JP6318430B2 - Composite hard film member and method for producing the same - Google Patents

Description

  The present invention relates to a composite hard coating member in which a diamond-like carbon (DLC) film is formed on a film-forming member made of a ferrous metal material or a non-ferrous metal material via an intermediate layer, and a method for manufacturing the same.

  A plating film formed by plating on the surface of a member, a coating film that has been dried by spraying a paint onto the member, and the like have a large environmental load due to the use of organic solvents and the necessity of waste liquid treatment. For this reason, DLC films having mechanical properties excellent in high hardness, wear resistance, and the like have been studied in various fields as a technology that can replace these.

  However, the DLC film formed on the surface of the base material is generally considered to have a large number of minute defects such as through-holes in the film, and there is a problem that the base material corrodes based on this. .

  In contrast, the present inventors focused on a silicon oxide film having excellent barrier properties, and formed a DLC composite film having a carbon-containing silicon film as an intermediate layer on a film-forming member made of a non-ferrous metal material. It has been clarified that it has high corrosion resistance (see Patent Document 1).

JP 2011-162865 A

  Even if the DLC composite film is applied to a film-forming member made of an iron-based metal material, the adhesion between the silicon oxide film and the iron-based metal material is poor, and the entire DLC composite film or a part of the film is peeled off after the film formation. As a result, there is a problem that the film forming member is corroded. Further, there is a need for a DLC composite film in which the adhesion of the silicon oxide film is slightly insufficient for some non-ferrous metal materials and higher corrosion resistance can be obtained.

  One aspect of the present invention is to provide a composite hard film member that can suppress corrosion of a ferrous metal material member or a non-ferrous metal material member on which a DLC film is formed, or a method for manufacturing the same.

  Since the DLC film is produced by a film-forming method that does not use an organic solvent, such as a sputtering method or a plasma CVD method, and has a low environmental load, DLC applied to a member made of a ferrous metal material or a non-ferrous metal material if the above problems can be solved. It is thought that the use of the film will be dramatically accelerated.

  Therefore, the present inventors have disclosed a composite film having a carbon-containing silicon film between a silicon oxide film and a film-forming member, specifically, a member-carbon-containing silicon film-silicon oxide film-carbon-containing silicon film from the member side. -Developed a composite coating that improves adhesion by depositing a DLC film and obtains high corrosion resistance to ferrous metal materials or non-ferrous metal materials.

  The DLC film has high hardness, low friction, low wear, chemical stability, and surface smoothness. The DLC film is translucent when the film thickness is small, but is black with an interference color when the film thickness is large. For this reason, the member to be deposited on which the DLC film is formed can have a decorativeness and a design that are superior to those in the case where another hard film is formed.

  One embodiment of the present invention includes a film-forming member made of an iron-based metal material or a non-ferrous metal material, a first carbon-containing silicon film formed on a surface of the film-formed member, and the first carbon-containing material. A silicon oxide film formed on the silicon film, a second carbon-containing silicon film formed on the silicon oxide film, and a diamond-like carbon film formed on the second carbon-containing silicon film. It is the composite hard film member characterized by comprising.

  According to one embodiment of the present invention, by forming the first carbon-containing silicon film, the silicon oxide film, and the second carbon-containing silicon film between the surface of the deposition target member and the diamond-like carbon film, Corrosion of the film-forming member made of an iron-based metal material or a non-ferrous metal material can be effectively suppressed.

  In one embodiment of the present invention, the iron-based metal material is iron or an iron-based alloy containing iron as a main component, and the non-ferrous metal material is aluminum, an aluminum alloy containing aluminum as a main component, or magnesium. One selected from the group consisting of magnesium alloy containing magnesium as a main component, titanium, titanium alloy containing titanium as a main component, zinc, zinc alloy containing zinc as a main component, nickel and nickel alloy containing nickel as a main component Material.

  Further, in one embodiment of the present invention, a plating layer is formed on a surface of the deposition target member, the first carbon-containing silicon film is formed on the plating layer, and the plating layer is A layer made of a non-ferrous metal material. This non-ferrous metal material is made of, for example, nickel or a nickel alloy containing nickel as a main component.

