JP2003171758A - Diamondlike carbon hard multilayer film formed body, and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard multilayer formed body in which an iron based material having a low hardness is used as a base material, and a DLC (diamondlike carbon) film capable of exhibiting excellent adhesion even when relatively, thickly formed is formed on the base material as an outermost surface layer. <P>SOLUTION: As an intermediate layer formed between an outermost surface layer essentially consisting of diamondlike carbon and a base material of an iron based material, a four layer structure where four layers of (1) a first metallic layer consisting of Cr and/or Al, (2) a second mixed layer consisting of a metal of Cr and/or Al, and one or more kinds of metals selected from W, Ta, Mo, and Nb, (3) a third metallic layer consisting of one or more kinds selected from the group consisting of W, Ta, Mo, and Nb, and (4) a fourth amorphous layer containing one or more kinds of metals selected from the group consisting of W, Ta, Mo and Nb, and carbon are formed in this order is made. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to wear-resistant mechanical parts such as automobile parts and the like, showing particularly good adhesion to an iron-based material as a base material and excellent wear resistance. The present invention relates to a hard multilayer film molded body having a diamond-like carbon film as a surface layer, and a method for producing the same.

[0002]

2. Description of the Related Art Hard carbon is a hard material generally called diamond-like carbon (hereinafter sometimes abbreviated as "DLC"). Hard carbon is also given various names such as hard amorphous carbon, amorphous carbon, hard amorphous carbon, i-carbon, and diamond-like carbon, but these terms are clearly distinguished. It does not mean that

The essence of DLC in which various terms are used in this way is structurally having an intermediate structure between diamond and graphite, and has a high hardness and wear resistance similar to diamond. , Solid lubricity,
Because of its excellent thermal conductivity and chemical stability, it is used as a protective film for various parts such as sliding members, molds, cutting tools, wear-resistant machine parts, abrasives, magnetic and optical parts, etc. It's starting.

As a method for forming such a DLC film, a physical vapor deposition method (PVD method) such as a sputtering method or an ion plating method, and a chemical vapor deposition method (CVD
However, while the DLC film usually has an extremely large internal stress during film formation and has a high hardness and Young's modulus, its deformability is extremely small, so that the adhesion to the base material is low. It is weak and easily peels off.

Various techniques have been proposed so far for improving the adhesion to a substrate. These techniques are roughly classified into (1) a method for controlling film stress, and (2) a substrate and carbon. There are two methods, that is, a method of providing an intermediate layer with the film. However, these techniques have the following problems, and the actual situation is that they are desired to be improved. First, in the above method (1), basically, the instability of adhesion at a different interface between the substrate and the carbon film has not been solved. In addition, in the method (2), basically, the base material and the DLC film are combined as a sizing layer with a layer having a property intermediate between the structure and the mechanical property between them as an adhesive layer. Although a material containing a hard brittle material is adopted, the CVD method or PVD is used.
Due to the enormous internal stress in the DLC film produced by the method, when a thick film having a thickness of several μm is formed or a hard film having a hardness of more than 40 GPa with many diamond components is formed, the problem of poor adhesion is caused. Is remarkable.

The present inventors have long been studying from the viewpoint of improving the adhesion of the DLC film to the base material,
As a part of the research, a technique such as Japanese Patent Laid-Open No. 2000-119843 is proposed. This technique uses a DLC film as the outermost layer, and W,
A first layer on the side of the substrate, which is made of one or more metal layers selected from the group consisting of Ta, Mo and Nb, and W, Ta, Mo
The present invention relates to a DLC hard multilayer film molded body having a two-layer structure composed of a second layer on the outermost surface side which is an amorphous layer containing carbon and one or more metal elements selected from the group consisting of Nb and Nb. . Then, in the DLC hard multilayer film molded product having such a film structure, good adhesion of the DLC film to the cemented carbide base material such as WC-Co was achieved.
However, even this technique has some problems to be solved.

[0007] The above-mentioned technology basically assumes the case where a cemented carbide such as WC-Co is used as a base material.
When the WC-Co based cemented carbide and the insulating material such as Si or Al ₂ O ₃ were used as the base material, the intermediate layer could secure good adhesion to the base material. When an iron-based material such as speed tool steel is used as a base material, the compatibility between the intermediate layer and the base material is not always good,
There is a problem that the adhesion between the intermediate layer and the base material becomes poor and the DLC film is likely to peel off.

