JP2992197B2 - Dielectric porcelain material and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric porcelain material, and more particularly to a dielectric porcelain material constituting a resonator or the like used in a microwave region and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, with the rapid increase in demand for mobile communication, there has been an increasing demand for downsizing of equipment. In these communications, a circuit such as a filter and a diplexer composed of a resonator element is used for frequency selection. However, downsizing of the resonator is required in accordance with a demand for downsizing of the communication device. Resonators are constructed using dielectric elements, but the size of the dielectric resonator is inversely proportional to the square root of the dielectric constant of the dielectric material. It is. In addition, as the operating frequency shifts to the higher frequency side, the packing density of components increases, and it becomes necessary to further reduce the size. As a result, attempts have been made to configure a circuit with a multilayer dielectric substrate. .

[0003] Accordingly, in addition to the conventional requirements that the dielectric material used has a large dielectric constant in the microwave region and a small rate of temperature change τ _f of the resonance frequency,
Simultaneous firing with a conductor is required. Conventionally, in a microwave dielectric material, Ba (Mg _1/3 T
a _2/3 ) O ₃ , Ba (Zn _1/3 Ta _2/3 ) O _{3 and the} like are known to have a large dielectric constant in a microwave region. However, the above Ba (Mg _1/3 Ta _2/3 )
Microwave dielectric materials such as O ₃ and Ba (Zn _1/3 Ta _2/3 ) O ₃ have a high firing temperature as high as 1300 ° C., and realize thin wiring and complicated wiring when simultaneously firing with a conductor. It is difficult. In addition, the firing temperature is low (glass + T
Materials such as iO ₂ ) have a small dielectric constant of about 10.

[0004]

SUMMARY OF THE INVENTION It is a primary object of the present invention to provide a dielectric ceramic material having a small temperature change rate of a resonance frequency in a microwave region, a large dielectric constant and a large Q.f value, and having a good low-temperature firing property. And a method of manufacturing the same.

[0005]

This and other objects are achieved by the present invention which is defined below as (1) to (14). (1) containing Pb, Ca, W, Fe and Nb in the form of an oxide; A dielectric porcelain material containing a phase having the following composition as a main phase and a sintering aid as an auxiliary component, wherein the sintering aid is a calcined body of Pb ₅ Ge ₃ O ₁₁ . (2) The dielectric ceramic material according to (1), wherein s, t, and u satisfy the following relationship. (3) Further, (Pb _1-x Ca _x ) (Fe _1/2 N
b _1/2 ) O ₃ (where 0.3 ≦ x ≦ 0.91), Ca
(Fe _1/2 Nb _1/2 ) O ₃ , one of Pb ₃ Nb ₄ O ₁₃
The dielectric porcelain material according to the above (1) or (2), wherein the dielectric porcelain contains one or more kinds as different phases. (4) The content of the sintering aid is Pb, Ca, W, F
The dielectric ceramic material according to any one of the above (1) to (3), wherein the content of the oxide of e and Nb is 2.0 to 10.0 wt%. (5) The dielectric ceramic material according to any one of (1) to (4), further containing Mn. (6) The Pb, Ca, W, F
The dielectric ceramic material according to the above (5), wherein the content of the oxide of e and Nb is 0.05 to 0.5 wt%. (7) Pb (Fe _2/3 W _1/3 ) O ₃
A first porcelain material mainly composed of: (Pb _1-x Ca _x )
(Fe _1/2 Nb _1/2 ) O ₃ (where 0.3 ≦ x ≦ 0.
91) and a second porcelain material mainly composed of
These were mixed and then subjected to a second calcination at a temperature lower than the calcination of the second porcelain material, and then the firing, Pb ₅ Ge ₃ as a sintering aid during the previous main firing this mixture A method for producing a dielectric porcelain material to which an O ₁₁ calcined body is added. (8) said first and second ceramic materials, y _{[Pb (Fe 2/3 W 1/3) O} 3 ] - (1-y) _{[(Pb 1-x Ca x)} (Fe 1/2 Nb _1/2 ) O ₃ ], where x and y are mixed in molar fractions, 0.3 ≦ x ≦ 0.91 0.01 ≦ y ≦ 0.7. )) A method for producing a dielectric ceramic material. (9) The method for producing a dielectric ceramic material according to (8), wherein 0.05 ≦ y ≦ 0.4. (10) The above (7) to above, wherein the firing temperature is 1100 ° C. or less.
(9) The method for producing a dielectric ceramic material according to any of (9). (11) The amount of the sintering additive added is equal to the first and second sintering aids.
Above (7) which is 2.0 to 10.0 wt% of the porcelain material of
(10) The method for producing a dielectric ceramic material according to any of (10). (12) Addition of a Mn compound before main firing as described in (7) to above
(11) The method for producing a dielectric ceramic material according to any of (11). (13) The method for producing a dielectric ceramic material according to the above (12), wherein the amount of the Mn compound added is 0.05 to 0.5 wt% in terms of Mn of the first and second porcelain materials.

