JPH11154604A - Sintered magnet and motor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ferrite magnet having high residual magnetic flux density and high coercive force, by realizing hexagonal structured ferrite both in high saturated magnetization and magnetic anisotropy. SOLUTION: Assuming at least one kind of element selected from Sr, Ba, Ca and Ps including Sr without fail using hexagonal structured ferrite to be a main phase as A, as well as at least one kind of element selected from rare earth element (including Y) and Bi including La without fail as R also Co or Co and Zn as M, ferrite particles, sintered magnet, bonded magnet, magnetic recording medium, etc., are composed of oxide magnetic material in the composition wherein the total composition ratio of respective metallic elements of A, R, Fe to the total element amount are as follow. A, 1-13 atomic %; R, 0.05-10 atomic %; Fe, 80-95 atomic %; M, 0.1-5 atomic%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a magnet powder and a sintered magnet each having ferrite, a bonded magnet and a magnetic recording medium each containing the magnet powder,
The present invention relates to a magnetic recording medium having a thin-film magnetic layer containing a ferrite phase, and a motor using such a magnet.

[0002]

2. Description of the Related Art Oxide permanent magnet materials include hexagonal S
There are r ferrite and Ba ferrite, but at present, magnetoplumbite (M type) Sr ferrite or Ba ferrite is mainly used, and these sintered magnets and bonded magnets are manufactured.

[0003] Of the magnet properties, particularly important are the residual magnetic flux density (Br) and the intrinsic coercive force (HcJ).

[0004] Br is determined by the density of the magnet and its degree of orientation,
It is determined by the saturation magnetization (4πIs) determined by the crystal structure, and is expressed by Br = 4πIs × degree of orientation × density. The 4πIs of M-type Sr ferrite and Ba ferrite is about 4.65 kG. Density and degree of orientation,
Even in the case of the sintered magnet that can obtain the highest value, 98
% Is the limit. Therefore, Br of these magnets
Is limited to about 4.46 kG, and high B of 4.5 kG or more
Obtaining r has heretofore been virtually impossible.

The present inventors have disclosed in Japanese Patent Application Laid-Open No. Hei 9-115715 that by adding an appropriate amount of, for example, La and Zn to M-type ferrite, 4πIs can be increased up to about 200G.
It has been found that Br can be increased to 4.5 kG or more. However, in this case, since the anisotropic magnetic field ( _HA ) described later decreases, it was difficult to simultaneously obtain Br of 4.5 kG or more and HcJ of 3.5 kOe or more.

[0006] HcJ is an anisotropic magnetic field ｛H _A (= 2K ₁ / I
s) Product of｝ and single domain particle ratio (fc) (H _A × fc)
Is proportional to Here, K ₁ is a crystal magnetic anisotropy constant, which is a constant determined by the crystal structure, like Is. M type B
For a ferrite, K ₁ = 3.3 × 10 ⁶ erg / cm ³ , and for M-type Sr ferrite, K ₁ = 3.5 × 10 ⁶ er.
g / cm ³ . As described above, it is known that M-type Sr ferrite has the maximum K ₁ , but it has been difficult to further improve K ₁ .

On the other hand, when the ferrite particles are in a single magnetic domain state, it is necessary to rotate the magnetization against the anisotropic magnetic field in order to reverse the magnetization, and thus the maximum HcJ is expected. In order to convert the ferrite particles into single domain particles, it is necessary that the size of the ferrite particles be equal to or less than the critical diameter (dc) described below.

Dc = 2 (k · Tc · K ₁ / a) ^1/2 / Is
^Two

Here, k is the Boltzmann constant, Tc is the Curie temperature, and a is the distance between iron ions. In the case of M-type Sr ferrite, dc is about 1 μm. For example, when manufacturing a sintered magnet, it is necessary to control the crystal grain size of the sintered body to 1 μm or less. Conventionally, it has been difficult to realize such fine crystal grains at the same time as high density and high degree of orientation for obtaining high Br. However, the present inventors disclosed in Japanese Patent Application Laid-Open No. 6-53064 a new production method. A method was proposed, and it was shown that high characteristics could not be obtained. However, also in this method, when Br is 4.4 kG, H
The cJ was about 4.0 kOe, and it was difficult to maintain a high Br of 4.4 kG or more and simultaneously obtain a high HcJ of 4.5 kOe or more.

Further, in order to control the crystal grain size of the sintered body to 1 μm or less, it is necessary to reduce the grain size in the forming step to preferably 0.5 μm or less in consideration of the grain growth in the sintering step. is there. When such fine particles are used, there is a problem that productivity generally decreases due to an increase in molding time and cracks during molding. For this reason, it has been very difficult to achieve both high characteristics and high productivity.

On the other hand, in order to obtain a high HcJ, Al ₂ O ₃
It has been conventionally known that the addition of Cr ₂ O ₃ is effective. In this case, since Al ³⁺ and Cr ³⁺ have the effect of replacing Fe ³⁺ having an “upward” spin in the M-type structure to increase _HA and suppress grain growth, it is 4.5 kOe or more. High HcJ is obtained. However, the sintering density tends to decrease as Is decreases, so that the Br decreases significantly. For this reason, only about 4.2 kG Br was obtained at the maximum with a composition in which HcJ was 4.5 kOe.

Incidentally, the temperature dependency of HcJ of the conventional sintered M-type ferrite magnet was about +13 Oe / ° C., and the temperature coefficient was a relatively large value of about +0.3 to + 0.5% / ° C. For this reason, HcJ was greatly reduced on the low temperature side, and there was a case where demagnetization occurred. In order to prevent this demagnetization, it is necessary to set HcJ at room temperature to a large value, for example, about 5 kOe, so that it was practically impossible to obtain high Br at the same time. The temperature dependency of HcJ of the M-type ferrite powder is superior to that of the anisotropic sintered magnet.
At about 8 Oe / ° C., the temperature coefficient was + 0.15% / ° C. or higher, and it was difficult to further improve the temperature characteristics.

The present inventors have proposed in Japanese Patent Application Laid-Open No. Hei 6-53064 that the rate of temperature change of HcJ can be reduced by introducing crystal strain into ferrite particles by grinding. However, in this case, since the HcJ of the particles is also reduced, it is difficult to simultaneously achieve high HcJ and excellent temperature characteristics of HcJ even when M-type Sr ferrite having a submicron size is used.

Since ferrite magnets are excellent in environmental resistance and inexpensive, they are often used for motors used in various parts of automobiles. Automobiles are sometimes used in cold or extremely hot environments, and motors are also required to operate stably in such harsh environments. But,
As described above, the conventional ferrite magnet has a problem that the coercive force is significantly deteriorated in a low-temperature environment, and irreversible demagnetization called "low-temperature demagnetization" may occur.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to realize a hexagonal ferrite having high saturation magnetization and high magnetic anisotropy, thereby achieving a high residual magnetic flux which cannot be achieved by a conventional hexagonal ferrite magnet. An object of the present invention is to provide a ferrite magnet having a high density and a high coercive force. Another object of the present invention is to provide a ferrite magnet having a high residual magnetic flux density and a high coercive force, having extremely excellent temperature characteristics of the coercive force, and having a small decrease in the coercive force even in a low temperature range. is there. Another object of the present invention is to provide a particle size of 1 μm
An object of the present invention is to realize a ferrite magnet having a high residual magnetic flux density and a high coercive force by using relatively coarse ferrite particles exceeding the above. Another object of the present invention is to provide a magnetic recording medium having a high residual magnetic flux density and being thermally stable. Another object of the present invention is to provide a motor that can be reduced in size and weight with high efficiency and high torque.

[0016]

This and other objects are achieved by any one of the following constitutions (1) to (16). (1) A ferrite having a hexagonal crystal structure as a main phase and at least one element selected from Sr, Ba, Ca and Pb, which always contains Sr,
When at least one element selected from the rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M, A,
The composition ratio of the total of the metal elements of R, Fe and M is as follows: A: 1 to 13 atom%, R: 0.05 to 10 atom%, Fe: 80 to 95 atom%, M: : An oxide magnetic material having a composition of 0.1 to 5 atomic%. (2) when expressed as _{I A 1-x R x (} Fe 12-y M y) z O 19, 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.7 ≦ z ≦ 1.2, wherein the oxide magnetic material according to (1) above. (3) The oxide magnetic material according to (1) or (2), wherein the ratio of Co in M is 10 atomic% or more. (4) Ferrite particles containing the oxide magnetic material according to any of (1) to (3). (5) when expressed as _{I A 1-x R x (} Fe 12-y M y) z O 19, 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 20, 0.7 ≦ z ≦ 1.2 The ferrite particles according to (4) above. (6) At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr,
When at least one element selected from rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M,
A, R, Fe and M, the absolute value of the temperature dependency (Oe / ° C) of the intrinsic coercive force (HcJ) at −50 ° C. to 50 ° C. is represented as | ΔHcJ / ΔT |, and the unit of HcJ is kOe. Where, intrinsic coercive force (HcJ) and temperature dependency (Oe) satisfying the formula III | ΔHcJ / ΔT | ≦ 5 / 3HcJ-7 / 3.
/ ° C). (7) A bonded magnet including the ferrite particles according to any of (4) to (6). (8) A sintered magnet containing the oxide magnetic material according to any one of (1) to (3).

(9) Formula II A _1-x R _x (Fe _{12- y My} ) _z O ₁₉ , where 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, The sintered magnet according to (8), wherein 0.4 ≦ x / y ≦ 4 and 0.7 ≦ z ≦ 1.2. (10) When the intrinsic coercive force HcJ (unit: kOe) and the residual magnetic flux density Br (unit: kG) at 25 ° C. are HcJ ≧ 4, the formula IV Br + ／ HcJ ≧ 5.75 is satisfied, and when HcJ <4 The sintered magnet according to any one of the above (8) to (9), which satisfies the formula: VBr + 1 / 10HcJ ≧ 4.82. (11) Any one of the above (8) to (10), wherein the coercive force HcJ (unit: kOe) and the residual magnetic flux density Br (unit: kG) at −25 ° C. satisfy the formula VI Br + ／ HcJ ≧ 5.95. Sintered magnet. (12) The above (8) to (1) wherein the absolute value of the temperature coefficient of the coercive force at −50 ° C. to 50 ° C. is 0.25% / ° C. or less.
The sintered magnet according to any of 1). (13) At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr, is A, and is at least one element selected from rare earth elements (including Y) and Bi Where R always contains La, and Co or Co and Zn is M, it contains A, R, Fe and M, and has a coercive force HcJ (unit: kOe) and a residual magnetic flux at 25 ° C. The density Br (unit: kG) is
A sintered magnet that satisfies the formula IV Br + ／ HcJ ≧ 5.75 when HcJ ≧ 4, and satisfies the formula VBr + 1 / 10HcJ ≧ 4.82 when HcJ <4. (14) At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr, is A, and at least one element selected from rare earth elements (including Y) and Bi When R is R that always contains La, and M is Co or Co and Zn, it contains A, R, Fe and M, and has a coercive force HcJ (unit kOe) at −25 ° C. and a residual A sintered magnet whose magnetic flux density Br (unit: kG) satisfies the formula VI Br + HcJ ≧ 5.95. (15) A motor having the sintered magnet according to any one of (8) to (14). (16) A magnetic recording medium having a thin-film magnetic layer containing the oxide magnetic material of (1) to (3).

[0018]

According to the present invention, as shown in the above formulas, at least L
The composition is such that both a and Co are contained in optimal amounts. As a result, without reducing the Is, it can increase the H _A by increasing K ₁ rather simultaneously enhancing Is,
As a result, high Br and high HcJ are realized. In particular,
In the sintered magnet of the present invention, characteristics satisfying the above formula IV or the above formula V are easily obtained at room temperature of about 25 ° C. With a conventional sintered Sr ferrite magnet, B of 4.4 kG
It has been reported that r and HcJ of 4.0 kOe were obtained, but none of those having HcJ of 4 kOe or more and satisfying the above formula IV was obtained. That is, when HcJ is increased, Br is decreased. In the sintered magnet of the present invention, when Co and Zn are added in combination, the coercive force is lower than that of Co alone and may be lower than 4 kOe, but the residual magnetic flux density is significantly improved. At this time,
Magnetic properties satisfying the above equation V are obtained. Conventionally, no Sr ferrite sintered magnet having an HcJ of less than 4 kOe satisfying the above formula V has been obtained.

Since the ferrite according to the present invention has a larger anisotropy constant (K ₁ ) or anisotropic magnetic field (H _A ) than conventional ferrite, a larger HcJ can be obtained with the same particle size, and If the same HcJ is obtained, the particle size can be increased. For example, if the average particle size of the sintered body is 0.3 to 1 μm, HcJ of 4.5 kOe or more can be obtained, and even if it is 1 to 2 μm, HcJ of 3.5 kOe or more can be obtained. For this reason, the pulverization time and the molding time can be shortened, and the product yield can be improved.

The M-type ferrite in the composition of the present invention comprises:
As the saturation magnetization (4πIs) increases by about 2%, the crystal magnetic anisotropy constant (K ₁ ) or the anisotropy magnetic field (H _A ) is at most 1
Increase by 0-20%. It is not easy to measure the crystal magnetic anisotropy constant (K ₁ ) or the anisotropic magnetic field ( _HA ) with high accuracy, and there is no established method. However, for example, measuring the torque curve of an anisotropic sample using a torque meter Calculate the crystal magnetic anisotropy constants (K ₁ , K _2, etc.) by analyzing the initial magnetization curve of the anisotropic sample in the easy axis direction (c-axis) and the hard axis direction (a-axis). ) To determine the anisotropic magnetic field (H _A ) from the intersection, or the direction of the hard axis (a
A method is obtained from the second derivative of the initial magnetization curve of (axis).

The initial magnetization curve of the anisotropic sample is measured in the easy axis direction (c axis) and the hard axis direction (a axis), and the anisotropic magnetic field ( _HA ) is determined from the intersection. ,
When _HA of the present invention is obtained, a high value of at least 19 kOe or more and at most 20 kOe or more is obtained as shown in Table 6 below. This is an improvement of up to 10% or more compared to the conventional composition of Sr ferrite.

Although the present invention has a large effect of improving HcJ especially when applied to a sintered magnet, a bonded magnet in which ferrite particles produced according to the present invention are mixed with a binder such as plastic or rubber may be used.

The ferrite particles and sintered magnet of the present invention have a small temperature dependency of HcJ, and particularly the ferrite particles of the present invention have a very small temperature dependency of HcJ. In particular,
The temperature coefficient (absolute value) of HcJ at −50 to 50 ° C. of the sintered magnet of the present invention is 12 Oe / ° C. or less (0.25% / ° C. or less), and 9 Oe / ° C. or less (0.20% / ° C. or less). ). The ferrite particles of the present invention have a temperature coefficient (absolute value) of HcJ at −50 to 50 ° C. of 7 Oe / ° C. or less (0.1% / ° C. or less), and 5 Oe / ° C. or less (0.05% / ° C.). Below), and the temperature coefficient can be set to zero. Since the temperature characteristics of HcJ are good, good magnetic characteristics satisfying the above formula VI can be obtained at −25 ° C.
Such a high magnetic property under a low temperature environment is the same as the conventional S
This cannot be achieved with an r ferrite magnet.

The present invention also includes a coating type magnetic recording medium having a magnetic layer in which the above ferrite particles are dispersed in a binder. The present invention also includes a magnetic recording medium having a thin-film magnetic layer having a hexagonal magnetoplumbite ferrite phase similar to the above-mentioned magnet. In any of these cases, a high output and high S / N magnetic recording medium is realized by utilizing the high residual magnetic flux density. Further, since the magnetic recording medium of the present invention can be used as a perpendicular magnetic recording medium, the recording density can be increased. Further, since the temperature coefficient (absolute value) of HcJ can be reduced, a thermally stable magnetic recording medium can be realized.

By the way, Bull.Acad.Sci.USSR, phys.Ser.
(English Transl.) Vol.25, (1961) pp1405-1408 (hereinafter,
Literature 1) describes a Ba ferrite represented by Ba _1-x M ³⁺ _x Fe _12-x M ²⁺ _x O ₁₉ . This Ba
In ferrite, M ³⁺ is La ³⁺ , Pr ³⁺ or Bi
³⁺ , and M ²⁺ is Co ²⁺ or Ni ²⁺ . It is unclear whether the Ba ferrite in Document 1 is a powder or a sintered body.
It is similar to the Sr ferrite of the present invention in containing a and Co. In Fig. 1 of Reference 1, La and Co
The change of the saturation magnetization with the change of x is described for the Ba ferrite containing, but in FIG. 1, the saturation magnetization decreases with the increase of x. Reference 1
Describes that the coercive force has increased several times, but does not describe specific numerical values.

On the other hand, according to the present invention, by using a composition containing the optimum amounts of La and Co in the Sr ferrite sintered magnet, not only the HcJ is remarkably improved, but also the Br is slightly increased, and the HcJ is improved. Significant improvements in temperature dependence have also been achieved. In the present invention, La and Co are contained in the Sr ferrite particles in optimal amounts, thereby increasing HcJ and remarkably reducing its temperature dependence. It was found for the first time in the present invention that such an effect is obtained when the composite addition of La and Co is applied to Sr ferrite.

