JP5613279B2 - Hard coating and method for manufacturing hard coating - Google Patents

Description

  The present invention relates to a hard coating formed on a cutting tool such as a chip, a drill, or an end mill, or a jig such as a forging die or a punch, and a method for manufacturing the hard coating.

  Conventionally, in a cutting tool, a hard film such as TiN, TiCN, or TiAlN is formed on a base material such as high-speed steel, cemented carbide, or cermet in order to increase wear resistance. In particular, since TiAlN has high wear resistance, it is suitably used in high-hardness material cutting tools such as high-speed cutting tools and hardened steel. Furthermore, with the recent increase in hardness and cutting speed of workpieces, the development of hard coatings with better wear resistance has been demanded. For example, Patent Document 1 describes that by using TiCrAlN instead of TiAlN, the ratio of the rock salt structure type AlN in the film can be increased, the hardness of the film can be increased, and at the same time the oxidation resistance can be improved. ing.

JP 2003-71610 A

  However, hard coatings such as TiAlN and TiCrAlN are excellent in oxidation resistance at high temperatures but have poor lubricity. Therefore, in the cutting tool formed with the hard coating, a part of the work material may adhere to the surface of the tool at the time of cutting, even in the jig tool (forging die, punch, etc.) formed with the hard coating, The frictional resistance at the contact surface is increased, and seizure may occur on the tool during forging or press molding.

  The present invention has been made paying attention to these problems, and is to provide a hard film excellent in hardness and lubricity and related technology.

The hard coating of the present invention that has solved the above problems is
(1)
_{(Al 1-ad-e V} a Mo d W e) a hard film composed of _{(C 1-X N X)} ,
0.2 ≦ a ≦ 0.75,
0 <d + e ≦ 0.3,
0.3 ≦ X ≦ 1
(Wherein, a, d, e and X independently represent an atomic ratio: one of d and e may be 0, but not both). Or (2)
A _{(Al 1-abc-d-} e V a Si b B c Mo d W e) hard coating consisting of _{(C 1-X N X)} , 0.2 ≦ a ≦ 0.75,
0 <b + c ≦ 0.20,
0 <d + e ≦ 0.3,
0.3 ≦ X ≦ 1
(In the formula, a, b, c, d, e and X independently represent an atomic ratio: one of b and c may be 0, but neither is 0. , D and e may be one, but not both)
It is characterized by being.

  The hard film containing Mo and / or W is particularly excellent in terms of lubricity and durability in a cutting tool under a high temperature condition of 600 ° C. or higher.

The hard coating of the present invention is
(3)
A hard film made of (Al _1-a-f-g V _a Hf _f Zr _g ) (C _1-X N _X ),
0.01 ≦ a ≦ 0.75,
0 <f + g ≦ 0.5,
0.3 ≦ X ≦ 1
(Wherein, a, f, g and X independently represent an atomic ratio: f and g may be one, but not both). Or (4)
A _{(Al 1-abc-f-} g V a Si b B c Hf f Zr g) (C 1-X N X) hard film consisting of,
0.01 ≦ a ≦ 0.75,
0 <b + c ≦ 0.20,
0 <f + g ≦ 0.5,
0.3 ≦ X ≦ 1
(Wherein a, b, c, f, g and X independently represent an atomic ratio: b and c may be either 0, but both are not 0. , F and g may be one, but not both)
It is characterized by being.

  The hard film containing Zr and / or Hf is particularly excellent in terms of hardness under a high temperature condition of 600 ° C. or higher.

  Moreover, it is preferable that the hard film of said (1)-(4) shows a NaCl type crystal structure.

It also consists of (Al _1-a V _a ) (C _1-X N _X )
0.27 ≦ a ≦ 0.75, 0.3 ≦ X ≦ 1 (wherein a and X independently represent an atomic ratio), or
(Al _1-abc V _a Si _b B _c ) (C _1-X N _X ), 0.1 ≦ a ≦ 0.75, 0 <b + c ≦ 0.20, 0.3 ≦ X ≦ 1 (formula In which a, b, c and X independently represent an atomic ratio: where b and c may be one, but not both) A layer made of a hard coating (hereinafter referred to as A layer);
A layer made of a compound obtained by selecting one or more of Mo and W and one or more of C and N (hereinafter referred to as B layer)
It is also preferable to form a laminated hard film formed by laminating At that time, the thicknesses of the A layer and the B layer are preferably B layer thickness ≦ A layer thickness ≦ 200 nm.

Furthermore, the A layer,
A layer made of a compound obtained by selecting one or more of Zr and Hf and one or more of C and N (hereinafter referred to as C layer)
It is also preferable to form a laminated hard film formed by laminating In that case, it is preferable that the thicknesses of the A layer and the C layer are C layer thickness ≦ A layer thickness ≦ 200 nm.

  The hard coating can be produced, for example, by evaporating and ionizing a metal in a film forming gas atmosphere and forming a film while promoting the plasma formation of the film forming gas together with the metal.

  In particular, in the arc ion plating method in which evaporation and ionization of the metal constituting the target is performed by arc discharge, a magnetic field line that diverges forward or travels in a direction substantially perpendicular to the evaporation surface of the target is formed. It is preferable to form a film while promoting the plasma formation of the film forming gas in the vicinity of the object to be processed.

  In that case, it is preferable that the magnetic flux density of the center part of the surface which forms the hard film of the said to-be-processed object is 10 gauss or more. In addition, it is preferable to form a magnetic field between the target and the object to be processed so that an angle formed by the magnetic force line and a normal line of the evaporation surface of the target is ± 30 ° or less.

  The hard coating of the present invention is extremely excellent in hardness and lubricity because Al in the Al nitride or Al carbonitride-based hard coating is replaced with an appropriate amount of V. Therefore, the cutting tool can extend its life, and the jig tool can reduce seizure.

FIG. 1 is a conceptual diagram of a manufacturing apparatus used in the manufacturing method of the present invention. FIG. 2 is a schematic view for showing the distribution of magnetic lines of force formed near the object to be processed when the manufacturing method of the present invention is used. FIG. 3 is a schematic view for showing the distribution of magnetic lines of force formed near the object to be processed when the manufacturing method of the present invention is used. FIG. 4 is a schematic diagram showing the distribution of magnetic field lines in the conventional arc ion plating method. FIG. 5 is a conceptual diagram of a manufacturing apparatus used in the manufacturing method of the present invention.