[0006]

In the present invention, the general formula (Pb _{1 -Z} Ca
_{Z) (W s Fe t Nb} u) O 3 ( hereinafter, the dielectric ceramic material may be referred to as PCWFN), the amount of each component 0.3 ≦ z ≦ 0.9 s + t + u = 1, 0.01 ≦ By regulating to s ≦ 0.2 0.5 ≦ t ≦ 0.6 0.2 ≦ u ≦ 0.49, the low-temperature firing property is good and simultaneous firing with the conductor becomes possible. In addition, since the temperature change rate of the resonance frequency in the microwave region is small and the dielectric constant and the Q · f value are large, a microwave resonator having good characteristics can be obtained.

Further, Pb ₅ Ge ₃ O _{11 is} used as a sintering aid.
Is added, the low-temperature firing property is further promoted. Further, by containing a predetermined amount of Mn, the insulation resistivity increases, and excellent characteristics are exhibited as a dielectric material of a capacitor used in a high-frequency circuit.

[0008]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

The dielectric porcelain material of the present invention comprises, as a main phase,
Is characterized in that it contains _{(Pb 1-Z Ca Z)} (W s Fe t Nb u) phase of O ₃ in the composition.

Here, the partial replacement amount of Pb by Ca is:
Assuming that the mole fraction is z, it is set so as to be in the range of 0.3 ≦ z ≦ 0.9. The partial replacement amount of Ca is
If the ratio exceeds the above range, the low-temperature firing property is impaired, while if it is less than the above range, the temperature change rate τ _f of the resonance frequency increases in the positive direction.

When the above-mentioned z is in the range of 0.3 ≦ z ≦ 0.8, especially 0.4 ≦ z ≦ 0.75, better low-temperature sinterability, high dielectric constant, and low resonance frequency temperature are obtained. The rate of change τ _f can be obtained.

When the mole fractions of W, Fe, and Nb are s, t, u, and s + t + u = 1, respectively, 0.01 ≦ s ≦ 0.2 0.5 ≦ t ≦ 0.6. It is preferable that 2 ≦ u ≦ 0.49.

The reason for such a molar fraction is as follows. First, as for s, if it is less than 0.01, the low-temperature firing property is impaired, and if it is more than 0.2, the temperature change rate τ _{f of the} resonance frequency increases in the + direction. Also,
If t is less than 0.5, the low-temperature firing property is impaired, and if it exceeds 0.6, the temperature change rate τ _{f of the} resonance frequency is +
In the direction of. Finally, for u,
If it is less than 0.2, the temperature change rate τ _f of the resonance frequency increases in the + direction, and _{if it} exceeds 0.49, the low-temperature firing property is impaired. The dielectric constant ε is 65 or more by being within the above composition range. And, in a preferred embodiment, values of 65 to 120, especially 80 to 120 are obtained.

