JP2002015913A - Magnetic ferrite powder, magnetic ferrite sintered body, laminated ferrite part and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated ferrite part, equipped with a hexagonal ferrite magnetic layer having a Z-phase as a primary phase. SOLUTION: Magnetic ferrite layers 2 and internal electrodes 3 are laminated alternately, and the internal electrodes 3 and has an outer electrodes 5 electrically connected to the internal electrodes 3 are provided to the laminate for the formation of a laminated chip bead 1. According to X-ray diffraction, the magnetic ferrite layer 2 is constituted of a magnetic hexagonal ferrite sintered body, that has a Z-phase (M3Me2Fe24O41: M is one or more from among alkaline earth metal elements, Me is one or more from among Co, Ni, Mn, Zn, Mg and Cu) as a primary phase and is 1 to 5 μm in average crystal grain diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic ferrite used for a multilayer chip ferrite component such as a multilayer chip bead, a multilayer inductor, a composite multilayer component represented by an LC composite multilayer component, and a multilayer ferrite component. Things.

[0002]

2. Description of the Related Art Laminated chip ferrite parts and composite laminated ferrite parts (collectively referred to as laminated ferrite parts in this specification) are used in various electric devices because of their small volume and high reliability. Have been. This laminated ferrite component is usually formed by laminating and integrating a sheet or paste for a magnetic layer made of magnetic ferrite and a paste for an internal electrode by a thick film laminating technique, and then firing and forming the resultant on the surface of the obtained sintered body. It is manufactured by printing or transferring an external electrode paste and then baking. Note that firing after lamination and integration is called simultaneous firing. Since Ag or Ag alloy is used as the material for the internal electrode because of its low resistivity, the magnetic ferrite material constituting the magnetic layer can be co-fired, in other words, it has a melting point lower than the melting point of Ag or Ag alloy. An absolute condition is that firing can be performed at a temperature. Therefore, in order to obtain a high-density, high-characteristic laminated ferrite component, the key is whether the magnetic ferrite can be fired at a low temperature equal to or lower than the melting point of Ag or an Ag alloy.
NiCuZn ferrite is known as a magnetic ferrite that can be fired at a low temperature equal to or lower than the melting point of Ag or an Ag alloy. In other words, NiCuZn ferrite using a raw material powder having a specific surface area of about 6 m ² / g or more by pulverization can be fired at a melting point of Ag (961.93 ° C.) or less, and thus is widely used for laminated ferrite parts. .

[0003] In recent years, hexagonal ferrite has attracted attention as the clock frequency increases. Among hexagonal ferrites, there are M type, U type, W type, X type, Y type and Z type.
There are six types of molds, which have different characteristics from cubic ferrites such as Mn-based and Ni-based. Among them, the Z type has a general formula of M ₃ Me ₂ Fe ₂₄ O ₄₁ . Here, M is an alkaline earth metal, and Me is a divalent metal ion. Among the Z-type hexagonal ferrites, the Z-type hexagonal ferrite containing cobalt metal ions has a large anisotropy, so that it can have a higher magnetic permeability than the spinel-type oxide magnetic material up to a high frequency range. is there. This Z-type hexagonal ferrite containing cobalt metal ions is:
It is called Co ₂ Z. It has been known for a long time that Z-type hexagonal ferrite has excellent high-frequency characteristics, but it has not yet been put to practical use due to some problems. In other words, M, W, Y
A phase appears, and the magnetic permeability is reduced due to the formation of the different phase. It has also been pointed out that the Z-type hexagonal ferrite sintered body has a low sintered body density. If the sintered body density is low, the mechanical strength when used as a surface mount component becomes a problem. Further, the sintered body density and the magnetic permeability have a close relationship, and if the sintered body density is low, the magnetic permeability itself becomes low, and the original magnetic properties cannot be exhibited.

[0004]

Japanese Unexamined Patent Publication No. Hei 9-110432 discloses a hexagonal ferrite material in which the density of a sintered body is increased and the decrease in magnetic permeability is suppressed even in a high frequency range. The hexagonal ferrite material disclosed in Japanese Unexamined Patent Publication No. Hei 9-110432 is characterized by adding predetermined amounts of SiO ₂ and CaO. However, Japanese Patent Application Laid-Open
The hexagonal ferrite material disclosed in 110432 is premised on firing at 1150 to 1350 ° C. Therefore, they cannot be fired at the same time, and it is difficult to apply them to laminated ferrite parts. Japanese Unexamined Patent Publication No. Hei 9-1 for correspondence to low-temperature sintering of hexagonal ferrite materials
No. 67703 proposes this. Specifically, (B
a, Sr, Pb) ₃ (Co _1-x Cu _x ) ₂ Fe ₂₄ O ₄₁ , that is, a part of the alkaline earth metal is replaced by Pb,
It also points out that densification can be performed at a low temperature by substituting a part of Co with Cu. However, the hexagonal ferrite material obtained according to JP-A-9-167703 has an M phase, a Y phase, a W phase, an X phase and a U phase as main phases, and has a high magnetic permeability up to a high frequency band. Some Z
A hexagonal ferrite material having a main phase as a phase has not yet been obtained. As described above, a hexagonal ferrite material that can be fired at a low temperature and has a Z phase as a main phase has not been obtained so far. Accordingly, an object of the present invention is to provide a hexagonal ferrite material having a Z phase as a main phase, which can be applied to a laminated ferrite component because it can be fired at a low temperature, and to provide a laminated ferrite component using the same. .

[0005]

Conventionally, Z-type hexagonal ferrite which can be used in the giga band has been used at 1250-1350 ° C.
Since magnetic properties cannot be obtained unless high-temperature firing is performed,
It could not be fired at 960 ° C. or lower, which is lower than the melting point of Ag, which is a material for internal electrodes, and it was not possible to obtain a multilayer chip ferrite component that required simultaneous firing with Ag. Further, although there is a proposal of a hexagonal ferrite material that can be fired at a low temperature, it does not have a Z phase as a main phase. In view of the above, the present inventors have studied additives for the calcining temperature, the particle size distribution of the powder before firing, the powder specific surface area, and the main composition, and solved the above-mentioned problems. Accordingly, the present invention provides a method for determining the Z
Phase (M ₃ Me ₂ Fe ₂₄ O ₄₁ : M = one or more of alkaline earth metals, Me = Co, Ni, Mn, Zn, Mg
And one or more of Cu) is 30% or more, and the peak value of the particle size distribution is 0.1 to 3%.
It is a magnetic ferrite powder characterized by being in the range of μm. The magnetic ferrite powder of the present invention comprises one of borosilicate glass, zinc borosilicate glass, CuO and Bi ₂ O ₃ .
Seed or two or more kinds can be added at 0.5 to 20 wt%. In particular, 0.5 of CuO and Bi ₂ O ₃ in total
When 20 wt% is added, it is effective for simultaneous firing. In the present invention, the Z phase represented by M ₃ Me ₂ Fe ₂₄ O ₄₁ (where M = Ba, Me = Co, Ni, Mn, Zn, Mg
And one or more of Cu) form a main phase;
There is provided a magnetic ferrite powder having a powder specific surface area of 5 to 30 m ² / g. By substituting a part of Ba with Sr in the magnetic ferrite powder of the present invention, it is possible to obtain a magnetic ferrite powder having excellent high-frequency characteristics, and to perform calcination at a temperature lower than the conventional calcination temperature. It becomes possible.

