JPH08127863A - Laminated body - Google Patents

Abstract

PURPOSE: To produce a laminated body of multi-layered film improved in wear resistance. CONSTITUTION: This laminated body contains at least two compound layers, containing, as principar components, one or more elements (first elements) selected from among the group consisting of the group IVa, Va, and VIa elements of the periodic table, Al, Si, and B and one or more elements (second elements) selected from among the group consisting of B, C, N, and O and having compositions dissimilar to each other, and a composition-modulated layer which is disposed between the compound layers and in which the composition (by atomic %) of the first elements varies in a thickness direction. Moreover, the compound layer and the composition-modulated layer are periodically laminated, and this laminated body has crystal lattices continuing more than one cycle between respective layers. By this method, the laminated body, excellent in heat resistance and corrosion resistance, can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film laminate, and more particularly, to a surface coating material provided for the purpose of improving wear resistance and the like, which is a surface coating for hard members such as cutting tools and wear resistant tools. The present invention relates to a thin film laminate useful as a material, a surface coating material for electric / electronic parts, sliding / mechanical parts, and the like.

[0002]

2. Description of the Related Art Conventionally, in the field of cutting tools,
PVD (Physical Vapor Deposition) on the surface of the base material made of cemented carbide or the like for the purpose of improving its wear resistance.
Physical vapor deposition) and CVD (Chemical Vapor Deposit)
ion; chemical vapor deposition method is used to form a coating layer (coating) made of carbides, nitrides, carbonitrides of Ti, Hf, Zr, or oxides of Al in one layer or multiple layers (composite layer). Placement is being done.

In particular, the PVD coating has the advantage that it is easy to improve the wear resistance without deteriorating the strength of the base material. For this reason, throw-away inserts for drills, end mills and milling cutters (Throw Away Ti
Such a surface coating is often used in a cutting tool that requires particularly high strength, such as p; "replaceable" tip).

However, the material (nitride or carbonitride) of the surface coating layer currently used is not sufficient in wear resistance and heat resistance, and the tool life is shortened especially in a tool for high speed cutting. There was a problem.

Under these circumstances, H.264. Hollleck
JP-A-61-235555 (German application, DE 3512986) discloses an entire coating film between two thin films of ceramics of TiC and TiB ₂ having a metal bonding property of 40 nm or less. 100 to 200 in total
No. 00, a multi-layer film having a structure formed by introducing a large number of “coherent or partially coherent interfaces”, which is produced by a sputtering method using TiC and TiB ₂ targets is described. .

[0006]

However, according to the study by the present inventors, the hardness of the above-mentioned multilayer film (one of the scales of abrasion resistance) was not always sufficient.

It is an object of the present invention to provide a multilayer film laminate having improved wear resistance.

Another object of the present invention is to provide a multilayer film laminate which provides a hard member having improved cutting performance.

As a result of earnest studies, the present inventor has conducted two or more types of layers (compound layers) composed of compounds having different compositions; a layer disposed between the compound layers, and the composition changes with a constant tendency. It has been found that forming a laminate including a layer (composition-modulating layer) that increases (decreases or decreases) is extremely effective in achieving the above object.

The laminated body of the present invention is based on the above findings, and more specifically, one or more elements selected from the IVa, Va, and VIa group elements of the periodic table, Al, Si, and B (first Element); and at least two kinds of compound layers having a composition different from each other, the main components of which are one or more kinds of elements (second elements) selected from B, C, N, and O, and arranged between the compound layers. And the composition (at
%) Of the composition-modulating layer, the compound layer and the composition-modulating layer are periodically laminated, and each layer has a crystal lattice continuous for one or more cycles. Is.

[0011]

As described above, the laminate of the present invention is a layer disposed between two or more "compound layers" and the compound layers, and the composition thereof changes (increases or decreases) with a constant tendency. And a “composition-modulating layer”. That is, each layer constituting the conventional laminated multilayer film has an “interface” (that is,
While the composition has a discontinuous surface), the laminate of the present invention does not have such an “interface” (at least in the periodic structure of the compound layer-composition modulation layer), Two or more compound layers are the above-mentioned "composition-modulating layer" disposed between them.
Is adjacent to.

According to the knowledge of the present inventor, in the composition modulation layer between two or more kinds of compound layers, the lattice is continuous with a slight distortion and the crystal structure is changed and stabilized, so that the strain energy is applied to the laminated film. Is stored. In this way, based on the strain energy stored in the entire laminated film, the hardness of the laminated film is improved, the wear resistance is increased (and / or the propagation of cracks is suppressed, and between the layers constituting the laminated body, Or, the peeling between the base material and the laminated body is suppressed). According to the experiments of the present inventor, when such a composition modulation layer is provided, compound layers having considerably different lattice constants and / or elastic constants (for example, TiN layer-AlN
It has been found that good matching is also easily obtained in layers).

Further, according to the knowledge of the present inventor, in the above-mentioned laminated body of the present invention, a laminating cycle (a laminating cycle in which abrasion resistance is improved) can be obtained in a wider range as compared with the conventional product. It has been found that there is a tendency. Therefore, in the laminate of the present invention, it becomes easy to obtain "greater wear resistance" in a wide range of lamination cycles (compared to the conventional product). In addition, it is easy to reduce the "number of layers" to obtain the same "thickness of laminated film" or "wear resistance" (compared to the conventional product). The body is easier to manufacture than conventional products.

On the other hand, the above Hollleck having an interface
In the multilayer film of, the dislocations (misfit dislocations) corresponding to the difference (misfit) of the lattice constants at the interface between substances having different lattice constants (usually, different substances have different lattice constants)
Is likely to occur, and the increase in hardness (improvement in wear resistance) due to “strain matching” is estimated to be extremely small. Further, stress is likely to be concentrated at the interface, and therefore peeling is likely to occur. Furthermore, in such a multilayer film, TiC-
At the interface between substances with different crystal structures such as TiB ₂ ,
Select a crystal orientation to partially match (TiC (111)
Therefore, it is presumed that one crystal structure does not change to one crystal structure as a whole due to the tendency of TiB ₂ (0001)).

The present invention will be described below in detail with reference to the drawings as necessary.

The laminate of the present invention comprises two or more kinds of compound layers and a composition modulation layer arranged between them.

(Compound layer) In the present invention, the "compound layer" means a layer in which the composition (at%) of the first element is substantially constant in the thickness direction (the "compound" in the present invention). Is used for the purpose of including “solid solution”). Here, the "first element" means an IVa group element (Ti, Zr, Hf), a Va group element (V, Nb, T) of the periodic table.
a), VIa group element (Cr, Mo, W), Al, Si, and one or more elements selected from B.