  In order to search for a hard film superior to TiAlN and TiAlCN (hereinafter sometimes collectively referred to as TiAl-based hard film), the present inventor forms various hard films, and has a crystal structure, hardness, and surface friction. Resistance and durability with cutting tools were evaluated. As a result, nitride or carbonitride in which V is combined with Al in place of Ti (VAlN, VAlCN, etc .; hereinafter may be collectively referred to as VAl-based hard coating) has hardness and lubricity (friction resistance on the surface). ), The present invention was found to be extremely excellent, leading to the present invention.

More specifically, when a VAl hard film is formed by using V instead of Ti of the TiAl hard film, V is relatively easily oxidized. Therefore, at the interface between the cutting material or workpiece and the hard film. It is considered that V oxides (V ₂ O ₅ etc.) are preferentially formed by frictional heat. Since this V oxide has a relatively low melting point and is soft, it reduces the frictional resistance at the interface. It is thought that there is. Further, the VAl type hard coating, like the TiAl type hard coating, increases in hardness as the Al ratio increases as long as the crystal structure of NaCl type (sometimes referred to as rock salt type, cubic type, etc.) is maintained. When the ratio becomes too high, the NaCl-type crystal structure collapses and tends to transition to a hexagonal type (sometimes referred to as ZnS type) and soften. In the VAl type hard coating, the Al concentration capable of maintaining the cubic crystal type is shifted to the high Al concentration side as compared with the TiAl type hard coating, and as a result, the coating hardness can be drastically improved. As a result, according to the VAl-based hard coating, both hardness and lubricity can be achieved at an extremely excellent level.

The VAl-based hard coating can be expressed as (Al _1-a V _a ) (C _1-X N _X ). In the formula, “a” and “X” independently represent an atomic ratio. The “a” is 0.27 or more. If the value of “a” is too small, the proportion of Al becomes too high, the film has a hexagonal structure, and the hardness decreases (friction coefficient increases). A preferable value of “a” is 0.3 or more, particularly 0.35 or more. As the value of “a” increases, the hardness and lubricity improve. However, if the value of “a” becomes too large, the accumulated amount of strain due to the combined use of Al and V decreases, so that the hardness decreases and the friction coefficient also increases. Therefore, “a” is set to 0.75 or less, preferably 0.6 or less, and more preferably 0.5 or less.

  The “X” may be 1 (that is, the hard coating may be a nitride), but the lubricity of the coating improves as the value of X decreases (that is, the amount of C increases). However, if X is too small, an unstable AlC compound is likely to be formed. Therefore, X is 0.3 or more, preferably 0.4 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more.

Si and / or B may be further added to the VAl-based hard coating, and this Si · B additional type VAl hard coating is (Al _1-abc V _a Si _b B _c ) (C _1-X N _X ). (Al _{1 -abc} V _a Si _b B _c ) (C _{1 -X} N _X ) is not only used when B forms carbonitride, but B forms borides with Al, V, Si, etc. It has a comprehensive meaning that also includes the case of doing. In the formula, “a”, “b”, “c” and “X” each independently represent an atomic ratio. When Si or B is added, the crystal grains of the VAl hard coating can be made finer, and the hardness is further improved. Although the details of the crystal grain refining effect are not clear, it is considered that the growth of crystal grains is suppressed by the formation of Si-N bonds or BN bonds at the crystal grain boundaries. In the Si / B additional type VAl hard coating, the value of “a” is 0.1 or more (preferably 0.27 or more, more preferably 0.3 or more, particularly 0.35 or more), or 0.75 or less. (Preferably 0.6 or less, more preferably 0.5 or less). The additional amount (b + c) of Si or B is more than 0, preferably 0.01 or more, more preferably 0.05 or more. Both Si and B may be added, or only one of them may be added. Therefore, one of “b” and “c” may be zero. However, B is superior to Si because it forms a BN bond having a lubricating action. Therefore, when importance is attached to improving lubricity, it is recommended to add both Si and B or only B. On the other hand, when Si or B is added excessively, the crystal structure of the VAl-based hard coating is likely to be transferred to a hexagonal type, and the hardness is likely to be lowered. Therefore, the additional amount (b + c) of Si or B is 0.20 or less, preferably 0.15 or less, and more preferably 0.10 or less. At that time, the lower limit of the value of “a” and “b + c” is preferably 0.4 or more, particularly 0.5 or more.

The hard film of the present invention is not limited to a film having a uniform composition as described above, but includes the above-described VAl-based hard film (including a Si / B additional type VAl-based hard film. The same applies hereinafter) or Mo / W described later. The hard film of the present invention also includes a film having the same composition as the combined hard film and the Zr / Hf combined hard film as the entire film. For example, a film (referred to as a multilayer hard film) in which a plurality of extremely thin thin films having a repetition period of about 80 nm or less is repeatedly laminated (referred to as a multilayer hard film) has an average composition of the VAl-based hard film (or Mo · W described later). If the composition of the combined hard coating and the combined Zr / Hf hard coating is satisfied, it is included in the hard coating of the present invention. This multi-layer hard coating (hereinafter sometimes referred to as the first multi-layer hard coating) has an individual thinness because each layer is extremely thin, and as if it is a single-layer coating as a whole. This is to show the characteristics. In addition, the multilayer hard film has an advantage that it can be easily produced by appropriately combining known targets (for example, AlN, AlVN, etc.) without producing a specific target according to the composition of the film. In addition, the said average composition means the ratio of the number of atoms which exist per unit area of a laminated body, and can be calculated | required with the following method. For example, in a laminate in which the A layer is (V _a Si _b ) N (film thickness X nm) and the B layer is (Al _c B _d ) N (film thickness Y nm),
The lattice constant (α) and the number of molecules in the unit cell (Z) of the compounds constituting the A layer and the B layer existing around 10 ⁶ nm ² are calculated by X-ray diffraction. The composition of each layer A and B is calculated using AES or the like, and the film thickness is calculated using TEM or the like. Using the obtained value, obtains the A layer of 10 ⁶ X × Z × for ^{V a / (α 3) /} (a + b) the number of atoms per unit area from the equation (Vm), for Si 10 ⁶ The number of atoms per unit area (Sim) is determined from the formula X × Z × b / (α ³ ) / (a + b). Similarly, the number of Al and B atoms [(Alm) and (Bm)] per unit area of the B layer is obtained. Using the obtained value of the number of atoms, the ratio of the number of atoms occupying per unit area [in V, (Vm / (Vm + Sim + Alm + Bm))] can be calculated to obtain the average composition.