  The iron-based alloy containing iron as a main component is an alloy containing 50 wt% or more of iron, preferably an alloy containing 65 wt% or more of iron, more preferably an alloy containing iron of 80 wt% or more. It is. The aluminum alloy mainly composed of aluminum is an alloy containing 65% by weight or more of aluminum, preferably an alloy containing 80% by weight or more of aluminum. A magnesium alloy containing magnesium as a main component is an alloy containing 80% by weight or more of magnesium, and a titanium alloy containing titanium as a main component is an alloy containing 70% by weight or more of titanium and contains zinc as a main component. The zinc alloy is a metal containing 90% by weight or more of zinc. The nickel alloy containing nickel as a main component is an alloy containing 50% by weight or more of nickel, preferably an alloy containing 65% by weight or more of nickel, more preferably an alloy containing 80% by weight or more of nickel. is there.

  In the above aspect of the present invention, the film-forming member may be a tool, a mold, an automobile wheel (Al, Mg), a mobile phone, a camera housing (Al, Mg), or the like, an iron-based or non-ferrous component. One member selected from the group consisting of

  In the above aspect of the present invention, the film-forming member may be an aluminum wheel for an automobile, a magnesium wheel for an automobile, an aluminum iron, an aluminum alloy door knob for an automobile, a magnesium alloy casing of a laptop computer, a camera It is preferably one member selected from the group consisting of an aluminum alloy casing, a magnesium alloy casing of a camera, and a magnesium alloy casing of a mobile phone. Thereby, while being able to give the outstanding decorating property and designability, corrosion of a film-forming member can be suppressed effectively.

In the composite hard coating member according to one aspect of the present invention, the first carbon-containing silicon film preferably has a thickness of 0.01 to 5 μm. The reason why the range of 0.01 to 5 μm is used is that the carbon-containing silicon film is too thick or too thin (ie, less than 0.01 μm or thicker than 5 μm), or the composite hard coating member is in close contact. This is because the strength decreases.
In the composite hard coating member according to one embodiment of the present invention, the silicon oxide film preferably has a thickness of 0.01 to 5 μm. The reason for setting the range of 0.01 to 5 μm is that if the film thickness of the silicon oxide film is less than 0.01 μm, the film forming member is easily corroded, and if the film thickness of the silicon oxide film is thicker than 5 μm, the composite hard This is because the film member is easily peeled off.
In the composite hard coating member according to one embodiment of the present invention, the second carbon-containing silicon film preferably has a thickness of 0.01 to 5 μm. The reason why the range of 0.01 to 5 μm is used is that the carbon-containing silicon film is too thick or too thin (ie, less than 0.01 μm or thicker than 5 μm), or the composite hard coating member is in close contact. This is because the strength decreases.

  In one embodiment of the present invention, a first carbon-containing silicon film using a first silicon compound gas is formed by a plasma CVD method on a surface of a deposition target member made of an iron-based metal material or a non-ferrous metal material, A silicon oxide film is formed on the first carbon-containing silicon film by a plasma CVD method using a second silicon compound gas and an oxygen gas, and a third silicon compound gas is formed on the silicon oxide film by a plasma CVD method. A method for producing a composite hard coating member, comprising: forming a second carbon-containing silicon film using a carbon; and forming a diamond-like carbon film on the second carbon-containing silicon film by a plasma CVD method. is there.

  In the aspect of the present invention described above, a plating layer is formed on a surface of the deposition target member, and the first carbon-containing silicon film is formed on the plating layer, and the plating layer Is a layer made of a non-ferrous metal material. This non-ferrous metal material is, for example, nickel or a nickel alloy containing nickel as a main component.

In the embodiment of the present invention, each of the first to third silicon compound gases may be hexamethyldisilazane (C ₆ H ₁₉ NSi ₂ ), hexamethyldisiloxane (C ₆ H ₁₈ OSi ₂ ), or tetra Methylsilane (C ₄ H ₁₂ Si) is preferred.

  ADVANTAGE OF THE INVENTION According to this invention, the composite hard coating member which can suppress the corrosion of the ferrous metal material member or nonferrous metal material member which formed the DLC film, or its manufacturing method can be provided.

It is a block diagram which shows schematically the plasma CVD apparatus by Embodiment 1 of this invention. (A) is sectional drawing which shows the composite hard film of Embodiment 1, (B), (C), (D) is sectional drawing which shows the composite hard film of a comparative example. It is a figure which shows the external appearance observation result of the base material 2 which consists of SCM after film-forming of the silicon oxide film 7 shown in FIG.2 (D), and the base material 2 which consists of a magnesium plate. (A)-(C) are figures which show a combined cycle test result. It is a photograph which shows the state which formed the composite hard film into the business card case by the method similar to Embodiment 1. FIG.

  Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments and examples below.