The compound layer contains the above-mentioned first element (one or more kinds of elements) and one or more kinds of elements selected from B, C, N and O (hereinafter, referred to as "second element"). It is a layer made of a compound as a main component.

In the present invention, the combination of the above-mentioned first element and second element is not particularly limited, but for example, the following combinations can be preferably used.

[0020] <first element><secondelement>_{<compound> Ti C TiC B C B 4} C W C W 2 C Ti C, N Ti (C x N 1-x) Ti N TiN Ti B TiB 2 Ti B, N Ti (B _x N _1-x ) B N BN Si N Si ₃ N ₄ Al N AlN Al O Al ₂ O ₃ Ti-Al N (Ti-Al) N Ti-Zr N (Ti-Zr) N Ti-CrN (Ti-Cr) NTi-HfN (Ti-Hf) N In the above compound layer, the relative value of the fluctuation range of the composition (at%) of the first element and / or the second element, that is, The (maximum value-minimum value) / maximum value is preferably 15% or less, more preferably 10% or less (particularly 5% or less) in the thickness direction.

The composition (at%) of the first element or the second element is determined by, for example, energy dispersive X-ray analysis (EDX) or electron energy loss spectroscopy (elec).
It can be confirmed by tronenergy-loss spectroscopy (EELS).

In this EDX or EELS analysis, for example, the following conditions can be preferably used.

<Measurement equipment> Measurement equipment: VG, HB501 EDX: KEVEX Super8000 quantitative total system Energy dispersive X-ray analyzer (Si <Li> semiconductor detector, UTW type) EELS: VG, ELS-80 Spectrometer (energy resolution: 0.56 eV) <Measurement conditions> Accelerating voltage: 100 kV Sample absorption current: 10 ^-9 A Counting time: 50 to 100 seconds Analytical probe diameter: 1 nmφ The thickness of the compound layer (1 layer) described above is , 100 nm or less, more preferably about 1 to 20 nm (especially 1
It is preferably about 10 nm). This layer thickness is 1
If the thickness is less than nm, the effect of providing the composition modulation layer tends to be insufficient. On the other hand, when the layer thickness exceeds 20 nm, the effects of improving hardness and abrasion resistance due to lamination tend to be insufficient. The thickness of such a compound layer (one layer) can be confirmed by, for example, a transmission electron microscope (TEM).

In this TEM analysis, for example, the following conditions can be preferably used.

<TEM analysis conditions> Measuring instrument: Hitachi, trade name: H-9000UHR Accelerating voltage: 300 kV Magnification: 200,000-8 million times (composition modulation layer) In the present invention, the "composition modulation layer" is as described above. Composition of first element and / or second element (at%)
Changes with a constant tendency in the thickness direction (ie,
A layer that increases or decreases in the thickness direction). In the composition modulation layer, it is sufficient that at least one of the first element and the second element is changed.

When the compound layers adjacent to the composition-modulating layer are referred to as "compound layer A" and "compound layer B", the composition on the side in contact with "compound layer A" of the composition-modulating layer is "compound layer A". It is preferable that it is substantially the same as the composition of ". The composition of the composition-modulating layer in contact with the “compound layer B” is preferably substantially the same as the composition of the “compound layer B”. That is, in such an aspect, the composition modulation layer has a composition that changes from “substantially the same composition as the compound layer A” to “substantially the same composition as the compound layer B” (or vice versa). ) Are preferred.

In the present invention, the thickness of the composition-modulating layer (one layer) is preferably 0.4 nm or more, more preferably 0.4 to 100 nm (particularly 0.4 to 20 nm).
It is preferred that The thickness of such a compound layer (one layer) is, for example, the same T as in the measurement of the thickness of the above compound layer.
It can be confirmed by EM measurement.

From the standpoint of preventing separation between compound layers or stabilizing "strain matching" in the entire laminate, the thickness of the compound layer is a (nm) and the thickness of the composition modulation layer is b (nm). When the thickness ratio (b / a) is 1/10
It is preferably about 10 and more preferably about 1/5 to 5.

In the present invention, the first element (and / or the second element;
The same applies to the following "composition modulation layer") (at%)
Preferably changes substantially continuously. Here, “substantially continuously changing” means that there is substantially no interface (a surface having a discontinuous composition) in the composition modulation layer. More specifically, the difference in composition (at%) between the “compound layer A” and the “compound layer B” with respect to the first element (E _a ) forming the “compound layer A” is defined as | E _a2 −E _a1 In the case of |, from the viewpoint of stabilizing the above “strain matching”, the absolute value of this difference is divided by the thickness b (nm) of the composition modulation layer to obtain a quotient (| E _a2 −
E _a1 | / b) is preferably 300 at% / nm or less, more preferably about 300 to 1 at% / nm (particularly 3
It is preferably about 0 to 5 at% / nm).

In addition, the first which constitutes the above-mentioned "compound layer B"
"Compound layer A" and "compound layer B" relating to the element (E _b ).
When the difference in composition (at%) from the above is defined as | E _b2 −E _b1 |, from the viewpoint of stabilizing the above “strain matching”, the absolute value of this difference is calculated as the thickness b (nm) of the composition modulation layer. Quotient (| E _b2 −
E _b1 | / b) is preferably 300 at% / nm or less, and more preferably 300 to 1 at% / nm (particularly 3
It is preferably about 0 to 5 at% / nm).

The "quotient" of the composition modulation layer relating to the "first element" described above is similarly applicable to the "second element".

(Laminate) The laminate of the present invention has a structure in which the above compound layer and the composition modulation layer are periodically laminated. An example of a laminated structure preferably used in the present invention is shown below (compound layer is indicated by symbol "C", composition modulation layer is indicated by symbol "M". The substrate side of the laminated structure is on the left side, and the surface side of the laminated body is on the right side. Shown in).

<When the laminate has two kinds of compound layers> C (composition A) → M (composition m) → C (composition B) → M (composition n) → C (composition A) → · (1 cycle <When the laminate has three kinds of compound layers> C (composition A) → M (composition m) → C (composition B) → M (composition n) → C (composition C) → M (composition p) → C (composition A) → ... (1 cycle) “1 cycle” for stacking means C in the above-mentioned embodiment.
The total film thickness of (composition A) + M (composition m) + C (composition B) + M (composition n) (when there are two types of compound layers) or C (composition A) + M (composition m) + C (composition B) ) + M
It means the total of the film thicknesses of (composition n) + C (composition C) + M (composition p) (in the case of having three kinds of compound layers).