[0027] Indian Journal of Pure & Applied Physi
cs Vol. 8, July 1970, pp. 412-415 (hereinafter referred to as Reference 2) includes the formula La ³⁺ Me ²⁺ Fe ³⁺ ₁₁ O ₁₉ (Me ²⁺ = Cu ²⁺ , Cd ²⁺ , Zn ^{2 +} , Ni ²⁺ , Co ²⁺ or Mg ²⁺ ). This ferrite is the same as the ferrite particles and the sintered magnet of the present invention in that La and Co are simultaneously contained. However, in Reference 2, the saturation magnetization s when Me ²⁺ = Co ²⁺ is 42 cgs unit at room temperature and 50 cg at 0K.
It is a low value of s unit. Although no specific value is shown, Document 2 describes that the coercive force is so low that it cannot be used as a magnet material. This is because the composition of the ferrite described in Document 2 is out of the range of the present invention (La and C).
o is too large).

Japanese Patent Application Laid-Open No. Sho 62-100417 (hereinafter, referred to as
The literature 3), equiaxed hexaferrite pigments of the composition represented by the formula _{M x (I) M y (} II) M z (IV) Fe 12- (y + z) O 19 is described. In the above formula, M (I) is Sr, Ba,
It is a combination of a rare earth metal or the like and a monovalent cation, wherein M (II) is Fe (II), Mn, Co, Ni, C
u, Zn, Cd or Mg, and M (IV) is Ti or the like. Hexaferrite pigments described in Document 3 are:
It is the same as the ferrite particles and the sintered magnet of the present invention in that the rare earth metal and Co can be simultaneously contained. However, Reference 3 does not disclose an example in which La and Co are simultaneously added, and does not disclose that both the saturation magnetization and the coercive force are improved by the simultaneous addition of La and Co. Moreover, Reference 3
In the examples to which Co was added among the examples of
Ti is added as (IV). Since the element M (IV), particularly Ti, is an element that lowers both the saturation magnetization and the coercive force, it is obvious that Document 3 does not suggest the configuration and effect of the present invention.

Japanese Patent Application Laid-Open No. Sho 62-119760 (hereinafter referred to as
Reference 4) describes a magneto-optical recording material characterized in that a part of Ba of magnetoplumbite-type barium ferrite is replaced with La and a part of Fe is replaced with Co. In this Ba ferrite, La
It also looks similar to the Sr ferrite of the present invention in that it contains Co and Co. However, the ferrite of Document 4 is a material for “magneto-optical recording” in which magnetic domains are written in a magnetic thin film using the thermal effect of light to record information, and information is read out using the magneto-optical effect. The technical field is different from the magnet and the "magnetic recording" material of the present invention. Further, Literature 4 requires Ba, La, and Co in the composition formula of (I), and in the formulas (II) and (IV), a case where a metal ion having four or more valences (unspecified) is added thereto Is only shown. On the other hand, the ferrite of the present invention is an Sr ferrite that requires Sr,
The composition differs from that of Reference 4 in that a and Co are added in appropriate amounts. That is, the Sr ferrite of the present invention is described in the above Reference 1.
As described in the above, by using a composition in which La and Co are respectively contained in the Sr ferrite in optimal amounts, HcJ
, And a slight increase in Br, and a remarkable improvement in the temperature dependency of HcJ. This was realized for the first time in a composition of the present invention different from Reference 4.

Japanese Patent Publication No. 5-41218 (hereinafter referred to as Reference 5) discloses that a calcined body of M-type Ba, Sr, and Pr ferrites is prepared by adding one of CaO, SIO ₂ , CoO, (Cr, Al ₂ O ₃ ) It is described that a ferrite sintered body having a high coercive force can be produced by adding (2 types). However, there is no description about rare earth elements such as La. Further, the magnetic properties described in the examples are also low, and when compared with those of the same Br, HcJ is 100 Oe
Only the degree has been improved. This is because, unlike the present invention, it does not contain a rare earth element such as La or the like, and the ferrite described in Literature 5 is clearly different from that of the present invention.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The oxide magnetic material of the present invention has hexagonal ferrite, preferably hexagonal magnetoplumbite (M type) ferrite as a main phase, and contains Sr, Ba, C
A is at least one element selected from a and Pb, which always contains Sr, and is at least one element selected from rare earth elements (including Y) and Bi and always contains La Let R be Co and C or C
When o and Zn are M, the total composition ratio of the metal elements of A, R, Fe and M is A: 1 to 13 atom%, R: 0.05 to 10 atom with respect to the total metal element amount. %, Fe: 80 to 95 atomic%, and M: 0.1 to 5 atomic%.

Preferably, A: 3 to 11 at%, R: 0.2 to 6 at%, Fe: 83 to 94 at%, M: 0.3 to 4 at%, more preferably A: 3 to 9 atomic%, R: 0.5 to 4 atomic%, Fe: 86 to 93 atomic%, M: 0.5 to 3 atomic%.

In each of the above constituent elements, A represents Sr, B
At least one element selected from a, Ca and Pb, which always contains Sr. If A is too small, M-type ferrite will not be formed or non-magnetic phase such as α-Fe ₂ O ₃ will increase. If A is too large, no M-type ferrite will be formed or a non-magnetic phase such as SrFeO _3-x will increase. A
The ratio of Sr therein is preferably at least 51 atomic%, more preferably at least 70 atomic%, and further preferably 100 atomic%. If the ratio of Sr in A is too low, it is impossible to obtain both the saturation magnetization and the remarkable improvement in coercive force.

R is a rare earth element (including Y) and Bi
At least one element selected from the group consisting of: In R,
La is always included. If R is too small, the amount of solid solution of M decreases, and the effect of the present invention cannot be obtained. If R is too large, non-magnetic hetero phases such as orthoferrite increase.
The proportion of La in R is preferably at least 40 at%, more preferably at least 70 at%, and it is most preferable to use only La as R in order to improve the saturation magnetization. This is because, when comparing the solid solution limit amount to hexagonal M-type ferrite, La is the largest. Therefore, if the proportion of La in R is too low, the solid solution amount of R cannot be increased, and as a result, the solid solution amount of element M cannot be increased, and the effect of the present invention is reduced. I will. Further, if Bi is used in combination, the calcining temperature and the sintering temperature can be lowered, which is advantageous in production.

The element M is Co or Co and Zn. If M is too small, the effects of the present invention cannot be obtained, and M
Is too large, Br and HcJ decrease conversely, and the effect of the present invention cannot be obtained. The ratio of Co in M is preferably at least 10 atomic%, more preferably at least 20 atomic%. Co
If the ratio is too low, the improvement in coercive force will be insufficient.

[0036] The oxide magnetic material of preferably the invention is represented formula _{I A 1-x R x (} Fe 12-y M y) z O 19 (x, y, z represents the number of moles) and In this case, 0.04 ≦ x ≦ 0.9, particularly 0.04 ≦ x ≦ 0.6, 0.04 ≦ y ≦ 0.5, and 0.7 ≦ z ≦ 1.2.

More preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.7 ≦ z ≦ 1.2, and even more preferably 0.1 ≦ x ≦ 0. 0.4, 0.1 ≦ y ≦ 0.4, 0.8 ≦ z ≦ 1.1, and particularly preferably 0.9 ≦ z ≦ 1.05.

In the above formula I, when x is too small, that is, when the amount of the element R is too small, the solid solution amount of the element M in the hexagonal ferrite cannot be increased, and the effect of improving the saturation magnetization and / or the anisotropic magnetic field The improvement effect becomes insufficient. If x is too large, the element R cannot be substituted in the hexagonal ferrite to form a solid solution. For example, orthoferrite containing the element R is generated, and the saturation magnetization is reduced. If y is too small, the effect of improving the saturation magnetization and / or the effect of improving the anisotropic magnetic field become insufficient. If y is too large, the element M cannot be substituted and solid-solved in the hexagonal ferrite. The element M
Is within the range that can be replaced by solid solution, the anisotropy constant (K ₁ )
And the deterioration of the anisotropic magnetic field ( _HA ) is increased. z
Is too small, the nonmagnetic phase containing Sr and the element R increases, and the saturation magnetization decreases. If z is too large, the α-Fe ₂ O ₃ phase or the nonmagnetic spinel ferrite phase containing the element M increases, and the saturation magnetization decreases. Note that the above formula I is defined as containing no impurities.

In the above formula I representing the composition, the number of moles of oxygen (O) is 19, which is the same as when R is all trivalent and x = y and z = 1. It shows a stoichiometric composition ratio. The number of moles of oxygen varies depending on the type of R and the values of x, y, and z. Further, for example, when the firing atmosphere is a reducing atmosphere, oxygen deficiency (vacancy) may occur. Further, Fe is M
Usually, trivalent is present in the type ferrite, but this may change to divalent or the like. Also, M such as Co
The valence of the element represented by may also change, and these change the ratio of oxygen to the metal element. In this specification, the number of moles of oxygen is indicated as 19 regardless of the type of R and the values of x, y, and z. However, the actual number of moles of oxygen slightly deviates from the stoichiometric composition ratio. Is also good. For example, Sr
When divalent Fe is formed in the ferrite, it is considered that the specific resistance of the ferrite decreases (Fe ²⁺ → Fe ³⁺ + e).
^- ). In the case of a polycrystalline body, the grain boundary resistance is usually higher than the intragranular resistance, but the specific resistance of the actual sintered magnet may change due to this cause.

The composition of the oxide magnetic material can be measured by a fluorescent X-ray quantitative analysis or the like. The presence of the main phase is confirmed by X-ray diffraction.

The oxide magnetic material may contain B ₂ O ₃ . By including B ₂ O ₃ , the calcining temperature and the sintering temperature can be lowered, which is advantageous in production.
The content of B ₂ O ₃ is preferably 0.5% by weight or less based on the oxide magnetic material. If the B ₂ O ₃ content is too large, the saturation magnetization will be low.

In the oxide magnetic material, Na, K and R
At least one kind of b may be contained. When these were converted to Na ₂ O, K ₂ O and Rb ₂ O, respectively,
The total of these contents is preferably 3% by weight or less of the whole oxide magnetic material. If these contents are too large, the saturation magnetization will be low. These elements are represented by M
When expressed in ^I, M ^I in the oxide magnetic material is contained in the form of for example ^{_{Sr 1.3-2a R a M I a-}} 0.3 Fe 11.7 M 0.3 O 19. In this case, 0.3 <a ≦ 0.
It is preferably 5. When a is too large, in addition to the saturation magnetization becomes low, a problem that the element M ^I is thus a large amount of evaporation occurs during firing.

In addition to these impurities, for example, Si,
Al, Ga, In, Li, Mg, Mn, Ni, Cr, C
u, Ti, Zr, Ge, Sn, VI, Nb, Ta, Sb,
As, W, Mo, etc. in the form of oxides, each containing 1% by weight or less of silicon oxide, 5% by weight or less of aluminum oxide, 5% by weight or less of gallium oxide, 3% by weight or less of indium oxide,
1% by weight or less of lithium oxide, 3% by weight of magnesium oxide
Below, manganese oxide 3% by weight, nickel oxide 3% by weight, chromium oxide 5% by weight, copper oxide 3% by weight, titanium oxide 3% by weight, zirconium oxide 3% by weight, germanium oxide 3% by weight , Tin oxide 3% by weight or less, vanadium oxide 3% by weight or less, niobium oxide 3
% By weight, 3% by weight or less of tantalum oxide, 3% by weight or less of antimony oxide, 3% by weight or less of arsenic oxide, 3% by weight or less of tungsten oxide, and 3% by weight or less of molybdenum oxide.

The ferrite particles of the present invention contain the above-mentioned oxide magnetic material, and have the formula IA _1-x R _x (Fe _12-y M _y ) _z O ₁₉ (x, y, z represent the number of moles) ), 0.04 ≦ x ≦ 0.9, in particular, 0.04 ≦ x ≦ 0.6, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 20, in particular 0. 8 ≦ x / y ≦ 5, 0.7 ≦ z ≦ 1.2.

More preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 5, 0.7 ≦ z ≦ 1.2, More preferably, 0.1 ≦ x ≦ 0.4, 0.1 ≦ y ≦ 0.4, 0.8 ≦ x / y ≦ 5, 0.8 ≦ z ≦ 1.1, and particularly preferably 0. 9 ≦ z ≦ 1.05.

In the above formula I, if x / y is too small or too large, the valences of the element R and the element M cannot be balanced, and a different phase is easily formed. Since the element M is divalent, when the element R is a trivalent ion, ideally x / y
= 1. The reason why the allowable range is large in the region where x / y exceeds 1 is that even when y is small, the valence can be balanced by the reduction of Fe ³⁺ → Fe ²⁺ . The other reasons for limiting x, y and z are the same as described above. When x / y is slightly larger than 1, there is also an effect that the magnetic characteristics (HcJ) become stable with respect to the atmosphere (oxygen partial pressure) during calcination.

The ferrite particles of the present invention contain the above-described oxide magnetic material. Even if the average particle size of the primary particles exceeds 1 μm, a higher coercive force can be obtained as compared with the conventional case. The average particle size of the primary particles is preferably 2 μm
The thickness is more preferably 1 μm or less, and still more preferably 0.1 to 1 μm. If the average particle size is too large,
If the ratio of the multi-domain particles in the magnet powder is increased and HcJ is decreased, and the average particle size is too small, magnetism is reduced due to thermal disturbance, and the orientation and formability during molding in a magnetic field are deteriorated.

Further, the ferrite particles of the present invention include Sr,
A is at least one element selected from Ba, Ca and Pb, which always contains Sr, and is at least one element selected from rare earth elements (including Y) and Bi.
When R is a kind of element that always contains La, and Co or Co and Zn is M, it contains A, R, Fe and M, and has a specific coercive force (−50 ° C. to 50 ° C.) The absolute value of the temperature dependency (Oe / ° C.) of HcJ) is expressed as ΔHcJ, and the unit of HcJ is KOe, and the intrinsic coercive force (HcJ) satisfying the formula III HcJ ≦ 5/3 × HcJ−7 / 3. And temperature dependence (Oe
/ ° C). For the ferrite particles having such properties, an oxide magnetic material having the above composition may be used. It can be obtained by the following manufacturing method and the like.

The ferrite particles are generally used for a bonded magnet in which the ferrite particles are bonded by a binder. As the binder, NBR rubber, chlorinated polyethylene, nylon 12 (polyamide resin), nylon 6 (polyamide resin) or the like is usually used.

The Curie temperature of the oxide magnetic material having the above composition is usually 425 to 460 ° C.

As a method for producing ferrite particles, various methods such as a solid phase reaction method, a liquid phase method such as a coprecipitation method and a hydrothermal synthesis method, a glass precipitation method, a spray pyrolysis method, and a gas phase method are used. is there. Among them, the solid-phase reaction method is currently the most widely used industrially as a method for producing ferrite particles for bonded magnets. Ferrite particles used for a coating type magnetic recording medium are mainly produced by a liquid phase method or a glass precipitation method.

In the solid-state reaction method, iron oxide powder, powder containing element A, element R and element M are used as raw materials, and a mixture of these powders is fired (calcined). In this calcined body, the primary particles of the ferrite are agglomerated and in a so-called “granular” state. Therefore, pulverization is often performed thereafter. The pulverization is performed by a dry or wet method. In this case, distortion is introduced into the ferrite particles and magnetic properties (mainly HcJ) are deteriorated.
An annealing treatment is often performed after the pulverization.

Further, when producing a sheet-like rubber magnet, it is necessary to orient the ferrite particles by mechanical stress. In this case, in order to obtain a high degree of orientation, the ferrite particles preferably have a plate shape.

When producing ferrite particles by the solid phase reaction method, the following points are important. Prevents agglomeration of ferrite particles. Removes distortion of ferrite particles. When the ferrite particles are mechanically oriented, the ferrite particles are formed into a plate shape. Adjust the size of the ferrite particles to an appropriate range.

In order to realize the above, in addition to the iron oxide powder, the powder containing the element A, the powder containing the element R, and the powder containing the element M, a chloride of Ba or Sr was further added. There is a method in which the mixture is calcined (calcined), and then the added chloride is washed and removed. Alternatively, there is a method of pulverizing a normal calcined body, adding a chloride of Ba or Sr or the like, calcining (calcining) again, and then washing and removing these chlorides (Japanese Patent Publication No. 55-19046). No.).

In addition to the above raw material powder, if necessary, B ₂ O ₃ and other compounds such as Si, Al, Ga, I
n, Li, Mg, Mn, Ni, Cr, Cu, Ti, Z
r, Ge, Sn, VI, Nb, Ta, Sb, As, W, M
A compound containing o or the like may be contained as an additive or an impurity such as an unavoidable component.

The calcination is performed, for example, in the
The heat treatment may be performed at 1350 ° C. for 1 second to 10 hours, particularly about 1 second to 3 hours.

The calcined body thus obtained has a substantially magnetoplumbite-type ferrite structure, and the primary particles have an average particle size of preferably 2 μm or less, more preferably 1 μm or less, and still more preferably. Is 0.1-1μ
m, most preferably 0.1-0.5 μm. The average particle size may be measured with a scanning electron microscope.

Next, the calcined body is usually pulverized or crushed to obtain ferrite particles. Then, the ferrite particles are kneaded with various binders such as resin, metal, and rubber,
Forming in a magnetic field or without a magnetic field. Thereafter, if necessary, curing is performed to obtain a bonded magnet.

Further, a ferrite particle is kneaded with a binder to form a paint, which is applied to a substrate made of a resin or the like, and cured if necessary to form a magnetic layer, thereby obtaining a coating type magnetic recording medium. be able to.