  The upper limit of the repetition period is preferably 50 nm, more preferably 30 nm, and particularly preferably 15 nm. As the upper limit of the repetition period becomes smaller, the uniformity as a film increases, and the hardness and lubricity increase. The lower limit of the repetition period is not particularly limited, and it becomes difficult to distinguish from the above-mentioned hard film having a uniform composition as it becomes smaller. The lower limit may be, for example, about 1 nm (particularly about 3 nm). The thickness of each layer is not particularly limited as long as the repetition period is in the above range, but may be set, for example, from a range of 50 nm or less, preferably 30 nm or less, and more preferably 10 nm or less.

  In a VAl-based hard coating made into a multilayer type, each layer is usually a nitride or carbonitride of at least one element selected from Al, V, Si and B [hereinafter referred to as nitride and carbonitride] The product may be referred to as (charcoal) nitride]. Preferred (carbon) nitrides include Al-based (carbon) nitride [Al (CN), AlSi (CN), AlB (CN), AlSiB (CN); and a compound in which the (CN) moiety is (N). Etc.], Si (CN), B (CN) and the like. The combination of each layer is also not particularly limited. For example, Al-containing (carbon) nitride [Al-based (carbon) nitride, AlV-based (carbon) nitride, etc.] and Al-free (carbon) nitriding. The product [V-based (charcoal) nitride, Si (CN), B (CN), etc.] may be combined. Specifically, Al (CN) / V (CN), Al (CN) / VSi (CN), AlSi (CN) / V (CN), AlSi (CN) / VB (CN), AlB (CN) / V (CN), AlB (CN) / VSi (CN), AlSiB (CN) / V (CN), AlV (CN) / Si (CN), AlV (CN) / B (CN), AlVSi (CN) / B Combinations of (CN), AlVB (CN) / Si (CN), AlVSiB (CN) / AlV (CN) and the like can be exemplified, and the (CN) portion may be (N).

  Further, the multilayer hard coating has, for example, the composition of at least one of the above-mentioned VAl hard coating (including Si / B additional type), Mo / W combined hard coating described later, or Zr / Hf combined hard coating. The hard layer may be the same as those (including the Si / B additional type), and the remaining layer may not significantly reduce the characteristics of the hard layer (second multilayer hard coating). Since the characteristics of the entire hard film are determined by the characteristics of the hard layer, the second multilayer hard film is excellent in hardness and lubricity and is included in the hard film of the present invention.

  Examples of the remaining layers that do not significantly reduce the characteristics of the hard layer include a layer made of TiAl nitride or carbonitride, a layer made of CrAl nitride or carbonitride, and the like. Since these layers are excellent in oxidation resistance, the oxidation resistance of the hard film can be improved by laminating the hard film (VAl hard film or Si / B additional type VAl hard film). it is conceivable that. Moreover, as long as the remaining layer and the hard layer are repeated, the number of the remaining layers in the repeating unit may be one or plural.

  The upper and lower limits of the repetition period and the upper and lower limits of each layer may be preferably the same as those of the first multilayer hard film.

  Further, the thickness of the hard layer (in the case of a plurality of layers) is, for example, 0.5 times or more (preferably 0.8 times or more, particularly 1.0 times or more) with respect to the remaining layers, It is 2.0 times or less (preferably 1.5 times or less). The thicker the hard layer relative to the remaining layers, the less affected by the remaining layers. The upper limit of the thickness of the hard layer with respect to the remaining layers is not particularly limited, and it becomes difficult to distinguish from the above-described hard film having a uniform composition as it increases. The upper limit may be, for example, about 10 times (particularly about 5 times, for example, about 2 times).

In the VAl-based hard coating (including Si / B additional type), a soft V oxide with a relatively low melting point is preferential due to frictional heat at the interface between the cutting material or workpiece and the hard coating as described above. As a result, it is considered that hardness and lubricity are increased. However, the melting point of the V oxide is around 600 ° C., and if sliding is performed at a higher temperature than this, the V component in the film tends to be oxidized and the film tends to deteriorate. Therefore, the present inventor has focused on Mo and W which form an oxide having a higher melting point than V oxide. By using Mo or W together with the (AlV) or (AlVSiB) component, oxides having a melting point higher than the V oxide [WO ₂ (melting point 1500 ° C.), WO ₃ (melting point 1470 ° C.), MoO ₂ (Melting point 1100 ° C.), MoO ₃ (melting point 795-801 ° C.)] could be formed. And such a hard film (hereinafter referred to as a Mo / W combined type VAl-based hard film, sometimes simply referred to as a Mo / W combined type hard film. In the case of Si / B addition type), it has been found that the oxidation rate can be suppressed even under a high temperature condition of 600 ° C. or higher, the wear resistance can be improved, and the friction coefficient can be suppressed low.

The content of the Mo and / or W (atomic ratio) (i.e. in the same manner as described above VAl-based hard _{coating, (Al 1-ad-e} V a Mo d W e) (C 1-X N X), (Al _{1-abc-d-e V} a Si b B c Mo d W e) ( the value of d + e when expressed as C _1-X N X)), for example 0, preferably above 0.05 or more, More preferably, if it is 0.1 or more, the friction coefficient of the hard coating can be kept low and the wear resistance can be enhanced. However, when these elements are contained excessively, the crystal structure of the hard coating is easily transferred from the highly hard NaCl type to the soft hexagonal type, and the wear resistance is lowered. Therefore, the content of the above elements (value of d + e) is desirably suppressed to 0.3 or less (preferably 0.2 or less).

  By the way, the lattice constants of VN and AlN (pure stable cubic type) existing in the hard coating are 0.414 nm and 0.412 nm, respectively, whereas for ZrN and HfN, the lattice constants are 0.456 nm and 0.4 respectively. 452 nm, which is larger than VN and AlN. Therefore, a hard film in which a compound having a lattice constant different from that of VN or AlN (for example, ZrN or HfN) is formed in the hard film (hereinafter referred to as a Zr / Hf combined type VAl-based hard film) is simply used in combination with Zr / Hf. This Zr / Hf combined type VAl-based hard film may be a Si / B additional type), and can be hardened by lattice strain to increase the hardness.

The content of the Zr and / or Hf (atomic ratio) (i.e. in the same manner as described above VAl-based hard _{coating, (Al 1-a-f} -g V a Hf f Zr g) (C 1-X N X), _{(Al 1-abc-f-} g V a Si b B c Hf f Zr g) the value of f + g when expressed as _{(C 1-X N X)} ) , for example 0, preferably above 0.1 More preferably, if it is 0.2 or more, hardness and wear resistance can be improved, but if added excessively, the crystal structure of the hard coating tends to transition to a hexagonal crystal, and wear resistance decreases. It becomes easy. Therefore, the content of the above element is desirably 0.5 or less (preferably 0.4 or less, more preferably 0.3 or less).