In the present invention, a Z phase represented by M ₃ Me ₂ Fe ₂₄ O ₄₁ (where M = Ba, Me = Co, Ni,
One or more of Mn, Zn, Mg and Cu) form a main phase, and CuO and Bi ₂ O ₃ are contained in a total amount of 0.1%.
5-20 wt%, CuO is mainly present in the crystal grains,
A magnetic ferrite sintered body characterized in that Bi ₂ O ₃ is mainly present at crystal grain boundaries is provided. In this sintered body, C
uO and Bi ₂ O ₃ function effectively for firing at 960 ° C. or lower. Further, in the magnetic ferrite sintered body of the present invention, a part of Ba can be replaced with Sr.

Further, the present invention is a laminated ferrite component having a magnetic ferrite layer and an internal electrode alternately laminated, and having an external electrode electrically connected to the internal electrode, wherein the magnetic ferrite layer Is the Z-phase of hexagonal ferrite (M ₃ Me ₂ Fe ₂₄ O ₄₁ : M
= One or more alkaline earth metals, Me = C
o, Ni, Mn, Zn, Mg, and Cu, one or more of which form a main phase, and have an average crystal grain size of 1 to 5
The present invention provides a laminated ferrite component comprising a magnetic ferrite sintered body having a thickness of μm, wherein the internal electrodes are composed of Ag or an Ag alloy. In the multilayer ferrite component of the present invention, the magnetic ferrite layer and the internal electrode layer are fired simultaneously, and the density of the magnetic ferrite layer can be 5 g / cm ³ or more. Further, in the multilayer ferrite component of the present invention, the magnetic ferrite layer may contain CuO and Bi ₂ O ₃ in a total amount of 0.5 to 0.5.
20% by weight, CuO is mainly present in the crystal grains,
It is desirable that i ₂ O ₃ exists mainly at the crystal grain boundary.

The above-described multilayer ferrite component of the present invention can be obtained by the following method of manufacturing a multilayer ferrite component of the present invention. That is, a method of manufacturing a laminated ferrite component in which a magnetic ferrite layer and internal electrodes are laminated, wherein a step of mixing raw powders of magnetic ferrite and a step of calcining the mixed raw powders in a temperature range of 1200 ° C. or more. And a step of pulverizing the obtained calcined body so that the peak value of the particle size distribution is in a range of 0.1 to 3 μm. A sheet or paste for forming a magnetic layer using the obtained pulverized powder Obtaining a laminated molded body by alternately laminating the sheet or paste and the material for an internal electrode, and firing the laminated molded body at a temperature of 960 ° C. or less, The ferrite phase is a hexagonal ferrite Z phase (M ₃ Me ₂ Fe ₂₄ O ₄₁ :
M = one or more of alkaline earth metals, Me = C
o, Ni, Mn, Zn, Mg, and Cu (one or two or more types) of a magnetic ferrite sintered body having a main phase. In the method of the present invention, the powder specific surface area of each raw material powder is preferably 4.5 m ² / g or more, and the powder specific surface area of the pulverized powder is preferably in the range of 8 to ²⁰ m ² / g.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
Will be explained. In the present invention, M_ThreeMe_TwoFe_{twenty four}O₄₁Indicated by
The peak intensity ratio of the Z phase is 30% or more,
Constitute. The higher the peak intensity ratio of the Z phase, the better, but
The current manufacturing technology has a limit of about 80%. Of the present invention
Raw material powder for obtaining magnetic ferrite powder and sintered body
As Fe _TwoO_ThreeAbout powder, and M and Me
Prepares oxide or carbonate powder. M is Ba, Sr
And the like, and particularly, Ba is desirable. M
Ba is selected as BaCO_ThreeAs powder
It is desirable to add. However, as shown in the examples described later.
As described above, part of Ba can be replaced with Sr. here
And Ba²⁺Has an ionic radius of 0.136 nm, while Sr²⁺
Has an ionic radius of 0.116 nm, and the ionic radius of both is
Significantly different. Therefore, part of Ba is replaced with Sr
This increases the anisotropy and broadens the frequency band.
Can be When replacing part of Ba with Sr,
The substitution amount can be 5 to 80%, and the desired substitution amount
Is 20-35%. By performing substitution within this range,
Thus, a higher magnetic permeability can be obtained, and
This has the effect of shifting the wavenumber band to the higher frequency side.
Further, the present inventor has proposed that by replacing Ba with Sr,
It was found that the melting point decreased. Ba in Sr 20% or less
Lowering the calcining temperature by about 50 ° C when replacing
Becomes possible. Due to this, in the pulverizing process after calcining,
Therefore, it is preferable that the obtained calcined body has a desired particle size distribution.
This facilitates mass production.

Me is Co, Ni, Mn, Zn, M
g and Cu are one or more of them.
o is desirable. However, as shown in Examples described later, Co
Is partially replaced by at least one of Ni, Mn, Zn, Mg, and Cu, the effect that μ ″ shifts to the high frequency side can be obtained. In the case of substitution with near Cu, the magnetic permeability shifts to the high frequency side with an increase in the amount of substitution of Cu, and the effect of excellent noise absorption in the giga band is exhibited.
It can be added as ₃ O ₄ , NiO, MnO, ZnO, MgO and CuO powder. However, this is an exemplification, and does not exclude addition in other forms. In the present invention, the composition may be selected according to the purpose. In order to obtain a magnetic permeability excellent in high frequency characteristics, in particular, Fe ₂ O ₃
Is 65 to 75 mol%, and BaCO ₃ is 17 to 27 mol.
% (Or the sum of BaCO ₃ and SrCO ₃ is 17 to 27 m
ol%), Co ₃ O ₄ , NiO, MnO, ZnO, MgO
One or more of CuO and 5 to 15 mol%
Is desirable. More preferably, F
e ₂ O ₃ is 67 to 70 mol%, BaCO ₃ is 18 to 2
0 mol%, Co ₃ O _4, etc. are 7 to 12 mol%. The magnetic properties of the magnetic ferrite have a very strong composition dependence, and in a region outside the above range, the magnetic permeability and the quality factor Q are low and insufficient. Specifically, for example, if the composition is out of the composition range shown above, the target magnetic ferrite cannot be produced, and a high magnetic permeability with excellent frequency characteristics cannot be obtained.

In the magnetic ferrite powder of the present invention, the peak value of the average particle size distribution (hereinafter, simply referred to as particle size distribution) is in the range of 0.1 to 3 μm. If the particle size distribution exceeds 3 μm, simultaneous firing becomes difficult. However, when the thickness is less than 0.1 μm, it becomes difficult to prepare a paste paint or a sheet paint necessary for obtaining the multilayer ferrite component of the present invention. That is, the paint gels. Desirable peak value of the particle size distribution is 0.5 to
2.0 μm, more preferably the peak value of the particle size distribution is 0.2 μm.
8 to 1.5 μm.