The sintered magnet of the present invention has a hexagonal ferrite as a main phase, and has a composition ratio of the above oxide magnetic material, in particular, a formula II A _{1 -x} R _x (Fe _{12 -y My} ) _z O ₁₉ When expressed, preferably 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.4 ≦ x / y ≦ 4, particularly 0.8 ≦ x / y ≦ 4, 0.7 ≤ z ≤ 1.2.

More preferably, 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 2, 0.7 ≦ z ≦ 1.2. .

Particularly preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 2, 0.7 ≦ z ≦ 1.2, Further, 0.8 ≦ x / y ≦ 1.7.

A, R, M, x, y, z in the above formula II
And the reasons for these limitations are the same as those in Formula I above. The reason for limiting x / y is the same as that in the formula I. Further, the impurities which may be contained in addition to these are the same as those in the case of the oxide magnetic material. When x / y is slightly larger than 1, there is also an effect that the magnetic characteristics (HcJ) become stable with respect to the atmosphere (oxygen partial pressure) at the time of main firing.

The sintered magnet is manufactured by molding and sintering the ferrite particles manufactured by the various methods described in the method of manufacturing the ferrite particles. In this case, the most widely used industrially for sintered magnets is
Although the method uses ferrite particles produced by a solid phase reaction method, ferrite particles produced by another method may be used, and there is no particular limitation.

Since the calcined body is generally in the form of granules, it is preferable to first carry out dry coarse pulverization in order to pulverize or crush it. Dry coarse pulverization also has the effect of reducing the coercive force HcB by introducing crystal strain into the ferrite particles. Due to the decrease in coercive force, aggregation of particles is suppressed, and dispersibility is improved.
Further, by suppressing the aggregation of the particles, the degree of orientation is improved. The crystal strain introduced into the particles is released in a later sintering step, and the coercive force is restored, so that the particles can be made permanent magnets. In the case of dry coarse pulverization, usually,
SiO ₂ and CaCO ₃ which becomes CaO upon firing are added. SiO ₂ and CaCO ₃ may be partially added before calcining. Impurities and added Si and Ca
Is segregated mostly at grain boundaries and triple junctions, but a part is also taken into the ferrite part (main phase) in the grains. Especially Ca
Is likely to be on the Sr site.

After the dry coarse pulverization, it is preferable to prepare a pulverization slurry containing ferrite particles and water, and to perform wet pulverization using the slurry.

After the wet pulverization, the pulverization slurry is concentrated to prepare a molding slurry. Concentration may be performed by centrifugation, a filter press, or the like.

The molding may be performed by a dry method or a wet method. However, in order to increase the degree of orientation, it is preferable to perform a wet method.

In the wet molding step, molding in a magnetic field is performed using a molding slurry. Molding pressure is 0.1-0.5ton / cm
^The applied magnetic field may be about ² to 15 kOe.

In wet molding, a non-aqueous dispersion medium or an aqueous dispersion medium may be used. When a non-aqueous dispersion medium is used, for example, as described in JP-A-6-53064, a surfactant such as oleic acid is added to an organic solvent such as toluene or xylene. And a dispersion medium. By using such a dispersion medium, it is possible to obtain a high degree of magnetic orientation of about 98% at the maximum even when ferrite particles having a submicron size that are difficult to disperse are used. On the other hand, as the aqueous dispersion medium, one obtained by adding various surfactants to water may be used.

After the molding step, the molded body is heat-treated at a temperature of 100 to 500 ° C. in the air or in nitrogen to sufficiently decompose and remove the added dispersant. Next, in the sintering step, the molded body is preferably for example 1150-12 in air.
Sintering is performed at a temperature of 70 ° C, more preferably 1160 to 1240 ° C for about 0.5 to 3 hours to obtain a sintered anisotropic ferrite magnet.

The average crystal grain size of the sintered magnet of the present invention is preferably 2 μm or less, more preferably 1 μm or less, and still more preferably 0.5 to 1.0 μm. , A sufficiently high coercive force can be obtained. The crystal grain size can be measured by a scanning electron microscope. Incidentally, the resistivity is the value of the degree 10 ⁰ [Omega] m or more.

The above compact was crushed using a crusher or the like, and the average particle size was reduced to 100 to 700 μm by sieving or the like.
m to obtain a magnetic field-oriented granule, which is subjected to dry magnetic field molding, and then sintered to obtain a sintered magnet.

The present invention also includes a magnetic recording medium having a thin-film magnetic layer. This thin film magnetic layer contains an oxide magnetic material having a hexagonal ferrite phase represented by the above formula I, like the ferrite particles of the present invention described above. Further, the content of impurities and the like is equivalent to that of the oxide magnetic material.

For forming the thin film magnetic layer, it is usually preferable to use a sputtering method. When a sputtering method is used, the sintered magnet may be used as a target, or a multi-source sputtering method using at least two kinds of oxide targets may be used. After the formation of the sputtering film, heat treatment may be performed in order to form a hexagonal magnetoplumbite structure.

By applying the oxide magnetic material of the present invention, the following effects can be generally obtained, and an excellent applied product can be obtained. In other words, if the shape is the same as that of a conventional ferrite product, the magnetic flux density generated from the magnet can be increased, so that a motor can achieve higher torque, etc., and if it is a speaker or headphone, the magnetic circuit can be strengthened. It can contribute to high performance of applied products, such as obtaining good sound quality with linearity. Further, if the same function as in the related art is sufficient, the size (thickness) of the magnet can be reduced (thinned), which contributes to downsizing and weight reduction (thinning).
Further, even in a motor in which a field magnet is conventionally a winding type electromagnet, this can be replaced with a ferrite magnet, which contributes to weight reduction, shortening of a production process, and cost reduction. In addition, because of its excellent coercive force (HcJ) temperature characteristics, it can be used even in low-temperature environments where there was a risk of low-temperature demagnetization (permanent demagnetization) of ferrite magnets, especially in cold regions and in the sky. The reliability of the manufactured product can be significantly increased.

The bonded magnet and sintered magnet using the oxide magnetic material of the present invention are processed into a predetermined shape and used for a wide range of applications as described below.

For example, for fuel pumps, power windows, ABS, fans, wipers, power steering, active suspensions, starters,
Automotive motors for door locks, electric mirrors, etc .; FD
For D spindle, VITR capstan, VITR rotating head, VITR reel, VITR loading, VIT
For R camera capstan, For VITR camera rotating head,
Motors for OA and AVI devices, such as for VITR camera zoom, VITR camera focus, boombox capstan, CD, LD, MD spindle, CD, LD, MD loading, CD, LD optical pickup, etc .; Motors for household appliances such as refrigerator compressor, electric tool drive, electric fan, microwave oven fan, microwave oven plate rotation, mixer drive, dryer fan drive, shaver drive, electric toothbrush, etc .;
Motors for FA equipment such as robot axes, joint drive, robot main drive, machine tool table drive, machine tool belt drive, etc .; motor generators, magnets for speakers and headphones, magnetron tubes, magnetic field generation for MRI It is suitably used for devices, clampers for CD-ROMs, sensors for distributors, sensors for ABS, fuel / oil level sensors, magnet latches, and the like.

[0080]

EXAMPLES Example 1 (Sintered Magnet: A-R-Fe-M Set)
The following materials were used as raw materials. Fe ₂ O ₃ powder (primary particle diameter 0.3 μm: Mn, Cr, Si, C
1), SrCO ₃ powder (primary particle diameter 2 μm: containing Ba and Ca as impurities), a mixture of Co ₃ O ₄ powder and CoO powder (primary particle diameter 1 to 5 μm), La ₂ O ₃ powder (purity 99.9%)

The above raw materials were blended so that the composition had a predetermined value. Furthermore, SiO ₂ powder (primary particle diameter 0.01
μm) and CaCO ₃ powder (primary particle diameter 1 μm) were added to and mixed with the above raw materials at 0.2% by weight and 0.15% by weight, respectively. The obtained mixture was pulverized with a wet attritor for 2 hours, dried and sized, and then calcined in air at 1200 ° C. for 3 hours to obtain a granular calcined body (magnet powder).

To the calcined body obtained by calcining at 1200 ° C., 0.4% by weight of the above SiO ₂ and 1.25% by weight of the above CaCO ₃ were added, and the ratio of the calcined body was determined by a dry rod mill. Grinding was performed until the surface area became 7 m ² / g.

Next, the calcined powder was wet-pulverized in a ball mill using xylene as a non-aqueous solvent and oleic acid as a surfactant. Oleic acid was added in an amount of 1.3% by weight based on the calcined powder. The calcined body powder in the slurry was 33% by weight. The pulverization has a specific surface area of 8 to
The operation was performed until 9 m ² / g was reached.

By the above-mentioned pulverization, pulverization strain was introduced into the calcined body powder, and the HcJ of the calcined body powder was reduced to 15 to 60% before the pulverization. Further, Fe and Cr are slightly mixed in from the pulverizer.

Next, the pulverized slurry was adjusted by a centrifugal separator so that the concentration of the calcined powder in the slurry was about 85% by weight. While removing the solvent from the slurry, about 1
It was formed into a column having a diameter of 30 mm and a height of 15 mm in a 3 kG height magnetic field. The molding pressure was 0.4 ton / cm ² . A part of the slurry was dried, calcined at 1000 ° C., and all the components were converted into oxides. Then, the amounts of the respective components were analyzed by a fluorescent X-ray quantitative analysis method. Table 1 shows the results.

[0086]

[Table 1]

Next, after heat treatment of the molded body at 100 to 300 ° C. to sufficiently remove oleic acid,
The temperature was raised at a rate of 5 ° C./min, and the temperature was maintained at 1200 ° C. for 1 hour to perform sintering to obtain a sintered body. After processing the upper and lower surfaces of the obtained sintered body, 4πIs, the residual magnetic flux density (B
r), coercive force (HcJ), Ir / Is, Hk / HcJ, maximum energy product [(BH) max], and sintered density were examined. Table 2 shows the results.

[0088]

[Table 2]

As is clear from Table 2, Sample No. 1
The sintered body cores of the present invention of Nos. 1 to 14 show extremely excellent properties.

Example 2 (Sintered magnet: based on RM substitution rate)
Comparative) The following materials were used as raw materials. Fe ₂ O ₃ powder (primary particle diameter 0.3 μm: Mn, Cr, Si, C
1), SrCO ₃ powder (primary particle diameter 2 μm: containing Ba and Ca as impurities), a mixture of Co ₃ O ₄ powder and CoO powder (primary particle diameter 1 to 5 μm), La ₂ O ₃ powder (purity 99.9%)

The above raw materials were blended so as to have a composition of Sr _1-x La _x Fe _12-y Co _y O ₁₉ . Furthermore, SiO ₂ powder (primary particle size 0.01 μm) and CaCO ₃ powder (primary particle size 1
μm) was added to and mixed with 0.2% by weight and 0.15% by weight of the above raw materials, respectively. The obtained mixture was pulverized with a wet attritor for 2 hours, dried and sized,
Calcination was performed in air at a temperature in the range of 1150 to 1300 ° C. for 3 hours to obtain a calcined body. Hereinafter, a sintered body was produced in the same manner as in Example 1.

After processing the upper and lower surfaces of the obtained sintered body, the residual magnetic flux density (Br), the coercive force (HcJ and HcB), the maximum energy product [(BH) max], and the substitution ratio x of La and Co , Y (where x = y). The results are shown in FIGS. 1 and 2 together with the sintering temperature.

From FIG. 1 and FIG. 2, when x and y are within the range of the present invention, by optimizing the sintering temperature, Br ≧
It can be seen that HcJ or HcB can be significantly improved while maintaining the high magnetic properties of 4.4 kG and (BH) max ≧ 4.6 MGOe. To illustrate this clearly, FIG.
The relationship between HcJ and Br and the relationship between HcJ and (BH) max when x is changed for a sintered body in which both the calcination temperature and the sintering temperature are 1200 ° C. are shown. For comparison, data on the sintered body described in Japanese Patent Application No. 8-145006 is also shown in FIG. 3 as “Comparative Example (LaZn substitution)”. The sintered body of this comparative example has a main phase represented by Sr _0.7 La _0.3 Fe _11.7 Zn _0.3 O ₁₉ . The sintered body (x = 0.1 to 0.4) of the embodiment shown in FIG. 3 has HcJ of 4 kOe or more, and Br and HcJ satisfy the above-described formula IV Br + ／ HcJ ≧ 5.75. It has become. On the other hand, the sintered body of the comparative example (HcJ is less than 4 kOe) shown in FIG. 3 does not satisfy the expression VBr + 1 / 10HcJ ≧ 4.82.

FIG. 4 shows the relationship between the Curie temperature (Tc) of the sintered body at a sintering temperature of 1220 ° C. and the substitution rates x and y (where x = y). From FIG. 4, it can be seen that as x and y increase, T
It can be seen that c decreases.

Example 3 (Sintered Magnet: Calcination Temperature and Sintering)
(Comparison by temperature) The raw materials are mixed so that the composition becomes x = 0.3 and y = 0.3 in Sr _1-x La _x Fe _12-y Co _y O ₁₉ , and the calcination temperature and sintering temperature are plotted. A sintered body was produced in the same manner as in Example 1 except that the sintered body was changed as shown in FIG. FIG. 5 shows the magnetic properties of these sintered bodies. As shown in FIG. 5, in order to obtain high Br and high HcJ, the calcination temperature is set to 1300 ° C.
It can be seen that the sintering temperature is preferably set to 1180 to 1220 ° C. However, even when the calcination was performed at 1300 ° C., when the sintering temperature was 1240 ° C.,
High magnetic properties such as r ≒ 4.4 kG and HcJ ≒ 4.0 kOe are obtained.

In order to analyze such a characteristic phenomenon, the microstructures of the calcined body and the sintered body were examined by a scanning electron microscope (SEM). 6, 7 and 8 show that the calcining temperature (T1) was 1200 ° C., 1250 ° C. and 130 ° C.
SEM photographs of the calcined body obtained at 0 ° C. are shown. In the calcined body obtained at a calcining temperature of 1300 ° C,
It can be seen that coarse particles having a particle size exceeding 10 μm account for a large proportion.

[0097] The structure of the sintered body was also examined by SEM. FIGS. 9 to 12 show SEM photographs. Fig. 9: T1 = 1200 ° C, T2 = 1200 ° C, Fig. 10: T1 = 1200 ° C, T2 = 1240 ° C, Fig. 11: T1 = 1300 ° C, T2 = 1200 ° C., FIG. 12: T1 = 1300 ° C., T2 = 1240 ° C. These photographs show a fracture surface parallel to the a-plane of the crystal. It can be seen that even in a sintered body in which HcJ of 4.5 kOe or more was obtained, relatively many crystal grains having a grain size exceeding 1 μm were present. In addition, when the calcination temperature was 1300 ° C., it was found that most of the crystal grains had a particle size of more than 1 μm. However, although HcJ as high as about 4 kOe is obtained despite the large crystal grain size, the magnetic properties, particularly the crystal grain size dependency of HcJ can be improved by the present invention. it is obvious.

The calcined body (x = 0.3, y = 0.3)
Average primary particle size is 1 when the calcination temperature is 1250 ° C or lower.
μm or less, and the sintered body obtained by sintering this at 1220 ° C. or less had an average crystal grain size of 1.5 μm or less.
On the other hand, the average primary particle size of the calcined body at a calcining temperature of 1300 ° C. is 3 μm or more.
The average crystal grain size of the sintered body obtained by sintering at 220 ° C. or less was 3 μm or less.

Example 4 (Sintered magnet: Sr ferrite magnet
And Ba ferrite magnet) The raw materials were blended such that the composition was x = y in Sr _1-x La _x Fe _12-y Co _y O ₁₉ and x and y were 0.2 or 0.3. Otherwise in the same manner as in Example 1, a calcined body was produced. The calcination temperature was 1200 ° C. The calcined body was sintered to obtain a sintered Sr ferrite magnet. The sintering temperature was selected from the range of 1180-1260C.

For comparison, the main phase composition is such that x = y in Ba _1-x La _x Fe _12-y Co _y O ₁₉ and x and y are 0.2 or 0.3. The raw materials are blended, the calcination temperature is set to 1200 ° C,
The sintering temperature was set to 1180 to 12 like the Sr ferrite magnet.
A Ba ferrite sintered magnet was obtained by selecting from the range of 60 ° C. Observation of the structure of the sintered body with a scanning electron microscope (SEM) revealed that Ba ferrite had a larger aspect ratio and was flattened. Among the obtained Ba ferrites, HcJ when x = 0.3 and y = 0.3, shrinkage in the a-axis (diameter) direction and c-axis (height) direction when the sintering temperature is 1220 ° C. Table 3 shows the ratios of the ratios and the sintered densities. In general, when the ratio of shrinkage (shh / shΦ) is large,
The particles tend to flatten. The anisotropic magnetic field (H _A ) of the Ba ferrite (x = 0.3) measured by the method of Example 7 was 16.6 kOe.

[0101]

[Table 3]

FIG. 13 shows the magnetic characteristics of each of these sintered bodies. FIG. 13 shows the characteristics of a plurality of sintered bodies having different sintering temperatures for each composition. Thereby, Ba
In the case of a system ferrite, a large HcJ cannot be obtained because the anisotropic magnetic field ( _HA ) is low and the particles are easily flattened. Actually, as shown in Table 3, HcJ is about 3.5 kOe at the maximum, which is a value obtained by the conventional Sr.

