JP2015130493A - Ferrite sintered magnet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ferrite sintered magnet having high magnet characteristics, and low calcination temperature dependency of magnet characteristics.SOLUTION: The composition of main phase composing a ferrite sintered magnet is represented by CaRAFeMO. R is at least one kind of element selected from a group consisting of rare earth elements and Bi and contains at least La, A is at least one kind of element selected from Sr and Ba, and M is at least one kind of element selected from a group consisting of Co, Mn, Mg, Ni, Cu and Zn, and contains at least Co. The ferrite sintered magnet contains at least S, and the content of S is 100-1300 ppm.

Description

  The present invention relates to a sintered ferrite magnet.

  As materials for permanent magnets made of oxides, hexagonal M-type (Magnet Plumbite-type) Sr ferrite or Ba ferrite is known. Ferrite magnetic materials made of these ferrites are provided as permanent magnets in the form of sintered ferrite or bonded magnets. In recent years, along with miniaturization and high performance of electronic components, permanent magnets made of a ferrite magnetic material have been required to have high magnetic properties while being small.

  Generally, residual magnetic flux density (Br) and coercive force (HcJ) are used as indicators of the magnetic characteristics of the permanent magnet, and it is evaluated that the higher these are, the higher the magnetic characteristics are. Conventionally, from the viewpoint of improving Br and HcJ of permanent magnets, investigations have been made by changing the composition, such as adding a predetermined element to a ferrite magnetic material.

  For example, Patent Document 1 discloses that a hexagonal crystal having high Br and HcJ and a high squareness ratio as a result of studying that CaLaCo ferrite has an anisotropic magnetic field greater than that of SrLaCo ferrite. It has been shown that an oxide magnetic material whose main phase is CaLaCo ferrite having an M-type magnetoplumbite structure and a sintered magnet containing the oxide magnetic material can be obtained.

  By the way, a sintered ferrite magnet is generally obtained by molding a powder and then firing it. In the firing step, magnet characteristics such as Br and HcJ can be suitably controlled by adjusting firing conditions. However, on an industrial production scale, it is difficult to control the firing process conditions, particularly the firing temperature, to be constant. Therefore, it is difficult to industrially obtain a sintered ferrite magnet having stable magnet characteristics.

  Furthermore, a ferrite sintered magnet having high magnet characteristics (particularly HcJ) tends to increase the firing temperature dependency of the magnet characteristics (particularly HcJ). Therefore, the higher the performance of sintered ferrite magnets, the more the magnet characteristics change due to the subtle changes in temperature during firing, making it difficult to obtain sintered ferrite magnets having stable magnet characteristics.

  In Example 3 of Patent Document 1, when the sintering temperature is increased from 1150 ° C. to 1170 ° C. by 20 ° C., HcJ decreases from 370.0 kA / m to 300.2 kA / m. That is, although the sintered magnet of Patent Document 1 has high performance, there is a problem that HcJ has a very high firing temperature dependency and has a large variation in HcJ.

  Therefore, in the ferrite sintered magnet, it is preferable to obtain high magnet characteristics and lower the firing temperature dependence of the magnet characteristics (particularly HcJ). However, if the magnet characteristics are improved, the dependency of the magnet characteristics on the firing temperature also increases. Therefore, it has never been easy in the past to obtain a sintered ferrite magnet having both high magnet characteristics and low firing temperature dependency.

JP 2006-104050 A

  Therefore, the present invention has been made in view of such circumstances, and an object thereof is to provide a sintered ferrite magnet having high magnet characteristics and having low magnet temperature characteristics (particularly HcJ) and low firing temperature dependency. To do.

In order to achieve the above object, the sintered ferrite magnet of the present invention is a sintered ferrite magnet having a main phase consisting of a ferrite phase having a hexagonal crystal structure,
The composition of the main phase constituting the ferrite sintered magnet is represented by the following formula (1):
_{Ca 1-w-x R w} A x Fe z M m O 19 ··· (1)
R is at least one element selected from the group consisting of rare earth elements and Bi and contains at least La, A is at least one element selected from Sr and Ba, M is Co, Mn, Mg, At least one element selected from the group consisting of Ni, Cu and Zn, including at least Co;
In the formula (1), w, x, z, and m satisfy the following formulas (2), (3), (4), and (5),
0.24 ≦ w ≦ 0.60 (2)
0.02 ≦ x ≦ 0.41 (3)
8.00 ≦ z ≦ 11.00 (4)
1.0 ≦ w / m ≦ 2.4 (5)
It contains at least S, and the content of S is 100 ppm or more and 1300 ppm or less.

  In the ferrite sintered magnet of the present invention, the composition of the main phase constituting the ferrite sintered magnet is represented by the formula (1), each element satisfies the conditions of the formulas (2) to (5), and the S component The S content is 100 ppm or more and 1300 ppm or less. Therefore, the sintered ferrite magnet of the present invention has improved HcJ firing temperature dependence and stably has high HcJ.

  The sintered ferrite magnet of the present invention preferably contains at least Si.

  By containing Si, a sintered sintered magnet is obtained in which the sinterability is good, the crystal grain size of the sintered body is appropriately adjusted, and the magnetic properties are well controlled.

The sintered ferrite magnet of the present invention preferably contains at least Si, and the Si content is preferably 0.60% by mass or more and 1.20% by mass or less in terms of SiO ₂ .

The content of Si, by a more than 0.60 wt% 1.20 wt% or less in terms of SiO _2, the sintering property becomes further improved and the crystal grain size of the sintered body is further adjusted moderately, In addition, a sintered ferrite magnet having a well-controlled magnetic property can be obtained.

The sintered ferrite magnet of the present invention contains at least Si, the Si content is a (mass%) in terms of SiO ₂ , the S content is b (ppm), and the physical quantity HIN is expressed by the following formula (6). In this case, HIN is preferably 100 or more and 1780 or less.
HIN = b + 13000 × (a−0.90) ² (6)

  By making the physical quantity HIN 100 or more, the firing temperature dependency of HcJ is improved. By setting HIN to 1780 or less, HcJ of the obtained sintered ferrite magnet can be improved.

FIG. 1 is a diagram showing the relationship between the S content of a sintered ferrite magnet and the firing temperature dependence of HcJ. FIG. 2 is a diagram showing the relationship between the S content, the Si content, the physical quantities HIN, and HcJ of the sintered ferrite magnet.

    Embodiments of the present invention will be described below.

