JP2002334803A - Permanent magnet and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ferrite magnet powder which is improved in magnetic properties and manufactured at a low manufacturing cost, a ferrite magnet, and its applied products, and to provide their manufacturing methods. SOLUTION: A ferrite magnet has a hexagonal M-type magnetoplumbite structure, in which Sr, Ba, Pb, or Ca is partially substituted with at least an element selected from among of rare earth elements containing Y and Bi, and Fe is also partially substituted with Cu or Cu and Co. Cu or Cu and Co as substituting elements are wholly or partially added to the ferrite of hexagonal M-type magnetoplumbite structure, in which Sr, Ba, Pb, or Ca has been partially substituted with other elements, and the ferrite loaded with the substituting elements is calcined and/or sintered again. Cu or the like is added to the ferrite, having already, a hexagonal M-type plumbite structure, so that the ferrite can be improved in magnetic properties by the addition of a small amount of loading.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ferrite magnet powder, a magnet using the magnet powder, and a method for producing the same.

[0002]

2. Description of the Related Art Ferrite is a general term for a compound formed by an oxide of a divalent cation metal and trivalent iron, and a ferrite magnet is used for various uses such as various rotating machines and speakers. As a material for the ferrite magnet, Sr ferrite (Sr ferrite) having a hexagonal magnetoplumbite structure is used.
Fe ₁₂ O ₁₉ ) and Ba ferrite (BaFe ₁₂ O ₁₉ ) are widely used. These ferrites are produced at relatively low cost by powder metallurgy using iron oxide and a carbonate such as strontium (Sr) or barium (Ba) as raw materials.

The basic composition of magnetoplumbite (M-type) ferrite is usually represented by the chemical formula of AO.6Fe ₂ O ₃ . Element A is a metal that becomes a divalent cation,
It is selected from Sr, Ba, Pb, Ca and others.

Heretofore, it has been known that magnetization is improved by substituting a part of Ba or Sr in a Ba ferrite or Sr ferrite with a rare earth element such as La and substituting a part of Fe with Zn. (Journal of Magneti
sm and Magnetic Materials vol. 31-34 (1983) 793-794;
Application number: Japanese Patent Application No. Hei 8-145006, Publication number:
Five).

Further, it is known that coercive force and magnetization are improved by substituting a part of Ba or Sr in a Ba ferrite or Sr ferrite with a rare earth element such as La and substituting a part of Fe with Co. (Bull. Acad.
Sci. USSR (Transl.) Phys.Sec. Vol.25 (1961) 1405-14
08, Japanese Patent Application No. 8-306072, Japanese Patent Application Laid-Open No. 10-149910).

On the other hand, in Sr ferrite, it has been reported that the coercive force and magnetization are improved by substituting a part of Sr with La and substituting a part of Fe with Co and Zn (see International Application). No. PCT / JP98 / 00764, International Publication No. WO98 / 38654).

In hexagonal ferrites such as Ba ferrite and Sr ferrite, Sr, Ba or C
In producing a magnet having a main phase of hexagonal ferrite containing a, Co, a rare earth element (including Y) and Bi, and Fe, a part or all of the constituent elements are
It has been reported that the main baking is performed after adding to a particle having at least Sr, Ba or Ca containing hexagonal ferrite as a main phase (International application number PCT / JP98 / 04243, International publication number WO99 / 16087). . According to this method, it is reported that a magnet having at least two Curie temperatures can be produced, and magnetization, coercive force, temperature characteristics of coercive force, and the like are improved.

[0008]

However, even with these ferrite magnets, it is insufficient to achieve both improved magnetic properties and low manufacturing costs. That is, B
In the case of ferrite in which a part of a or Sr is replaced by La and a part of Fe is replaced by Zn, it is reported that the magnetization is improved, but there is a problem that the coercive force is significantly reduced. In the case of ferrite in which Ba or Sr is partially replaced by La and Fe is partially replaced by Co, it is reported that the coercive force is improved. However, the above Ba or Sr is partially replaced by La. Compared with ferrite in which part of Fe was replaced by Zn, improvement in magnetization was not sufficient. Also, Sr
It has been reported that ferrite in which a part of La is replaced by La and a part of Fe is replaced by Co and Zn improves both magnetization and coercive force. However, grain growth tends to occur during sintering, and coercive force decreases. There was a problem that it would. Further, in the case of ferrite using a rare earth element such as La or Co as a substitution element, since the raw materials of these substitution elements are expensive, there is a problem that the use of a large amount of these substitutes increases the raw material cost. Of ferrite magnets, which is relatively lower than that of rare earth magnets.

The present invention has been made in view of the above points, and a main object of the present invention is to provide a ferrite magnet capable of improving magnetic properties at a low manufacturing cost and a method for manufacturing the same.

[0010]

This object is achieved by the following constitutions (1) to (24).

(1) An oxide magnetic material having a main phase of ferrite having a hexagonal M-type magnetoplumbite structure, wherein at least one element selected from the group consisting of Sr, Ba, Pb and Ca A, Y composed of
R, Fe, Cu, or C, which is at least one element selected from the group consisting of rare earth elements containing Bi and Bi
u and Co, and the composition ratio of each of A, R, Fe, Co, and Cu is A: 4.5 atomic% with respect to the total amount of the elements A, R, Fe, Co, and Cu. At least 9.0 at%, R: 0.13 at% to 3.2 at%, Fe: 86.3 at% to 93.0 at%, Co: 0 at% to 3.2 at%. , Cu: 0.
An oxide magnetic material that satisfies the relationship of not less than 06 atomic% and not more than 3.2 atomic%.

(2) A, R, Fe, Co, and Cu
Of the formula 1: (1-x) AO. (X /
_{2) R 2 O 3 · (} n-y / 2-y '/ 2) Fe 2 O 3 · yC
It is expressed by oO · y′CuO and satisfies the relational expression of 0.02 ≦ x ≦ 0.35 0 ≦ y ≦ 0.35 0.01 ≦ y ′ ≦ 0.35 5.0 ≦ n ≦ 6.7 The oxide magnetic material according to the above (1).

(3) A, R, Fe, Co, and Cu
Are represented by the formula 2: (1-x) AO. (X /
_{2) R 2 O 3 · (} n-y / 2-y '/ 2) Fe 2 O 3 · yC
expressed as oO · y′CuO, 0.02 ≦ x ≦ 0.3
5, 0 ≦ y ≦ 0.35, 0 ≦ y ′ ≦ 0.35, 5.0 ≦
The above (1), wherein Cu or an oxide of Cu and Co is added in an amount of 0.06% by weight or more and 6.0% by weight or less to the oxide magnetic material satisfying the relational expression of n ≦ 6.7. Oxide magnetic material.

(4) The oxide magnetic material according to the above (2) or (3), wherein n is in the range of 6.0 <n ≦ 6.7.

(5) A ferrite magnet powder containing the oxide magnetic material according to any one of (1) to (4).

(6) At least one raw material powder selected from the group consisting of SrCO ₃ , BaCO ₃ , PbO and CaCO ₃ , a rare earth element oxide containing Y and Bi ₂
Mixing at least one oxide powder selected from the group consisting of O ₃ , Fe ₂ O ₃ powder, Co oxide powder, and Cu oxide powder; Preparing the raw material mixed powder produced by (1), and calcining the raw material mixed powder at a temperature of 1100 ° C. or more and 1450 ° C. or less, whereby (1-x) AO · (x / 2)
R ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO
Y′CuO (A is at least one element selected from the group consisting of Sr, Ba, Pb and Ca, R is at least one element selected from rare earth elements including Y and Bi, 0.02 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0.
Forming a calcined ferrite body having a composition of 01 ≦ y ′ ≦ 0.35, 5.0 ≦ n ≦ 6.7).

