JP2001050935A - Magnetic sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a magnetic sensor for detecting the amount of rotation that has improved hard magnetic properties and temperature properties and can be operated at high temperatures, and further has improved detection accuracy. SOLUTION: A magnetic sensor 1 is adopted, where the sensor 1 is provided with first and second magnets 9 and 13 and first and second magnetic detection elements 10 and 12 for detecting the magnetic field of the magnets 9 and 13, the magnets 9 and 13 use Co as the main constituent, one type or at least two types of elements Q and Sm among P, C, Si, and B are included, and a hard magnetic property alloy powder with an amorphous phase and a fine crystalline phase with an average crystal particle diameter of 100 nm or less is mixed with resin for hardening formation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic sensor, and more particularly to a magnetic sensor provided with a magnet having a small variation in surface magnetic flux density.

[0002]

2. Description of the Related Art In general, ferrite magnets and alnico magnets (Al-Ni-
(Co-Fe-based magnet). More recently, Sm-Co
2. Description of the Related Art Magnetic sensors including a system magnet, an Nd-Fe-B system magnet, and the like are known.

[0003]

However, Nd-Fe-
The B-based magnet is a magnet having a large coercive force (iHc), a remanent magnetization (Ir), and a maximum magnetic energy product ((BH) _max ) and excellent in hard magnetic properties. In addition, there is a problem that it cannot be applied to a magnetic sensor such as used under high temperature.

[0004] Further, the Sm-Co-based magnet has a magnetic property depending on temperature.
Sm and Co are very expensive, although the change in gas characteristics is small
Therefore, the raw material cost is high and
Maximum magnetic energy product ((BH)_max)But
Lower, not always optimal for application to magnetic sensors
There was a problem that. Further, an anisotropic Sm-Co magnet
, The maximum magnetic energy product ((BH) _max) Is high
However, on the other hand, the variation of the surface magnetic flux density increases,
For detecting the amount of rotation that requires extremely high precision
When used for the detection part of a pneumatic sensor, the angle of the rotating body
The output becomes unstable with respect to changes, and the magnetic sensor detects
There is a problem that accuracy is reduced.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has excellent hard magnetic characteristics and temperature characteristics, can be operated at a high temperature, and has a high detection accuracy. It is an object to provide a magnetic sensor.

[0006]

In order to achieve the above object, the present invention employs the following constitution. The magnetic sensor according to the present invention includes a magnet and a magnetic detection element that detects a magnetic field of the magnet, wherein the magnet has Co as a main component,
One or more elements Q of P, C, Si and B
And a hard magnetic alloy powder containing an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less, and a resin, and solidified and molded. I do. Preferably, the magnet is provided with magnetic isotropy.

The magnetic sensor according to the present invention is the magnetic sensor described above, wherein: a first rotating body having a worm gear; and a second rotating body having a worm meshing with the worm gear. A first detecting a rotation amount of the second rotating body;
A rotation amount detection unit, wherein the first rotation amount detection unit is disposed at a distance from an annular first magnet fitted to the second rotator on an outer peripheral side of the first magnet. And a first magnetism detecting element for detecting a magnetic field change of the first magnet, wherein the first magnet has Co as a main component, P,
One or more elements Q and S of C, Si and B
m, a hard magnetic alloy powder having an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less, and a resin, mixed and solidified and formed. . Further, the first magnet may be provided with magnetic isotropy.

The magnetic sensor according to the present invention is the above-described magnetic sensor, further comprising a second rotation amount detecting unit for detecting a rotation amount of the second rotating body. A rotation amount detection unit, comprising: a detection body including a second magnet capable of moving forward and backward in a rotation axis direction of the second rotation body when the second rotation body rotates.
A second magnetic detection element that is disposed apart from the second magnet and detects a change in the magnetic field of the second magnet;
The second magnet has Co as a main component and P, C, Si,
A hard magnetic alloy powder containing one or more elements Q and Sm of B and having an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less is mixed with a resin. Characterized by being solidified and formed. Further, the second magnet may be provided with magnetic isotropy.

Further, the magnetic sensor according to the present invention is the above-described magnetic sensor, wherein one or both of the first and second magnets contain Co as a main component and P, C ,
One or more elements Q of Si and B, and Sm
And one or more of Nb, Zr, Ta, Hf, Mo, W, Ti, and V, and an element M, and an amorphous phase and fine crystals having an average crystal grain size of 100 nm or less. A hard magnetic alloy powder having a high quality phase and a resin are mixed and solidified and formed.

The magnetic sensor according to the present invention is the above-described magnetic sensor, wherein one or both of the first and second magnets contain Co as a main component and P, C ,
One or more elements Q of Si and B, and Sm
And Nb, Zr, Ta, Hf, Mo,
One or more of W, Ti, and V are defined as an element M, and Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
One or two or more of the above elements as element R;
When one or more of l, Ge, Ga, Ag, Pt, Au, and Cu are the element X, at least one or more of the element M, the element R, and the element X Element, further comprising an amorphous phase and an average crystal grain size of 100
A hard magnetic alloy powder having a fine crystalline phase of not more than nm and a resin are mixed and solidified and formed.

Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein the hard magnetic alloy powder comprises a single phase of a fine crystalline phase having an average particle diameter of 100 nm or less. And Further, in the magnetic sensor according to the present invention, the hard magnetic alloy powder includes at least 50% by volume or more of a fine crystalline phase having an average crystal grain size of 100 nm or less in a structure.
The remainder may consist of an amorphous phase. Further, in the magnetic sensor according to the present invention, the hard magnetic alloy powder contains at least 50% by volume or more of a fine crystalline phase having an average crystal grain size of 50 nm or less in the structure, and the remainder consists of an amorphous phase. There may be.

The magnetic sensor according to the present invention is the magnetic sensor described above, wherein a mixed phase of a soft magnetic phase and a hard magnetic phase is formed in the structure of the hard magnetic alloy powder. Features. The soft magnetic phase is bcc-F
e phase, bcc- (FeCo) phase, fcc- (CoFe)
Phase, at least one of a D ₂₀ E ₃ Q phase containing solid solution atoms and a residual amorphous phase, and the hard magnetic phase preferably contains at least an E ₂ D ₁₇ phase containing solid solution atoms. . Here, D is at least one element or two or more elements of Fe, Co, and Ni, and E is Sm, S
c, Y, La, Ce, Pr, Nd, Pm, Eu, Gd,
One of Tb, Dy, Ho, Er, Tm, Yb, Lu
A species or two or more elements, Q is P, C, Si,
B is one or more elements.

A magnetic sensor according to the present invention is the above-described magnetic sensor, wherein the hard magnetic alloy powder is represented by the following composition formula. _{(Co 1-f T f)} 100-xyzt M x Sm y R z Q t where, T is, Fe, wherein one or both one of Ni, M is, Nb, Zr, Ta, Hf , Mo ,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
One or more of C, Si and B, 0 ≦ f <0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5
Atomic% ≦ t ≦ 10 atomic%, 5 atomic% ≦ x + y + z ≦ 16
Atomic%. In the above composition formula, the composition ratio y
And the range of the composition ratio (x + y + z) are each 8 atomic%.
≦ y ≦ 16 at%, 8 at% ≦ x + y + z ≦ 16 at%
It is good.

A magnetic sensor according to the present invention is the above-described magnetic sensor, wherein the hard magnetic alloy powder is represented by the following composition formula. _{(Co 1-f T f)} 100-xyztu M x Sm y R z Q t X u where, T is, Fe, wherein one or both one of Ni, M is, Nb, Zr, Ta, Hf , Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
X is one or more of C, Si and B, and X is Al, Ge, Ga, Ag, Pt, Au, Cu
And at least one element of 0 ≦ f <
0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16
Atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5 atomic% ≦ t ≦
10 atomic%, 0 atomic% ≦ u ≦ 5 atomic%, 5 atomic% ≦ x +
y + z ≦ 16 atomic%. In the above composition formula, the ranges of the composition ratio y and the composition ratio (x + y + z) are respectively 8 atom% ≦ y ≦ 16 atom% and 8 atom% ≦ x + y + z
It may be ≦ 16 atomic%.

Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein f representing the composition ratio of the hard magnetic alloy powder is in the range of 0.2 ≦ f <0.5. It is characterized by the following. The magnetic sensor of the present invention is the magnetic sensor described above, wherein the hard magnetic alloy powder always contains Nb.

The magnetic sensor of the present invention is the magnetic sensor described above, wherein the hard magnetic alloy powder is manufactured by a liquid quenching method.
Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein the hard magnetic alloy powder has a temperature of 600 to 800 ° C.
Characterized in that it has been heat treated.

Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein a metal material or an oxide material is mixed and solidified and molded in place of the resin or in addition to the resin. You may. Further, a magnetic sensor according to the present invention is the magnetic sensor described above, wherein the first and second magnetic sensors are provided.
Is characterized in that the magnet contains 50% by volume or more of the hard magnetic alloy powder. Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein the first and second magnets contain the hard magnetic alloy powder in an amount of 60% by volume or more.

The magnetic sensor according to the present invention is the magnetic sensor described above, wherein the first and second magnets comprise the hard magnetic alloy powder, the resin, the metal material, and the oxide. It is characterized by being mixed with any one or more of the material materials and solidified by a compression molding method. Further, the magnetic sensor of the present invention is the magnetic sensor described above, wherein the first and second magnets are formed of the hard magnetic alloy powder, the resin, the metal material, and the oxide material. One or more of them are mixed and solidified by an injection molding method.

[0019]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a plan view of the internal structure of a magnetic sensor according to an embodiment of the present invention, and FIG. 2 shows a side view of the internal structure of the magnetic sensor.

The magnetic sensor 1 shown in FIGS. 1 and 2 includes a first rotating body 2, a second rotating body 3, and a first rotation amount detecting section 4.
And the second rotation amount detection unit 5. The first rotating body 2 is rotatably supported by a support member (not shown). Further, the second rotating body 3 is rotatably supported by a support body 6 arranged on the lower side in the figure. Second
The rotating body 3 is arranged so that the direction of the rotation axis thereof is substantially orthogonal to the direction of the rotation axis of the first rotating body 2. Also the first
A worm gear 7 is mounted on the outer peripheral surface 2a of the rotating body 2, and a worm 8 is mounted substantially at the center of the second rotating body 3, and the worm gear 7 and the worm 8 are engaged with each other. This worm gear 7 and worm 8
With the above operation, the second rotating body 3 is configured to rotate when the first rotating body 2 rotates.

The first rotation amount detecting section 4 is disposed on the outer peripheral side of the first magnet 9 with a ring-shaped first magnet 9 fitted on the outer peripheral surface 3 a of the second rotating body 3. A pair of first
And a magnetic sensing element 10. The first magnet 9 is magnetized to two poles. The first magnetic detecting elements 10 and 10 are mounted on a support 6 disposed on the lower side of the second rotating body 3 in the figure, and are disposed at a position facing the outer peripheral surface 9a of the first magnet 9. I have. The first magnetic detecting elements 10, 10 are, for example, Hall elements or the like, and convert a change in the magnetic field of the first magnet 9 into an electric signal. With the above configuration, when the first magnet 9 rotates together with the second rotating body 3,
The magnetic field component of the first magnet 9 acting on the first magnetic detection elements 10 and 10 changes, and the change in the magnetic field is detected by the first magnetic detection elements 10 and 10 and converted into an electric signal. The amount of rotation of the rotating body 3 is detected. First magnetic sensing element 10, 1
The electric signal output by 0 changes according to the rotation angle of the second rotating body 3, and its detection range is in the range of 0 ° to 360 ° when represented by the rotating angle of the second rotating body 3.

The second rotation amount detecting section 5 includes a detecting member 11 attached to the second rotating member 3 and a second magnetic detecting element 12 disposed at a lower side of the detecting member 11 in the drawing. It is composed of The detection body 11 includes a second magnet 13,
While holding the second magnet 13, the second magnet 13
And a connecting member 14 for connecting the second rotating body 3 to the second rotating body 3. A hole 15 is formed in the connecting member 14, and a female screw portion 16 is formed on the inner peripheral surface of the hole 15. A male screw part 17 is formed on a part of the second rotating body 3. Then, the second rotating body 3 is inserted into the hole 15 of the connecting member 14, and the male thread 17 of the second rotating body 3 is screwed into the female thread 16 of the connecting member 14. By the operation of the male screw part 17 and the female screw part 16, the rotational movement of the second rotating body 3 is converted into the linear movement of the detecting body 11. Therefore, the detection body 11 moves forward and backward in the rotation axis direction of the second rotating body 3 when the second rotating body 3 rotates. The movement range of the detector 11 corresponding to the rotation amount of the second rotating body 3 adjusts, for example, the pitch of each tooth of the worm gear 7 and the worm 8 and / or the pitch of each of the male screw portion 17 and the female screw portion 16. Can be determined. The second magnet 13 is attached to the lower side of the connecting member 14 in the drawing. This second
Is magnetized to two poles. The second magnetic detection element 12 is mounted on the support 6 at a position below the second magnet 13 in the drawing. Second magnetic sensing element 12
Is formed of, for example, a Hall element, and converts a change in the magnetic field of the second magnet 13 into an electric signal.

With the above configuration, the second magnet 13 and the detection body 11 are used together with the female screw portion 1 when the second rotating body 3 rotates.
6 and the male screw portion 17 move forward and backward in the direction of the rotation axis (the left-right direction in the figure). At this time, the change in the magnetic field component of the second magnet 13 in the lower direction in the drawing is detected by the second magnetic detection element 12 and converted into an electric signal, and the rotation amount of the second rotating body 3 is detected. The electric signal output from the second magnetic detection element 12 changes in accordance with the rotation angle of the second rotating body 3,
The detection range is determined by the movable range of the detection body 11 corresponding to the rotation amount of the second rotating body 3. For example, the movable range of the moving body is 720 ° of the rotation amount of the second rotating body 3.
When it corresponds to minutes, the detection range of the second magnetic detection element 12 is in the range of 0 ° to 720 °.

