TWI502098B - Hard film-coated member and method of producing the same - Google Patents

Description

Hard film covering member coated with hard film and manufacturing method thereof

The present invention relates to a hard film covering member coated with a hard film and a method for producing the same.

In order to improve the abrasion resistance, weather resistance, acid resistance, alkali resistance, and the like of a substrate containing a soft metal, a surface treatment technique in which a surface of a substrate is coated with a hard film such as an amorphous carbon film is known. However, it has been pointed out that when the base material contains a soft metal such as aluminum or aluminum alloy, the hardness difference between the base material and the hard film is large, and thus the hard film is easily peeled off from the substrate. Therefore, it is desirable to form the hard film on the surface of the substrate with good adhesion.

An example of a patent application that is intended to form a hard film with a good adhesion to a surface of a substrate is disclosed in Japanese Laid-Open Patent Publication No. 2004-346353 (Patent Document 1). Patent Document 1 discloses a film forming method in which an amorphous carbon film is formed on a surface of an aluminum substrate via electroless Ni-P plating. In the film formation method of Patent Document 1, the electroless Ni-P layer is crystallized by applying heat treatment to the electroless Ni-P film at the time of film formation of the amorphous carbon film, and the hardness of the film is self-induced. The base material is gradually increased toward the amorphous carbon film, whereby the adhesion between the amorphous carbon film and the lower layer is improved. Further, in Japanese Laid-Open Patent Publication No. Hei-3-134184 (Patent Document 2), it is also disclosed that the electroless Ni-P layer formed between the aluminum substrate and the hard film is heated and hardened. The hardness is gradually increased from the substrate side toward the surface, so that the adhesion between the hard film and the lower layer is improved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-346353

[Patent Document 2] Japanese Patent Laid-Open No. Hei 3-134184

According to the verification by the present inventors, the adhesion between the hard film and the lower layer in the prior hard film covering member in which the hard film is coated with the soft metal is not sufficient. Accordingly, an object of the present invention is to provide a hard film coating member in which a hard film such as an amorphous carbon film is coated on a substrate containing a soft metal more preferably with better adhesion.

A hard film covering member according to an embodiment of the present invention includes: a base material comprising a soft metal; an amorphous electroless nickel plating layer formed on the base material; and a hard film formed on the electroless plating described above On the nickel layer. In the prior hard film coating member having the electroless nickel plating layer, the electroless nickel plating layer is crystallized by heat treatment. However, in one embodiment of the present invention, the hard film coating member is in the manufacturing step. The heating inhibition of the electrolytic nickel plating layer is less than 260 ° C, so that the electroless nickel plating layer in the finished body of the hard film coating member has an amorphous structure.

According to various embodiments of the present invention, it is possible to provide a hard film covering member in which a hard film such as an amorphous carbon film is coated on a substrate containing a soft metal more preferably with better adhesion.

Fig. 1 is a schematic view showing a cross section of a hard film covering member 1 according to an embodiment of the present invention. As shown in the figure, the hard film covering member 1 includes a substrate 10, a zinc substitution layer 20 formed on one surface of the substrate 10, and an amorphous layer formed on the surface of the zinc substitution layer 20 opposite to the substrate 10. The electroless nickel plating layer 30 and the hard film 40 formed on the surface of the electroless nickel plating layer 30 opposite to the zinc substitution layer 20 are formed. In this manner, the hard film covering member 1 according to the embodiment of the present invention is configured by sequentially laminating the substrate 10, the zinc substitution layer 20, the electroless nickel plating layer 30, and the hard film 40.

The substrate 10 contains various materials such as soft metals such as aluminum, magnesium, or the like. The aluminum alloy used as the material of the substrate 10 according to an embodiment of the present invention includes, for example, various aluminum alloys belonging to the AC series, the ADC series, and the AJ series. In the case where aluminum is used as the material of the substrate 10, the hardness of the substrate 10 is about 50 to 200 Hv as expressed by Vickers hardness, and the coefficient of thermal linear expansion is about 23 × 10 ^-6 /°C. Here, the value of the coefficient of thermal linear expansion varies depending on the temperature at which the substrate exists. In one aspect of the present invention, the surface of the substrate 10 is roughened by sand blasting or honing treatment, chemical etching using a chemical liquid, or the like, whereby the substrate 10 and the zinc substitution layer 20 can be made. Or, in place of the zinc substitution layer 20, the adhesion of the layer in which the electroless nickel plating layer 30 is in close contact with the substrate 10 is improved.

The zinc substitution layer 20 is formed as an undercoat layer on one surface of the substrate 10. The zinc substitution layer 20 is provided to allow the electroless nickel plating layer 30 to be in close contact with the substrate 10, and can be formed by any known method. An example of a film formation method will be described below. The thickness of the zinc-substituted layer 20 is very thin compared to the other layers (the substrate 10, the electroless nickel plating layer 30, and the hard film 40), for example, about 50 to 200 nm. When an anodized film is formed on the surface of the substrate 10 to ensure insulation of the substrate 10 from the upper layer, a zinc substitution layer 20 is formed on the anodized film. The coefficient of thermal linear expansion of the zinc-substituted layer 20 is about 26 x 10 ^-6 /°C.

In another embodiment of the present invention, in order to make the electroless nickel plating layer 30 adhere to the substrate 10, a catalyst such as Pd may be added to the surface of the substrate 10 instead of the zinc substitution layer 20. Further, on the surface of the substrate 10, various adhesion layers such as a metal thin film formed by a dry plating method such as a sputtering method or a vapor deposition method, or various wet plating films may be provided instead of the zinc substitution layer 20. The adhesion layer may be a single layer or a plurality of layers. For example, when the substrate 10 contains aluminum or an aluminum alloy, an anodized film may be formed on the surface layer of the substrate 10, and thereafter a zinc substitution layer 20 is formed, whereby the anodized film is used as an insulating layer. Undercoat. Further, instead of the zinc substitution layer 20, electroless Cu plating or electrolytic plating Cu may be used as the undercoat layer. Electroless Cu plating or electrolytic Cu plating may also be formed on the roughened substrate 10. Further, in order to form electroless Cu plating, a catalyst such as Pd may be applied to the surface of the substrate 10.