(Sintered ferrite magnet)
The sintered ferrite magnet according to one embodiment of the present invention has a main phase composed of a ferrite phase having a hexagonal crystal structure. The ferrite phase is preferably magnetoplumbite type (M type) ferrite (hereinafter referred to as “M type ferrite”). Here, “main phase consisting of ferrite phase” means that a ferrite sintered magnet usually consists of “main phase (crystal particles)” and “grain boundary part”, and this “main phase” is the ferrite phase. Means. The proportion of the main phase in the sintered body is preferably 90% by mass or more.

  As described above, the sintered ferrite magnet is in the form of a sintered body and has a structure including crystal grains (main phase) and grain boundaries. The average crystal grain size of crystal grains in this sintered body is preferably 2.0 μm or less, and more preferably 0.5 to 1.6 μm. By having such an average crystal grain size, high HcJ is easily obtained. The average crystal grain size mentioned here is an arithmetic mean value of the grain diameters in the hard axis (a-axis) direction in the crystal grains in the sintered body of M-type ferrite. The crystal grain size of the ferrite sintered body can be measured with a scanning electron microscope.

The sintered ferrite magnet of the present embodiment has a main phase composition represented by the following formula (1).
_{Ca 1-w-x R w} A x Fe z M m O 19 (1)

  Here, in formula (1), R is at least one element selected from the group consisting of rare earth elements and Bi and contains at least La, and A is at least one element selected from Sr and Ba, M is at least one element selected from the group consisting of Co, Mn, Mg, Ni, Cu and Zn and contains at least Co.

In the formula (1), w, x, z and m represent atomic ratios of R, A, Fe and M, respectively, and the following formulas (2), (3), (4) and (5) Satisfy all.
0.24 ≦ w ≦ 0.60 (2)
0.02 ≦ x ≦ 0.41 (3)
8.00 ≦ z ≦ 11.00 (4)
1.0 ≦ w / m ≦ 2.4 (5)

  Moreover, the ferrite sintered magnet contains at least S in addition to the composition of the main phase described above, and the S content is 100 ppm or more and 1300 ppm or less.

  The composition ratio of oxygen is affected by the composition ratio of each metal element and the valence of each element (ion), and increases or decreases so as to maintain electrical neutrality in the crystal. Further, in the firing step described later, oxygen deficiency may occur when the firing atmosphere is a reducing atmosphere.

  Hereinafter, the composition of the ferrite sintered magnet described above will be described in more detail.

The atomic ratio (1-w-x) of Ca in the composition of the metal elements constituting the ferrite sintered magnet is preferably 0.20 or more and 0.62 or less, more preferably 0.26 or more and 0.59 or less. Is more preferable. If the atomic ratio of Ca is too small, the ferrite phase may not be M-type ferrite. In addition to an increase in the proportion of non-magnetic phases such as α-Fe ₂ O ₃ , there is a risk that R may be excessive and non-magnetic hetero phases such as orthoferrite may be generated, resulting in deterioration of magnetic properties (particularly Br and HcJ). There is.

On the other hand, if the atomic ratio of Ca is too large, M-type ferrite may not be formed, and nonmagnetic phases such as CaFeO _3-x increase, which may deteriorate the magnetic characteristics.

  The ferrite sintered magnet of this embodiment contains S as will be described later. In addition, a subcomponent may be further included, and a component included in the main phase may be included as a subcomponent. For example, when Ca is contained as a subcomponent, the amount of Ca analyzed from the sintered ferrite magnet is the total amount of the main phase and subcomponent. That is, when the Ca component is used as the subcomponent, the Ca atomic ratio (1-wx) in the general formula (1) is a value including the subcomponent. Since the range of the atomic ratio (1-wx) is specified based on the composition analyzed after firing, it can be applied both when the Ca component is included as a subcomponent and when it is not included.

  The element represented by R includes at least La, and other than La is preferably at least one selected from the group consisting of rare earth elements and Bi, and more preferably at least one selected from the group consisting of rare earth elements. However, the content of La is preferably 51 atomic% or more when the content of R is 100 atomic%, and includes only La (the content of La is 100 atomic% with the content of R being 100 atomic%). In that case, it is particularly preferable from the viewpoint of improving the anisotropic magnetic field. R may also be included as a subcomponent.

  The atomic ratio (w) of R in the composition of the main phase constituting the ferrite sintered magnet is 0.24 or more and 0.60 or less, and within this range, Br, HcJ and Hk / HcJ (angle) A ferrite sintered magnet having a good mold ratio) can be obtained. If the atomic ratio of R is too small, the solid solution amount of M in the ferrite sintered magnet becomes insufficient, and Br and HcJ decrease. On the other hand, if it is too large, a non-magnetic hetero phase such as orthoferrite is generated, and Hk / HcJ becomes low, making it difficult to obtain a practical magnet. From such a viewpoint, the atomic ratio of R is preferably 0.25 or more and less than 0.60, more preferably 0.28 or more and less than 0.55, and further preferably 0.30 or more and less than 0.53. It is preferable.

  The element represented by A is at least one element selected from Sr and Ba. The Sr content is preferably 51 atomic% or more when the A content is 100 atomic%, and contains only Sr (when the Sr content is 100 atomic%). Is particularly preferably 100 atomic%.

  The atomic ratio (x) of A is 0.02 or more and 0.41 or less. By being in this range, favorable Br, HcJ and Hk / HcJ are satisfied. When the atomic ratio of A is too large, Br and HcJ become insufficient. When the atomic ratio of A is too small, HcJ and Hk / HcJ are insufficient. From such a viewpoint, the atomic ratio of A is preferably 0.03 or more and less than 0.39, more preferably 0.05 or more and less than 0.37, and even more preferably 0.10 or more and less than 0.31. It is preferable.

  The atomic ratio (z) of Fe is not less than 8.00 and not more than 11.00. By being in this range, good Br, HcJ and Hk / HcJ are satisfied. If the atomic ratio of Fe is too small or too large, Br and HcJ are disadvantageously reduced. The atomic ratio of Fe is preferably 8.50 or more and less than 10.50, more preferably 8.50 or more and less than 9.90, and further preferably 8.70 or more and less than 9.50.

  The element represented by M is at least one element selected from Co, Mn, Mg, Ni, Cu and Zn, and contains at least Co. When it contains M other than Co, it preferably contains at least one selected from the group consisting of Mn, Ni and Zn. However, the content of Co is preferably 51 atomic% or more when the content of M is 100 atomic%, and includes only Co (the content of Co is 100 atomic%. In that case, it is particularly preferable from the viewpoint of improving the anisotropic magnetic field.