When the molar fraction is 0.02 ≦ s ≦ 0.1 0.5 ≦ t ≦ 0.55 0.35 ≦ u ≦ 0.48, the low-temperature firing property is good and the resonance frequency temperature The rate of change τ _f is smaller, which is particularly desirable.

Here, the above τ _f is preferably as close to 0 as possible, and is generally +100 ppm / ° C. or more, -100 ppm / ° C.
In the following, it is not desirable as a microwave dielectric. In the present invention, within ± 100 ppm / ° C., in a preferred embodiment ± 60 pp
within m / ° C, especially within ± 50 ppm / ° C, and even ± 30 ppm /
Within ° C is obtained.

The larger the value of ε is, the more desirable it is. This is because, for example, in a resonator, the size is inversely proportional to the square root of ε of the dielectric material, and therefore, when miniaturization is attempted, ε must necessarily be increased. It is important to be big.

Such (Pb _{1 -Z} Ca _Z ) (W _s Fe)
_t Nb _u) the presence of O ₃ phase X-ray diffraction spectrum (XR
D). In the dielectric ceramic material of the present invention, the _{(Pb 1-Z Ca Z)} (W s Fe t Nb u) O 3
It may be composed of a single phase.

[0018] In the dielectric ceramic material of the present invention, the a _{(Pb 1-Z Ca Z)} (W s Fe t Nb u) O 3 as a main _{phase, (Pb 1-x Ca x} ) (Fe 1/2 Nb _1/2 ) O ₃ (where 0.3 ≦ x ≦ 0.91, especially 0.3 ≦ x ≦ 0.
9), Ca (Fe _1/2 Nb _1/2 ) O ₃ , Pb ₃ Nb ₄ O
One of the pyrochlores containing Pb and Nb such as ₁₃ mag
Species, or more, may be included as foreign phases. The presence of these different phases is also confirmed by XRD.
The ratio of the main phase calculated by using an electron probe microanalyzer (EPMA) or the like is usually 70% by weight or more, especially 8 wt%.
0 to 100% by weight. Usually, the average grain size of the main phase is 0.5 to 15 μm, especially 1 to 10 μm.

It is desirable that the dielectric ceramic material of the present invention contains a sintering aid as an auxiliary component so that the firing temperature can be reduced. As a sintering aid, ZnO,
Although oxides such as Bi ₂ O ₃ , CuO, PbO, and PbSiO ₃ are possible, it is particularly preferable to use Pb ₅ Ge ₃ O ₁₁ . The content of Pb ₅ Ge ₃ O ₁₁ is preferably the whole of the main phase and the hetero phase, that is, Pb, Ca, W,
It is 2.0 to 10.0 wt% of the total of the Fe and Nb oxides, and more preferably 2.0 to 5.0 wt% of the whole dielectric material. If the content of Pb ₅ Ge ₃ O ₁₁ is too small, the effect of the addition at low temperatures will be lost. On the other hand, if the content is too large, the Q · f value decreases, and the temperature characteristics deteriorate. These sintering aids usually remain at grain boundaries after sintering.

Further, in the dielectric ceramic material of the present invention, M
n may be contained. Mn content is calculated as Mn,
0.05 to 0.5% by weight, especially 0.05 to 0.4% of the total sum of the main phase and hetero phase component raw materials (excluding the sintering aid)
wt%, preferably 0.05 to 0.3 wt%. The insulation resistance is improved by adding Mn. After sintering, Mn is usually present in a main phase or a different phase.

Next, a method for producing the dielectric ceramic composition of the present invention will be described. As a starting material, an oxide of a metal element constituting the dielectric ceramic composition, for example, lead oxide, calcium oxide, tungsten oxide, iron oxide, niobium oxide, or the like may be used. Further, various compounds that can be converted into oxides by firing, for example, carbonates such as calcium carbonate, oxalates, and the like may be used. The mixing ratio of the starting materials is selected so that the ratio of each metal element is the same as the final composition. The average particle size of the starting materials is about 0.5 to 10 μm. Alternatively, some components may be added as solutions such as sulfates and nitrates.