The electroless nickel plating layer 30 according to an embodiment of the present invention is formed on the surface of the zinc substitution layer 20 by electroless plating. In one embodiment of the present invention, the electroless nickel plating layer 30 has an amorphous structure in the completed body of the hard film covering member 1. The electroless nickel plating layer 30 according to an embodiment of the present invention includes, for example, electroless Ni-P plating or electroless Ni-B plating. In an embodiment of the present invention, the electroless Ni-B layer may be formed on the surface of the electroless Ni-P layer, and the electroless nickel plating layer 30 may be formed to include an electroless Ni-P layer. A two-layer structure of electroless Ni-B plating. Further, an electrolytic nickel plating layer may be formed on the surface of the electroless nickel plating layer 30. Since the electroless nickel plating layer 30 is amorphous, the electroless nickel plating layer 30 has a hardness of about 500 to 600 Hv and a coefficient of thermal linear expansion of about 13 × 10 ^-6 /°C. The electroless nickel plating layer 30 can be formed into various thicknesses depending on the use and usage of the substrate 10. The electroless nickel plating layer 30 is usually formed to a thickness of 0.1 to 40 μm. Further, since the electroless nickel plating layer 30 is amorphous in the hard film covering member 1, there is no defect in the crystal structure in the film. As a result, excellent weather resistance can be imparted to the substrate 10. On the hard film 40 described below, pinholes due to arcing in the plasma process, adhesion of foreign matter, and the like are formed in many cases, and the acid or alkali is impregnated into the substrate 10 by the pinhole to corrode the substrate 10. The situation. In the hard film covering member 1 according to the embodiment of the present invention, the amorphous electroless nickel plating layer 30 is provided between the substrate 10 and the hard film 40, so that pinholes are formed on the hard film 40. In this case, the intrusion of an acid or a base into the substrate 10 can be prevented, and the peeling of the hard film 40 can be suppressed.

If the electroless Ni-P layer exceeds about 260 ° C, it will transition from an amorphous structure to a crystalline structure, causing a significant decrease in ductility and an increase in hardness (refer to the Electroplating Research Society, "Electroless Plating - Basics and Applications , Nikkan Kogyo Shimbun, May 30, 1994, p. 37). When the ratio of phosphorus (P) in the electroless Ni-P layer is low, the presence or absence of the electroless Ni-P layer is not deposited as an amorphous structure but as a crystal structure, and thus, in one embodiment, The ratio of P in the electroless plated Ni-P layer was set to 8 wt% or more. In one embodiment of the present invention, the film formation treatment of the electroless Ni-P layer and the treatment after the electroless Ni-P layer is formed (the formation of the electrolytic nickel layer or the hard film 40) Both were carried out at about 260 ° C to prevent crystallization of the electroless Ni-P layer deposited in an amorphous structure.

Further, as an embodiment of the present invention, the electroless nickel plating layer 30 is not heated to a high temperature, so that the electroless nickel plating layer 30 is formed on the hard film covering member 1 (as a completed hard film coating). The constituent layer of the member 1 is a non-magnetic body. In particular, when the treatment of the electroless Ni-P layer is performed at about 260 ° C, the concentration of P contained in the electroless nickel plating layer 30 is adjusted so as to be about 11 When the wt% is more than 12% by weight, the electroless nickel plating layer 30 can be made non-magnetic in a state in which the film is formed on the hard film covering member 1. Further, when the treatment of the electroless Ni-P layer is performed at about 200 ° C, the concentration of P contained in the electroless nickel plating layer 30 is adjusted so as to be about 10 wt. In the above, the electroless nickel plating layer 30 can be made non-magnetic in a state in which the film is formed on the hard film covering member 1. In this way, the electroless nickel plating layer 30 is made non-magnetic, whereby the hard film covering member 1 can be prevented from being magnetized. Further, even in the case where the hard film 40 is formed by a hard film forming apparatus that controls a plasma or an electron beam by a magnetron (magnetic field), the electroless nickel plating layer 30 is not magnetized, so that it can be homogeneously formed into a hard material. Film 40. In addition, the hard film covering member 1 according to the embodiment of the present invention is used in a magnetic separator that uses a permanent magnet or an electromagnet, a component transfer feeder that uses a magnetic force to transport a component, an electrostatic chuck mechanism, or a magnet chuck. In the case of a part processing device such as a mechanism, it is possible to prevent the conveyance of the workpiece or the metal garbage from adhering to the feeder, and it is possible to prevent the occurrence of a problem caused by the magnet on the electronic component or the machine.

When the electroless plating Ni-B layer exceeds about 300 ° C, the transition from the amorphous structure to the crystalline structure causes a significant decrease in ductility and an increase in hardness similarly to the electroless Ni-P plating. Ratio of boron (B) in the electroless Ni-B layer In the case where the electroless plating Ni-B layer is not deposited as an amorphous structure but as a crystal structure, in one embodiment, the ratio of B in the electroless Ni-B layer is set to 3 wt. %the above. In one embodiment of the present invention, the film formation by the electroless plating of the Ni-B layer and the treatment after the electroless plating of the Ni-B layer are formed (the formation of the electrolytic nickel layer or the hard film 40, etc.) It is carried out at about 300 ° C to prevent crystallization of the electroless Ni-B layer deposited in an amorphous structure.

In one embodiment, the hard film 40 includes an amorphous carbon film such as diamond-like carbon (DLC, Diamond-Like Carbon), an amorphous carbon film containing various metal elements such as DLC containing Si, TiAlN, AlN, and TiCN. Hard film such as TiC, TiN, CrC, CrN, SiC or SiOX. These hard films are formed on the surface of the electroless nickel plating layer 30 by, for example, PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition). The hardness of the hard film 40 containing these materials is approximately 1000 to 4000 Hv. Although the thermal expansion coefficient of the hard film is various, it is much smaller than the aluminum (23×10 ^-6 /°C) or magnesium (25×10 ^-6 /°C) of the soft substrate. For example, in an amorphous carbon film such as a DLC film, it is about 2 × 10 ^-6 / ° C before and after, and is about 6.6 × 10 ^-6 / ° C in lanthanum carbide (SiC). The hard film 40 can be formed into various thicknesses depending on the use of the substrate, and is formed to be 10 nm to 10 μm in one aspect and 0.1 μm to 3 μm in the other aspect.