  In order to form a hard coating on a large number of large-scale products, it is necessary to mass-produce using a large reaction tank, and the chemistry is simpler than physical vapor deposition (PVD), which makes the structure of the apparatus complicated. The chemical vapor deposition method (CVD method) is advantageous. The advantage of the CVD method is that plasma can be formed with a simple structure such as a vacuum exhaust system, plasma power supply, and source gas supply device, and it is possible to form a film with good circulation even with large and complex shapes, and maintenance is also possible. Compared with the PVD method, it is much simpler.

(Embodiment 1)
FIG. 1 is a block diagram schematically showing a plasma CVD apparatus according to Embodiment 1 of the present invention. This plasma CVD apparatus is an apparatus for forming a composite hard film using a high frequency power source of 100 kHz.

  The plasma CVD apparatus has a vacuum chamber (chamber) 1, and a work holder (not shown) for holding a work 2 is disposed in the vacuum chamber 1. The work 2 is a film-forming member made of a ferrous metal material or a non-ferrous metal material, such as a tool, a mold, an automobile wheel (Al, Mg), a mobile phone, a camera casing (Al, Mg), etc. It may be one member selected from the group consisting of ferrous and non-ferrous parts.

  The work 2 includes, for example, an aluminum wheel, a magnesium wheel, an aluminum iron, an aluminum alloy door knob for automobiles, a magnesium alloy casing for a notebook computer, an aluminum alloy casing for a camera, a magnesium alloy casing for a camera, and It may be one member selected from the group consisting of magnesium alloy casings for mobile phones.

  Further, the workpiece 2 has a plated layer formed on the surface thereof, and the plated layer may be a layer made of a non-ferrous metal material. The non-ferrous metal material is mainly made of nickel or nickel, for example. It may be made of a nickel alloy as a component.

  The iron-based metal material is iron or an iron-based alloy containing iron as a main component. The iron-based alloy is an alloy containing 50% by weight or more of iron, preferably an alloy containing 65% by weight or more of iron, more preferably an alloy containing 80% by weight or more of iron.

  Non-ferrous metal materials include aluminum, aluminum alloy mainly composed of aluminum, magnesium, magnesium alloy composed mainly of magnesium, titanium, titanium alloy composed mainly of titanium, zinc, zinc alloy composed mainly of zinc, nickel And a material selected from the group consisting of nickel alloys whose main component is nickel. The aluminum alloy is an alloy containing 65% by weight or more of aluminum, preferably an alloy containing 80% by weight or more of aluminum. The magnesium alloy is an alloy containing 80 wt% or more of magnesium, the titanium alloy is an alloy containing 70 wt% or more of titanium, and the zinc alloy is a metal containing 90 wt% or more of zinc. The nickel alloy is an alloy containing 50% by weight or more of nickel, preferably an alloy containing 65% by weight or more of nickel, more preferably an alloy containing 80% by weight or more of nickel.

  A substrate bias power supply system 4 is electrically connected to the work 2 via a work holder, and this substrate bias power supply system 4 has a substrate matching unit and a 100 kHz high frequency power supply (RF power supply). The work holder also acts as an RF electrode. The substrate bias power supply system 4 applies high-frequency power to the workpiece 2 via a workpiece holder. That is, in this plasma CVD apparatus, the substrate bias power supply system 4 supplies a high-frequency current of 100 kHz to the work holder to generate plasma of the source gas in the vicinity of the work 2.

  In the present embodiment, a frequency of 100 kHz is used. However, other frequencies may be used as long as they are within a range of 50 to 500 kHz, and more preferably, a frequency of 300 kHz or less is used. Is to use a frequency of 250 kHz or less. When a high-frequency power source of 300 kHz or less is used, there is an advantage that matching can be achieved with a low-cost matching device using a matching transformer or the like. Further, when the frequency of the high-frequency power source is lower than 50 kHz, a problem that induction heating occurs in the work 2 occurs. Further, when the frequency of the high frequency power source exceeds 500 kHz, the bias applied to the work 2 is lowered, and a problem that a hard film is difficult to be formed occurs.