The mixing of the powders of the starting materials is preferably performed in a wet manner using a ball mill or the like. After mixing, calcination is performed. This mixing and calcination is performed using iron and lead tungstate Pb.
(Fe _2/3 W _1/3 ) O ₃ (hereinafter referred to as PFW);
Iron / lead niobate in which part of Pb is substituted by Ca (Pb
_1-x Ca _x ) (Fe _1/2 Nb _1/2 ) O ₃ (hereinafter referred to as PCF
N) are performed separately. This is because if the mixing and calcining of the raw materials are performed at once, CaWO ₄ is easily generated, and the desired (Pb Ca) (W Fe Nb) O
_{This is because 3} cannot be synthesized.

Therefore, in PFW, PbO, Fe ₂ O ₃ and WO ₃ are used as starting materials, while PC
In FN, PbO, Fe ₂ O ₃ , Nb ₂ O ₅ , C
aCO ₃ is used separately for each. Where PCF
The partial substitution amount of P (Pb) by C (Ca) in N is set such that x is in the range of 0.3 ≦ x ≦ 0.91 when the molar fraction is x.

If the partial substitution amount of Ca exceeds the above range, the low-temperature sinterability is impaired, while if it is less than that, the temperature change rate τ _f of the resonance frequency increases in the + direction. It is.

When x is in the range of 0.3 ≦ x ≦ 0.9, especially 0.4 ≦ x ≦ 0.7, it shows better low-temperature sinterability, increases the dielectric constant, and increases the resonance frequency. it is possible to reduce the temperature change rate tau _f.

The above calcination is 800 to
At a temperature of about 900 ° C, in PCFN, 1000
It is preferable to carry out at a temperature of about 1200 ° C. for about 1 to 4 hours. After calcination, each is preferably wet-pulverized by a ball mill or the like. The average particle size after pulverization is 0.7-3.
It should be about 0 μm.

Next, PFW and PCFN are prepared. The mixing ratio at this time is set in the range of 0.01 ≦ y ≦ 0.7, where the mole fraction of PFW is y and the whole is 1. If it exceeds this range, the temperature change rate τ _f of the resonance frequency increases in the + direction, while if it is less than this, the low-temperature firing property is impaired.

When y is in the range of 0.05 ≦ y ≦ 0.4, good characteristics can be obtained.

Next, PFW and PCFN having the above composition ranges are mixed and calcined. This calcination is usually performed in air at 700
１1100 ° C., especially 900-1050 ° C., and even 90
It is preferable to carry out at a temperature of about 0 to 1000 ° C. for about 1 to 4 hours. After calcination, it is pulverized by a ball mill or the like.
The average particle size after pulverization is about 0.7 to 1.5 μm.

Next, a binder such as polyvinyl alcohol is added to the calcined body powder and molded into a predetermined shape. Pb ₅ Ge
_The sintering aid of ₃ O ₁₁ (PGO) is mixed with the calcined powder before molding. In addition, you may mix and use the raw material in the above-mentioned second calcination. Further, it may be mixed with the raw material for the second calcining and calcined, and thereafter, another calcined powder or PGO may be further mixed.

At this time, Pb ₅ Ge ₃ O as a sintering aid
₁₁ amount is 1 of the whole dielectric material of PFW and PCFN.
0.0 wt% or less, preferably 2.0 to 5.0 wt%. This is because low temperature firing is particularly promoted in this range. Pb ₅ Ge ₃ O ₁₁ when mixed with the calcined body powder
The average particle size of the sintering aid is 1.0 μm or less, generally 0.5 μm.
It is preferable to set it to 1.0 μm. Pb ₅ Ge ₃ O
_If the particle size of ₁₁ is too large, it will be necessary to raise the firing temperature.