(Crystal Structure) The crystal structure or X-ray diffraction pattern of the entire laminate or each layer constituting the laminate is as follows:
Commonly known crystal systems (eg cubic, hexagonal, etc.)
Can be used without any particular limitation, but the strain energy is increased (or the wear energy is improved due to the increased energy).
From the point of, among the above “two or more compound layers”,
At least one compound layer has a different crystal structure from other layers (compound layer and / or composition modulation layer) at room temperature, atmospheric pressure and equilibrium state, and a single X-ray diffraction is obtained for the entire laminate. It is preferable to have a pattern (X-ray diffraction pattern corresponding to a single crystal system). From the viewpoint of oxidation resistance or chemical stability, each layer constituting the laminate has either a cubic crystal structure or a hexagonal crystal structure, and a cubic X-ray diffraction pattern for the entire lamination. It is preferable to have.

The crystal structure or X-ray diffraction pattern of each of the layers or the whole laminate is, for example, X-ray under the following conditions.
It can be confirmed by the line diffraction method.

<Conditions for X-ray Diffraction> X-ray diffraction apparatus: manufactured by Rigaku Denki Co., Ltd., product name: RINT-15
00, Observation of X-ray diffraction peak: Observation of diffraction line by thin film X-ray diffraction method (incident angle θ = 1 °) using a diffractometer using a copper target and nickel filter X-ray source: Cu-Kα Line (1.54 angstrom) FIGS. 1 to 8 show typical X of a thin film or a multilayer film formed on a WC-Co sintered body (including TiC as a sintering aid) substrate.
A line diffraction pattern is shown.

FIG. 1 schematically shows a thin film X-ray diffraction pattern. In the figure, ◆ indicates a TiN / AlN multilayer film,
● indicates TiN and ▲ Wurtzite type (hexagonal) AlN.

In FIG. 1, pattern (A): λ = 2.
5 nm has a single cubic pattern (rather than a hexagonal pattern). Furthermore, the position of the peak (horizontal axis =
The diffraction angle) is located between TiN and cubic AlN. These two points (the pattern is unified and the diffraction peak is located in the middle of the “two kinds of compound layers”) are the characteristics of the diffraction pattern of the modulation film in the above embodiment.

On the other hand, pattern (B): λ = 30
nm has a pattern in which the TiN pattern and the hexagonal AlN pattern are combined (overlapped) (hexagonal A
1N pattern is very weak).

The circles in FIG. 2 are typical cubic crystals (TiN).
A diffraction pattern is shown. In FIG. 2, + indicates WC (substrate), ×
Mark is TiC (substrate) ,? The mark is the membrane peak? -Sub mark indicates substrate peak.

The triangle mark in FIG. 3 indicates a typical cubic crystal (TiN).
A diffraction pattern is shown. In FIG. 3, ▲ indicates Al. Other symbols are the same as those in FIG.

FIG. 4 shows a typical diffraction pattern (single pattern) of the TiN / AlN modulation film.

FIG. 5 shows a typical diffraction pattern of ZrN (cubic crystal), and FIG. 6 shows a diffraction pattern of TiN. The symbol T represents TiN and the symbol Z represents ZrN.

FIG. 7 shows a typical pattern (single pattern) of the TiN / ZrN modulation film. In FIG. 7, in the cubic crystal diffraction pattern, the peak position is between TiN and ZrN.

On the other hand, FIG. 8 shows a typical pattern (not a single pattern) of the TiN / ZrN modulation film. In FIG. 8, the diffraction pattern is a combination of two cubic crystal patterns (TiN pattern and ZrN pattern) whose peak positions are slightly shifted.

As described above, when the entire stack has a single diffraction pattern, the patterns typically shown in FIGS. 4 and 7 are obtained.

However, in the laminated body of the present invention, the portion (modulation film) which is strain-matched (for example, due to the variation of the laminating period (layer thickness)) and the portion which is not strain-matched are mixed. In some cases, the unified X-ray pattern and the X-ray pattern of each layer are mixed.

In the present invention, from the point of view that the AlN high pressure layer (cubic crystal) can be used and / or the hardness, oxidation resistance and / or chemical stability of the laminated body as a whole, A layer having a hexagonal crystal structure ”is (Ti _x , A
It is preferable to have a composition of 1 _1−x ) N, (0 ≦ x <0.3).

On the other hand, in terms of oxidation resistance and hardness (wear resistance), the above-mentioned "layer having a cubic crystal structure" is (T
It is preferable to have a composition of i _x , Al _{1 -x} ) N, (0.3 ≦ x ≦ 1).

The above (Ti _x , Al _1-x ) N, (0≤x <
A “hexagonal structure layer” having a composition of 0.3), and (Ti
_x , Al _1-x ) N, and a “cubic crystal structure layer” having a composition of (0.3 ≦ x ≦ 1) are combined to form microscopic adhesion between layers having the same composition. It is preferable from the viewpoint of improving the property.

In the present invention, it is particularly preferable that the above-mentioned two kinds of compound layers each comprise a TiN layer and an AlN layer, and the composition modulation layer comprises a TiAlN layer.
In such a case, the TiN layer and the AlN layer, which are compound layers, have both polarities in their crystal structures, and the strain energy that can be stored becomes the largest, so that the hardness of the composition modulation layer also becomes high, which is preferable.

In the present invention, from the viewpoint of the balance between the adhesion to the substrate and the wear resistance, the total film thickness of the above laminate is
The thickness is preferably about 5 nm to 15 μm, more preferably about 0.5 μm to 10 μm. If the total film thickness is less than 5 nm, the abrasion resistance tends to be insufficiently improved. On the other hand, if the total film thickness exceeds 15 μm, the adhesion strength between the laminate and the base material may tend to decrease due to the influence of residual stress in the film forming the laminate.

(Substrate) The laminate of the present invention described above is extremely useful as a coating layer arranged on various substrates (or base materials). When used in such a mode, the base material is used for the above-mentioned laminate (for example, surface coating material for hard members such as cutting tools and wear resistant tools, or surface coating for electric / electronic parts, sliding / mechanical parts). It can be appropriately selected depending on the material) and is not particularly limited. When used as a surface coating material for a hard member such as the above-mentioned tool, as the base material, for example, a hard base material such as cemented carbide (for example, WC-based cemented carbide), cermet, or high speed steel is preferably used. .