  About the contents of V, Si, B, C, and N (that is, the value of a in the above chemical formula, the value of b + c, the value of X, etc.) of the Mo · W combined type hard coating or the Zr · Hf combined type hard coating, It may be in the same range as the VAl hard coating (including Si / B additional type). However, since Mo, W, Hf, and Zr have the effect of improving the wear resistance as described above, the lower limit of the V content (value of a) is VAl based hard coating or Si / B additional type. It may be less than the VAl type hard coating. In the Mo / W combined type hard coating, the lower limit of the V content (value of a) should be 0.2 (preferably 0.27, more preferably 0.3, particularly preferably 0.35). In the Zr / Hf combined hard coating, the lower limit of the V content (value of a) is 0.01 (preferably 0.2, more preferably 0.27, particularly preferably 0.3, most preferably Can be 0.35).

  Further, Mo and / or W, or Zr and / or Hf include the above-described VAl-based hard coating (including Si · B additional type) in addition to the single-layer type contained in the coating as described above. And a layer of a compound obtained from one or more of Mo and W and one or more of C and N (hereinafter referred to as B layer), or one or more of Zr and Hf and C, N It is good also as a lamination-type hard film | membrane which laminated | stacked the layer (henceforth C layer) of the compound obtained from 1 or more types of these.

  At that time, metals such as Mo, W, Hf, and Zr have low hardness, and if they are laminated as they are, the wear resistance of the entire laminated hard coating is lowered. Therefore, it is necessary to use a carbonitride compound together with C and N as described above. However, Mo, W, Hf, Zr, etc., even if they are carbonitride-based compounds, have a lower hardness than VAl-based hard coatings (including Si / B additional types), so this carbon such as Mo, W, Hf, Zr, etc. If the nitride-based compound layer is thicker than the VAl-based hard coating layer, the hardness and wear resistance of the entire hard coating will be impaired. For this reason, the B layer and the C layer are preferably thinner than the A layer. Further, if the thickness of each layer becomes too large, the effect of forming a laminated type cannot be obtained. Therefore, the thickness of each layer is desirably 200 nm or less (preferably 50 nm or less, more preferably 20 nm or less).

  Hard coating of the present invention [VAl hard coating (including Si / B additional type), Mo / W combined hard coating (including Si / B additional type), Zr / Hf combined hard coating (Si / B additional) Type), multilayer hard coating, etc.] may have a crystal structure in which cubic and hexagonal crystals are mixed as long as desired hardness and lubricity (coefficient of friction) can be satisfied, but preferably substantially Shows a cubic NaCl-type crystal structure. The higher the proportion of cubic crystals, the higher the hardness of the film.

  Whether it is NaCl type or not can be determined by X-ray diffraction. More specifically, the peak intensities of cubic (111), (200) and (220) planes and hexagonal (100), (102) and (110) planes were measured. The ratio of cubic crystals is calculated based on the following formula (1). When the ratio of the cubic crystal is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, it can be said to be of the NaCl type. In the case of mixed molding of less than 0.7, 0.4 or more, particularly 0.5 or more is preferable.

(In the formula, IB (111), IB (200) and IB (220) indicate the peak intensity of each face of the cubic crystal. IH (100), IH (102) and IH (110) are the faces of the hexagonal crystal. Of the peak intensity).

  X-ray diffraction is performed by the θ-2θ method. Cubic X-ray diffraction is performed using a CuKα radiation source. For the (111) plane, for example, around 2θ = 37.78 °, and for the (200) plane, for example, near 2θ = 43.9 °, For the (220) plane, for example, the peak intensity around 2θ = 63.8 ° is measured. The hexagonal X-ray diffraction uses Cu Kα rays, and the (100) plane is, for example, around 2θ = 32 ° to 33 °, and the (102) plane is, for example, around 2θ = 48 ° to 50 ° ( For the 110) plane, for example, the peak intensity around 2θ = 57 ° to 58 ° is measured.

  The peak positions of the cubic and hexagonal crystals are in accordance with the JCPDS card, but the peak positions of each face of the crystal [especially hexagonal (ZnS type)] are Ti, V, Cr, Mo, Ta, If W or the like is included, there may be a slight deviation from the value indicated on the JCPDS card. In such a case, the position of the target peak may be determined from the positional relationship with other peaks or the relationship with the peaks of other compounds.

  Other hard coatings, metal layers or alloy layers may be laminated on one side or both sides of the hard coating to form a heterogeneous composite type hard coating.

  The other hard coating is precisely a hard coating having a metal nitride-based, metal carbide-based, or metal carbonitride-based NaCl-type crystal structure, and may be appropriately selected depending on the application. Specifically, Cr hard coating [Cr (CN), CrAl (CN), etc .; and (CN) portion is (N) or (C)], Ti hard coating [Ti (CN), TiAl (CN) ), TiSi (CN), and the like; and the (CN) portion is (N) or (C)], a TiCr-based hard coating [TiAlCr (CN); and the (CN) portion is (N) or (C)], etc. Is exemplified.

  The metal layer or alloy layer is precisely at least one metal layer or alloy layer selected from Group 4A elements, Group 5A elements, Group 6A elements, Al or Si of the periodic table, and these layers. Since the hardness is lower than that of the hard coating of the present invention, an object to be treated (particularly, an iron-based substrate having a relatively low adhesion to the hard coating such as high-speed tool steel (SKH51) is provided via a metal layer or an alloy layer. Or SKD, etc.), the adhesion between the hard film and the object to be treated can be increased. The layer is exemplified.

  The thickness of the hard coating (including the laminated hard coating and the heterogeneous composite hard coating) varies depending on the use, but is 0.5 μm or more (preferably 1 μm or more), 20 μm or less (preferably 15 μm or less, more preferably 10 μm or less).

  Examples of the iron-based substrate on which the hard film is formed include high-speed tool steel (SKH51, SKD11, SKD61, etc.), cemented carbide, and the like.

  The hard film can be manufactured using a known method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD). From the standpoint of adhesion and the like, it is preferable to manufacture using a PVD method. Specific examples include sputtering, vacuum deposition, and ion plating. Preferably, a vapor phase coating method [sputtering or ion plating (particularly, arc ion plating)] is employed. Is recommended.