When Mn is contained, a Mn compound is added. As the Mn compound, in addition to an oxide, for example, MnO ₂ , a compound that becomes an oxide by firing, for example, a carbonate, an oxalate, or the like can be used. Further, a composite oxide with another constituent component, for example, (Pb Ca) (Mn
_1/3 Nb _{2/3) O 3} or the like can be used. In these cases, the average particle size is about 0.5 to 1.0 μm.
In addition, sulfates and nitrates can be added,
The amount of the Mn compound added was the PFW content and the PCFN in Mn conversion.
In other words, the total amount of the oxides of Pb, Ca, W, Fe and Nb and the sintering aid is 0.5 wt% or less, particularly 0.05 to 0.3 wt%. The timing of adding the Mn compound is the same as that of the sintering aid.

After molding, firing is usually performed in the atmosphere. The sintering temperature is 900 to 1100 ° C., particularly about 900 to 1050 ° C. When Pb ₅ Ge ₃ O ₁₁ is used as a sintering aid, it is dense even when sintering at a low temperature range of 900 to 950 ° C. A sintered body having high mechanical strength can be obtained.
In addition, the temperature holding time at the time of baking may be usually about 1 to 3 hours.

When the high-frequency dielectric material of the present invention is applied to a resonator, a paste containing an organic binder and an organic solvent is added to the calcined powder, and the paste is laminated by a printing method or a sheet method. A strip line is formed between the dielectric layers and fired. As a conductive material used for the internal electrode layer, an inexpensive low melting point metal, for example, an Ag-based metal can be used.

The dielectric material of the present invention can be used not only for a resonator but also for a band-pass filter, a diplexer, and the like. A chip in which dielectric layers and internal electrode layers are alternately laminated, fired, and provided with external electrodes is provided. It is also applicable to capacitors and the like. The high frequency is applicable to a frequency of 300 MHz to 3 GHz.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

PbO, Fe ₂ O ₃ , WO as starting materials
₃ was weighed in a predetermined amount, mixed and calcined (at the temperature shown in Table 2 for 2 hours) to obtain PFW, while PbO and CaCO 3 were obtained.
₃ , a predetermined amount of Fe ₂ O ₃ and Nb ₂ O ₅ were weighed, mixed and calcined (at the temperature shown in Table 2 for 2 hours) to obtain PCFN, each of which was wet-pulverized by a ball mill.

These were weighed and blended as shown in Table 2 below to obtain the final composition shown in Table 1 below, and mixed.
Calcination was performed at the temperature shown in Table 2 for 2 hours. By this calcination,
_{(Pb 1-Z Ca Z)} (W s Fe t Nb u) O 3 ( hereinafter,
PCWFN) was obtained.

[0039]

[Table 1]

Next, the P thus obtained by calcination is
CWFN is wet-pulverized by a ball mill and has an average particle size of 0.
The calcined powder was 9 μm (measured by a laser diffraction type particle size distribution meter).

Further, Pb ₅ Ge ₃ O as a sintering aid
₁₁ was obtained by reacting a predetermined amount of lead oxide (PbO) and germanium dioxide (GeO ₂ ) in a wet manner at 500 ° C. This was wet-pulverized by a ball mill. The average particle size was 1.0 μm.

Next, this Pb ₅ Ge ₃ O ₁₁ was added in an amount of 3.0% by weight of the calcined body powder, and was wet-mixed with a ball mill.

Next, polyvinyl alcohol as an organic binder was added to the calcined body powder mixed with Pb ₅ Ge ₃ O ₁₁ , granulated, and molded at a pressure of ² ton / cm ² to obtain a powder having a diameter of 1 ton / cm ^2.
A 2.5 mm-thick, 12 mm-thick columnar molded body was obtained.