In FIG. 13, a sintered Sr ferrite (HcJ
(All of which are 4 kOe or more) satisfy the above-mentioned formula IV. On the other hand, a Ba ferrite sintered body (HcJ is less than 4 kOe) does not satisfy the above formula V.

Example 5 (Temperature characteristics of ferrite particles: HcJ)
Properties) With respect to the calcined Sr ferrite having the composition and the calcining temperature shown in Table 4, the IH hysteresis curve was determined by VSM in the temperature range shown in FIG. From this IH hysteresis curve, the temperature dependence of HcJ was examined. HcJ
Is shown in FIG. Using these results, the temperature coefficient of HcJ was calculated by linear approximation in the range from -50 ° C to + 50 ° C. Temperature coefficient and -50 to 50
Table 4 shows the correlation coefficient at ° C. The temperature coefficient ΔHcJ / HcJ / ΔT in Table 4 is a rate of change with respect to HcJ at 25 ° C.

[0105]

[Table 4]

Table 4 shows that the combined addition of La and Co significantly reduces the temperature coefficient of HcJ of the calcined Sr ferrite.

Example 6 (Sintered magnet: temperature of HcJ and Br)
Degree Characteristics) A sintered Sr ferrite having a phase composition of x = y = 0 to 1 and z = 1 was produced. The calcination temperature and the sintering temperature were both 1200 ° C. These sintered bodies are 5 mm in diameter,
It was processed into a columnar shape with a height of 6.5 mm (the height direction was the c-axis direction), and the temperature dependency of HcJ was examined in the same manner as in Example 5.
The results are shown in FIG. In Table 5, 25
Also shown are Br and HcJ at -25 ° C and Br and HcJ at -25 ° C.

[0108]

[Table 5]

From Table 5, it can be seen that the combined addition of La and Co significantly improves the temperature characteristics of HcJ of the Sr ferrite sintered body.

Regarding the magnetic properties at 25 ° C., the sintered body with x = 0.3 and y = 0.3 (HcJ is 4 kOe or more) has Br + ／ HcJ = 6.07. X = 0, y
The sintered body of = 0 (HcJ less than 4 kOe) has Br + 1 / 10HcJ = 4.78, which does not satisfy the above formula V. Regarding the magnetic properties at −25 ° C., the sintered body with x = 0.3 has Br + ／ HcJ = 6.44, which satisfies the above formula VI, whereas x = 0, y
The sintered body of = 0 is only Br + ／ HcJ = 5.89, which does not satisfy the above formula VI.

Example 7 (Sintered Magnet: Anisotropic Magnetic Field) When the composition is Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ , x and y (where x = y) become the values shown in Table 6. The raw materials were mixed as described above, and the others were the same as in Example 1 to produce a sintered body. From these sintered bodies, cubes each having a side of 12 mm were cut out. As shown in FIG. 16, one side of the cube is orthogonal to the c-axis. The first quadrant of the 4πI-H curve was measured in each of the a-axis direction and the c-axis direction in these cubes, and the anisotropic magnetic field ( _HA ) was determined from the intersection. Table 6 shows the results. Table 6 also shows the saturation magnetization 4πIs and density of each cube.

[0112]

[Table 6]

From Table 6, x = 0.1 within the scope of the present invention.
4πIs and H _{A at} 〜0.4, y = 0.1-0.4
It can be seen that both increase. This also allows K
_It can be seen that ₁ [= ( _HA · Is) / 2] also increased.

Example 8 (Sintered magnet, ferrite particles: L
a ≠ Co) composition is Sr _0.7 La _0.3 Fe _11.7 (Co _(1-v) F _v ) _0.3 O ₁₉ [where Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ , y = 0 .3 (1-v) and v = 0.3-y /
The calcined body and the sintered body were produced in the same manner as in Example 1 except that the raw materials were blended so as to be 0.3. v
FIG. 17 shows the change in the magnetic characteristics of the calcined body with the change in the calcined temperature, together with the calcining temperature. FIG. 18 shows the change in the magnetic properties of the sintered body with the change in v, together with the calcination temperature and the sintering temperature.

FIG. 17 shows that when calcination was performed at 1200 ° C. and when calcination was performed at 1250 ° C., HcJ was 6%.
It can be seen that ferrite particles having an unprecedentedly high HcJ of kOe or more (up to 6.6 kOe) can be obtained. _{However, Sr 0.7 La 0.3 Fe 11.7 (} Co (1-v) Fe v) 0.3 in O ₁₉ v> 0.8, i.e. _{Sr 1-x La x Fe 12} -v Co v in O ₁₉ is La / Co = x It can be seen that in the range of / y> 5, the magnetic characteristics deteriorate significantly.

FIG. 18 shows that v> 0.5 in Sr _0.7 La _0.3 Fe _11.7 (Co _(1-v) F _v ) _0.3 O ₁₉ , that is, Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ It can be seen that the magnetic characteristics significantly deteriorated in the range of La / Co = x / y> 2.

Example 9 (Sintered magnet: Co + Zn added) _Same as Example 1 except that the raw materials were blended so that the composition was Sr _0.7 La _0.3 Fe _11.7 (Co _(1-w) Zn _w ) _0.3 O _19. Thus, a calcined body and a sintered body were produced. Calcination temperature 120
The change in the magnetic properties due to the change in w of the sintered body at 0 ° C.
FIG. 19 shows the sintering temperature.

From FIG. 19, by changing the ratio between Co and Zn, 4πIs can be mainly improved or HcJ can be improved.
It can be seen that it is possible to improve the characteristics of the high saturation magnetization type and the high coercive force type continuously.

Example 10 (Sintered magnet) The raw materials were blended so that the main phase composition was Sr _0.7 La _0.3 Fe _11.7 M _0.3 O ₁₉ (M = Zn, Mg, Mn, Ni, Co, Li + Fe). A sintered body was produced in the same manner as in Example 1, except that the firing temperature was 1200 ° C and the sintering temperature was 1220 ° C. The magnetic properties and density of these sintered bodies were measured. Table 7 shows the results.

[0120]

[Table 7]

Table 7 clearly shows the effect of improving the coercive force by the composite addition of La and Co. When M = Zn, high Br and high (BH) max are obtained, but HcJ is low. When an element other than Zn is added, all the properties are inferior to the case where M = Co.

In the Sr ferrite produced in each of the above embodiments, when a part of La was replaced by Bi,
It was found that the calcination temperature could be lowered by the addition. That is, the calcination temperature at which the best properties were obtained was shifted to the lower temperature side, and the coercive force was hardly deteriorated. Also,
When a calcined body and a sintered body were produced with a composition in which La was partially replaced by another rare earth element, improvement of HcJ was recognized by the composite addition with Co as in the above-described respective examples.

Further, the coating type magnetic layer containing the Sr ferrite particles prepared in each of the above Examples was formed on a substrate,
A magnetic card was manufactured. In these magnetic cards, the same results as those of the above embodiments can be obtained according to the replacement ratios x and y.
When the substitution rates x and y were within the range of the present invention, high output and high S / N were obtained.

Further, a thin film is formed on a substrate by a sputtering method, and this is heat-treated to form a hexagonal magnetoplumbite type ferrite phase similar to that of the above-described embodiment to form a thin-film magnetic layer. Was prepared. In these magnetic recording media, the same results as in the above embodiments were obtained in accordance with the replacement ratio x, and high output and high S / N were obtained when the replacement ratios x and y were within the range of the present invention.

Example 11 (Sintered Magnet: Measurement of Specific Resistance) In Example 2, the calcination temperature was 1200 ° C., the sintering temperature was 1180 ° C., and the other conditions were the same as in Example 2.
-1, y: A sample was prepared in which the value was changed from 0 to 1 (where x = y). The specific resistance greatly changed depending on the values of x and y. Although the cause is not clear, generation of Fe ²⁺ is considered.

With respect to each of the obtained samples, the DC specific resistance in the a-axis direction and the c-axis direction was measured. Table 8 shows the results. As described above, although the specific resistance is reduced, it is within a range in which there is no problem in practical use.

[0127]

[Table 8]

Example 12 (Sintered magnet: calcination temperature 1200)
In La added comparison by weight) Example 1 at ° C., the final composition, when formed into a _{Sr 1-x La x Fe 11.7} Co 0.3 O 19, and blended to prepare a raw material which becomes x = 0.0 to 1.0 , The calcination temperature was set to 1200 ° C, and the Br-HcJ characteristics, ρs and HcJ, HK / HcJ and [BH] max were measured. The obtained results are shown in FIGS. B-
The anisotropic magnetic field _HA was determined from the initial magnetization curve in the hard axis direction and the hysteresis curve in the easy magnetization direction for the sintered body at 1240 ° C. using an H tracer. Table 9 shows the results. Further, the specific resistance in the c-axis direction (height direction) of the sintered body fired at 1200 ° C. in the atmosphere was measured. Table 10 shows the results. x
Samples with 0.1 and 0.2 had high specific resistances of 10 ⁶ or more, which exceeded the measurement range of the measuring instrument used.

[0129]

[Table 9]

[0130]

[Table 10]

As is clear from FIGS. 20 to 22, x =
In the case of 0.3 and 0.4, the Br-HcJ characteristic curves were almost the same, and the highest magnetic characteristics were obtained under these conditions. Both had comparable HK / HcJ. The saturation magnetization per unit weight ([sigma] s) hardly changed in the range of x = 0 to 0.4, but HcJ decreased considerably rapidly as the amount of La or Sr decreased.

In Table 9, the measured value of the anisotropic magnetic field is x = 0.
The value monotonically increased to 3 and reached a substantially constant value of 20 kOe in the range of x = 0.3 to 0.8, and decreased again at x = 1.0.

Example 13 (Sintered magnet: calcination temperature 1300)
In La added comparison by weight) Example 1 at ° C., the final composition, when formed into a _{Sr 1-x La x Fe 11.7} Co 0.3 O 19, and blended to prepare a raw material which becomes x = 0.0 to 1.0 , Calcination temperature at 1300 ° C., Br-HcJ characteristics, HcJ and HK / HcJ and Br, x, Br and HcJ
Was evaluated. The obtained results are shown in FIGS.

As is clear from FIGS. 23 to 25, the magnetic properties were highest when x = 0.4, and both Br and HcJ increased with the firing temperature. However, 1200
At a sintering temperature of 1240 ° C. in which Br and HcJ are increased to almost the same level as in the case of the calcination at ℃, HK / HcJ is 86.5%.
Has dropped. In the case of calcining at 1200 ° C., x = 0.3,
0.4, which was almost the same characteristic, but when calcined at 1300 ° C., the characteristic was higher when x = 0.4. Also, x = 0.8
As a result, HcJ became a high value of 6 kOe or more.

Example 14 (Sintered magnet: magnetism by x, y
Evaluation of Characteristics) In Example 1, when the final composition was Sr _1-x La _x Fe _12-7 Co _y O ₁₉ , the calcining temperature was set to 1250 ° C. so that x and y became predetermined values. A calcined body and a sintered body were prepared in the same manner as in Example 1 except that the above conditions were changed, and the magnetic properties were evaluated. Each component was analyzed in the same manner as in Example 1.

FIG. 26 shows the magnetic characteristics (σs and HcJ) of the calcined body.
Is shown. Table 11 shows the analysis values of each sample that was subjected to the experiment. Table 11 also shows x, y, and z values calculated based on the analysis values. FIG.
Magnetic properties of sintered body fired at 0 ° C for 1 hour (Br and HcJ)
Is plotted against x and y in Table 11. FIG. 28 shows a result of plotting a value obtained by subtracting HcJ of the sintered body when the oxygen concentration is 20% from HcJ of the sintered body when the oxygen concentration at the time of the main firing is 100%.

[0137]

[Table 11]

As is clear from the drawing, it can be seen that high magnetic characteristics are obtained in the range of the present invention. At this time, X
As a result of analysis by line diffraction, the presence of a magnetoplumbite phase (M phase) was confirmed at any point. From FIGS. 27 and 28, it can be seen that high HcJ can be obtained when x / y = 1.3-2. Further, it can be seen that the dependency of HcJ on the firing atmosphere is reduced in this range.

Example 15 (Ferrite particles for bonded magnets)
Child) In Example 14, x = y = 0 (comparative example) and x = y
= 0.3 (Example) was calcined with a dry vibration mill, and then annealed in air at 1000 ° C. for 5 minutes. At this time, HcJ and the temperature characteristics of HcJ of the ferrite particles were measured. In addition, the temperature characteristics of HcJ and HcJ were similarly measured by VSM for commercially available pramag.
The results are shown below.

[0140]

[Table 12]

As is clear from the above table, the samples of the present invention had improved HcJ and HcJ temperature characteristics.

To the ferrite particles for a bonded magnet prepared as described above, a silane coupling agent was added and surface-treated, and 90 parts by weight of ferrite particles and 12:10 parts by weight of nylon were blended and kneaded. And granulation. Thereafter, molding was performed by an injection molding machine in a magnetic field, and the magnetic properties and the like were evaluated. As a result, the temperature characteristics of HcJ were improved as in the above-described embodiment.

Embodiment 16 (Application of Sintered Magnet) In the same manner as in Embodiment 1, except that the sample of the present invention was changed from a cylindrical shape for measurement to a field magnet for a C-type motor. Thus, a C-shaped sintered magnet for a motor was obtained.
The obtained core material was incorporated into a motor in place of a conventional sintered magnet, and when operated under rated conditions, good characteristics were exhibited. When the torque was measured, it was higher than that of the motor using the conventional core material.

The effects of the present invention are clear from the above examples.

[0145]

As described above, according to the present invention, by increasing simultaneously the saturation magnetization and the magnetic anisotropy of the hexagonal ferrite, a high residual magnetic flux density which cannot be achieved with the conventional hexagonal ferrite magnet is obtained. And a ferrite magnet having a high coercive force. Another object of the present invention is to provide a ferrite magnet having a high residual magnetic flux density and a high coercive force, having extremely excellent temperature characteristics of the coercive force, and having a small decrease in the coercive force even in a low temperature range. is there. Another object of the present invention is to realize a ferrite magnet having a high residual magnetic flux density and a high coercive force using relatively coarse ferrite particles having a particle size exceeding 1 μm. Another object of the present invention is to provide a magnetic recording medium having a high residual magnetic flux density. Another object of the present invention is to provide a motor that can be reduced in size and weight with high efficiency and high torque.

[Brief description of the drawings]

FIG. 1 shows that La and Co are used for Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 2 shows that La and Co are used for Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 3 shows that La and Co are used for an Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 4 shows that La and Co are used for Sr ferrite sintered body.
4 is a graph showing the relationship between the substitution rate (x, y) and the Curie temperature (Tc).

FIG. 5 is a graph showing the relationship between the calcination temperature and the sintering temperature and the magnetic properties of the Sr ferrite sintered body.

FIG. 6 is a drawing substitute photograph showing a particle structure, and is a scanning electron micrograph of a calcined Sr ferrite.

FIG. 7 is a drawing substitute photograph showing a grain structure, and is a scanning electron micrograph of a calcined body of Sr ferrite.

FIG. 8 is a drawing substitute photograph showing a grain structure, and is a scanning electron microscope photograph of a calcined Sr ferrite.

FIG. 9 is a drawing substitute photograph showing a particle structure, and is a scanning electron micrograph of a cross section of Sr ferrite sintered body (a cross section parallel to the a-plane of the crystal).

FIG. 10 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (cross section parallel to the a-plane of the crystal).

FIG. 11 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (a cross section parallel to the a-plane of a crystal).

FIG. 12 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (a cross section parallel to the a-plane of a crystal).

FIG. 13 is a graph showing the relationship between HcJ and (BH) max and Br for Sr ferrite sintered bodies and Ba ferrite sintered bodies.

FIG. 14 is a graph showing the temperature dependence of HcJ of a calcined Sr ferrite.

FIG. 15 is a graph showing the temperature dependency of HcJ of the Sr ferrite sintered body.

FIG. 16 shows a cube S used for anisotropic magnetic field (H _A ) measurement.
It is a perspective view which shows the direction of the crystal axis of r ferrite sintered compact.

FIG. 17 is a graph showing the effect of the relationship between the substitution rate of La and the substitution rate of Co on the magnetic properties of the calcined Sr ferrite.

FIG. 18 is a graph showing the effect of the relationship between the substitution rate of La and the substitution rate of Co on the magnetic properties of the Sr ferrite sintered body.

FIG. 19 is a graph showing the influence of the relationship between the substitution rate of Co and the substitution rate of Zn on the magnetic properties of the Sr ferrite sintered body.

FIG. 20 is a graph comparing the magnetic properties depending on the difference in the amount of La added.
FIG. 4 is a diagram showing r-HcJ characteristics.

FIG. 21 is a graph comparing magnetic properties depending on the difference in the amount of La added, and shows ρ when the calcination temperature is 1200 ° C.
FIG. 4 is a diagram showing characteristics of s and HcJ.

FIG. 22 is a graph comparing magnetic properties depending on the difference in the amount of La added.
It is the figure which showed K / HcJ and (BH) max.

FIG. 23 is a graph comparing magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing r-HcJ characteristics.

FIG. 24 is a graph comparing magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing characteristics of cJ and HK / HcJ and Br.

FIG. 25 is a graph comparing the magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing a relationship between Br and HcJ.

FIG. 26 is a graph showing the magnetic properties (σs and HcJ) of the calcined body when the calcining temperature is 1250 ° C.