(Intermediate Layer) When the laminate of the present invention is formed on the above-mentioned base material, from the viewpoint of further improving the adhesion strength between the base material and the laminate, It is preferable to provide an intermediate layer for improving the adhesion strength of the laminate.
For example, when the base material and the laminate (the layer closest to the base material) are made of substances having largely different properties, an intermediate layer having intermediate properties should be arranged between the base material and the laminate. Thereby, the change of the characteristics can be controlled stepwise, and the residual stress of the film can be reduced.

From the viewpoint of effectively improving the adhesion strength between the base material and the laminate, the above intermediate layer has periodic tables IVa, Va,
And one or more elements selected from Group VIa elements (third
Element) and one or more compounds selected from the group consisting of C, N, and O and one or more elements (fourth element).

In the present invention, the combination of the above-mentioned third element and fourth element is not particularly limited, but for example, the following combinations can be preferably used.

[0057] <Third element><Fourthelement>_{<compound> Ti C TiC B C B 4} C W C W 2 C Ti C, N Ti (C x N 1-x) Ti N TiN Ti B TiB 2 Ti B, N Ti (B _x N _1-x ) B N BN Si N Si ₃ N ₄ Al N AlN Al O Al ₂ O ₃ Ti-Al N (Ti-Al) N Ti-Zr N (Ti-Zr) N Ti-CrN (Ti-Cr) NTi-HfN (Ti-Hf) N In the present invention, the composition of the intermediate layer is the composition of the layer (compound layer or composition modulation layer) of the laminate adjacent to the intermediate layer. It is preferable that it is the same as or similar to the above from the viewpoint of improving the adhesion strength between the base material and the laminate.

In the present invention, the thickness of the intermediate layer is 0.
The thickness is preferably 05 μm or more, and more preferably 0.05 to
The thickness is preferably about 5 μm (particularly about 0.05 to 1 μm). When the thickness of the intermediate layer is less than 0.05 μm, the improvement of the adhesion strength tends to be insufficient, while when the thickness of the intermediate layer exceeds 5 μm, the improvement of the adhesion strength tends to reach its limit and the productivity tends to decrease. is there.

The thickness of such an intermediate layer can be confirmed by, for example, the TEM measurement similar to the above-described "compound layer thickness" measurement.

(Surface Layer) On the uppermost layer (outermost surface) of the laminate of the present invention, a surface layer for the performance of the wear resistant member may be arranged, if necessary.

The outermost surface of the laminate of the present invention (for example, when used as a wear-resistant coating) is often exposed to a very harsh environment (wear at high temperatures, etc.), so that the outermost surface of the laminate or the wear partner material Reaction is likely to occur. When such abrasion occurs, the surface of the coating is likely to be deteriorated and the abrasion resistance may be impaired. Therefore, it is preferable that the uppermost layer of the laminate has a composition with low reactivity with the mating material. On the other hand, as the composition of each layer constituting the laminate, such a “low-reactivity composition” is not always preferable in view of productivity during lamination.

When a surface layer having a composition excellent in the reaction atmosphere of the laminated body and the mating material is disposed on the uppermost layer of the laminated body, the abrasion of the surface of the laminated body due to surface reaction or the like is caused by the surface layer. Since it can be suppressed, it is possible to increase the degree of freedom of the composition of each layer constituting the laminated body.

From the viewpoint of improving the wear resistance and the adhesion strength with the laminate (uppermost layer), the above surface layer has periodic tables IVa and V.
at least one compound selected from the group consisting of a and VIa elements (fifth element); and at least one element selected from C, N, and O (sixth element); It is preferable to have a composition containing

In the present invention, the combination of the above-mentioned fifth element and sixth element is not particularly limited, but for example, the following combinations can be preferably used.

[0065] <Fifth element><6element>_{<compound> Ti C TiC B C B 4} C W C W 2 C Ti C, N Ti (C x N 1-x) Ti N TiN Ti B TiB 2 Ti B, N Ti (B _x N _1-x ) B N BN Si N Si ₃ N ₄ Al N AlN Al O Al ₂ O ₃ Ti-Al N (Ti-Al) N Ti-Zr N (Ti-Zr) N Ti-CrN (Ti-Cr) NTi-HfN (Ti-Hf) N In the present invention, the composition of the surface layer is the composition of the layer (compound layer or composition modulation layer) of the laminate adjacent to the surface layer. It is preferable that it is the same as or similar to the above from the viewpoint of improving the adhesion strength between the base material and the laminate.

In the present invention, the surface layer has a thickness of 0.
The thickness is preferably 05 μm or more, and more preferably 0.05 to
The thickness is preferably about 5 μm (particularly about 0.05 to 1 μm). If the thickness of the surface layer is less than 0.05 μm, the abrasion resistance is not sufficiently improved. On the other hand, if the thickness exceeds 5 μm, peeling of the surface layer is likely to occur, and the abrasion resistance is not improved. Tends to be sufficient.

The thickness of such a surface layer can be confirmed, for example, by the TEM measurement similar to the above-mentioned measurement of "thickness of compound layer".

FIG. 3 is a schematic cross-sectional view showing an example of the constitution of the laminated body of the present invention in which both the above-mentioned intermediate layer and surface layer are provided. Referring to FIG. 3, an intermediate layer 2 is arranged on a base material 1 made of cemented carbide or the like; at least two kinds of compound layers having different compositions, and a composition modulation layer arranged between the compound layers. A periodic stacking layer 3 consisting of is arranged on the intermediate layer 2; and a surface layer 4 is further arranged on the periodic stacking layer 3.

A cutting tool (cutting tip) is used for the laminate of the present invention.
When used as a coating layer for the cutting tool, the "flank surface" and "rake surface" of the cutting tool are used according to the characteristics required for each surface of the insert.
As the laminated film, a laminated body in which the laminated thin films have different periods may be coated as necessary.

(Method for Forming Laminate) As a method for forming the laminate of the present invention (if necessary, an intermediate layer and / or a surface layer), a vapor deposition method such as a CVD method or a PVD method is particularly limited. It is possible to use without. When the PVD method (sputtering method, ion plating method, etc.) is used, it is easier to maintain the strength of the base material as compared with the CVD method, and in applications such as tools, high wear resistance, fracture resistance, etc. Easy to maintain at the level. In the present invention, from the viewpoint that it is easy to form a layer having a cubic and / or hexagonal crystal structure, a layer having a high ionization rate and high crystallinity is formed among the PVD methods. The ion plating method (particularly the arc type ion plating method) which is easy to use is particularly preferably used.