The detection range of the second magnetic detection element 12 is the first range.
It partially overlaps the detection range of the magnetic detection element 10. In the case of the magnetic sensor 1 described above, the detection range of the first magnetic detection element 10 is narrower than the detection range of the second magnetic detection element 12, but the detection resolution of the rotation amount of the second rotating body 3 is the first. The magnetic detecting element 10 is higher than the second magnetic detecting element 12. Therefore, in the magnetic sensor 1 described above, the first magnetic detection element 10 and the second magnetic detection element 12 have a mutually complementary relationship in detection range and detection resolution.

One or both of the first and second magnets 9 and 13 have Co as a main component and P, C, Si,
The hard magnetic alloy powder containing one or more elements Q of B and Sm and comprising an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less, and a resin It is mixed and solidified.

One or both of the first and second magnets 9 and 13 have Co as a main component and P, C,
One or more elements Q of Si and B, and Sm
And an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less containing one or more elements M of Nb, Zr, Ta, Hf, Mo, W, Ti, and V. May be formed by mixing a hard magnetic alloy powder made of

Further, one or both of the first and second magnets 9 and 13 have Co as a main component and P, C,
One or more elements Q of Si and B, and Sm
And Nb, Zr, Ta, Hf, Mo, W,
One or more elements of Ti and V, M, Sc,
Y, La, Ce, Pr, Nd, Pm, Eu, Gd, T
b, Dy, Ho, Er, Tm, Yb, Lu, at least one element R, Al, Ge, Ga, Ag, P
A hard phase comprising at least one element of at least one element X of at least one element of t, Au, and Cu and comprising an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less. The magnetic alloy powder and the resin may be mixed and solidified and formed.

The above resin binds a hard magnetic alloy powder having a hard magnetic property and retains the shape of the first and second magnets 9 and 13, and is made of a material that does not cause a large loss in the magnetic property. Preferably, for example, polyamide, polypropylene, polyethylene, polystyrene, paraffin, polytetrafluoroethylene, polycarbonate,
Examples include silicone resins, epoxy resins, phenolic resins, polyurethane resins, unsaturated polyesters, and the like. Particularly, polyamide (-6) (6-nylon), polyamide (-12) (12-nylon), polyethylene chloride,
Epoxy resins are promising.

When the hard magnetic alloy powder is solidified and molded using a low melting point metal material instead of the above resin, the strengths of the first and second magnets 9 and 13 are higher than in the case where the resin is used. It is possible to do. This metal material is preferably made of a material having a relatively low melting point, particularly a material having a melting point lower than that of the hard magnetic alloy powder. Zn, Al, In, Sn, Sb, P
b and the like. Further, in addition to the above resin, another metal material or oxide material may be mixed and solidified and molded.

The hard magnetic alloy powder constituting the first and second magnets 9 and 13 has at least 50% by volume of its structure.
The above include a fine crystalline phase having an average crystal grain size of 100 nm or less, preferably an average crystal grain size of 50 nm or less, and the remainder consisting of an amorphous phase. The organization is formed. The hard magnetic alloy powder may have a structure composed of a single phase of a fine crystalline phase of 100 nm or less.

The fine crystalline phase contains at least bcc
-Fe phase, bcc- (FeCo) phase, fcc- (CoF
e) a soft magnetic phase consisting of at least one of a phase or a D ₂₀ E ₃ Q phase containing solid solution atoms, and an E ₂ phase containing solid solution atoms.
And a hard magnetic phase consisting of D ₁₇ phase is precipitated. Also,
The remaining amorphous phase forms a soft magnetic phase similarly to the bcc-Fe phase and the like. D represents one or more of transition metals, specifically, one or more of Fe, Co, and Ni, and particularly one or both of Fe and Co. Preferably, there is. Also, E
Are Sm, Sc, Y, La, Ce, Pr, Nd, Pm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u represents one or more elements, and Q represents one or two of P, C, Si, and B as described above.
Indicates more than one element. In the hard magnetic alloy powder, a mixed phase of the soft magnetic phase and the hard magnetic phase is formed in the structure.

In this hard magnetic alloy powder, H, H
e, Li, Be, N, O, F, Ne, Na, Mg, A
1, S, Cl, Ar, K, Ca, V, Cr, Mn, C
u, Zn, Ga, Ge, As, Se, Br, Kr, R
b, Sr, Tc, Ru, Rh, Pd, Ag, Cd, I
n, Sn, Sb, Te, I, Xe, Cs, Ba, Re,
Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, P
Even if elements such as o, At, and Rn are added to such an extent that the magnetic properties are not deteriorated, the effect of the present invention is not impaired.

Unlike the conventional SmCo-based magnet material, this hard magnetic alloy powder is mainly composed of a fine crystalline phase of 100 nm or less, so that even if the powder is further refined, distortion is generated inside the crystal grains. It does not occur and hard magnetic characteristics do not deteriorate. For example, even if the average particle size of the hard magnetic alloy powder is set to about 5 to 100 μm, the coercive force (iHc) and the maximum magnetic energy product ((B
H) The hard magnetic properties such as _max ) do not deteriorate. Therefore, it is possible to reduce the particle size of the hard magnetic alloy powder without deteriorating the hard magnetic characteristics, thereby increasing the packing density of the hard magnetic alloy powder in the first and second magnets 9 and 13. The hard magnetic properties of the second magnets 9 and 13 themselves, in particular, the maximum magnetic energy product ((BH) _max ) can be improved.

The first and second magnets 9 and 13 can provide magnetic anisotropy, but can also provide isotropic magnetic characteristics. The first and second magnets 9 and 13 provided with magnetic anisotropy exhibit excellent hard magnetic properties,
The detection sensitivity of the magnetic field in the first and second magnetic detection elements 10 and 12 can be increased. On the other hand, depending on the shape of the magnet,
When the anisotropy is provided, it may be difficult to uniformly provide the magnetic anisotropy over the entirety of the first and second magnets 9 and 13, and as a result, the first and second magnets 9 and 13 may be difficult to obtain. Magnets 9 and 13
The non-uniformity of the surface magnetic flux density on the surface is slightly increased. In particular, in the case of the annular first magnet 9, if the easy magnetization direction is formed in one direction, the non-uniformity of the surface magnetic flux density may increase. Therefore, it is preferable to use a magnet having magnetic anisotropy for the second magnet 13.

The first and second magnets 9 and 13 having the isotropic magnetic properties are slightly lower than the case where the hard magnetic properties are provided with anisotropy, but have a low surface magnetic flux density. The uniformity becomes extremely small. This means that the change of the surface magnetic flux density of the first and second magnets 9 and 13 is smooth (less noise), and when this magnet is used in the magnetic sensor 1 described above. Provides an extremely stable output with respect to a change in the measurement object such as an angle change. Also,
Since the first and second magnets 9 and 13 have excellent magnetization temperature characteristics, the magnetization does not decrease even when used at a high temperature, and the first and second magnetic detection elements 10 and 12 are stable. To output a detection signal.

In order to manufacture the first and second magnets 9 and 13, first, a hard magnetic alloy powder is prepared. The hard magnetic alloy powder according to the present invention is produced by a step of obtaining a powder of an alloy having an amorphous phase as a main phase, and a step of heat-treating the powder.

The powder (granules) of an alloy having an amorphous phase as a main phase is obtained by rapidly cooling a molten alloy having a predetermined composition. When it is obtained as a ribbon, it can be obtained by further pulverizing and pulverizing the ribbon. The particle diameter of the obtained alloy powder is about 5 μm to 100 μm.

The method for obtaining an alloy having an amorphous phase as a main phase from the above-mentioned molten alloy is a so-called liquid quenching method. Specifically, a molten metal is sprayed onto a rotating drum and rapidly cooled to form a ribbon. And a method in which a molten metal is jetted into a cooling gas and rapidly cooled in a droplet state to form a powder.
The alloy powder having an amorphous phase as a main phase used in the present invention is preferably prepared by any of these methods. The alloy powder obtained by the above-described liquid quenching method has a single phase of an amorphous phase or a structure containing an amorphous phase as a main phase and containing a slightly fine crystalline phase.

Then, the alloy powder was heated to 600 to 800 ° C.
By heat treatment, the amorphous phase in the alloy powder is crystallized or a fine crystalline phase is grown to form a fine crystalline phase having an average crystal grain size of 100 nm or less, preferably an average crystal grain size of 50 nm or less. Is formed as a mixed phase of a soft magnetic phase and a hard magnetic phase in a structure precipitated as a main phase, thereby exhibiting hard magnetic properties, or the average crystal grain size of 100 nm or less, preferably an average crystal grain size of 100 nm or less. 50 nm
The following fine crystalline phase is precipitated and the above-mentioned mixed phase state is formed, whereby hard magnetic properties are exhibited, and magnetic anisotropy is imparted by the orientation of the easy axis of magnetization of the hard magnetic phase. In this way, a hard magnetic alloy powder having hard magnetic properties is obtained.

The above heat treatment is preferably performed at a temperature in the range of 600 ° C. to 800 ° C., more preferably 600 ° C. to 750 ° C. If the heat treatment temperature is lower than 600 ° C,
Since the precipitation amount of the E ₂ D ₁₇ phase which is responsible for the hard magnetic properties is small, sufficient hard magnetic properties cannot be obtained, which is not preferable. On the other hand, if the heat treatment temperature exceeds 800 ° C., the crystal grains of the fine crystalline phase grow and become coarse, and the hard magnetic properties deteriorate, which is not preferable. The heat treatment time is from 0 minutes to 60 minutes, more preferably from 0 minutes to 30 minutes. If the heat treatment time exceeds 60 minutes, the fine crystalline phase grows and coarsens, and the hard magnetic properties of the hard magnetic alloy powder are undesirably deteriorated.

In particular, the conditions are selected so that the fine crystalline phase having an average crystal grain size of 100 nm or less, more preferably 50 nm or less is 50% by volume or more of the structure and the remainder is an amorphous phase. Bcc-F in the microcrystalline phase
e phase, bcc- (FeCo) phase, fcc- (CoFe)
A soft magnetic phase which is at least one of a phase, a D ₂₀ E ₃ Q phase containing a solid solution atom or a remaining amorphous phase, and E ₂ D ₁₇
If a hard magnetic phase containing at least a phase is generated, a hard magnetic alloy powder having extremely high hard magnetic properties can be obtained.

Then, the obtained hard magnetic alloy powder is mixed with a resin, and this is solidified and formed by a compression molding method or an injection molding method to obtain bulky first and second magnets 9 and 13.

The mixing ratio between the hard magnetic alloy powder and the resin can be appropriately changed depending on the desired characteristics of the first and second magnets 9 and 13. It is preferable to add the hard magnetic alloy powder so as to contain 50% by volume or more, preferably 60% by volume or more. If the volume ratio of the hard magnetic alloy powder is less than 50% by volume, the amount of resin becomes excessive, and the hard magnetic properties of the first and second magnets 9 and 13 may be lowered, which is not preferable. Further, when the addition amount of the hard magnetic alloy powder exceeds 95% by volume in the first and second magnets 9 and 13, the amount of resin decreases and the first and second magnets 9 and 13 are reduced. It is not preferable because solidification molding becomes difficult.

In the case where the hard magnetic alloy powder and the resin are solidified by a compression molding method, the hard magnetic alloy powder is mixed with a powdered resin to form a mixture, and the mixture is filled into a predetermined mold and compressed. And compression molding by heating to 150 to 200 ° C. to melt the resin. Alternatively, the hard magnetic alloy powder and the resin may be mixed while heating to 150 ° C. to 200 ° C. to make the resin in a molten state, and the resin may be filled in a predetermined mold and compressed to perform compression molding. As the resin used here, a material having a small loss in magnetic properties is used,
For example, polyamide, polypropylene, polyethylene,
Examples include polystyrene, paraffin, polytetrafluoroethylene, polycarbonate, silicone resin, epoxy resin, phenolic resin, polyurethane resin, and unsaturated polyester. In particular, polyamide (-6)
(6-nylon), polyamide (-12) (12-nylon), polyethylene chloride, and epoxy resin are promising.

In particular, according to the compression molding method, the mixing ratio of the hard magnetic alloy powder in the mixture can be made higher than in the case of the injection molding method described later, and the hardening of the first and second magnets 9 and 13 can be improved. This is preferable because the magnetic properties can be further improved.

When the hard magnetic alloy powder and the resin are solidified and formed by an injection molding method, the obtained hard magnetic alloy powder is mixed with the above resin, and the mixture is heated to 150 to 200 ° C. to melt the resin. Then, this is injected into a predetermined mold cavity and molded.

If the alloy powder is directly solidified and formed, the first and second magnets 9 and 13 having isotropic magnetic characteristics can be obtained. In addition, magnetic anisotropy can be imparted to the alloy powder by crystallization under uniaxial stress. By mixing such a powder with a resin and compression-molding in a magnetic field, a powder having magnetic anisotropy can be obtained. First and second magnets 9 and 13 are obtained.

Further, a metal material having a low melting point may be used in place of the resin. In this case, the hard magnetic alloy powder and the powder of the metal material are mixed and heated to a temperature equal to or higher than the melting point of the metal material, and the mixture is filled in a predetermined mold and compressed, or is mixed with the hard magnetic alloy powder. By heating the metal material to bring the metal material into a molten state and filling it in a mold or injecting it into a predetermined mold cavity and molding the first and second metal materials,
Are obtained. Examples of the metal material used here include Zn, Al, In, Sn, Sb, and Pb. In addition to the resin, another metal material (Nd-Fe
-B magnet, SmCo magnet) or an oxide material (e.g., ferrite) may be mixed and solidified.

The hard magnetic alloy powder constituting the first and second magnets 9 and 13 is hardened by crystallizing or growing the alloy powder having the amorphous phase as a main phase under stress. The easy axis of magnetization of the magnetic phase is oriented, and the alloy is given magnetic anisotropy. As a result, the remanent magnetization (Ir) and the maximum magnetic energy product ((BH) _max ) are increased, resulting in an excellent hardness. Magnetic properties can be exhibited.