FIG. 27 is a graph showing magnetic properties (Br and HcJ) of a sintered body obtained by firing the calcined body of FIG. 26 at 1220 ° C. for 1 hour in air.

FIG. 28 shows the calcined body of FIG.
From the HcJ of the sintered body at 0%, the oxygen concentration is 20%
It is the figure which plotted the value which subtracted HcJ of the sintered compact at the time of making.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 28, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

[Title of the Invention] Sintered magnet and motor

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sintered magnet and a motor using such a sintered magnet.

[0002]

2. Description of the Related Art Oxide permanent magnet materials include hexagonal S
There are r ferrite and Ba ferrite, but at present, magnetoplumbite (M type) Sr ferrite or Ba ferrite is mainly used, and these sintered magnets and bonded magnets are manufactured.

[0003] Of the magnet properties, particularly important are the residual magnetic flux density (Br) and the intrinsic coercive force (HcJ).

[0004] Br is determined by the density of the magnet and its degree of orientation,
It is determined by the saturation magnetization (4πIs) determined by the crystal structure, and is expressed by Br = 4πIs × degree of orientation × density. The 4πIs of M-type Sr ferrite and Ba ferrite is about 4.65 kG. Density and degree of orientation,
Even in the case of the sintered magnet that can obtain the highest value, 98
% Is the limit. Therefore, Br of these magnets
Is limited to about 4.46 kG, and high B of 4.5 kG or more
Obtaining r has heretofore been virtually impossible.

The present inventors have disclosed in Japanese Patent Application Laid-Open No. Hei 9-115715 that by adding an appropriate amount of, for example, La and Zn to M-type ferrite, 4πIs can be increased up to about 200G.
It has been found that Br can be increased to 4.5 kG or more. However, in this case, since the anisotropic magnetic field ( _HA ) described later decreases, it was difficult to simultaneously obtain Br of 4.5 kG or more and HcJ of 3.5 kOe or more.

[0006] HcJ is an anisotropic magnetic field ｛H _A (= 2K ₁ / I
s) Product of｝ and single domain particle ratio (fc) (H _A × fc)
Is proportional to Here, K ₁ is a crystal magnetic anisotropy constant, which is a constant determined by the crystal structure, like Is. M type B
For a ferrite, K ₁ = 3.3 × 10 ⁶ erg / cm ³ , and for M-type Sr ferrite, K ₁ = 3.5 × 10 ⁶ er.
g / cm ³ . As described above, it is known that M-type Sr ferrite has the maximum K ₁ , but it has been difficult to further improve K ₁ .

On the other hand, when the ferrite particles are in a single magnetic domain state, it is necessary to rotate the magnetization against the anisotropic magnetic field in order to reverse the magnetization, and thus the maximum HcJ is expected. In order to convert the ferrite particles into single domain particles, it is necessary that the size of the ferrite particles be equal to or less than the critical diameter (dc) described below.

Dc = 2 (k · Tc · K ₁ / a) ^1/2 / Is ²

Here, k is the Boltzmann constant, Tc is the Curie temperature, and a is the distance between iron ions. In the case of M-type Sr ferrite, dc is about 1 μm. For example, when manufacturing a sintered magnet, it is necessary to control the crystal grain size of the sintered body to 1 μm or less. Conventionally, it has been difficult to realize such fine crystal grains at the same time as high density and high degree of orientation for obtaining high Br. However, the present inventors disclosed in Japanese Patent Application Laid-Open No. 6-53064 a new production method. A method was proposed, and it was shown that high characteristics could not be obtained. However, also in this method, when Br is 4.4 kG, H
The cJ was about 4.0 kOe, and it was difficult to maintain a high Br of 4.4 kG or more and simultaneously obtain a high HcJ of 4.5 kOe or more.

Further, in order to control the crystal grain size of the sintered body to 1 μm or less, it is necessary to reduce the grain size in the forming step to preferably 0.5 μm or less in consideration of the grain growth in the sintering step. is there. When such fine particles are used, there is a problem that productivity generally decreases due to an increase in molding time and cracks during molding. For this reason, it has been very difficult to achieve both high characteristics and high productivity.

On the other hand, in order to obtain a high HcJ, Al ₂ O ₃
It has been conventionally known that the addition of Cr ₂ O ₃ is effective. In this case, since Al ³⁺ and Cr ³⁺ have the effect of replacing Fe ³⁺ having an “upward” spin in the M-type structure to increase _HA and suppress grain growth, it is 4.5 kOe or more. High HcJ is obtained. However, the sintering density tends to decrease as Is decreases, so that the Br decreases significantly. For this reason, only about 4.2 kG Br was obtained at the maximum with a composition in which HcJ was 4.5 kOe.

Incidentally, the temperature dependency of HcJ of the conventional sintered M-type ferrite magnet was about +13 Oe / ° C., and the temperature coefficient was a relatively large value of about +0.3 to + 0.5% / ° C. For this reason, HcJ was greatly reduced on the low temperature side, and there was a case where demagnetization occurred. In order to prevent this demagnetization, it is necessary to set HcJ at room temperature to a large value, for example, about 5 kOe, so that it was practically impossible to obtain high Br at the same time. The temperature dependency of HcJ of the M-type ferrite powder is superior to that of the anisotropic sintered magnet.
At about 8 Oe / ° C., the temperature coefficient was + 0.15% / ° C. or higher, and it was difficult to further improve the temperature characteristics.

The present inventors have proposed in Japanese Patent Application Laid-Open No. Hei 6-53064 that the rate of temperature change of HcJ can be reduced by introducing crystal strain into ferrite particles by grinding. However, in this case, since the HcJ of the particles is also reduced, it is difficult to simultaneously achieve high HcJ and excellent temperature characteristics of HcJ even when M-type Sr ferrite having a submicron size is used.

Since ferrite magnets are excellent in environmental resistance and inexpensive, they are often used for motors used in various parts of automobiles. Automobiles are sometimes used in cold or extremely hot environments, and motors are also required to operate stably in such harsh environments. But,
As described above, the conventional ferrite magnet has a problem that the coercive force is significantly deteriorated in a low-temperature environment, and irreversible demagnetization called "low-temperature demagnetization" may occur.

[0015]

SUMMARY OF THE INVENTION The object of the present invention is to
Realize hexagonal ferrite with high magnetization and high magnetic anisotropy
As a result, conventional hexagonal ferrite magnets cannot achieve
Has high residual magnetic flux density and high coercivity that were possible
It is to provide a sintered magnet. Another aspect of the present invention
The target is to have both high residual magnetic flux density and high coercive force.
In addition, the temperature characteristics of the coercive force are extremely excellent, especially in the low temperature range.
Even if the coercive force does not decrease much.
You. Another object of the present invention is to provide a powder having a particle size exceeding 1 μm.
High residual magnetic flux density and high retention using relatively coarse ferrite particles
It is to realize a sintered magnet having magnetic force. Also,
Another object of the present invention is to reduce the size and weight with high efficiency and high torque.
Is to provide a possible motor.

[0016]

This and other objects are achieved by any one of the following constitutions (1) to (9). (1) At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr,
When at least one element selected from rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M,
Coercive force HcJ at 25 ° C containing A, R, Fe and M
(Unit kOe) and residual magnetic flux density Br (unit kG) are HcJ
A sintered magnet which satisfies the formula IV Br + ／ HcJ ≧ 5.75 when ≧ 4, and satisfies the formula VBr + 1 / 10HcJ ≧ 4.82 when HcJ <4. (2) At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr,
When at least one element selected from rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M,
A, R, Fe and M, and the coercive force H at −25 ° C.
A sintered magnet in which cJ (unit: kOe) and residual magnetic flux density Br (unit: kG) satisfy the formula: VI Br + ／ HcJ ≧ 5.95. (3) The sintered magnet according to the above (1) or (2), wherein the ratio of Co in M is 10 atomic% or more. (4) A is a ferrite having a hexagonal crystal structure as a main phase, and at least one element selected from Sr, Ba, Ca and Pb, which always contains Sr,
When at least one element selected from the rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M, A,
The composition ratio of the total of the metal elements of R, Fe and M is as follows: A: 1 to 13 at% , R: 0.05 to 10 at% , Fe: 92 to 95 at% , M : : A sintered magnet having a composition of 0.1 to 5 atomic% . (5) _{II A 1-x R x (} Fe 12-y M y) when expressed as _{z O 19, 0.04 ≦ x ≦} 0.9, 0.04 ≦ y ≦ 0.5, 0.4 ≦ x / y ≦ 4, and 1.0 ≦ z ≦ 1.2 . (6) The sintered magnet according to the above (4) or (5), wherein the ratio of Co in M is 10 atomic% or more. (7) The above (4) to (6), wherein the absolute value of the temperature coefficient of the coercive force at −50 ° C. to 50 ° C. is 0.25% / ° C. or less.
Any of the sintered magnets. (8) When the coercive force HcJ (unit kOe) and the residual magnetic flux density Br (unit kG) at 25 ° C. are HcJ ≧ 4, the formula IV Br + HcJ ≧ 5.75 is satisfied, and when HcJ <4, the formula is The sintered magnet according to any one of the above (4) to (7), which satisfies V Br + 1 / 10HcJ ≧ 4.82. (9) A motor having the sintered magnet according to any one of (1) to (8).

[0017]

According to the present invention, as shown in the above formulas, at least L
The composition is such that both a and Co are contained in optimal amounts. As a result, without reducing the Is, it can increase the H _A by increasing K ₁ rather simultaneously enhancing Is,
As a result, high Br and high HcJ are realized. In particular,
In the sintered magnet of the present invention, characteristics satisfying the above formula IV or the above formula V are easily obtained at room temperature of about 25 ° C. With a conventional sintered Sr ferrite magnet, B of 4.4 kG
It has been reported that r and HcJ of 4.0 kOe were obtained, but none of those having HcJ of 4 kOe or more and satisfying the above formula IV was obtained. That is, when HcJ is increased, Br is decreased. In the sintered magnet of the present invention, when Co and Zn are added in combination, the coercive force is lower than that of Co alone and may be lower than 4 kOe, but the residual magnetic flux density is significantly improved. At this time,
Magnetic properties satisfying the above equation V are obtained. Conventionally, no Sr ferrite sintered magnet having an HcJ of less than 4 kOe satisfying the above formula V has been obtained.

Since the ferrite according to the present invention has a larger anisotropy constant (K ₁ ) or anisotropic magnetic field (H _A ) than conventional ferrite, a larger HcJ can be obtained with the same particle size, If the same HcJ is obtained, the particle size can be increased. For example, if the average particle size of the sintered body is 0.3 to 1 μm, HcJ of 4.5 kOe or more can be obtained, and even if it is 1 to 2 μm, HcJ of 3.5 kOe or more can be obtained. For this reason, the pulverization time and the molding time can be shortened, and the product yield can be improved.

The M-type ferrite in the composition of the present invention comprises:
As the saturation magnetization (4πIs) increases by about 2%, the crystal magnetic anisotropy constant (K ₁ ) or the anisotropy magnetic field (H _A ) is at most 1
Increase by 0-20%. It is not easy to measure the crystal magnetic anisotropy constant (K ₁ ) or the anisotropic magnetic field ( _HA ) with high accuracy, and there is no established method. However, for example, measuring the torque curve of an anisotropic sample using a torque meter Calculate the crystal magnetic anisotropy constants (K ₁ , K _2, etc.) by analyzing the initial magnetization curve of the anisotropic sample in the easy axis direction (c-axis) and the hard axis direction (a-axis). ) To determine the anisotropic magnetic field (H _A ) from the intersection, or the direction of the hard axis (a
A method is obtained from the second derivative of the initial magnetization curve of (axis).

The initial magnetization curve of the anisotropic sample is measured in the easy axis direction (c axis) and the hard axis direction (a axis), and the anisotropic magnetic field ( _HA ) is determined from the intersection. ,
When _HA of the present invention is obtained, a high value of at least 19 kOe or more and at most 20 kOe or more is obtained as shown in Table 6 below. This is an improvement of up to 10% or more compared to the conventional composition of Sr ferrite.

The sintered magnet of the present invention has a remarkably low temperature dependency of HcJ. Specifically, the sintered magnet of the present invention has a -50 to
The temperature coefficient (absolute value) of HcJ at 50 ° C. is 12 Oe / ° C.
Or less (0.25% / ° C. or less), and can easily be 9 Oe / ° C. or less (0.20% / ° C. or less). Further, the ferrite particles used in the present invention have a size of -50 to 50.
The temperature coefficient (absolute value) of HcJ at 70 ° C. is 7 Oe / ° C. or less (0.1% / ° C. or less), and 5 Oe / ° C. or less (0.05%).
% / ° C. or less), and the temperature coefficient can be set to zero. Since the temperature characteristics of HcJ are good, the above equation at −25 ° C.
Good magnetic properties satisfying VI are obtained. Such high magnetic properties in a low-temperature environment cannot be achieved with a conventional Sr ferrite magnet.

By the way, Bull.Acad.Sci.USSR, phys.Ser.
(English Transl.) Vol.25, (1961) pp1405-1408 (hereinafter,
Literature 1) describes a Ba ferrite represented by Ba _1-x M ³⁺ _x Fe _12-x M ²⁺ _x O ₁₉ . This Ba
In ferrite, M ³⁺ is La ³⁺ , Pr ³⁺ or Bi
³⁺ , and M ²⁺ is Co ²⁺ or Ni ²⁺ . It is unclear whether the Ba ferrite in Document 1 is a powder or a sintered body.
It is similar to the Sr ferrite of the present invention in containing a and Co. In Fig. 1 of Reference 1, La and Co
The change of the saturation magnetization with the change of x is described for the Ba ferrite containing, but in FIG. 1, the saturation magnetization decreases with the increase of x. Reference 1
Describes that the coercive force has increased several times, but does not describe specific numerical values.

On the other hand, in the present invention, by using a composition containing the optimum amounts of La and Co in the Sr ferrite sintered magnet, not only the HcJ is remarkably improved, but also the Br is slightly increased, and the HcJ is improved. Significant improvements in temperature dependence have also been achieved. In the present invention, La and Co are contained in the Sr ferrite particles in optimal amounts, thereby increasing HcJ and remarkably reducing its temperature dependence. It was found for the first time in the present invention that such an effect is obtained when the composite addition of La and Co is applied to Sr ferrite.

[0024] Indian Journal of Pure & Applied Physi
cs Vol. 8, July 1970, pp. 412-415 (hereinafter referred to as Reference 2) includes the formula La ³⁺ Me ²⁺ Fe ³⁺ ₁₁ O ₁₉ (Me ²⁺ = Cu ²⁺ , Cd ²⁺ , Zn ^{2 +} , Ni ²⁺ , Co ²⁺ or Mg ²⁺ ). This ferrite is the same as the sintered magnet of the present invention in that it contains La and Co simultaneously. However, in Reference 2, the saturation magnetization s when Me ²⁺ = Co ²⁺ is a low value of 42 cgs unit at room temperature and 50 cgs unit at 0K. Although no specific value is shown, Document 2 describes that the coercive force is so low that it cannot be used as a magnet material. This is probably because the composition of the ferrite described in Document 2 is out of the range of the present invention (the amounts of La and Co are too large).

Japanese Patent Application Laid-Open No. Sho 62-100417 (hereinafter, referred to as
The literature 3), equiaxed hexaferrite pigments of the composition represented by the formula _{M x (I) M y (} II) M z (III) Fe 12- (y + z) O 19 is described. In the above formula, M (I) is Sr, Ba,
It is a combination of a rare earth metal or the like and a monovalent cation, wherein M (II) is Fe (II), Mn, Co, Ni, C
u, Zn, Cd or Mg, and M (III) is Ti or the like. The hexaferrite pigments described in Document 3 are the same as the sintered magnet of the present invention in that they can simultaneously contain a rare earth metal and Co. However, Reference 3 does not disclose an example in which La and Co are simultaneously added, and does not disclose that both the saturation magnetization and the coercive force are improved by the simultaneous addition of La and Co. Moreover, among the examples of Reference 3, C
In the case where o is added, at the same time, T as the element M (III)
i is added. Since the element M (III) , particularly Ti, is an element that lowers both the saturation magnetization and the coercive force, it is obvious that Document 3 does not suggest the configuration and effect of the present invention.

Japanese Patent Application Laid-Open No. Sho 62-119760 (hereinafter referred to as "
Reference 4) describes a magneto-optical recording material characterized in that a part of Ba of magnetoplumbite-type barium ferrite is replaced with La and a part of Fe is replaced with Co. In this Ba ferrite, La
It also looks similar to the Sr ferrite of the present invention in that it contains Co and Co. However, the ferrite of Document 4 is a material for “magneto-optical recording” in which magnetic domains are written in a magnetic thin film using the thermal effect of light to record information, and information is read out using the magneto-optical effect. The technical field is different from the sintered magnet of the present invention. Reference 4 describes (I)
Ba, La, and Co are essential in the composition formula, and Formulas (II) and (III) show the case where a metal ion having a valence of 4 or more (unspecified) is added thereto. It is just that. On the other hand, the ferrite of the present invention is an Sr ferrite which essentially contains Sr, and differs from the composition of Reference 4 in that La and Co are added in appropriate amounts. That is, the Sr ferrite of the present invention, as described in
By using a composition containing the optimum amounts of La and Co in Sr ferrite, HcJ can be significantly improved,
This realizes a slight increase in r and remarkably improves the temperature dependency of HcJ. This was realized for the first time in a composition of the present invention different from Reference 4.