Further, in order to further improve the adhesion between the electroless nickel plating layer 30 and the hard film 40, various intermediate layers (not shown) may be formed between the electroless nickel plating layer 30 and the hard film 40. The intermediate layer is formed such that the electroless nickel plating layer 30 does not reach a specific temperature (for example, 260 ° C) or more. It is preferable that the intermediate layer has good adhesion to both the electroless nickel plating layer 30 and the hard film 40, and the coefficient of thermal linear expansion has a coefficient of thermal linear expansion of the electroless nickel plating layer 30 and a coefficient of thermal linear expansion of the hard film 40. an intermediate value (about 7 × 10 ^-6 / ℃). An example of such an intermediate layer is, for example, a chromium layer. The chromium layer is formed by a known method such as electrolytic plating, PVD, or sputtering. For example, the hardness of the hard chrome plating film formed by the electrolytic plating method is Hv 1000 or more in terms of Vickers hardness, but the hardness of the hard chrome plating film which has been subjected to heat treatment at 300 ° C or higher is reduced to about Hv 800. In one embodiment of the present invention, the hard chromium plating layer constituting one portion of the hard film covering member 1 is not heated to more than 300 ° C, and the higher hardness can be utilized as a part of the hardness inclined structure of the hard film covering member 1 . .

The removal of hydrogen embrittlement of the electroless nickel plating layer is generally carried out by heat treatment (baking treatment) at 150 ° C or higher. Therefore, in one embodiment of the present invention, the hard film 40 can be formed at a temperature of from 150 ° C to less than 260 ° C or from 150 ° C to less than 300 ° C. By forming the hard film 40 in this temperature range, the crystal structure of the electroless nickel plating layer 30 can be suppressed, and hydrogen embrittlement of the electroless nickel plating layer 30 can be suppressed.

In the hard film covering member 1 configured as described above, the electroless nickel plating layer 30 having an amorphous structure between the lower layer portion including the base material 10 and the zinc substitution layer 20 and the hard film 40 can be used for the hard film 40. The applied stress is relieved by the electroless nickel plating layer 30 and transferred to the substrate 10. Thereby, the stress applied to the substrate 10 containing a soft metal or the like can be reduced, and the deformation of the substrate 10 can be suppressed. As a result, it is possible to suppress the hard film caused by the deformation of the substrate 10. 40 is peeled off from the substrate 10. Therefore, in the hard film covering member 1 according to the embodiment of the present invention, the cured film is formed on the surface of the member, and the inside of the member is maintained in a soft structure. Therefore, the wear resistance is the same as that of "carburizing". High toughness.

Further, in an embodiment of the present invention, in the manufacturing step of the hard film covering member 1, heating of about 300 ° C or higher is not performed, so that the substrate 10 can be prevented from becoming high in temperature. Thereby, deterioration of the mechanical properties of the substrate 10, oxidation, discoloration, and/or stress deformation due to heating can be suppressed. For example, when the substrate 10 contains aluminum or an aluminum alloy, the recrystallization temperature of the aluminum and the aluminum alloy is present at about 200 ° C to 260 ° C, so that the hard film covering member 1 can be produced at about 200 ° C. The deformation due to recrystallization of the substrate 10 is prevented.

Further, in the hard film covering member 1, the hardness is gradually increased from the base material 10 side toward the hard film 40 side (aluminum alloy base material 10: about 50 to 200 Hv, and electroless nickel plating layer 30: 500 to 600 Hv) , hard film 40: 1000~4000 Hv), and the coefficient of thermal linear expansion is reduced stepwise (aluminum alloy substrate 10: 23 × 10 ^-6 / ° C, electroless nickel plating 30: 13 × 10 ^-6 / ° C, hard When the film 40 is, for example, an amorphous carbon film: 2 × 10 ^-6 /° C., the hardness and the coefficient of thermal expansion are gradually changed between the layers, and the peeling of the adjacent layers can be suppressed. Therefore, the hard film covering member 1 according to the embodiment of the present invention suppresses the deformation of the substrate 10 by the electroless nickel plating layer 30 of an amorphous structure, and the hardness and the coefficient of thermal linear expansion between the layers are gentle, so that the substrate 10 can be used. The hard film 40 is formed with good adhesion. In particular, by forming the electroless nickel plating layer 30 into an amorphous structure, the adhesion between the substrate 10 and the hard film 40 is higher than that of the prior hard film covering member represented by Patent Document 1 or Patent Document 2. Upgrade.

Next, a method of forming the hard film covering member 1 according to an embodiment of the present invention will be described. First, a zinc substitution layer 20 is formed on the surface of the substrate 10. The zinc substitution layer 20 can be formed by a well-known method well known to those skilled in the art, for example, by a degreasing step, an acidic etching step, a nitric acid impregnation step, a first zinc substitution step, a zinc nitrate stripping step, and a second zinc substitution step. A film is formed on the substrate 10. In one aspect, first, the substrate 10 is immersed in a weak alkali solution for degreasing, and then immersed in an acid solution such as sulfuric acid for etching, followed by nitric acid immersion treatment. Next, the substrate subjected to the nitric acid immersion treatment is immersed in a zinc substitution solution of a strong base containing NaOH as a main component to perform zinc substitution chromatography (first zinc substitution step). Next, the substrate 10 on which the zinc-substituted layer is formed is immersed in nitric acid to remove the scale. Then, the substrate 10 after being immersed in nitric acid is again immersed in a zinc substitution solution to be chromatographed by zinc substitution (second zinc substitution step). The zinc substitution layer 20 can also be formed into a film in the same manner as in the case where an anodized film is formed on the substrate 10. Further, in the nitric acid immersion step or the zinc substitution step, the anodic oxide film may be dissolved by adjusting the immersion time of the substrate 10 in a nitric acid or a strong alkali solution to remove the anodic oxide film from the substrate 10. For example, when the film thickness of the anodic oxide film is 10 μm, steps such as degreasing, etching, acid leaching, first zinc substitution, acid leaching, and second zinc substitution are performed for about 30 seconds to 1 minute, respectively. The anodic oxide film can be dissolved.

Next, an electroless nickel plating layer 30 is formed on the surface of the zinc substitution layer 20. Forming an electroless Ni-P layer by electroless Ni-P plating as an electroless nickel plating layer In the case of 30, the substrate 10 on which the zinc substitution layer 20 is formed is immersed in a plating solution in which nickel ions and hypophosphorous ions are placed, and Ni-P plating is formed on the zinc substitution layer 20. As is well known to the art, if the nickel ions in the plating solution come into contact with the hypophosphorous acid ions as the reducing agent, the aluminum substrate acts as a catalyst to cause dehydrogenation and decomposition, and the hydrogen atoms generated by the dehydrogenation decomposition are adsorbed to the zinc. Activated on top of the replacement layer 20. The activated hydrogen atoms are brought into contact with the nickel ions in the plating solution to reduce the nickel to a metal. Therefore, nickel is deposited on the surface of the zinc substitution layer 20. Further, the activated hydrogen atoms are also reacted with phosphoric acid ions in the plating solution to reduce the phosphorus in the ions, and the reduced phosphorus is alloyed with nickel. Then, the precipitated nickel becomes a catalyst, and the above-described nickel reduction plating reaction is continued. That is, the plating is continued by the self-catalytic action of nickel. By the action of the self-catalyst, a plating film can be uniformly formed on the surface of the zinc-substituted layer as long as the void of the plating solution can be distributed on the surface of the zinc-substituted layer of the aluminum substrate. Further, since the thickness of the plating film is proportional to the plating time, the thickness of the plating film can be managed by the control of the plating time. Further, the electroless plating Ni-B layer is formed by the same method as the electroless Ni-P plating layer by using an electroless plating solution containing a nickel-based ion and a boron-based agent such as an amine borane as a reducing agent.