When the above-mentioned multilayer film is formed on the surface of an iron-based material as a base material, the DLC of the outermost surface layer is used.
Since the internal stress of the film is large, the adhesion between the intermediate layer and the DLC film deteriorates, and it is difficult to secure sufficient adhesion, especially for a thick DLC film having a high hardness and a film thickness exceeding 3 μm. .

Further, iron-based materials are widely used, and have the usefulness that they are inexpensive and have excellent toughness as compared with cemented carbides. The reality is that establishment is desired. In particular, when it is used as a machine part for automobile parts, it is common that a bearing steel having a hardness lower than that of the high speed tool as described above, a stainless steel material, a carbon steel or the like is used as a base material, It is necessary to exhibit excellent adhesion even to such a low hardness iron-based material.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to use a low hardness iron-based material as a base material and A hard multilayer film molded body having a DLC film capable of exhibiting excellent adhesion even if formed relatively thick as the outermost surface layer,
And to provide a useful method for forming such a rigid multilayer film molded body.

[0011]

The DLC hard multilayer film molding according to the present invention, which has been able to achieve the above object, comprises a film mainly composed of diamond-like carbon as an outermost surface layer, and further an intermediate layer and a substrate. And the base material is made of an iron-based material, and the intermediate layer has the following (1) to
The gist is that the four layers of (4) have a four-layer structure formed in the order described from the base material side to the outermost surface layer side. (1) First layer composed of a metal layer of Cr and / or Al (2) Metal of Cr and / or Al and W, Ta, M
Second layer consisting of a mixed layer of one or more metals selected from the group consisting of o and Nb (3) Third layer consisting of one or more metal layers selected from the group consisting of W, Ta, Mo and Nb Layer (4) Fourth layer consisting of an amorphous layer containing carbon and at least one metal selected from the group consisting of W, Ta, Mo and Nb
layer

In the DLC hard multilayer film molding of the present invention, the second layer has a graded composition in which the content of Cr and / or Al decreases gradually or continuously toward the outermost surface layer side. It is preferably configured to have. The fourth layer is made of W, Ta, Mo and N.
The content of at least one metal selected from the group consisting of b is preferably configured so as to have a graded composition that gradually or continuously decreases toward the outermost surface layer side.

The above-mentioned objects of the present invention are (1) to (4) above.
The following (5) to (8) instead of the intermediate layer consisting of 4 layers
It is also achieved by providing a DLC hard multilayer film molded body having a four-layer structure in which the above four layers are formed in the order described from the substrate side toward the outermost surface layer side. (5) First layer composed of a metal layer of Cr and / or Al (6) Second layer composed of a mixed layer of a metal of Cr and / or Al and a compound containing WC as a main component (7) Main component of WC Third layer consisting of a compound containing (8) A fourth layer consisting of an amorphous layer containing a compound containing WC as a main component and carbon

D of the present invention employing such an intermediate layer structure
In the LC rigid multilayer film molded body, the second layer is made of Cr.
It is preferable that the content of Al and / or Al is configured so as to have a graded composition that gradually or continuously decreases toward the outermost surface layer side. Further, the fourth layer is preferably configured to have a graded composition in which the content of the compound containing WC as a main component decreases stepwise or continuously toward the outermost surface layer side. .

Whichever construction is adopted, in the DLC hard multilayer film molding of the present invention, it is effective to form a stress relaxation layer made of carbon between the fourth layer and the outermost surface layer. The stress relaxation layer has a hardness close to that of the intermediate fourth layer at the interface on the side of the intermediate layer, increases gradually or continuously as it approaches the outermost surface layer, and near the outermost surface layer. It is preferably configured to have a hardness close to that of a film mainly composed of DLC. Further, the DL
The film mainly composed of C is (a) W, Ta, Mo, Nb, C
a layer containing at least one metal selected from the group consisting of r and Al in the range of 5 to 20 atom%, or (b)
A structure in which at least one layer containing at least one metal selected from the group consisting of W, Ta, Mo, Nb, Cr and Al in the range of 5 to 20 atomic% and at least one diamond-like carbon layer are laminated. Is preferred.

