling step is not limited to the vacuum atmosphere, but may be performed in an inert gas atmosphere such as helium or argon where the substrate does not react. You may. However, also in this case, it is preferable that the inside of the vacuum chamber 1 be in a reduced pressure state.

(Second Embodiment for Forming Internal Hardened Layer) Next, a second embodiment will be described. The purpose and basic operation of each step in the second embodiment are the same as those in the first embodiment described above. The second embodiment is different from the first embodiment in that a heating step and a curing step are performed under atmospheric pressure. When the heating step is performed under atmospheric pressure, since the base material is an active metal, it is necessary to prevent the member from reacting with impurity components other than nitrogen and oxygen components in the vacuum chamber. The point is that an active gas is introduced. Also in the second embodiment, the heating step is preferably performed under an atmosphere adjusted to atmospheric pressure by introducing an inert gas into the vacuum chamber after evacuating the vacuum chamber. The process may be performed under a reduced pressure state where the inside of the tank is evacuated. By performing the heating step in such an atmosphere, it is possible to prevent the base material from reacting with impurities other than nitrogen and oxygen components (introduced in the curing treatment step).

In the curing treatment step after the heating step, the inside of the vacuum chamber is evacuated to a high vacuum to remove the inert gas, and then a mixed gas mainly composed of nitrogen containing a trace amount of oxygen is introduced into the vacuum chamber. At the same time, the inside of the vacuum chamber is adjusted to the atmospheric pressure, and the inside of the vacuum chamber 1 is heated at a temperature of 700 to 800 ° C. for a predetermined time, so that nitrogen and oxygen are diffused and dissolved from the surface of the substrate to the inside. Various gases containing oxygen can be used as the trace amount of oxygen component contained in the mixed gas used in the curing treatment step. For example, oxygen gas, hydrogen gas, water vapor, and alcohol gas such as ethyl alcohol and methyl alcohol are examples of the oxygen component. Further, a carbon dioxide gas or a carbon monoxide gas may be contained together with the water vapor.

After the curing step, the cooling step of cooling the substrate to room temperature is preferably not performed in the same gas atmosphere as the curing step, as in the first embodiment. That is, in the cooling step, the inside of the vacuum chamber is evacuated to a high vacuum to remove a nitrogen-based mixed gas containing a trace amount of an oxygen component, and then an inert gas is introduced into the vacuum chamber to adjust it to atmospheric pressure. It is preferable to cool to room temperature. The cooling step may be performed under a vacuum atmosphere.

Hereinafter, specific treatment conditions of the surface treatment method according to the present embodiment will be described. First, similarly to the first embodiment, as a base material (member to be processed), a titanium type 2 material defined by JIS standards is formed into a desired shape by hot forging, cold forging, or a combination of both. A processed substrate was produced. Next, the base material 100 was polished by buffing, so that the surface of the base material was mirror-finished. Next, the surface hardening treatment of the base material 100 was performed using the surface treatment device shown in FIG. First, the inside of the vacuum chamber 1 is evacuated by a vacuum pump 7 through a gas exhaust pipe 5 to evacuate to a pressure of 1 × 10 ⁻² Torr or less at which the influence of the residual gas atmosphere is eliminated, and then the electromagnetic valve 8 is closed. . Subsequently, the gas introduction valve 6 is opened, argon gas (inert gas) is introduced into the vacuum chamber 1 through the gas introduction pipe 4, and the vent valve 10 of the atmosphere opening pipe 9 is opened to reduce the pressure in the vacuum chamber 1. Adjust to atmospheric pressure. Under this atmosphere, the base material 10 is heated by the heater 3.
0 is heated to 650 to 830 ° C. for 30 minutes to perform an annealing treatment (heating step). Next, while closing the vent valve 10 of the atmosphere opening pipe 9 and the gas introduction valve 6 of the gas introduction pipe 4,
The electromagnetic valve 8 of the gas exhaust pipe 5 is opened, and vacuum evacuation by the vacuum pump 7 is executed. The evacuation is performed in a vacuum chamber
Continue until the pressure is below ^-2 Torr.

Thereafter, the electromagnetic valve 8 of the gas exhaust pipe 5 is closed, and the gas introduction valve 6 of the gas introduction pipe 4 is opened, and 99.7% of nitrogen is introduced into the vacuum chamber 1 at 3000 ppm (0.3 ppm).
%) Of a mixed gas to which steam is added. At this time, the vent valve 10 of the atmosphere opening pipe 9 is opened, and the pressure in the vacuum chamber 1 is adjusted to the atmospheric pressure. Then, heating is performed for 5 hours while substantially maintaining the temperature (650 to 830 ° C.) at the time of the annealing treatment (hardening treatment step). By this hardening process, the nitrogen 104 and oxygen 105 are adsorbed and diffused on the surface of the base material 100, and the nitrogen 104 and oxygen 105 are solid-dissolved from the surface of the member 100 to the inside to form a first hardened layer 102 Then, an internal cured layer 101 composed of the second cured layer 103 is formed (see FIG. 2).

After the curing process is completed, the atmosphere opening pipe 9
The vent valve 10 and the gas introduction valve 6 of the gas introduction pipe 4 are closed, the solenoid valve 8 of the gas exhaust pipe 5 is opened, and the vacuum pump 7 evacuates the vacuum chamber 1 to a pressure of 1 × 10 ⁻² Torr or less. Evacuation is performed to remove the mixed gas. Subsequently, the electromagnetic valve 8 of the gas exhaust pipe 5 is closed, and the gas introduction valve 6 of the gas introduction pipe 4 is opened to introduce argon gas. At the same time, the vent valve 10 of the atmosphere opening pipe 9 is opened, and the pressure in the vacuum chamber 1 is adjusted to the atmospheric pressure. The substrate was cooled to room temperature in this atmosphere (cooling step).