Specifically, the VAl-based hard coating and the Si / B additional type VAl-based hard coating use the targets (i) to (iv) described below, and a gas phase coating method (preferably Can be produced by the arc ion plating method.
(I) Al and V
(Ii) Al, V and Si
(Iii) Al, V and B
(Iv) Al, V, Si and B
In particular,
When obtaining a hard coating composed of (Al _1-a V _a ) (C _1-X N _x ), a target composed of (Al _1-a V _a ) and satisfying 0.27 ≦ a ≦ 0.75 (wherein a represents an atomic ratio),
When obtaining a hard film made of (Al _{1 -abc} V _a Si _b B _c ) (C _{1 -X} N _x ), it is made of (Al _{1 -abc} V _a Si _b B _c ), and 0.1 ≦ a ≦ 0. A target in which 75 and 0 <b + c ≦ 0.2 (wherein a, b and c independently represent an atomic ratio: b and c may be either 0, but both are 0 Can be used).

  In addition, as a target used in the manufacture of the Mo · W combined hard coating or the Zr · Hf combined hard coating, Mo and / or W, or Zr and / or Hf are further added to the targets (i) to (iv) above. The contained target can be used.

  The present inventor also examined the characteristics of the target. As a result, in the target having a low relative density, micropores and the like are easily formed in the target, resulting in uneven vaporization of the target, and a hard, uniform composition and film thickness. In the case of a target having a low density because the film has been manufactured, the vacancies in the target are consumed locally and rapidly during film formation, the target depletion rate is increased, the life of the target is shortened, and the vacancies are further reduced. It was discovered that if there are many parts, the strength of the target deteriorates and cracks occur. Therefore, by setting the relative density of the target to 95% or more (preferably 98% or more), the above problem can be solved, and at the same time, discharge is performed when the alloy components constituting the target are evaporated or ionized by arc discharge. The state could be stabilized and a hard film could be obtained satisfactorily.

  The relative density of the target means a value obtained from the formula [(weight of 1 cm square used) / (density of target consisting of pure composition (theoretical density)) × 100]. The calculation method of the theoretical density can be calculated using a known method.

  The method for producing the target is not particularly limited. For example, after the raw materials (V powder and Al powder) whose amount ratio, particle size, etc. are appropriately adjusted are mixed uniformly with a V-type mixer or the like to obtain a mixed powder It can be produced by using a cold isostatic pressing process (CIP process) or a hot isostatic pressing process (HIP process), a hot extrusion method, an ultra-high pressure hot press method, or the like.

  The present inventor also examined an apparatus for producing a hard coating by the arc ion plating method. In the apparatus used in the conventional AIP method, a magnetic field is generated as shown in a schematic diagram of its function in FIG. Since the target 106 is disposed between the magnet 109 to be processed and the workpiece W, the magnetic force lines 102 generated from the magnet 109 are almost parallel to the target surface in the vicinity of the evaporation surface of the target, and the magnetic force lines 102 are processed. It is difficult to extend to the vicinity of the body W. For this reason, the plasma density of the film forming gas is high in the vicinity of the target, but decreases as it approaches the workpiece W. Therefore, the magnetic lines of force are formed so as to be substantially orthogonal to the evaporation surface of the target, and a part of the electrons e generated by the discharge collide with N and / or C in the gas, thereby converting N and / or C into plasma. It has been found that a hard coating can be produced more efficiently. Specifically, as shown in FIGS. 2 and 3, a magnet or an electromagnet provided with a coil and a coil power source that generates a magnetic field (also referred to as magnetic field forming means in this specification) 8 or 9 is used. It is arranged between the target 6 and the workpiece W, and the angle between the line of magnetic force and the normal of the evaporation surface of the target 6 is ± 30 ° or more (preferably 20 ° or more). Can do. Furthermore, by making the magnetic flux density near the target and the object to be processed higher than that of the conventional AIP apparatus, AlN having a rock salt type crystal structure that is a non-equilibrium layer is likely to be formed under normal temperature and normal pressure. The hardness of the film can be increased. Also, by promoting the plasmaization of the coating material vaporized from the target and the plasma conversion of N as the atmospheric gas, the plasmaized N becomes high-energy particles, generating rock salt type AlN that is a non-equilibrium phase. It is thought that it becomes easy to do.

  As illustrated in FIG. 2, the magnetic field forming unit may be disposed on the target 6 and / or on the evaporation surface S side of the target so as to sandwich or surround the target 6. 3, the magnetic field forming means 9 may be disposed between the evaporation surface S of the target 6 and the workpiece W. Further, as illustrated in FIG. 2, the chamber may be an anode, or a dedicated anode having a cylindrical shape surrounding the front of the side surface of the target may be provided.

  The intensity of the magnetic field to be generated is preferably adjusted so that the magnetic flux density at the center of the surface on which the hard film to be processed is formed is 10 gauss or more (preferably 30 gauss or more).

  The film-forming gas may be set according to the desired composition of the hard film. Specifically, N is 0.3% or more (preferably 0.4 or more with respect to the total of N and C atoms). More preferably, it may be set within a range of 0.6 or more, particularly preferably 0.8 or more.

  The temperature of the object to be processed at the time of film formation may be appropriately selected according to the type of object to be processed, but if it is too high, the residual stress of the hard film may be reduced, and excessive residual stress acts on the hard film. However, the adhesion to the object to be processed may be impaired. Therefore, it is recommended that the temperature is set to 300 ° C. or higher, preferably 400 ° C. or higher. If the temperature of the object to be treated is too high, the residual stress will be reduced, but at the same time the compressive stress will be reduced, and the effect of increasing the bending strength of the object to be treated may be impaired. The object to be processed may be deformed. Therefore, it is recommended that the temperature of the object to be processed is 800 ° C. or lower, preferably 700 ° C. or lower. In addition, when a substrate such as HSS (high speed tool steel, SKH51, etc.) or hot tool steel such as SKD11, SKD61, etc. is used as the object to be processed, the substrate temperature at the time of manufacture is set below the tempering temperature of the substrate material. It is also preferred to maintain the mechanical properties of the substrate. The tempering temperature can be appropriately selected depending on the substrate material. In general, when SKH51 is used as the base material, 550 to 570 ° C., when SKD61 is used, 550 to 680 ° C. and SKD11 are used. The temperature may be 500 to 530 ° C. In that case, the temperature of the substrate at the time of manufacture is preferably set lower than these tempering temperatures, and specifically, it is preferably set to 50 ° C. or less with respect to the tempering temperature.