On the other hand, in manufacturing the DLC hard multilayer film molding of the present invention, the diamond-like carbon film is formed by an unbalanced magnetron sputtering method (hereinafter, may be abbreviated as "UBM sputtering method"). Preferably. Also, UBM
When the film mainly composed of DLC is formed by the sputtering method, it is preferable to form the film while controlling the substrate temperature at 100 to 300 ° C.

In producing the DLC hard multilayer film molding of the present invention, the base material temperature is controlled to 150 to 350 ° C. at the stage of forming the intermediate first to third layers on the base material. It is preferable to form a diffusion layer between the material and the first layer and between the layers.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have studied the structure of an intermediate layer for ensuring good adhesion between a DLC film and a base material when an iron-based material is used as the base material. , Examined from various angles. As a result, as the structure of the intermediate layer, a first layer on the side of the base material made of a metal or alloy of Cr and / or Al and an outermost surface made of an amorphous layer containing a metal element of Cr and / or Al and carbon It has been found that a two-layer structure including the second layer on the layer side can ensure good adhesion between the base material and the DLC film even when an iron-based material is used as the base material. Since the technical significance was recognized, the application was filed first (Japanese Patent Application No. 2001-62395).
issue). However, even in such a technique, some problems to be improved still remain.

According to this technique, the first layer on the base material side made of a metal or alloy of Cr and / or Al and the outermost surface layer made of an amorphous layer containing a metal element of Cr and / or Al and carbon. By interposing the intermediate layer having a two-layer structure including the second layer between the base material and the DLC film, these metals are interdiffused at the interface with the iron-based material base material, and are excellent in the base material. The adhesion was secured. And in such a technique, the previously proposed intermediate layers, that is, W, Ta, M
a first layer on the side of the base material composed of one or more metal layers selected from the group consisting of o and Nb, and W, Ta, Mo and N
a second layer on the outermost surface layer side that is an amorphous layer containing carbon and one or more metal elements selected from the group consisting of b
Compared with the case where the intermediate layer having a layered structure is adopted, the adhesion to the base material made of an iron-based material is remarkably improved.

However, such an effect was remarkably exhibited when the iron-based material used as the base material was an iron-based material having a relatively high hardness such as high speed tool steel. When a bearing steel, a stainless steel material, a carbon steel or the like having a hardness lower than that of the high speed tool steel is used as the base material, the adhesion is still insufficient. In particular, when a DLC film having higher hardness and a thicker film (3 μm or more) is formed in order to further improve the wear resistance of the DLC film, such a problem becomes apparent.

Therefore, as a result of further study by the inventors of the present invention on a film structure capable of coping with such a situation, when an intermediate layer consisting of four layers as described above is formed, an iron-based material having a relatively low hardness is used as a base. The inventors have found that even when used as a material, good adhesion can be secured and excellent abrasion resistance is exhibited, and the present invention has been completed.

In the DLC hard multilayer film molding of the present invention, the adhesion between the substrate and the DLC film is guaranteed by the intermediate layer interposed therebetween. In this intermediate layer, the layer (first layer) made of a metal of Cr and / or Al that constitutes the layer on the base material side has good compatibility with the iron-based material that is the base material, and also for this iron-based material. It will exhibit good adhesion. Then, such a layer on the substrate side (the first
A layer and a middle layer (first layer).
Layer) and adhesion can be secured.

The intermediate third layer of the present invention comprises one or more metal layers selected from the group consisting of W, Ta, Mo and Nb, and the intermediate second layer constitutes the first layer. It is a layer composed of a mixed layer of the metal and the metal constituting the third layer, and the interposition of these layers can secure the adhesiveness between the intermediate first layer and the third layer.

In the second layer, the metal gradually decreases from the first layer side (base material side) toward the DLC film side (surface layer side) (that is, the third layer is formed). The gradient composition is preferably such that the constituent element concentration increases from 0% to 100%. By adopting such a film structure, the mechanical properties of the multilayer film can be changed stepwise or continuously from the base material side to the DLC side, thereby preventing peeling due to local stress concentration due to thermal shock or the like. can do.