In the second embodiment, as the base material (member to be processed), a base material made of a second class titanium material defined by the JIS standard and having a mirror-like appearance is used. The heating step and the curing treatment step were performed with the treatment temperature varied in a temperature range of 650 to 830 ° C. Thereafter, hardness, surface roughness, and the size of crystal grains in the surface texture were measured and evaluated. The hardness was measured by a Vickers hardness tester, and a hardness Hv = 750 or more at a depth of 1.0 μm from the surface was regarded as acceptable. As for the surface roughness, the average surface roughness Ra was measured using a surface roughness meter, and a value of 0.4 μm or less was regarded as acceptable. Regarding the size of the crystal grains Rc, the crystal structure of the surface was measured with an electron microscope, and those having a size in the range of 20 to 65 μm were accepted. Table 6 shows the measurement results.

[0076]

[Table 6]

In Table 6, sample numbers S21 to S24
Is a substrate obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 6, the sample No. S21 (treatment temperature 650 ° C.) shows that the average surface roughness Ra after the surface treatment and the crystal grain size Rc are both untreated pure titanium substrates (sample number). Good appearance quality equivalent to that of Sc) was maintained. However, from the surface 1.0
The hardness at a depth of μm showed a low value of Hv = 360. Sample No. S24 (processing temperature of 830 ° C.) has a high hardness of Hv = 1410 at a depth of 1.0 μm from the surface, but has a large average surface roughness of Ra = 1.3 μm and also has a crystal grain of Rc = 80. Coarsened to ~ 250 μm,
Surface roughness was remarkably observed. In order to use the substrate for decorative articles, the degree of such surface roughness is out of an allowable range.

On the other hand, sample numbers S22 and S2
3 has a hardness Hv = 1.0 μm from the surface.
840 to 1050, a sufficiently high value, average surface roughness Ra = 0.25 to 0.35 μm, crystal grain size R
When c = 30 to 60 μm, the same good appearance quality as that of the untreated pure titanium base material (sample No. Sc) was maintained. From this result, the sample numbers S22 and S23 were similar to the base materials of the sample numbers S2 and S3 in Example 1 described above.
0.6 to 8.0% by weight at a depth of 1.0 μm from the surface
2 and 1.0 to 14.0% by weight of oxygen, respectively, and it can be easily inferred that the first cured layer 102 shown in FIG. 2 is formed.

Further, oxygen of 0.5 to 14.0% by weight is contained at a depth of 20 μm from the surface, and it is easy to form the second hardened layer 103 shown in FIG. I can guess. Thus, a substrate having an internal cured layer is obtained. The base materials of Sample Nos. S22 and S23 maintained the same mirror quality as the base material before the surface hardening treatment. Further, in the curing process, even when helium gas was selected as the inert gas introduced into the vacuum chamber 1, the same result was obtained. Note that the heating step and the curing treatment step are performed by changing the treatment temperature in the same temperature range of 650 to 830 ° C. as in the second embodiment, and thereafter, the hardness, the surface roughness, and the crystal structure The size was measured and evaluated respectively. Table 7 below shows the measurement results when helium gas was selected as the inert gas.

[0080]

[Table 7]

In Table 7, sample numbers S25 to S28
Is a substrate obtained by changing the processing temperature in the heating step and the curing step. As shown in Table 7, the sample No. S25 (processing temperature 650 ° C.) shows that the average surface roughness Ra after the surface treatment and the crystal grain size Rc are both untreated pure titanium base materials (sample No. Good appearance quality equivalent to that of Sc) was maintained. However, from the surface 1.0
The hardness at a depth of μm showed a low value of Hv = 330. Sample No. S28 (processing temperature: 830 ° C.) has a high hardness of Hv = 1220 at a depth of 1.0 μm from the surface, but has a large average surface roughness of Ra = 1.0 μm and crystal grains of Rc = 80. Coarsened to ~ 200 μm,
Surface roughness was remarkably observed. In order to use the substrate for decorative articles, the degree of such surface roughness is out of an allowable range.

On the other hand, sample numbers S26 and S2
7 has a hardness Hv = 1.0 μm from the surface.
It shows a sufficiently high value of 780 to 840, an average surface roughness Ra = 0.25 to 0.3 μm, and a crystal grain size Rc =
It had a good appearance quality equivalent to that of an untreated pure titanium base material (sample No. Sc) at 30 to 60 μm. From these results, the sample Nos. S26 and S27 were 0.6 to 8.0% by weight at a depth of 1.0 μm from the surface, similarly to the base materials of the sample numbers S2 and S3 in Example 1 described above. It can be easily inferred that they contain nitrogen and 1.0 to 14.0% by weight of oxygen, respectively, and form the first cured layer 102 shown in FIG.

Further, 0.5 to 14.0% by weight of oxygen is contained at a depth of 20 μm from the surface, so that the second hardened layer 103 shown in FIG. 2 can be easily formed. I can guess. In the present embodiment, the heating step is performed in an argon atmosphere at atmospheric pressure or in a helium atmosphere at atmospheric pressure. However, the heating step is not limited to these atmospheres, and the heating step may be performed in a vacuum atmosphere. In the present embodiment, the cooling step is performed in an argon atmosphere at atmospheric pressure or in a helium atmosphere at atmospheric pressure. However, the cooling step is not limited to these atmospheres, and the cooling step may be performed in a vacuum atmosphere.

The present invention is not limited to the above embodiments. In each of the above embodiments, the base material is heated using the heater 3 to form a solid solution of nitrogen and oxygen. Alternatively, for example, the base material may be formed into a solid solution of nitrogen and oxygen using plasma. Good. Further, the mixed gas mainly composed of nitrogen containing a trace amount of oxygen component introduced into the vacuum chamber 1 in the curing treatment step is not limited to the one used in each of the above-mentioned embodiments. A gas containing an oxygen component such as nitrogen dioxide, carbon monoxide, or carbon dioxide may be added. In addition,
A trace amount of an inert gas such as helium, neon, or argon, or a gas containing a hydrogen component, a boron component, or a carbon component may be added.