It is preferable that the hard magnetic alloy powder constituting the first and second magnets 9 and 13 has a composition represented by the following composition formula. _{(Co 1-f T f)} 100-xyzt M x Sm y R z Q t ( where, T is, Fe, is one or more elements of Ni, M is, Nb, Zr, Ta , Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
One or more of C, Si and B, 0 ≦ f <0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5
Atomic% ≦ t ≦ 10 atomic%, 5 atomic% ≦ x + y + z ≦ 16
Atomic%)

Co gives hard magnetic properties,
It is an essential element for the first and second magnets 9 and 13 of the present invention. The amorphous phase having the element D containing Co and the element E includes:
When heat treatment is performed at an appropriate temperature in the range of 600 ° C. to 800 ° C., an E ₂ D ₁₇ phase which is a hard magnetic phase, a bcc-Fe phase, a bcc- (FeCo) phase which is a soft magnetic phase, and fc
At least one of a c- (CoFe) phase, a D ₂₀ E ₃ Q phase containing a solid solution atom, and a remaining amorphous phase is generated.

In the above formula, T represents one or both of Fe and Ni. These elements T
Has the effect of increasing the residual magnetization (Ir), but when the concentration of the element T is increased by substitution with Co, the concentration of Co decreases and the coercive force (iHc) decreases. Therefore, if the first and second magnets 9 and 13 having particularly high remanent magnetization (Ir) are required, the element T is added to the first and second magnets 9 and 13 having large coercive force (iHc). If necessary, a magnet having optimal hard magnetic properties can be manufactured according to the application by not adding the element T. Further, by replacing expensive Co with inexpensive Fe or Ni, the manufacturing cost of the first and second magnets 9 and 13 can be reduced. F indicating the composition ratio of the element T is preferably 0 or more and less than 0.5 in order to exhibit excellent hard magnetic properties.
More preferably, it is set to 2 or more and less than 0.5.

Sm gives hard magnetic properties like Co, and is an essential element for the first and second magnets 9 and 13 of the present invention. Further, it is an element that easily forms an amorphous phase. The amorphous phase containing Co (element D) and Sm (element E) is a hard magnetic phase (Fe, Co) ₁₇ Sm ₂ when heat-treated at an appropriate temperature in the range of 600 ° C. to 800 ° C.
Phase, bcc-Fe phase, bcc-
A (FeCo) phase, an fcc- (CoFe) phase or a D ₂₀ E ₃ Q phase containing a solid solution atom is precipitated. The remaining amorphous phase also functions as a soft magnetic phase. Y (atomic%) indicating the composition ratio of Sm is 5 atomic% or more and 16 atomic% when the element R which is a rare earth element is simultaneously added in addition to Sm.
Or less, more preferably 8 to 16 atomic%, and more preferably 9 to 13 atomic%.
It is most preferable to set the following. When the composition ratio y is less than 5 atomic%, the coercive force (i
Hc) is decreased, and an amorphous phase is hardly formed. If the composition ratio y exceeds 16 atomic%, the concentrations of Co and the element T decrease, and the saturation magnetization (I
s) decreases, and the residual magnetization (Ir) decreases accordingly, which is not preferable.

When the element R is not added simultaneously with Sm, y (atomic%) indicating the composition ratio of Sm is preferably set to 8 atomic% to 16 atomic%, and more preferably 9 atomic% to 13 atomic%. % Is more preferable.

In the above formula, R is a rare earth element other than Sm, and Sc, Y, La, Ce, Pr, Nd, Pm,
Represents one or more elements of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Element R is
It is an element that easily forms an amorphous phase. 50% by weight in alloy
In order to form a sufficient amorphous phase and crystallize it to generate a sufficient amount of a fine crystalline phase and to realize good hard magnetic characteristics, the composition ratio z of the element R is required.
Must be at least 1 atomic%, more preferably 2 atomic%.
Atomic% or more.

On the other hand, the saturation magnetization (Is) of the obtained first and second magnets 9 and 13 tends to decrease as the composition ratio z of the element R increases. High remanent magnetization (I
In order to obtain r), the composition ratio z of the element R needs to be 5 atomic% or less. When part or all of the element R is composed of Nd and / or Pr, higher hard magnetic properties can be obtained. Further, the element R can be replaced with Sm, forms an E ₂ D ₁₇ phase, and can exhibit hard magnetic properties.

In the above formula, the element M is Nb, Zr,
One or two of Ta, Hf, Mo, W, Ti, V
Represents more than one element. Since these elements M have a high ability to form an amorphous phase, by adding this element M, a sufficient amorphous phase is generated even if the composition ratio of the expensive element R (rare earth element) is reduced. be able to. However, when the composition ratio x (atomic%) of the element M is increased by replacing it with Co and the element T, the obtained saturation magnetization (Is) of the first and second magnets 9 and 13 decreases. If the composition ratio x of the element M is reduced, a sufficient amorphous phase cannot be formed. From this viewpoint, the composition ratio x of the element M is preferably from 0 to 4 at%, more preferably from 1 to 4 at%. Among these elements M, Nb is particularly effective. When part or all of the element M is replaced with Nb, the coercive force (iHc) of the first and second magnets 9 and 13 increases, and the oxidation of the first and second magnets 9 and 13 relatively decreases. Can be prevented.

The above-mentioned Sm, element R, and element M are elements having common properties in that they easily form an amorphous phase, and are the total amount of the composition ratio of these elements (x + y + z). Is preferably at least 5 at% and at most 16 at%, more preferably at least 9 at% and at most 13 at%. If the composition ratio (x + y + z) is less than 5 atomic%, it is not preferable because the amorphous phase is not sufficiently precipitated. On the other hand, if (x + y + z) exceeds 16 atomic%, the hard magnetic properties deteriorate, which is not preferable.

In the above formula, Q is P, C, Si, B
And one or more of these elements, and these elements Q are also semimetals that easily form an amorphous phase. The amorphous phase having the elements D including Co, the element Q including B, and the element E including Sm is a soft magnetic phase when heat-treated at an appropriate temperature in the range of 600 ° C to 800 ° C. bcc-F
e phase, bcc- (FeCo) phase, fcc- (CoFe)
Phases or precipitating D ₂₀ E ₃ Q phase. In order to form a sufficient amount of the amorphous phase in the alloy and to obtain a sufficient amount of the fine crystalline phase by crystallizing the same, the composition ratio t of the element Q must be:
0.5 atomic% or more is necessary, and particularly preferably 3 atomic% or more. However, when the composition ratio t (atomic%) of the element Q is excessively increased, the saturation magnetization (Is), the remanence magnetization (Ir), and the retention of the obtained first and second magnets 9 and 13 are accordingly increased. Since the magnetic force (iHc) tends to decrease, the composition ratio t of Q needs to be 10 atom% or less, especially 9 atom% or less in order to obtain good hard magnetic properties. preferable.

The first and second magnets 9 and 13
May be added with one or more elements X of Al, Ge, Ga, Ag, Pt, Au, and Cu. In that case, the first and second magnets 9 and 13 may be It can be represented by the following composition formula. _{(Co 1-f T f)} 100-xyztu M x Sm y R z Q t X u ( where, T is, Fe, is one or more elements of Ni, M is, Nb, Zr , Ta, Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
X is one or more of C, Si and B, and X is Al, Ge, Ga, Ag, Pt, Au, Cu
And at least one element of 0 ≦ f <
0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16
Atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5 atomic% ≦ t ≦
10 atomic%, 0 atomic% ≦ u ≦ 5 atomic%, 5 atomic% ≦ x +
y + x ≦ 16 atomic%)

In this case, f indicating the composition ratio of the element T is preferably 0 or more and less than 0.5, and more preferably 0.2 or more and less than 0.5 in order to exhibit excellent hard magnetic properties. . Y (atomic%) indicating the composition ratio of Sm in the above composition formula
Is not less than 5 atomic% and not more than 16
Atomic% or less, more preferably 9 atomic% or more and 13 atomic% or less.

Z representing the composition ratio of the element R in the above composition formula
(Atomic%) is 0 atomic% in order to provide excellent hard magnetic properties and to obtain a good amorphous phase and a fine crystalline phase.
It is necessary that the content be at least 2 atomic%. On the other hand, the element R decreases the saturation magnetization (Is) of the obtained first and second magnets 9 and 13 as the composition ratio z increases. In addition, it is necessary to set the composition ratio z of the element R to 5 atomic% or less.

X representing the composition ratio of element M in the above composition formula
(Atomic%) is preferably 0 atomic% or more and 4 atomic% or less, more preferably 1 atomic% or more and 3 atomic% or less, in order to obtain good hard magnetic properties. Among these elements M, Nb is particularly effective. When part or all of the element M is replaced with Nb, the first and second magnets 9 and 13
Has a relatively large coercive force (iHc). The first,
Oxidation of the second magnets 9 and 13 can be relatively prevented.

The above-mentioned Sm, element R, and element M are elements having common properties in that they easily form an amorphous phase, and are the total amount of the composition ratio of these elements (x + y + z). Is preferably 5 to 16 atomic%, more preferably 8 to 16 atomic%, further preferably 10 to 14 atomic%. When the element R is always added in addition to Sm, the lower limit of (x + y + z) is preferably set to 5 atomic% or more, and when the element R is not added in addition to Sm, the lower limit of (x + y + z) is set. Is preferably at least 5 atomic%. When the composition ratio (x + y + z) is less than 5 atomic% or less than 8 atomic%, formation of an amorphous phase is not sufficient, which is not preferable. Also, (x + y + z) is 1
If the content exceeds 6 atomic%, the hard magnetic properties deteriorate, which is not preferable.

T representing the composition ratio of element Q in the above composition formula
(Atomic%) is required to be 0.5 atomic% or more in order to obtain a good amorphous phase and a fine crystalline phase.
It is preferable to make the above. In order to obtain good hard magnetic properties, the composition ratio t of Q needs to be 10 atomic% or less, and particularly preferably 9 atomic% or less.

In the above formula, the element X is Al, Ge,
It is one or more of Ga, Ag, Pt, Au and Cu, and these elements X mainly improve the corrosion resistance of the first and second magnets 9 and 13. Since Ag, Pt, Au, and Cu of the element X do not form a solid solution in Fe, when a fine crystalline phase is precipitated by heat treatment,
It has the effect of promoting the refinement of crystal grains. Further, Ge, Ga, and Al among the elements X have an effect of promoting the formation of a nano-multiphase structure which is a mixed phase of a fine crystalline phase and an amorphous phase. Composition ratio u of element X (atomic%)
Is preferably at least 0 atomic% and at most 5 atomic%,
It is more preferable that the content be 1 atomic% or more and 3 atomic% or less.
If u exceeds 5 atomic%, the ability to form an amorphous phase is reduced, and the hard magnetic properties are also lowered. In particular, Al is the cheapest element among the elements X, and is preferable because the cost of the first and second magnets 9 and 13 can be reduced.

In the above element X, Cu may be omitted. That is, the element X is Al, Ge, Ga, Ag, Pt, A
One or more of u may be used. C
u acts to separate the hard magnetic phase composed of the E ₂ D ₁₇ phase from the soft magnetic phase and precipitates it.
Since u is a non-magnetic material, the first and second magnets 9 and 13
It is said that it is desirable to reduce the amount of addition as much as possible in order to lower the magnetization of. In the present invention, the first heat treatment is performed by forming an amorphous ribbon by a liquid quenching method and then performing a heat treatment.
By manufacturing the second magnets 9 and 13, the hard magnetic phase composed of the E ₂ D ₁₇ phase can be separated and precipitated from the soft magnetic phase without adding Cu. May not be included.

In the magnetic sensor 1 according to the present invention, P, C, Si, B
First and second magnets 9 made of a hard magnetic alloy powder containing one or more of the above elements Q and Sm, having an amorphous phase and a fine crystalline phase, and a resin. , 13 and the first and second magnets 9 and 13 have a nano-composite structure composed of a fine crystalline phase and an amorphous phase. Characteristics can be exhibited, and thereby the sensitivity of the magnetic sensor 1 can be increased. Further, since the first and second magnets 9 and 13 are formed by binding hard magnetic alloy powder with a resin,
A permanent magnet having a high degree of freedom in shape, small size, and strong hard magnetism can be obtained.

Further, the first and second magnets 9 and 13 according to the present invention have a small non-uniformity of the surface magnetic flux density distribution. The linearity of the detection signal when the relative position with respect to the magnets 9 and 13 changes changes, and the detection accuracy of the magnetic sensor 1 can be increased. Further, since the first and second magnets 9 and 13 according to the present invention have excellent temperature characteristics of magnetization, the magnetization does not decrease even at a high temperature, and the magnetic sensor 1 according to the present invention can be used.
Can be operated stably even when used in a relatively high temperature environment.

Further, Nb, Zr, Ta,
One or more elements M of Hf, Mo, W, Ti, V, and Sc, Y, La, Ce, Pr, Nd, P
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b, a hard magnetic alloy powder containing at least one element of one or more elements R of Lu,
The ability to form an amorphous phase can be further enhanced, and Al, G
The hard magnetic alloy powder containing one or more elements X of e, Ga, Ag, Pt, and Au can optimize the microstructure, so that the hard magnetic alloy powders of the first and second magnets 9 and 13 can be hardened. The magnetic characteristics can be further improved, and the sensitivity of the magnetic sensor 1 can be increased.

In the hard magnetic alloy powder constituting the first and second magnets 9 and 13, at least 50% by volume of the structure has an average crystal grain size of 100 nm or less, preferably an average crystal grain size of 50 nm or less. A fine crystalline phase,
Since a mixed phase state of a soft magnetic phase and a hard magnetic phase is formed in the tissue, it is possible to have extremely high hard magnetic characteristics. Further, the first and second magnets 9 and 13 can be given characteristics of a soft magnetic phase and a hard magnetic phase.

Further, the first and second magnets 9 and 13 are
Unlike conventional SmCo-based magnets, the average crystal grain size is 100
Since it is mainly composed of a fine crystalline phase of not more than nm, even if the powder has a small particle size, distortion is hardly generated inside the crystal grains, and hard magnetic characteristics are not deteriorated. Therefore, a hard magnetic alloy powder having a smaller particle size can be used as a raw material for the first and second magnets 9 and 13, and thereby the packing density of the hard magnetic alloy powder in the first and second magnets 9 and 13 can be increased. Therefore, the hard magnetic characteristics of the first and second magnets 9 and 13 can be made higher than those of the conventional SmCo-based bonded magnet, and the detection sensitivity of the magnetic sensor 1 can be increased.