A gas system 5 is connected to the vacuum chamber 1, and the source gas is supplied into the vacuum chamber 1 from the introduction port by the gas system 5. The source gas is argon gas, oxygen gas, silicon compound gas, and toluene. The silicon compound gas is, for example, hexamethyldisilazane (C ₆ H ₁₉ NSi ₂ ) or hexamethyldisiloxane (C ₆ H ₁₈ OSi ₂ ) (hereinafter collectively referred to as HMDS) or tetramethylsilane (C ₄ H ₁₂ Si). The gas system 5 has a gas introduction path for introducing a raw material gas into the vacuum chamber 1, and the gas introduction path has a gas pipe. The gas pipe is provided with a flow meter for measuring the gas flow rate and a gas flow controller for controlling the gas flow rate. Appropriate amounts of argon gas, oxygen gas, HMDS, and toluene are supplied into the vacuum chamber 1 from the gas inlet by the flow meter. The vacuum chamber 1 is connected to an exhaust system 6 that evacuates the inside thereof. The exhaust system 6 has a vacuum pump. This vacuum pump is composed of a mechanical booster pump and an oil rotary pump that are inexpensive and easy to maintain, without using a turbo molecular pump or a diffusion pump that is expensive and complicated to maintain. Yes. With such a simple pump, only a vacuum degree of about 0.5 to 1 Pa can be obtained, but with the method according to the present embodiment, a high-quality film can be produced even with such a low vacuum.

  Next, a method for forming a composite hard film on the workpiece surface as shown in FIG. 2A using the plasma CVD apparatus of FIG. 1 will be described.

  First, as a workpiece (film forming member), a base material 2 made of chromium molybdenum steel (SCM, size: 20 mm × 50 mm × 3 mm) as an iron-based base material, and a magnesium plate (size: 20 mm) as a non-ferrous base material. A base material 2 made of × 50 mm × 5 mm) is prepared, the substrate 2 is subjected to ultrasonic cleaning for 30 minutes in acetone, and then mounted on a work holder in the vacuum chamber 1.

  Next, the inside of the vacuum chamber 1 is exhausted to 0.7 Pa or less by the exhaust system 6, and then argon gas is introduced into the vacuum chamber 1. Next, an argon plasma is formed in the vicinity of the base material 2 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source at an output of 250 W, and ion etching is performed for 20 minutes to clean the surface of the base material 2. . Thereby, the surface of the base material 2 is washed.

  Thereafter, the pressure in the vacuum chamber 1 is maintained at 0.6 Pa or less by the exhaust system 6, and hexamethyldisilazane which is a raw material gas for the carbon-containing silicon film is introduced into the vacuum chamber 1 at a flow rate of 8 cc / min. Next, a carbon-containing silicon film (Si film) 10 having a film thickness of 0.2 μm is formed on the surface of the substrate 2 by supplying a high-frequency current of 100 kHz to the work holder using a high-frequency power source with an output of 250 W. Is done. The carbon-containing silicon film 10 preferably contains 10 to 50 at% carbon, 20 to 50 at% silicon, and 10 to 40 at% hydrogen, and may further contain nitrogen and oxygen. Note that the composition of the carbon-containing silicon film 10 is considered to vary depending on the film forming conditions and the like.

Next, hexamethyldisilazane is introduced into the vacuum chamber 1 as a source gas for the silicon oxide film at a flow rate of 5 cc / min and oxygen gas at a flow rate of 50 cc / min. Next, a silicon oxide film (SiO _X film) 7 having a thickness of 0.4 μm is formed on the carbon-containing silicon film 10 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source with an output of 300 W. Be filmed.

  Thereafter, the oxygen gas of the source gas is stopped, and hexamethyldisilazane, which is the source gas of the carbon-containing silicon film, is introduced into the vacuum chamber 1 at a flow rate of 8 cc / min. Next, a high-frequency current of 100 kHz is supplied to the work holder using a high-frequency power source with an output of 250 W, whereby a carbon-containing silicon film (Si film) 8 having a thickness of 0.8 μm is formed on the silicon oxide film 7. Is done. The carbon-containing silicon film 8 preferably contains 10 to 50 at% carbon, 20 to 50 at% silicon, and 10 to 40 at% hydrogen, and may further contain nitrogen and oxygen. Note that the composition of the carbon-containing silicon film 8 is considered to vary depending on the film forming conditions and the like.

  Next, the source gas hexamethyldisilazane is stopped, and toluene, which is the source gas of the DLC film, is introduced into the vacuum chamber 1 at a flow rate of 10 cc / min. Next, a DLC film 9 having a thickness of 2.3 μm is formed on the carbon-containing silicon film 8 by supplying a high-frequency current of 100 kHz to the work holder using a high-frequency power source with an output of 300 W.