  Note that a hard coating can be more efficiently formed by applying a negative potential to the object to be processed at the time of film formation. The higher the bias voltage, the higher the energy of the plasma-forming film forming gas and metal ions, and the hard film showing the resulting cubic crystal structure can be easily obtained. It is preferable to set it to 10V or more, especially 30V or more. However, when the bias voltage is increased, the film is etched by the plasma forming film forming gas, and the film forming speed may be extremely reduced. Therefore, it is preferable that the negative value is 200 V or less, particularly 150 V or less in absolute value. When the proportion of Al is relatively small, even if the bias voltage is somewhat low, the above-described pulling effect works effectively, and a hard coating film having a cubic crystal structure is easily obtained.

  Further, as described above, when a hard coating is manufactured as a laminate composed of a plurality of layers, for example, an apparatus including a plurality of targets 6A, magnetic field forming means 8A, etc. as shown in FIG. Thus, a hard film made of a laminate can be manufactured by manufacturing each layer.

The physical properties of the hard coating obtained in the following experimental examples were determined according to the following method.
[Composition of hard coating]
Measured by EPMA. At that time, it was confirmed that the amount of impurity elements other than metal elements and nitrogen in the hard coating was 5 at% or less for each of oxygen and carbon.

[Crystal structure analysis conditions]
The crystal structure is evaluated by X-ray analysis of the hard coating by the θ-2θ method using an X-ray diffractometer manufactured by Rigaku Electric Co., Ltd. At that time, for a cubic crystal, a CuKα radiation source is used. For the (111) plane, around 2θ = 37.78 °, for the (200) plane, near 2θ = 43.9 °, for the (220) plane. The peak intensity around 2θ = 63.8 ° is measured. X-ray diffraction of hexagonal crystal uses Cu Kα ray, (110) near (2) = 32 ° to 33 ° for the (100) plane, and around 2θ = 48 ° to 50 ° for the (102) plane. For the surface, the peak intensity around 2θ = 57 ° to 58 ° is measured. Using these values, the following formula (1)

(In the formula, IB (111), IB (200) and IB (220) indicate the peak intensity of each face of the cubic crystal. IH (100), IH (102) and IH (110) are the faces of the hexagonal crystal. Shows peak intensity)
The value calculated by introducing into (in the table, “value of the formula (1)”) of 0.8 or more is recognized as the NaCl type (shown as B in the table), and the value of 0 is hexagonal. It was made of a structure (indicated as H in the table), and a mixed type (indicated as B + H in the table) was greater than 0 and less than 0.8.

[Measurement of hardness]
Using a micro Vickers hardness tester, the load was 0.25 N and the holding time was 15 seconds.

[Measurement of friction coefficient]
A ball-on-disk test was conducted under the following test conditions using a sliding test disk (manufactured by SKD61: φ55 mm × 5 mm thickness, single-sided mirror polished) on which the hard coating of the present invention was formed. It was measured.
Sliding test conditions Test method: Ball-on-disk Ball: SUJ2 (diameter 9.54 mm), hardness HRC60
Vertical load: 5N
Sliding speed: 1m / s
Atmospheric temperature: 500 ° C. for Experimental Examples 1-4, 800 ° C. for Experimental Examples 5-8
Sliding distance: 1000m

[Observation of wear width]
A hard coating of the present invention is formed on the surface of a cemented carbide ball end mill (diameter: 10 mm, two blades), and is determined under the following conditions A (Experimental Examples 1 to 4) or Conditional B (Experimental Examples 5 to 8). Then, the cutting edge of the end mill coated with the hard film was observed with an optical microscope.
-Condition A-
Work Material: SKD61 Hardened Steel (HRC50)
Cutting speed: 220 m / min Blade feed rate: 0.06 mm / tooth Shaft cutting: 4.5 mm
Radial notch: 1mm
Other: Down cut, dry cut, air blow only Cutting length: 20m
-Condition B-
Work material: SKD11 (HRC60)
Cutting speed: 150 m / min Blade feed rate: 0.04 mm / blade Shaft cutting: 4.5 mm
Radial notch: 0.2mm
Other: Down cut, dry cut, air blow only Cutting length: 50m

[Apparatus used to form hard coating]
For Experimental Examples 1, 2, and 4-6, an AIP apparatus having the outline shown in FIG. 1 was used. In the figure, 1 indicates a chamber, 2 indicates an arc evaporation source, 3 indicates a support base, 4 indicates a bias power source, 6 indicates a target, 7 indicates an arc power source, and 8 indicates a magnetic field forming means. (Magnet), 11 indicates an exhaust port, 12 indicates a gas supply port, and W indicates an object to be processed.

  For Experimental Examples 3, 7, and 8, hard coatings were produced using an AIP apparatus having the outline shown in FIG. The AIP device of FIG. 5 is the same as the AIP device of FIG. 1, but further includes an arc evaporation source 2A, a bias power source 4A, a target 6A, an arc power source 7A, and a magnetic field forming means (magnet) 8A.

[Type of object to be processed]
In each experimental example, [1] cemented carbide tip (for crystal structure and hardness measurement), [2] cemented carbide end mill (diameter 10 mm, two blades) (for wear width measurement) and [3] sliding Three types of workpieces were used: test disks (manufactured by SKD61: φ55 mm × 5 mm thickness, single-side mirror polishing) (for friction coefficient measurement).

(Experimental example 1)
[Hard film formation]
The target 6 having a composition having the “composition ratio (atomic ratio) of the target” shown in Table 1 was used.

  After the chamber 1 was evacuated, the object to be processed was heated to 500 ° C. with a heater (not shown). A single or mixed gas having a composition of “film forming gas composition ratio (atomic ratio)” in Table 1 was supplied from the gas supply port 12 so that the pressure in the chamber 1 was 2.66 Pa. The bias power supply 4 applies a voltage of 20 to 100 V to the object to be processed so that the object W has a negative potential with respect to the ground voltage, the arc power supply 7 starts arc discharge, and the target 6 Was vaporized and ionized to form a hard film having a thickness of 3 μm on the surface of the workpiece W.

[Physical properties of hard coating]
Table 1 shows the crystal structure of the obtained hard film and the measurement results of the value of formula (1), hardness, friction coefficient, and wear width.