The hard film 40 is formed by various methods such as a CVD (chemical vapor deposition) method such as a plasma CVD method or a physical vapor deposition (PVD) method such as a sputtering method. The plasma CVD method used in the embodiment of the present invention includes a high voltage DC (Direct Current) micropulse plasma CDV method, a high voltage pulse plasma CVD method, a high frequency plasma CVD method using high frequency discharge, and utilization. A direct current plasma CVD method for direct current discharge and a microwave plasma CVD method using microwave discharge. In straight In the flow plasma CVD method, since the current is continuously supplied, it is preferable to control the temperature of the substrate by the cooling device. The plasma PVD method includes various sputtering methods and vacuum evaporation methods. In one aspect of the present invention, in the film forming step of the hard film 40, in order to prevent the electroless nickel plating layer 30 from reaching a specific temperature (for example, 260 ° C) or more, the workpiece in the film formation can be appropriately cooled. For example, in an embodiment of the present invention, the following operations may be performed: monitoring the temperature of the workpiece during the film formation process, and interrupting the plasma forming process to achieve natural cooling of the workpiece before reaching a specific temperature (for example, 260 ° C). The plasma forming process is started again after the workpiece is sufficiently cooled. Further, in another embodiment of the present invention, a cooling device capable of cooling the workpiece is used, and the workpiece can be cooled in the plasma process. In still another embodiment of the present invention, by adjusting the duty ratio of the pulse power source of the plasma generating device, the temperature of the workpiece can be adjusted so as not to reach a specific temperature (for example, 260 ° C) or more. For example, when the hard film 40 is formed by the high-voltage DC micropulse plasma CVD method, the Duty ratio of the power source can be controlled within the range of 2% to 10%, so that the film formation temperature can be easily controlled to a low temperature. Moreover, in the low-temperature sputtering apparatus, the workpiece can be placed on the cooling mechanism with the refrigerant, so that the portion of the electroless nickel plating layer 30 of the workpiece can be kept at a specific temperature (for example, about 260 ° C) without being directly used. The hard film 40 is formed by the PVD method.

[Examples]

Hereinafter, an embodiment of the hard film covering member 1 according to various embodiments of the present invention will be described. The following examples are merely illustrative, and the invention is not limited to the examples described below.

Preparation of the substrate

Prepare a plurality of 5000 series of plate-shaped aluminum alloy substrates (5052 material). As the substrate, a sheet of 20 mm × 100 mm and a sheet thickness of 1 mm was prepared.

Formation of zinc substitution layer

Next, a zinc substitution layer was formed on the surface of the substrate by the following method. Specifically, first, the substrate was immersed in an aluminum detergent NE-6 solution (concentration: 60 g/L) manufactured by Meltex Co., Ltd., and degreased at 70 ° C for 60 seconds to utilize the degreased substrate. Tap water for 30 seconds. Next, the substrate after the water washing was immersed in a mixed solution of Akutan E-10 having a concentration of 100 ml/L and Akutan 70 having a concentration of 10 g/L, and etching was performed at 70 ° C for 30 seconds. Next, the substrate after the etching was subjected to water washing with tap water twice every 30 seconds. Then, it was subjected to acid immersion in a mixed aqueous solution of 67% nitric acid (500 ml/L), 98% sulfuric acid (250 ml/L), and Akutan 70 (120 g/L) at room temperature for 10 seconds, and performed twice. Washing with tap water every 30 seconds. Next, the cleaned substrate was immersed in a zinc substitution liquid containing Alonon EN as a main component at a concentration of 200 ml/L at 25 ° C for 90 seconds to precipitate a zinc substitution layer on the surface of the substrate. Thereafter, water washing by tap water was performed twice every 30 seconds. Next, the substrate on which the zinc-substituted layer was formed was immersed in 65% nitric acid at normal temperature for 15 seconds to remove the scale. Next, the base material from which the dirt was removed was subjected to tap water washing for 30 times every time for 30 times. Then, the cleaned substrate was immersed in a zinc substitution liquid containing Alonon EN having a concentration of 200 ml/L as a main component at 25 ° C for 60 seconds, and subjected to a second zinc substitution treatment, followed by washing with tap water.

Formation of electroless nickel plating

Next, each substrate on which the zinc-substituted layer is formed is immersed in a mixture of 55 ml/L of Melplate NI-2280LF Ml, 100 ml/L of Melplate NI-2280LF M2 and other extenders at 90 ° C to make phosphorus Electroless nickel plating having a concentration of 12.8 wt% was precipitated on the zinc substitution layer with a thickness of 20 μm. In this way, a plurality of substrates having an electroless nickel plating layer formed thereon are prepared.

Preparation of sample 1 (comparative example)