  Next, as a comparative example, the DLC composite film shown in FIGS. 2B, 2C, and 2D is fabricated using the plasma CVD apparatus of FIG. 1, and the DLC composite shown in FIGS. A film corrosion test was performed and will be described.

  First, a method for forming the DLC composite film shown in FIG. 2B using the plasma CVD apparatus in FIG. 1 will be described.

  The same base material 2 is ultrasonically cleaned by the same method as the DLC composite film shown in FIG. 2A, mounted on a work holder in the vacuum chamber 1, and ion-etched for 20 minutes. Thereafter, hexamethyldisilazane is introduced into the vacuum chamber 1 in the same manner as the DLC composite film shown in FIG. Next, a carbon-containing silicon film (Si film) 10 is formed on the surface of the substrate 2 by supplying a high-frequency current of 100 kHz to the work holder using a high-frequency power source. This carbon-containing silicon film 10 is the same as the carbon-containing silicon film 10 shown in FIG.

  Next, the source gas hexamethyldisilazane is stopped and toluene is introduced into the vacuum chamber 1 by the same method as the DLC composite film shown in FIG. Next, a DLC film 9 is formed on the carbon-containing silicon film 8 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source. This DLC film 9 is the same as the DLC film 9 shown in FIG.

  Next, a method for forming the DLC composite film shown in FIG. 2C using the plasma CVD apparatus in FIG. 1 will be described.

  The process until the carbon-containing silicon film (Si film) 10 is formed on the surface of the substrate 2 is the same as the process shown in FIG.

Next, hexamethyldisilazane and oxygen gas are introduced into the vacuum chamber 1 as source gases by the same method as the DLC composite film shown in FIG. Next, a silicon oxide film (SiO _X film) 7 is formed on the carbon-containing silicon film 10 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source. This silicon oxide film 7 is similar to the silicon oxide film 7 shown in FIG.

  Next, the raw material gases hexamethyldisilazane and oxygen gas are stopped and toluene is introduced into the vacuum chamber 1 by the same method as the DLC composite film shown in FIG. Next, a DLC film 9 is formed on the silicon oxide film 7 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source. This DLC film 9 is the same as the DLC film 9 shown in FIG.

  Next, a method for forming the DLC composite film shown in FIG. 2D using the plasma CVD apparatus in FIG. 1 will be described.

The substrate 2 is ultrasonically cleaned by the same method as the DLC composite film shown in FIG. 2A, mounted on a work holder in the vacuum chamber 1, and ion-etched for 20 minutes. Thereafter, hexamethyldisilazane and oxygen gas are introduced into the vacuum chamber 1 as source gases by the same method as the DLC composite film shown in FIG. Next, a silicon oxide film (SiO _X film) 7 is formed on the surface of the substrate 2 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source. This silicon oxide film 7 is similar to the silicon oxide film 7 shown in FIG.

  Next, the raw material gases hexamethyldisilazane and oxygen gas are stopped and toluene is introduced into the vacuum chamber 1 by the same method as the DLC composite film shown in FIG. Next, a DLC film 9 is formed on the silicon oxide film 7 by supplying a high frequency current of 100 kHz to the work holder using a high frequency power source. This DLC film 9 is the same as the DLC film 9 shown in FIG.

  Next, FIG. 3 shows the external appearance observation results of the base material 2 made of SCM and the base material 2 made of a magnesium plate after the silicon oxide film 7 and the DLC film 9 shown in FIG. From this figure, it can be seen that the entire surface peels in the SCM plate (base material) and the partial peel occurs in the Mg plate (base material). This is considered to be caused by poor adhesion between the substrate 2 and the silicon oxide film 7. Since the function of surface protection cannot be expected by peeling the film, only the FIGS. 2A to 2C were used for the following corrosion tests.

Next, the corrosion test of the DLC composite film was performed by the following method.
2A to 2C were subjected to a combined cycle test in which a cycle of salt spray (2 hours) → drying (4 hours) → wetting (2 hours) was repeated for 7 days. When the corrosion resistance of the DLC composite film was evaluated by this combined cycle test, the results shown in FIG. 4 were obtained.

  FIG. 4B shows a state after performing a combined cycle test on the test piece (Si-DLC) of FIG. 2B in which the carbon-containing silicon film 10 is formed as an intermediate layer between the base material 2 and the DLC film 9. The surface state of is shown. From this figure, it can be seen that the SCM plate (base material) is totally corroded, and the Mg plate (base material) has a large number of pitting corrosion.