In each embodiment, the processing time of the heating step is set to 30 minutes. However, the present invention is not limited to this, and can be set arbitrarily, for example, in the range of 30 minutes to 2 hours. Furthermore, in each embodiment, the processing time of the curing process is set to 5 hours, but is not limited to this, and can be set arbitrarily as needed. However, if the treatment time of the curing treatment step is less than 1 hour, diffusion solid solution of nitrogen and oxygen does not sufficiently proceed,
The required hardness may not be obtained. On the other hand, if the treatment time of the curing treatment step exceeds 10 hours, the surface of the substrate may be roughened. Therefore, the treatment time of the curing treatment step is preferably set in the range of 1 to 10 hours.

(Example 1) A hard decorative film having a golden color tone is coated on the substrate made of titanium or titanium alloy steel on which the internal hardened layer has been formed as described above. FIG. 6 is referred to for this description. As shown in the figure, an internal hardened layer 101 formed on a surface of a camera body as a base material 100
Is coated with a TiN film 23 made of titanium nitride as a golden hard decorative film by an ion plating method, which is one of dry plating methods.

A method for forming the TiN film 23 will be described. First, the camera body on which the internal hardened layer 101 was formed was washed with an organic solvent such as isopropyl alcohol, and placed in an ion plating apparatus. Since the ion preting apparatus may be a commonly used apparatus, its description will be omitted including the drawings.

Next, the inside of the apparatus was set to 1.0 × 10 ⁻⁵ Torr.
After exhausting the gas, argon gas was used as an inert gas.
It was introduced up to 0 × 10 ⁻³ Torr. Next, the thermoelectron filament and the plasma electrode provided inside the apparatus were driven to form argon plasma. At the same time, a potential of -50 V was applied to the camera body 1, and bombard cleaning was performed for 10 minutes.

Next, after the introduction of the argon gas was stopped, a nitrogen gas was introduced into the apparatus to 2.0 × 10 ⁻³ Torr. Then, after plasma is generated by an electron gun provided inside the apparatus, titanium is evaporated for 10 minutes to form a TiN film 23 on the internal hardened layer 101 of the camera body by 0.5 mm.
It was formed with a film thickness of μm.

The camera body thus obtained is
Since the TiN film 23 has the same optical characteristics as gold, it has a uniform golden color tone. As a result, the decorative value of the camera body could be further enhanced. The surface hardness (HV) of the camera body coated with the TiN film 23 reached 800 with a load of 50 g. TiN
The camera body coated with the coating 23 has excellent wear resistance,
It had corrosion resistance and scratch resistance. In addition, even if a strong force is applied to the surface of the coating, it is difficult to form irregularities on the surface of the substrate, and the coating is not peeled off. As described above, by coating the TiN film 23 which is harder than the inner hardened layer 101, the camera body which has been subjected to the surface hardening treatment is further less likely to be damaged.

The dry plating method is not limited to the above-described ion plating method, and any known method such as a sputtering method or a vacuum evaporation method can be used.

Further, as a golden hard decorative film coated by a dry plating method, elements 4a, 5a and 6a of the periodic table (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W) nitrides, carbides, oxides, nitrocarbides and nitrocarbonates can be employed. 4a, 5a, 6a of the periodic table
When the group element is represented by M and the nitride of M is represented by MNx, as the value of x indicating the degree of nitridation becomes smaller than 1, the color tone of the film of the nitride MNx of the M approaches from gold to pale yellow. . Further, as the value of x indicating the degree of nitridation becomes larger than 1, the gold color of the coating becomes reddish.
If the value of x indicating the degree of nitridation is in the range of 0.9 to 1.1, a gold color close to the color tone of gold or a gold alloy can be formed on the nitride MNx film. In particular, when the value of x indicating the degree of nitriding is x = 1, the coating of the nitride MNx of M is a hard decorative coating having sufficient hardness,
It has a gold color closest to that of gold or gold alloy.

[0093] Carbides, oxides, nitrocarbides, and nitrocarboxylates of elements M of Groups 4a, 5a and 6a in the periodic table are also controlled by controlling their degree of carbonization, degree of oxidation, and degree of nitridation to predetermined ranges. A gold color tone closest to the color tone of gold or a gold alloy can be given to those films. In particular, the TiN film and the ZrN film are preferable because they are hard decorative films having sufficient hardness and at the same time exhibit a gold color closest to the color tone of gold or a gold alloy. If the thickness of the nitride MNx of M is small, it is not possible to obtain effective wear resistance, corrosion resistance and scratch resistance of the coating. Conversely, if the thickness of the coating is large, the time required for coating is long, and the cost of the coating is high. Therefore, the film thickness of the nitride MNx film is preferably in the range of 0.1 to 10 μm, more preferably 0.2 to 5 μm.
It is controlled in the range of μm.

(Embodiment 2) A color tone different from that of Embodiment 1 is placed on the body of a mobile phone, which is a base material 100 made of titanium or a titanium alloy, on which an internal hardened layer is formed by the same method as in Embodiment 1. With a hard decorative film. FIG. 7 is referred to for this description. As shown in the figure, on the internal hardened layer 101 formed on the surface of the body of the mobile phone,
The TiC coating 24 made of titanium carbide is coated as a white-colored hard decorative coating by the dry plating method. Using an ion plating method, which is one of the dry plating methods, titanium was evaporated in an ethylene gas atmosphere, and the surface of the mobile phone body was coated with a TiC film 24. Other coating conditions were the same as in Example 1.

The thus obtained mobile phone body exhibited a uniform white tone due to the coating of the TiC coating 24. Thereby, the decorative value of the mobile phone body could be further enhanced. The surface hardness (HV) of the mobile phone body coated with the TiC coating 24 reached 800 under a load of 50 g. The mobile phone body coated with the TiC coating 24 had excellent abrasion resistance, corrosion resistance, and scratch resistance. Thus, the coating 2 harder than the inner hardened layer 101
By coating No. 4, the mobile phone body subjected to the surface hardening treatment was further hardly damaged.