  The hard coatings (Examples 1 to 14) of the present invention consisting of Al, V, C and N are all compared to conventional TiAlN (Comparative Example 1), CrAlN (Comparative Example 2) and VN (Comparative Example 3). The hardness was high, the friction coefficient was small, and the wear width was narrow. Those outside the composition range defined in the present invention (Comparative Examples 4 to 8) include a hexagonal crystal structure, and compared with conventional hard coatings (Comparative Examples 1 to 3), hardness, friction coefficient, and wear width. Either was inferior. Further, those containing C in the deposition gas (Examples 10 to 14) had lower frictional resistance and better lubricity than those containing no C in the deposition gas (Example 5).

(Experimental example 2)
[Hard film formation]
An experiment was conducted in the same manner as in Experimental Example 1 except that a target having a composition having the “target composition ratio (atomic ratio)” in Table 2 was used.

[Physical properties of hard coating]
Table 2 shows the crystal structure of the obtained hard coating and the measurement results of the value of formula (1), hardness, friction coefficient, and wear width.

  The hard coatings (Examples 15 to 33) of the present invention all had higher hardness, a smaller friction coefficient, and a smaller wear width than conventional TiAlN (Comparative Example 1) and CrAlN (Comparative Example 2). Moreover, the hard film | membrane (Examples 16-33) which contained Si and B in the hard film had the effect equivalent to or more than the hard film | membrane (Example 15) of this invention which does not contain Si and B. . However, the compositions outside the range defined by the present invention (Comparative Examples 9 to 11) include a ZnS structure in the crystal structure and are equivalent in terms of hardness and wear width compared to conventional hard coatings (Comparative Examples 1 and 2). Or it was inferior.

(Experimental example 3)
[Hard film formation]
Using the apparatus schematically shown in FIG. 5, a target 2 having a composition composed of “target composition ratio (atomic ratio)” of “A layer (upper stage)” in Table 3 was used. A target 2A having a composition composed of “target composition ratio (atomic ratio)” of “B layer (lower stage)” in Table 3 was used. In Examples 39 and 41, the film was formed without using the target 2.

-Formation of the hard film of Examples 34-38 and 40 After making the inside of the chamber 1 into a vacuum state, the to-be-processed object W was heated at 500 degreeC with the heater (not shown). Then, a single or mixed gas having the “deposition gas composition (atomic ratio)” in Table 3 was supplied from the gas supply port 12 so that the pressure in the chamber 1 was 2.66 Pa. Arc discharge is started by the arc power source 7, the target 6 is vaporized and ionized, and the object to be processed is set to 20 to 100V by the bias power source 4 so that the object W has a negative potential with respect to the ground voltage. An A layer was formed on the surface of the object to be processed so as to have the thickness described in Table 3. Next, arc discharge is started by the arc power source 7A, the target 6A is vaporized and ionized, and the bias power source 4A receives 20 to 100 V so that the workpiece W has a negative potential with respect to the ground voltage. A B-layer hard coating was formed on the surface of the workpiece W on which the A layer was formed, so as to have the thickness described in Table 3, when applied to the treated body W. The above operation was repeated for the “number of layers” in Table 3 to form a hard film composed of a laminate.

-Formation of the hard film of Examples 39 and 41 Using the object to be processed on which the hard film of "A layer" described in Table 3 was formed, 500 W to be processed with a heater (not shown) Heated to ° C. A single or mixed gas having the composition ratio (atom ratio) of the film forming gas shown in Table 3 was supplied from the gas supply port 12 so that the pressure in the chamber 1 was 2.66 Pa. Arc discharge is started by the arc power source 7A, the target 6A is vaporized and ionized, and the object to be processed is set to 20 to 100 V by the bias power source 4A so that the object W has a negative potential with respect to the ground voltage. B layer was formed on the surface of the workpiece W so as to have the thickness described in Table 3.

[Evaluation of hard coating]
Table 3 shows the crystal structure of the obtained hard film and the results of measurement of the value of formula (1), hardness, friction coefficient, and wear width.

  The hard coatings (Examples 34 to 41) having the laminated structure of the present invention have higher hardness, lower friction coefficient, and wear width than the conventional TiAlN (Comparative Example 1) and CrAlN (Comparative Example 2). It was narrow.

(Experimental example 4)
V, Al, Si, and B powders (each particle size is 100 mesh or less) were mixed with a V-type mixer to prepare the compositions shown in Table 4. Then, the target was manufactured under the conditions of sintering (reducing atmosphere, firing temperature: 550 ° C.), HIP (10000 atm, 480 ° C.), hot casting (residual heat temperature: 450 ° C.). . They were attached to the AIP apparatus shown in FIG. 1, a hard film was formed on the surface of the workpiece W, the state of discharge and the state of the formed film were observed, and the results are shown in Table 4. The deposition gas used was 100% nitrogen for Examples 42 and 43, and a mixed gas of nitrogen and methane (nitrogen: methane = 80: 20 (atomic ratio)) for 44 and 45.

  A film obtained using a target having a relative density of less than 95% (Comparative Examples 14 and 15) could not be formed, and a hard film obtained using a target having a relative density of 95% or more (Example 42). ~ 45), a film could be formed.

(Experimental example 5)
[Hard film formation]
An experiment was conducted in the same manner as in Experimental Example 1 except that a target having the composition having the “target composition ratio (atomic ratio)” shown in Table 5 was used.

[Physical properties of hard coating]
Table 5 shows the crystal structure of the obtained hard film and the measurement results of the value of formula (1), hardness, friction coefficient, and wear width.

  The hard films of Examples 47 to 59 show the results of the hard film of the present invention containing W and Mo. For comparison, the hard film of the present invention (Example 46) which does not contain W and Mo is compared with the conventional hard film. The results of the hard coating (Comparative Examples 1 and 2) were also described. Under sliding conditions of 800 ° C., the hard film containing Mo or W (Examples 47 to 59) was superior to the conventional hard film in any of hardness, friction coefficient, and wear width. In particular, when the V content was 0.27 or more, the hardness, friction coefficient, and wear width could be improved by adding W or Mo to the hard film as compared with the hard film of Example 46. (Examples 47-52 and 54-56). However, when the total content of W and Mo was 0.39 or more, a hexagonal crystal structure appeared, and as a result, a decrease in hardness and an increase in wear width were observed (Comparative Example 16).

(Experimental example 6)
[Hard film formation]
An experiment was conducted in the same manner as in Experimental Example 1 except that a target having the composition having the “composition ratio (atomic ratio) of target” in Table 6 was used.

[Physical properties of hard coating]
Table 6 shows the crystal structure of the obtained hard film and the measurement results of the value of formula (1), hardness, friction coefficient, and wear width.