Japanese Patent Publication No. 5-41218 ( hereinafter referred to as Reference 5) discloses that a calcined body of M-type Ba, Sr, and Pb ferrite is provided with CaO, SiO ₂ , CoO, ( Cr ₂ O ₃ , Al ₂ O).
_It is described that a ferrite sintered body having a high coercive force can be produced by adding one or two of ( ₃ ).
However, there is no description about rare earth elements such as La. Further, the magnetic properties described in the examples are low, and when compared with those of the same Br, HcJ is 100O.
e only improved. This is because, unlike the present invention, it does not contain a rare earth element such as La or the like, and the ferrite described in Literature 5 is clearly different from that of the present invention.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The sintered magnet of the present invention comprises Sr, B
at least one element selected from a, Ca and Pb
Element that contains Sr and must contain Sr is a rare earth element
(Including Y) and at least one selected from Bi
Is an element which necessarily contains La and is R, and Co is
Or Co and Zn as M, A, R, Fe and
Coercive force HcJ at 25 ° C (unit: kOe)
When the residual magnetic flux density Br (unit: kG) is HcJ ≧ 4, the equation IV Br + ＨHcJ ≧ 5.75 is satisfied, and when HcJ <4, the equation VBr + 1 / 10HcJ ≧ 4.82 is satisfied.

Further , each of the above-mentioned A, R, Fe and M
A: 1 to 13 atomic%, R: 0.05 to 10 atomic%, Fe: 80 to 95 atomic%, M: 0.1 to 5 with respect to the total amount of metal elements. It is preferred to have a composition that is at .

More preferably , A: 3 to 11 at%, R: 0.2 to 6 at%, Fe: 83 to 94 at%, M: 0.3 to 4 at%,

More preferably, A: 3 to 9 atomic%, R: 0.5 to 4 atomic%, Fe: 86 to 93 atomic%, and M: 0.5 to 3 atomic%.

In each of the above constituent elements, A represents Sr, B
At least one element selected from a, Ca and Pb, which always contains Sr. If A is too small, M-type ferrite will not be formed or non-magnetic phase such as α-Fe ₂ O ₃ will increase. If A is too large, no M-type ferrite will be formed or a non-magnetic phase such as SrFeO _3-x will increase. A
The ratio of Sr therein is preferably at least 51 atomic%, more preferably at least 70 atomic%, and further preferably 100 atomic%. If the ratio of Sr in A is too low, it is impossible to obtain both the saturation magnetization and the remarkable improvement in coercive force.

R is a rare earth element (including Y) and Bi
At least one element selected from the group consisting of: In R,
La is always included. If R is too small, the amount of solid solution of M decreases, and the effect of the present invention cannot be obtained. If R is too large, non-magnetic hetero phases such as orthoferrite increase.
The proportion of La in R is preferably at least 40 at%, more preferably at least 70 at%, and it is most preferable to use only La as R in order to improve the saturation magnetization. This is because, when comparing the solid solution limit amount to hexagonal M-type ferrite, La is the largest. Therefore, if the proportion of La in R is too low, the solid solution amount of R cannot be increased, and as a result, the solid solution amount of element M cannot be increased, and the effect of the present invention is reduced. I will. Further, if Bi is used in combination, the calcining temperature and the sintering temperature can be lowered, which is advantageous in production.

The element M is Co or Co and Zn. If M is too small, the effects of the present invention cannot be obtained, and M
Is too large, Br and HcJ decrease conversely, and the effect of the present invention cannot be obtained. The ratio of Co in M is preferably at least 10 atomic%, more preferably at least 20 atomic%. Co
If the ratio is too low, the improvement in coercive force will be insufficient.

Further, when the sintered magnet preferably present invention, expressed as the formula _{I A 1-x R x (} Fe 12-y M y) z O 19 (x, y, z represents the number of moles) 0.04 ≦ x ≦ 0.9, especially 0.04 ≦ x ≦ 0.6, 0.04 ≦ y ≦ 0.5, and 0.7 ≦ z ≦ 1.2.

More preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.7 ≦ z ≦ 1.2, and even more preferably 0.1 ≦ x ≦ 0. 0.4, 0.1 ≦ y ≦ 0.4, 0.8 ≦ z ≦ 1.1, and particularly preferably 0.9 ≦ z ≦ 1.05.

In the above formula I, if x is too small, that is, if the amount of the element R is too small, the solid solution amount of the element M in the hexagonal ferrite cannot be increased, and the effect of improving the saturation magnetization and / or the anisotropic magnetic field The improvement effect becomes insufficient. If x is too large, the element R cannot be substituted in the hexagonal ferrite to form a solid solution. For example, orthoferrite containing the element R is generated, and the saturation magnetization is reduced. If y is too small, the effect of improving the saturation magnetization and / or the effect of improving the anisotropic magnetic field become insufficient. If y is too large, the element M cannot be substituted and solid-solved in the hexagonal ferrite. The element M
Is within the range that can be replaced by solid solution, the anisotropy constant (K ₁ )
And the deterioration of the anisotropic magnetic field ( _HA ) is increased. z
Is too small, the nonmagnetic phase containing Sr and the element R increases, and the saturation magnetization decreases. If z is too large, the α-Fe ₂ O ₃ phase or the nonmagnetic spinel ferrite phase containing the element M increases, and the saturation magnetization decreases. Note that the above formula I is defined as containing no impurities.

In the above formula I representing the composition, the number of moles of oxygen (O) is 19, which is the same as when R is all trivalent and x = y and z = 1. It shows a stoichiometric composition ratio. The number of moles of oxygen varies depending on the type of R and the values of x, y, and z. Further, for example, when the firing atmosphere is a reducing atmosphere, oxygen deficiency (vacancy) may occur. Further, Fe is M
Usually, trivalent is present in the type ferrite, but this may change to divalent or the like. Also, M such as Co
The valence of the element represented by may also change, and these change the ratio of oxygen to the metal element. In this specification, the number of moles of oxygen is indicated as 19 regardless of the type of R and the values of x, y, and z. However, the actual number of moles of oxygen slightly deviates from the stoichiometric composition ratio. Is also good. For example, Sr
When divalent Fe is formed in the ferrite, it is considered that the specific resistance of the ferrite decreases (Fe ²⁺ → Fe ³⁺ + e).
^- ). In the case of a polycrystalline body, the grain boundary resistance is usually higher than the intragranular resistance, but the specific resistance of the actual sintered magnet may change due to this cause.

The composition of the sintered magnet can be measured by a fluorescent X-ray quantitative analysis or the like. The presence of the main phase is confirmed by X-ray diffraction.

The sintered magnet may contain B ₂ O ₃ . By including B ₂ O ₃ , the calcining temperature and the sintering temperature can be lowered, which is advantageous in production. B ₂ O ₃
Is preferably 0.5% by weight or less based on the oxide magnetic material. If the B ₂ O ₃ content is too large,
The saturation magnetization becomes low.

The sintered magnet may contain at least one of Na, K and Rb. These when converted into Na ₂ O, K ₂ O and Rb ₂ O, respectively, the total content thereof is preferably not more than 3 wt% of the total sintered magnet. If these contents are too large, the saturation magnetization will be low. When these elements expressed in M ^I, M ^I in the sintered magnet is contained in the form of for example ^{_{Sr 1.3-2a R a M I a-}} 0.3 Fe 11.7 M 0.3 O 19. In this case, 0.3 <a ≦ 0.
It is preferably 5. When a is too large, in addition to the saturation magnetization becomes low, a problem that the element M ^I is thus a large amount of evaporation occurs during firing.

In addition to these impurities, for example, Si,
Al, Ga, In, Li, Mg, Mn, Ni, Cr, C
u, Ti, Zr, Ge, Sn, V , Nb, Ta, Sb,
As, W, Mo, etc. in the form of oxides, each containing 1% by weight or less of silicon oxide, 5% by weight or less of aluminum oxide, 5% by weight or less of gallium oxide, 3% by weight or less of indium oxide,
1% by weight or less of lithium oxide, 3% by weight of magnesium oxide
Below, manganese oxide 3% by weight, nickel oxide 3% by weight, chromium oxide 5% by weight, copper oxide 3% by weight, titanium oxide 3% by weight, zirconium oxide 3% by weight, germanium oxide 3% by weight , Tin oxide 3% by weight or less, vanadium oxide 3% by weight or less, niobium oxide 3
% By weight, 3% by weight or less of tantalum oxide, 3% by weight or less of antimony oxide, 3% by weight or less of arsenic oxide, 3% by weight or less of tungsten oxide, and 3% by weight or less of molybdenum oxide.

The ferrite particles used in the present invention
When expressed Formula _{I A 1-x R x (} Fe 12-y M y) z O 19 (x, y, z represents the number of moles) and, 0.04 ≦ x ≦ 0.9, particularly 0 0.04 ≦ x ≦ 0.6, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 20, especially 0.8 ≦ x / y ≦ 5, 0.7 ≦ z ≦ 1.2 Preferably, there is .

More preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 5, 0.7 ≦ z ≦ 1.2, More preferably, 0.1 ≦ x ≦ 0.4, 0.1 ≦ y ≦ 0.4, 0.8 ≦ x / y ≦ 5, 0.8 ≦ z ≦ 1.1, and particularly preferably 0. 9 ≦ z ≦ 1.05.

In the above formula I, if x / y is too small or too large, the valences of the element R and the element M cannot be balanced, and a heterogeneous phase is easily formed. Since the element M is divalent, when the element R is a trivalent ion, ideally x / y
= 1. The reason why the allowable range is large in the region where x / y exceeds 1 is that even when y is small, the valence can be balanced by the reduction of Fe ³⁺ → Fe ²⁺ . The other reasons for limiting x, y and z are the same as described above. When x / y is slightly larger than 1, there is also an effect that the magnetic characteristics (HcJ) become stable with respect to the atmosphere (oxygen partial pressure) during calcination.

The ferrite particles used in the present invention can obtain a higher coercive force than conventional ones even if the average particle size of the primary particles exceeds 1 μm. The average particle size of the primary particles is preferably 2 μm or less, more preferably 1 μm or less, and still more preferably 0.1 to 1 μm. If the average particle size is too large, the ratio of multi-domain particles in the magnet powder will be high and HcJ will be low. If the average particle size is too small,
The magnetism is reduced by thermal disturbance, and the orientation and moldability during molding in a magnetic field are deteriorated.

The ferrite particles used in the present invention
Is at least one element selected from Sr, Ba, Ca and Pb, and always contains Sr and is A, and is at least one element selected from rare earth elements (including Y) and Bi. R that contains La
And when Co or Co and Zn is M,
A, R, Fe and M, the absolute value of the temperature dependence (Oe / ° C) of the intrinsic coercive force (HcJ) at -50 ° C to 50 ° C is expressed as | ΔHcJ / ΔT |, and the unit of HcJ is KOe. Where, intrinsic coercive force (HcJ) and temperature dependency (Oe) satisfying the formula III | ΔHcJ / ΔT | ≦ 5/3 × HcJ−7 / 3.
/ ° C). Ferrite particles having such characteristics can be obtained by using an oxide magnetic material having the above composition, or by a production method described below.

The Curie temperature of the ferrite having the above composition is as follows.
Usually, it is 425-460 ° C.

As a method for producing ferrite particles, various methods such as a solid phase reaction method, a liquid phase method such as a coprecipitation method and a hydrothermal synthesis method, a glass precipitation method, a spray pyrolysis method, and a gas phase method are used. is there.

In the solid-state reaction method, iron oxide powder, powder containing element A, element R and element M are used as raw materials, and a mixture of these powders is fired (calcined). In this calcined body, the primary particles of the ferrite are agglomerated and in a so-called “granular” state. Therefore, pulverization is often performed thereafter. The pulverization is performed by a dry or wet method. In this case, distortion is introduced into the ferrite particles and magnetic properties (mainly HcJ) are deteriorated.
An annealing treatment is often performed after the pulverization.

When producing ferrite particles by the solid-phase reaction method, the following points are important. Prevents agglomeration of ferrite particles. Removes distortion of ferrite particles. When the ferrite particles are mechanically oriented, the ferrite particles are formed into a plate shape. Adjust the size of the ferrite particles to an appropriate range.

In order to realize the above, in addition to the iron oxide powder, the powder containing the element A, the powder containing the element R, and the powder containing the element M, chlorides of Ba or Sr were further added. There is a method in which the mixture is calcined (calcined), and then the added chloride is washed and removed. Alternatively, there is a method of pulverizing a normal calcined body, adding a chloride of Ba or Sr or the like, calcining (calcining) again, and then washing and removing these chlorides (Japanese Patent Publication No. 55-19046). No.).

In addition to the above raw material powder, if necessary, B ₂ O ₃ and other compounds such as Si, Al, Ga, I
n, Li, Mg, Mn, Ni, Cr, Cu, Ti, Z
r, Ge, Sn, V , Nb, Ta, Sb, As, W, M
A compound containing o or the like may be contained as an additive or an impurity such as an unavoidable component.

The calcination is performed, for example, in the
The heat treatment may be performed at 1350 ° C. for 1 second to 10 hours, particularly about 1 second to 3 hours.

The calcined body thus obtained has a substantially magnetoplumbite-type ferrite structure, and the primary particles have an average particle size of preferably 2 μm or less, more preferably 1 μm or less, and still more preferably. Is 0.1-1μ
m, most preferably 0.1-0.5 μm. The average particle size may be measured with a scanning electron microscope.

Alternatively, the sintered magnet of the present invention has a hexagonal structure
Sr, Ba, C
at least one element selected from a and Pb
Therefore, the element that always contains Sr is designated as A, and the rare earth element (Y is
At least one element selected from the group consisting of
R that always contains La, and whether it is Co or C
When o and Zn are M, A, R, Fe and M
The composition ratio of the total of each metal element is
On the other hand, A: 1 to 13 atomic% , R: 0.05 to 10 atomic% , Fe: 92 to 95 atomic% , and M: 0.1 to 5 atomic% .

When the main phase is hexagonal ferrite and represented by the formula II A _1-x R _x (Fe _12-y M _y ) _z O ₁₉ , 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.4 ≦ x / y ≦ 4, particularly 0.8 ≦ x / y ≦ 4, 1.0 ≦ z ≦ 1.2 , and more preferably 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 2, and 1.0 ≦ z ≦ 1.2.

Particularly preferably, 0.04 ≦ x ≦ 0.5, 0.04 ≦ y ≦ 0.5, 0.8 ≦ x / y ≦ 2, 1.0 ≦ z ≦ 1.2, Further, 0.8 ≦ x / y ≦ 1.7.

A, R, M, x, y, z in the above formula II
And the reasons for these limitations are the same as those in Formula I above. The reason for limiting x / y is the same as that in the formula I. Further, the impurities that may be contained in addition to these are the same as those described above . Also, x /
When y is slightly larger than 1, there is also an effect that the magnetic characteristics (HcJ) become stable with respect to the atmosphere (oxygen partial pressure) at the time of main firing.

The sintered magnet is manufactured by molding and sintering the ferrite particles manufactured by the various methods described in the method of manufacturing ferrite particles. In this case, the most widely used industrially for sintered magnets is
Although the method uses ferrite particles produced by a solid phase reaction method, ferrite particles produced by another method may be used, and there is no particular limitation.

Since the calcined body is generally in the form of granules, it is preferable to first perform dry coarse pulverization in order to pulverize or pulverize the calcined body. Dry coarse pulverization also has the effect of reducing the coercive force HcB by introducing crystal strain into the ferrite particles. Due to the decrease in coercive force, aggregation of particles is suppressed, and dispersibility is improved.
Further, by suppressing the aggregation of the particles, the degree of orientation is improved. The crystal strain introduced into the particles is released in a later sintering step, and the coercive force is restored, so that the particles can be made permanent magnets. In the case of dry coarse pulverization, usually,
SiO ₂ and CaCO ₃ which becomes CaO upon firing are added. SiO ₂ and CaCO ₃ may be partially added before calcining. Impurities and added Si and Ca
Is segregated mostly at grain boundaries and triple junctions, but a part is also taken into the ferrite part (main phase) in the grains. Especially Ca
Is likely to be on the Sr site.

After the dry coarse pulverization, it is preferable to prepare a pulverization slurry containing ferrite particles and water, and to perform wet pulverization using the slurry.

After the wet pulverization, the pulverizing slurry is concentrated to prepare a molding slurry. Concentration may be performed by centrifugation, a filter press, or the like.

The molding may be performed by a dry method or a wet method. However, in order to increase the degree of orientation, it is preferable to perform a wet method.

In the wet molding step, molding in a magnetic field is performed using a molding slurry. Molding pressure is 0.1-0.5ton / cm
^The applied magnetic field may be about ² to 15 kOe.

In the wet molding, a non-aqueous dispersion medium or an aqueous dispersion medium may be used. When a non-aqueous dispersion medium is used, for example, as described in JP-A-6-53064, a surfactant such as oleic acid is added to an organic solvent such as toluene or xylene. And a dispersion medium. By using such a dispersion medium, it is possible to obtain a high degree of magnetic orientation of about 98% at the maximum even when ferrite particles having a submicron size that are difficult to disperse are used. On the other hand, as the aqueous dispersion medium, one obtained by adding various surfactants to water may be used.