One substrate on which an electroless nickel plating layer was formed was heat-treated at 310 ° C for 30 minutes. Next, on the surface of the heat-treated substrate, a 160 nm amorphous carbon film containing ruthenium was formed as an intermediate layer for adhesion, and a 340 nm amorphous carbon film was formed on the intermediate layer. Specifically, the substrate after the heat treatment was first immersed in isopropyl alcohol, followed by ultrasonic cleaning for 5 minutes. Thereafter, each of the substrates was placed on a high-voltage DC pulse plasma CVD apparatus to form an amorphous carbon film under the following conditions. That is, first, a high voltage DC pulse plasma CVD apparatus was evacuated up until 7 × 10 ^-4 Pa, then a gas flow 30 SCCM, gas pressure of 2 Pa argon plasma at an applied voltage -5 kV, a pulse frequency of 10 The substrate was washed for about 5 minutes at kHz and a pulse width of 10 μs. Next, after argon gas was discharged from the CVD apparatus, the substrate was allowed to stand for about 10 minutes to naturally cool it. Then, tetramethyl decane having a flow rate of 30 SCCM and a gas pressure of 2 Pa was introduced into the CVD apparatus, and film formation was carried out for 8 minutes under the conditions of an applied voltage of -4.5 Kv, a pulse frequency of 10 kHz, and a pulse width of 10 μs, in an electroless nickel plating layer. An intermediate layer for bonding with ruthenium is formed thereon. Next, after the tetramethyl decane gas in the CVD apparatus was discharged, the substrate was allowed to stand for 20 minutes to naturally cool it. Then, for the CVD apparatus, acetylene having a flow rate of 30 SCCM and a pressure of 2 Pa was introduced into the CVD apparatus, and amorphous carbon was formed in 10 minutes under the conditions of a voltage of -5 Kv, a pulse frequency of 10 kHz, and a pulse width of 10 μs. membrane. Next, the substrate on which the amorphous carbon film was formed was placed in a CVD apparatus for 20 minutes to be naturally cooled and cooled. Then, acetylene having a flow rate of 30 SCCM and a pressure of 2 Pa was introduced into the CVD apparatus again, and an amorphous carbon film was formed again for 10 minutes under the conditions of a voltage of -5 Kv, a pulse frequency of 10 kHz, and a pulse width of 10 μs. And sample 1 was obtained.

Confirmation of the temperature of the electroless nickel plating layer on the substrate in the film formation of amorphous carbon film

It is prepared to attach a temperature label having a discoloration temperature of 260 ° C to a substrate on which an electroless nickel plating layer is formed. On the substrate, a 160 nm amorphous carbon film containing ruthenium was formed as an intermediate layer for adhesion by the same procedure as in Sample 1 (without heating at 310 ° C), and 340 nm was formed on the intermediate layer. Amorphous carbon film. It was confirmed that the temperature label did not undergo discoloration after the amorphous carbon film was formed in this manner. Therefore, it was confirmed that in the film formation step of the amorphous carbon film of the sample 1, the temperature of the substrate including the electroless nickel plating layer was maintained at less than 260 °C.

Preparation of sample 2 (comparative example)

After heat-treating one substrate on which the electroless nickel plating layer was formed at 280 ° C for 60 minutes, an amorphous carbon film containing ruthenium 160 nm was formed as an intermediate layer for adhesion, in the same manner as in Sample 1. A 340 nm amorphous carbon film was formed on the intermediate layer, and Sample 2 was obtained.

Preparation of sample 3 (Example)

On the substrate on which the electroless nickel plating layer was formed, the same method as that of the sample 1 (without heating at 310 ° C) was used to form a 160 nm-containing crucible. The crystalline carbon film was used as an intermediate layer for adhesion, and a 340 nm amorphous carbon film was formed on the intermediate layer to obtain a sample 3. As described above, the temperature of the substrate was always maintained at less than 260 ° C by the film formation step of the amorphous carbon film.

Preparation of sample 4 (Example)

One substrate on which an electroless nickel plating layer was formed was subjected to heat treatment at 230 ° C for 60 minutes. Next, on the substrate after the heat treatment, a 160 nm-containing amorphous carbon film containing ruthenium was formed as an intermediate layer for adhesion in the same manner as in Sample 1 (without heating at 310 ° C). A 340 nm amorphous carbon film was formed thereon, and Sample 4 was obtained. As described above, the temperature of the substrate was always maintained at less than 260 ° C by the film formation step of the amorphous carbon film.

For each of the obtained Sample 1 to Sample 4, a frictional abrasion test was performed. The frictional wear test was carried out using a tribo-gear HHS-2000 manufactured by Shinto Scientific Co., Ltd., and an amorphous carbon film was formed in each sample under the following conditions at normal temperature and without lubrication. On the surface, the friction coefficient of the surface of each sample was measured while reciprocating the head of SUJ2 having a diameter of 2.0 mm. The measurement of the coefficient of friction is carried out by addition and subtraction of the round-trip measurement.

Measurement condition 1

‧Measurement distance: 20 mm

‧Measurement speed: 5 mm/sec

‧Minimum load: 700 g

‧Maximum load: 950 g

Determination condition 2

‧Measurement distance: 20 mm

‧Measurement speed: 5 mm/sec

‧Minimum load: 500 g

‧Maximum load: 700 g

2 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 1 under the measurement condition 1, and FIG. 3 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 1 under the measurement condition 2. 2 and 3, the horizontal axis represents the number of abrasions, and the vertical axis represents the measured friction coefficient. As shown in Fig. 2, under the measurement condition 1, the friction coefficient of the sample 1 was rapidly increased from about 0.2 μ to 0.5 μ or more immediately after the start of the test, and when the number of abrasions was 10 (that is, when the indenter was reciprocated 10 times) The amorphous carbon film was destroyed. The test was terminated at the point of time when it was confirmed that the sample 1 was destroyed. Fig. 4 is a photograph showing the surface of the sample 1 obtained by photographing the indenter back and forth 10 times under the measurement condition 1. The photograph of Fig. 4 was obtained by photographing at a magnification of 200 times using a CCD (Charge Coupled Device) camera. In addition, similar photographs in this specification are all obtained by photographing at a magnification of 200 times using a CCD camera. As shown in the figure, on the surface of the sample 1 after the indentation was repeated 10 times, the trajectory of the sphere was exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster was exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed. Further, as shown in Fig. 3, under the measurement condition 2, the friction coefficient of the sample 1 was rapidly increased immediately after the start of the test, and when the number of abrasions was 31, the amorphous carbon film was broken. The test was terminated at the point of time when it was confirmed that the sample 1 was destroyed. Fig. 5 is a photograph showing the surface of the sample 1 obtained by photographing the indenter 31 times under the measurement condition 2. As shown in the figure, after the head is reciprocated 31 times, the sample 1 is shown. On the surface, a trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and a base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed.

6 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 2 under the measurement condition 1, and FIG. 7 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 2 under the measurement condition 2. As shown in Fig. 6, under the measurement condition 1, the friction coefficient of the sample 2 rapidly rose to nearly 0.5 μ immediately after the start of the test, and when the number of abrasions was 23, the amorphous carbon film formed on the surface thereof was destroyed. The test was terminated at the time when it was confirmed that the sample 2 was destroyed. Fig. 8 is a photograph showing the surface of the sample 2 obtained by photographing the indenter 23 times under the measurement condition 1. As shown in the figure, on the surface of the sample 2 after the indentation 23 times, the trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed. Further, as shown in Fig. 7, under the measurement condition 2, the friction coefficient of the sample 2 was rapidly increased to nearly 0.5 μ immediately after the start of the test, and when the number of abrasions was 21, the amorphous carbon film was destroyed. The test was terminated at the time when it was confirmed that the sample 2 was destroyed. Fig. 9 is a photograph showing the surface of the sample 2 obtained by photographing the indenter 21 times under the measurement condition 2. As shown in the figure, on the surface of the sample 2 after the indentation 21 times, the trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed.