From the viewpoint of obtaining a higher ionization rate, at least one element selected from IVa, Va, VIa group elements, Al, Si, and B of the periodic table without using a nitride or carbonitride target. A plurality of metal or alloy targets containing the above elements (first elements); B, C,
Reactive PVD using as a raw material a gas containing at least one element (second element) selected from N and O
It is preferable to use the method.

When a gas is used as a raw material, for the purpose of improving the crystallinity of the compound to be formed, an inert gas such as Ar or He, a gas having an etching effect such as H ₂ other than the raw material gas. It is also possible to introduce the above into the film forming apparatus separately from the source gas or simultaneously with the source gas.

(Formation of Laminated Body Using Arc Type Ion Plating Method) One mode of forming the laminated body of the present invention using the ion plating method (arc type ion plating method) by vacuum arc discharge will be described. .

FIG. 4 is a schematic vertical sectional view showing an example of a film forming apparatus for forming the laminate of the present invention by arc type ion plating.

Referring to FIG. 4, in the vacuum chamber 11,
A substrate holder 12 for holding a substrate (not shown) is rotatably arranged, and a substrate power source 13 is provided in the substrate holder 12.
Are electrically connected. On the other hand, a plurality of targets 14 are arranged on the inner wall of the vacuum chamber 11 facing the substrate holder 12, and the targets 14 are
The arc power supply 15 is electrically connected.

Referring to FIG. 11 which is a schematic plan view of the film forming apparatus, a base material 16 on which the laminate of the present invention is to be deposited is arranged on the outer wall surface of the base material holder 12. ,
Depending on the rotation of the substrate holder 12, a predetermined target (1
4a or 14b).
In such a film forming apparatus, by adjusting the rotation speed of the base material holder 12 and the discharge current of the vacuum arc (that is, the evaporation amount of the target materials 14a and / or 14b), each layer constituting the laminated body is adjusted. It is possible to control the layer thickness of. The thickness of the composition modulation layer and the change in composition can be controlled by adjusting the degree of “overlap” of the plasmas 15a and 15b of the targets 14a and 14b. The degree of "overlapping" of the plasma can be changed by the arrangement of the targets 14a and 14b and / or the pressure during arc current film formation.

When the laminated body of the present invention is formed using such a film forming apparatus, for example, first, the vacuum chamber 1
1 is evacuated (pressure: about 10 ⁻⁵ Torr), and then Ar (argon) gas is introduced into the vacuum chamber 11 to maintain the pressure of about 10 ⁻² Torr on the substrate 16 at 200 After heating up to about 800 ° C. and applying a voltage of about −800 V to −1000 V to the base material 16 to clean the surface of the base material, Ar gas is exhausted. Then, one or a plurality of kinds of gases such as N ₂ gas, CH ₄ gas, etc. are controlled in the vacuum chamber 11 in accordance with the rotation of the base material 16 to perform time control, and 25 to 400 cc / m 2
The target 14a, 14b is evaporated or ionized by vacuum arc discharge while being introduced at a rate of about in.
As a result, when the base material 16 that moves based on the rotation of the base material holder 12 passes in front of the targets 14a and 14b, the target material and the layer of the compound such as C and / or N in the introduced gas are the base materials. It is formed on the material 16.

Referring to FIG. 11, in the formation of the laminated film, at the position where the position of the base material 16 faces the target 14a, the target 14a (for example, Ti) and the elements (C, N) in the introduced gas are formed. Etc.) and a compound (for example, Ti
Layer N) is formed on the substrate 16. Then, the base material 16
Is located between the target 14a and the target 14b, the element of the target 14a (for example, Ti), the element of the target 14b (for example, Al), and the element (C, N in the introduced gas). And the like) (for example, (Ti _x , Al _1-x ) N) is formed on the base material 16. When forming such a TiAlN layer, the plasma 15a derived from the target 14a
When, with the plasma 15b from the target 14b degree of "overlap" (i.e., the target 14a, the relative positional relationship of the substrate 16 for 14b) in response to the above _{(Ti x, Al 1-x} ) N The composition is determined. From the position where the base material 16 faces the target 14a, the composition is
Since it continuously changes to a position facing the target 14b, according to such a method, continuous (Ti _x , A
A composition modulation film having a composition of 1 _1−x ) N can be formed.

Further, the position of the base material 16 is the target 14b.
The target 14a (for example, A
A layer of a compound (for example, AlN) consisting of 1) and the elements (C, N, etc.) in the introduced gas is formed on the base material 16. Therefore, by such a method, the compound layer (TiN)
→ composition modulation layer (Ti _x , Al _1-x ) N → compound layer (Al
N) → the composition modulation layer (Ti _x, it is possible to form a periodic layered structure, such as Al _1-x) N → compound layer (TiN) → ···.

The thickness and / or composition of each layer (compound layer, composition modulation layer) can be controlled by the degree of "overlapping" of the plasma from each target. The degree of "overlapping" of the plasma can be controlled by the arrangement of the targets, the arc current, and the pressure during film formation.

(Layer Cycle of Rake Face / Flanking Surface) According to the inventor's knowledge, the laminating period of the film laminate to be arranged on the rake face (the face where crater wear is likely to occur) in the cutting tool tip or the like is determined. It has been confirmed that the cutting performance and the life of the cutting tip are remarkably improved when the cycle is longer than the cycle of the laminated body to be arranged on the flank (the surface where flank wear is likely to occur).

On the other hand, in the case of different tip shapes and cutting applications, conversely to the above, when the stacking period (j) on the flank is made larger than the stacking period (k) on the rake face, cutting of the cutting tip It has been confirmed that performance and life may be significantly improved.

According to the knowledge of the present inventor, this is because the characteristics such as wear resistance and oxidation resistance required for the "flank surface" and the "rake surface" are different depending on each application. It is presumed that this is due to the difference in the preferable cycle of the laminated body.

(Characteristics and Uses of Laminate) The Vickers hardness of the laminate (front side) of the present invention is 3 under a load of 25 gf.
× 10 ³ kgf / mm ² or more, further 3.2 × 10 ³ k
gf / mm ² or more (especially 3.4 × 10 ³ kgf / mm ²
Or more) is preferable. Such Vickers hardness is measured by a known method (for example, Japanese Industrial Standard (JIS)).
It can be measured by a method using a micro hardness meter described in B-7734-1991. 3 x at a load of 25 gf
Vickers hardness of 10 ³ kgf / mm ² is almost 1
This corresponds to a Vickers hardness of 4 × 10 ³ kgf / mm ² in gf.