  The composition of the main phase constituting the sintered ferrite magnet satisfies the condition that w / m is 1.0 or more and 2.4 or less for the atomic ratio (m) of M. Satisfactory Br, HcJ and Hk / HcJ can be obtained by satisfying this condition. When the atomic ratio of M is too small, good Br and HcJ cannot be obtained. In particular, when the ratio of Co is too small, good HcJ cannot be obtained. On the other hand, when the atomic ratio of M is too large, Br and HcJ tend to decrease rather.

  From this viewpoint, w / m is preferably 1.0 or more and less than 2.2, more preferably 1.1 or more and less than 2.0, and further preferably 1.2 or more and less than 2.0. Further, m / z exceeds 0.017 and is preferably less than 0.065, more preferably 0.019 or more and less than 0.044, more preferably 0.021 or more and less than 0.039, and even more preferably 0. 0.02 or more and less than 0.036 is more preferable.

  The sintered ferrite magnet in the present invention contains S in addition to the composition of the main phase described above, and the content of S is 100 ppm or more and 1300 ppm or less in terms of mass ratio with respect to the entire sintered ferrite magnet. By including S, the firing temperature dependency of HcJ is improved, and a sintered ferrite magnet having high HcJ can be stably obtained. The S content is preferably 100 ppm or more and 1000 ppm or less, more preferably 100 ppm or more and 750 ppm or less, more preferably 100 ppm or more and 450 ppm or less, and even more preferably 100 ppm or more and 320 ppm or less.

  In addition to the composition of the main phase described above, the sintered ferrite magnet in the present invention may contain subcomponents described later. The accessory component can be contained in both the main phase and the grain boundary of the sintered ferrite magnet. In the ferrite sintered magnet, components other than subcomponents are the main components. From the viewpoint of obtaining sufficient magnetic properties, the content of the main phase in the sintered ferrite magnet is preferably 90% by mass or more, and more preferably 95% by mass or more.

  Here, the firing temperature dependence of HcJ in the present application is defined.

  Two types of samples are produced at different firing temperatures. And the one where HcJ is larger is HcJ (a), the one where HcJ is smaller is HcJ (b), and the firing temperatures at that time are T (a) and T (b). The firing temperature dependency (% / ° C.) of HcJ at this time is defined as (HcJ (a) −HcJ (b)) / HcJ (a) / (T (a) −T (b)) × 100.

  According to the above definition, assuming that HcJ: 430 ± 15 kA / m, 7σ on one side as a reference, and the temperature error that occurs when producing in a mass production furnace is 10 ° C., the absolute value of the firing temperature dependence of HcJ is (430-415) /7/430/10×100=0.05%/° C. is an allowable upper limit. That is, in an actual mass production furnace, the absolute value of the firing temperature dependence of HcJ is desired to be 0.05% / ° C. or less, preferably 0.04% / ° C. or less, more preferably 0.03% / ° C. or less, More preferably, it is 0.02% / ° C. or less. In the case of Example 3 of Patent Document 1 described above, the absolute value of the firing temperature dependency is 0.94% / ° C.

  The sintered ferrite magnet includes the main phase composition described above and at least the S component. The content of the S component can be measured by combustion in an oxygen stream-infrared absorption method. The composition of the sintered ferrite magnet can be measured by fluorescent X-ray quantitative analysis. The presence of the main phase can be confirmed by X-ray diffraction or electron beam diffraction.

The ferrite sintered magnet of this embodiment may contain components other than the S component as subcomponents. As other subcomponents, for example, Al and / or Cr may be included. By containing these subcomponents, the HcJ of the ferrite sintered magnet tends to be improved. From the viewpoint of obtaining a good effect of improving HcJ, the content of Al and / or Cr is 0.1% by mass in total in terms of Al ₂ O ₃ or Cr ₂ O ₃ with respect to the entire ferrite sintered magnet. The above is preferable. However, since these components may lower Br of the ferrite sintered magnet, it is desirable that the content is 3% by mass or less from the viewpoint of obtaining good Br.

As the subcomponent may include boron B, for example, as a B ₂ O _3. By containing B, the calcining temperature at the time of obtaining a ferrite calcined body and the firing temperature at the time of obtaining a ferrite sintered body can be lowered, and a ferrite sintered magnet can be obtained with high productivity. However, since the saturation magnetization of the ferrite sintered magnet may decrease if there is too much B, the content of B is 0.5% by mass or less in terms of B ₂ O ₃ with respect to the entire ferrite sintered magnet. It is preferable that

Further, as a subcomponent, silicon Si may be included as, for example, SiO ₂ . By including Si, the sinterability becomes good, and the sintered product has a ferrite sintered magnet in which the crystal grain size of the sintered body is appropriately adjusted and the magnetic properties are well controlled. However, if there is too much Si, a large amount of Si, which is a nonmagnetic component, will be contained in the sintered ferrite magnet, so the magnetic properties (particularly Br) may be lowered. Therefore, the content of Si is preferably 2.0% by mass or less in terms of SiO ₂ with respect to the entire sintered ferrite magnet, and is 0.60% by mass or more and 1.20% by mass or less. Is more preferable.

The inventors experimentally found a physical quantity HIN = b + 13000 × (a−0.90) ² calculated from the Si content a (mass%) and the S content b (ppm). .

  As the physical quantity HIN is smaller, HcJ tends to be improved. Further, if the physical quantity HIN is less than 100, the firing temperature dependency of HcJ is increased, and therefore, it is preferably 100 or more. Specifically, HIN is preferably from 100 to 1780, more preferably from 100 to 1380, more preferably from 100 to 980, more preferably from 100 to 580, More preferably, it is 100 or more and 180 or less.