Fig. 10 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 3 under the measurement condition 1, and Fig. 11 is a view showing the sample 3 under the measurement condition 2. A graph of the change in friction coefficient corresponding to the number of wears. As shown in FIG. 10 and FIG. 11 , the friction coefficient of the sample 3 is low and stable, regardless of whether the measurement conditions 1 and 2 are both 0.2 μm before and after the presence of the amorphous carbon film. No substantial increase in the coefficient of friction due to this experiment was found. Fig. 12 is a photograph showing the surface of the sample 3 obtained by taking the indenter back and forth 100 times under the measurement condition 1, and Fig. 13 is a photograph showing the surface of the sample 3 obtained by taking the indenter back and forth 100 times under the measurement condition 2. As shown in the figure, the trajectory of the indenter was not observed on the surface of the sample 3 after the indentation was repeated 100 times regardless of the conditions under which the experiment was conducted under the measurement conditions. From the results of these tests, it was confirmed that the sample 3 exhibited good frictional wear resistance.

14 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 4 under the measurement condition 1, and FIG. 15 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 4 under the measurement condition 2. As shown in FIG. 14 and FIG. 15 , the friction coefficient of the sample 4 is low and stable, regardless of whether the measurement conditions 1 and 2 are both 0.2 μm before and after the presence of the amorphous carbon film. No substantial increase in the coefficient of friction due to this experiment was found. Fig. 16 is a photograph showing the surface of the sample 4 obtained by photographing the indenter back and forth 100 times under the measurement condition 1, and Fig. 17 is a photograph showing the surface of the sample 4 obtained by photographing the indenter 100 times under the measurement condition 2. As shown in the figure, the trajectory of the indenter was not observed on the surface of the sample 4 after the indentation was repeated 100 times regardless of the conditions under which the experiment was conducted under the measurement conditions. From the results of these tests, it was confirmed that the sample 4 exhibited good frictional wear resistance.

Next, Samples 5 to 7 were prepared by the same method as Samples 1 to 3. Samples 5 to 7 had an electroless nickel plating layer having a film thickness of 3 μm thinner than the samples 1 to 3. With In the same manner as the sample 1, the sample 5 was formed by laminating a substrate, a zinc-substituted layer, an electroless nickel plating layer (3 μm), and an amorphous carbon film to form an amorphous carbon film. The substrate was previously heat treated at 310 ° C for 30 minutes. In the same manner as the sample 2, the sample 6 was formed by laminating a substrate, a zinc-substituted layer, an electroless nickel plating layer (3 μm), and an amorphous carbon film, and the substrate was formed by forming an amorphous carbon film. It was obtained by heat-treating at 280 ° C for 60 minutes. In the same manner as the sample 3, the sample 7 was formed by laminating a substrate, a zinc-substituted layer, an electroless nickel plating layer (3 μm), and an amorphous carbon film. In the same manner as the sample 3, the film formation step of the electroless nickel plating layer of the sample 7 through the amorphous carbon film was always less than 260 °C. Thus, the thickness of the electroless nickel plating layer of the samples 5 to 7 was 3 μm, and the samples 5 to 7 were different from the samples 1 to 3 in this respect.

For each of the obtained samples 5 to 7, the frictional abrasion test was carried out in the same manner as in the samples 1 to 3. 18 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 5 under the measurement condition 1, and FIG. 19 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 5 under the measurement condition 2. As shown in Fig. 18, under the measurement condition 1, the friction coefficient of the sample 5 was rapidly increased to about 1.2 μ at the beginning of the test, and when the number of abrasions was 5, the amorphous carbon film was destroyed. The test was terminated at the time when it was confirmed that the sample 5 was destroyed. Fig. 20 is a photograph showing the surface of the sample 5 obtained by photographing the indenter five times after the measurement condition 1. As shown in the figure, on the surface of the sample 5 after the urging head is reciprocated five times, the trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed. Further, as shown in Fig. 19, under the measurement condition 2, the friction coefficient of the sample 5 sharply rises immediately after the start of the test. To about 0.8 μ, the amorphous carbon film is destroyed when the number of abrasions is 5. The test was terminated at the time when it was confirmed that the sample 5 was destroyed. Fig. 21 is a photograph showing the surface of the sample 5 obtained by photographing the indenter five times after the measurement condition 2. As shown in the figure, on the surface of the sample 5 after the urging head is reciprocated five times, the trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed.

22 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 6 under the measurement condition 1, and FIG. 23 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 6 under the measurement condition 2. As shown in Fig. 22, under the measurement condition 1, the friction coefficient of the sample 6 was rapidly increased to 0.8 μ immediately after the start of the test, and when the number of abrasions was 6, the amorphous carbon film formed on the surface thereof was destroyed. The test was terminated at the time when it was confirmed that the sample 6 was destroyed. Fig. 24 is a photograph showing the surface of the sample 6 obtained by photographing the indenter six times after the measurement condition 1. As shown in the figure, on the surface of the sample 6 after the urging head was reciprocated six times, the trajectory of the sphere was exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster was exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed. Further, as shown in Fig. 23, under the measurement condition 2, the friction coefficient of the sample 6 was rapidly increased to 0.7 μ immediately after the start of the test, and when the number of abrasions was 5, the amorphous carbon film was destroyed. The test was terminated at the time when it was confirmed that the sample 6 was destroyed. Fig. 25 is a photograph showing the surface of the sample 6 obtained by photographing the indenter five times after the measurement condition 2. As shown in the figure, on the surface of the sample 6 after the reciprocation of the indenter 5 times, the trajectory of the sphere is exhibited in a strip extending in the left-right direction, and the metallic luster is exposed along the trajectory. The base of the amorphous carbon film. Thereby, it was confirmed that the amorphous carbon film was destroyed.