(7) At least one raw material powder selected from the group consisting of SrCO ₃ , BaCO ₃ , PbO and CaCO ₃ , a rare earth element oxide containing Y and Bi ₂
Mixing at least one oxide powder selected from the group consisting of O ₃ , Fe ₂ O ₃ powder, Co oxide powder, and Cu oxide powder; Preparing the raw material mixed powder produced by (1), and calcining the raw material mixed powder at a temperature of 1100 ° C. or more and 1450 ° C. or less, whereby (1-x) AO · (x / 2)
R ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO
Y′CuO (A is at least one element selected from the group consisting of Sr, Ba, Pb and Ca, R is at least one element selected from rare earth elements including Y and Bi, 0.02 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0 ≦
y ′ ≦ 0.35, 5.0 ≦ n ≦ 6.7) forming a calcined body of ferrite having a composition of 5.0 ≦ n ≦ 6.7), and adding the Cu oxide raw material or Cu and Co Preparing a calcined body mixed powder to which a powder of an oxide raw material is added.

(8) a chloride of at least one element selected from the group consisting of Sr, Ba, Pb and Ca;
Chloride of at least one element selected from the group consisting of rare earth elements including Y and Bi, chloride of Fe, Co
Preparing a mixed solution in which a chloride of Cu and a chloride of Cu are dissolved, wherein the mixed solution satisfies ph <6; and spraying the mixed solution into a heated atmosphere at 800 ° C. or higher and 1400 ° C. or lower. And (1−x) AO · (x / 2) R ₂ O _3. (Ny / 2)
−y ′ / 2) Fe ₂ O ₃ .yCoO.y′CuO (A is S
R is at least one element selected from the group consisting of r, Ba, Pb and Ca; R is at least one element selected from rare earth elements including Y and Bi; 0.02 ≦ x ≦
0.35, 0 ≦ y ≦ 0.35, 0.01 ≦ y ′ ≦ 0.3
5, a step of forming a calcined body of ferrite having a composition of 5.0 ≦ n ≦ 6.7).

(9) a chloride of at least one element selected from the group consisting of Sr, Ba, Pb and Ca;
Chloride of at least one element selected from the group consisting of rare earth elements including Y and Bi, chloride of Fe, Co
Preparing a mixed solution in which a chloride of Cu and a chloride of Cu are dissolved, wherein the mixed solution satisfies ph <6; and spraying the mixed solution into a heated atmosphere at 800 ° C. or higher and 1400 ° C. or lower. And (1−x) AO · (x / 2) R ₂ O _3. (Ny / 2)
−y ′ / 2) Fe ₂ O ₃ .yCoO.y′CuO (A is S
R is at least one element selected from the group consisting of r, Ba, Pb and Ca; R is at least one element selected from rare earth elements including Y and Bi; 0.02 ≦ x ≦
0.35, 0 ≦ y ≦ 0.35, 0 ≦ y ′ ≦ 0.35,
5.0 ≦ n ≦ 6.7) forming a calcined body of ferrite having a composition of: calcination by adding a Cu oxide raw material or a Cu and Co oxide raw material powder to the ferrite calcined body. Preparing a calcined ferrite body comprising the step of preparing a body mixed powder.

(Claim 10) The method for producing a calcined ferrite according to the above (6) or (7), wherein cobalt oxide is used instead of the Co oxide.

(11) The method for producing a calcined ferrite according to the above (8) or (9), wherein cobalt hydroxide is used instead of the chloride of Co.

(12) A, R,
The method for producing a calcined ferrite according to the above (6) or (7), wherein a sulfate of at least one element selected from the group consisting of Fe, Co, and Cu is added.

(13) A, R, F
The method for producing a calcined ferrite according to the above (8) or (9), wherein a sulfate of at least one element selected from the group consisting of e, Co, and Cu is added.

(14) In at least one of the step of preparing the raw material mixed powder, the step of preparing the mixed solution, and the step of pulverizing the calcined ferrite, B ₂ O ₃ and / or H _The method for producing a calcined ferrite according to any one of the above (6) to (13), wherein ₃ BO ₃ is added.

(15) The ferrite calcined body formed by the method for producing a ferrite calcined body according to any one of the above (6) to (14) is pulverized, and the average particle size measured by an air permeation method is set to 0.1. A method for producing a calcined ferrite body, comprising: forming a ground ferrite powder within a range of 2 μm to 2.0 μm; and calcining the ground ferrite powder at a temperature of 900 ° C. to 1450 ° C.

(16) The range of n is 6.0 <n ≦ 6.7.
The method for producing a calcined ferrite body according to any one of the above (6) to (15).

(17) The calcined body formed by the method for producing a calcined ferrite body according to any one of (6) to (16) is pulverized, and has an average particle size of 0.2 μm measured by an air permeation method. A method for producing a magnet powder in a range of at least 2.0 μm.

(18) Any of the above (6) to (16)
Formed by the method of manufacturing a calcined ferrite described in
CaO, SiO on the calcined body_Two, Cr_TwoO_ThreeAnd A
l_TwoO _Three(CaO: 0.3% by weight or more and 1.5% by weight or less,
SiO_Two: 0.2% by weight or more and 1.0% by weight or less, Cr_TwoO
_Three: 0 wt% or more and 5.0 wt% or less, Al_TwoO_Three: 0 weight
% Or more and 5.0% by weight or less).
Preparing and pulverizing the calcined body mixed powder,
Average particle size measured by excess method is 0.2 μm or more and 2.0 μm or less
Step of forming a ground ferrite powder in the range below
And a method for producing a magnet powder comprising:

(19) A bonded magnet containing the ferrite magnet powder according to (5).

(20) A bonded magnet containing a magnet powder produced by the method for producing a magnet powder according to the above (17) or (18).

(21) A step of subjecting the magnet powder produced by the method of producing a magnet powder according to the above (17) or (18) to a heat treatment, and producing a bonded magnet from the heat-treated magnet powder. And a method for producing a magnet.

(22) The heat treatment is performed at 700 ° C. or higher 11
The method for producing a magnet according to the above (21), wherein the method is performed at a temperature of 00 ° C. or lower.

(23) A sintered magnet containing the ferrite magnet powder according to (5).

(24) A sintered magnet produced from the magnet powder produced by the method for producing a magnet powder according to the above (17) or (18).

(25) A sintered magnet formed from the ferrite magnet powder according to (5), wherein CaO, S
containing iO ₂ , Cr ₂ O ₃ and Al ₂ O ₃ , each of which is added in an amount of 0.3 to 1.5% by weight of CaO;
SiO ₂ : 0.2% by weight or more and 1.0% by weight or less, Cr ₂ O
_3: 0 wt% to 5.0 wt% or less, Al ₂ O _3: 0 wt% to 5.0 sintered magnet is% by weight or less. (26) A step of preparing a magnet powder produced by the method for producing a magnet powder according to the above (17) or (18), and concentrating, kneading, molding in a magnetic field or molding in a non-magnetic field, and baking the magnet powder. And a sintering step.

(27) A step of preparing a magnet powder produced by the method for producing a magnet powder according to the above (17) or (18), and concentrating, kneading, drying, disintegrating, and dispersing the magnet powder in a magnetic field. Molding or sintering in the absence of a magnetic field.

(28) The method for producing a sintered magnet according to the above (26) or (27), wherein a dispersant is added in a solid content ratio of 0.2% by weight or more and 2.0% by weight or less during pulverization or kneading.

(29) A rotary machine provided with the sintered magnet according to any one of (23) to (25).

(30) A, R, Fe, Co, and C
u is expressed by the following formula: (1−x) AO · (x /
_{2) R 2 O 3 · (} n-y / 2-y '/ 2) Fe 2 O 3 · yC
expressed as oO · y′CuO, 0.02 ≦ x ≦ 0.3
5, 0 ≦ y ≦ 0.35, 0 ≦ y ′ ≦ 0.35, 5.0 ≦
When the molar amount of Co added and the molar amount of Cu added to 1 mol of the oxide magnetic material represented by n ≦ 6.7 are Y ′ and 0.2 ≦ (Y + Y ′) / The oxide magnetic material according to the above (1), wherein the relationship x ≦ 0.8 is satisfied.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a hexagonal M-type magnetoplumbite structure ferrite (AO.6Fe ₂ O ₃ : A) is used.
Is at least one element selected from the group consisting of Sr, Ba, Pb and Ca, and a part of the element A is replaced with at least one element selected from the group consisting of a rare earth element containing Y and Bi. ), And a part of Fe is replaced by Cu or Cu and Co.