Also, the first and second magnets 9 and 13 of the present invention
Can provide magnetic anisotropy, and the first and second magnets 9 and 13 provided with magnetic anisotropy have improved hard magnetic characteristics, so that the detection sensitivity of the magnetic sensor 1 is further improved. be able to.

Also, the first and second magnets 9 and 13 of the present invention
Can be made magnetically isotropic, and in the first and second magnets 9 and 13 provided with the isotropic property, the hard magnetic properties are slightly reduced as compared with the case where the anisotropy is provided. However, the non-uniformity of the surface magnetic flux density becomes extremely small. For example, when the first and second magnets 9 and 13 are used in the magnetic sensor 1, the first and second magnetism detecting elements 10 are used. , 12 and the first and second magnets 9, 13 change in linearity of the detection signal when the relative position changes, and the detection accuracy of the magnetic sensor 1 can be further increased.

Since the hard magnetic alloy powder constituting the first and second magnets 9 and 13 is represented by the following composition formula, when the alloy melt is rapidly cooled, the amorphous phase is mainly contained. An alloy as a phase can be easily obtained, and a heat-treated alloy can precipitate a fine crystalline phase, so that the first and second magnets 9 and 13 exhibit excellent hard magnetic properties. be able to. _{That, (Co 1-f T f} ) 100-xyzt M x Sm y R z Q t ( where, T is, Fe, is one or more elements of Ni, M is, Nb, Zr , Ta, Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
One or more of C, Si and B, 0 ≦ f <0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5
Atomic% ≦ t ≦ 10 atomic%, 5 atomic% ≦ x + y + z ≦ 16
Is atomic%) _{or, (Co 1-f T f} ) 100-xyztu M x Sm y R z Q t X u ( where, T is, Fe, be one or more elements of Ni , M are Nb, Zr, Ta, Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
X is one or more of C, Si and B, and X is Al, Ge, Ga, Ag, Pt, Au, Cu
And at least one element of 0 ≦ f <
0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16
Atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5 atomic% ≦ t ≦
10 atomic%, 0 atomic% ≦ u ≦ 5 atomic%, 5 atomic% ≦ x +
y + z ≦ 16 atomic%)

Further, in the above composition formula, when f indicating the composition ratio is in the range of 0.2 ≦ a <0.5, more excellent hard magnetic characteristics can be exhibited. Furthermore, the first,
When Nb is added to the second magnets 9, 13, the first,
The coercive force (iHc) of the second magnets 9 and 13 increases, and the oxidation of the hard magnetic alloy powder can be relatively prevented.

[0077]

EXAMPLES (Example 1) Co, Fe, Sm, Zr and B
Is weighed in a predetermined amount as a raw material, and is evacuated under a reduced pressure Ar atmosphere.
In the high frequency induction heating device or
Dissolve in an incandescent heater to produce an ingot of the specified composition
Produced. Dissolve this ingot in a crucible,
Blows molten metal from nozzle to rotating roll and quench
(Co) under a reduced pressure Ar atmosphere by a single roll method
_0.72Fe_0.28)_98-ytSm_yZr_TwoB _t(However, y = 6,
8, 10, 12, 14, 16, t = 3, 5, 7, 9, 1,
1) A quenched ribbon having the following composition was obtained. Similarly, (C
o_0.72Fe_0.28)_98-ytSm_yNb_TwoB_t(However, y =
8, 10, 12, 14, 16, t = 3, 5, 7, 9)
A quenched ribbon having the following composition was obtained. About the obtained quenched ribbon,
The state of the tissue of the ribbon was examined by X-ray diffraction analysis. Change
Then, VSM (vibrating sample type magnetic force
At room temperature in an applied magnetic field of 1.5 T and in vacuum.
The coercive force (iHc) was measured. Fig. 3 and Fig.
It is shown in FIG.

As shown in FIG. 3, (Co _0.72 Fe _0.28 )
The _98-yt Sm quenched ribbons of _y Zr ₂ B _t a composition,
y = 8 at% or more and t = 11 at% or more, or y
= 14 at% or more and t = 3 at% or more, almost all of the structure becomes an amorphous phase, y = 6 at%, 3 at% ≦ t ≦ 9 at% becomes a crystalline phase, Under the condition (1), an amorphous phase and a crystalline phase are mixed. Accordingly, the _{(Co 0.72 Fe 0.28) 98-} yt Sm y Zr 2 For quenched ribbon of B _t a composition, when the concentration of Sm in the alloy is 8 atomic% or more, by quenching the molten alloy non It can be seen that it is preferable to obtain a quenched ribbon having a crystalline phase as a main phase.
Thus, when M = Zr, if the concentration of Sm is 8 atomic% or more, a uniform and fine crystalline phase can be deposited after the heat treatment. Further, the coercive force (iHc) is about 64 to 114 Oe for any ribbon, and the quenched ribbon without heat treatment has a coercive force (iHc).
It can be seen that c) is small.

As shown in FIG. 4, (Co _0.72 Fe
For _{0.28) 98-yt} Sm quenched ribbons of _y Nb ₂ B _t a composition, y = 10 atomic% or more and t = 5 atomic% or more, or, y = 14 atomic% or more and t = 3 atomic% or more Under the conditions, almost all of the structure becomes an amorphous phase, and under other conditions, the amorphous phase and the crystalline phase are mixed. Therefore,
In _{(Co 0.72 Fe 0.28) 98-} yt Sm y Nb 2 For quenched ribbon of B _t a composition is to obtain a quenched ribbon of the amorphous phase as a main phase by quenching the molten alloy, the alloy It can be seen that the concentration of Sm in the medium should be at least 9 atomic% or more. Thereby, when M = Nb, if the concentration of Sm is 9 atomic% or more, a uniform and fine crystalline phase can be precipitated after the heat treatment. Further, the coercive force (iHc) is about 64 to 74 Oe for any ribbon, and the quenched ribbon without heat treatment has a coercive force (iHc).
It can be seen that c) is small. Although the data of the ribbon-shaped sample is shown in Experimental Example 1, similar data can be obtained even when the ribbon is pulverized into a powder.

(Experimental Example 2) In the same manner as in Experimental Example 1, (C
o_0.72Fe_0.28)₈₃Sm_TenNb_TwoB_Five, (Co_0.72Fe
_0.28)₈₁Sm_TenNb_TwoB₇, (Co_0.72Fe_0.28)₇₉Sm
_TenNb_TwoB₉, (Co _0.72Fe_0.28)₈₃Sm_TenZr_TwoB_Five,
(Co_0.72Fe_0.28)₈₁Sm_TenZr_TwoB₇, (Co_0.72F
e_0.28)₇₉Sm_TenZr_TwoB₉, (Co_0.72Fe_0.28)₈₁S
m₁₂Nb_TwoB_Five, (Co_0.72Fe_0.28)₇₉Sm₁₂Nb
_TwoB₇, (Co_0.72Fe_0.28)₇₇Sm₁₂Nb _TwoB₉, (Co
_0.72Fe_0.28)₈₁Sm₁₂Zr_TwoB_Five, (Co_0.72F
e_0.28)₇₉Sm₁₂Zr_TwoB₇, (Co_0.72Fe_0.28)₇₇S
m₁₂Zr_TwoB₉, (Co_0.72Fe_0.28)₈₅Sm₈Zr
_TwoB_Five, (Co_0.72Fe_0.28)₈₃Sm₈Zr_TwoB₇, (Co
_0.72Fe_0.28)₇₉Sm₁₄Zr_TwoB_Five, (Co_0.72F
e_0.28)₇₇Sm₁₄Zr_TwoB₇, (Co_0.72Fe_0.28)₇₅S
m₁₄Zr_TwoB₉, (Co_0.72Fe_0.28)₇₉Sm₁₂Nb
_TwoB₇, (Co_0.66Fe _0.34)₇₉Sm₁₂Nb_TwoB₇, (Co
_0.60Fe_0.40)₇₉Sm₁₂Nb_TwoB₇, (Co_0.72F
e_0.28)₈₁Sm₁₂B₇, (Co_0.72Fe_0.28)₇₉Sm₁₂
Nb_TwoB₇(Co_0.72Fe_0.28)₇₇Sm₁₂Nb_FourB₇, (C
o_0.72Fe_0.28)₈₁Sm₁₂Nb_TwoB_Five, (Co_{0. 66}Fe
_0.34)₈₁Sm₁₂Nb_TwoB_Five, (Co_0.60Fe_0.40)₈₁Sm
₁₂Nb_TwoB_Five, (Co_0.72Fe_0.28)₈₃Sm₁₂B_Five, (C
o_0.72Fe_0.28)₈₁Sm₁₂Nb_TwoB_Five, (Co_0.72Fe
_0.28)₇₉Sm₁₂Nb_FourB_FiveQuenched ribbon having the following composition:
Next, for the obtained quenched ribbon, 5 × 10^-FivePa or less
873K at a heating rate of 3K / sec in an infrared image furnace
(600 ° C) to 1173K (900 ° C)
By heat treatment under the condition of holding for 3 minutes, fine
A ribbon sample in which a crystalline phase was precipitated was obtained. Next, the obtained thin
Using a VSM (vibrating sample magnetometer) for the band sample,
Magnetization at room temperature in 1.5T applied magnetic field and vacuum
(I_1.5), Remanent magnetization (Ir), squareness ratio (Ir / I_1.5)
And the coercive force (iHc) were measured. The results are shown in FIGS.
Show.

In FIG. 5, (Co_0.72Fe_0.28)_88-t
Sm_TenNb_TwoB_tA ribbon sample having a composition of (t = 5, 7, 9)
Is between 923K (650 ° C) and 1073K (800 ° C)
There is no significant change in hard magnetic properties in the heat treatment temperature range.
No heat treatment temperature dependence is observed. On the other hand, FIG.
Then, Nb in the ribbon sample of FIG. 5 was replaced with Zr (Co
_0.72Fe _0.28)_88-tSm_TenZr_TwoB_t(T = 5, 7, 9)
In the case of a ribbon sample having the following composition, the squareness ratio (Ir /
I_1.5) Gradually exceeds 1023K (750 ° C)
And the coercive force (iHc) is 1073 to 1123
It can be seen that K indicates a maximum. Further, the coercive force (i
Hc) is shown in FIG._0.72Fe_0.28)
_88-tSm_TenNb_TwoB_tOf the sample containing Zr shown in FIG.
It can be seen that the coercive force (iHc) is larger than the material. Magnetization
(I_1.5), The residual magnetization (Ir) includes Zr
The sample has a higher magnetization (I_1.5), Residual magnetism
(Ir) is high.

Next, referring to FIG._0.72F
e_0.28)_86-tSm₁₂Nb_TwoB_t(T = 5, 7, 9)
The resulting sample has a heat treatment temperature of 923K (650 ° C) to 10
Coercive force (iHc) in the range of 23K (750 ° C)
Indicates 3 to 9 kOe, and FIG._0.72F
e_0.28)_88-tSm_TenNb_TwoB_tCoercive force (iH
It can be seen that c) has increased. FIG.
Then, Nb in the ribbon sample of FIG. 7 was replaced with Zr (Co
_0.72Fe _0.28)_86-tSm₁₂Zr_TwoB_t(T = 5, 7, 9)
In the case of a ribbon sample having the following composition, the coercive force (iHc) is N
b, but smaller than the sample containing
(I_1.5), The residual magnetization (Ir) is high.

Further, in FIG. 9, (Co _0.72 F
_{e 0.28) 90-t Sm 8} Zr 2 B t (t = 5,7) comprising the sample composition, the coercive force (iHc) is, the heat treatment temperature 1023K
(750 ° C), but increases sharply, but up to 2 kO
e and slightly lower than those of samples of other compositions. Next, in FIG. 10, (Co _0.72 Fe _0.28 ) _84-t Sm ₁₄
In a sample having a composition of Zr ₂ B _t (t = 5, 7, 9), when the heat treatment temperature is higher than 1023 K (750 ° C.), the coercive force (iHc) and the squareness ratio (Ir / I _1.5 ) tend to decrease. In the sample having the composition of (Co _0.72 Fe _0.28 ) ₇₉ Sm ₁₄ Zr ₂ B ₅ , the heat treatment temperature is 923 K (650 K).
° C) to 1023K (750 ° C).
It can be seen that a coercive force (iHc) equal to or greater than Oe is obtained.

Next, in FIG. 11, (Co _0.72 Fe
_{0.28) 83-t Sm 12 Nb} t B 5 (t = 0,2,4) comprising a sample of the composition, magnetization (I _1.5), the residual magnetization (Ir), squareness ratio (Ir / I _1.5) together, the heat treatment temperature Is 1023K (7
If the temperature exceeds 50 ° C.), it can be seen that the temperature has rapidly deteriorated.
Regarding the dependence of each property on the amount of Nb added, the sample having a composition of t = 2 has poor magnetization (I _1.5 ) and remanent magnetization (Ir), but the coercive force (iHc) has t = 4.
As a result, a value as large as 6 kOe or more was obtained. In FIG. 12, (Co _0.72 Fe _0.28 ) _81-t Sm ₁₂
The sample having the composition of Nb _t B ₇ (t = 0, 2, 4) shows the same tendency as in FIG. 11, and the heat treatment temperature is 1023 K (75
0 ° C.), it can be seen that each characteristic is deteriorated.
Further, the coercive force (iHc) of the sample having the composition of t = 2 was obtained.
Is as large as 9 kOe.