26 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 7 under the measurement condition 1, and FIG. 27 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 7 under the measurement condition 2. As shown in Fig. 26, under the measurement condition 1, the friction coefficient of the sample 7 was rapidly increased to 1 or more immediately after the start of the test, and when the number of abrasions was 5, the amorphous carbon film formed on the surface thereof was destroyed. The test was terminated at the time when it was confirmed that the sample 7 was destroyed. Further, as shown in Fig. 27, the friction coefficient of the sample 7 was low and stable around 0.2 μm indicating the presence of the amorphous carbon film under the measurement condition 2, even after the test of 100 times of abrasion. A substantial increase in the coefficient of friction will be found. Fig. 28 is a photograph showing the surface of the sample 7 obtained by photographing the indenter five times after the measurement condition 1. As shown in the figure, on the surface of the sample 7 after the experimental head is reciprocated 5 times under the measurement condition 1, the trajectory of the sphere is exhibited in a strip extending in the left-right direction, and a metallic luster is exposed along the trajectory. The base of the carbon film. Thus, it was confirmed that the amorphous carbon film was destroyed. Fig. 29 is a photograph showing the surface of the sample 7 obtained by photographing the indenter 100 times after the measurement condition 2. As shown in the figure, the trajectory of the indenter was found on the surface of the sample 7 after the indentation was repeated 100 times, but as in the case where the change in the friction coefficient of Fig. 27 was confirmed, the measurement condition 2 of the sample 7 was confirmed. The coefficient of friction was stable to about 0.2 μ from the start to the end of the test, and the amorphous carbon film was maintained on the surface of the sample 7. Therefore, it is understood that the sample 7 exhibits good frictional wear resistance at least in the case of the measurement condition 2 in which the load is relatively small. On the other hand, sample 5 and sample 6 are determined regardless of measurement conditions. What happens, the amorphous carbon film is destroyed. Therefore, from the results of these tests, it was confirmed that the sample 7 exhibited more excellent frictional wear resistance than the sample 5 and the sample 6.

Next, Samples 8 to 9 were produced by the same method as Samples 1 to 3. Specifically, in the sample 8 , a substrate, a zinc-substituted layer, an electroless nickel plating layer (10 μm), an electrolytic nickel plating layer (10 μm), and an amorphous carbon film were laminated in the same manner as in the sample 1. Forming, the substrate was placed at 310 ° C for 30 minutes before the film formation of the amorphous carbon film. In the same manner as the sample 3, the sample 9 was formed by laminating a substrate, a zinc-substituted layer, an electroless nickel plating layer (10 μm), an electrolytic nickel plating layer (10 μm), and an amorphous carbon film. Similarly to the sample 3, the electroless nickel plating layer of the sample 9 was always less than 260 ° C by the film formation step of the amorphous carbon film. The electrolytic nickel plating layers of Samples 8 to 9 are formed by various methods well known to those skilled in the art, for example, using nickel sulfonate, nickel chloride, boric acid, and an additive material (gloss material) by maintaining at 55 ° C. It is formed by energization of the left and right solutions. Among them, in the step of forming the electrolytic nickel plating layer, the temperature management is performed such that the temperature of the electroless nickel plating layer is always less than 260 °C. Each of the samples 8 to 9 has an electrolytic nickel plating layer, which is different from the samples 1 to 3 in this respect. Further, the thickness of the electroless nickel plating layer of the samples 8 to 9 was 10 μm, and the samples 8 to 9 were different from the samples 1 to 3 in this respect.

For each of the obtained samples 8 to 9, the frictional abrasion test was carried out in the same manner as in the samples 1 to 3. FIG. 30 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 8 under the measurement condition 1, and FIG. 31 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 8 under the measurement condition 2. As shown in Fig. 30, under the measurement condition 1, the friction coefficient of the sample 8 was tested. After the start of the test, it suddenly rises to 0.5 μ, and when the number of wear is 3, the amorphous carbon film is destroyed. The test was terminated at the time when it was confirmed that the sample 8 was destroyed. Fig. 32 is a photograph showing the surface of the sample 8 obtained by photographing the indenter three times after the measurement condition 1. As shown in the figure, on the surface of the sample 8 after the indentation three times, the trajectory of the sphere is exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster is exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed. Further, as shown in Fig. 31, under the measurement condition 2, the friction coefficient of the sample 8 was rapidly increased to 0.5 μ immediately after the start of the test, and when the number of abrasions was 16, the amorphous carbon film was broken. The test was terminated at the time when it was confirmed that the sample 8 was destroyed. Fig. 33 is a photograph showing the surface of the sample 8 obtained by photographing the indenter 16 times after the measurement condition 2. As shown in the figure, on the surface of the sample 8 after the embossing was repeated 16 times, the trajectory of the sphere was exhibited in a strip shape extending in the left-right direction, and the base of the amorphous carbon film having a metallic luster was exposed along the trajectory. Thereby, it was confirmed that the amorphous carbon film was destroyed.

Fig. 34 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 9 under the measurement condition 1. As shown in the figure, under the measurement condition 1, the coefficient of friction of the sample 9 showed a value of 0.2 μ lower until the number of abrasions was about 70 times, and then increased. From this, it is understood that when the number of abrasions is about 70, the amorphous carbon film is broken and the friction coefficient is increased. It was confirmed that the sample 8 which was heated was destroyed when the number of abrasions was three, whereas the sample 9 maintained the amorphous carbon film until the number of abrasions was 70, and the adhesion of the amorphous carbon film was remarkably improved. Fig. 35 is a photograph showing the surface of the sample 9 obtained by photographing the indenter 100 times after the measurement condition 1. as the picture shows, It was confirmed that the substrate having the trajectory of the sphere and exposing the amorphous carbon film having the metallic luster along the trajectory was considered to be caused by the peeling of the amorphous carbon film after the abrasion time of 70 times.

The hard film covering member described in the present specification and the method for producing the same are merely exemplified, and various modifications can be made without departing from the spirit and scope of the invention. For example, a Ni thin film or a Cu thin film may be formed between the substrate 10 and the zinc substitution layer 20, and/or between the zinc substitution layer 20 and the electroless nickel plating layer 30 by a sputtering method or a vapor deposition method. Further, a flash copper film may be formed between the zinc substitution layer 20 and the electroless nickel plating layer 30. These Ni thin films, Cu thin films, and flash copper plating films are formed so as to have a film thickness of 300 nm or less, and thus have no substantial influence on the adhesion of the hard film 40. In addition to what is specifically described in the present specification, between the substrate 10 and the zinc-substituted layer 20, between the zinc-substituted layer 20 and the electroless nickel-plated layer 30, between the electroless nickel-plated layer 30 and the hard film 40, Various films may be provided without departing from the gist of the invention. Moreover, the base material 10, the zinc substitution layer 20, the electroless nickel plating layer 30, and the hard film 40 can be surface-treated suitably according to the objective.