The obtained molded body was fired at a temperature shown in Table 2 in air for 2 hours. At the time of firing, the calcined body powder as a compact and a co-material was sealed in a sagger to prevent evaporation of Pb from the compact. The obtained sintered body was processed into a diameter of 10 mm and a thickness of 5 mm.
o. 2-12, 14, 17 were obtained.

The sintering aid Pb ₅ Ge ₃ O ₁₁ was not used, or the amount of Pb ₅ Ge ₃ O ₁₁ added was 6.0.
Dielectric samples Nos. 1, 13, 15, and 16 of the examples were obtained in the same manner as described above except that the content was changed to wt% and 10.0 wt%.

Of the above samples, sample No. 12
When the phase constitution was examined by X-ray diffraction, it was found that, as shown in FIG. 1, Sample No. 12 was substantially composed of a single phase of PCWFN. On the other hand, as shown in FIG. 2, Sample No. 2 contains PCWFN as a main phase and contains Ca (Fe _1/2 Nb _1/2 ) O ₃ (CFN).
And Pyrochlore containing Pb and Nb as a different phase, and it was found that Samples Nos. 5 and 6 contained PCWFN as a main phase, and contained PCFN and the aforementioned pyrochlore as a different phase.

As a comparative example, as shown in Table 1, a dielectric sample having a composition outside the composition range of the present invention was used.
Nos. 18 to 21 were produced.

With respect to these dielectric samples, electrical characteristics, that is, dielectric constant ε, Q · f value, resonance frequency f ₀ , and temperature change rate τ _f of the resonance frequency were measured by a columnar resonance method. In calculating τ _f , the resonance frequency was measured in steps of 20 ° C. from −40 ° C. to + 80 ° C., and the value at 20 ° C. was used as a reference. Table 2 shows the results.

[0049]

[Table 2]

From the results shown in Table 2, the effect of the present invention is clear. That is, by the composition and the manufacturing method satisfying the present invention, a dielectric ceramic composition having a small temperature change rate τ _f of the resonance frequency in the microwave region, a large dielectric constant ε and a high Q · f value, and having good low-temperature firing properties. Obtained.

In addition, Pb having the same composition as a sintering aid
The sample No. 1 using no ₅ Ge ₃ O ₁₁ and the sample No. 2 used were fired at different firing temperatures as shown in Table 3, and the density (g / cm ³ ) was measured for each. However, as shown in Table 3, Pb ₅ Ge ₃ O ₁₁
Was better in low-temperature firing.

[0052]

[Table 3]

Similarly, Pb ₅ Ge ₃ O _{11 is} used as a sintering aid.
Sample No. 13 without the above and the above sample using the
Nos. 14, 15, and 16 were fired at different firing temperatures, and the density was measured for each. The results are shown in FIG. When Pb ₅ Ge ₃ O ₁₁ was added, the low-temperature firing property was clearly better.

Further, Pb (Fe _2/3 W
_1/3 ) O ₃ , as PCFN (Pb _0.325 Ca _0.675 )
(Fe _1/2 Nb _1/2 ) O ₃ is prepared, and y (PFW) =
When 0.21, 1-y (PCFN) = 0.79, PG
O was added in an amount of 3.0 wt% and MnCO ₃ in the amounts shown in Table 4, and at a firing temperature of 930 ° C., Sample No.
To 35 were produced. Table 4 shows the results. The effect of increasing the insulation resistance by containing Mn is apparent.

[0055]

[Table 4]

[0056]

The dielectric ceramic material according to the present invention has a relative dielectric constant ε of 65 or more and a Q · f of about 1300.
(GHz) or more, and the absolute value of the temperature change rate τ _f of the resonance frequency was about 50 (ppm / ° C.) or less. In addition, 10
Since firing can be performed at a low temperature of 00 ° C. or less, simultaneous firing with a silver electrode that reduces the loss of microwave signals is possible.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction chart of Sample No. 12 of Example.