[0012] Since the generated phase of the magnetic ferrite of the present invention is determined by the calcining temperature, the calcining temperature is particularly important. That is, the peak intensity ratio of the Z phase is set to 30.
%, Or in order to make the Z phase the main phase, the calcination needs to be performed at a high temperature of 1200 ° C. or more. However, if the calcination is performed at a high temperature, the particles become hard and the subsequent pulverization process takes a long time, resulting in composition deviation and the like, so that extreme care is required. Further, even if the calcination is performed in a temperature range exceeding 1350 ° C., the Z phase is not generated, and it is impossible to obtain excellent frequency characteristics of magnetic permeability. Therefore, a desirable calcining temperature is 1250 to 1330 ° C. However,
As described above, when Ba is replaced with Sr by 20% or more, the melting point is lowered.
0-1280 ° C. Co and C as Me
When u is selected and the total amount is 5 to 15 mol%, the peak intensity ratio of the Z phase becomes 30% or more around 1250 ° C. due to the low-temperature sintering effect of Cu. Therefore, also in this case, it can be said that the desirable calcining temperature is 1230 to 1280 ° C. The calcination time is not particularly limited, and may be appropriately determined according to the composition and the calcination temperature, but about 0.1 to 5 hours is sufficient.

For co-firing, ie, low-temperature firing, borosilicate glass, zinc borosilicate glass, Cu
O, it is important that one or more of Bi ₂ O ₃ is added 0.5-20%. Among them, CuO, Bi ₂ O ₃
It is effective to add
It is desirable that the content be 1 to 10% by weight, more preferably 3 to 8% by weight. Both CuO and Bi ₂ O ₃ are effective for low-temperature firing, but in the sintered body, the former mainly exists in the crystal grains, and the latter mainly exists in the crystal grain boundaries. By the way, M
Also when selecting Cu as e, CuO can be used. However, CuO as Me is added before calcination, whereas CuO added as an additive component for low-temperature calcination is added after calcination.

FIG. 20 is a schematic sectional view showing an example of a laminated chip bead which is an embodiment of the laminated chip ferrite component of the present invention, and FIG. 21 is a plan partial sectional view.
The laminated chip beads are manufactured using a printing lamination method. As another manufacturing method, there is a sheet laminating method. 20 and 21, a multilayer chip bead 1 has a multilayer chip body 4 in which a magnetic ferrite layer 2 and an internal electrode 3 are alternately laminated and integrated. , External electrodes 5 and 5 electrically connected to the internal electrode 3 are provided. The magnetic ferrite layer 2 constituting the laminated chip beads 1 is made of the hexagonal ferrite sintered body of the present invention. That is, the magnetic ferrite powder of the present invention is alternately printed and laminated with a paste for the magnetic ferrite layer 2 and a paste for the internal electrode 3 obtained by kneading a binder such as ethyl cellulose and a solvent such as terpineol and butyl carbitol, and then firing. Can be formed.

The content of the binder and the solvent in the magnetic ferrite layer paste is not limited. For example, the content of the binder is 1 to 10% by weight and the content of the solvent is 10 to 10% by weight.
It can be set in the range of about 50% by weight. Also,
In the paste, a dispersant, a plasticizer, a dielectric, an insulator, and the like can be contained in a range of 10% by weight or less as needed. Further, the magnetic ferrite layer 2 can be formed using a magnetic ferrite layer sheet. That is, a slurry obtained by kneading the magnetic ferrite powder of the present invention in a ball mill together with a binder containing polyvinyl butyral or acryl as a main component and a solvent such as toluene, xylene, or ethyl alcohol, was doctor-bladed on a polyester film or the like. It is applied by a method or the like and dried to obtain a sheet for a magnetic ferrite layer. This magnetic ferrite layer sheet is alternately laminated with the internal electrode paste, and then fired. The content of the binder in the magnetic ferrite layer sheet is not limited, and can be set, for example, in a range of about 1 to 20% by weight. Also, in the magnetic ferrite layer sheet, if necessary, dispersant, plasticizer, dielectric,
An insulator or the like can be contained in a range of 10% by weight or less.

The internal electrodes 3 constituting the multilayer chip beads 1 are formed using a conductive material mainly composed of Ag having a small resistivity in order to obtain a practical quality factor Q as an inductor. Each layer of the internal electrode 3 has an oval shape, and each layer of the adjacent internal electrode 3 has a spiral conduction. Therefore, the internal electrode 3 forms a closed magnetic circuit coil (winding pattern). External electrodes 5 and 5 are connected to both ends.
The outer shape and dimensions of the chip body 4 of the multilayer chip beads 1 are not particularly limited, and can be appropriately set according to the application.
Usually, the outer shape is substantially a rectangular parallelepiped shape, and the size is 1.0-4.
It can be about 5 mm × 0.5 to 3.2 mm × 0.6 to 1.9 mm. The thickness between the electrodes and the base thickness of the magnetic ferrite layer 2 are not particularly limited, and the thickness between the electrodes (the interval between the internal electrodes 3 and 3) can be set to about 10 to 100 μm, and the base thickness can be set to about 250 to 500 μm. . Further, the thickness of the internal electrode 3 is usually 5 to 30 μm.
The pitch of the winding pattern is 10 to 10
The number of turns can be about 0 μm and the number of turns can be about 1.5 to 20.5 turns. The firing temperature after alternately printing and laminating the magnetic ferrite layer paste or sheet and the internal electrode paste is 800 to 960 ° C., preferably 850 ° C.
~ 930 ° C. If the sintering temperature is lower than 800 ° C., the sintering becomes insufficient. On the other hand, if the sintering temperature exceeds 960 ° C., Ag, which is an internal electrode material, diffuses into the magnetic ferrite layer 2, and the electromagnetic characteristics may be significantly reduced. The firing time can be set in the range of 0.05 to 5 hours, preferably 0.1 to 3 hours. In the present invention, since firing is performed at such a low temperature, the crystal grain size of the magnetic ferrite layer 2 is as fine as 1 to 5 μm on average.

FIG. 22 is a schematic sectional view showing an example of an LC composite component which is an embodiment of the laminated LC composite component of the present invention. In FIG. 22, the LC composite component 11 is obtained by integrating a chip capacitor section 12 and a chip ferrite section 13, and an external electrode 15 is provided at this end. The chip capacitor section 12 has a multilayer structure in which ceramic dielectric layers 21 and internal electrodes 22 are alternately stacked and integrated. The ceramic dielectric layer 21 is not particularly limited, and various dielectric materials can be used, and a titanium oxide-based dielectric having a low firing temperature is preferable. Further, a titanate-based composite oxide, a zirconate-based composite oxide, or a mixture thereof can also be used. further,
To lower the firing temperature, various glasses such as borosilicate glass may be contained. The internal electrode 22 is formed using a conductive material mainly composed of Ag having a small resistivity.
Each layer of the internal electrode 22 is alternately connected to another external electrode.