After the molding step, the molded body is heat-treated at a temperature of 100 to 500 ° C. in the air or in nitrogen to sufficiently decompose and remove the added dispersant. Next, in the sintering step, the molded body is preferably for example 1150-12 in air.
Sintering is performed at a temperature of 70 ° C, more preferably 1160 to 1240 ° C for about 0.5 to 3 hours to obtain a sintered anisotropic ferrite magnet.

The average crystal grain size of the sintered magnet of the present invention is preferably 2 μm or less, more preferably 1 μm or less, and still more preferably 0.5 to 1.0 μm. , A sufficiently high coercive force can be obtained. The crystal grain size can be measured by a scanning electron microscope. Incidentally, the resistivity is the value of the degree 10 ⁰ [Omega] m or more.

The compact was crushed using a crusher or the like, and the average particle size was reduced to 100 to 700 μm by sieving or the like.
m to obtain a magnetic field-oriented granule, which is subjected to dry magnetic field molding, and then sintered to obtain a sintered magnet.

By applying the sintered magnet of the present invention,
Generally, the following effects can be obtained, and excellent application products can be obtained. In other words, if the shape is the same as that of a conventional ferrite product, the magnetic flux density generated from the magnet can be increased, so that a motor can achieve higher torque, etc., and if it is a speaker or headphone, the magnetic circuit can be strengthened. It can contribute to high performance of applied products, such as obtaining good sound quality with linearity. Further, if the same function as in the related art is sufficient, the size (thickness) of the magnet can be reduced (thinned), which contributes to downsizing and weight reduction (thinning). Also,
Conventionally, even in a motor in which the field magnet is a winding type electromagnet, this can be replaced with a ferrite magnet, which contributes to weight reduction, shortening of the production process, and cost reduction. In addition, because of its excellent coercive force (HcJ) temperature characteristics, it can be used even in low-temperature environments where there was a risk of low-temperature demagnetization (permanent demagnetization) of ferrite magnets, especially in cold regions and in the sky. The reliability of the manufactured product can be significantly increased.

The sintered magnet of the present invention is processed into a predetermined shape and is used for a wide range of applications as described below.

For example, for fuel pump, power window, ABS, fan, wiper, power steering, active suspension, starter,
Automotive motors for door locks, electric mirrors, etc .; FD
For D spindle, For VTR capstan, For VTR rotating head, For VTR reel, For VTR loading, VT
For R camera capstan, For VTR camera rotating head,
Motors for OA and AVI devices, such as for VTR camera zoom, VTR camera focus, radio-cassette capstan, CD, LD, MD spindle, CD, LD, MD loading, CD, LD optical pickup, etc .; Motors for home appliances such as for refrigerator compressor, electric tool drive, electric fan, microwave oven fan, microwave plate rotation, mixer drive, dryer fan drive, shaver drive, electric toothbrush, etc .;
Motors for FA equipment such as robot axes, joint drive, robot main drive, machine tool table drive, machine tool belt drive, etc .; motor generators, magnets for speakers and headphones, magnetron tubes, magnetic field generation for MRI It is suitably used for devices, clampers for CD-ROMs, sensors for distributors, sensors for ABS, fuel / oil level sensors, magnet latches, and the like.

[0073]

EXAMPLES Example 1 (Sintered Magnet: A-R-Fe-M Set)
The following materials were used as raw materials. Fe ₂ O ₃ powder (primary particle diameter 0.3 μm: Mn, Cr, Si, C
1), SrCO ₃ powder (primary particle diameter 2 μm: containing Ba and Ca as impurities), a mixture of Co ₃ O ₄ powder and CoO powder (primary particle diameter 1 to 5 μm), La ₂ O ₃ powder (purity 99.9%)

The above raw materials were blended so that the composition had a predetermined value. Furthermore, SiO ₂ powder (primary particle diameter 0.01
μm) and CaCO ₃ powder (primary particle diameter 1 μm) were added to and mixed with the above raw materials at 0.2% by weight and 0.15% by weight, respectively. The obtained mixture was pulverized with a wet attritor for 2 hours, dried and sized, and then calcined in air at 1200 ° C. for 3 hours to obtain a granular calcined body (magnet powder).

To the calcined body obtained by calcining at 1200 ° C., 0.4% by weight of the above SiO ₂ and 1.25% by weight of the above CaCO ₃ were added, and the ratio of the calcined body was determined by a dry rod mill. Grinding was performed until the surface area became 7 m ² / g.

Next, the calcined powder was wet-pulverized in a ball mill using xylene as a non-aqueous solvent and oleic acid as a surfactant. Oleic acid was added in an amount of 1.3% by weight based on the calcined powder. The calcined body powder in the slurry was 33% by weight. The pulverization has a specific surface area of 8 to
The operation was performed until 9 m ² / g was reached.

By the above pulverization, pulverization strain was introduced into the calcined powder, and the HcJ of the calcined powder was reduced to 15 to 60% before the pulverization. Further, Fe and Cr are slightly mixed in from the pulverizer.

Next, the pulverized slurry was adjusted by a centrifugal separator so that the concentration of the calcined powder in the slurry was about 85% by weight. While removing the solvent from the slurry, about 1
It was formed into a column having a diameter of 30 mm and a height of 15 mm in a 3 kG height magnetic field. The molding pressure was 0.4 ton / cm ² . A part of the slurry was dried, calcined at 1000 ° C., and all the components were converted into oxides. Then, the amounts of the respective components were analyzed by a fluorescent X-ray quantitative analysis method. Table 1 shows the results.

[0079]

[Table 1]

Next, after the molded body is heat-treated at 100 to 300 ° C. to sufficiently remove oleic acid,
The temperature was raised at a rate of 5 ° C./min, and the temperature was maintained at 1200 ° C. for 1 hour to perform sintering to obtain a sintered body. After processing the upper and lower surfaces of the obtained sintered body, 4πIs, the residual magnetic flux density (B
r), coercive force (HcJ), Ir / Is, Hk / HcJ, maximum energy product [(BH) max], and sintered density were examined. Table 2 shows the results.

[0081]

[Table 2]

As is clear from Table 2, Sample No. 1
The sintered body cores of the present invention of Nos. 1 to 14 show extremely excellent properties.

Example 2 (Sintered magnet: based on RM substitution rate)
Comparative) The following materials were used as raw materials. Fe ₂ O ₃ powder (primary particle diameter 0.3 μm: Mn, Cr, Si, C
1), SrCO ₃ powder (primary particle diameter 2 μm: containing Ba and Ca as impurities), a mixture of Co ₃ O ₄ powder and CoO powder (primary particle diameter 1 to 5 μm), La ₂ O ₃ powder (purity 99.9%)

The above raw materials were blended so as to have a composition of Sr _1-x La _x Fe _12-y Co _y O ₁₉ . Furthermore, SiO ₂ powder (primary particle size 0.01 μm) and CaCO ₃ powder (primary particle size 1
μm) was added to and mixed with 0.2% by weight and 0.15% by weight of the above raw materials, respectively. The obtained mixture was pulverized with a wet attritor for 2 hours, dried and sized,
Calcination was performed in air at a temperature in the range of 1150 to 1300 ° C. for 3 hours to obtain a calcined body. Hereinafter, a sintered body was produced in the same manner as in Example 1.

After processing the upper and lower surfaces of the obtained sintered body, the residual magnetic flux density (Br), the coercive force (HcJ and HcB), the maximum energy product [(BH) max], and the substitution ratio x of La and Co , Y (where x = y). The results are shown in FIGS. 1 and 2 together with the sintering temperature.

From FIG. 1 and FIG. 2, when x and y are within the range of the present invention, by optimizing the sintering temperature, Br ≧
It can be seen that HcJ or HcB can be significantly improved while maintaining the high magnetic properties of 4.4 kG and (BH) max ≧ 4.6 MGOe. To illustrate this clearly, FIG.
The relationship between HcJ and Br and the relationship between HcJ and (BH) max when x is changed for a sintered body in which both the calcination temperature and the sintering temperature are 1200 ° C. are shown. For comparison, data on the sintered body described in Japanese Patent Application No. 8-145006 is also shown in FIG. 3 as “Comparative Example (LaZn substitution)”. The sintered body of this comparative example has a main phase represented by Sr _0.7 La _0.3 Fe _11.7 Zn _0.3 O ₁₉ . The sintered body (x = 0.1 to 0.4) of the embodiment shown in FIG. 3 has HcJ of 4 kOe or more, and Br and HcJ satisfy the above-described formula IV Br + ／ HcJ ≧ 5.75. It has become. On the other hand, the sintered body of the comparative example (HcJ is less than 4 kOe) shown in FIG. 3 does not satisfy the expression VBr + 1 / 10HcJ ≧ 4.82.

FIG. 4 shows the relationship between the Curie temperature (Tc) of the sintered body at a sintering temperature of 1220 ° C. and the substitution rates x and y (where x = y). From FIG. 4, it can be seen that as x and y increase, T
It can be seen that c decreases.

Example 3 (Sintered Magnet: Calcination Temperature and Sintering)
(Comparison by temperature) The raw materials are mixed so that the composition becomes x = 0.3 and y = 0.3 in Sr _1-x La _x Fe _12-y Co _y O ₁₉ , and the calcination temperature and sintering temperature are plotted. A sintered body was produced in the same manner as in Example 1 except that the sintered body was changed as shown in FIG. FIG. 5 shows the magnetic properties of these sintered bodies. As shown in FIG. 5, in order to obtain high Br and high HcJ, the calcination temperature is set to 1300 ° C.
It can be seen that the sintering temperature is preferably set to 1180 to 1220 ° C. However, even when the calcination was performed at 1300 ° C., when the sintering temperature was 1240 ° C.,
High magnetic properties such as r ≒ 4.4 kG and HcJ ≒ 4.0 kOe are obtained.

In order to analyze such a characteristic phenomenon, the microstructures of the calcined body and the sintered body were examined by a scanning electron microscope (SEM). 6, 7 and 8 show that the calcining temperature (T1) was 1200 ° C., 1250 ° C. and 130 ° C.
SEM photographs of the calcined body obtained at 0 ° C. are shown. In the calcined body obtained at a calcining temperature of 1300 ° C,
It can be seen that coarse particles having a particle size exceeding 10 μm account for a large proportion.

The structure of the sintered body was also examined by SEM. FIGS. 9 to 12 show SEM photographs. Fig. 9: T1 = 1200 ° C, T2 = 1200 ° C, Fig. 10: T1 = 1200 ° C, T2 = 1240 ° C, Fig. 11: T1 = 1300 ° C, T2 = 1200 ° C., FIG. 12: T1 = 1300 ° C., T2 = 1240 ° C. These photographs show a fracture surface parallel to the a-plane of the crystal. It can be seen that even in a sintered body in which HcJ of 4.5 kOe or more was obtained, relatively many crystal grains having a grain size exceeding 1 μm were present. In addition, when the calcination temperature was 1300 ° C., it was found that most of the crystal grains had a particle size of more than 1 μm. However, although HcJ as high as about 4 kOe is obtained despite the large crystal grain size, the magnetic properties, particularly the crystal grain size dependency of HcJ can be improved by the present invention. it is obvious.

The calcined body (x = 0.3, y = 0.3)
Average primary particle size is 1 when the calcination temperature is 1250 ° C or lower.
μm or less, and the sintered body obtained by sintering this at 1220 ° C. or less had an average crystal grain size of 1.5 μm or less.
On the other hand, the average primary particle size of the calcined body at a calcining temperature of 1300 ° C. is 3 μm or more.
The average crystal grain size of the sintered body obtained by sintering at 220 ° C. or less was 3 μm or less.

Example 4 (Sintered magnet: Sr ferrite magnet
And Ba ferrite magnet) The raw materials were blended such that the composition was x = y in Sr _1-x La _x Fe _12-y Co _y O ₁₉ and x and y were 0.2 or 0.3. Otherwise in the same manner as in Example 1, a calcined body was produced. The calcination temperature was 1200 ° C. The calcined body was sintered to obtain a sintered Sr ferrite magnet. The sintering temperature was selected from the range of 1180-1260C.

Further, for comparison, the main phase composition is such that x = y in Ba _1-x La _x Fe _12-y Co _y O ₁₉ and x and y are 0.2 or 0.3. The raw materials are blended, the calcination temperature is set to 1200 ° C,
The sintering temperature was set to 1180 to 12 like the Sr ferrite magnet.
A Ba ferrite sintered magnet was obtained by selecting from the range of 60 ° C. Observation of the structure of the sintered body with a scanning electron microscope (SEM) revealed that Ba ferrite had a larger aspect ratio and was flattened. Among the obtained Ba ferrites, HcJ when x = 0.3 and y = 0.3, shrinkage in the a-axis (diameter) direction and c-axis (height) direction when the sintering temperature is 1220 ° C. Table 3 shows the ratios of the ratios and the sintered densities. In general, when the ratio of shrinkage (shh / shΦ) is large,
The particles tend to flatten. The anisotropic magnetic field (H _A ) of the Ba ferrite (x = 0.3) measured by the method of Example 7 was 16.6 kOe.

[0094]

[Table 3]

FIG. 13 shows the magnetic characteristics of each of these sintered bodies. FIG. 13 shows the characteristics of a plurality of sintered bodies having different sintering temperatures for each composition. Thereby, Ba
In the case of a system ferrite, a large HcJ cannot be obtained because the anisotropic magnetic field ( _HA ) is low and the particles are easily flattened. Actually, as shown in Table 3, HcJ is about 3.5 kOe at the maximum, which is a value obtained by the conventional Sr.

In FIG. 13, a sintered Sr ferrite (HcJ
(All of which are 4 kOe or more) satisfy the above-mentioned formula IV. On the other hand, a Ba ferrite sintered body (HcJ is less than 4 kOe) does not satisfy the above formula V.

Example 5 (Temperature characteristics of ferrite particles: HcJ)
Properties) With respect to the calcined Sr ferrite having the composition and the calcining temperature shown in Table 4, the IH hysteresis curve was determined by VSM in the temperature range shown in FIG. From this IH hysteresis curve, the temperature dependence of HcJ was examined. HcJ
Is shown in FIG. Using these results, the temperature coefficient of HcJ was calculated by linear approximation in the range from -50 ° C to + 50 ° C. Temperature coefficient and -50 to 50
Table 4 shows the correlation coefficient at ° C. The temperature coefficient ΔHcJ / HcJ / ΔT in Table 4 is a rate of change with respect to HcJ at 25 ° C.

[0098]

[Table 4]

Table 4 shows that the combined addition of La and Co significantly reduces the temperature coefficient of HcJ of the calcined Sr ferrite.

Example 6 (Sintered magnet: temperature of HcJ and Br)
Degree Characteristics) A sintered Sr ferrite having a phase composition of x = y = 0 to 1 and z = 1 was produced. The calcination temperature and the sintering temperature were both 1200 ° C. These sintered bodies are 5 mm in diameter,
It was processed into a columnar shape with a height of 6.5 mm (the height direction was the c-axis direction), and the temperature dependency of HcJ was examined in the same manner as in Example 5.
The results are shown in FIG. In Table 5, 25
Also shown are Br and HcJ at -25 ° C and Br and HcJ at -25 ° C.

[0101]

[Table 5]

From Table 5, it can be seen that the combined addition of La and Co significantly improves the HcJ temperature characteristics of the Sr ferrite sintered body.

Regarding the magnetic properties at 25 ° C., the sintered body with x = 0.3 and y = 0.3 (HcJ is 4 kOe or more) has Br + ／ HcJ = 6.07. X = 0, y
The sintered body of = 0 (HcJ less than 4 kOe) has Br + 1 / 10HcJ = 4.78, which does not satisfy the above formula V. Regarding the magnetic properties at −25 ° C., the sintered body with x = 0.3 has Br + ／ HcJ = 6.44, which satisfies the above formula VI, whereas x = 0, y
The sintered body of = 0 is only Br + ／ HcJ = 5.89, which does not satisfy the above formula VI.

Example 7 (Sintered Magnet: Anisotropic Magnetic Field) When the composition is Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ , x and y (where x = y) become the values shown in Table 6. The raw materials were mixed as described above, and the others were the same as in Example 1 to produce a sintered body. From these sintered bodies, cubes each having a side of 12 mm were cut out. As shown in FIG. 16, one side of the cube is orthogonal to the c-axis. The first quadrant of the 4πI-H curve was measured in each of the a-axis direction and the c-axis direction in these cubes, and the anisotropic magnetic field ( _HA ) was determined from the intersection. Table 6 shows the results. Table 6 also shows the saturation magnetization 4πIs and density of each cube.

[0105]

[Table 6]

From Table 6, x = 0.1 within the scope of the present invention.
4πIs and H _{A at} 〜0.4, y = 0.1-0.4
It can be seen that both increase. This also allows K
_It can be seen that ₁ [= ( _HA · Is) / 2] also increased.

Example 8 (Sintered magnet, ferrite particles: L
a ≠ Co) composition is Sr _0.7 La _0.3 Fe _11.7 (Co _(1-v) F _v ) _0.3 O ₁₉ [where Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ , y = 0 .3 (1-v) and v = 0.3-y /
The calcined body and the sintered body were produced in the same manner as in Example 1 except that the raw materials were blended so as to be 0.3. v
FIG. 17 shows the change in the magnetic characteristics of the calcined body with the change in the calcined temperature, together with the calcining temperature. FIG. 18 shows the change in the magnetic properties of the sintered body with the change in v, together with the calcination temperature and the sintering temperature.