In the present invention, a hexagonal M-type magnetoplumbite structure ferrite in which at least a part of the element A is substituted by the element R is prepared, and then the above-mentioned substitution element Cu or Cu and Co
And heat treatment is performed by adding part or all of the above.

Conventionally, when a part of Fe is replaced by a divalent ion such as Co or Cu, or a part of Ba or Sr is replaced by a trivalent ion such as La, from the viewpoint of charge compensation, F
It is necessary to simultaneously perform a part of e and a part of Ba or Sr, etc.
It has been thought that it is necessary to perform charge compensation at a constant rate.

The present inventor is not bound by the technical common sense, and is in a state where the charge compensation is not completely performed, that is, compared with the amount of replacing a part of the element A with the element R.
The present inventors have found that a hexagonal M-type magnetoplumbite structure ferrite can be obtained even when the amount of substituting a part of e with a divalent ion such as Co or Cu is significantly small, or even when the substituting is not performed. I came to imagination.

That is, since the concept of the conventional charge compensation has been released, even if only a part of the element A is replaced with the element R, it is difficult to obtain a material such as orthoferrite (RFeO ₃ ) or hematite (α-Fe ₂ O ₃ ). Hexagonal M without formation of foreign phase
Type magnetoplumbite structure ferrite can be obtained, and by adding a Cu oxide or a Cu and Co oxide to the ferrite, the same effect as in the case where conventional charge compensation is performed can be obtained, and It has been found that the amount of addition can be significantly smaller than the amount of addition of Cu oxide or Cu and Co oxide required for conventional charge compensation, and led to the present invention. Was.

The ferrite according to the present invention contains Cu as an essential element. By adding Cu,
The effect of improving the density of the sintered body and increasing the residual magnetic flux density Br is obtained. Further, it was found that the coercive force did not decrease so much. The addition of Cu may be performed after forming the calcined ferrite without adding Cu. According to the experiment of the present inventor, preferable characteristics were obtained when Cu was added after the formation of the calcined ferrite body.

Note that, apart from the concept of charge compensation, the magnetic properties may be degraded depending on the ratio of each substitution element. Therefore, it is necessary to add each substitution element at an optimum ratio. In the present invention, the magnetic properties have been successfully improved by adding a predetermined amount of each of the substitution elements so as to obtain the optimum addition ratio and optimizing the manufacturing method, composition, additives and the like.

The oxide magnetic material of the present invention has the following formula 1:
x) AO · (x / 2 ) R 2 O 3 · (n-y / 2-y '/
2) represented by Fe ₂ O ₃ .yCoO.y'CuO, 0.0
2 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0.01 ≦ y ′
It is a ferrite having an M-type magneto-privite structure that substantially satisfies the relationship of ≦ 0.35, 5.0 ≦ n ≦ 6.7.

The oxide magnetic material of the present invention has the following formula 2:
(1-x) AO · ( x / 2) R 2 O 3 · (n-y / 2-
y ′ / 2) represented by Fe ₂ O ₃ .yCoO.y′CuO;
0.02 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0 ≦ y ′
After preparing a ferrite having a substantially M-type magneto-privite structure satisfying the relationship of ≦ 0.35, 5.0 ≦ n ≦ 6.7, an oxide of Cu or Cu and Co (I.e., Cu oxide and Co oxide) are added, and a second heat treatment is performed by calcination and / or sintering. The existence form can take various forms such as a calcined body, a magnet powder, a bonded magnet, a sintered magnet, and a magnetic recording medium.

The improvement of the magnetic properties is more remarkable when Sr is selected than when Ba, Pb or Ca is selected as the element A. Therefore, as element A, Sr
Is desirably selected as an essential component. However, depending on the application, it is more advantageous to select Ba or the like from the viewpoint of cost reduction.

As the element R, when La is selected, the improvement of the magnetic properties is most remarkable. Therefore, it is desirable to select only La as the element R. However, depending on the use, from the viewpoint of cost reduction, it is preferable that La is essential, and a rare earth element including Y, Bi and the like are selectively added.

In the above formulas 1 and 2, if x is smaller than the above range, the replacement amount of the element A by the element R becomes small, and the improvement of the magnetic properties becomes small. Conversely, if x is larger than the above range, the magnetic properties deteriorate and
The cost rises. Further, at the stage of producing the ferrite represented by the above formula 2, a different phase such as orthoferrite or hematite is produced, causing grain growth in the second heat treatment by calcination and / or sintering, and the like. The characteristics deteriorate. Therefore, x is 0.02 ≦ x ≦ 0.3
5, preferably in the range of 0.05 ≦ x ≦ 0.3
More preferably, it is 0.

In the above formulas 1 and 2, y and y '
Is smaller than the above range, the substitution amount of the element A by the element R becomes small, and the improvement of the magnetic properties becomes small. On the other hand, if y and y 'are too large, a different phase such as spinel ferrite will be generated, deteriorating magnetic properties and increasing costs. Therefore, the above equation 1
In the formula, y and y ′ are 0 ≦ y ≦ 0.35, 0.01
≦ y ′ ≦ 0.35, preferably 0.05
It is more preferable that 3 ≦ y ≦ 0.30 and 0.02 ≦ y ′ ≦ 0.30. Further, in the above formula 2, y and y ′ are preferably in the range of 0 ≦ y ≦ 0.35, 0 ≦ y ′ ≦ 0.35, and 0 ≦ y ≦ 0.30, 0 ≦ y ′ ≦
More preferably, it is 0.30.

The amount of Cu oxide or Cu and Co oxide added to the ferrite represented by the above formula 2 is preferably 0.06% by weight or more and 6.0% by weight or less. The more preferable addition amount of Cu oxide or Cu and Co oxide is 0.32% by weight or more and 5.1% by weight or less.

If the addition amount of these oxides is too small,
Since the effect of the addition is small, the improvement of the magnetic properties becomes insufficient. Conversely, if the addition amount is too large, not only will the magnetic properties deteriorate, but also the material costs will increase.

Assuming that the molar amount of Co to be added to 1 mol of the ferrite represented by the above formula 2 is Y and the molar amount of Cu to be added is Y ′, if (Y + Y ′) / x is too small, Since the effect of the addition is small, the improvement of the magnetic properties is small. On the other hand, if (Y + Y ′) / x is too large, the magnetic properties deteriorate and the cost increases. Therefore,
Preferably, the relationship of 0.2 ≦ (Y + Y ′) / x ≦ 0.8 is satisfied, and more preferably, the relationship of 0.3 ≦ (Y + Y ′) / x ≦ 0.8 is satisfied.

If n in the above formulas 1 and 2 is too small, the nonmagnetic phase containing the element A will increase, and if n is too large, hematite and the like will increase, deteriorating the magnetic properties. With respect to this n, conventionally, the stoichiometric composition of hexagonal M-type magnetoplumbite structure ferrite is n
= 6, a single-phase M-type magnetoplumbite structure ferrite can be obtained in the range of n ≦ 6. However, if n exceeds 6 a little, a different phase such as hematite is generated, and the magnetic properties deteriorate. Was thought. For this reason,
Ferrites having a hexagonal M-type magnetoplumbite structure have been produced under conditions where n ≦ 6.

However, the present inventors have found that in the oxide magnetic material of the present invention, a single-phase M-type magnetoplumbite structure ferrite can be obtained even in the range of n> 6, and the magnetic properties are improved. . Specifically, 5.0 <n ≦
Although it may be 6.7, it is preferable that 6.0 <n ≦ 6.7.

In the ferrite magnet of the present invention,
The constituent ratio of each of the element A, the element R, Fe, Co, and Cu is preferably in the following range with respect to the total amount of the elements A, R, Fe, Co, and Cu.