(Embodiment 3) On the body of a portable radio, which is a substrate 100 made of titanium or a titanium alloy, on which an internal hardened layer is formed by the same method as in Embodiment 1,
A hard carbon coating is coated as a black-colored hard decorative coating. Hard carbon coatings are widely known as diamond-like carbon (DLC) because they have excellent properties similar to diamond. FIG. 8 is referred to for this description. As shown in the figure, a black hard carbon film 25 is coated on the internal hardened layer 101 formed on the surface of the body of the portable radio by a dry plating method.

The method of forming the hard carbon film 25 is, for example, as follows. First, the portable radio body on which the internal cured layer 101 was formed was washed with an organic solvent such as isopropyl alcohol, and placed in a vacuum device. Then, using a high-frequency plasma CVD method, a carbon hard decorative film 5 is applied to the inner hardened layer 101 by 2 μm on the internal hardened layer 101 under the following conditions.
m was formed. [Formation conditions] Gas type: methane gas Film formation pressure: 0.1 Torr High frequency power: 300 watts Film formation rate: 0.1 μm / min In this way, the hard carbon film 25 becomes the inner hardened layer 1
01 with good adhesion.

The portable radio body thus obtained exhibited a uniform black tone due to the coating of the hard carbon coating 25. As a result, the decorative value of the portable radio body could be further enhanced. The surface hardness (H) of the portable radio body coated with the hard carbon
V) reached 3000 to 5000. in this way,
By coating the coating 25, which is harder than the inner hardened layer 101, the body of the portable radio which has been subjected to the surface hardening treatment is further less likely to be damaged.

The thickness of the hard carbon coating 25 is preferably in the range of 0.1 to 3.0 μm, more preferably 0.5 to 3.0 μm.
It is controlled in the range of .about.2.5 .mu.m. Further, in order to coat the hard carbon film 25, in addition to the RFP-CVD method, D
Various vapor deposition methods such as a C plasma CVD method and an ECR method can be used. In addition, a physical vapor deposition method such as an ion beam method, a sputtering method, or an ion plating method may be employed.

Further, as shown in FIG.
1 and the hard carbon coating 25 are preferably formed because the hard carbon coating 25 adheres more strongly to the surface of the substrate 1. The method of forming the intermediate layer 26 is, for example, as follows. By a dry plating method, for example, a sputtering method, a Ti film 26a, which is a lower layer mainly composed of titanium, is formed on the inner hardened layer 101 by 0.1 μm.
Coated. Further, the Si film 26b, which is the upper layer mainly composed of silicon, is
a was coated on top of a. Thereafter, the hard carbon film 25 is coated on the Si film 26b by 2 μm according to the above-described conditions by using, for example, a high-frequency plasma CVD method.
m.

The Ti coating 26a is made of chromium (Cr)
It can be replaced by a coating. In addition, the above Si coating 26
b can be replaced by a germanium (Ge) coating. Furthermore, instead of Si film 26b, which is an upper layer mainly composed of silicon, an upper layer mainly composed of any of tungsten, tungsten carbide, silicon carbide, and titanium carbide can be employed. As the intermediate layer, in addition to such a laminated film, a single layer of a carbide of a group IVa or group Va metal may be coated. In particular, a coating of titanium carbide containing an excessive amount of carbon is preferred because of its high adhesion strength to the carbon hard decorative coating.

(Example 4) A gold-colored hard decorative coating is applied to a part of the surface of the body of a video camera which is a substrate 100 made of titanium or a titanium alloy having an internal hardened layer formed by the same method as in Example 1. Is coated. For this description, reference is made to FIGS. As shown in FIG. 11, a part of the surface of the body of the video camera is made of TiN made of titanium nitride as a hard decorative film having a golden tone by an ion plating method which is one of dry plating methods.
The coating 27 is coated.

Hereinafter, a method of partially forming the golden TiN film 27 will be described. First, as shown in FIG. 10, an organic masking agent or a masking ink made of an epoxy resin is printed on a desired portion of each surface of the video camera body on which the internal cured layer 101 is formed, and the masking layer 28 is formed. Was formed. Next, the body of the video camera on which the masking layer 28 was formed was washed with an organic solvent such as isopropyl alcohol and placed in an ion plating apparatus. The ion pretending device may be a commonly used ion pretensioning device, and a description thereof will be omitted including the drawings.

Next, the inside of the apparatus was set to 1.0 × 10 ⁻⁵ Torr.
And then purged with argon gas, which is an inert gas.
It was introduced up to 0 × 10 ⁻³ Torr. Next, the thermoelectron filament and the plasma electrode provided inside the apparatus were driven to form argon plasma. At the same time, a potential of -50 V is applied to each body of the video camera to
Bombard cleaning was performed for a minute.

Next, after the introduction of the argon gas was stopped, a nitrogen gas was introduced into the apparatus up to 2.0 × 10 ⁻³ Torr. Then, after plasma was generated by a plasma gun provided inside the apparatus, titanium was evaporated for 10 minutes. Therefore, as shown in FIG. 11, a TiN film 27 is formed on the surface of the hardened layer 101 of each body of the video camera, and a TiN film 27a is formed on the surface of the masking layer 28 by 0.5 μm.
m.

Next, the masking layer 28 is swollen with ethyl methyl ketone (EMK) or a stripping solution obtained by adding formic acid and hydrogen peroxide to ethyl methyl ketone (EMK), and the masking layer 28 and the top of the masking layer 28 are lifted off. The laminated TiN film 27a was peeled off. Therefore, as shown in FIG. 12, a video camera body having a portion exhibiting a gold color covered with the TiN film 27 and a portion exhibiting silver white of titanium or titanium alloy steel not covered with the TiN film is obtained. Was. As a result, the decorative value of the video camera body could be further enhanced.