FIG. 2 is an X-ray diffraction chart of each of Sample Nos. 2, 5, and 6 in Examples.

FIG. 3 is a graph showing the relationship between the sintering temperature and the density of each of Sample Nos. 13, 14, 15, and 16 of Examples.

Continuation of front page (56) References JP-A-56-156609 (JP, A) JP-A-1-100052 (JP, A) JP-A-2-263671 (JP, A) JP-A-61-128404 (JP, A) JP-A-61-158616 (JP, A) JP-A-62-230623 (JP, A) Ceramics 27 (1992) No. 8, p. 728-733 (58) Field surveyed (Int.Cl. ⁶ , DB name) H01B 3/12 306 H01B 3/12 313 C04B 35/46 H01P 7/10

Claims (13)

(57) [Claims] 1. A method comprising the steps of: containing Pb, Ca, W, Fe and Nb in the form of an oxide; A sintering aid as a secondary component, wherein the sintering aid is Pb ₅
A dielectric porcelain material that is a calcined body of Ge ₃ O ₁₁ . 2. The dielectric ceramic material according to claim 1, wherein said s, t, and u satisfy the following relationship. 3. _{Further, (Pb 1-x Ca x} ) (Fe 1/2
Nb _1/2 ) O ₃ (where 0.3 ≦ x ≦ 0.91), C
_{3. The} composition according to claim 1, wherein at least one of a (Fe _1/2 Nb _1/2 ) O ₃ and Pb ₃ Nb ₄ O ₁₃ is contained as a heterogeneous phase.
Dielectric porcelain material. 4. The method according to claim 1, wherein the content of the sintering aid is Pb or C.
2.0 to 10.0 wt% of oxides of a, W, Fe and Nb
% Of the dielectric porcelain material according to claim 1. 5. The dielectric ceramic material according to claim 1, further comprising Mn. 6. The method according to claim 1, wherein the Mn content is Pb or C in terms of Mn.
0.05 to 0.5 wt% of oxides of a, W, Fe and Nb
%. 7. Each of Pb (Fe _2/3 W) is calcined by calcination.
_1/3 ) a first porcelain material mainly composed of O ₃ and (Pb
_1-X Ca _X ) (Fe _1/2 Nb _1/2 ) O ₃ (where 0.
First, a second porcelain material whose main component is 3 ≦ x ≦ 0.91) is prepared, mixed, and then subjected to a second calcination at a lower temperature than the calcination of the second porcelain material. Then, main firing is performed, and Pb ₅ Ge _{3 is} used as a sintering aid between this mixing and before main firing.
A method for producing a dielectric porcelain material to which an O ₁₁ calcined body is added. 8. The method according to claim 1, wherein the first and second porcelain materials are y [Pb (Fe _2/3 W _1/3 ) O ₃ ] − (1-y) [(Pb _1-x Ca _x ) (Fe _{1 / 2} Nb _1/2 ) O ₃ ], wherein x and y are mixed in a molar fraction such that 0.3 ≦ x ≦ 0.91 0.01 ≦ y ≦ 0.7. Item 8. The method for producing a dielectric ceramic material according to Item 7. 9. The method for producing a dielectric ceramic material according to claim 8, wherein 0.05 ≦ y ≦ 0.4. 10. The method for producing a dielectric ceramic material according to claim 7, wherein the firing temperature is 1100 ° C. or lower. 11. The production of a dielectric porcelain material according to claim 7, wherein an amount of said sintering aid is 2.0 to 10.0 wt% of said first and second porcelain materials. Method. 12. The method for producing a dielectric ceramic material according to claim 7, wherein a Mn compound is added before the main firing. 13. The method for producing a dielectric ceramic material according to claim 12, wherein the amount of the Mn compound added is 0.05 to 0.5 wt% of the first and second ceramic materials in terms of Mn.