A: 4.5 at% to 9.0 at% R: 0.13 at% to 3.2 at% Fe: 86.3 at% to 93.0 at% Co: 0 at% Not less than 3.2 at% and Cu: not less than 0.06 at% and not more than 3.2 at%.

Next, an example of the method for producing a magnet powder according to the present invention will be described.

First, a powder of SrCO ₃ , BaCO ₃ , PbO or CaCO _{3 and} a powder of Fe ₂ O ₃ were mixed (1-0.0
2) Mix at a molar ratio ranging from 5.0 to (1−0.35): 6.7. At this time, an oxide of a rare earth element containing Y, at least one oxide of Bi ₂ O ₃ , an oxide of Cu, and an oxide of Co are added to the raw material powder.

The addition of the rare earth element containing Y and Bi, Cu, and Co can be added as respective oxide powders as described above. However, a compound that becomes an oxide in a subsequent calcination step (for example, carbonate) Powders and solutions of salts, hydroxides, nitrates, chlorides, etc.) can also be added. Also, S
Rare earth elements including r, Ba, Pb, Ca, Y, Bi, C
A compound composed of at least two elements selected from the group consisting of o, Cu and Fe may be added.

A boron compound (B
₂ O ₃ or H ₃ BO ₃ ) may be added. Further, cobalt hydroxide such as Co (OH) ₂ and / or Co (OH) ₃ may be used as a raw material of Co, or S
Rare earth elements including r, Ba, Pb, Ca, Y, Bi, C
A sulfate of at least one element selected from the group consisting of o, Cu and Fe may be used. By using these additives and raw materials, M
The reactivity to the ferrite phase of the magnetoplumbite structure is improved, and the magnetic properties are improved. This effect has been
This is remarkable in the range of n> 6 in the above formulas 1 and 2 where it was considered that a single phase of the ferromagnetic magnetoplumbite structure was not obtained and good magnetic properties were not obtained.

If necessary, Ba may be added to the above raw material powder.
Other chloride compounds including Cl _{2 and the} like may be added at about 3% by weight.

In addition to the above raw material powder, if necessary, other compounds such as Si, Ca, Pb, Al, Ga, Cr,
Sn, In, Co, Ni, Ti, Mn, Cu, Ge,
A compound containing V, Nb, Zr, Li, Mo, Bi, and / or a rare earth element (including Y) may be added in an amount of about 3% by weight or less. Further, impurities such as unavoidable components may be contained in a small amount.

In the present specification, the step of preparing the raw material mixed powder means not only the case where the raw material mixed powder is prepared from the beginning, but also the case where the raw material mixed powder prepared by a third party is purchased. And the case of mixing powder produced by a third party.

The mixed raw material powder is then heated to 1100 ° C. or higher using a batch furnace, a continuous furnace, a rotary kiln or the like.
The ferrite compound is heated to a temperature of 50 ° C. or lower and forms an M-type magnetoplumbite ferrite compound by a solid-phase reaction.
In this specification, this process is referred to as “calcination” or “first-stage calcination”, and the obtained compound is referred to as “calcined body” or “first-stage calcination”. Here, the term "first stage" is used because once a calcined body of ferrite is formed, C
This is because when adding a part or all of the oxide of u or the oxides of Cu and Co, it is distinguished from “calcination (second-stage calcination)” performed after the addition. Simply "calcination"
Means "first stage calcined" and "calcined body"
Means "the first-stage calcined body".

The calcination time may be from 1 second to 10 hours, preferably from 0.5 hour to 3 hours.

In the calcination step, a ferrite phase is formed by a solid phase reaction with an increase in temperature, and the formation of the ferrite phase is completed at about 1100 ° C. When the calcining step is completed at a temperature of about 1100 ° C. or lower, unreacted hematite remains, so that the magnet characteristics deteriorate. When the calcination temperature exceeds 1100 ° C, the effect of the present invention is exhibited,
The effect of the present invention is that the calcination temperature is 1100 ° C. or higher and 1150 ° C.
When the temperature is lower than ° C., the effect is relatively small, and the effect increases as the temperature increases. However, the calcining temperature is 1350
If the temperature exceeds ℃, the crystal grains may grow too much, which may cause inconveniences such as a long time required for pulverization in the pulverization step.

From the above, it is preferable that the calcining temperature be set in the range of 1150 ° C. to 1350 ° C.

The calcined body of the M-type magnetoplumbite structure ferrite according to the present invention can also be produced by a spray pyrolysis method in which a mixed solution in which the raw material components are dissolved is sprayed in a heated atmosphere, and calcination is performed. . In this case, the mixed solution comprises at least one element selected from the group consisting of Sr, Ba, Pb and Ca, and at least one element selected from the rare earth element containing Y and the chloride of Bi. It is produced by dissolving elemental chloride, Fe chloride, Cu chloride, and Co chloride.

Hereinafter, an example of a method for producing a powder of a calcined ferrite body by the spray pyrolysis method will be described.

First, a solution of strontium chloride and ferrous chloride was prepared by mixing (1-0.
02): 10.0 to (1−0.35): 13.4. At this time, a chloride solution of La, a chloride solution of Cu, and a chloride solution of Co are added to the mixed solution to prepare a spray solution.

The spray solution can be prepared by preparing a chloride solution for each of the following raw material element groups and mixing them.

1. A carbonate of at least one element selected from the group consisting of Sr, Ba, Pb, and Ca;
Nitrate, sulfate, chloride, or oxide.

2. A carbonate of at least one element selected from the group consisting of rare earth elements including Y and Bi;
Nitrate, sulfate, chloride, or oxide.

3. Carbonates of Fe, Cu, and Co;
Nitrates, chlorides, hydroxides, oxides, or metals.

As described above, the spray solution may be prepared by mixing a chloride solution of each raw material element.
It is also efficient to directly dissolve the raw material compound in the ferrous chloride solution.

As the ferrous chloride solution, it is also possible to use waste acid generated when pickling a steel plate or the like in a rolling process of an ironworks.

The spray solution may contain other compounds containing boron compounds (such as B ₂ O ₃ and H ₃ BO ₃ ) in an amount of about 1% by weight or other compounds, for example, Si, Ca, Pb, Al, G
a, Cr, Sn, In, Co, Ni, Ti, Mn, C
A compound containing u, Ge, V, Nb, Zr, Li, Mo, Bi, and / or a rare earth element (including Y) may be added at about 3% by weight or less. Further, impurities such as unavoidable components may be contained in a small amount.

The prepared spray solution was applied to a roasting furnace or the like for 8 hours.
Drying and calcination are performed simultaneously by spraying into a heating atmosphere at a temperature of from 00 ° C. to 1400 ° C. to form a calcined body of M-type magnetoplumbite ferrite. If the temperature of the heating atmosphere is too low, unreacted hematite or the like remains, while if it is too high, magnetite (FeFe ₂ O ₄ ) is generated or the composition deviation of the formed ferrite calcined body tends to occur. The temperature of the heating atmosphere is 900 ° C or higher1
The temperature range is preferably 300 ° C. or lower, more preferably 10 ° C.
It is not less than 00 ° C and not more than 1200 ° C.

If the above powder solution is calcined using a hydrochloric acid recovery device in an ironworks, a calcined body by spray pyrolysis can be efficiently produced.

The calcined body obtained by these calcining steps
Is (1-x) AO. (X / 2) R _TwoO_Three・ (Ny / 2
-Y '/ 2) Fe_TwoO_Three・ YCoO ・ y'CuO
Having a substantially M-type magnetoplumbite structure.
Is a cellite.

By performing a pulverizing step of pulverizing and / or pulverizing the calcined M-type magnetoplumbite ferrite, a ferrite magnet powder according to the present invention can be obtained. The average particle size is preferably 2 μm or less, more preferably 0.2 μm or more and 1 μm. A more preferable range of the average particle size is 0.4 μm or more and 0.9 μm or less. In addition, these average particle sizes are measured by the air permeation method.