Then, as a layer on the outermost surface side of the intermediate layer (the fourth layer), a brittle carbide layer is not formed, and an amorphous layer of metal and carbon constituting the third layer is formed.
Here, the amorphous layer refers to a layer in which a crystal phase cannot be confirmed with a transmission electron microscope. In this way, by making the intermediate fourth layer a layer which does not contain a fine precipitate layer inside, the intermediate layer itself has no fragile portion, and internal peeling or destruction can be prevented. Further, also for the intermediate third layer, generation of stress due to lattice mismatch or the like is relaxed, and the adhesion can be secured by using the same kind of metal element. Further, since the DLC film forming the outermost surface layer is also an amorphous film, the adhesion with the amorphous layer formed of the mixed layer of the metal element and carbon as described above is improved.

However, the metal elements composing the adjacent layers do not necessarily have to be the same, and the above effect is exhibited even if the metal elements contained in one layer and the metal elements contained in the other layer are different. However, [for example,
Cr layer (first layer) and Al / W layer (second layer)], preferably both metal elements are the same [for example, Cr layer (first layer) Cr / W layer (second layer)] , So that the element contained in at least one layer is contained in the other layer [eg W / M
It is preferable to use an o layer (third layer) and a W / C layer (fourth layer).

Similarly to the second layer, the metal in the fourth layer is gradually or continuously reduced from the third layer side (base material side) toward the DLC film side (surface layer side) ( That is,
The gradient composition is preferably such that the carbon concentration is increased from 0% to 100%. By adopting such a film structure, the mechanical properties of the multilayer film can be changed stepwise or continuously from the base material side to the DLC side, thereby preventing peeling due to local stress concentration due to thermal shock or the like. can do. However, the metal concentration (ie,
Even if the carbon concentration is constant, the object of the present invention can be achieved if it is amorphous.

In the DLC hard multilayer film molding of the present invention, the layer (the third intermediate layer) made of at least one metal selected from the group consisting of W, Ta, Mo and Nb is tungsten carbide (WC). A compound whose main component is (for example,
It is also possible to replace it with a cemented carbide material). In such a case, compared to W, Ta, Mo, Nb, etc.,
There is also an advantage that a film can be formed even if a cheaper target material is used.

When forming such a third layer, the composition of the adjacent second, fourth layers may be appropriately controlled according to the composition of the third layer as described above. Even when such a film structure is adopted, it is not possible to locally change the composition of the second layer and the fourth layer in consideration of the composition of the adjacent layers so as to approach them. It is effective in preventing peeling due to concentration.

In the DLC hard multilayer film molding of the present invention, whichever configuration is adopted, a stress relaxation layer made of carbon may be formed between the intermediate fourth layer and the outermost surface layer. It is effective, and this stress relaxation layer is
At the interface on the layer side, the hardness is close to that of the third layer, and the hardness gradually or continuously increases toward the outermost surface layer, and near the outermost surface layer, the hardness is close to that of a film mainly composed of DLC. It is preferable that it is configured as follows. Further, the Vickers hardness H _{1 of the} interface on the outermost surface side in the stress relaxation layer is
Specifically, the difference ΔH from the Vickers hardness H ₂ of the outermost surface layer
It is better to adjust so that (= | H ₂ −H ₁ |) is 1000 or less.

By controlling the hardness of the stress relaxation layer as described above, the difference in hardness between the adjacent layers can be minimized, the stress concentrated at the layer interface can be reduced, and the adhesion can be further improved. The carbon constituting the stress relaxation layer has a non-bonded form (similar to the DLC film except hardness),
By interposing carbon in such a form between the outermost surface layer and the intermediate fourth layer, the function as a stress relaxation layer can be effectively exhibited.

The thickness of the intermediate layer (the total thickness of the first layer to the fourth layer) preferably accounts for 10 to 50% of the total thickness of the multilayer film. High adhesion can be obtained without damaging the film quality of the DLC multilayer film surface.

In the DLC hard multilayer film molding of the present invention, the outermost layer mainly composed of DLC may be formed of only DLC, but W, Ta, Mo, Nb, C may be formed.
It is also preferable to use a mixed layer containing one kind or two or more kinds selected from the group consisting of r and Al, and a laminated structure containing at least one such mixed layer and one pure DLC layer. With such a film structure, D
The internal stress of the LC film itself can be relaxed, the toughness can be further improved, the followability to the deformation of the base material can be improved, and the occurrence of peeling can be reduced as much as possible.