  The hard films of Examples 60 to 75 show the results of the hard film of the present invention containing Zr and Hf. For comparison, the hard film of the present invention not containing Zr and Hf (Example 46) and the conventional one. The results of the hard coating (Comparative Examples 1 and 2) were also described. Under sliding conditions at a temperature of 800 ° C., the hard coatings of Examples 60 to 75 were superior to conventional hard coatings in any of hardness, friction coefficient, and wear width. Further, as compared with the hard coating of Example 46, by containing Zr and Hf, the hardness could be increased and the wear width could be reduced without significantly changing the friction coefficient. When the content of the above elements (Zr, Hf) was 0.45 or more, a hexagonal crystal structure appeared, and a decrease in hardness and an increase in wear width began (Examples 64 and 65). If the decrease is about 64 and 65, it does not fall below the conventional examples (Comparative Examples 1 and 2), but if the total content of Zr and Hf is further increased, the decrease in hardness and the increase in wear width are remarkable. It becomes.

(Experimental example 7)
[Hard film formation]
Using the apparatus schematically shown in FIG. 5, for Examples 77 to 87, a target 2 having a composition consisting of “target composition ratio (atomic ratio)” of “A layer (upper stage)” in Table 7 was prepared. The target 2A having a composition consisting of the “target composition ratio (atomic ratio)” of “B layer (lower stage)” in Table 7 is used. Example 76 is hard without using the target 2. A film was produced. About the thing except the above, it carried out according to the manufacturing method of Experimental example 3.

[Evaluation of hard coating]
Table 7 shows the measurement results of the hardness, friction coefficient, and wear width of the obtained hard coating.

  The laminated hard coatings of the present invention (Examples 77 to 87) all had higher hardness, a smaller friction coefficient, and a smaller wear width than the conventional hard coatings (Comparative Examples 1 and 2). Furthermore, by using a laminated type (Experimental Examples 77 to 83), the friction coefficient and the wear width could be reduced as compared with the single-layer hard coating (Example 46). Furthermore, from the results of the single-layer hard coating of Example 76 and the laminated hard coatings of Examples 84 to 87, it was shown that the aspect of the present invention has a sufficient effect on the hard coating containing Si. .

(Experimental example 8)
[Hard film formation]
Using the apparatus schematically shown in FIG. 5, for Examples 88 to 98, a target 2 having a composition composed of “target composition ratio (atomic ratio)” of “A layer (upper stage)” in Table 7 was prepared. Then, a hard coating was produced by using the target 2A having a composition consisting of “composition ratio (atomic ratio)” of “B layer (lower stage)” in Table 7. About the thing except the above, it carried out according to the manufacturing method of Experimental example 7.

[Evaluation of hard coating]
Table 8 shows the results of measurement of the hardness, friction coefficient, and wear width of the obtained hard coating.

The laminated hard coatings of the present invention (Examples 88 to 98) all had higher hardness, a smaller friction coefficient, and a smaller wear width than the conventional hard coatings (Comparative Examples 1 and 2). Furthermore, the laminated hard coating (Experimental Examples 87 to 93) can improve the hardness while maintaining the same coefficient of friction as the single-layered hard coating (Example 46), and can also reduce the wear width. did it.
Further, the embodiment of the present invention was sufficiently effective for a hard film containing Si (Examples 95 to 98).

  Since the hard coating of the present invention is extremely excellent in hardness and lubricity, in addition to cutting tools (chips, drills, end mills, etc.), jigs (forging dies, punching punches, etc.), etc. It can also be used for moving members.

1. Vacuum container 2, 2A. 2. Arc type evaporation source Support base 4, 4A. Bias power supply 6, 6A. Target 7, 7A. Arc power supplies 8, 8A, 9, 109. Magnetic field forming means (magnet or permanent magnet)
11. Exhaust port 12. Gas supply port W, 106. Processing object 102. Magnetic field lines

Claims (9)

A hard film made of (Al _1-a-f-g V _a Hf _f Zr _g ) (C _1-X N _X ),
0.01 ≦ a ≦ 0.75,
0 <f + g ≦ 0.5,
0.3 ≦ X ≦ 1
(In the formula, a, f, g and X independently represent an atomic ratio: f and g may be either 0, but neither is 0)
Hard coating characterized by being A _{(Al 1-abc-f-} g V a Si b B c Hf f Zr g) (C 1-X N X) hard film consisting of,
0.01 ≦ a ≦ 0.75,
0 <b + c ≦ 0.20,
0 <f + g ≦ 0.5,
0.3 ≦ X ≦ 1
(Wherein a, b, c, f, g and X independently represent an atomic ratio: b and c may be either 0, but both are not 0. , F and g may be one, but not both)
Hard coating characterized by being   The hard film according to claim 1, which shows a NaCl-type crystal structure. (Al _1-a V _a ) (C _1-X N _X )
0.27 ≦ a ≦ 0.75, 0.3 ≦ X ≦ 1 (wherein a and X independently represent an atomic ratio), or
(Al _1-abc V _a Si _b B _c ) (C _1-X N _X ), 0.1 ≦ a ≦ 0.75, 0 <b + c ≦ 0.20, 0.3 ≦ X ≦ 1 (formula In which a, b, c and X independently represent an atomic ratio: where b and c may be one, but not both) A layer made of a hard coating (hereinafter referred to as A layer);
A layer made of a compound obtained by selecting one or more of Zr and Hf and one or more of C and N (hereinafter referred to as C layer)
A laminated hard film made by laminating The thickness of the A layer and the C layer is
C layer thickness ≦ A layer thickness ≦ 200 nm
The multilayer hard coating according to claim 4.   6. The method for producing a hard coating film according to claim 1, wherein the metal is evaporated and ionized in a film forming gas atmosphere to promote plasma formation of the film forming gas together with the metal. The manufacturing method of the hard film | membrane characterized by making a film | membrane.   In the arc ion plating method in which the metal constituting the target is evaporated and ionized by arc discharge, a magnetic field line that diverges forward or travels substantially perpendicular to the evaporation surface of the target is formed, and this magnetic field line is used for processing. The manufacturing method of the hard film | membrane of Claim 6 which forms into a film, promoting the plasma-izing of the film-forming gas in the body vicinity.   The method for producing a hard coating film according to claim 7, wherein a magnetic flux density in a central portion of a surface on which the hard coating film of the object is formed is 10 gauss or more.   9. The magnetic field is formed between the target and the object to be processed so that an angle formed by the magnetic force line and a normal line of the evaporation surface of the target is ± 30 ° or less. A method for producing a hard coating.

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