As the masking means, in addition to providing the chemical masking layer as described in this embodiment, a mechanical masking means may be used. That is, before coating the titanium nitride film, a metal cap is put on any part of the piece in advance, and after coating the titanium nitride film,
The cap may be removed. Then, the portion of the piece covered with the cap is not covered with the titanium nitride film, and the portion not covered with the cap is covered with the titanium nitride film.

In this embodiment, an example was described in which a titanium nitride film was used as a hard decorative film partially coated on the surface of the body 1 of the video camera. However, as described in Example 1, as the golden hard decorative film coated by the dry plating method, 4a, 5a, 6a of the periodic table.
Group-element nitrides, carbides, oxides, nitrocarbides and nitrocarbonates can be employed. In particular, the titanium carbide coating used in Example 2 can be partially applied to the surface of the body of the video camera. Then, a body of a video camera having a portion exhibiting a white color covered with the titanium carbide film and a portion exhibiting silver white of titanium or titanium alloy not covered with the titanium carbide film is obtained. Alternatively, the hard carbon coating used in the third embodiment may be adopted as a partially covered hard decorative coating. As a result, a video camera body having a black color portion covered with the hard carbon film and a silver or titanium alloy portion not coated with the hard carbon film is obtained.

(Example 5) A hard decorative film having a golden color tone was formed on the surface of a lighter body, which was a substrate 100 made of titanium or titanium alloy steel, on which an internal hardened layer was formed in the same manner as in Example 1. Coated. Further, a gold alloy coating is coated on the golden hard decorative coating.
FIG. 13 is referred to for this description. As shown in the figure, the surface of the lighter body on which the internal hardened layer 101 has been formed is formed of a gold hard decorative film made of titanium nitride by an ion plating method, which is one of dry plating methods.
The N film 29 is coated. A gold-titanium alloy film 30 as a gold alloy film is coated on the TiN film 29.

Hereinafter, a method for forming the TiN film 29 and the gold-titanium alloy film 30 in this embodiment will be described. First,
The lighter body on which the internal cured layer 101 was formed was washed with an organic solvent such as isopropyl alcohol, and placed in an ion plating apparatus. Since the ion preting apparatus may be a commonly used apparatus, its description will be omitted including the drawings. Next, the inside of the
After evacuation to × 10 ^-5 Torr, an inert gas, argon gas, was introduced to 3.0 × 10 ^-3 Torr. Next, the thermoelectron filament and the plasma electrode provided inside the apparatus were driven to form argon plasma.
At the same time, a potential of -50 V is applied to the writer body,
Bombard cleaning was performed for 0 minutes.

Then, after the plasma is generated by the plasma gun provided inside the apparatus, the titanium is evaporated for 10 minutes, and a TiN film 29 is formed on the entire surface of the lighter body by a 0.1N coating method.
It was formed with a thickness of 5 μm. Next, the evaporation of titanium and the introduction of nitrogen gas were stopped, and the inside of the apparatus was evacuated to 1.0 × 10 ⁻⁵ Torr. Next, 1.0 × argon gas was introduced into the apparatus.
After generating plasma by introducing up to 10 ^-3 Torr,
A gold-titanium mixture consisting of 50 atomic% of gold and 50 atomic% of titanium was evaporated to form a gold-titanium alloy coating 30. The thickness of the gold-titanium alloy film 30 is 0.3 μm.
When it reached m, the evaporation of the gold-titanium mixture was stopped.

The lighter body thus obtained is
A uniform golden hue was exhibited. As a result, the decorative value of the lighter body could be increased. In addition, since the outermost layer coating is coated with the gold-titanium alloy coating 30, the T
A lighter body exhibiting a warmer golden tone than the iN coating 29 was obtained. As a result, the beauty of the lighter body could be further enhanced.

In general, unless the thickness of the gold alloy coating itself exceeds 10 μm, effective wear resistance, corrosion resistance or scratch resistance cannot be obtained. Gold is a very expensive metal. Therefore, thick coating of such a gold alloy coating greatly increases the cost of the coating. However, in this embodiment, a hard TiN film was provided under the outermost layer film made of a gold alloy film. TiN
Since the coating has excellent wear resistance, corrosion resistance, and scratch resistance, the outermost coating made of a gold alloy coating may be thin. This has the advantage that the cost of the coating can be reduced because the amount of expensive gold used is reduced.

It is also possible that the outermost coating consisting of a thinly coated gold alloy coating may be partially worn and the underlying TiN coating may be exposed, but any localized wear of the outermost coating will never occur. It does not stand out. Because, TiN
This is because the coating has the same optical properties as gold and has a golden color tone. From the part where the outermost layer coating made of the gold-colored gold alloy coating is worn down, the same gold-colored TiN
A coating appears. Therefore, even if the outermost layer film made of the gold alloy film is made thin, its wear is not visually recognized, so that aesthetic appearance and decorative value can be maintained.

In this example, the titanium nitride film was used as the hard decorative film. In addition, as the golden hard decorative film coated by the dry plating method, 4a, 5a and 5b of the periodic table were used.
a, nitrides, carbides, oxides, nitrided carbides of Group 6a elements,
Carbonitrides can be employed. In addition to the gold-titanium alloy layer, Al, S
i, V, Cr, Fe, Co, Ni, Cu, Zn, Ge,
Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, C
An alloy of at least one selected from d, In, Sn, Hf, Ta, W, Ir, and Pt and gold can be formed.

However, when a lighter body coated with several gold alloy films selected from the above combinations comes into contact with the skin, metal ions are eluted by an electrolytic solution such as sweat. This can cause a metal allergy on the skin that the lighter body contacts. In particular, eluted nickel ions are known as metal ions most frequently causing metal allergies. Conversely, iron is a metal with very few cases of metal allergy. No cases of metal allergy with titanium have been reported yet. Therefore, in consideration of metal allergy, a gold-iron alloy or a gold-titanium alloy is preferable as the gold alloy film used for the outermost layer film.