When the outermost surface layer has the above-mentioned laminated structure, at least one layer is required for each layer, and the upper limit of the number of laminated layers is not limited.
It is preferable that at least the mixed layer is formed on the fourth layer side and a pure DLC film is formed on the outermost surface side.

Further, by incorporating an appropriate amount of metal element into the DLC film, the sliding characteristics of the DLC film can be further improved. From the viewpoint of exerting the effect of stress relaxation, such a metal element is preferably contained in the DLC film in an amount of 5 atom% or more. Not only the wear resistance is impaired but also the sliding characteristics are deteriorated, so the content is preferably 20 atomic% or less.

The above-mentioned intermediate layers and the film mainly composed of DLC are
It is preferably formed by the UBM sputtering method. The principle of this UBM sputtering method will be described with reference to the drawings. First, as shown in FIG. 1, the cathode structure in the normal sputtering method is, for example, a ferrite magnet (or an Sm-based rare earth magnet or Nd).
(Rare earth magnets) are magnets with the same magnetic properties in the center and the peripheral part of a round target, and a closed loop of magnetic lines of force is formed in the vicinity of the target material. The substance forming the is formed on the substrate. On the other hand, in the cathode structure in the UBM sputtering method, as shown in FIG. 2, magnets having different magnetic characteristics are arranged in the central portion and the peripheral portion of the round target, and a stronger magnet is generated while forming plasma. A part of the magnetic lines of force that reach the vicinity of the substrate.

From the above, in the UBM sputtering method, the effect that the plasma (for example, Ar plasma) generated during the sputtering along the lines of magnetic force is diffused to the vicinity of the substrate can be obtained. According to the UBM sputtering method as described above, the ion assist effect that Ar ions and electrons reach the substrate more along the magnetic field lines reaching the vicinity of the substrate as described above, is dense and has a high hardness. It becomes possible to form a DLC film. According to such UBM sputtering method,
In the intermediate layer, W, Ta, Mo having high carbide forming ability
With respect to Nb and Nb, a uniform amorphous layer can be formed without forming a carbide.

In producing the DLC hard multilayer film molding of the present invention according to the present invention, when the second layer or the fourth layer is made to have the above-mentioned graded composition, these are formed by a sputtering method (preferably the UBM method described above). It is only necessary to control the sputtering power while forming the layer. Further, when manufacturing the diamond-like carbon hard multilayer film formed with the stress relaxation layer, when changing the hardness of the stress relaxation layer continuously or stepwise, a DC or pulse bias voltage applied to the substrate is applied. It may be adjusted by the control of.

In forming the intermediate first to third layers, the substrate temperature is set to 15 at the stage of forming these layers on the substrate.
By controlling at 0 to 350 ° C., preferably at 250 to 350 ° C., diffusion of the metal element in the intermediate first layer to the substrate and diffusion between each genus are promoted, and adhesion between the first layer and the base material is promoted. And the adhesion between the first to third layers are further improved, which is preferable. However, the DLC layer (and the fourth layer containing carbon)
Layers), these layers are sensitive to heat,
At the stage of forming each layer, the substrate temperature is preferably about 300 to 100 ° C, more preferably 200 to 100 ° C.
It is better to control the degree.

The type of the iron-based material used as the base material in the present invention is not particularly limited, and bearing steel, stainless steel, carbon steel or the like having a hardness lower than that of the high speed tool steel is used as the base material. When used, it is most effective when applied to these steel materials (iron-based materials) from the viewpoint that a DLC film can be formed on these substrate surfaces with good adhesion. Of course, it can be applied to iron-based materials having a relatively high hardness such as high speed tool steel.

Next, the constitution and effects of the present invention will be explained more specifically with reference to examples. However, the present invention is not limited by the examples below, and is within a range applicable to the gist of the preceding and following. It is of course possible to carry out the modification with the above, and all of them are included in the technical scope of the present invention.