  Furthermore, the sintered ferrite magnet of the present embodiment includes Ga, Mg, Cu, Mn, Ni, Zn, In, Li, Ti, Zr, Ge, Sn, V, Nb, Ta, Sb, As, as subcomponents. W, Mo, or the like may be included in the form of an oxide. The content of these specifically exemplified subcomponents is 5% by mass or less of gallium oxide, 5% by mass or less of magnesium oxide, 5% by mass or less of copper oxide, and oxides in terms of the stoichiometric composition of each atom. Manganese 5% by mass or less, Nickel oxide 5% by mass or less, Zinc oxide 5% by mass or less, Indium oxide 3% by mass or less, Lithium oxide 1% by mass or less, Titanium oxide 3% by mass or less, Zirconium oxide 3% by mass or less, Germanium oxide 3 mass% or less, tin oxide 3 mass% or less, vanadium oxide 3 mass% or less, niobium oxide 3 mass% or less, tantalum oxide 3 mass% or less, antimony oxide 3 mass% or less, arsenic oxide 3 mass% or less, tungsten oxide 3 It is preferable that it is below mass% and molybdenum oxide is below 3 mass%. However, when a plurality of subcomponents are included in combination, in order to avoid a decrease in magnetic properties, the total content is 5% by mass or less in terms of an oxide having a stoichiometric composition of each atom. It is desirable to do.

  The sintered ferrite magnet of this embodiment preferably does not contain an alkali metal element (Na, K, Rb, etc.) as a subcomponent. Alkali metal elements tend to reduce the saturation magnetization of sintered magnets. However, the alkali metal element may be contained in a raw material for obtaining a ferrite sintered magnet, for example, and if it is unavoidably contained, it is contained in the ferrite sintered magnet. Also good. The content of alkali metal elements that do not significantly affect the magnetic properties is 3% by mass or less in terms of oxides of stoichiometric composition of each atom.

(Manufacturing method of ferrite sintered magnet)
In the following embodiment, an example of a method for producing a ferrite sintered magnet will be described. In this embodiment, the ferrite sintered magnet can be manufactured through a blending process, a calcination process, a pulverization process, a molding process, and a firing process. Moreover, the drying process and kneading | mixing process of a fine grinding | pulverization slurry may be included between a grinding | pulverization process and a shaping | molding process, and the degreasing | defatting process may be contained between a shaping | molding process and a baking process. Each step will be described below.

<Mixing process>
In the blending step, raw materials for the sintered ferrite magnet are blended to obtain a raw material mixture. First, as a raw material of a ferrite sintered magnet, a compound (raw material compound) containing one or more of the elements constituting the ferrite magnet is exemplified. The raw material compound is preferably, for example, a powder. Examples of the raw material compound include oxides of the respective elements or compounds (carbonates, hydroxides, nitrates, etc.) that become oxides upon firing. For example, SrCO ₃ , La (OH) ₃ , Fe ₂ O ₃ , BaCO ₃ , CaCO _3, and Co ₃ O ₄ can be exemplified. The average particle diameter of the raw material compound powder is preferably about 0.1 to 2.0 μm, for example, from the viewpoint of enabling homogeneous blending.

  In addition, the raw material of the S component in the ferrite sintered magnet is not particularly limited, and examples thereof include a sulfur element or a sulfide or sulfate of an element contained in the ferrite sintered magnet. Moreover, you may mix | blend the raw material (element simple substance, an oxide, etc.) of other subcomponents with a raw material mixture as needed.

  For example, each raw material is weighed and mixed so that the desired composition of the sintered ferrite magnet is obtained, and then mixed and pulverized for about 0.1 to 20 hours using a wet attritor, ball mill, or the like. This can be done.

In this blending step, it is not necessary to mix all the raw materials, and a part thereof may be added after calcination described later. For example, a raw material of S component and a raw material of Ca that is a constituent element of the composition of the main phase (for example, CaCO ₃ ) may be added in a pulverization (particularly fine pulverization) step after calcining described later. The timing of addition may be adjusted so that a desired composition and magnetic characteristics can be easily obtained.

<Calcination process>
In the calcining step, the raw material powder obtained in the blending step is calcined. The calcination is preferably performed in an oxidizing atmosphere such as air. The calcination temperature is preferably in the temperature range of 1100 to 1400 ° C, more preferably 1100 to 1300 ° C, still more preferably 1150 to 1300 ° C. The calcination time can be 1 second to 10 hours, and is preferably 1 second to 5 hours. The calcined body obtained by calcining contains 70% or more of the main phase (M phase) as described above. The primary particle size of the calcined body is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 2 μm or less.

<Crushing process>
In the pulverization step, the calcined body that has been granulated or agglomerated in the calcination step is pulverized and again powdered. Thereby, the shaping | molding in the shaping | molding process mentioned later becomes easy. In this pulverization step, as described above, raw materials that were not blended in the blending step may be added. The pulverization step may be performed in a two-step process in which, for example, the calcined body is pulverized (coarse pulverization) into a coarse powder, and then further finely pulverized (fine pulverization).

The coarse pulverization is performed using, for example, a vibration mill or a rod mill until the average particle size becomes 0.5 to 5.0 μm. In the fine pulverization, the coarsely pulverized material obtained by the coarse pulverization is further pulverized by a wet attritor, a ball mill, a jet mill or the like. In pulverization, the average particle size of the obtained finely pulverized material is preferably 0.08 to 2.0 μm, more preferably 0.1 to 1.0 μm, and still more preferably about 0.1 to 0.5 μm. As such, fine grinding is performed. The specific surface area of the finely pulverized material (for example, determined by the BET method) is preferably about 4 to 12 m ² / g. The suitable pulverization time varies depending on the pulverization method. For example, in the case of a wet attritor, about 30 minutes to 20 hours is preferable, and in the case of wet pulverization using a ball mill, about 1 to 50 hours is preferable.

When a part of the raw material is added in the pulverization step, for example, the addition can be performed at the time of fine pulverization. In this embodiment, SrSO ₄ containing an S component, CaCO ₃ that is a Ca component, SiO ₂ containing an Si component, and the like can be added during fine pulverization. It may be added.

  In the fine pulverization step, in the case of a wet method, in addition to water, non-aqueous solvents such as toluene and xylene can be used as a dispersion medium. When the non-aqueous solvent is used, high orientation tends to be obtained during wet molding described later. On the other hand, when an aqueous solvent is used, it is advantageous from the viewpoint of productivity.

  In the pulverization step, for example, a known polyhydric alcohol or a dispersant may be added in order to increase the degree of orientation of the sintered body obtained after firing.

<Molding and firing process>
In the molding / firing step, the pulverized material (preferably finely pulverized material) obtained after the pulverizing step is molded to obtain a molded body, and then the molded body is baked to obtain a sintered body. Molding can be performed by any of dry molding, wet molding, or CIM molding (Ceramic Injection Molding). In the dry molding method, for example, a magnetic field is applied while pressure-molding the dried magnetic powder to form a compact, and then the compact is fired. In the wet molding method, for example, a liquid component is removed while pressure-forming a slurry containing magnetic powder while applying a magnetic field to form a molded body, and then the molded body is fired.