FIG. 4C shows a test piece (Si—SiO _X -DLC) in FIG. 3C in which a carbon-containing silicon film 10 and a silicon oxide film 7 are formed as intermediate layers between the base material 2 and the DLC film 9. Shows the surface state after the combined cycle test. From this figure, it can be seen that the SCM plate (base material) is totally corroded, and the Mg plate (base material) peels off the DLC film.

On the other hand, FIG. 4A shows the carbon-containing silicon film 10, the silicon oxide film 7, and the carbon-containing silicon film 8 formed as intermediate layers between the base material 2 and the DLC film 9, as shown in FIG. the test piece _{(Si-SiO X -Si-DLC} ) shows the surface state after the combined cycle test. From this figure, several point-like corrosion is confirmed in the SCM plate (base material), but it is better than FIGS. 4 (b) and (C), and in the Mg material (base material), It can be seen that no separation is observed.

From the above results, a carbon-containing silicon film (Si film) is formed at the interface so that a silicon oxide film (SiO _X film) with good barrier properties can have good adhesion to the substrate and the DLC film. _Si-SiO X -Si-DLC film is iron-based substrate, it was found to have high corrosion resistance against non-ferrous substrates.

(Embodiment 2)
FIG. 5 is a photograph showing a state in which a composite hard coating is formed on the surface of the business card case using the plasma CVD apparatus of FIG. 1 in the same manner as in the first embodiment. This composite hard film is a carbon-containing silicon film, silicon oxide film, carbon-containing silicon film, or DLC film formed on a business card case. The business card case is made of magnesium alloy

  The business card case shown in FIG. 5 has excellent corrosion resistance as described in the first embodiment, and is excellent in wear resistance, decoration, and design. In order to impart decorativeness and design properties, it is preferable that the thickness of the DLC film is 1.0 μm or more. Thereby, it can be set as a color as shown in FIG.

  Note that the plasma CVD apparatus shown in FIG. 1 can easily form a film on a large product other than the business card case because the effective film formation zone can be widened even with a small apparatus.

DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber 2 ... Work 4 ... Substrate bias power supply system 5 ... Gas system 6 ... Exhaust system 7 ... Silicon oxide film 8 ... Carbon containing silicon film 9 ... DLC film 10 ... Carbon containing silicon film

Claims (7)

A film-forming member made of a ferrous metal material or a non-ferrous metal material;
A first carbon-containing silicon film formed on the surface of the film-forming member;
A silicon oxide film formed on the first carbon-containing silicon film;
A second carbon-containing silicon film formed on the silicon oxide film;
A diamond-like carbon film formed on the second carbon-containing silicon film;
A composite hard film member comprising: In claim 1,
The ferrous metal material is iron or an iron-based alloy containing iron as a main component,
The non-ferrous metal material is aluminum, aluminum alloy mainly containing aluminum, magnesium, magnesium alloy mainly containing magnesium, titanium, titanium alloy mainly containing titanium, zinc, zinc alloy mainly containing zinc, A composite hard coating member characterized by being one material selected from the group consisting of nickel and a nickel alloy containing nickel as a main component. In claim 1 or 2,
A plating layer is formed on the surface of the deposition member,
The first carbon-containing silicon film is formed on the plating layer;
The composite hard coating member, wherein the plating layer is a layer made of a non-ferrous metal material. In any one of Claims 1 thru | or 3,
The film thickness of the first carbon-containing silicon film is 0.01 to 5 μm, the film thickness of the silicon oxide film is 0.01 to 5 μm, and the film thickness of the second carbon-containing silicon film is 0. A composite hard film member having a thickness of 01 to 5 μm. Forming a first carbon-containing silicon film using a first silicon compound gas on the surface of a film-forming member made of an iron-based metal material or a non-ferrous metal material by a plasma CVD method;
Forming a silicon oxide film on the first carbon-containing silicon film by a plasma CVD method using a second silicon compound gas and an oxygen gas;
Forming a second carbon-containing silicon film using a third silicon compound gas on the silicon oxide film by a plasma CVD method;
A method for producing a composite hard coating member, comprising forming a diamond-like carbon film on the second carbon-containing silicon film by a plasma CVD method. In claim 5,
A plating layer is formed on the surface of the deposition member,
The first carbon-containing silicon film is formed on the plating layer;
The method for producing a composite hard film member, wherein the plating layer is a layer made of a non-ferrous metal material. In claim 5 or 6,
Each of the first to third silicon compound gases is hexamethyldisilazane, hexamethyldisiloxane, or tetramethylsilane.