FIG. 17 shows that when calcination was performed at 1200 ° C. and when calcination was performed at 1250 ° C., HcJ was 6%.
It can be seen that ferrite particles having an unprecedentedly high HcJ of kOe or more (up to 6.6 kOe) can be obtained. _{However, Sr 0.7 La 0.3 Fe 11.7 (} Co (1-v) Fe v) 0.3 in O ₁₉ v> 0.8, i.e. _{Sr 1-x La x Fe 12} -v Co v in O ₁₉ is La / Co = x It can be seen that in the range of / y> 5, the magnetic characteristics deteriorate significantly.

FIG. 18 shows that v> 0.5 in Sr _0.7 La _0.3 Fe _11.7 (Co _(1-v) F _v ) _0.3 O ₁₉ , that is, Sr _{1 -x} La _x Fe _{12 -y} Co _y O ₁₉ It can be seen that the magnetic characteristics significantly deteriorated in the range of La / Co = x / y> 2.

Example 9 (Sintered magnet: Co + Zn added) _Same as Example 1 except that the raw materials were blended so that the composition was Sr _0.7 La _0.3 Fe _11.7 (Co _(1-w) Zn _w ) _0.3 O _19. Thus, a calcined body and a sintered body were produced. Calcination temperature 120
The change in the magnetic properties due to the change in w of the sintered body at 0 ° C.
FIG. 19 shows the sintering temperature.

From FIG. 19, by changing the ratio of Co to Zn, 4πIs can be mainly improved or HcJ can be improved.
It can be seen that it is possible to improve the characteristics of the high saturation magnetization type and the high coercive force type continuously.

Example 10 (Sintered Magnet) The raw materials were blended so that the main phase composition was Sr _0.7 La _0.3 Fe _11.7 M _0.3 O ₁₉ (M = Zn, Mg, Mn, Ni, Co, Li + Fe). A sintered body was produced in the same manner as in Example 1, except that the firing temperature was 1200 ° C and the sintering temperature was 1220 ° C. The magnetic properties and density of these sintered bodies were measured. Table 7 shows the results.

[0113]

[Table 7]

Table 7 clearly shows the effect of improving the coercive force by the composite addition of La and Co. When M = Zn, high Br and high (BH) max are obtained, but HcJ is low. When an element other than Zn is added, all the properties are inferior to the case where M = Co.

In the Sr ferrite produced in each of the above embodiments, when La was partially replaced by Bi,
It was found that the calcination temperature could be lowered by the addition. That is, the calcination temperature at which the best properties were obtained was shifted to the lower temperature side, and the coercive force was hardly deteriorated. Also,
When a calcined body and a sintered body were produced with a composition in which La was partially replaced by another rare earth element, improvement of HcJ was recognized by the composite addition with Co as in the above-described respective examples.

Example 11 (Sintered Magnet: Measurement of Specific Resistance) In Example 2, the calcination temperature was 1200 ° C., the sintering temperature was 1180 ° C., and the other conditions were the same as in Example 2.
-1, y: A sample was prepared in which the value was changed from 0 to 1 (where x = y). The specific resistance greatly changed depending on the values of x and y. Although the cause is not clear, generation of Fe ²⁺ is considered.

For each of the obtained samples, the DC specific resistance in the a-axis direction and the c-axis direction was measured. Table 8 shows the results. As described above, although the specific resistance is reduced, it is within a range in which there is no problem in practical use.

[0118]

[Table 8]

Example 12 (Sintered magnet: calcination temperature 1200)
In La added comparison by weight) Example 1 at ° C., the final composition, when formed into a _{Sr 1-x La x Fe 11.7} Co 0.3 O 19, and blended to prepare a raw material which becomes x = 0.0 to 1.0 , The calcination temperature was set to 1200 ° C, and the Br-HcJ characteristics, ρs and HcJ, HK / HcJ and [BH] max were measured. The obtained results are shown in FIGS. B-
The anisotropic magnetic field _HA was determined from the initial magnetization curve in the hard axis direction and the hysteresis curve in the easy magnetization direction for the sintered body at 1240 ° C. using an H tracer. Table 9 shows the results. Further, the specific resistance in the c-axis direction (height direction) of the sintered body fired at 1200 ° C. in the atmosphere was measured. Table 10 shows the results. x
Samples with 0.1 and 0.2 had high specific resistances of 10 ⁶ or more, which exceeded the measurement range of the measuring instrument used.

[0120]

[Table 9]

[0121]

[Table 10]

As is clear from FIGS. 20 to 22, x =
In the case of 0.3 and 0.4, the Br-HcJ characteristic curves were almost the same, and the highest magnetic characteristics were obtained under these conditions. Both had comparable HK / HcJ. The saturation magnetization per unit weight ([sigma] s) hardly changed in the range of x = 0 to 0.4, but HcJ decreased considerably rapidly as the amount of La or Sr decreased.

In Table 9, the measured value of the anisotropic magnetic field is x = 0.
The value monotonically increased to 3 and reached a substantially constant value of 20 kOe in the range of x = 0.3 to 0.8, and decreased again at x = 1.0.

Example 13 (Sintered magnet: calcination temperature 1300)
In La added comparison by weight) Example 1 at ° C., the final composition, when formed into a _{Sr 1-x La x Fe 11.7} Co 0.3 O 19, and blended to prepare a raw material which becomes x = 0.0 to 1.0 , Calcination temperature at 1300 ° C., Br-HcJ characteristics, HcJ and HK / HcJ and Br, x, Br and HcJ
Was evaluated. The obtained results are shown in FIGS.

As is clear from FIGS. 23 to 25, the magnetic properties were highest when x = 0.4, and both Br and HcJ increased with the firing temperature. However, 1200
At a sintering temperature of 1240 ° C. in which Br and HcJ are increased to almost the same level as in the case of the calcination at ℃, HK / HcJ is 86.5%.
Has dropped. In the case of calcining at 1200 ° C., x = 0.3,
0.4, which was almost the same characteristic, but when calcined at 1300 ° C., the characteristic was higher when x = 0.4. Also, x = 0.8
As a result, HcJ became a high value of 6 kOe or more.

Example 14 (Sintered magnet: magnetism by x, y
Evaluation of Characteristics) In Example 1, when the final composition was Sr _1-x La _x Fe _12-y Co _y O ₁₉ , the calcining temperature was set to 1250 ° C. so that x and y became predetermined values. A calcined body and a sintered body were prepared in the same manner as in Example 1 except that the above conditions were changed, and the magnetic properties were evaluated. Each component was analyzed in the same manner as in Example 1.

FIG. 26 shows the magnetic properties (σs and HcJ) of the calcined body.
Is shown. Table 11 shows the analysis values of each sample that was subjected to the experiment. Table 11 also shows x, y, and z values calculated based on the analysis values. FIG.
Magnetic properties of sintered body fired at 0 ° C for 1 hour (Br and HcJ)
Is plotted against x and y in Table 11. FIG. 28 shows a result of plotting a value obtained by subtracting HcJ of the sintered body when the oxygen concentration is 20% from HcJ of the sintered body when the oxygen concentration at the time of the main firing is 100%.

[0128]

[Table 11]

As is clear from the drawing, it can be seen that high magnetic characteristics are obtained in the range of the present invention. At this time, X
As a result of analysis by line diffraction, the presence of a magnetoplumbite phase (M phase) was confirmed at any point. From FIGS. 27 and 28, it can be seen that high HcJ can be obtained when x / y = 1.3-2. Further, it can be seen that the dependency of HcJ on the firing atmosphere is reduced in this range.

Example 15 (Ferrite Particles) In Example 14, x = y = 0 (comparative example) and x = y
= 0.3 (Example) was calcined with a dry vibration mill, and then annealed in air at 1000 ° C. for 5 minutes. At this time, HcJ and the temperature characteristics of HcJ of the ferrite particles were measured. In addition, the temperature characteristics of HcJ and HcJ were similarly measured by VSM for commercially available pramag.
The results are shown below.

[0131]

[Table 12]

As is clear from the above table, the sample of the present invention had improved HcJ and HcJ temperature characteristics.

To the ferrite particles prepared as described above, 90 parts by weight of ferrite particles subjected to a surface treatment by adding a silane coupling agent and 12:10 parts by weight of nylon were mixed, kneaded and granulated. Was done. Thereafter, molding was performed by an injection molding machine in a magnetic field, and the magnetic properties and the like were evaluated.
As a result, the temperature characteristics of HcJ were improved as in the above-described embodiment.

Embodiment 16 (Application of Sintered Magnet) In the same manner as in Embodiment 1, except that the sample of the present invention was changed from a cylindrical shape for measurement to a field magnet for a C-type motor. Thus, a C-shaped sintered magnet for a motor was obtained.
The obtained core material was incorporated into a motor in place of a conventional sintered magnet, and when operated under rated conditions, good characteristics were exhibited. When the torque was measured, it was higher than that of the motor using the conventional core material.

The effects of the present invention are clear from the above examples.

[0136]

As described above, according to the present invention, hexagonal crystal
Simultaneously increasing the saturation magnetization and magnetic anisotropy of ferrite
Is impossible to achieve with conventional hexagonal ferrite magnets.
Sintered magnet with high residual magnetic flux density and high coercive force
Stone can be provided. In addition, high residual magnetic flux density
High coercive force and extremely good temperature characteristics of coercive force
Excellent in coercive force, especially at low temperatures.
A magnet can be provided. Also, the particle size exceeds 1μm
Magnetic flux density using relatively coarse ferrite particles
Sintered magnets with high coercive force and
You. In addition, high efficiency, high torque, compact and lightweight models
Data can be provided.

[Brief description of the drawings]

FIG. 1 shows that La and Co are used for Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 2 shows that La and Co are used for Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 3 shows that La and Co are used for an Sr ferrite sintered body.
3 is a graph showing the relationship between the substitution rate (x, y) and magnetic properties.

FIG. 4 shows that La and Co are used for Sr ferrite sintered body.
4 is a graph showing the relationship between the substitution rate (x, y) and the Curie temperature (Tc).

FIG. 5 is a graph showing the relationship between the calcination temperature and the sintering temperature and the magnetic properties of the Sr ferrite sintered body.

FIG. 6 is a drawing substitute photograph showing a particle structure, and is a scanning electron micrograph of a calcined Sr ferrite.

FIG. 7 is a drawing substitute photograph showing a grain structure, and is a scanning electron micrograph of a calcined body of Sr ferrite.

FIG. 8 is a drawing substitute photograph showing a grain structure, and is a scanning electron microscope photograph of a calcined Sr ferrite.

FIG. 9 is a drawing substitute photograph showing a particle structure, and is a scanning electron micrograph of a cross section of Sr ferrite sintered body (a cross section parallel to the a-plane of the crystal).

FIG. 10 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (a cross section parallel to the a-plane of a crystal).

FIG. 11 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (a cross section parallel to the a-plane of a crystal).

FIG. 12 is a drawing substitute photograph showing a particle structure, wherein Sr
5 is a scanning electron micrograph of a cross section of a ferrite sintered body (a cross section parallel to the a-plane of a crystal).

FIG. 13 is a graph showing the relationship between HcJ and (BH) max and Br for Sr ferrite sintered bodies and Ba ferrite sintered bodies.

FIG. 14 is a graph showing the temperature dependence of HcJ of a calcined Sr ferrite.

FIG. 15 is a graph showing the temperature dependency of HcJ of the Sr ferrite sintered body.

FIG. 16 shows a cube S used for anisotropic magnetic field (H _A ) measurement.
It is a perspective view which shows the direction of the crystal axis of r ferrite sintered compact.

FIG. 17 is a graph showing the effect of the relationship between the substitution rate of La and the substitution rate of Co on the magnetic properties of the calcined Sr ferrite.

FIG. 18 is a graph showing the effect of the relationship between the substitution rate of La and the substitution rate of Co on the magnetic properties of the Sr ferrite sintered body.

FIG. 19 is a graph showing the influence of the relationship between the substitution rate of Co and the substitution rate of Zn on the magnetic properties of the Sr ferrite sintered body.

FIG. 20 is a graph comparing the magnetic properties depending on the difference in the amount of La added.
FIG. 4 is a diagram showing r-HcJ characteristics.

FIG. 21 is a graph comparing magnetic properties depending on the difference in the amount of La added, and shows ρ when the calcination temperature is 1200 ° C.
FIG. 4 is a diagram showing characteristics of s and HcJ.

FIG. 22 is a graph comparing magnetic properties depending on the difference in the amount of La added.
It is the figure which showed K / HcJ and (BH) max.

FIG. 23 is a graph comparing magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing r-HcJ characteristics.

FIG. 24 is a graph comparing magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing characteristics of cJ and HK / HcJ and Br.

FIG. 25 is a graph comparing the magnetic characteristics depending on the difference in the amount of La added.
FIG. 4 is a diagram showing a relationship between Br and HcJ.

FIG. 26 is a graph showing the magnetic properties (σs and HcJ) of the calcined body when the calcining temperature is 1250 ° C.

FIG. 27 is a graph showing magnetic properties (Br and HcJ) of a sintered body obtained by firing the calcined body of FIG. 26 at 1220 ° C. for 1 hour in air.

FIG. 28 shows the calcined body of FIG.
From the HcJ of the sintered body at 0%, the oxygen concentration is 20%
It is the figure which plotted the value which subtracted HcJ of the sintered compact at the time of making.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiko Minachi 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation

Claims (16)

[Claims] 1. A method in which at least one element selected from Sr, Ba, Ca and Pb, which contains ferrite having a hexagonal structure as a main phase, and which always contains Sr, is used.
When at least one element selected from rare earth elements (including Y) and Bi and always including La is R, and Co or Co and Zn is M, A, R, Fe And M, the total composition ratio of the metal elements is A: 1 to 13 atomic%, R: 0.05 to 10 atomic%, Fe: 80 to 95 atomic%, M: 0. An oxide magnetic material having a composition of 1 to 5 atomic%. 2. The formula IA _1-x R _x (Fe _{12- y My} ) _z O ₁₉ , wherein 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0 2. The oxide magnetic material according to claim 1, wherein 0.7 ≦ z ≦ 1.2. 3. The oxide magnetic material according to claim 1, wherein the ratio of Co in M is 10 atomic% or more. 4. Ferrite particles containing the oxide magnetic material according to claim 1. 5. The formula IA _1-x R _x (Fe _{12- y My} ) _z O ₁₉ , wherein 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0 5. The ferrite particles according to claim 4, wherein 0.8 ≦ x / y ≦ 20 and 0.7 ≦ z ≦ 1.2. 6. At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr, is A, and at least one element selected from rare earth elements (including Y) and Bi When R is an element that always contains La and Co is Co or Zn is M, it contains A, R, Fe and M, and is -50 ° C. to 50 ° C.
Temperature dependence of intrinsic coercivity (HcJ) at ℃ (Oe /
° C) is expressed as | ΔHcJ / ΔT |, and when the unit of HcJ is kOe, the intrinsic coercive force (HcJ) and temperature dependency satisfying the formula III | ΔHcJ / ΔT | ≦ 5 / 3HcJ−7 / 3 Sex (Oe
/ ° C). 7. A bonded magnet comprising the ferrite particles according to claim 4. 8. A sintered magnet containing the oxide magnetic material according to claim 1. 9. Formula II A _1-x R _x (Fe _{12- y My} ) _z O ₁₉ , wherein 0.04 ≦ x ≦ 0.9, 0.04 ≦ y ≦ 0.5, 0 9. The sintered magnet according to claim 8, wherein 4 ≦ x / y ≦ 4 and 0.7 ≦ z ≦ 1.2. 10. The inherent coercive force HcJ at 25 ° C. (unit: kO
e) and the residual magnetic flux density Br (unit: kG) satisfies the formula IV Br + ／ HcJ ≧ 5.75 when HcJ ≧ 4, and satisfies the formula VBr + 1 / 10HcJ ≧ 4.82 when HcJ <4. Item 8. The sintered magnet according to any one of Items 8 to 9. 11. Coercive force HcJ at -25 ° C. (unit: kOe)
The sintered magnet according to any one of claims 8 to 10, wherein the residual magnetic flux density Br (unit: kG) satisfies the following formula: VI Br + ／ HcJ ≧ 5.95. 12. An absolute value of a temperature coefficient of a coercive force at −50 ° C. to 50 ° C. is 0.25% / ° C. or less.
11. The sintered magnet according to any of 11 above. 13. At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr, and is at least one element selected from rare earth elements (including Y) and Bi When R is an element which necessarily contains La and Co is Co or Zn is M, it contains A, R, Fe and M, and has a coercive force HcJ (unit: kOe) at 25 ° C. A sintered magnet which satisfies the formula IV Br + ／ HcJ ≧ 5.75 when the residual magnetic flux density Br (unit: kG) is HcJ ≧ 4, and satisfies the formula VBr + 1 / 10HcJ ≧ 4.82 when HcJ <4. 14. At least one element selected from Sr, Ba, Ca and Pb, which always contains Sr, is A, and at least one element selected from rare earth elements (including Y) and Bi When R is an element which necessarily contains La and Co is Co or Zn is M, it contains A, R, Fe and M, and has a coercive force HcJ at -25 ° C. (unit: kOe) And residual magnetic flux density Br (unit: kG)
Is a sintered magnet that satisfies the formula VI Br + ／ HcJ ≧ 5.95. 15. A motor having the sintered magnet according to claim 8. 16. A magnetic recording medium having a thin-film magnetic layer containing the oxide magnetic material according to claim 1.