The laminate of the present invention is useful as a surface coating material for hard members such as cutting tools (chips, drills, end mills, etc.) and wear resistant tools. The laminate of the present invention is also useful as a surface coating material for electric / electronic parts, sliding / mechanical parts and the like.

When the laminate of the present invention is used as a wear-resistant film or protective film for electric, electronic, sliding and mechanical parts, the total film thickness of electric and electronic parts is 5 nm to 10 μm.
The thickness is preferably about 5 nm to 0.5 μm, and about 0.1 μm to 10 μm (further about 0.5 to 5 μm) for mechanical parts.

Hereinafter, the present invention will be described more specifically with reference to Examples.

[0088]

EXAMPLES In the examples, the layer thickness and the lamination period of each compound of the ultrathin film laminate were determined by observation with a transmission electron microscope (TEM). The composition change of each layer was confirmed by the microscopic area EDX provided with TEM. The crystal structure of the entire ultrathin film laminate was determined by an X-diffraction pattern, and the crystal structure of a minute portion was confirmed by a TED (selected area electron diffraction) pattern of a transmission electron microscope. The X-ray diffraction peak was observed by a thin film X-ray diffraction method using a diffractometer using a copper target and a nickel filter to measure the diffraction line of Cu-Kα rays. The film hardness was measured by the above-mentioned known Vickers hardness measuring method (load 25 gf).

Example 1 As a base material, the composition was JIS standard P30 (JIS B-
4053-1989), the shape is JIS standard SNGN12.
Cemented carbide cutting tip of 0408 (JIS B-4121-1985) (size: about 1.3 cm x 1.3 cm x
0.4 cm) was used.

The base material 16 is mounted on the substrate holder 12 of the film forming apparatus whose schematic plan view is shown in FIG. 12, and the surface of the base material 16 is subjected to an ion plating method by vacuum arc discharge in accordance with the present invention. A laminate was formed.

Referring to FIG. 12, the vacuum chamber 11 is evacuated (pressure: 10 ⁻⁵ Torr), and then Ar
(Argon) gas is introduced into the vacuum chamber 11,
While maintaining the pressure of 10 ^-2 Torr,
After heating to 0 ° C. and applying a voltage of −1000 V to the base material 16 to clean the surface of the base material, Ar gas was exhausted. Next, in the vacuum chamber 11, N ₂ gas and C
H ₄ gas or (N ₂ + CH ₄ ) gas is used as the base material 16
200cc / mi by controlling the time corresponding to the rotation of
While introducing at a rate of n, the targets 14a (Ti) and 14b (Al) were vaporized and ionized by vacuum arc discharge. When (N ₂ + CH ₄ ) gas was used, the flow rate ratio of these gases was changed according to the desired N / C ratio.

The thickness and / or composition of each layer (compound layer, composition modulation layer) constituting the above-mentioned laminate could be controlled by the degree of "overlapping" of the plasma derived from each target. Further, the degree of "overlapping" of the plasma could be controlled by the arrangement of the targets, the arc current, and the pressure during film formation.

By the film formation by the above-mentioned arc type ion plating method, the compound layer (TiN) → the composition modulation layer (T
_{i x, Al 1-x)} N → compound layer (AlN) → composition modulation layer _{(Ti x, Al 1-x} ) N → compound layer (TiN) → ···
To form a periodic laminated structure.

When the intermediate layer is formed prior to the formation of the above laminated body on the base material 16, two targets 14a (Ti) and a target 14b (Al) 2 used in the above laminated body formation. Instead of the individual target 14a (T
i) An intermediate layer having a predetermined thickness was formed in the same manner as in the formation of the laminated body, except that only two pieces were used and N ₂ was used as the reaction gas.

Further, when the surface layer is formed after the above-mentioned laminated body, the target 14 used in the above-mentioned laminated body is formed.
Instead of two a (Ti) and two targets 14b (Al), only two targets 14a (Ti) are used,
Further, a surface layer having a predetermined thickness was formed in the same manner as in the formation of the laminated body, except that (N ₂ + CH ₄ ) gas was used as the reaction gas.

The structure of the laminate including the periodic laminate structure (wear resistant layer) of the laminate of the present invention (Sample Nos. 1 to 10) formed as described above is shown in Table 1 below. ) Are shown in Table 2, respectively.

[0097]

[Table 1]

[0098]

[Table 2]

The other samples shown in Tables 1 to 3 are the same as the samples (Nos. 1 to 1) except that the following conditions were changed.
It was prepared in the same manner as the preparation of (0).

Samples 11 to 16: composition of target 14a is (Ti / Zr = 5/5) Samples 17 to 22: composition of target 14b is Zr Samples 23 to 29: composition of target 14b is Cr, and gas is ( CH ₄ / N ₂ = 3/7) Samples 30 to 36: The composition of the target 14a is (Ti / A
1 = 3/7), and the composition of the target 14b is (Ti /
Al = 1/9) Sample 37: The composition of the target 14a is (Hf / Al = 7
/ 3), and the composition of the target 14b is (Ti / Hf =
5/5) Sample 38: composition of target 14a is Nb, composition of target 14b is Cr Sample 39: composition of target 14a is (Nb / Al = 7
/ 3), and the composition of the target 14b is (V / Al = 7
/ 3) Sample 40: The composition of the target 14a is (Ti / Zr = 6
/ 4), and the composition of the target 14b is (Ti / Cr =
5/5) Sample 41: composition of target 14a is Ti, composition of target 14b is Ti, and C ₂ H ₂ / N ₂ is adjusted to 6/4 → 3/7 according to rotation Sample 42: composition of target 14a Is ZrC, and the composition of the target 14b is Zr (C _0.1 , N _0.9 ). Sample 43: The composition of the target 14a is (Ti / Al = 3).
/ 7) Sample 44: composition of target 14a is Hf Sample 45: composition of target 14a is Ti, composition of target 14b is Al, and N ₂ / O ₂ = 9/1 Comparative Example 1 A schematic plan view is shown in FIG. Using the film-forming apparatus, the targets 14c and 4d were Ti, and the gas was CH ₄ / N ₂ = 2.
Sample No. 1 was used in the same manner as in Example 1 except that No. 46 was produced.

Comparative Example 2 Sample No. 1 was formed by a known ion plating method. 47 was produced.

Comparative Example 3 Sample No. 1 was formed by a known CVD method. 48 was produced.

Example 2 With respect to the surface-coated cutting tip samples (Sample Nos. 1 to 48; Table 1) produced in the above-mentioned Example 1 and Comparative Examples 1 to 3,
Under the conditions shown in Table 4 below, a continuous cutting test and an intermittent cutting test were performed to measure the flank wear width (mm) of the cutting edge. The performance evaluation of the obtained laminate is shown in Table 3.