  In general, the dry molding method has the advantage that the time required for the molding process is short because the dried magnetic powder is pressure-molded in a mold, but the degree of orientation of the magnetic powder due to the magnetic field during molding is low. Improvement is difficult, and the resulting magnetic properties of the sintered magnet are inferior to those of the sintered magnet obtained by the wet molding method. In the wet molding method, the magnetic powder is easily oriented by the magnetic field at the time of molding, and the magnetic characteristics of the sintered magnet are good. However, since pressing is performed while removing the liquid component, it takes time to mold. There is.

  In the CIM molding method, the dried magnetic powder is heat-kneaded together with a binder resin, and the formed pellets are injection-molded in a mold to which a magnetic field is applied to obtain a preform. This is a method of firing after the binder removal treatment.

  The method for forming the ferrite sintered magnet according to the above-described embodiment is not particularly limited, but preferably CIM molding or wet molding. Hereinafter, CIM molding and wet molding will be described in detail.

(CIM molding / firing)
When obtaining a ferrite sintered magnet by the CIM molding method, the finely pulverized slurry containing magnetic powder is dried after wet pulverization. The drying temperature is preferably 80 to 500 ° C, more preferably 100 to 400 ° C. The drying time is preferably 1 second to 100 hours, more preferably 1 second to 50 hours. The moisture content of the magnetic powder after drying is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. The average particle size of the primary particles of the magnetic powder after drying is preferably in the range of 0.08 to 2 μm, more preferably in the range of 0.1 to 1 μm.

  The dried magnetic powder is kneaded with a binder resin, waxes, a lubricant, a plasticizer, a sublimation compound (hereinafter referred to as “organic component”), and formed into pellets with a pelletizer or the like. The organic component is preferably contained in the molded body in an amount of 35 to 60% by volume, more preferably 40 to 55% by volume. The kneading may be performed by, for example, a kneader. As the pelletizer, for example, a twin-screw single-screw extruder is used. Moreover, you may implement kneading | mixing and pellet shaping | molding, heating according to the melting temperature of the organic component to be used.

  As the binder resin, a polymer compound such as a thermoplastic resin is used. As the thermoplastic resin, for example, polyethylene, polypropylene, ethylene vinyl acetate copolymer, atactic polypropylene, acrylic polymer, polystyrene, polyacetal, or the like is used. .

  As waxes, synthetic waxes such as paraffin wax, urethanized wax, and polyethylene glycol are used in addition to natural waxes such as carnauba wax, montan wax, and beeswax.

  As the lubricant, for example, a fatty acid ester or the like is used, and as the plasticizer, for example, a phthalic acid ester is used.

  The addition amount of the binder resin is preferably 3 to 20% by mass with respect to 100% by mass of the magnetic powder, the addition amount of waxes is preferably 3 to 20% by mass, and the addition amount of the lubricant is preferably 0.1. ˜5 mass%. The addition amount of the plasticizer is preferably 0.1 to 5% by mass with respect to 100% by mass of the binder resin.

  In the present embodiment, for example, the pellets are injection molded into a mold using a magnetic field injection molding apparatus. Before injection into the mold, the mold is closed, a cavity is formed inside, and a magnetic field is applied to the mold. Note that the pellets are heated and melted, for example, at 160 to 230 ° C. inside the extruder and injected into the mold cavity by a screw. The temperature of the mold is 20 to 80 ° C. The applied magnetic field to the mold may be about 80 to 2000 kA / m.

  Next, the preformed body obtained by CIM molding is heat-treated at a temperature of 100 to 600 ° C. in the air or in nitrogen, and a binder removal treatment is performed to obtain a molded body. If the binder removal process is insufficient or the temperature rise rate during removal of the binder is abrupt, cracking or cracking will occur in the molded body or sintered body due to the rapid volatilization of the organic components mentioned above and the generation of decomposition gas. End up. Therefore, depending on the organic component to be debindered, the temperature increase rate in the temperature range where it volatilizes or decomposes is appropriately adjusted, for example, to a slow temperature increase rate of about 0.01 to 1 ° C./min. The binder removal process may be performed. On the contrary, if the binder removal process is excessive, the molded product has insufficient shape-retaining force and causes chipping, so that the heat treatment temperature and temperature profile control are required. In addition, when a plurality of organic components are used, the binder removal process may be performed in a plurality of times.

  Next, in the firing step, the molded body subjected to the binder removal treatment is fired at a temperature of preferably 1100 to 1250 ° C., more preferably 1160 to 1230 ° C. for about 0.2 to 3 hours in the air, and the present invention is applied. A ferrite sintered magnet is obtained. If the temperature is too low or the temperature holding time is too short, the desired magnetic properties can be obtained due to insufficient sintered body density and insufficient reaction of the added elements. I can't. Also, if the firing temperature is too high or the temperature holding time is too long, the desired magnetic properties cannot be obtained due to abnormal growth of crystal grains or formation of a different phase other than M-type ferrite. . In addition, even if a baking process is implemented continuously with the above-mentioned binder removal process, after performing a binder removal process once, it may cool to room temperature and may implement baking.

(Wet molding / firing)
In the case of obtaining a ferrite sintered magnet by a wet molding method, for example, after obtaining the slurry by performing the above-described fine grinding step in a wet manner, the slurry is concentrated to a predetermined concentration to obtain a slurry for wet molding, It is preferable to perform molding using this. Concentration of the slurry can be performed by centrifugation, filter press, or the like. The wet molding slurry is preferably such that the finely pulverized material accounts for about 30 to 80% by mass in the total amount thereof. In the slurry, water is preferable as a dispersion medium for dispersing the finely pulverized material. In this case, a surfactant such as gluconic acid, gluconate or sorbitol may be added to the slurry. Further, a non-aqueous solvent may be used as the dispersion medium. As the non-aqueous solvent, an organic solvent such as toluene or xylene can be used. In this case, it is preferable to add a surfactant such as oleic acid. The slurry for wet molding may be prepared by adding a dispersion medium or the like to the finely pulverized material in a dry state after pulverization.

In the wet molding, the wet molding slurry is then molded in a magnetic field. In that case, the molding pressure is preferably about 9.8 to 98 MPa (0.1 to 1.0 ton / cm ² ), and the applied magnetic field may be about 400 to 1600 kA / m. Further, the pressing direction and the magnetic field application direction during molding may be the same direction or orthogonal directions.