FIG. 13 is a graph showing the dependence of each characteristic on the ratio of Co to Fe and the heat treatment temperature.
_1-f Fe _f ) ₇₉ Sm ₁₂ Nb ₂ B ₇ (f = 0.28, 0.3
4, 0.4), the magnetization (I _1.5 ) and the residual magnetization (Ir) decrease as the Co concentration increases, but the coercive force (iHc) is t = 0.28, and
The sample of the composition having the highest concentration of
10k at (700 ° C) to 1023K (750 ° C)
Oe and a large value can be obtained. Further, FIG. 14 shows (Co _1-f Fe _f ) ₈₁ Sm ₁₂ Nb ₂ B ₅ (f = 0.2
FIG. 8 is a diagram showing the dependence of each characteristic on the ratio of Co and Fe of a sample having a composition of 8, 0.34, and 0.4) and the heat treatment temperature. As in the case of FIG. 13, the magnetization (I _1.5 ) and the remanence magnetization (Ir) decrease as the Co concentration increases, but the coercive force (iHc) is f = 0.28 and the composition having the highest Co concentration. The sample of the heat treatment temperature 923K (650
℃) ~ 973K (700 ℃) 7kOe and f =
Values larger than those of the samples having the compositions of 0.34 and 0.4 are obtained. When the heat treatment temperature is higher than 1023 K (750 ° C.), it can be seen that the coercive force (iHc) is rapidly deteriorated, particularly in the sample with f = 0.28.

As described above, the squareness ratio (I
r / I _1.5 ) exceeds 0.6, indicating that the exchange-coupled magnet has a nano-multiphase structure. Therefore,
It can be seen that the hard magnetic alloy powder according to the present invention obtained by pulverizing these ribbon-shaped samples has excellent hard magnetic properties.

(Experimental Example 3) In the same manner as in Experimental Example 1, (C
o _0.72 Fe _0.28 ) ₇₇ Sm ₁₂ Zr ₂ B ₉ , (Co _0.72 Fe
_0.28 ) A quenched ribbon having a composition of ₈₁ Sm ₁₂ Nb ₂ B ₅ was obtained. Next, the obtained quenched ribbon was heat-treated at a heating rate of 3 K / sec, a heat treatment temperature of 650 to 850 ° C., and a holding time of 3 minutes to obtain a ribbon sample. The state of the structure of the obtained ribbon sample was examined by X-ray diffraction analysis. The results are shown in FIGS.
6 is shown.

As shown in FIGS. 15 and 16, the quenched ribbon before the heat treatment has a halo pattern.
It can be confirmed that the amorphous phase is a single phase. Heat treatment temperature 6
At around 50 ° C., the (Fe, Co) ₁₇ Sm ₂ phase starts to precipitate. When the temperature exceeds 700 ° C., the precipitation of the (Fe, Co) ₂₀ Sm ₃ B phase or the bcc- (FeCo) phase is observed. In addition,
Although the data of the sample in the form of a ribbon is also shown in Experimental Example 3, similar data can be obtained even when the ribbon is pulverized into a powder. Therefore, in the hard magnetic alloy powder constituting the first and second magnets according to the present invention, a fine crystalline phase starts to precipitate by heat treatment, and this crystalline phase is
(Fe, Co) ₁₇ Sm ₂ phase which is a hard magnetic phase and (Fe, Co) ₂₀ Sm ₃ B phase or bc which is a soft magnetic phase
Since it contains the c- (FeCo) phase, it can be seen that the magnet exhibits good exchange coupling properties. The fcc- (CoFe) phase, which is a soft magnetic phase, could not be detected from this diffraction pattern. It is estimated that the amount of precipitation is small or the crystal growth is not sufficient.

(Experimental Example 4) In the same manner as in Experimental Example 1, (C
o_0.72Fe_0.28)₇₇Sm₁₂Zr_TwoB₉, (Co_0.72Fe
_0.28)₇₉Sm₁₂Zr_TwoB₇, (Co_0.72Fe_0.28)₈₁Sm
₁₂Zr_TwoB_Five, (Co _0.72Fe_0.28)₈₁Sm₁₂Nb_TwoB_Five,
(Co_0.72Fe_0.28)₇₉Sm₁₂Nb_TwoB₇, (Co_0.72F
e_0.28)₇₇Sm₁₂Nb_TwoB₉, (Co_0.72Fe_0.28)₈₁S
m_TenNb_TwoB₇, (Co_0.72Fe_0.28)₇₉Sm_TenNb_TwoB₉
A quenched ribbon having the following composition was obtained. Next, on the resulting quenched ribbon
About 5 × 10^-FiveIn an infrared image furnace below Pa,
873K (600 ° C) to 1173K at a heating rate of 3K / sec
(900 ° C) and heat treatment under the condition of holding for about 3 minutes.
Strip test to precipitate a fine crystalline phase
I got the fee. Next, for the obtained ribbon sample,
Average particle size of fine crystalline phase by electron microscope (TEM)
Was measured. Table 1 shows the results.

As is clear from Table 1, the heat treatment temperature was 6
In a ribbon sample at a temperature of 00 ° C. or higher, the average grain size of the crystal grains is about 50.
nm, which indicates that a fine crystalline phase is precipitated.

[0091]

[Table 1]

(Experimental example 5) In the same manner as in Experimental example 1, (Co
_1-fFe_f)_86-ySm₁₂Nb_TwoB_y, (Co_0.72Fe _0.28)
_88-xySm₁₂Nb_xB_y, (Co_0.72Fe_0.28)_98-xyS
m_yNb_TwoB_x, (Co_0.72Fe_0.28)_98-xySm_yZr_Two
B_xA quenched ribbon having the following composition was obtained. Then each quenched thin obtained
For the band alloy, the heating rate was 3K / sec, the heat treatment temperature was 650-
Heat treatment under conditions of 850 ° C and holding time of 3 minutes
I got Next, about the obtained sample, Fe, Nb, B,
Coercive force (iHc) and residual magnetization by variously changing the concentration of Sm
(Ir), magnetization (I_1.5)
And the dependence of each magnetic property on the concentration of these elements
The properties were measured. The obtained results are shown in FIGS.

FIG. 17 shows (Co _1-f Fe _f ) _86-y Sm ₁₂ N
For b ₂ B _y having a composition (y = 5, 7 atomic%) of the ribbon sample, shows the dependence of the magnetic properties to the concentration of Fe (f). As is clear from FIG. 17, the coercive force (iHc) was 7 atomic% higher than that of the sample having a B concentration (y) of 5 atomic%.
The sample of higher is higher in remanent magnetization (Ir) and magnetization (I _1.5 ).
Tends to increase as the Fe concentration (f) increases. Therefore, in order to obtain a coercive force (iHc) of 1000 Oe or more while maintaining a high remanent magnetization (Ir) of 100 emu / g or more and a high magnetization (I _1.5 ) of 80 emu / g or more, the Fe concentration (f) It is understood that it is better to set at least 0.5 or less.

FIG. 18 shows (Co _0.72 Fe _0.28 ) _88-xy S
For m ₁₂ Nb _x ribbon samples of B _y having the composition (y = 5, 7 atomic%), showing the respective magnetic characteristics when Nb concentration (x) was varied in the range of 0 to 5 atomic%. As is clear from FIG. 18, both the samples having the B concentration (y) of 5 at% and 7 at% have a particularly high coercive force (iHc) when the Nb concentration (x) is 2 to 4 at%. It turns out that it shows. FIG.
As shown in FIG. 8, in order to obtain a coercive force (iHc) of 1000 Oe or more while maintaining high remanent magnetization (Ir) and high magnetization (I _1.5 ), it is preferable that the Nb concentration be 0 to 4 atomic%. Understand.

FIG. 19 shows (Co _0.72 Fe _0.28 ) _98-xy S
For ribbon samples of m _y Nb ₂ B _x having a composition (y = 8,10,12 atomic%), B concentration (x) .5 to 11 atomic%
Each magnetic characteristic when it is changed in the range is shown. As is clear from FIG. 19, in the sample in which the Sm concentration (y) is 12 atomic%, by setting the B concentration (x) to 0.5 to 10 atomic%, the high residual magnetization (Ir) and the high magnetization (I _A coercive force (iHc) higher than 1000 Oe is obtained while maintaining _1.5 ). In particular, it can be seen that a larger coercive force can be obtained by setting the B concentration (x) to 9 atomic% or less or 2 atomic% or more.

FIG. 20 shows (Co _0.72 Fe _0.28 ) _98-xy S
indicating the respective magnetic characteristics when the m has _y Zr ₂ B _x having a composition (y = 8, 10, 12, 14 atomic%) varied from 0.5 to 11 atomic% sample B concentration (x) of. As is clear from FIG. 20, in a sample having a B concentration (x) of 10 atomic% or less, it is possible to obtain (iHc) of 1000 Oe or more while maintaining high remanent magnetization (Ir) and high magnetization (I _1.5 ). Can be. Further, it can be seen that the B concentration (x) is preferably set to 2 to 10 atomic% in order to surely obtain a coercive force (iHc) of 1000 Oe. Therefore, the hard magnetic alloy powder according to the present invention obtained by pulverizing these ribbon-shaped samples has excellent hard magnetic properties and improves the hard magnetic properties of the first and second magnets. Can be.

(Experimental Example 6) In the same manner as in Experimental Example 1, (C
o _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm ₁₂ B ₅ , (Co _0.72 Fe
_0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇ and (Co _0.72 Fe _0.28 ) ₈₀ N
A quenched ribbon made of an amorphous phase having a composition of b ₂ Sm ₁₃ B ₅ was obtained. Next, the quenched ribbon having the composition of (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B _{7 was} heated in an infrared image furnace at 5 × 10 ⁻⁵ Pa or less at a heating rate of 3 K / sec and a heat treatment temperature (T
a) By performing a heat treatment at 600 ° C., 700 ° C., 800 ° C. and a holding time of 3 minutes, a ribbon sample in which a fine crystalline phase was precipitated was obtained. The state of the structure of the obtained ribbon sample was examined by X-ray diffraction analysis. FIG. 21 shows the X of each ribbon sample.
3 shows a line diffraction pattern.

In FIG. 21, a thin film heat-treated at 600 ° C.
(Fe, Co)₁₇Sm _TwoPhase diffraction peak
To be observed. When the heat treatment temperature is 800 ° C.,
(Fe, Co)₁₇Sm_TwoIn addition to the phases (Fe, Co)₂₀S
m_ThreeA phase B diffraction peak is also observed. In addition, optimal heat treatment
In the case of 700 ° C., which is considered to be the
-The diffraction peak of the (Fe, Co) phase was not confirmed.
Therefore, in the ribbon sample of this experimental example, at least c
Magnetic phase (Fe, Co)₁₇Sm_TwoAt least
Is also a soft magnetic phase (Fe, Co)₂₀Sm_ThreeB phase again
Indicates magnetic properties due to exchange coupling with the remaining amorphous phase.
Is considered to be determined.

Next, (Co_0.72Fe_0.28)₈₁Nb_TwoSm
₁₂B_Five, (Co_0.72Fe_0.28)₇₉Nb _TwoSm₁₂B₇as well as
(Co_0.72Fe_0.28)₈₀Nb_TwoSm₁₃B_FiveQuenching of different compositions
About the ribbon, Differential Scanning Calorimeter (Differential Scann
ing Calorimeter: Hereinafter referred to as DSC. ) To 700
DSC between K (427 ° C) and 1100K (827 ° C)
The curve was measured. The results are shown in FIG. In FIG.
In the quenched ribbon, two
An exothermic peak (indicated by a circle in the figure) is observed. For example, (Co
_0.72Fe_0.28)₇₉Nb_TwoSm₁₂B₇Quenched ribbons of different composition
The DSC curve in FIG. 22 and the X-ray diffraction pattern in FIG.
Considering this in addition, about 873K (6
The exothermic peak around (00 ° C) is mainly (Fe, Co)₁₇Sm
_TwoIt is estimated that the heat was generated when the phase was precipitated, and
The exothermic peak around 0K (657 ° C) is mainly (Fe, C
o)₂₀Sm_ThreePresumed to be due to heat generated when B phase precipitated
Is done.

FIG. 23 shows that (Co _0.72 Fe _0.28 ) ₈₁ Nb
₂ Sm ₁₂ B ₅ and (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇
The magnetic properties of a ribbon sample obtained by heat-treating a quenched ribbon having the following composition at 600 to 800 ° C. for 3 minutes are shown. As shown in FIG. 23, the coercive force (iH
c) shows the maximum value, and it is understood that the heat treatment temperature of 700 ° C. is optimal for the coercive force (iHc). Considering this together with the result of FIG.
At 0 ° C., a hard magnetic phase (Fe, Co) ₁₇ S
It is considered that the hard magnetic properties were improved due to the moderate precipitation of the m ₂ phase and grain growth. The coercive force (iH) when the heat treatment temperature is less than 700 ° C. and exceeds 700 ° C.
Although c) shows a low value, this is because at less than 700 ° C., the amount of (Fe, Co) ₁₇ Sm ₂ phase precipitated is smaller than that of the remaining amorphous phase (soft magnetic phase), and sufficient hard magnetic properties are obtained. When the temperature exceeds 700 ° C. (Fe, C
o) The crystal grains composed of the ₂₀ Sm ₃ B phase are enlarged and the hard magnetic properties are reduced. The relationship between the coercive force and the heat treatment temperature is, in particular, (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm
It is clear in the case of ₁₂ B ₇ a composition.

The relationship between the heat treatment temperature and the size of the crystal grains of the (Fe, Co) ₁₇ Sm ₂ phase can be inferred from the results shown in FIGS. 21 and 22. That is, (Co _0.72 F
In ribbon sample of _{e 0. 28) 79 Nb 2 Sm} 12 B 7 having a composition, are exothermic peak at around 657 ° C. as described above observation _{(Fe, Co) 20 Sm 3} B phase is precipitated (FIG. 22), but the heat treatment temperature 700 shown in FIG.
(Fe, Co) ₂₀ Sm ₃
No B phase is observed. Therefore, it is considered that the crystal grains of the (Fe, Co) ₂₀ Sm ₃ B phase, which is a soft magnetic phase at a temperature lower than 700 ° C., have a small grain size and a small precipitation amount. On the other hand, as shown in FIG. 21, in the diffraction pattern at the heat treatment temperature of 800 ° C., many diffraction peaks of the (Fe, Co) ₂₀ Sm ₃ B phase are observed, and (Fe, Co) ₂₀ Sm ₃
It is easily presumed that the B phase crystal grains are enlarged and the amount of precipitation is large, which is considered to be the cause of the deterioration of the hard magnetic properties.