[0042]

EXAMPLES Various hard multi-layer film molded products having the film structure shown in Table 1 below were produced by the following procedure. As a base material, a mirror surface (R
a = 0.02 μm) 12 cm square, 5 mm thick S
UJ2 was ultrasonically cleaned in an alkaline tank and a pure water tank and then dried. Substrates that have undergone such treatment are
M sputtering equipment ("UBMS504": Kobe Steel Ltd.)
After mounting inside, 5 × 10 ^-3 Pa (3.8 × 10 ^-5 T
vacuum to about (orr) and bake with a heater,
After that, after etching the substrate surface with Ar plasma, U
DLC multilayer films having various layer configurations shown in Table 1 were formed by the BM sputtering method. At this time, the DLC of the outermost surface layer has a high hardness D by controlling the bias voltage during film coating to a high bias (DC bias voltage: -200V).
An LC film (Hv: about 3000 to 4000) was formed.

In the step of forming the intermediate first layer, the test No. 1
Only No. 4 was heated with a heater from the previous stage, the substrate temperature at the start of film formation was controlled to 300 ° C., and a diffusion layer was formed between the intermediate first layer and the substrate material. Other test No. 1 to
With respect to Nos. 13 and 15, the substrate temperature was controlled at 200 ° C. Test No. In forming the second layer of 6 to 15, the sputtering power of the metal and carbon targets was adjusted,
The composition ratio of metal and carbon was graded. Further, in the formation of the stress relaxation layer (Nos. 5, 12 and 14), only the carbon target was sputtered at a constant power and the DC bias was controlled to adjust the hardness in the layer.

Regarding the various hard multilayer film moldings obtained,
Scratch test and Rockwell impression test (HRC test)
Adhesion (adhesion strength and presence or absence of peeling) was evaluated by. At this time, in the scratch test, the sample was fixed to a moving stage, the stage was moved at 10 mm / min while applying a load at a load speed of 100 N / min on the sample surface using a diamond indenter, and scratch marks were observed with a microscope. The peeling load of the film was measured. Also, HR
In the C test, a diamond indenter was driven into the sample with a load of 150 kg using a Rockwell hardness tester, and the peeling condition around the indentation was observed. For hardness measurement, a sample having a film thickness of 3 μm was prepared separately under the same conditions as the interface film formation conditions for each layer, and evaluated with a micro Vickers (10 g).

The evaluation results are collectively shown in Table 1 below. In addition, Table 1 also shows the molded product (Test No. 1) in which the DLC film was directly formed on the surface of the substrate without forming the intermediate layer.

[0046]

[Table 1]

As is clear from these results, those satisfying the requirements defined in the present invention (Nos. 6 to 15) were subjected to the scratch test even if the DLC film with high hardness was formed with a thick film of about 3 μm. It can be seen that a stable and stable adhesion strength of 40 N or more is obtained. In particular, the stress relaxation layer (Test No. 1
2, 14) and a diffusion layer (Test No. 14) are formed, and the outermost surface layer has a two-layer structure (Test No. 2).
13 and 15), it can be seen that the adhesion strength of 50 N or more is exhibited in the scratch test.

[0048]

EFFECTS OF THE INVENTION The present invention is configured as described above, and uses a low-hardness iron-based material as a base material, and exhibits excellent adhesion even if formed relatively thickly with respect to the base material. It was possible to realize a hard multilayer film molded product in which a DLC film capable of being formed was formed as the outermost surface layer. Further, this hard multilayer film formed body is extremely useful as a material for wear-resistant mechanical parts such as automobile parts.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing a cathode structure in a normal sputtering method.

FIG. 2 is a schematic explanatory view showing a cathode structure in the UBM sputtering method.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hidemi Mori             1-1, Showa-cho, Kariya city, Aichi stock market             Inside the company DENSO (72) Inventor Nozomi Okumura             1-1, Showa-cho, Kariya city, Aichi stock market             Inside the company DENSO (72) Inventor Koichiro Akari             2-3-3 Niihama, Arai-cho, Takasago, Hyogo Prefecture             Takasago Works, Kobe Steel, Ltd. (72) Inventor Toshimitsu Ohara             2-3-3 Niihama, Arai-cho, Takasago, Hyogo Prefecture             Takasago Works, Kobe Steel, Ltd. F-term (reference) 4K029 AA02 BA01 BA03 BA07 BA11                       BA16 BA34 BB02 BB10 BC02                       BD03 BD05 CA05 EA08