Instead of using the above ferrite magnet powder as a raw material powder for a sintered magnet, it can be used as a magnet powder for a bonded magnet or a magnetic recording medium, for example.

After the first-stage calcined body is formed, Cu, which is a substitution element, or a ferrite calcined body to which some or all of Cu and Co are added is used as a magnet powder for a bonded magnet or a magnetic recording medium. In this case, it is preferable that the obtained ferrite magnet powder is calcined again ("second-stage calcination"), and further pulverized and / or crushed. In other cases, the second-stage calcining step and the pulverizing step may be performed in order to obtain a more uniform magnet powder.

The calcination temperature in the second-stage calcination step is lower than the calcination temperature in the first-stage calcination step since the M-type magnetoplumbite structure has already been generated in the first-stage calcination step. And may be in the range of 900 ° C to 1450 ° C. In order to suppress the growth of crystal grains, the second stage calcination temperature is desirably 900 ° C. or more and 1200 ° C. or less. The calcination time may be about 1 second to 10 hours, preferably 0.5 hour to 3 hours.

A bonded magnet can be manufactured by subjecting the above ferrite magnet powder to a heat treatment, and then mixing and hardening with various binders such as flexible rubber and hard and light plastics. In this case, after the magnet powder of the present invention is kneaded with a binder, molding is performed. During kneading, it is preferable to add various known dispersants and surfactants in a solid content ratio of 0.2% by weight or more and 2.0% by weight or less. The molding process is performed in a magnetic field or in a non-magnetic field by a method such as injection molding, extrusion molding, and roll molding.

The heat treatment is performed in order to remove the crystal strain introduced into the calcined body particles during the step of pulverizing the calcined body.
By the heat treatment at 700 ° C. or more, the crystal strain in the calcined body particles is relaxed, and the coercive force is restored. However, when the heat treatment is performed at 1100 ° C. or more, the coercive force decreases because the powder starts to grow. The magnetization increases with the coercive force up to a heat treatment temperature of 1000 ° C., but decreases above this temperature due to a decrease in the degree of orientation. It is considered that the reason for this is that fusion of the powder particles occurs. From the above, it is preferable that the heat treatment be performed at a temperature of 700 ° C. to 1100 ° C. for 1 second to 3 hours. A more preferable range of the heat treatment temperature is 900 ° C. or more and 1000 ° C. or less.

Further, after the above-mentioned ferrite magnet powder is subjected to a heat treatment, it is kneaded with various known binders and applied, whereby a coating type magnetic recording medium can be produced.

Next, a method of manufacturing a ferrite magnet according to the present invention will be described.

First, an M-type magnetoplumbite ferrite calcined body is manufactured by the method described above. Next, if necessary, an oxide of Cu or an oxide of Cu and Co is added to the calcined body, and then the calcined body is subjected to a fine pulverization process using a vibration mill, a ball mill and / or an attritor. Has an average particle size of 0.2 μm measured by an air permeation method.
The particles are pulverized into fine particles having a size in a range of not less than m and not more than 2.0 μm. The average particle size of the fine particles is preferably 0.4 μm or more and 0.9 μm or less (air permeation method). The fine grinding process is
Dry grinding (coarse grinding exceeding 1 μm) and wet grinding (1 μm
It is preferable to carry out in combination with the following pulverization.

As a Co raw material added at the time of pulverization,
Cobalt hydroxide may be used. Further, another compound including a boron compound or a sulfate may be added.

The obtained finely pulverized ferrite powder may be subjected to a second-stage calcining step and a pulverizing step in order to obtain a more uniform ferrite magnet powder.

First, when producing a sintered magnet, the above temporary
When performing the pulverization process for the fired body,
For the purpose, CaO, SiO_Two, Cr_TwoO_ThreeAnd A
l_TwoO _Three(CaO: 0.3% by weight or more and 1.5% by weight or less,
SiO_Two: 0.2% by weight or more and 1.0% by weight or less, Cr_TwoO
_Three: 0 wt% or more and 5.0 wt% or less, Al_TwoO_Three: 0 weight
% Or more and 5.0% by weight or less).

For wet grinding, an aqueous solvent such as water or various non-aqueous solvents can be used. During wet grinding, a slurry in which the solvent and the calcined body powder are mixed is generated. It is preferable that various known dispersants and surfactants are added to the slurry in a solid content ratio of 0.2% by weight or more and 2.0% by weight or less. In the pulverization step, other compounds including Bi ₂ O _{3 and the} like may be added in an amount of about 1% by weight or less.

Thereafter, press molding is performed in a magnetic field or in a non-magnetic field while removing the solvent in the slurry. Or
After the slurry is dried, crushed, granulated, etc., it is press-formed in a magnetic field or in a non-magnetic field.

After the press forming, a ferrite magnet product is finally completed through known manufacturing processes such as a degreasing step, a sintering step, a processing step, a washing step, and an inspection step. The sintering step may be performed in air at a temperature of, for example, 1100 ° C. or more and 1250 ° C. or less for 0.5 hour or more and 2 hours or less.
The average particle size of the sintered magnet obtained in the sintering step is, for example, 0.1.
5 μm or more and 2.0 μm or less.

Thus, first, (1-x) AO. (X /
_{2) R 2 O 3 · (} n-y / 2-y '/ 2) Fe 2 O 3 · yC
After producing a ferrite represented by oO.y'CuO and having a substantially M-type magnetoplumbite structure, an oxide of Cu or an oxide of Cu and Co is added at the time of pulverization. According to the method of performing heat treatment by sintering and / or sintering, even if ferrite having an M-type magnetoplumbite structure, which is a base material, is a material having a certain composition, Cu oxide or oxidation of Cu and Co during pulverization. By appropriately changing the amount of addition of a substance or the like, ferrite magnets having a wide range of magnetic characteristics can be easily manufactured and separated, which is very advantageous for a manufacturing process for manufacturing ferrite magnets having various magnetic characteristics. Further, when Cu or Cu and Co are added after the first-stage calcination, there is an advantage that the degree of progress of grain growth during the calcination process can be suppressed. For this reason, these elements are not added before the first-stage calcination, or
It is preferable to reduce the amount to be added before the stage calcination and to add after the second stage calcination (Cu or post-addition of Cu and Co).

The rotating machine of the present invention is characterized in that it has a ferrite magnet manufactured by the above method, and its specific structure is the same as that of a known rotating machine. May be.

Further, when used for the magnetic recording medium of the present invention, it is preferable to use a sputtering method for forming the thin film magnetic layer. The above ferrite magnet may be used as a target for sputtering. Further, an oxide of each element may be used as a target. By subjecting the thin film formed by the sputtering method to heat treatment, the ferrite thin film magnetic layer of the present invention can be manufactured.

[0102]

The present invention will be described below with reference to examples.

(Example 1) First, (1-x) SrO ·
(X / 2) La_TwoO_Three-(Ny / 2-y '/ 2) Fe_Two
O_ThreeIn the composition of yCoO.y'CuO, 0.05
≦ x ≦ 0.5, y = 0.05, 0 ≦ y ′ ≦ 0.45, x
= Y + y ', n = 6.0 so that SrCO _ThreePowder,
La_TwoO_ThreePowder, Fe_TwoO_ThreePowder, Co_ThreeO_FourPowder and Cu
Various raw material powders of O powder were blended. The obtained raw material powder
The mixture was pulverized with a wet ball mill for 4 hours, dried and sized. So
After that, calcine at 1300 ° C for 3 hours in the air.
Thus, a calcined body magnet powder was produced.

Next, CaC was added to the calcined magnet powder.
0.7% by weight of O ₃ powder and 0.4% by weight of SiO ₂ powder were added, and finely pulverized by a wet ball mill using water as a solvent until the average particle size by an air permeation method became 0.55 μm.

Thereafter, press forming was performed in a magnetic field while removing the solvent in the finely pulverized slurry. The molded body was placed in air
Sintering was performed at 00 ° C. for 30 minutes to produce a sintered magnet. Also,
Similarly to the above method, (1-x) SrO. (X / 2)
La ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCo
In the composition of O.y'CuO, x = 0.02, y =
A sample in which 0, y '= 0.01 and n = 6.0 (sample 1) and a sample in which x = y = y' = 0 and n = 6.0 (comparative example 1) were also prepared.