The chip ferrite section 13 is a multilayer chip inductor, and includes a ferrite magnetic layer 32 and an internal electrode 3.
Reference numeral 3 denotes a chip body having a multilayer structure alternately stacked and integrated. The ferrite magnetic layer 32 is made of the magnetic ferrite of the present invention. That is, the magnetic ferrite powder of the present invention is kneaded with a binder such as ethyl cellulose and a solvent such as terpineol and butyl carbitol, and the paste for the ferrite magnetic layer is alternately printed and laminated with the paste for the internal electrodes, and then fired. Can be formed. Alternatively, the magnetic ferrite powder of the present invention is kneaded in a ball mill together with a binder containing polyvinyl butyral or acrylic as a main component and a solvent such as toluene and xylene to prepare a slurry. The ferrite magnetic layer sheet obtained by applying and drying by a blade method or the like is alternately laminated with the internal electrode paste, and then fired. The internal electrodes 33 are spirally conductive to form a closed magnetic circuit coil (winding pattern), and both ends are connected to the external electrodes 15. This internal electrode 33
Is formed using a conductive material mainly composed of Ag having a small resistivity. The thickness between the electrodes and the base thickness of the ferrite magnetic layer 32 of the chip ferrite portion 13 are not particularly limited, and the thickness between the electrodes (the interval between the internal electrodes 33, 33) is 10 to 1
The thickness can be set to be about 00 μm and the base thickness can be about 10 to 500 μm. Further, the thickness of the internal electrode 33 can be usually set in the range of 5 to 30 μm, the pitch of the winding pattern is about 10 to 400 μm, and the number of turns is 1.5 to 50.5.
It can be around a turn. The outer shape and dimensions of the LC composite component 11 of the present invention are not particularly limited and can be appropriately set according to the application. Usually, the outer shape is substantially a rectangular parallelepiped shape, and the size is 1.6 to 10.0 mm × 0. 8 ~ 15.0m
It can be about mx 1.0-5.0 mm.

[0019]

Next, the present invention will be described in more detail with reference to specific examples. (Example 1) After the raw material powders were blended to have the compositions shown in Tables 1 and 2, calcination and pulverization were performed. Table 1 shows hexagonal ferrite, and Table 2 shows NiCuZn ferrite. The conditions for blending, calcining and pulverizing are as follows. Table 3 shows the specific surface area of each raw material powder. The specific surface area of each raw material powder is 4.5 m ² / g or more. Compounding and crushing pot: Use of stainless steel ball mill pot (Sample Nos. 2 to 4 are crushed polypots) Compounding and crushing media: Use of steel ball (Sample No. 2 is crushed by ZrO ₂ ball) Compounding time: 16 hours Conditions: Sample Nos. 1, 3, 4 = 1300 ° C. × 2 hours Sample No. 2 = 1200 ° C., 1250 ° C., 1300 ° C., 1350 ° C. × 2 hours Sample No. 5 = 750 ° C. × 10 hours Milling time: 90 hours

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

With respect to the ground powder of Sample No. 2, the phases were identified by an X-ray diffraction method, and the X-ray peak intensity ratio of the identified phase was determined. The result is shown in FIG. The X-ray peak intensity ratio is defined as the ratio of the highest peak intensity of each phase to the sum of the highest peak intensity of the diffraction line for the identified phase. The X-ray diffraction conditions are as follows. X-ray generator: 3 kW, tube voltage: 45 kV, tube current: 40 mA, sampling width: 0.02 deg, scanning speed: 4.00 deg / min, divergence slit: 1.00 deg, scattering slit: 1.00 deg, light receiving slit: 0.30 mm As shown in FIG. 1, when the calcining temperature is 1200 ° C., M
The phases, Y phase, Z phase, Ba ₂ Fe ₂ O ₅ phase (Ba ferrite phase) and BaCO ₃ phase were identified. At this calcination temperature, the M phase has the highest peak intensity ratio. When the calcining temperature is 1250 ° C., the M phase, the Y phase, the Z phase,
Five phases of the Ba ferrite phase and the BaCO ₃ phase were identified, and the peak intensity ratio of the Z phase was the highest at 35%, indicating that the Z phase was the main phase. Calcination temperature 1200
Looking at the behavior of each phase between １２1250 ° C., the Z phase is the main phase,
That is, in order for the peak intensity ratio of the Z phase to be greater than the peak intensity ratio of the other phases, it is necessary to calcine at a temperature of 1220 ° C. or higher. Further, in order to make the peak intensity ratio of the Z phase 30% or more, it is necessary to calcine at a temperature of 1240 ° C. or more. When the calcining temperature reaches 1300 ° C., the identified phases become _three phases of a Z phase, a Ba ferrite phase, and a BaCO ₃ phase, and the peak intensity ratio of the Z phase reaches 60%. When the calcination temperature exceeds 1330 ° C., the peak intensity ratio of the Z phase decreases, and the peak intensity ratio of the Ba ferrite phase becomes the highest. As described above, in order to make the Z phase the main phase, the calcining temperature is desirably 1220 ° C. or higher, and more desirably 125 ° C.
0 ° C. or higher and 1330 ° C. or lower, preferably 13 ° C.
It should be below 20 ° C.

The shrinkage ratio (ΔL) when the crushed powders of samples Nos. 1, 2 and 5 after calcination were heated to a predetermined temperature.
/ L) was measured. This shrinkage ratio is a measure of the easiness of firing, and it can be considered that the higher the shrinkage ratio at the same temperature, the easier the firing. The results are shown in FIG. In addition, the diagram in FIG. 2 is called a heat shrinkage curve. As shown in FIG. 2, the sample No. 2 has a larger shrinkage rate at the same temperature than the sample No. 5, that is, NiCuZn ferrite, which has conventionally been able to be fired at a low temperature. Therefore, it can be seen that the powder of sample No. 2 can sufficiently co-fire with Ag. The difference between Sample No. 2 and Sample No. 1 is that the former added CuO and Bi ₂ O ₃ . Therefore, it can be seen that CuO and Bi ₂ O ₃ are effective for improving the shrinkage, that is, for enabling low-temperature sintering.

FIG. 4 shows the particle size distribution of the pulverized powders of Sample Nos. 2 to 4. Samples Nos. 2, 3, and 4 have the same composition as shown in Table 1. The peak values of the particle size distribution are 1.0 μm for sample No. 2, 1.65 μm for sample No. 3, and 3.3 μm for sample No. 4. For Samples Nos. 3 and 4, the shrinkage ratio (ΔL / L) when heated to a predetermined temperature was measured in the same manner as described above. The results are shown in FIG. 5 together with the results of Sample No. 2, and it can be seen that the shrinkage at the same temperature is larger in the order of Sample Nos. 2, 3, and 4. That is,
4 and 5 that the smaller the peak value of the particle size distribution of the pulverized powder is, the more desirable it is for low-temperature sintering. However, if the peak value of the particle size distribution is too small, the specific surface area of the powder becomes large, and it becomes difficult to obtain a paste or sheet for obtaining a laminated ferrite component. Therefore, the present invention proposes that the peak value of the particle size distribution be in the range of 0.1 to 3 μm.