[0104]

[Table 3]

[0105]

[Table 4]

From the results shown in Table 3 above, it was found that the cutting tip sample provided with the laminate of the present invention as the surface coating layer had excellent wear resistance in both continuous cutting and intermittent cutting. That is, it was found that when the laminate of the present invention is used as a surface coating material for a hard member of a cutting tool, the cutting performance and life of the cutting tool are significantly improved.

Separately, the sample No. of Table 1 was changed except that the kind of the base material was changed as shown in Table 5 below. 4, no. 25, no.
33, No. 46, No. 47 and No. 47. A sample was prepared in the same manner as the preparation of 48.

[0108]

[Table 5]

The contents of items * 1 to * 4 in Table 5 are as follows.

* 1: TiC-Al ₂ O ₃ Sintered Body Using a cemented carbide pot and balls, aluminum oxide powder, titanium carbide powder, and yttrium oxide powder were mixed together.
The mixture was mixed at a volume ratio of 0: 29.5: 0.5 and sintered at 1800 ° C. for 30 minutes.

* 2: Si ₃ N ₄ Sintered Body Using a cemented carbide pot and a ball, silicon nitride powder, aluminum oxide powder, and yttrium oxide powder were mixed together.
The mixture was mixed at a volume ratio of 5: 3: 2, and sintered by HIP method in N ₂ atmosphere at 1800 ° C. and 300 kg / cm ² for 30 minutes.

* 3: cBN sintered body Using a cemented carbide pot and ball, TiN powder and aluminum powder were mixed at a weight ratio of 80:20 to obtain a binder powder. Next, the binder powder and the cBN powder were mixed so as to have a volume ratio of 45 vol% and 55 vol%, and then filled in a Mo container and 1400 at a pressure of 48 kb.
Sintered for 20 minutes at ° C.

* 4: Diamond sintered body 85 diamond powder, TiN powder and Co powder
After mixing so as to have a volume ratio of vol%, 5 vol% and 10 vol%, the mixture was filled in a Mo container and sintered at 1400 ° C. for 20 minutes at a pressure of 48 kb.

For each of the samples thus produced,
Under the cutting conditions shown in Table 5 above, the flank wear width of the cutting edge (m
m) was measured. The performance evaluation of the obtained laminate is shown in Table 6 below.
And shown in Table 7.

[0115]

[Table 6]

[0116]

[Table 7]

Example 3 (Measurement of Composition Change Profile) Referring to FIG. 12, the sample No. of Table 1 was changed except that the substrate holder 12 was not rotated. Film formation was performed on the base material 16 for 10 minutes under the same conditions as in 6 (gas pressure, arc current, bias voltage). At this time, the base material 16 is (1
No.) from the front of the next Al target (No. 17) to the front of the next Ti target 14a (No. 33)
Up to 33 pieces were arranged at equal intervals.

The film thickness of the film thus formed on the substrate 16 at each position in the circumferential direction of the substrate holder 12 is SEM.
(Scanning electron microscope) and the composition of the film (Ti
/ Al ratio) was measured by the EDX attached to the SEM (the composition of the substrate at each position and the film thickness obtained here are the composition of the film formed in the vacuum chamber 11 and the film formation rate). Presumed to correspond to). The composition ratio data thus measured is shown in the graph of FIG. 14, and the film thickness data is shown in the graph of FIG.

The following conditions were used in the above EDX analysis.

<EDX analysis conditions> SEM measuring device: manufactured by JEOL Ltd., trade name: JSM6300-M incidental EDX device manufactured by LINK (currently Oxford), trade name: eXL Detector: Si (Li) semiconductor detector Measurement conditions Acceleration voltage: 15 eV Irradiation current: 0.3 nA Open type (detector protection window opened) The composition data of the film on each substrate obtained above was added up sequentially on the vertical axis (relative value 16) is plotted on the horizontal axis, the graph (composition change profile) of FIG. 16 is obtained (two targets are arranged in the vacuum chamber of FIG. A composition change profile is obtained). One cycle of the stacking cycle of the stacked film corresponds to 0.5 cycle of the composition change profile of FIG. 16 (when a stacked film having a stacking cycle of 20 nm is formed, the entire horizontal axis of FIG. 16 corresponds to 10 nm). .

Based on the data shown in FIG. 16, a composition change profile of the entire laminated film was obtained as shown in the graph of FIG. It can be understood from the composition change profile of FIG. 17 that the laminate having the composition modulation film of the present invention does not have an interface (a surface having a discontinuous composition).

FIG. 18 shows an example of EDX data obtained by measuring the entire laminated film (the upper graph shows Al distribution, the middle graph shows Ti distribution, and the lower graph shows N distribution). The data in FIG. 18 is obtained by analyzing a laminated body having a thickness of about 30 nm using an EDX with TEM (TEM).
/ EDX has a resolution of about 1 nm, which is about the same as the film thickness of each layer (compound layer, composition modulation layer) forming the laminated body, and therefore the resolution of the data in FIG. 18 has a certain limitation.

Measuring equipment: VG, HB501 EDX: KEVEX Super8000 quantitative total system Energy dispersive X-ray analyzer (Si <Li> semiconductor detector, UTW type) EELS: VG, ELS-80 spectrometer (energy) Resolution: 0.56 eV) Example 4 (TEM observation of laminated film) Sample No. TEM 4
An image observed with (Hitachi, trade name: H-900UHR) is shown in FIG. 18 (magnification 8 million times, 4 cm on the image is
Corresponding to 5 nm).

In FIG. 18, the part where the contrast is bright is A
The 1N layer and the dark portion are the TiN layer, and a “composition-modulated structure” in which the boundary between bright and dark is not clear is observed (composition modulation period 4.8 nm). Each "grain" on the TEM image corresponds to approximately one atom. It can be seen that the TiN layer, the composition modulation layer, and the AlN layer are regularly arranged in several layers and lattice-matched.

Example 5 (Crystal Structure Analysis by TED) Sample No. 1 in Table 1 4 to T
The diffraction pattern analyzed by ED (Hitachi, trade name: H-900UHR) is shown in FIG. 18 ("A" is a pattern on the surface side,
“B” is shown in the pattern on the front side. From this diffraction pattern, it was confirmed that the laminated film as a whole had a NaCl type (cubic crystal) crystal structure.

In this diffraction pattern, satellite patterns are recognized around the central point and the left and right spots, which corresponds to the periodic laminated structure.