[0106] The sintered magnet thus obtained were measured and the B _r and H _cJ. FIG. 1 shows the measurement results. As is clear from FIG. 1, sample 1 and 0.05 ≦ x ≦
It can be seen that high characteristics are obtained in the range of 0.35.

In the same manner as in the above method, a C-shaped sintered magnet for a motor was prepared, and this was replaced with a sintered magnet of a conventional material and incorporated into a motor, and operated under rated conditions. Properties were obtained. When the torque was measured, the torque was higher than that of a motor using a conventional sintered magnet made of a material.

Further, by the spray pyrolysis method, (1-x) S
rO · (x / 2) La 2 O 3 · (n-y / 2-y '/ 2)
In the composition of Fe ₂ O ₃ .yCoO.y'CuO, 0.1%
05 ≦ x ≦ 0.5, y = 0.05, 0 ≦ y ′ ≦ 0.4
5. A calcined body powder was prepared so that x = y + y 'and n = 6.0, and a sintered magnet was prepared in the same manner as described above. As a result, a result similar to that of the sintered magnet of this example was obtained.

A magnetic recording medium having a thin-film magnetic layer was produced by sputtering using the above-mentioned sintered magnet as a target. As a result, a high output and a high S / N were obtained.

(Example 2) (1-x) SrO. (X /
2) La ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .y
In the composition of CoO.y'CuO, 0.05 ≦ x ≦
0.5, 0 ≦ y ≦ 0.45, y ′ = 0.05, x = y +
y ', except that blending various raw material powders such that n = 6.0 in the same manner as in Example 1 to prepare a sintered body, the sintered magnet obtained, measuring the B _r and H _cJ did. FIG. 2 shows the measurement results. As is clear from FIG.
It can be seen that high characteristics are obtained in the range of 0.05 ≦ x ≦ 0.35.

Example 3 (1-x) SrO. (X /
2) La ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .y
In the composition of CoO.y'CuO, x = 0.2, y =
A sintered body was prepared in the same manner as in Example 1 except that various raw material powders were blended so that 0.15, y ′ = 0.05, and 4.5 ≦ n ≦ 7.5. for sintered magnet, to measure the B _r and H _{c J.} FIG. 3 shows the measurement results. As is clear from FIG. 3, it can be seen that high characteristics are obtained in the range of 5.0 ≦ n ≦ 6.7.

Example 4 First, (1-x) SrO.
_{(X / 2) La 2 O} 3 · (n-y / 2-y '/ 2) Fe 2
In the composition of O ₃ .yCoO.y'CuO, x = 0.
2. A calcined body magnet powder was produced in the same manner as in Example 1 except that various raw material powders were blended so that y = y ′ = 0 and n = 6.0.

With respect to these calcined body magnet powders, assuming that the added molar amount of Co is Y and the added molar amount of Cu is Y 'with respect to 1 mol of the calcined body magnet powder, 0 ≦ Y ≦ 0.
15, 0 ≦ Y ′ ≦ 0.15, 0 ≦ (Y + Y ′) / x ≦
1.5, Co ₃ O ₄ powder and Cu so that Y = Y ′
O powder was added, and thereafter a sintered body was produced in the same manner as in Example 1.

[0114] The sintered magnet thus obtained were measured and the B _r and H _cJ. FIG. 4 shows the measurement results. As is clear from FIG. 4, 0.2 ≦ (Y + Y ′) / x ≦ 0.8
In the range, high characteristics are obtained.

Example 5 (1-x) SrO · (x /
2) La ₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .y
In the composition of CoO.y'CuO, x = 0.2, y =
Various raw material powders were blended so as to be 0.15, y '= 0.05, and n = 6.0, and the mixture was pulverized with a wet ball mill for 4 hours, dried and sized, and then dried in the air at 1000 ° C. to 1500 ° C. After calcination at 3 ° C. for 3 hours, a sintered body was produced in the same manner as in Example 1.

[0116] The sintered magnet thus obtained were measured and the B _r and H _cJ. FIG. 5 shows the measurement results. As is clear from FIG. 5, the calcination temperature was 1100 ° C. or higher and 1450 ° C.
High characteristics are obtained in the range of not more than ℃.

(Example 6) In the same manner as in Example 1, (1
-X) SrO · (x / 2 ) La 2 O 3 · (n-y / 2-
y ′ / 2) In the composition of Fe ₂ O ₃ .yCoO.y′CuO, x = 0.2, y = 0.15, y ′ = 0.05, n
= 6.0, and finely pulverized by a wet ball mill using water as a solvent until the average particle size by an air permeation method becomes 1.0 µm. Thereafter, drying and crushing were performed, and heat treatment was performed at 500 ° C. to 1200 ° C. to produce a ferrite magnet powder.

[0118] The obtained powder of the B _r and H _cJ measured at a vibrating sample magnetometer (VSM). The result is shown in FIG. FIG. 6 shows that H _cJ increases with the heat treatment at 1100 ° C. or lower, and decreases at a temperature higher than this temperature. On the other hand, it can be seen that the magnetization increases with the coercive force up to about 1000 ° C., but decreases above this temperature.

A bonded magnet having a shape for a motor was prepared from the above ferrite magnet powder, and this was mounted in a motor instead of a bonded magnet of a conventional material, and operated under rated conditions. As a result, good characteristics were obtained. . Also, when the torque was measured, it was higher than that of a motor using a conventional bonded magnet made of a material.

When the above ferrite magnet powder was used for a magnetic recording medium, a high output and a high S / N were obtained.

(Example 7) In the same manner as in Example 1, (1
-X) SrO · (x / 2 ) La 2 O 3 · (n-y / 2-
y ′ / 2) In the composition of Fe ₂ O ₃ .yCoO.y′CuO, x = 0.2, y = 0.15, y ′ = 0.05, n
= 6.0, CaO, SiO ₂ , Cr ₂ O ₃ and Al ₂ O ₃ were added to this as shown in Table 1 and pulverized. In the same manner as in Example 1, a sintered body was produced. Measurement results of the B _r and H _cJ of the resultant sintered magnets are shown in Table 1.

[0122]

[Table 1]

(Example 8) As a Co raw material,_ThreeO_FourPowder
Instead of Co (OH)_ThreeExample 3 except that powder was used
A sintered body was prepared in the same manner as described above.
And that B_rAnd H_cJWas measured. Fig.
FIG. As is clear from FIG. _ThreeO_FourPowder
Instead Co (OH)_ThreeUsing powder gives better properties
Was done. Co (OH)_ThreeIn the case of using powder, in particular, 6.0
Excellent characteristics are shown in the range of <n ≦ 6.7.

Also, (1-x) SrO. (X / 2) La
₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO.
In the composition of y'CuO, x = 0.2, y = y '=
A calcined body magnet powder was prepared in the same manner as in Example 1 except that various raw material powders were blended so as to satisfy 0, 4.5 ≦ n ≦ 7.5. With respect to 1 mol of the calcined body magnet powder, the added molar amount of Co is Y, C
When the added molar amount of u is Y ′, Y = 0.1, Y ′ ≦
0.05, so that Co (OH) ₃ powder and Cu
O powder was added, and thereafter a sintered body was produced in the same manner as in Example 1. As a result, a result similar to that of the sintered magnet of this example was obtained.

[0125] Also, by making each sample 2-11 below, the sintered magnet thus obtained were measured and the B _r and H _cJ. Table 2 shows the measurement results. Sintered body of each sample, (1-x) SrO · (x / 2) La 2 O 3 · (n
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
X = 0.2, y = 0.15, y ′ =
The production was performed in the same manner as in Example 1 except that various raw material powders were blended so that 0.05 and n = 6.2.

Sample 2: SrCO ₃ as Sr raw material
Was added with 0.5% by weight of SrSO ₄ .