The powder of Sample No. 2 was calcined at 910 ° C. for 2 hours, and the X-ray diffraction pattern was measured. FIG. 6 shows the result. In FIG. 6, Z phase, Y phase and B phase
a The ferrite phase was identified. The peak showing the highest intensity of each phase is as shown in FIG. 6, and it can be seen that the highest peak intensity of the Z phase is the largest and the Z phase forms the main phase.
Further, when the peak intensity ratio of the Z phase was calculated from the highest peak intensity of each phase, it was 41.93%. CuO and B
In order to confirm the location of i ₂ O _{3 in} the sintered body, the vicinity of the grain boundary was analyzed by TEM-EDX. The results are shown in FIG. 3, where Bi ₂ O ₃ is present at the grain boundaries and liquid phase sintering has been achieved by adding Bi ₂ O ₃ . On the other hand, the concentration of CuO is higher in the grains than in the grain boundaries, and it is presumed that CuO is taken into Co ₃ O ₄ sites. CuO is a low melting point oxide and contributes to low temperature firing. That is, CuO and Bi ₂ O ₃ both contribute to low-temperature firing, but each has a different mechanism contributing to low-temperature firing, so it is desirable to add both in combination. Further, when the average crystal grain size of the sintered body was measured, it was in the range of 1 to 5 μm. Since the sintered body according to the present invention is sintered at a low temperature of 910 ° C., the crystal grain size is fine.

The toroidal cores prepared using the pulverized powders of Sample Nos. 1, 2 and 5 were inserted into a coaxial sample holder, and the complex magnetic permeability (μ ′, μ ″) in a high frequency band (1 MHz to 1.8 GHz) was obtained. Was measured using an impedance analyzer (manufactured by Hewlett-Packard Co., Ltd.).
In addition, the toroidal core was produced by baking at 930 ° C. for 2 hours. FIG. 7 shows the results. In FIG. 7, 1-
The symbol μ 'indicates the real part of the complex permeability of Sample No. 1, 1
The notation “−μ” means the imaginary part of the complex magnetic permeability of the sample No. 1, and the same applies to other cases. The toroidal core of the sample No. 2 has a flat portion of μ ′ which is smaller than that of the sample Nos. 1 and 5. It extends to the high frequency band, suggesting that it can be used in higher frequency bands.

2.5 parts by weight of ethyl cellulose and 40 parts by weight of terpineol were added to 100 parts by weight of the powders of Sample Nos. 2 and 5, and kneaded with a three-roll mill to prepare a paste for a magnetic ferrite layer. On the other hand, the average particle size is 0.
25 parts by weight of ethyl cellulose and 40 parts by weight of terpineol were added to 100 parts by weight of 8 μm Ag, and the mixture was kneaded with a three-roll mill to prepare an internal electrode paste. After alternately printing and laminating the paste for the magnetic ferrite layer and the paste for the internal electrode as described above, the paste is fired at 910 ° C. for 2 hours to obtain 1608 as shown in FIGS.
A multilayer chip bead 1 of the type was obtained. The dimensions of the laminated chip beads 1 are 1.6 mm × 0.8 mm × 0.8 m
m and the number of turns was 2.5 turns. Next, an external electrode 5 was formed by baking the end of the laminated chip bead 1 at about 600 ° C. These two stacked chip beads 1
The impedance Z was measured at a measurement frequency of 100 KHz to 1.8 GHz using a network impedance analyzer (manufactured by Hewlett-Packard Co., Ltd.). FIG. 8 shows the results. FIG. 8 shows that the sample No.
2 shows that the value of the impedance Z is shifted to the high frequency side as compared with the sample No. 5 of the comparative example, and it can be seen that higher frequency noise absorption becomes possible.

Example 2 Sample No. 1 used in Example 1
By changing the pulverization time after calcination of No. 2, pulverized powders having various specific surface areas shown in Table 4 were obtained. A toroidal core was prepared in the same manner as in Example 1 using this ground powder. The magnetic permeability μ (100 MHz) of the core, the density, and the shrinkage during sintering were measured. The results are shown in Table 4. When the specific surface area is 1 m ² / g, the sintered density is as low as 4.5 g / cm ³ . Correspondingly, the magnetic permeability μ is also insufficient at 2.5. As the specific surface area increases, the density of the sintered body also increases. If the specific surface area is 10 m ² / g or more, a sintered density of 5 g / cm ³ or more can be obtained, and a high value of the magnetic permeability μ can be obtained. Each of the pulverized powders shown in Table 4 was evaluated for coating. This is because the pulverized powder is supplied to the paste paint and the sheet paint in the process of manufacturing the laminated component. As a result, it was confirmed that when the specific surface area was 35 m ² / g, the coating material gelled and application became difficult. From the above results, in order to produce a multilayer ferrite components, it is desirable to a specific surface area of the powder and 5 to 30 m ² / g, it is desirable to further 10~25m ² / g.

[0030]

[Table 4]

(Example 3) A toroidal core was prepared by using the raw material powder having the composition shown in Table 5 in the same manner as in Sample No. 2 of Example 1. In Table 5, sample N
Nos. 6 to 9 are examples in which a part of Co ₃ O ₄ was replaced by NiO, samples Nos. 10 to 13 were examples in which a part of Co ₃ O ₄ was replaced by MnO, and samples Nos. 14 to 17 were Co ₃ Part of O ₄ is ZnO
Samples Nos. 18 to 21 are examples in which a part of Co ₃ O ₄ was replaced with MgO. The peak value of the average particle size distribution of each sample was 1.0 μm, and the specific surface area was 11 m ² / g.
It is. The magnetic permeability of the obtained core was measured in the same manner as in Example 1. In the third embodiment, the measurement was performed up to the frequency band up to 6 GHz. The result is shown in Sample No. 2.
9 to 12 are shown together with the measurement results.

[0032]

[Table 5]

In FIG. 9, the sample N containing no NiO
The peak value of μ ″ was obtained at a frequency of about 1.5 GHz for O.2. On the other hand, the peak value of μ ″ of Sample No. 6 in which part of Co ₃ O ₄ was replaced with NiO was About 2.5
It can be seen from the fact that the peak value of μ ″ was shifted to the high frequency side from the result obtained at GHz. The peak value of μ ″ of sample No. 7 was obtained at a frequency of about 3 GHz, and the sample N
It can be inferred that the peak values of μ ″ in o.8 and 9 will be obtained at frequencies above 6 GHz. From the above results,
It can be seen that when a part of Co ₃ O ₄ is replaced with NiO and the replacement amount increases, the peak value of μ ″ shifts to the high frequency side. This indicates that μ ″ according to the frequency band in which noise is to be absorbed. It is suggested that a material having a peak value of can be obtained by a simple method of setting the replacement amount of NiO. There is a similar tendency in FIGS. Therefore, not only NiO but also MnO, Z
By appropriately setting the substitution amount of nO and MgO,
The peak of "μ" can be positioned in a desired frequency band. X-ray diffraction of sintered bodies of Sample Nos. 9 (substituted with NiO), 13 (substituted with MnO), 17 (substituted with ZnO) and 21 (substituted with MgO) The results are shown in Fig. 13. Fig. 13 also shows the X-ray diffraction data of sample No. 2, and the same phase structure as that of sample No. 2 is obtained even when the sample is replaced with NiO or the like. Was confirmed.