1‧‧‧hard film covering member

10‧‧‧Substrate

20‧‧‧Zinc replacement layer

30‧‧‧Electroless nickel plating

40‧‧‧hard film

Fig. 1 is a view schematically showing a hard film covering member according to an embodiment of the present invention.

Fig. 2 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 1 under the measurement condition 1.

Fig. 3 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 1 under the measurement condition 2.

Fig. 4 is a photograph of the surface of the sample 1 obtained by photographing the indenter 10 times after the measurement condition 1.

Fig. 5 is a photograph of the surface of the sample 1 obtained by photographing the indenter 31 times after the measurement condition 2.

Fig. 6 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 2 under the measurement condition 1.

Fig. 7 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 2 under the measurement condition 2.

Fig. 8 is a photograph of the surface of the sample 2 obtained by photographing the indenter 23 times after the measurement condition 1.

Fig. 9 is a photograph of the surface of the sample 2 obtained by photographing the indenter 21 times after the measurement condition 2.

Fig. 10 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 3 under the measurement condition 1.

Fig. 11 is a graph showing changes in the friction coefficient of the sample 3 under the measurement condition 2 in accordance with the number of abrasions.

Fig. 12 is a photograph of the surface of the sample 3 obtained by photographing the indenter 100 times after the measurement condition 1.

Fig. 13 is a photograph of the surface of the sample 3 obtained by photographing the indenter 100 times after the measurement condition 2.

Fig. 14 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 4 under the measurement condition 1.

Fig. 15 is a graph showing changes in the friction coefficient of the sample 4 under the measurement condition 2 in accordance with the number of abrasions.

Fig. 16 is a photograph of the surface of the sample 4 obtained by photographing the indenter 100 times after the measurement condition 1.

Fig. 17 is a photograph of the surface of the sample 4 obtained by photographing the indenter 100 times after the measurement condition 2.

Fig. 18 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 5 under the measurement condition 1.

Fig. 19 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 5 under the measurement condition 2.

Fig. 20 is a photograph of the surface of the sample 5 obtained by photographing the indenter five times after the measurement condition 1.

Fig. 21 is a photograph of the surface of the sample 5 obtained by photographing the indenter five times after the measurement condition 2.

Fig. 22 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 6 under the measurement condition 1.

Fig. 23 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 6 under the measurement condition 2.

Fig. 24 is a photograph of the surface of the sample 6 obtained by photographing the indenter six times after the measurement condition 1.

Fig. 25 is a photograph of the surface of the sample 6 obtained by photographing the indenter five times after the measurement condition 2.

Fig. 26 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 7 under the measurement condition 1.

Fig. 27 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 7 under the measurement condition 2.

Fig. 28 is a photograph of the surface of the sample 7 obtained by photographing the indenter five times after the measurement condition 1.

Fig. 29 is a photograph of the surface of the sample 7 obtained by photographing the indenter 100 times after the measurement condition 2.

Fig. 30 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 8 under the measurement condition 1.

Fig. 31 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 8 under the measurement condition 2.

Fig. 32 is a photograph of the surface of the sample 8 obtained by photographing the indenter three times after the measurement condition 1.

Fig. 33 is a photograph of the surface of the sample 8 obtained by photographing the indenter 16 times after the measurement condition 2.

Fig. 34 is a graph showing changes in the friction coefficient corresponding to the number of abrasions of the sample 9 under the measurement condition 1.

Fig. 35 is a photograph of the surface of the sample 9 taken after the indentation was repeated 100 times under the measurement condition 1.

1‧‧‧hard film covering member

10‧‧‧Substrate

20‧‧‧Zinc replacement layer

30‧‧‧Electroless nickel plating

40‧‧‧hard film

Claims (20)

A hard film covering member comprising: a substrate comprising a soft metal; an amorphous electroless nickel plating layer formed on the substrate; and a hard film directly formed on the electroless nickel plating layer. The hard film coating member according to claim 1, wherein the electroless nickel plating layer is an electroless Ni-P plating layer. The hard film coating member according to claim 1, wherein the electroless nickel plating layer is an electroless Ni-B plating layer. The hard film coating member according to claim 2, wherein the content of phosphorus in the electroless plating Ni-P layer is 8 wt% or more. The hard film coating member according to claim 3, wherein the content of boron in the electroless plating Ni-B layer is 3% by weight or more. The hard film coating member according to claim 2, wherein the hard film film is formed so that the electroless Ni-P layer is kept at less than 260 °C. The hard film coating member according to claim 3, wherein the hard film film is formed so that the electroless Ni-B layer is kept at less than 300 °C. The hard film covering member of claim 1, wherein the substrate comprises aluminum or an aluminum alloy. The hard film coating member according to claim 1, wherein the hard film comprises an amorphous carbon film selected from the group consisting of amorphous carbon film or Si, Ti, AlN, TiCN, TiC, TiN, TiAlN, CrC, CrN, SiC. And one or more hard film materials of the group consisting of SiOX. The hard film covering member according to claim 1, wherein the substrate and the above A zinc-substituted layer is formed between the electroless nickel plating layers. A method for manufacturing a hard film covering member, comprising the steps of: preparing a substrate comprising a soft metal, forming an amorphous electroless nickel plating layer on the substrate, and directly forming a hard film on the electroless nickel plating layer; . The method of claim 11, wherein the electroless nickel plating layer is an electroless Ni-P plating layer. The method of claim 11, wherein the electroless nickel plating layer is an electroless Ni-B plating layer. The method of claim 12, wherein the content of phosphorus in the electroless Ni-P layer is 8 wt% or more. The method of claim 13, wherein the content of boron in the electroless Ni-B layer is 3% by weight or more. The method of claim 12, wherein the hard film is formed by holding the electroless Ni-P layer at a temperature of less than 260 °C. The method according to claim 13, wherein the hard film film is formed so that the electroless Ni-B layer is kept at less than 300 °C. The method of claim 11, wherein the substrate comprises aluminum or an aluminum alloy. The method of claim 11, wherein the hard film comprises one or more selected from the group consisting of diamond-like carbon, ruthenium-containing diamond carbon, TiAlN, TiCN, TiC, TiN, CrC, CrN, SiC, and SiOX. Hard film material. The method of claim 11, further comprising forming on the substrate The step of replacing the layer with zinc, and the electroless nickel plating layer is formed on the surface of the zinc substitution layer.