[0127]

As described above, according to the present invention, at least one element (first element) selected from the group IVa, Va, and VIa elements of the periodic table, Al, Si, and B; C,
At least two kinds of compound layers containing, as a main component, one or more kinds of elements (second elements) selected from N and O, and having different compositions from each other; A composition modulation layer in which the composition (at%) of one element changes; the compound layer and the composition modulation layer are periodically laminated; and a crystal lattice having one or more continuous cycles between the layers A laminated body is provided.

When the laminate of the present invention is used as a coating layer,
It becomes possible to remarkably improve the wear resistance, heat resistance, or corrosion resistance of cutting tools, abrasion resistant tools, electric and electronic parts, sliding parts, and mechanical parts.

When the laminate of the present invention is used as a surface coating material for hard members such as cutting tools (chips, drills, end mills, etc.) and wear resistant tools, the cutting performance and life of these cutting tools are remarkably improved. It is possible to improve.

Furthermore, even when the laminate of the present invention is used as a wear-resistant film or a protective film for electric / electronic parts, sliding and mechanical parts, it is excellent as in the case of being applied to the above cutting tools and the like. Wear resistance is obtained.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a typical example of a thin film X-ray diffraction pattern.

FIG. 2 shows a typical cubic (TiN) diffraction pattern.

FIG. 3 shows a typical cubic (TiN) diffraction pattern.

FIG. 4 is a diagram showing a typical diffraction pattern (single pattern) of a TiN / AlN modulation film.

FIG. 5 is a diagram showing a typical diffraction pattern of ZrN (cubic crystal).

FIG. 6 is a diagram showing a diffraction pattern of TiN.

FIG. 7 is a diagram showing a typical pattern (single pattern) of a TiN / ZrN modulation film.

FIG. 8 is a diagram showing a typical pattern (not a single pattern) of a TiN / ZrN modulation film.

FIG. 9 is a schematic cross-sectional view showing one aspect of the structure of the laminate of the present invention.

FIG. 10 is a schematic cross-sectional view showing one embodiment of a film forming apparatus that can be used for forming the laminate of the present invention.

FIG. 11 is a film forming apparatus that can be used to form the laminate of the present invention (with “overlapping” of plasmas from different targets).
It is a schematic plan view showing one embodiment.

FIG. 12 is a schematic plan view showing a film forming apparatus used for forming a laminate in Examples.

FIG. 13 is a schematic plan view showing a film forming apparatus (without “overlapping” of plasmas derived from different targets) used for forming a laminate (without composition modulation layer) of a comparative example.

FIG. 14 is a composition distribution (substrate position-Ti / Al) of each substrate obtained by composition profile analysis in an example.
It is a graph which shows an example of a composition ratio.

FIG. 15 is a graph showing an example of film thickness distribution (substrate position-film thickness) obtained by composition profile analysis in Examples.

FIG. 16 is a graph showing an example of a composition profile (distance in film thickness direction−Ti / Al composition ratio) for one stacking period, which is obtained based on the analysis results of the composition distribution and the film thickness distribution.

FIG. 17 is a graph showing an example of a composition profile (distance in the film thickness direction−Ti / Al composition ratio) of several stacking periods obtained based on the analysis result of the composition distribution and the film thickness distribution.

FIG. 18 is a graph showing distributions of Al, Ti, and N in the film thickness direction obtained by TEM / EDX analysis in the example.

FIG. 19 is a photograph (replica) showing a TEM image obtained by high-power TEM measurement in an example.

FIG. 20 is a photograph (replica) showing a diffraction pattern obtained by TED measurement in an example.

[Explanation of symbols]

1 ... Base material, 2 ... Intermediate layer, 3 ... Laminated structure, 4 ... Surface layer, 1
DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber, 12 ... Substrate holder, 14a, 14
b ... Target, 15a, 15b ... Plasma, 16 ... Base material.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akihiko Shibata 1-1-1 Kunyo Kita, Itami City, Hyogo Prefecture Sumitomo Electric Industries, Ltd. Itami Works

Claims (14)

[Claims] 1. A periodic table IVa, Va, VIa group element, A
1 or more elements selected from l, Si, and B (first element); and 1 or more elements selected from B, C, N, and O (second element) as main components, At least two compound layers having different compositions from each other and a composition of elements (at
%) Of the composition modulation layer, wherein the compound layer and the composition modulation layer are periodically laminated,
A laminated body having a crystal lattice in which one or more cycles are continuous between the layers. 2. The compound layer (1 layer) has a thickness of 1 to 20.
The laminate according to claim 1, which is in the range of nm. 3. The laminate according to claim 1, wherein the composition (at%) of the elements changes substantially continuously in the thickness direction of the composition modulation layer. 4. The laminate according to claim 1, wherein the thickness of the composition modulation layer is 1/10 to 10 of the thickness of the compound layer. 5. At least one compound layer of the two or more compound layers has a crystal structure different from other layers at room temperature, atmospheric pressure and equilibrium state, and a single X layer is formed as a whole stack. The laminate according to claim 1, which has a line diffraction pattern. 6. The laminate according to claim 5, wherein each layer constituting the laminate has a cubic or hexagonal crystal structure, and the entire laminate has a cubic X-ray diffraction pattern. 7. The layer having a hexagonal crystal structure is (Ti _x ,
The laminated body according to claim 6, comprising Al _1-x ) N and (0 ≦ x <0.3). 8. The layer having a cubic structure is (Ti _x , A
The laminate according to claim 7, which comprises l _1-x ) N, (0.3 ≦ x ≦ 1). 9. The two compound layers are made of TiN, respectively.
Layer and an AlN layer, and the composition modulation layer is TiA
The laminated body according to claim 1, comprising an IN layer. 10. The laminate according to claim 1, which has a total film thickness of 5 nm to 15 μm. 11. One or more elements selected from Group IVa, Va, and VIa elements of the periodic table; C, N, and O
The laminate according to claim 1, wherein an intermediate layer containing one or more kinds of compounds consisting of one or more kinds of elements selected from the above is arranged on the surface of the base material side. 12. The thickness of the intermediate layer is 0.05 to 5 μm.
The laminate according to claim 11, which is 13. One or more elements selected from Group IVa, Va, and VIa elements of the periodic table; C, N, and O
The laminated body according to claim 1, wherein a surface layer containing one or more kinds of compounds consisting of one or more kinds of elements selected from the above is arranged on the surface opposite to the base material side. 14. The thickness of the intermediate layer is 0.05 to 5 μm.
The laminate according to claim 13, which is