  Firing of the molded body obtained by wet molding can be performed in an oxidizing atmosphere such as the air. The firing temperature is preferably 1050 to 1270 ° C, more preferably 1080 to 1240 ° C. Moreover, it is preferable that baking time (time to hold | maintain to baking temperature) is about 0.5 to 3 hours.

  In the above, the suitable manufacturing method of the ferrite sintered magnet was demonstrated, However, A manufacturing method is not limited above, Conditions etc. can be changed suitably.

  The form of the sintered ferrite magnet obtained by the present invention is not particularly limited. For example, it can have various shapes such as an arc segment shape having anisotropy, a flat plate shape, and a cylindrical shape. The arc segment shape is a shape in which a flat plate is curved in an arc shape in one direction. The sintered ferrite magnet of the present invention has a good firing temperature dependency of HcJ regardless of the shape, and a high Hk / HcJ can be obtained while maintaining high Br and HcJ. However, high Hk / HcJ can be obtained while maintaining high Br and HcJ.

  The ferrite magnet in the present embodiment can be used for general motors, rotating machines, and the like.

  Ferrite magnets in this embodiment are, for example, for fuel pumps, for power windows, for ABS (antilock brake system), for fans, for wipers, for power steering, for active suspension, for starters, for door locks, It can be used as a member for motors for automobiles such as electric mirrors and drives.

  Also for FDD spindle, VTR capstan, VTR rotary head, VTR reel, VTR loading, VTR camera capstan, VTR camera rotary head, VTR camera zoom, VTR camera focus, radio cassette etc. It can be used as a member of a motor for OA / AV equipment such as a CD / DVD / MD spindle, a CD / DVD / MD loading, and a CD / DVD optical pickup.

  Furthermore, it can also be used as a member for motors for home appliances such as an air conditioner compressor, a freezer compressor, a power tool drive, a dryer fan, a shaver drive, and an electric toothbrush. Furthermore, it can also be used as a member of a motor for FA equipment such as a robot shaft, joint drive, robot main drive, machine tool table drive, machine tool belt drive and the like. Other applications include motorcycle generators, speaker / headphone magnets, magnetron tubes, MRI magnetic field generators, CD-ROM clampers, distributor sensors, ABS sensors, fuel / oil level sensors, magnet latches, isolators. And a member such as a generator. Alternatively, it can also be used as a target (pellet) when forming the magnetic layer of the magnetic recording medium by vapor deposition or sputtering.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

[Example 1]
<Mixing process>
First, a metal element compound powder constituting a ferrite sintered magnet was prepared as a starting material. As starting materials, iron oxide (Fe ₂ O ₃ ), lanthanum hydroxide (La (OH) ₃ ), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), and cobalt oxide (Co ₃ O ₄ ) were used. . SiO ₂ was appropriately added to the obtained mixed raw material.

<Calcination process>
The mixed raw material to which SiO ₂ was added was wet blended with an attritor to obtain a slurry-like raw material composition. After this raw material composition was dried, a calcining treatment was performed in the atmosphere at 1250 ° C. for 2 hours to obtain a calcined body.

<Crushing process>
The obtained calcined body was coarsely pulverized with a rod mill to obtain a coarsely pulverized material. The main phase constituting the sintered ferrite magnet after firing is Ca _0.47 La _0.39 Sr _0.14 Fe _9.10 Co _0.25 O ₁₉ , and the Si content relative to the entire ferrite sintered magnet is SiO _With respect to the obtained coarsely pulverized material so as to be 0.76% by mass in terms of ₂ , calcium carbonate (CaCO ₃ ), silicon dioxide (SiO ₂ ), strontium carbonate (SrCO ₃ ), strontium sulfate (SrSO ₄ ), lanthanum hydroxide (La (OH) ₃ ), and cobalt oxide (Co ₃ O ₄ ) were added as appropriate. Next, fine pulverization was performed in a wet ball mill for 28 hours to obtain a slurry having a solid content concentration of 33%. Here, the S content was changed by adjusting the amount of strontium sulfate added. The slurry obtained after pulverization was adjusted so that the solid content concentration would be 70 to 75%, and a slurry for wet molding was obtained.

<Molding and firing process>
Next, a preform was obtained using a wet magnetic field molding machine. The molding pressure was 50 MPa, and the applied magnetic field was about 800 kA / m. Moreover, the pressurizing direction and the magnetic field application direction during molding were set to the same direction. The preformed body obtained by wet molding was cylindrical, and had a diameter of 30 mm and a height of 15 mm.

  The preform was fired in the air at a temperature (1210 ° C. or 1220 ° C.) shown in Samples 1-1 to 14-2 in Table 1 for 1 hour to obtain a sintered ferrite magnet as a sintered body. .

Each ferrite sintered magnet of the example was subjected to fluorescent X-ray quantitative analysis, and the composition of the main phase of each ferrite sintered magnet was Ca _0.47 La _0.39 Sr _0.14 Fe _9.10 Co _0.25. it was confirmed that is the O _19. The content of Si is on the whole ferrite sintered magnet was confirmed to be 0.76 wt% in terms of SiO _2. About each ferrite sintered magnet of an Example, S content was measured by the combustion in an oxygen stream-infrared absorption method. Table 1 shows the S content of each ferrite sintered magnet.

<Measurement of magnetic properties (Br, HcJ, Hk / HcJ)>
For each sample of the example, after processing the upper and lower surfaces of each ferrite sintered magnet, magnetic properties (residual magnetic flux density) using a BH tracer with a maximum applied magnetic field of 1989 kA / m in an air atmosphere at 25 ° C. Br, coercive force HcJ, squareness ratio Hk / HcJ). Furthermore, the firing temperature dependence of HcJ was calculated. The results are shown in Table 1. Here, Hk is the external magnetic field strength when the magnetic flux density is 90% of the residual magnetic flux density in the second quadrant of the magnetic hysteresis loop. Furthermore, the relationship between the S content in each sample and the firing temperature dependence of HcJ is graphed and shown in FIG. Here, the firing temperature dependence of HcJ was considered favorable from −0.05% / ° C. to + 0.05% / ° C. In FIG. 1, a line indicating ± 0.05% / ° C. is indicated by a dotted line. Br made 440 mT or more favorable. 450 mT or more is more preferable. HcJ was set to 400 kA / m or higher. 410 kA / m or more is more preferable, 420 kA / m or more is more preferable, and 430 kA / m or more is more preferable. Hk / HcJ was determined to be 75% or more. 80% or more is more preferable, and 85% or more is more preferable.