Claims (11)

[Claims] 1. A film mainly composed of diamond-like carbon as an outermost layer, further comprising an intermediate layer and a base material, wherein the base material is made of an iron-based material, and the intermediate layer has the following (1): A diamond-like carbon hard multilayer film molded body having a four-layer structure in which the four layers (4) to (4) are formed in this order from the base material side to the outermost surface layer side. (1) First layer composed of a metal layer of Cr and / or Al (2) Metal of Cr and / or Al and W, Ta, M
Second layer consisting of a mixed layer of one or more metals selected from the group consisting of o and Nb (3) Third layer consisting of one or more metal layers selected from the group consisting of W, Ta, Mo and Nb Layer (4) Fourth layer consisting of an amorphous layer containing carbon and at least one metal selected from the group consisting of W, Ta, Mo and Nb
layer 2. The second layer comprises Cr and / or Al
2. The diamond-like carbon hard multilayer film molding according to claim 1, wherein the content of is a composition having a graded composition that gradually or continuously decreases toward the outermost surface layer side. 3. The fourth layer comprises W, Ta, Mo and N
The content of at least one metal selected from the group consisting of b is configured to have a graded composition that gradually or continuously decreases toward the outermost surface layer side. The diamond-like carbon hard multilayer film molded article according to 1. 4. A film mainly composed of diamond-like carbon as an outermost layer, further comprising an intermediate layer and a base material, wherein the base material is made of an iron-based material, and the intermediate layer has the following (5): A diamond-like carbon hard multilayer film molded body having a four-layer structure in which the four layers (8) to (8) are formed in this order from the substrate side to the outermost surface layer side. (5) First layer composed of a metal layer of Cr and / or Al (6) Second layer composed of a mixed layer of a metal of Cr and / or Al and a compound containing WC as a main component (7) Main component of WC Third layer consisting of a compound containing (8) A fourth layer consisting of an amorphous layer containing a compound containing WC as a main component and carbon 5. The second layer comprises Cr and / or Al
5. The diamond-like carbon hard multilayer film molding according to claim 4, wherein the content of is a graded composition that gradually or continuously decreases toward the outermost surface layer side. 6. The fourth layer is configured to have a graded composition in which the content of the compound containing WC as a main component is gradually or continuously reduced toward the outermost surface layer side. The diamond-like carbon hard multilayer film molded body according to claim 4 or 5. 7. A stress relaxation layer made of carbon is formed between the intermediate layer and the outermost surface layer, and the stress relaxation layer is close to the intermediate fourth layer at an interface on the intermediate layer side. The hardness is such that the hardness gradually or continuously increases toward the outermost surface layer, and near the outermost surface layer, the hardness is close to that of a film mainly composed of diamond-like carbon. Item 1. A diamond-like carbon hard multilayer film molded article according to items 1 to 6. 8. The film containing diamond-like carbon as a main component contains (a) 5 to 2 of at least one metal selected from the group consisting of W, Ta, Mo, Nb, Cr and Al.
A layer containing 0 atomic% or (b) W, T
a layer containing at least one metal selected from the group consisting of a, Mo, Nb, Cr and Al in the range of 5 to 20 atomic% and a diamond-like carbon layer.
The diamond-like carbon hard multilayer film molding according to any one of claims 1 to 7, which has a structure in which each layer is laminated. 9. In manufacturing the diamond-like carbon hard multilayer film forming body according to claim 1, the film mainly containing the diamond-like carbon is formed by an unbalanced magnetron sputtering method. A method for producing a diamond-like carbon hard multilayer film molded body, comprising: 10. The method for producing a diamond-like carbon hard multilayer film molded article according to claim 9, wherein the film containing diamond-like carbon as a main component is formed while controlling the substrate temperature at 100 to 300 ° C. 11. When manufacturing the diamond-like carbon hard multilayer film molding according to any one of claims 1 to 8, the substrate temperature is set to 150 at the stage of forming the intermediate first to third layers on the substrate. A method for producing a diamond-like carbon hard multilayer film molding, which comprises forming a diffusion layer between the substrate and the first layer and between the layers by controlling the temperature to ˜350 ° C.