Sample 3: SrCO ₃ as Sr raw material
Was added to part of the mixture by adding 1.0% by weight of SrSO ₄ .

Sample 4: SrCO ₃ as Sr raw material
Was added 2.0% by weight of SrSO ₄ .

Sample 5: 0.2 wt% of H ₃ BO ₃ was added when blending various raw material powders.

Sample 6: 0.5 wt% of H ₃ BO ₃ was added when compounding various raw material powders.

Sample 7: When blending various raw material powders, 1.0% by weight of H ₃ BO ₃ was added.

Sample 8: Co (OH) ₃ powder was used as the Co raw material instead of Co ₃ O ₄ powder, and 1.0 wt% of SrSO ₄ was added to a part of SrCO ₃ as the Sr raw material.

Sample 9: Co (OH) ₃ powder was used instead of Co ₃ O ₄ powder as a Co raw material, and 0.5 wt% of H ₃ BO ₃ was added when compounding various raw material powders.

Sample 10: Co ₃ O ₄ as a Co raw material
Co (OH) ₃ powder was used in place of the powder, 1.0% by weight of SrSO ₄ was used as a part of SrCO ₃ as Sr raw material
In addition, 0.5 wt% of H ₃ BO ₃ was added when compounding various raw material powders.

Sample 11: SrSO ₄ , H ₃ BO ₃ ,
Co (OH) ₃ or the like is not used.

[0136]

[Table 2]

[0137]

According to the present invention, a hexagonal M-type magnetoplumbite structure ferrite is obtained by substituting a part of Sr or the like with an element R and replacing a part of Fe with Cu or C.
By substituting with u and Co, the magnetic properties of the ferrite magnet can be improved while achieving a low manufacturing cost.

[Brief description of the drawings]

FIG. 1 (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(0.05 ≦ x ≦ 0.5, y = 0.05, 0 ≦ y ′ ≦
0.45, x = y + y ′, n = 6.0), for the sintered magnet according to the present invention, the composition ratio x and the residual magnetic flux density B
₆ is a graph showing the relationship between _r and the coercive force _HcJ .

FIG. 2 shows the relationship between (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(0.05 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.45, y ′ =
0.05, x = y + y ′, n = 6.0) for the sintered magnet according to the present invention, the composition ratio x and the residual magnetic flux density B
₆ is a graph showing the relationship between _r and the coercive force _HcJ .

FIG. 3 (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(X = 0.2, y = 0.15, y ′ = 0.05, 4.5
For the sintered magnet of the present invention represented by ≦ n ≦ 7.5), is a graph showing the relationship between the residual magnetic flux density B _r and coercivity H _cJ composition ratio n.

FIG. 4: (1-x) SrO · (x / 2) La_TwoO_Three・ (N
-Y / 2-y '/ 2) Fe_TwoO_Three・ YCoO ・ y'CuO
(X = 0.2, y = y ′ = 0, n = 6.0)
Ferrite with M-type magnetoplumbite structure
Per unit, Co _ThreeO_FourTo Y / 3 mol, CuO
Y ′ mol (0 ≦ Y ≦ 0.15, 0 ≦ Y ′ ≦ 0.15, 0
≦ (Y + Y ′) / x ≦ 1.5, Y = Y ′)
For the sintered magnet according to Akira, the composition ratio (Y + Y ') / x
Residual magnetic flux density B_rAnd coercive force H_cJA graph showing the relationship with
It is.

FIG. 5: (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(X = 0.2, y = 0.15, y ′ = 0.05, n =
For the sintered magnet of the present invention represented by 6.0) is a graph showing the relationship between the calcining temperature and the residual magnetic flux density B _r and coercivity H _cJ.

FIG. 6: (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(X = 0.2, y = 0.15, y ′ = 0.05, n =
6.0), the heat treatment temperature, the residual magnetic flux density _Br, and the coercive force H
It is a graph which shows the relationship with _cJ .

FIG. 7: (1-x) SrO. (X / 2) La ₂ O _3. (N
-Y / 2-y '/ 2 ) Fe 2 O 3 · yCoO · y'CuO
(X = 0.2, y = y ′ = 0, 4.5 ≦ n ≦ 7.5) With respect to the ferrite magnet powder of the present invention, Co (OH) is used as a Co raw material instead of Co ₃ O ₄ powder. ) in ₃ if powder with a graph showing the relationship between the residual and the composition ratio n magnetic flux density B _r and coercivity H _cJ.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiichi Hosokawa 2- 15-17 Egawa, Shimamoto-cho, Mishima-gun, Osaka F-term in Sumitomo Special Metals Co., Ltd. Yamazaki Works (reference) 4G018 AA08 AA09 AA10 AA11 AA12 AA20 AA22 AA24 AA27 AA28 AA31 AA34 AA37 AB04 AB08 AC01 AC06 5E040 AB04 CA01 HB01 HB03 HB06 HB19 NN02 NN18 5E062 CD01 CD02 CF01 CG02

Claims (30)