(Example 6) Further, the gold alloy coating described in Example 5 was coated only on the gold-colored hard decorative coating partially coated on the surface of the substrate described in Example 4. You may. This example is shown in FIGS.

Hereinafter, a method of partially forming a TiN film 31 made of titanium nitride as a hard decorative film having a gold color tone and a gold-titanium alloy film 32 as a gold alloy film will be briefly described. A masking layer 33 was formed by printing an organic masking agent made of an epoxy resin or a masking ink on a desired portion of the surface of the main body of the personal computer, which is the base material 100 on which the internal cured layer 101 was formed. Next, the personal computer main body 1 on which the masking layer 33 was formed was washed with an organic solvent such as isopropyl alcohol and placed in an ion plating apparatus.

Next, the surface of the internal hardened layer 101 of the body of the personal computer and the surface of the masking layer 33 are formed by ion plating, which is one of the dry plating methods.
The iN coatings 31 and 31a were formed with a thickness of 0.5 μm.
Next, gold-titanium alloy films 32 and 32a were formed on the TiN films 31 and 31a to a thickness of 0.3 μm.

Next, the masking layer 33 is immersed in ethyl methyl ketone (EMK) or a stripping solution obtained by adding formic acid and hydrogen peroxide to ethyl methyl ketone (EMK), whereby the masking layer 33 is swollen, and the masking layer 33 is lifted off. 33 and the TiN film 31a and the gold-titanium alloy film 32a laminated thereon were peeled off. Therefore, T
A personal computer body having a portion exhibiting a gold color covered with the iN film 31 and the gold-titanium alloy film 32 and a portion exhibiting titanium or a titanium alloy steel silver white not covered with the film was obtained. .

In this embodiment, as described in Embodiment 5, various hard decorative coatings other than the titanium nitride coating can be employed. Various gold alloy layers other than the gold-titanium alloy layer can be employed.

(Example 7) The first hard decorative film is coated on the surface of the substrate on which the internal hardened layer has been formed by the same method as in Example 1. Further, a second color having a color different from that of the first hard decorative coating is partially provided on the surface of the first hard decorative coating.
Is applied. For this description, reference is made to FIGS.

As shown in FIG. 16, in the same manner as in Example 1, the surface of the wristwatch case, which is the base material 100 on which the internal hardened layer 101 was formed, was coated with the first hard decorative film of a golden tone. A TiN film 23 made of titanium was coated. A masking layer 33 was formed on a desired portion of the surface of the TiN film 23 by printing an organic masking agent made of an epoxy resin or a masking ink.

Next, as shown in FIG. 17, the same method as in Example 2 was used to apply a TiC film made of titanium carbide having a white color tone as a second hard decorative film on the surface of the TiN film 23.
The coating 34 was formed by coating the surface of the masking layer 33 with the TiC coating 34a.

Next, the substrate 100 is immersed in a stripping solution,
Therefore, the masking layer 33 is swollen, and the masking layer 33 and the TiC
The coating 34a was peeled off. Therefore, as shown in FIG.
A part of the surface of the golden TiN film 23 is coated with white TiC.
The coating 34 was laminated. Thus, the TiN coating 2
3, a portion exhibiting a golden tone and a TiC coating 3
A wristwatch case having a white part coated with No. 4 was obtained. As a result, the decorative value of the watch case could be further enhanced. In addition, the internal hardened layer 101
By coating the harder coatings 23 and 34, the case of the wristwatch subjected to the surface hardening treatment was further less likely to be damaged.

As described in the fifth embodiment, various hard decorative coatings other than the titanium nitride and titanium carbide coatings can be used as the hard decorative coating in this embodiment. Alternatively, any one of the first hard decorative coating and the second hard decorative coating,
The carbon hard decorative coating described in the third embodiment can be obtained. Further, the type of the masking layer 13 and the type of the stripping solution can be appropriately selected according to the type of the film.

When the elements of groups 4a, 5a and 6a of the periodic table are represented by M and the nitride of M is represented by MNx, both the first hard decorative film and the second hard decorative film are referred to as MNx film. You can also. In this case, if the coating is performed so that the value of x indicating the degree of nitridation in the first hard decorative coating is different from the value of x in the second hard decorative coating, the first hard decorative coating and the second hard decorative coating are provided. Can be coated in different colors. The same applies to carbides, oxides, nitrocarbides, and nitrocarboxylates.

(Example 8) A first hard decorative film is coated on a part of the surface of the substrate on which the internal cured layer is formed by the same method as in Example 1. Further, another part of the surface of the substrate is coated with a second hard decorative coating having a color tone different from that of the first hard decorative coating. This explanation is based on FIGS.
1 is referenced.

As shown in FIG. 19, in the same manner as in Example 4, a part of the surface of the wristwatch band, which is the base material 100 on which the internal hardened layer 101 is formed, is provided with a first hard decorative film of gold. A TiN coating 27 made of titanium nitride having a color tone was coated. A masking layer 35 was formed on the desired surface of the surface of the TiN film 27 and the surface of the piece 1 continuous with the TiN film 27.

Next, as shown in FIG. 20, a TiN film 27 and a masking layer 3 are formed in the same manner as in the second embodiment.
5 and the surface of the remaining piece were coated with a second hard decorative film, a TiC film 36 made of titanium carbide having a white color tone.

Next, the substrate 100 is immersed in a stripping solution,
The masking layer 35 is swollen, and the masking layer 35 and the TiC coating 3 laminated thereon are lifted off by a lift-off method.
6 was peeled off. Therefore, as shown in FIG. 21, a three-color portion having a gold color portion covered with the TiN film 27, a white portion covered with the TiC film 36, and a portion where the surface of the piece 1 is exposed is provided. I got a band piece. Thereby, the decorative value of the band could be further enhanced.