  From Table 1 and FIG. 1, in the case of sample numbers 2-1 to 12-2 in which the S content in each sample is 100 ppm to 1300 ppm, the absolute value of the firing temperature dependency of HcJ is 0.05% / C. or lower, HcJ was 380 kA / m or higher, Hk / HcJ was 75% or higher, and Br was 430 mT or higher. When the S content was less than 100 ppm, the absolute value of the firing temperature dependence of HcJ was too high. When the S content exceeded 1300 ppm, one or more of HcJ, Hk / HcJ, and Br were reduced. Moreover, as shown in Table 1, in the case of sample numbers 2-1 to 11-2 in which the S content in each sample is 100 ppm to 1000 ppm, the absolute value of the firing temperature dependence of HcJ is 0.05. % / ° C. or lower, HcJ is 400 kA / m or higher, Hk / HcJ is 80% or higher, and Br is 440 mT or higher, which is a more preferable result. Further, as shown in Table 1, in the case of sample numbers 2-1 to 9-2 in which the S content in each sample is 100 ppm to 750 ppm, the absolute value of the firing temperature dependence of HcJ is 0.05. % / ° C. or less, HcJ was 410 kA / m or more, Hk / HcJ was 80% or more, and Br was 440 mT or more, which was a more preferable result. As shown in Table 1, in the case of sample numbers 2-1 to 8-2 in which the S content in each sample is 100 ppm to 450 ppm, the absolute value of the firing temperature dependence of HcJ is 0.05. % / ° C. or less, HcJ is 420 kA / m or more, Hk / HcJ is 85% or more, and Br is 450 mT or more, which is a more preferable result. Moreover, as shown in Table 1, in the case of sample numbers 2-1 to 7-2 in which the S content in each sample is 100 ppm to 320 ppm, the absolute value of the firing temperature dependency of HcJ is 0.05. % / ° C. or less, HcJ is 430 kA / m or more, Hk / HcJ is 85% or more, and Br is 450 mT or more, which is a more preferable result.

[Example 2]
Samples 8-3 (S content 450 ppm) were prepared in the same manner as in Example 1 except that samples 8-1 and 8-2 (S content 450 ppm) were fired at 1230 ° C. Similarly, Samples 10-1 and 10-2 (S content 840 ppm) were similarly prepared as Sample 10-3 (S content 840 ppm). Table 2 shows HcJ, Hk / HcJ and Br of Samples 8-1 to 10-3. In all samples, HcJ was 400 kA / m or more and Br was 440 mT or more. Moreover, about sample 8-3, 10-3, although Hk / HcJ fell, it became 75% or more which is in a favorable range. Furthermore, the absolute value of the HcJ firing temperature dependence between the samples was 0.05% / ° C. or less. That is, even when the range of the firing temperature was expanded, the firing temperature dependence of HcJ was within the good range.

[Example 3]
Except that the composition of the main phase constituting the sintered ferrite magnet after firing was varied w such that _{Ca 0.86-w La w Sr 0.14} Fe 9.10 Co 0.25 O 19 , respectively Samples 21 to 40 were produced in the same manner as Sample 4-1 of Example 1. Table 3 shows HcJ, Hk / HcJ and Br of Samples 21 to 40. At the same time, samples 21 to 40 were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C., and the firing temperature dependence of HcJ was measured and shown in Table 3.

  In Samples 22 to 37 that satisfy 0.24 ≦ w ≦ 0.60 and 1.0 ≦ w / m ≦ 2.4, the absolute value of the firing temperature dependency of HcJ is 0.05% / ° C. or less, and HcJ is 380 kA. / M or more, Hk / HcJ was 75% or more, and Br was 430 mT or more. In contrast, Samples 21 and 38 to 40 that do not satisfy 0.24 ≦ w ≦ 0.60 and / or 1.0 ≦ w / m ≦ 2.4 are one or more of HcJ, Hk / HcJ, and Br. Was inferior to Samples 22-37.

  In Table 3, the w / m value is rounded off to the second decimal place.

[Example 4]
By changing x so that the composition of the main phase constituting the sintered ferrite magnet after firing becomes Ca _0.61-x La _0.39 Sr _x Fe _9.10 Co _0.25 O ₁₉ , ferrite sintering Samples 41 to 55 were produced in the same manner as the sample 4-1 of Example 1 except that the Si content with respect to the entire magnet was converted to SiO ₂ to be 0.85% by mass. Table 4 shows HcJ, Hk / HcJ and Br of Samples 41 to 55. At the same time, samples 41 to 55 were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C., and the firing temperature dependence of HcJ was measured and shown in Table 4.

  Samples 42 to 53 that satisfy 0.02 ≦ x ≦ 0.41 have an absolute value of the firing temperature dependence of HcJ of 0.05% / ° C. or less, HcJ of 380 kA / m or more, Hk / HcJ of 75% or more, Br became 430 mT or more. In contrast, Samples 41, 54, and 55 that did not satisfy 0.02 ≦ x ≦ 0.41 resulted in HcJ and / or Hk / HcJ being inferior to Samples 42-53.

[Example 5]
Example except that z is changed so that the composition of the main phase constituting the sintered ferrite magnet after firing becomes Ca _0.47 La _0.39 Sr _0.14 Fe _z Co _0.25 O ₁₉ , respectively. Samples 61 to 76 were prepared in the same manner as Sample 1 4-1. Table 5 shows HcJ, Hk / HcJ and Br of Samples 61 to 76. At the same time, samples 61 to 76 were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C., and the firing temperature dependence of HcJ was measured and shown in Table 5.

  In Samples 62 to 75 that satisfy 8.00 ≦ z ≦ 11.00, the absolute value of the firing temperature dependency of HcJ is 0.05% / ° C. or less, HcJ is 380 kA / m or more, Hk / HcJ is 75% or more, Br became 430 mT or more. On the other hand, the samples 61 and 76 that do not satisfy 8.00 ≦ z ≦ 11.00 have HcJ inferior to the samples 62 to 75.