Further, although the remanent magnetization (Ir) and the squareness ratio (Ir / Is) in FIG. 23 gradually decrease with the increase in the heat treatment temperature, the amount of change is small, and the change in the heat treatment temperature is smaller than the coercive force (iHc). Influence is small. Therefore,
Regarding the remanent magnetization (Ir) and the squareness ratio (Ir / Is), the heat treatment temperature is slightly lower at 700 ° C. than at 500 ° C.
Since the coercive force (iHc) shows the maximum value at 700 ° C., it is considered that the optimum heat treatment temperature for the ribbon sample having the above composition is 700 ° C.

FIG. 24 shows (Co _0.72 Fe _0.28 ) ₈₁ Nb
₂ Sm ₁₂ B ₅ and (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇
The magnetization curve (JH loop) of a ribbon sample obtained by heat-treating each quenched ribbon having the following composition at 700 ° C. for 3 minutes to precipitate a fine crystalline phase is shown. A unique inflection point such as a step is not observed on the magnetization curve of FIG. 24, and a magnetization curve similar to that of a magnetic material composed of a single hard magnetic phase is obtained. The reason for this is that the magnet according to the present invention has a mixture of a soft magnetic phase and a hard magnetic phase, and the magnetization rotation of the fine soft magnetic phase is magnetically coupled by the fine hard magnetic phase. This is considered to be the result of being strongly constrained by the hard magnetic phase. The first and second magnets of the present invention have excellent hard magnetic properties because they have the characteristics of exhibiting a magnetization curve similar to that of a magnetic material composed of a single hard magnetic phase, that is, the magnetic properties of an exchange spring magnet. It demonstrates its characteristics.

(Experimental Example 7) In the same manner as in Experimental Example 1, (C
_{o 0.72 Fe 0.28) 98-yt} Nb 2 Sm y B t ( where, y = 1
1-16 atomic%, t = 3-9 atomic%). 5 × 10 ^-5 P for the quenched ribbon
The heat treatment is performed in an infrared image furnace under a at a heating rate of 3 K / sec, a heat treatment temperature (Ta) of 700 ° C., and a holding time of 3 minutes. Obtained. The composition and coercive force (iH
c), the relationship between the residual magnetization (Ir) and the maximum magnetic energy product ((BH) _max ) are shown in FIGS.

As shown in FIG. 25, y + t = 18 atomic%
In the case of a composition satisfying (total amount of Sm and B), 650 k
It can be seen that a high coercive force (iHc) of A / m or more is obtained. It can be seen that by adding B in this manner, a high coercive force can be obtained even at a relatively low Sm concentration. As shown in FIG. 26, (Co _0.72 F
e _0.28) in _{98-yt Nb 2 Sm x B} y, at least 1
If 3 atomic% ≦ y ≦ 15 atomic% and 3 atomic% ≦ t ≦ 7 atomic%, the maximum magnetic energy product ((BH) _max ) ≧
60 kJ / m ³ , and 11 atomic% ≦ y ≦ 1
≧ 7 if 5 atomic% and 3 atomic% ≦ t ≦ 5 atomic%
0 kJ / m ³ can be obtained, and it can be seen that it has excellent hard magnetic properties.

(Experimental example 8) In the same manner as in Experimental example 1, (C
o _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇ quenched ribbon was obtained. The quenched ribbon is heat-treated in an infrared image furnace at 5 × 10 ⁻⁵ Pa or less under the conditions of a heating rate of 3 K / sec, a heat treatment temperature (Ta) of 700 ° C., and a holding time of 3 minutes to obtain fine crystals. A ribbon sample in which a quality phase was precipitated was obtained. About this ribbon sample, a transmission electron microscope (TE
The tissue was observed by M). FIG. 27 shows a TEM photograph of the tissue. In addition, the state of the atomic arrangement near numbers 1, 2, and 3 shown in FIG. 27 was analyzed by electron beam diffraction. The results are shown in FIGS.

As is clear from the distribution forms of the diffraction spots of the electron beam diffraction shown in FIGS. It turns out that it is phase 3). The crystal phase of the crystalline phase near the No. 1 (crystalline phase 1) is about 60 nm,
The crystalline grain size of the crystalline phase (crystalline phase 2) was about 20 nm. The reason why the crystalline phase 1 has a larger crystal grain size than the crystalline phase 2 is considered to be that the crystalline phase 1 was precipitated before the crystalline phase 2.

Here, the compositions in the crystalline phase 1, the crystalline phase 2 and the amorphous phase 3 were analyzed by energy dispersive X-ray analysis (EDS: Energy Dispersive Spectrometry). Table 2 shows the results. From Table 2, the crystalline phases 1 and 2 are both hard magnetic phases (Fe, Co) ₁₇ Sm ₂
It turns out that it is a phase. In addition, when the crystalline phases 1 and 2 are compared with the amorphous phase 3, it is found that Nb is concentrated in the amorphous phase 3.

[0109]

[Table 2]

Also, (Co _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm
Except that a ₁₂ B ₅ having a composition in the same manner as described above, to obtain a ribbon samples. The structure of this ribbon sample was observed with a transmission electron microscope (TEM). FIG. 31 shows the T of the organization.
An EM photograph is shown.

Electron diffraction analysis revealed that the portions numbered 4 and 5 in FIG. 31 were crystalline phases and the portion numbered 6 was an amorphous phase. Therefore, FIG.
Composition analysis of the portions numbered 4 and 5 in 1 by the electron beam diffraction method revealed that the portion numbered 4 was a crystalline phase composed of bcc- (Co, Fe),
The part numbered 5 was found to be a crystalline phase composed of Sm ₂ (Co, Fe) ₁₇ .

Based on the above results, a schematic diagram of a TEM photograph of FIG. 31 was prepared. This schematic diagram is shown in FIG. It is clear that the ribbon sample according to the present invention is composed of a hard magnetic phase composed of Sm ₂ (Co, Fe) ₁₇ , a soft magnetic phase composed of bcc- (Co, Fe), and an amorphous phase. Became.

(Experimental example 9) In the same manner as in Experimental example 1, (C
_{o 0.72 Fe 0.28) 83-x} Sm 12 Nb x B 5, (Co 0. 72 Fe
_0.28 ) _81-x Sm ₁₂ Nb _x B ₇ , (Co _0.72 Fe _0.28 ) _80-x
A quenched ribbon having a composition of Sm ₁₃ Nb _x B ₇ (where x = 0 to 4 at%) was obtained. 5 × 10 ^-5 for the above quenched ribbon
In an infrared image furnace of Pa or lower, the heating rate is 3 K / sec,
By performing a heat treatment under the conditions of a heat treatment temperature (Ta) of 700 ° C. and a holding time of 3 minutes, a ribbon sample in which a fine crystalline phase was precipitated was obtained. FIG. 33 shows the relationship between the Nb concentration (x) and the magnetic characteristics for each ribbon sample. As is apparent from FIG. 33, the hard magnetic properties are improved by adding 1 to 2 atomic% of Nb.

(Experimental Example 10) In the same manner as in Experimental Example 1, quenched ribbons of various compositions each having a structure having an amorphous phase as a main phase were obtained. It was pulverized by pulverizing in the inside. Particle size 3 in the obtained powder
Those having a size of 7 to 105 μm were selected and used as raw material powder in the subsequent steps. Next, the raw material powder is heat-treated in an infrared image furnace of 5 × 10 ⁻⁵ Pa or less under the conditions of a heating rate of 3 K / sec, a heat treatment temperature (Ta) of 700 ° C., and a holding time of 3 minutes, thereby obtaining fine A crystalline phase was precipitated to obtain a hard magnetic alloy powder.

The obtained hard magnetic alloy powder and epoxy resin were mixed to form a mixture, and this mixture was solidified and formed by a compression molding method and an injection molding method to obtain a bulk magnet according to the present invention. .

In the compression molding method, the above mixture is filled in a predetermined mold, and the mixture is charged at 500 to 530 kg / cm ^2.
While compressing under the pressure described above, the mixture was heated to 160 ° C. and maintained for 30 minutes, and then solidified by melting the resin. Also,
In the injection molding method, the above mixture was heated to make the resin in the mixture in a molten state, and the mixture was injected toward a cavity of a predetermined mold to perform solidification molding.

Tables 3 and 4 show the molding method, resin content, density and hard magnetic properties of the obtained bulk magnet. Looking at the coercive force (iHc) in Tables 3 and 4, the magnet containing Nb has a higher coercive force (iHc) than the magnet containing Zr.
It can be seen that c) is higher.

In Tables 3 and 4, the relationship between the molding method and the content of the resin in the magnet is seen. The magnet obtained by the compression molding method has a lower resin content than the injection molding method. This shows that the content of the hard magnetic alloy powder was high. Accordingly, the density of the magnet obtained by the compression molding method is higher than that of the injection molding method. This is because in the case of the injection molding method, it is necessary to increase the fluidity of the mixture to some extent, so that it is necessary to increase the resin amount. Looking only at these results, it seems that the compression molding method is superior, but the injection molding method can form a large amount of compacts in a short time, so it is more suitable for mass production. It can be said that there is. Further, according to these forming methods, the degree of freedom of the shape of the magnet is increased, and there is no occurrence of chipping or cracking, and the processing accuracy is excellent.

[0119]

[Table 3]

[0120]

[Table 4]

(Experimental Example 11) [Production of Bulk Magnet of Example] In the same manner as in Experimental Example 1, a structure having an amorphous phase as a main phase (Co _0.72 Fe
_0.28) to give a ₈₀ Sm ₁₁ Nb ₂ quenched ribbon of B ₇ a composition, the melt spun ribbons were powdered by grinding in air using a ball mill. Particle size 5-100 μm in the obtained powder
Was used as a raw material powder in the subsequent steps.
Next, the raw material powder was heated in an electric furnace under a nitrogen gas atmosphere at a temperature rising rate of 0.17 K / sec and a heat treatment temperature (Ta) of 923 K (6
Heat treatment was performed under the conditions of (50 ° C.) and a holding time of 30 minutes to precipitate a fine crystalline phase, thereby obtaining a hard magnetic alloy powder.

The obtained hard magnetic alloy powder and a resin are mixed to form a mixture, and the mixture is solidified and formed by an injection molding method, whereby the length according to the present invention is 10 mm and the width is 5 m.
Thus, a rectangular parallelepiped isotropic small magnet having a thickness of 3 mm was obtained.
As a comparative example, a small magnet of a comparative example was obtained in the same manner as in the above case using a conventional isotropic SmCo-based magnet powder.

When the relative density of the obtained small magnet was measured, the relative density of the small magnet according to the present invention was 64.
8%, and the relative density of the small magnet of the comparative example is 57.8%.
Met.

Table 5 shows various magnetic characteristics of the small magnet of the present invention and the small magnet of the comparative example. As is evident from Table 5, the small magnet of the present invention has a hard magnetic property, particularly a maximum magnetic energy product ((B
H) _max ) is higher. Therefore, by using the hard magnetic alloy powder of the present invention, a bonded magnet having an isotropic and high maximum magnetic energy product (BH) _max can be obtained.

Thus, the relative density and (BH) _max
The high bonded magnet was obtained because the hard magnetic alloy powder according to the present invention is composed of a fine crystalline phase having an average crystal grain size of 100 nm or less and an amorphous phase. This is because fine powder can be obtained without causing distortion in the crystal grains, and the packing density of the powder can be increased by injection molding using the fine powder.
It is difficult for the isotropic SmCo magnet obtained by the conventional injection molding method to have (BH) _max of 15 kJm ^-3 or more as described above. On the other hand, in the isotropic magnet obtained by the injection molding of the present invention, (BH) _max can be set to 20 kJm ⁻³ or more.

[0126]

[Table 5]

(Experimental Example 12) [Temperature Characteristics of Magnet] The composition was (Co _0.72 Fe _0.28 ) ₇₉ Sm
A raw material powder having a particle size of 5 to 100 μm was obtained in the same manner as in Experimental Example 11 except that it was ₁₂ Nb ₂ B ₇ . Next, this raw material powder was heated at a heating rate of 0.17 K / sec at a heat treatment temperature (T
a) Heat treatment was performed at 923 K (650 ° C.) for a holding time of 30 minutes to precipitate a fine crystalline phase to obtain a hard magnetic alloy powder.

The obtained hard magnetic alloy powder and resin are mixed to form a mixture, and the mixture is solidified and formed by a compression molding method to obtain an isotropic bulk magnet according to the embodiment of the present invention. Was. The shape of this magnet is 5mm x 5mm x
It was a rectangular parallelepiped of 5 mm, and the relative density was 90%. Further, as a comparative example, an anisotropic SmCo-based magnet powder having a conventional composition was used, and an anisotropic magnet of a comparative example was obtained in the same manner as described above.

For the obtained bulk product, 293-42
The temperature was maintained at a temperature of 3 K (20 to 150 ° C.) for 30 minutes. When the temperature of the bulk body became equal to the ambient temperature, the magnetization was measured by a Gauss meter to determine the magnetization reduction rate.
Here, the magnetization reduction rate is a reduction rate based on the magnetization at a temperature of 293 K (20 ° C.). FIG. 34 shows the relationship between the magnetization reduction rate and the temperature. As is clear from FIG. 34, the magnet of the example shows a magnetization reduction rate equivalent to that of the conventional magnet of the comparative example, and has a temperature characteristic of magnetization equivalent to that of the conventional SmCo magnet. . Therefore, according to the present invention, it can be seen that a magnet having a high maximum magnetic energy product ((BH) _max ) and having excellent temperature characteristics of magnetization can be obtained.

(Experimental Example 13) [Survey of Surface Magnetic Flux Density Distribution (1)] First, a raw material powder having a particle size of 5 to 100 μm was obtained in the same manner as in Experimental Example 11. Next, this raw material powder was heated in a nitrogen gas atmosphere at a heating rate of 0.
17K / sec, heat treatment temperature (Ta) 923K (650
C), and heat treatment under the condition of a holding time of 30 minutes,
A fine crystalline phase was precipitated to obtain a hard magnetic alloy powder.

The obtained hard magnetic alloy powder and resin were mixed to form a mixture, and this mixture was solidified and formed by an injection molding method to obtain an isotropic magnet of an example according to the present invention. As a comparative example, isotropic SmCo of the conventional composition was used.
An anisotropic magnet of a comparative example was obtained in the same manner as described above, using the system magnet powder.