(Example 4) In order to obtain the composition shown in Table 6.
After blending the raw material powder, calcination and pulverization were performed.
In Table 6, Sample Nos. 22 to 25 correspond to C of Sample No. 2.
o_ThreeO_FourIs an example in which a part of is replaced by CuO. Mixing, calcining
The conditions for grinding and grinding are as follows. In addition, each raw material
Table 3 shows the specific surface area of the powder.
Is 4.5m ^Two/ G or more. Mixing and crushing pot: Use stainless steel ball mill pot Mixing and crushing media: Use steel ball Mixing time: 16 hours Pre-baking conditions: Sample No. 23 = 900 ° C, 1000 ° C, 1100 ° C, 1200 ° C, 1250 ° C × 2 hours Sample No. 22, 24 to 25 = 1200 ° C, 1250 ° C x 2 hours Pulverization time: 90 hours

[0035]

[Table 6]

For the powder of sample No. 23, 900
℃, 1000 ℃, 1100 ℃, 1200 ℃, 1250 ℃
After sintering each for 2 hours, the X-ray diffraction pattern was measured. The result is shown in FIG. In FIG. 14,
(A) is a calcining temperature of 900 ° C., (b) is a calcining temperature of 10.
(C) shows the measurement results of the X-ray diffraction pattern at a calcination temperature of 1100 ° C, (d) shows the measurement results of the calcination temperature of 1200 ° C, and (e) shows the measurement results of the X-ray diffraction pattern at the calcination temperature of 1250 ° C. In addition,
The conditions for X-ray diffraction are the same as in Example 1.

When the calcining temperature is 900 ° C. (FIG. 14A)
4), four phases of M phase, Ba ferrite phase, Y phase and Z phase were identified. At this calcination temperature, the M phase has the highest peak intensity ratio. Calcination temperature 100
In the case of 0 ° C. (see FIG. 14B) and the calcining temperature 11
Even in the case of 00 ° C. (see FIG. 14C), the M peak has the highest peak intensity ratio, but the calcining temperature is 1200.
In the case of ° C. (see FIG. 14D), the peak intensity ratio of the Z phase is the highest at 22.4%, which indicates that the Z phase is the main phase. In the case of a calcining temperature of 1250 ° C. (FIG. 14)
In (e), the identified phases were two phases of a Y phase and a Z phase, and the peak intensity ratio of the Z phase was calculated to be 49.5.
%Met. As described above, when a part of Co ₃ O ₄ is replaced by CuO, in order to make the Z phase the main phase, the calcining temperature is 1
It is desirable that the temperature be 220 ° C to 1280 ° C.

Next, a toroidal core was prepared in the same manner as in Example 1 using the pulverized powder of Sample Nos. 22 to 25 after calcining. The magnetic permeability (500 MHz), sintering density, shrinkage ratio during sintering, and dielectric constant (1 MHz) of the core were measured. Result when calcined at 1200 ° C and 1250
Table 7 also shows the results of calcining at ° C. In each case, the firing temperature was 930 ° C., and the firing time was 2 hours.

[0039]

[Table 7]

As shown in Table 7, the calcining temperature was 1200
In the case of ° C., the magnetic permeability (μ) of Sample Nos. 22 to 25 is a low value of 2 or less. Vacuum permeability (μ) is 1
In view of the above, a material having a magnetic permeability (μ) of 2 or less is not suitable as a magnetic material. On the other hand, if the calcining temperature is 12
In the case of 50 ° C., the magnetic permeability (μ) of each of Sample Nos. 22 to 24 is 2 or more, which is a good value. The sintering density and shrinkage also exceeded all the values when the calcination temperature was 1200 ° C. Note that Co ₃ O ₄ is replaced by Cu
For sample No. 25, which was replaced by 75% with O, 125
When calcined at 0 ° C., it was melted. As described above, when a part of Co ₃ O ₄ is replaced with CuO, 1250 ° C.
It was found that good sintering density, shrinkage and magnetic permeability (μ) can be obtained even in the calcination of.

Sample No. 22 calcined at 1250 ° C.
The toroidal core prepared using the pulverized powder of No. 24 was inserted into a coaxial tube sample holder, and a high frequency band (1 MHz to
Complex permeability (μ ', μ ") at 1.8 GHz) was measured using an impedance analyzer (Hewlett-Packard Co., Ltd.).
Was used for the measurement. FIG. 15 shows the result together with the measurement result of Sample No. 2. In the toroidal cores of Sample Nos. 22 to 24, the flat portion of μ ′ extends to a higher frequency band than that of Sample No. 2, suggesting that it can be used in a higher frequency band. In particular, Co ₃ O ₄ is replaced by CuO
It is noteworthy that the sample No. 22 substituted by 5% in Example 2 has μ ′ of 3 or more and its flat portion extends to the high frequency band.

In FIG. 15, a part of Co ₃ O ₄ is replaced with CuO.
The frequency of about 1.
At 5 GHz, a peak value of μ ″ was obtained.
Sample No. 22 (5) in which a part of Co ₃ O ₄ was replaced with CuO
% Substitution), the frequency is about 2.5 GHz, and the sample No.
About 23 (25% substitution), the frequency is about 4.5 GHz,
For sample No. 24 (50% replacement), the frequency was about 5.
The peak value of μ ″ was obtained at 0 GHz. From the above results, even when a part of Co ₃ O ₄ was replaced with CuO, the peak value of μ ″ shifted to the high frequency side as the replacement amount increased. I understand. Therefore, similarly to the case where a part of Co ₃ O ₄ is replaced with NiO, MnO, ZnO and MgO, the peak of μ ″ can be located in a desired frequency band by appropriately setting the replacement amount of CuO. It is supposed that a desirable substitution amount in the case where a part of Co ₃ O ₄ is substituted with CuO is in a range where the substitution amount does not exceed 70%, but a more desirable substitution amount is 1%.
６０60%, furthermore 2-30%.