[Example 6]
Ferrite sintered composition of the main phase constituting the sintered magnet alters the m such that the _{Ca 0.46 La 0.39 Sr 0.15 Fe 9.25} Co m O 19 , respectively, the whole ferrite sintered magnet after sintering Samples 81 to 99 were produced in the same manner as the sample 4-1 of Example 1 except that the Si content relative to the SiO ₂ was 0.85% by mass in terms of SiO ₂ . Table 6 shows HcJ, Hk / HcJ and Br of Samples 81 to 99. At the same time, samples 81 to 99 were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C., and the firing temperature dependence of HcJ was measured and shown in Table 6.

  Samples 83 to 95 satisfying 1.0 ≦ w / m ≦ 2.4 have an absolute value of the firing temperature dependency of HcJ of 0.05% / ° C. or less, HcJ of 380 kA / m or more, and Hk / HcJ of 75%. As described above, Br was 430 mT or more. In contrast, Samples 81, 82, and 96 to 99 that do not satisfy 1.0 ≦ w / m ≦ 2.4 are inferior to Samples 83 to 95 in any one or more of HcJ, Hk / HcJ, and Br. It was.

  In Table 6, the value of m is rounded to the third decimal place, and the value of w / m is rounded to the second decimal place. For example, in Table 6, the values of m appear to be equal between the sample 82 and the sample 83. However, in actuality, the value of m is different when it is expressed to the third decimal place. Therefore, the value of w / m is different between the sample 82 and the sample 83.

[Example 7]
Except that the content of Si with respect to the entire sintered ferrite magnet after firing was changed to 0.60 to 1.20% by mass in terms of SiO ₂ , the same as in Sample 4-1 of Example 1. Samples 111 to 119 were prepared. Table 7 shows HcJ, Hk / HcJ and Br of Samples 111 to 119. At the same time, samples 11 to 119 were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C., and the firing temperature dependency of HcJ was measured and shown in Table 7.

  In all of the samples 111 to 119, the absolute value of the firing temperature dependency of HcJ was 0.05% / ° C. or less, HcJ was 380 kA / m or more, Hk / HcJ was 75% or more, and Br was 430 mT or more.

[Example 8]
Samples 121 to 139 were prepared in the same manner as Sample 4-1 of Example 1 except that the physical quantity HIN = b + 13000 × (a−0.90) ² of the sintered ferrite magnet after firing was changed. It was measured.

  Table 8 and FIG. 2 show the results of measuring HcJ for the sample having a firing temperature of 1210 ° C., the samples 111 to 119 produced in Example 7, and the samples 121 to 139 in Example 1. It can be seen from Table 8 and FIG. 2 that HcJ tends to increase as the physical quantity HIN decreases. Specifically, the sample satisfying 100 ≦ HIN ≦ 1780 has HcJ of 385 kA / m or more. A sample satisfying 100 ≦ HIN ≦ 1380 has an HcJ of 400 kA / m or more. A sample satisfying 100 ≦ HIN ≦ 980 has an HcJ of 415 kA / m or more. A sample satisfying 100 ≦ HIN ≦ 580 has an HcJ of 430 kA / m or more. A sample satisfying 100 ≦ HIN ≦ 180 has an HcJ of 445 kA / m or more.

  Moreover, about the said samples 121-139, the sample was produced on the same conditions except having changed the calcination temperature from 1210 degreeC to 1220 degreeC, and the calcination temperature dependence of HcJ was measured. Further, samples 121 to 139 were prepared under the same conditions except that the S content was less than 100 ppm, and the firing temperature dependence of HcJ was measured when the S content was less than 100 ppm. .

  The absolute value of the firing temperature dependence of HcJ in Samples 121 to 139 was lower than the absolute value of the firing temperature dependence of HcJ when the S content was less than 100 ppm.

[Example 9]
The composition of the main phase constituting the sintered ferrite magnet after firing is selected from the group consisting of Ca _0.47 R _0.39 A _0.14 Fe _9.10 M _0.25 O ₁₉ (R is a rare earth element and Bi). Is at least one element selected from the group consisting of Sr and Ba, and M is selected from the group consisting of Co, Mn, Mg, Ni, Cu and Zn. Various samples in the same manner as Sample 4-1 (S content 140 ppm) of Example 1 except that R, A, and M were changed so that they were at least one element and contained at least Co). Was made. At the same time, samples were prepared under the same conditions except that the firing temperature was changed from 1210 ° C. to 1220 ° C. for each sample, and the firing temperature dependence of HcJ was measured. Further, for each sample, samples were prepared under the same conditions except that the S content was less than 100 ppm, and the HcJ firing temperature dependence was measured when the S content was less than 100 ppm.

As rare earth elements other than La and Bi materials, rare earth elements and Bi hydroxides were used. As a raw material for Ba, barium carbonate (BaCO ₃ ) and / or barium sulfate (BaSO ₄ ) was used. As raw materials for M other than Co, oxides of the respective elements were used.

  For all the samples prepared by changing R, A, and M, the absolute value of the firing temperature dependence of HcJ when the S content is 140 ppm is that of HcJ when the S content is less than 100 ppm. It was lower than the absolute value of the firing temperature dependency.

Claims (4)

A ferrite sintered magnet having a main phase composed of a ferrite phase having a hexagonal crystal structure,
The composition of the main phase is represented by the following formula (1):
_{Ca 1-w-x R w} A x Fe z M m O 19 ··· (1)
R is at least one element selected from the group consisting of rare earth elements and Bi and contains at least La, A is at least one element selected from Sr and Ba, M is Co, Mn, Mg, At least one element selected from the group consisting of Ni, Cu and Zn, including at least Co;
In the formula (1), w, x, z, and m satisfy the following formulas (2), (3), (4), and (5),
0.24 ≦ w ≦ 0.60 (2)
0.02 ≦ x ≦ 0.41 (3)
8.00 ≦ z ≦ 11.00 (4)
1.0 ≦ w / m ≦ 2.4 (5)
A ferrite sintered magnet comprising at least S and having a content of S of 100 ppm to 1300 ppm.   The ferrite sintered magnet according to claim 1, comprising at least Si. 3. The sintered ferrite magnet according to claim 1, wherein the ferrite sintered magnet contains at least Si, and the content of Si is 0.60% by mass or more and 1.20% by mass or less in terms of SiO ₂ . When at least Si is included, the Si content is a (mass%) in terms of SiO ₂ , the S content is b (ppm), and the physical quantity HIN is expressed by the following formula (6), the HIN is 100 or more and 1780. The ferrite sintered magnet according to any one of claims 1 to 3, wherein:
HIN = b + 13000 × (a−0.90) ² (6)

Images