The obtained isotropic magnet and anisotropic magnet were used as the first magnet of the magnetic sensor shown in FIGS. 1 and 2, respectively, and when these magnets were rotated together with the second rotating body. The detection signal of the first magnetic detection element was measured, and the distribution state of the surface magnetic flux density of each of the isotropic magnet and the anisotropic magnet was investigated. The results are shown in FIG. In FIG. 35, the maximum and minimum detection signal values are set to 1 and −1, respectively, and for other detection signal values, a relative value based on the maximum and minimum signal values is calculated to obtain a signal curve. This signal curve indicates the relative value of the surface magnetic flux density.

As shown in FIG. 35, in the case of the isotropic magnet, the surface magnetic flux density changes relatively smoothly with the change in the rotation angle of the magnet, and there is no slight change in the curve. In the case of the non-magnetic magnet, the change in the surface density has a larger variation in the curve than in the case of the isotropic magnet, indicating that the distribution of the surface magnetic flux density is non-uniform. Therefore, in the magnetic sensor of the present invention, it can be seen that the use of an isotropic magnet as the first magnet can increase the detection accuracy of the rotation angle of the magnetic sensor.

(Experimental Example 14) [Survey of Surface Magnetic Flux Density Distribution (2)] First, a raw material powder having a particle size of 5 to 100 μm was obtained in the same manner as in Experimental Example 11. Next, this raw material powder was heated in a nitrogen gas atmosphere at a heating rate of 0.
17K / sec, heat treatment temperature (Ta) 923K (650
C), and heat treatment under the condition of a holding time of 30 minutes,
A fine crystalline phase was precipitated to obtain a hard magnetic alloy powder.

The obtained hard magnetic alloy powder and resin were mixed to form a mixture, and this mixture was solidified and formed by an injection molding method to obtain an isotropic magnet of an example according to the present invention. As a comparative example, isotropic SmCo of the conventional composition was used.
An anisotropic magnet of a comparative example was obtained in the same manner as described above, using the system magnet powder.

The obtained isotropic magnet and anisotropic magnet were used as the second magnet of the magnetic sensor shown in FIGS. 1 and 2, respectively, and the movement of each magnet when the second rotating body was rotated. The detection signal corresponding to the distance was measured, and the distribution state of the surface magnetic flux density of each of the isotropic magnet and the anisotropic magnet was investigated. The results are shown in FIGS. 36 and 37. 36 and 37
In the graph, the output voltage and the linearity range from the second magnetic detection element are on the vertical axis, and the moving distance of each magnet is on the horizontal axis.
The case where the moving distance of the magnet is 0 mm is defined as the reference position of the second rotating body, and the output signal and linearity of the second magnetic detecting element when the second rotating body is rotated clockwise and counterclockwise from this reference position, respectively. The range was measured.

In the case of the isotropic magnet according to the present invention, as shown in FIG. 36, the linearity of the output voltage is high, and the change in the linearity range is within a range of ± 0.5%, and the change is small. . On the other hand, in the case of the anisotropic magnet of the comparative example, FIG.
As shown in the figure, the linearity range greatly fluctuates when the moving distance is in the range of −2 mm to 2 mm, and the change in the nearness range also exceeds ± 0.5%, indicating that the fluctuation is large. Therefore, in the magnetic sensor of the present invention, the second
It can be understood that the use of an isotropic magnet as the magnet of (1) can improve the detection accuracy of the rotation angle of the magnetic sensor. In particular, in the magnetic sensor of the present invention, (BH) _max is 20 k
By using a magnet exhibiting excellent hard magnetic properties of Jm ^-3 or more, the output stability against noise such as an external magnetic field is improved more than using a conventional isotropic magnet obtained by injection molding. be able to.

[0138]

As described above, in the magnetic sensor of the present invention, the first and second rotation amount detecting sections each include Co as a main component and one of P, C, Si, and B. A first hard magnetic alloy powder containing a seed or two or more elements Q and Sm, having an amorphous phase and a fine crystalline phase, and a resin;
A second magnet is provided, and the first and second magnets have a nano-multiphase structure composed of a fine crystalline phase and an amorphous phase. Can be exhibited, thereby increasing the sensitivity of the magnetic sensor. Further, since the first and second magnets are formed by binding hard magnetic alloy powder with a resin, a permanent magnet having a high degree of freedom in shape, a small size, and strong hard magnetism may be used. it can.

In the first and second magnets according to the present invention, the non-uniformity of the surface magnetic flux density distribution is small.
The linearity of the detection signal when the relative position between the second magnetism detecting elements 10 and 12 and the first and second magnets changes is increased,
The detection accuracy of the magnetic sensor can be increased. Furthermore, since the first and second magnets according to the present invention have excellent magnetization temperature characteristics, the magnetization does not decrease even at high temperatures, and the magnetic sensor of the present invention was used in a relatively high temperature environment. Even in this case, it can be operated stably.

Further, Nb, Zr, Ta,
One or more elements M of Hf, Mo, W, Ti, V, and Sc, Y, La, Ce, Pr, Nd, P
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b, a hard magnetic alloy powder containing at least one element of one or more elements R of Lu,
The ability to form an amorphous phase can be further enhanced, and Al, G
The hard magnetic alloy powder containing one or more elements X of e, Ga, Ag, Pt, and Au can optimize the microstructure, so that the hard magnetic properties of the first and second magnets are improved. It can be more excellent, and the sensitivity of the magnetic sensor can be increased.

In the hard magnetic alloy powder constituting the first and second magnets, at least 50% by volume or more of the microstructure has an average crystal grain size of 100 nm or less, preferably an average crystal grain size of 50 nm or less. A bcc-Fe phase, a bcc- (FeCo) phase,
fcc- (CoFe) phase, D ₂₀ E ₃ Q containing solid solution atoms
Phase or a soft magnetic phase containing at least one of the remaining amorphous phases, and an E ₂ D containing at least solid solution atoms.
_Since a mixed phase with a hard magnetic phase including ₁₇ phases is formed, extremely high hard magnetic characteristics can be obtained. In addition, the first and second magnets can be given characteristics of a soft magnetic phase and a hard magnetic phase.

Further, the above-mentioned first and second magnets are made of a conventional S
Unlike mCo-based magnets, they are mainly composed of a fine crystalline phase having an average crystal grain size of 100 nm or less. Hard magnetic characteristics do not deteriorate. Therefore, a hard magnetic alloy powder having a smaller particle size can be used as a raw material for the first and second magnets, whereby
Since the filling density of the hard magnetic alloy powder in the second magnet can be increased, the hard magnetic characteristics of the first and second magnets are reduced by the conventional S
It can be higher than the mCo-based bonded magnet, and the detection sensitivity of the magnetic sensor can be increased.

Further, the first and second magnets of the present invention can be made magnetically isotropic, and the first and second magnets provided with this isotropic property have different hard magnetic characteristics. Although slightly lower than the case where anisotropy is provided, the non-uniformity of the surface magnetic flux density becomes extremely small. For example, when the first and second magnets are used in the above-described magnetic sensor, 1st, 2nd
The linearity of the detection signal when the relative position between the magnetic detection element and the first and second magnets changes increases, and the detection accuracy of the magnetic sensor can be further increased.

Since the hard magnetic alloy powder constituting the first and second magnets is represented by the following composition formula, when the molten alloy is rapidly cooled, the amorphous phase becomes the main phase. An alloy can be easily obtained, and a heat-treated alloy can precipitate a fine crystalline phase, so that the first and second magnets can exhibit excellent hard magnetic properties. _{That, (Co 1-f T f} ) 100-xyzt M x Sm y R z Q t ( where, T is, Fe, is one or more elements of Ni, M is, Nb, Zr , Ta, Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
One or more of C, Si and B, 0 ≦ f <0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5
Atomic% ≦ t ≦ 10 atomic%, 5 atomic% ≦ x + y + z ≦ 16
Is atomic%) _{or, (Co 1-f T f} ) 100-xyztu M x Sm y R z Q t X u ( where, T is, Fe, be one or more elements of Ni , M are Nb, Zr, Ta, Hf, Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
X is one or more of C, Si and B, and X is Al, Ge, Ga, Ag, Pt, Au, Cu
And at least one element of 0 ≦ f <
0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16
Atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5 atomic% ≦ t ≦
10 atomic%, 0 atomic% ≦ u ≦ 5 atomic%, 5 atomic% ≦ x +
y + z ≦ 16 atomic%)

Further, in the above composition formula, when f indicating the composition ratio is in the range of 0.2 ≦ a <0.5, more excellent hard magnetic characteristics can be exhibited. Furthermore, the first,
When Nb is added to the second magnet, the coercive force (iHc) of the first and second magnets increases, and the oxidation of the hard magnetic alloy powder can be relatively prevented.

Further, the hard magnetic alloy powder constituting the first and second magnets of the present invention is manufactured by a liquid quenching method, so that an alloy having an amorphous phase as a main phase can be obtained. By subjecting this to a heat treatment, a fine crystalline phase can be precipitated, so that a nano-multiphase structure composed of a fine crystalline phase and a residual amorphous phase can be easily formed. The hard magnetic properties of the second magnet can be improved.

Further, by solidifying and molding using a metal material instead of the resin, the strength of the first and second magnets themselves can be increased.

The first and second magnets of the present invention contain hard magnetic alloy powder in an amount of 50% by volume or more, more preferably 60% by volume or more, so that excellent hard magnetic characteristics can be exhibited. Further, by solidifying and molding the hard magnetic alloy powder and the resin by a compression molding method, the content of the hard magnetic alloy powder can be increased, and the hard magnetic properties of the first and second magnets are further improved. be able to. Furthermore, by solidifying and molding the hard magnetic alloy powder and resin by the injection molding method,
A large number of magnets can be obtained in a short time.

[Brief description of the drawings]

FIG. 1 is a schematic plan view showing the internal structure of a magnetic sensor according to an embodiment of the present invention.

FIG. 2 is a schematic side view showing the internal structure of the magnetic sensor according to the embodiment of the present invention.

[3] _{(Co 0.72 Fe 0.28) 98-} yt Sm y Zr 2 B t
(However, y = 6, 8, 10, 12, 14, 16, t =
It is a figure which shows the state of a structure | tissue and the coercive force (iHc) of the quenched ribbon of the composition of 3,5,7,9,11).

[4] _{(Co 0.72 Fe 0.28) 98-} yt Sm y Nb 2 B t
(However, y = 8, 10, 12, 14, 16, t = 3,
It is a figure which shows the state of a structure | tissue and the coercive force (iHc) of the rapidly quenched ribbon of the composition of 5, 7, 9).

FIG. 5 (Co _0.72 Fe _0.28 ) ₈₃ Sm ₁₀ Nb ₂ B ₅ ,
_{(Co 0.72 Fe 0.28) 81 Sm} 10 Nb 2 B 7 and (Co _0.72
Magnetization (I _1.5 ), remanence magnetization (Ir), and squareness ratio (Ir / I 2) of a ribbon sample having a composition of Fe _0.28 ) ₇₉ Sm ₁₀ Nb ₂ B ₉
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 6 (Co _0.72 Fe _0.28 ) ₈₃ Sm ₁₀ Zr ₂ B ₅ ,
_{(Co 0.72 Fe 0.28) 81 Sm} 10 Zr 2 B 7 and (Co _0.72
Fe _0.28 ) ₇₉ Sm ₁₀ Zr ₂ B ₉ The magnetization (I _1.5 ), remanence magnetization (Ir), squareness ratio (Ir /
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 7 (Co _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ Nb ₂ B ₅ ,
_{(Co 0.72 Fe 0.28) 79 Sm} 12 Nb 2 B 7 and (Co _0.72
The magnetization (I _1.5 ), remanent magnetization (Ir), and squareness ratio (Ir / I.sub.2) of a ribbon sample having a composition of Fe _0.28 ) ₇₇ Sm ₁₂ Nb ₂ B ₉
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 8 (Co _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ Zr ₂ B ₅ ,
_{(Co 0.72 Fe 0.28) 79 Sm} 12 Zr 2 B 7 and (Co _0.72
Magnetization (I _1.5 ), remanence magnetization (Ir), and squareness ratio (Ir / I.sub.2) of a ribbon sample having a composition of Fe _0.28 ) ₇₇ Sm ₁₂ Zr ₂ B _9.
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 9 (Co_0.72Fe_0.28)₈₅Sm₈Zr_TwoB_Five,
(Co_0.72Fe_0.28) ₈₃Sm₈Zr_TwoB₇Composition ribbon
Sample magnetization (I_1.5), Remanent magnetization (Ir), squareness ratio (I
r / I_1.5), The dependence of coercivity (iHc) on heat treatment temperature
FIG.

FIG. 10 (Co _0.72 Fe _0.28 ) ₇₉ Sm ₁₄ Zr
_{2 B 5, (Co 0.72 Fe} 0.2 8) 77 Sm 14 Zr 2 B 7 , and (C
o _0.72 Fe _0.28 ) ₇₅ Sm ₁₄ Zr ₂ B ₉ Magnetization (I _1.5 ), remanence magnetization (Ir), squareness ratio (Ir /
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 11 (Co _0.72 Fe _0.28 ) ₈₃ Sm ₁₂ B ₅ , (C
o _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ Nb ₂ B ₅ and (Co _0.72 Fe
_0.28 ) Magnetization (I) of a ribbon sample having a composition of ₇₉ Sm ₁₂ Nb ₄ B ₅
FIG. 5 is a graph showing the heat treatment temperature dependence of _1.5 ), residual magnetization (Ir), squareness ratio (Ir / I _1.5 ), and coercive force (iHc).

FIG. 12 (Co _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ B ₇ , (C
o _0.72 Fe _0.28 ) ₇₉ Sm ₁₂ Nb ₂ B ₇ and (Co _0.72 Fe
_0.28 ) Magnetization (I) of a ribbon sample having a composition of ₇₇ Sm ₁₂ Nb ₄ B ₇
FIG. 5 is a graph showing the heat treatment temperature dependence of _1.5 ), residual magnetization (Ir), squareness ratio (Ir / I _1.5 ), and coercive force (iHc).