The options of the first hard decorative film and the second hard decorative film, or the options of the stripping solution and the masking layer are the same as those described in Example 7. Further, one or both of the first hard decorative film and the second hard decorative film may be coated with the gold alloy film described in the fifth embodiment.

In the above Examples 2 and 4 to 8, the ion plating method was used as the dry plating method, but a known coating means such as a sputtering method or a vacuum evaporation method can be used. In addition, the substrate made in each of Examples 2 to 8 is also unlike the substrate made in Example 1 in that even if a strong force is applied to the surface of the coating, it becomes difficult to form irregularities on the surface of the substrate, and the coating is peeled off. Is gone.

[0134]

As described above, according to the present invention, an object of the present invention is to prevent the decorative coating from being scratched even when a strong force is applied to the coating surface, and also to prevent irregularities on the substrate surface. In addition, it is possible to provide a substrate having a decorative hard film and a method of manufacturing the same, which can minimize peeling of the film. Further, it is possible to provide a substrate having a hard coating made of a titanium or titanium alloy substrate having excellent appearance quality capable of keeping the surface beautiful even after long-term use, and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a view showing the results of measuring the Vickers hardness of a surface-treated member according to the present invention.

FIG. 2 is a schematic diagram showing the structure of a titanium or titanium alloy base material according to the first embodiment and the second embodiment of the present invention.

FIG. 3 is a schematic view showing an outline of a surface treatment apparatus used in an embodiment of the present invention.

FIG. 4 is a diagram showing the results of measuring the nitrogen content and the oxygen content with respect to the depth from the surface of the substrate according to the first embodiment of the present invention.

FIG. 5 is a view showing a result of measuring a nitrogen content and an oxygen content with respect to a depth from a surface of a base material according to the second embodiment of the present invention.

FIG. 6 is a schematic diagram illustrating a structure of a camera body according to the first embodiment of the present invention.

FIG. 7 is a schematic diagram illustrating a structure of a mobile phone body according to a second embodiment of the present invention.

FIG. 8 is a schematic diagram illustrating a structure of a portable radio body according to a third embodiment of the present invention.

FIG. 9 is a schematic diagram illustrating a structure of a portable radio body according to a third embodiment of the present invention.

FIG. 10 is a schematic view illustrating a surface treatment step of a video camera body in Embodiment 4 of the present invention.

FIG. 11 is a schematic view showing a surface treatment step of a video camera body in Embodiment 4 of the present invention.

FIG. 12 is a schematic diagram illustrating a structure of a video camera body according to a fourth embodiment of the present invention.

FIG. 13 is a schematic view illustrating a structure of a lighter body according to a fifth embodiment of the present invention.

FIG. 14 is a schematic diagram showing a surface treatment step of a personal computer main body according to a sixth embodiment of the present invention.

FIG. 15 is a schematic diagram illustrating a structure of a personal computer main body according to a sixth embodiment of the present invention.

FIG. 16 is a schematic view showing a surface treatment step of a wristwatch case in Embodiment 7 of the present invention.

FIG. 17 is a schematic diagram showing a surface treatment step of a wristwatch case in Embodiment 7 of the present invention.

FIG. 18 is a schematic view showing a structure of a wristwatch case according to a seventh embodiment of the present invention.

FIG. 19 is a schematic view showing a surface treatment step of a wristband piece according to Embodiment 8 of the present invention.

FIG. 20 is a schematic diagram showing a surface treatment step of a case band piece of a wristwatch according to an eighth embodiment of the present invention.

FIG. 21 is a schematic view showing a structure of a case band piece of a wristwatch according to an eighth embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum tank 3 Heater 4 Gas introduction pipe 5 Gas exhaust pipe 6 Gas introduction valve 7 Vacuum pump 8 Solenoid valve 9 Atmospheric release pipe 10 Vent valve 23 TiN coating 24 TiC coating 25 Hard carbon coating 26 Intermediate layer 27 TiN coating 28 Masking layer 29 TiN coating 30 Gold-titanium alloy coating 31 TiN coating 32 Gold-titanium alloy coating 33 Masking layer 34 TiC coating 35 Masking layer 36 TiC coating 100 Base 101 Internal hardened layer 102 First hardened layer 103 Second hardened Layer 104 nitrogen 105 oxygen

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C23C 14/06 C23C 14/06 AB 16/27 16/27 F term (reference) 4F100 AA12C AA15C AA15E AA16E AA17C AA36A AA36B AA37C AA40C AB01E AB11E AB12A AB12B AB12D AB13D AB25E AB31A AB31B AB31E BA03 BA05 BA07 BA10B BA10C BA10E BA13 BA25 BA26 EG002 EH662 EJ082 EJ242 EJ262 EJ422 EJ502 EJ522 EJ582 EJ592 EJ602 EJ612 EJ852 GB41 GB48 HB00C JB12A JB12B JK12C JL10C JM02C YY00A YY00B YY00C 4K029 AA02 AA26 BA55 BA60 BB02 BB03 BD00 BD06 CA03 EA01 EA03 FA04 HA02 4K030 AA09 BA28 BB13 CA02 CA11 FA01 HA04 JA09 JA12 LA24

Claims (18)