(Example 5) After blending the raw material powders so as to have the composition shown in Table 8, calcination and pulverization were performed.
In Table 8, Sample Nos. 26 to 34 correspond to B of Sample No. 2.
Example in which a part of aCO ₃ was replaced with SrCO ₃ , sample No. 3
Sample No. 5 is an example in which all of BaCO ₃ of Sample No. 2 was replaced with SrCO ₃ . The conditions for blending, calcining and pulverizing are as follows. Table 3 shows the specific surface area of each raw material powder. The specific surface area of each raw material powder is 4.5 m ² / g or more. Mixing and crushing pot: using a stainless steel ball mill pot Mixing and crushing media: using steel balls Mixing time: 16 hours Pre-baking conditions: Sample No. 26-29 = 1300 ° C. × 2 hours Sample No. 30, 32-34 = 1250 ° C × 2 hours Sample No. 31 = 1100 ° C., 1200 ° C., 1250 ° C. × 2 hours Sample No. 35 = 1250 ° C. × 2 hours Grinding time: 90 hours

[0044]

[Table 8]

For the powder of sample No. 31, 1100
After baking at 1200 ° C., 1200 ° C. and 1250 ° C. for 2 hours, the X-ray diffraction pattern was measured. FIG. 16 shows the result. In FIG. 16, (a) shows the calcining temperature 1100.
C., (b) shows the measurement results of the X-ray diffraction pattern when the calcination temperature was 1200 ° C., and (c) shows the measurement results of the X-ray diffraction pattern when the calcination temperature was 1250 ° C. The conditions of X-ray diffraction are the same as in Example 1.

When the calcining temperature is 1100 ° C. (FIG. 16)
In (a)), two phases, M phase and Y phase, were identified. At this calcination temperature, the M phase has the highest peak intensity ratio. When the calcining temperature is 1200 ° C (Fig. 1
6 (b)), a Z phase was identified in addition to the M phase and the Y phase, and the peak intensity ratio of the Z phase at this calcining temperature was 24.5%. In the case of the calcining temperature of 1250 ° C. (see FIG. 16C), three phases of the M phase, the Y phase and the Z phase were identified. The peak intensity ratio of the Z phase at this calcining temperature was the highest at 48.3%, indicating that the Z phase was the main phase. As described above, in order to make the Z phase the main phase when BaCO ₃ is partially replaced with SrCO ₃ , the calcining temperature may be set to 1220 ° C. to 1280 ° C.

Next, a toroidal core was prepared in the same manner as in Example 1 using the pulverized powders of samples Nos. 26 to 35 after calcination, and the complex permeability (500 MHz), sintering density and sintering of the core were determined. The shrinkage at the time was measured. Table 9 shows the results. In each case, the firing temperature was 930 ° C., and the firing time was 2 hours. In addition, about sample No. 35, 1
When calcined at 250 ° C, it melted.

[0048]

[Table 9]

As shown in Table 9, a part of BaCO ₃ was converted to S
Although the sintering density and shrinkage tend to decrease as the amount replaced with rCO ₃ (hereinafter, appropriately referred to as “Sr replacement amount”) increases, the sintered density of sample Nos. 26 to 31 is 4.5 g / It shows good values of not less than cm ³ and shrinkage of not less than 15%. Here, for sample Nos. 30 and 31, the calcining temperature was 1250 ° C.
It is noteworthy that despite having been calcined at a lower temperature of 50 ° C. than that of o.26-29, it shows good sintering density and shrinkage. From this result, the Sr substitution amount was 20
%, It was found that sufficient sintering density and shrinkage could be obtained by calcining at 1250 ° C. Next, the relationship between the amount of Sr substitution and μ ′ is shown using Table 9 and FIG. In FIG. 17, when the amount of Sr substitution is small, μ ′ is lower than that of Sample No. 2 without Sr substitution. However, when the Sr substitution amount becomes 20 to 35%,
It can be seen that μ ′ is higher than that of Sample No. 2 in which Sr substitution is not performed, showing a very good value of 3.5 or more. In Table 9, μ ″ shows almost the same tendency as μ ′, and Sample Nos. ₃₀ to 32 in which BaCO ₃ is replaced with SrCO ₃ by 20 to 35% show particularly high μ ″. From the above results, it has become clear that there is an optimum amount of Sr substitution for obtaining high μ ′ and μ ″.

Sample No. 28 calcined at 1300 ° C.
29, a toroidal core prepared using the pulverized powder of Sample Nos. 30 to 34 calcined at 1250 ° C. was inserted into a coaxial tube sample holder, and was placed in a high frequency band (1 MHz to 1.8).
The complex magnetic permeability (μ ′, μ ″) at (GHz) was measured using an impedance analyzer (manufactured by Hewlett-Packard Co.). Similarly, the results are shown in FIG. Sample Nos. 30 to 3 are shown.
The μ ′ of the toroidal core according to Sample No. 2 was higher than that of Sample No. 2 containing no SrCO ₃ , and the flat portion of μ ′ was extended to a higher frequency band than Sample No. 2. Therefore, B
The ACO ₃ by replacing SrCO ₃ 20 to 35%, a material excellent in a and frequency characteristic with high permeability could be obtained. Sample Nos. 28 and 29,
As for 33 and 34, the flat portion of μ ′ extends to the high frequency band, which suggests that it can be used in a higher frequency band.

[0051] In FIG. 18, the peak value of mu "sample No.2 containing no SrCO ₃ were obtained at a frequency of about 1.5 GHz. In contrast, by replacing part of BaCO ₃ in SrCO ₃ sample The peak value of μ ″ of No. 28 (8% substitution) is obtained at a frequency of about 5.5 GHz, and it can be seen that the peak value of μ ″ is shifted to the high frequency side. As a result of measuring μ ”of Sample No. 34,
9 (16% substitution) at a frequency of 4.0 GHz, and sample No. 30 (20% substitution) at a frequency of 2.6 GHz.
z, frequency 2.0 GHz for sample No. 31 (25% substitution), frequency 2.8 GHz for sample No. 32 (35% substitution), sample No. 33 (50% substitution)
About the frequency of 3.8 GHz, sample No. 34 (75
% Substitution) peak value in the frequency 4.0 GHz mu "was obtained for. That is, any sample No.28~34 substituted with SrCO ₃ a part of BaCO ₃ is a frequency of about 2.
Above 0 GHz, a peak value of μ ″ was obtained, and SrC
The peak value of μ ″ of sample No. 2 containing no O ₃ was shifted to the high frequency side. From the above results, it was found that a material having excellent high frequency characteristics was obtained by replacing a part of BaCO ₃ with SrCO _3. The desired substitution amount is 5 to 80%, more preferably 10 to 60%, more preferably 2 to 80%.
0 to 35%. BaCO ₃ with SrCO ₃ 20-35
When% is substituted, a high magnetic permeability excellent in frequency characteristics can be obtained.

(Example 6) Sample No. 36 shown in Table 10
A heat shrinkage curve was obtained in the same manner as in Example 1 using the raw material powders having the compositions shown in FIGS. The peak value of the average particle size distribution of each sample was 1.0 μm, and the specific surface area was 11 m ² / g. Further, glasses A and B in Table 10 are zinc borosilicate glasses, and their compositions are as shown in Table 11. The obtained heat shrinkage curve is shown in FIG. 19 together with the heat shrinkage curve of Sample No. 1 of Example 1. Sample Nos. 36 and 37 were
It can be seen that the shrinkage at the same temperature is larger than that of Sample No. 1. Therefore, the addition of borosilicate glass and zinc borosilicate glass in the present invention can contribute to low-temperature firing.