[Claims] 1. An oxide magnetic material having a main phase of ferrite having a hexagonal M-type magnetoplumbite structure, comprising at least one element selected from the group consisting of Sr, Ba, Pb and Ca. R, Fe, Cu, or Cu and Co, which are at least one element selected from the group consisting of rare earth elements including A, Y and Bi, wherein A, R, Fe, Co, and Each constituent ratio of Cu is
A: 4.5 atomic% or more and 9.0 atomic% or less, R: 0.13 atomic% or more and 3.2 atomic% or less, with respect to the total element amount of A, R, Fe, Co, and Cu; An oxide magnetic material that satisfies the relationship of 86.3 at% to 93.0 at%, Co: 0 to 3.2 at%, Cu: 0.06 to 3.2 at%. . 2. The composition ratio of each of A, R, Fe, Co, and Cu is represented by the formula 1: (1-x) AO. (X / 2) R ₂
O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO.
Claimed by y'CuO and satisfying the relational expression 0.02≤x≤0.35 0≤y≤0.35 0.01≤y'≤0.35 5.0≤n≤6.7. 2. The oxide magnetic material according to 1. 3. The composition ratio of each of A, R, Fe, Co, and Cu is represented by the formula 2: (1-x) AO. (X / 2) R ₂
O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO.
expressed as y′CuO, 0.02 ≦ x ≦ 0.35, 0 ≦
y ≦ 0.35, 0 ≦ y ′ ≦ 0.35, 5.0 ≦ n ≦ 6.
7 or 0.06% by weight of an oxide of Cu and Co with respect to the oxide magnetic material satisfying the relational expression 7.
2. The oxide magnetic material according to claim 1, which is added in an amount of not less than 6.0% by weight. 4. The oxide magnetic material according to claim 2, wherein n is in the range of 6.0 <n ≦ 6.7. 5. A ferrite magnet powder comprising the oxide magnetic material according to claim 1. 6. SrCO_Three, BaCO_Three, PbO and C
aCO_ThreeAt least one raw material powder selected from the group consisting of:
Powder and oxide of rare earth element containing Y and Bi _TwoO_ThreeFrom
Raw material powder of at least one oxide selected from the group consisting of:
End and Fe_TwoO_ThreeRaw material powder and Co oxide raw material powder
And the raw material powder of Cu oxide by mixing
A step of preparing the prepared raw material mixed powder;
Calcined at a temperature, thereby obtaining (1-x) AO. (X /
2) R_TwoO_Three-(Ny / 2-y '/ 2) Fe_TwoO_Three・ YC
oO.y'CuO (A is Sr, Ba, Pb and Ca
At least one element selected from the group consisting of
At least one selected from the group consisting of rare earth elements containing Bi and Bi
Element of 0.02 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35,
0.01 ≦ y ′ ≦ 0.15, 5.0 ≦ n ≦ 6.7)
Forming a calcined body of ferrite having a composition.
A method for producing a calcined ferrite body. 7. SrCO_Three, BaCO_Three, PbO and C
aCO_ThreeAt least one raw material powder selected from the group consisting of:
Powder and oxide of rare earth element containing Y and Bi _TwoO_ThreeFrom
Raw material powder of at least one oxide selected from the group consisting of:
End and Fe_TwoO_ThreeRaw material powder and Co oxide raw material powder
And the raw material powder of Cu oxide by mixing
A step of preparing the prepared raw material mixed powder;
Calcined at a temperature, thereby obtaining (1-x) AO. (X /
2) R_TwoO_Three-(Ny / 2-y '/ 2) Fe_TwoO_Three・ YC
oO.y'CuO (A is Sr, Ba, Pb and Ca
At least one element selected from the group consisting of
At least one selected from the group consisting of rare earth elements containing Bi and Bi
Element of 0.02 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35,
0 ≦ y ′ ≦ 0.35, 5.0 ≦ n ≦ 6.7)
Forming a calcined body of ferrite to be formed;
Calcined body mixed with powder of u and Co oxide raw materials
Preparing a ferrite calcined body including a step of preparing a powder.
Construction method. 8. A chloride of at least one element selected from the group consisting of Sr, Ba, Pb and Ca, a rare earth element containing Y and a chloride of at least one element selected from the group consisting of Bi. Preparing a mixed solution in which a chloride of Fe, a chloride of Co, and a chloride of Cu are dissolved, wherein the mixed solution satisfies ph <6; and the mixed solution is 800 ° C. or more and 1400 ° C. or less. Calcined by spraying into a heated atmosphere of
(1-x) AO · ( x / 2) R 2 O 3 · (n-y / 2-
y ′ / 2) Fe ₂ O ₃ .yCoO.y′CuO (A is S
R is at least one element selected from the group consisting of r, Ba, Pb and Ca; R is at least one element selected from rare earth elements including Y and Bi; 0.02 ≦ x ≦
0.35, 0 ≦ y ≦ 0.35, 0.01 ≦ y ′ ≦ 0.3
5, a step of forming a calcined body of ferrite having a composition of 5.0 ≦ n ≦ 6.7). 9. A chloride of at least one element selected from the group consisting of Sr, Ba, Pb and Ca, a rare earth element containing Y and a chloride of at least one element selected from the group consisting of Bi. Preparing a mixed solution in which a chloride of Fe, a chloride of Co, and a chloride of Cu are dissolved, wherein the mixed solution satisfies ph <6; Calcined by spraying into a heated atmosphere of
(1-x) AO · ( x / 2) R 2 O 3 · (n-y / 2-
y ′ / 2) Fe ₂ O ₃ .yCoO.y′CuO (A is S
R is at least one element selected from the group consisting of r, Ba, Pb and Ca; R is at least one element selected from rare earth elements including Y and Bi; 0.02 ≦ x ≦
0.35, 0 ≦ y ≦ 0.35, 0 ≦ y ′ ≦ 0.35,
5.0 ≦ n ≦ 6.7) forming a calcined body of ferrite having a composition of: calcination by adding a Cu oxide raw material or a Cu and Co oxide raw material powder to the ferrite calcined body. Preparing a calcined ferrite body including a step of preparing a body mixed powder. 10. The method for producing a calcined ferrite according to claim 6, wherein cobalt hydroxide is used instead of the Co oxide. 11. The method for producing a calcined ferrite according to claim 8, wherein cobalt hydroxide is used instead of the chloride of Co. 12. The raw material mixed powder contains A, R, Fe,
The method for producing a calcined ferrite body according to claim 6, wherein a sulfate of at least one element selected from the group consisting of Co and Cu is added. 13. The mixed solution contains A, R, Fe, C
at least one selected from the group consisting of o, and Cu
The method for producing a calcined ferrite body according to claim 8, wherein a sulfate of a certain element is added. 14. In at least one of the step of preparing the raw material mixed powder, the step of preparing the mixed solution, and the step of pulverizing the calcined ferrite, B ₂ O ₃ and / or H ₃ method for producing a ferrite calcined body according to any one of claims 6 13, characterized in that the addition of BO _3. 15. A ferrite calcined body formed by the method for producing a calcined ferrite body according to claim 6, which has an average particle size of 0.2 μm or more as measured by an air permeation method. A method for producing a calcined ferrite body, comprising: forming a ground ferrite powder within a range of 0 μm or less; and calcining the ground ferrite powder at a temperature of 900 ° C. to 1450 ° C. 16. The method for producing a calcined ferrite according to claim 6, wherein n is in the range of 6.0 <n ≦ 6.7. 17. A calcined body formed by the method for producing a calcined ferrite body according to claim 6, wherein the calcined body has a mean particle size of 0.2 μm measured by an air permeation method.
A method for producing a magnet powder in a range of not less than 2.0 μm and not more than 2.0 μm. 18. The method according to claim 6, wherein:
A calcined body formed by a method for producing a calcined ferrite body
In addition, CaO, SiO_Two, Cr_TwoO_ThreeAnd Al_TwoO _Three(Ca
O: 0.3% by weight or more and 1.5% by weight or less, SiO_Two:
0.2% by weight or more and 1.0% by weight or less, Cr_TwoO_Three: 0 weight
% To 5.0% by weight, Al_TwoO_Three: 0% by weight or more5.
0% by weight or less)
And pulverizing the calcined body mixed powder and measuring the average value by an air permeation method.
The average particle size is in the range of 0.2 μm or more and 2.0 μm or less
Forming a ground ferrite powder
Powder manufacturing method. 19. A bonded magnet comprising the ferrite magnet powder according to claim 5. 20. A bonded magnet comprising a magnet powder produced by the method for producing a magnet powder according to claim 17 or 18. 21. A step of performing a heat treatment on the magnet powder produced by the method for producing a magnet powder according to claim 17; and a step of producing a bonded magnet from the magnet powder subjected to the heat treatment. A method for producing a magnet comprising: 22. The heat treatment is performed at 700 ° C. or higher and 1100 ° C.
The method for manufacturing a magnet according to claim 21, which is performed at the following temperature. 23. A sintered magnet comprising the ferrite magnet powder according to claim 5. A sintered magnet produced from the magnet powder produced by the method for producing a magnet powder according to claim 17 or 18. 25. A sintered magnet formed from the ferrite magnet powder according to claim 5, wherein the sintered magnet is CaO, SiO ₂ ,
It contains Cr ₂ O ₃ and Al ₂ O ₃ , and the added amount of each is as follows: CaO: 0.3 to 1.5% by weight, SiO ₂ : 0.2 to 1.0% by weight, Cr ₂ O ₃ : 0 to 5.0 wt%, Al ₂ O ₃ : 0 to 5.0 wt% sintered magnet. 26. A step of preparing a magnet powder produced by the method for producing a magnet powder according to claim 17; and concentrating, kneading, molding in a magnetic field or molding in a magnetic field, and sintering the magnet powder. And producing a sintered magnet. 27. A step of preparing a magnetic powder produced by the method for producing a magnetic powder according to claim 17; and concentrating, kneading, drying, pulverizing, molding in a magnetic field, or no magnetic field A method for producing a sintered magnet, comprising the steps of: forming and sintering. 28. The method for producing a sintered magnet according to claim 26, wherein a dispersant is added in a solid content ratio of 0.2% by weight or more and 2.0% by weight or less during pulverization or kneading. 29. A rotating machine provided with the sintered magnet according to claim 23. 30. The composition ratio of each of A, R, Fe, Co, and Cu is represented by the formula 2: (1-x) AO. (X / 2) R
₂ O _3. (Ny−2-y ′ / 2) Fe ₂ O ₃ .yCoO.
expressed as y′CuO, 0.02 ≦ x ≦ 0.35, 0 ≦
y ≦ 0.35, 0 ≦ y ′ ≦ 0.35, 5.0 ≦ n ≦ 6.
Assuming that the added molar amount of Co and the added molar amount of Cu are Y ′ and Y ′ with respect to 1 mol of the oxide magnetic material satisfying the relational expression 7, 0.2 ≦ (Y + Y ′) / x ≦ 2. The oxide magnetic material according to claim 1, wherein a relationship of 0.8 is satisfied.