[Claims] 1. A substrate having a hard decorative coating on the surface, wherein the substrate is made of titanium or a titanium alloy, and the substrate is formed of nitrogen and oxygen formed at an arbitrary depth from the surface toward the inside. An inner hardened layer consisting of a first hardened layer that forms a solid solution, a second hardened layer formed at an arbitrary depth from the first hardened layer toward the inside, and covers the surface of the inner hardened layer A substrate having a hard decorative film, comprising: a hard decorative film formed. 2. The internal hardened layer includes a first hardened layer,
0.6 to 8.0 W% of nitrogen and 1.0 to 14.0 W% of oxygen are dissolved, and 0.5 to 14.0 W% is added to the second cured layer.
2. The substrate having a hard decorative film according to claim 1, wherein oxygen is dissolved as a solid solution. 3. The internal cured layer formed on the substrate, wherein the first cured layer is formed in a range of about 1 μm from the surface toward the inside, and the second cured layer is formed of the first cured layer. 2. The substrate having a hard decorative coating according to claim 1, wherein the substrate is formed deeper than the hardening and in a range of about 20 [mu] m from the surface toward the inside. 4. The hard decorative film according to claim 1, wherein the hard decorative film comprises 4a of the periodic table,
The substrate having a hard decorative coating according to claim 1, wherein the substrate is a nitride, carbide, oxide, nitrocarbide or nitrocarboxylate of a group 5a or 6a element. 5. The substrate having a hard decorative coating according to claim 1, wherein the hard decorative coating is a hard carbon coating. 6. A two-layer structure comprising a lower layer mainly composed of chromium or titanium and an upper layer mainly composed of silicon or germanium between the internal hardened layer formed on the base material and the hard decorative coating. The substrate having a hard decorative coating according to claim 5, further comprising an intermediate layer. 7. A lower layer mainly composed of titanium, between the internal hardened layer formed on the base material and the hard decorative coating,
The base material having a hard decorative film according to claim 5, further comprising an intermediate layer having a two-layer structure including an upper layer mainly composed of tungsten, tungsten carbide, silicon carbide, and titanium carbide. 8. The hard decorative coating has a thickness of 0.1 to 3.0 μm.
The base material having a hard decorative coating according to claim 1, wherein the base material is formed in a range of m. 9. The substrate having a hard decorative film according to claim 1, wherein the surface of the hard decorative film has a golden color tone. 10. The substrate having a hard decorative film according to claim 9, wherein the surface of the hard decorative film is coated with a film made of gold or a gold alloy. 11. The body having the hard decorative coating is one of a camera body, a mobile phone body, a mobile radio body, a video camera body, a writer body, and a personal computer body. A substrate having the hard decorative coating according to claim 2 or 3. 12. A heating step of arranging a substrate made of titanium or a titanium alloy in a vacuum chamber and performing an annealing treatment, and introducing a mixed gas mainly composed of nitrogen containing a trace amount of oxygen component into the vacuum chamber; 700 to 8 in the vacuum chamber under a predetermined reduced pressure
By heating at a temperature of 00 ° C. for a predetermined time, a hardening treatment step of diffusing and dissolving nitrogen and oxygen from the surface of the titanium or titanium alloy substrate into the inside thereof, and bringing the titanium or titanium alloy substrate to room temperature A cooling step of cooling, a polishing step of polishing the surface of the base material, a cleaning step of cleaning the base material, an evacuation step of setting and evacuation of the base material in a vacuum chamber, An ion bombarding step of introducing and ionizing argon to ion bombard the substrate surface, a step of forming an intermediate layer made of metal or metal carbide by sputtering on the substrate surface, and argon in the vacuum chamber. Exhausting the gas and introducing a gas containing carbon into the vacuum chamber; generating plasma in the vacuum chamber; and performing plasma CVD on the surface of the intermediate layer. Process for producing a substrate having a step of forming a Yamondo like carbon coating, the rigid decorative coating, characterized in that it consists. 13. The step of forming the intermediate layer comprises introducing argon into the vacuum chamber and ionizing the same to target any one of silicon, tungsten, titanium carbide, silicon carbide, and chromium carbide. 13. The method for producing a substrate having a hard decorative coating according to claim 12, wherein one of tungsten, titanium carbide silicon carbide, and chromium carbide is mainly used. 14. The step of forming the intermediate layer includes the step of: introducing argon into the vacuum chamber and ionizing the first layer to form a lower layer mainly composed of chromium or titanium with chromium or titanium as a target. 13. The hard material according to claim 12, comprising: a forming step; and, subsequent to the forming step, a second intermediate layer forming step of forming an upper layer mainly composed of silicon or germanium using silicon or germanium as a target. A method for producing a substrate having a decorative coating. 15. The step of forming the intermediate layer includes the steps of: introducing argon into the vacuum chamber and ionizing the same, forming a lower layer mainly composed of titanium with titanium as a target, 13. The production of a substrate having a hard decorative film according to claim 12, comprising a second intermediate layer forming step of forming an upper layer mainly composed of tungsten, using tungsten as a target, following said step. Method. 16. The step of forming the intermediate layer includes the steps of: introducing argon into the vacuum chamber and ionizing the same to form a lower layer mainly composed of titanium with titanium as a target; Subsequent to this step, a second intermediate layer forming step of introducing a gas containing carbon into the vacuum chamber, targeting tungsten or silicon, and forming an upper layer mainly containing tungsten carbide or silicon carbide,
The method for producing a substrate having a hard decorative coating according to claim 12, comprising: 17. A heating step of placing a substrate made of titanium or a titanium alloy in a vacuum chamber and performing an annealing treatment, and introducing a mixed gas mainly composed of nitrogen containing a trace amount of an oxygen component into the vacuum chamber. 700 to 8 in the vacuum chamber under a predetermined reduced pressure
By heating at a temperature of 00 ° C. for a predetermined time, a hardening treatment step of diffusing and dissolving nitrogen and oxygen from the surface of the titanium or titanium alloy substrate to the inside thereof, A cooling step of cooling, a polishing step of polishing the surface of the base material, a cleaning step of cleaning the base material, an evacuation step of setting and evacuation of the base material in a vacuum chamber, An ion bombarding step of introducing argon to ionize and ion bombarding the surface of the substrate, and applying ion plating or sputtering treatment to the surface of the substrate, 4a of the periodic table,
Forming a hard decorative coating made of a nitride, carbide, oxide, nitrided carbide or carbonitride of a group 5a or 6a element. 18. The method of manufacturing a substrate having a hard decorative film, the method comprising: after the step of forming the hard decorative film, forming a gold or gold alloy film on the surface of the hard decorative film by ion plating or sputtering. The method for producing a substrate having a hard decorative film according to claim 17, comprising a step of forming.