[0053]

[Table 10]

[0054]

[Table 11]

[0055]

As described in detail above, according to the present invention,
It is possible to provide a multilayer ferrite component including a magnetic ferrite layer in which a Z phase forms a main phase.

[Brief description of the drawings]

FIG. 1 is a graph showing the effect of calcination temperature on a phase change.

FIG. 2 is a graph showing heat shrinkage curves of Sample Nos. 1, 2 and 5.

FIG. 3 shows TE in the vicinity of a grain boundary of a sintered body of sample No. 2.
It is a graph which shows an M-EDX analysis result.

FIG. 4 is a graph showing the particle size distributions of Sample Nos. 2, 3 and 4.

FIG. 5 is a graph showing heat shrinkage curves of Sample Nos. 2, 3 and 4.

FIG. 6 is an X-ray diffraction pattern of Sample No. 2.

FIG. 7 is a graph showing frequency characteristics of μ ′ and μ ″ of Sample Nos. 1, 2, and 5;

FIG. 8 is a graph showing the frequency characteristics of the impedance of a chip for samples Nos. 2 and 5.

FIG. 9 is a graph showing frequency characteristics of μ ′ and μ ″ of the NiO substitution material.

FIG. 10 is a graph showing the frequency characteristics of μ ′ and μ ″ of the MnO-substituted material.

FIG. 11 is a graph showing frequency characteristics of μ ′ and μ ″ of a ZnO substitution material.

FIG. 12 is a graph showing frequency characteristics of μ ′ and μ ″ of the MgO-substituted material.

FIG. 13 is an X-ray diffraction pattern in Example 3.

FIG. 14 is an X-ray diffraction pattern of Sample No. 23.

FIG. 15 is a graph showing frequency characteristics of μ ′ and μ ″ of a CuO substitution material.

FIG. 16 is an X-ray diffraction pattern of Sample No. 31.

FIG. 17 is a graph showing the relationship between the amount of SrCO ₃ substitution and μ ′.

FIG. 18 is a graph showing frequency characteristics of μ ′ and μ ″ of the SrCO ₃ substitution material.

FIG. 19 is a graph showing a heat shrinkage curve measured in Example 6.

FIG. 20 is a schematic cross-sectional view showing an example of a laminated chip bead which is one embodiment of the laminated chip ferrite component of the present invention.

FIG. 21 is a partial plan sectional view of the multilayer chip bead shown in FIG. 20;

FIG. 22 is a schematic cross-sectional view showing an example of an LC composite component which is an embodiment of the composite laminated component of the present invention.

[Explanation of symbols]

1 ... Laminated chip beads, 2 ... Magnetic ferrite layer, 3 ...
Internal electrode, 4 ... Chip body, 5 ... External electrode, 11 ... LC
Composite parts, 12: chip capacitor part, 13: chip ferrite part, 15: external electrode, 21: ceramic dielectric layer, 22: internal electrode, 32: ferrite magnetic layer, 33 ...
Internal electrode

Claims (13)

[Claims] 1. The method of claim 1 wherein the hexagonal ferrite is analyzed by X-ray diffraction.
Z phase (M_ThreeMe_TwoFe _{twenty four}O₄₁: M = 1 of alkaline earth metal
Species or two or more, Me = Co, Ni, Mn, Zn, M
g and Cu).
The ratio is 30% or more, and the peak value of the particle size distribution is in the range of 0.1 to 3 μm.
A magnetic ferrite powder characterized by the following. 2. Borosilicate glass, zinc borosilicate glass, Cu
One or more of O and Bi ₂ O ₃
The magnetic ferrite powder according to claim 1, wherein 20 wt% is added. _{3. A} total amount of CuO and Bi ₂ O ₃ of 0.5 to
The magnetic ferrite powder according to claim 1, wherein 20 wt% is added. 4. A Z phase represented by M ₃ Me ₂ Fe ₂₄ O ₄₁ (where M = Ba, Me = Co, Ni, Mn, Zn, Mg
And one or more of Cu) form a main phase, and have a powder specific surface area of 5 to 30 m ² / g. 5. The magnetic ferrite powder according to claim 4, wherein Ba is partially replaced by Sr. 6. A Z phase represented by M ₃ Me ₂ Fe ₂₄ O ₄₁ (where M = Ba, Me = Co, Ni, Mn, Zn, Mg
And one or more of Cu) forms the main phase, 0.5-20 further CuO and Bi ₂ O ₃ in total
%, Wherein CuO is mainly present in crystal grains and Bi ₂ O ₃ is mainly present in crystal grain boundaries. 7. The magnetic ferrite sintered body according to claim 6, wherein a part of Ba is replaced with Sr. 8. A laminated ferrite component having a magnetic ferrite layer and an internal electrode alternately laminated and having an external electrode electrically connected to the internal electrode, wherein the magnetic ferrite layer is an X-ray In the diffraction, the Z phase of hexagonal ferrite (M ₃ Me ₂ Fe ₂₄ O ₄₁ : M = one or more of alkaline earth metals, Me = Co, Ni, Mn,
One or more of Zn, Mg and Cu) constitutes a main phase, and is composed of a magnetic ferrite sintered body having an average crystal grain size of 1 to 5 μm, and the internal electrode is composed of Ag or an Ag alloy. A laminated ferrite component characterized by being made. 9. The multilayer ferrite component, wherein the magnetic ferrite layer and the internal electrode layer are fired simultaneously, and the density of the magnetic ferrite layer is 5 g / cm.
The multilayer ferrite component according to claim 8, wherein the number is ³ or more. 10. The magnetic ferrite layer contains CuO and Bi ₂ O ₃ in a total amount of 0.5 to 20 wt%, CuO is mainly present in crystal grains, and Bi ₂ O ₃ is mainly present in crystal grain boundaries. The laminated ferrite component according to claim 8, wherein the component is present. 11. A method for producing a laminated ferrite component in which a magnetic ferrite layer and an internal electrode are laminated, wherein a step of mixing a raw material powder of a magnetic ferrite, and a step of mixing the mixed raw material powder in a temperature range of 1200 ° C. or higher. And calcining the obtained calcined body so that the peak value of the particle size distribution is 0.1 to 3 μm.
m, a step of obtaining a sheet or paste for forming a magnetic layer using the obtained crushed powder, and a step of alternately stacking the sheet or paste and the material for the internal electrode to form a laminate. And baking the laminated molded body at a temperature of 960 ° C. or lower, wherein the magnetic ferrite layer has a hexagonal ferrite Z phase (M ₃ Me ₂ Fe ₂₄ O ₄₁ : M = one or more of alkaline earth metals, Me = Co, Ni, M
one or more of n, Zn, Mg and Cu)
Characterized by comprising a magnetic ferrite sintered body having a peak intensity ratio of 30% or more. 12. The powder specific surface area of each of the raw material powders is 4.
Method for producing a multilayer ferrite component according to claim 11 5 m ² / g or more. 13. The pulverized powder having a powder specific surface area of 8 to 2
The method for producing a laminated ferrite component according to claim 11, wherein the content is in a range of 0 m ² / g.