FIG. 13 (Co _0.72 Fe _0.28 ) ₇₉ Sm ₁₂ Nb
_{2 B 7, (Co 0.66 Fe} 0.3 4) 79 Sm 12 Nb 2 B 7 , and (C
o _0.60 Fe _0.40 ) ₇₉ Sm ₁₂ Nb ₂ B ₇ Magnetization (I _1.5 ), remanence magnetization (Ir), squareness ratio (Ir /
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 14 (Co _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ Nb
_{2 B 5, (Co 0.66 Fe} 0.3 4) 81 Sm 12 Nb 2 B 5 , and (C
o _0.60 Fe _0.40 ) ₈₁ Sm ₁₂ Nb ₂ B ₅ Magnetization (I _1.5 ), remanence magnetization (Ir), squareness ratio (Ir /
I _1.5 ) and the dependence of coercive force (iHc) on heat treatment temperature.

FIG. 15 (Co _0.72 Fe _0.28 ) ₇₇ Sm ₁₂ Zr ₂ B ₉
It is a figure which shows the result of having measured the X-ray-diffraction of the ribbon sample obtained by heat-processing the quenched ribbon of the composition which becomes 650-850 degreeC.

FIG. 16 (Co _0.72 Fe _0.28 ) ₈₁ Sm ₁₂ Nb ₂ B ₅
It is a figure which shows the result of having measured the X-ray-diffraction of the ribbon sample obtained by heat-processing the quenched ribbon with the composition of 600-800 degreeC.

FIG. 17: (Co _1-f Fe _f ) _86-y Sm ₁₂ Nb ₂ B
_y (y = 5, 7) magnetization (I _1.5 ) of a ribbon sample having a composition of
Remanent magnetization (Ir), coercive force (iHc) Fe concentration (f)
FIG.

FIG. 18 (Co _0.72 Fe _0.28 ) _88-xy Sm ₁₂ Nb _x
B _y magnetization of (y = 5,7) consisting ribbon samples of composition (I _1.5), N of residual magnetization (Ir), coercive force (iHc)
It is a figure which shows dependence of b density | concentration (x).

[19] _{(Co 0.72 Fe 0.28) 98-} xy Sm y Nb 2
B (magnitude (I _1.5 ), remanent magnetization (Ir), coercive force (iHc) of a ribbon sample having a composition of B _x (y = 8, 10, 12)
It is a figure which shows the dependence of density (x).

[20] _{(Co 0.72 Fe 0.28) 98-} xy Sm y Nb 2
The magnetization (I _1.5 ), residual magnetization (Ir), and coercive force (iH) of a ribbon sample having a composition of B _x (y = 8, 10, 12, 14)
It is a figure which shows the dependency of B concentration (x) of c).

FIG. 21 (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇
It is a figure which shows the result of the X-ray-diffraction analysis of the ribbon sample of composition.

FIG. 22 (Co _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm
₁₂ B _5, a diagram illustrating a _{(Co 0.72 Fe 0.2 8) 79} Nb 2 Sm 12 B 7 and _{(Co 0.72 Fe 0.28) 80 Nb} 2 Sm 13 DSC curve of melt spun ribbons of B ₅ a composition.

FIG. 23 (Co _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm ₁₂ B ₅
And _{(Co 0.72 Fe 0 .28) 79} Nb 2 Sm 12 residual magnetization of ribbon samples of B ₇ a composition (Ir), shows a thermal treatment temperature dependence of the squareness ratio (Ir / Is) and coercive force (iHc) It is.

FIG. 24 (Co _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm ₁₂ B ₅
And is a diagram showing a _{(Co 0.72 Fe 0 .28) 79} Nb 2 Sm 12 magnetization curves of ribbon samples of B ₇ a composition (J-H loop).

[Figure 25] _{(Co 0.72 Fe 0.28) 98-} yt Nb 2 Sm y
B _t (where, y = 11 to 16 atomic%, t = 3 to 9 atomic%) is a diagram showing the coercivity (iHc) and residual magnetization of the ribbon samples of a composition with (Ir).

[26] _{(Co 0.72 Fe 0.28) 98-} yt Nb 2 Sm y
B _t (where y = 11 to 16 at%, t = 3 to 9 at%) The maximum magnetic energy product ((B
It is a figure which shows H) _max ).

FIG. 27 (Co _0.72 Fe _0.28 ) ₇₉ Nb ₂ Sm ₁₂ B ₇
3 is a transmission electron microscope (TEM) photograph of a ribbon sample having the following composition.

FIG. 28 is a view showing a result of electron beam diffraction of the crystalline phase 1 in FIG. 27.

29 is a diagram showing a result of electron beam diffraction of crystalline phase 2 in FIG. 27.

30 is a view showing a result of electron diffraction of the amorphous phase 3 in FIG. 27.

FIG. 31 shows (Co _0.72 Fe _0.28 ) ₈₁ Nb ₂ Sm ₁₂ B ₅
3 is a transmission electron microscope (TEM) photograph of a ribbon sample having the following composition.

FIG. 32 shows a transmission electron microscope (TE) shown in FIG.
M) It is a schematic diagram of a photograph.

FIG. 33 (Co _0.72 Fe _0.28 ) _83-x Sm ₁₂ Nb _x B
_{5, (Co 0.72 Fe 0 .28} ) 81-x Sm 12 Nb x B 7 and (C
o _0.72 Fe _0.28 ) _80-x Sm ₁₃ Nb _x B ₇ is a graph showing the Nb concentration dependence of the remanent magnetization (Ir), the squareness ratio (Ir / I _1.5 ), and the coercive force (iHc) of a ribbon sample having the composition of: is there.

FIG. 34 (Co _0.72 Fe _0.28 ) ₇₉ Sm ₁₂ Nb ₂ B ₇
FIG. 3 is a diagram showing a relationship between a magnetization reduction rate and a temperature of a bulk body having a different composition.

FIG. 35 is a graph showing the distribution of the surface magnetic flux density when the annular isotropic magnet and the anisotropic magnet are each rotated by 0 to 360 °.

FIG. 36 is a graph showing an output signal and a linearity range when a rectangular parallelepiped isotropic magnet is used for a magnetic sensor.

FIG. 37 is a graph showing an output signal and a linearity range when a rectangular parallelepiped anisotropic magnet is used for a magnetic sensor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Magnetic sensor 2 1st rotating body 2a outer peripheral surface 3 2nd rotating body 3a outer peripheral surface 4 1st rotation amount detection part 5 2nd rotation amount detection part 6 support body 7 worm gear 8 worm 9 1st magnet (magnet) 9a Outer peripheral surface 10 First magnetic detecting element 11 Detecting body 12 Second magnetic detecting element 13 Second magnet (magnet) 14 Connecting member 15 Hole 16 Female screw part 17 Male screw part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01F 1/08 C22C 1/00 A // C22C 1/00 1/02 501E 1/02 501 19/07 19 / 07 45/04 E 45/04 C22F 1/00 B C22F 1/00 608 608 621 621 660D 660 691B 691 H01F 1/04 HA (72) Inventor Takashi Hatanai Takashi Hatanai 1-7, Yutani Otsukacho, Ota-ku, Tokyo No. Alps Electric Co., Ltd. (72) Inventor Ichiro Tokunaga 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Toshio Ogawa 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alp (72) Inventor Hirofumi Okumura 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd.

Claims (22)

[Claims] 1. A magnet comprising: a magnet; and a magnetic detection element for detecting a magnetic field of the magnet, wherein the magnet has Co as a main component, and one or more of P, C, Si, and B Phase and an average crystal grain size of 100
A magnetic sensor characterized in that a hard magnetic alloy powder having a fine crystalline phase of not more than nm and a resin are mixed and solidified and molded. 2. The magnetic sensor according to claim 1, wherein the magnet has magnetic isotropy. 3. A first rotating body provided with a worm gear;
A second rotator provided with a worm meshing with the worm gear; and a first rotation detector for detecting a rotation of the second rotator, wherein the first rotation detector detects the second rotation. An annular first magnet fitted into the rotating body, and a first magnetism detecting element that is arranged at a distance from the outer periphery of the first magnet and detects a change in the magnetic field of the first magnet; The first magnet has Co as a main component and P, C, Si,
A hard magnetic alloy powder containing one or more elements Q and Sm of B and having an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less is mixed with a resin. The magnetic sensor according to claim 1, wherein the magnetic sensor is formed by solidification. 4. A second rotation amount detection unit for detecting a rotation amount of the second rotation body, wherein the second rotation amount detection unit detects the rotation amount of the second rotation body when the second rotation body rotates. A detection body including a second magnet that is movable back and forth in the direction of the rotation axis, and a second magnetic detection element that is disposed apart from the second magnet and detects a magnetic field change of the second magnet; The second magnet has Co as a main component, and P, C, Si,
A hard magnetic alloy powder containing one or more elements Q and Sm of B and having an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less is mixed with a resin. The magnetic sensor according to any one of claims 1 to 3, wherein the magnetic sensor is formed by solidification. 5. One or both of the first and second magnets contain Co as a main component and P, C, Si, B
One or more of the elements Q, Sm, and N
b, Zr, Ta, Hf, Mo, W, Ti, V
A hard magnetic alloy powder containing an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less, containing a seed or two or more elements, and a resin; The magnetic sensor according to claim 3 or 4, wherein the magnetic sensor is a magnetic sensor. 6. One or both of the first and second magnets contain Co as a main component and P, C, Si, B
One or two or more elements Q and Sm, and one or more elements of Nb, Zr, Ta, Hf, Mo, W, Ti, and V M, Sc,
Y, La, Ce, Pr, Nd, Pm, Eu, Gd, T
One or more of b, Dy, Ho, Er, Tm, Yb, and Lu are defined as element R, and Al, Ge, G
When one or more of a, Ag, Pt, Au, and Cu are defined as the element X, at least one of the elements M, R, and X is included. Further, a hard magnetic alloy powder having an amorphous phase and a fine crystalline phase having an average crystal grain size of 100 nm or less, and a resin are mixed and solidified and formed. The magnetic sensor according to claim 3 or 4. 7. The hard magnetic alloy powder has an average particle size of 10
The magnetic sensor according to any one of claims 1 to 6, comprising a single phase of a fine crystalline phase of 0 nm or less. 8. The hard magnetic alloy powder according to claim 1, wherein the structure contains at least 50% by volume of a fine crystalline phase having an average crystal grain size of 100 nm or less, and the remainder is an amorphous phase. The magnetic sensor according to claim 1. 9. The hard magnetic alloy powder contains at least 5 fine crystalline phases having an average crystal grain size of 50 nm or less in the structure.
The magnetic sensor according to claim 1, wherein the magnetic sensor contains 0% by volume or more and the remainder is an amorphous phase. 10. The magnetic sensor according to claim 1, wherein a mixed phase of a soft magnetic phase and a hard magnetic phase is formed in the structure of the hard magnetic alloy powder. . 11. The soft magnetic phase comprises bcc-Fe
Phase, bcc- (FeCo) phase, fcc- (CoFe)
Phases, comprising at least one D ₂₀ E ₃ Q phase containing dissolved atoms or residual amorphous phase, the hard magnetic phase, characterized in that it comprises at least laden E ₂ D ₁₇ phase solid solution atoms The magnetic sensor according to claim 10, wherein Where D is F
e, at least one or more of Co, Ni, and E is Sm, Sc, Y, La, Ce, P
r, Nd, Pm, Eu, Gd, Tb, Dy, Ho, E
r is one or more of Tm, Yb, and Lu; and Q is one or more of P, C, Si, and B. 12. The magnetic sensor according to claim 1, wherein the hard magnetic alloy powder is represented by the following composition formula. _{(Co 1-f T f)} 100-xyzt M x Sm y R z Q t where, T is, Fe, wherein one or both one of Ni, M is, Nb, Zr, Ta, Hf , Mo ,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
One or more of C, Si and B, 0 ≦ f <0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦
y ≦ 16 at%, 0 at% ≦ z ≦ 5 at%, 0.5 at% ≦ t ≦ 10 at%, 5 at% ≦ x + y + z ≦ 16 at%. 13. The magnetic sensor according to claim 1, wherein the hard magnetic alloy powder is represented by the following composition formula. _{(Co 1-f T f)} 100-xyztu M x Sm y R z Q t X u where, T is, Fe, wherein one or both one of Ni, M is, Nb, Zr, Ta, Hf , Mo,
One or more of W, Ti, and V elements, and R is Sc, Y, La, Ce, Pr, Nd, Pm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Wherein Q is P,
X is one or more of C, Si and B, and X is Al, Ge, Ga, Ag, Pt, Au, Cu
And at least one element of 0 ≦ f <
0.5, 0 atomic% ≦ x ≦ 4 atomic%, 5 atomic% ≦ y ≦ 16
Atomic%, 0 atomic% ≦ z ≦ 5 atomic%, 0.5 atomic% ≦ t ≦
10 atomic%, 0 atomic% ≦ u ≦ 5 atomic%, 5 atomic% ≦ x +
y + z ≦ 16 atomic%. 14. The magnetic sensor according to claim 12, wherein f representing the composition ratio of the hard magnetic alloy powder is in the range of 0.2 ≦ f <0.5. 15. The magnetic sensor according to claim 1, wherein the hard magnetic alloy powder always contains Nb. 16. The method according to claim 1, wherein the hard magnetic alloy powder is manufactured by a liquid quenching method.
The magnetic sensor according to claim 14. 17. The method according to claim 17, wherein the hard magnetic alloy powder is 600 to 8
The magnetic sensor according to any one of claims 1 to 16, wherein the magnetic sensor has been heat-treated at 00C. 18. The magnetic sensor according to claim 1, wherein a metal material is used instead of the resin. 19. The magnetic sensor according to claim 3, wherein the first and second magnets include the hard magnetic alloy powder in an amount of 50% by volume or more. 20. The magnetic sensor according to claim 3, wherein the first and second magnets contain the hard magnetic alloy powder in an amount of 60% by volume or more. 21. The magnetic sensor according to claim 3, wherein the first and second magnets are solidified by a compression molding method. 22. The magnetic sensor according to claim 3, wherein the first and second magnets are formed by injection molding.