JPH05211007A - Dielectric porcelain composition for microwave - Google Patents

Abstract

PURPOSE:To obtain a dielectric porcelain composition whose dielectric constant epsilonis large and temperature coefficient tauf of a resonance frequency is large in the negative side, enhance a Q value of the dielectric porcelain composition, and provide the dielectric porcelain composition whose temperature coefficient tauf of a resonance frequency is nearly zero. CONSTITUTION:When this dielectric porcelain composition is expressed by a composition formula (A<1+>1/2.B<3+>1/2) TiO3, Li<1+> is selected for A<1+>, Nd<3+>, Sm<3+>, Co<3+> or Pr<3+> is selected for B<3+>. MgO, CoO, ZnO, CaCO3 or SrCO3 is added to this (A<1+>1/2.B<3+>1/2) TiO3 so as to enhance a Q value.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition used as a resonator material used in a microwave region of several GHz band.

[0002]

2. Description of the Related Art In recent years, attempts have been made to use dielectric materials for resonators and filters used in transceivers such as satellite communication / broadcasting using microwaves of several GHz band, mobile communication, or mobile identification devices. Has been done.

Conventionally, as this kind of dielectric ceramic material,
For example, Japanese Patent Application Laid-Open No. 61-8806 (H01B 3/1
BaO-TiO ₂ has been proposed in 2) or the like -Nd ₂ O ₃ -
There is a composition of Bi ₂ O ₃ . In this conventional porcelain composition,
The dielectric constant ε is about 70 to 90. Also. The temperature coefficient τf of these dielectric ceramic compositions is also +10 to +20 PPM /
It was as large as ℃, and sufficient characteristics were not obtained.

By the way, when a dielectric resonator is constructed,
Since the size of the resonator can be reduced by using a material having a higher dielectric constant ε, a material having a higher dielectric constant ε is desired.

As a material having a large dielectric constant ε, for example, S
Examples include rTiO ₃ and CaTiO ₃ . However, although its permittivity ε is extremely large at 300 and 180, the temperature coefficient τf of the resonance frequency is very large at +1700 PPM / ° C. and +800 PPM / ° C. and cannot be used.

The temperature coefficient τ of such a dielectric ceramic composition
As a method of lowering f, the dielectric constant ε is as large as possible,
There is also a method of combining a material having a negative temperature coefficient τf with this. According to this method, a ceramic composition having a large dielectric constant ε and a small temperature coefficient τf of the resonance frequency can be obtained by an appropriate combination.

However, in general, as the permittivity ε increases, the temperature coefficient τf increases toward the plus side, and a material having a large permittivity ε and a large temperature coefficient τf toward the minus side is not known.

[0008]

In view of the above points, the present invention has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency.
Is intended to obtain a dielectric ceramic composition having a large negative value.

Another object of the present invention is to improve the Q value of such a dielectric ceramic composition.

A further object of the present invention is to provide a dielectric porcelain composition using such a dielectric porcelain composition which has a large dielectric constant ε and a temperature coefficient τf of resonance frequency close to zero. Is.

[0011]

A dielectric ceramic composition for microwaves according to a first aspect of the present invention has a composition formula (A ¹⁺
When expressed in _{^{1/2 · B 3+ 1/2) TiO 3}} , as A ¹⁺ Li ¹⁺
However, Nd ³⁺ , Sm ³⁺ , Co ³⁺ or Pr ³⁺ is selected as B ³⁺ .

The present invention is also based on this (A ¹⁺ _1/2.
B ³⁺ _1/2 ) TiO _{3 with} respect to MgO, CoO, ZnO,
CaCO ₃ or SrCO ₃ is appropriately selected and added.

Further, the dielectric ceramic composition for microwaves according to the second aspect of the present invention has a composition formula wA ¹⁺ ₂ O-xA '.
_{^{1+ 2 O-yB 3+ 2 O}} 3 -zTiO 2 ( where, w + x + y + z
= 100% mol), A ¹⁺ is Li ¹⁺ , A ′
¹⁺ as Na ¹⁺ is one in which Nd ³⁺ or Sm ³⁺ is selected as B ^3+.

Furthermore, the dielectric ceramic composition for microwaves according to the third aspect of the present invention has the composition formula vB ' ³⁺ ₂ O ₃ -wA.
_{^{1+ 2 O-xA '1+ 2}} O-yB 3+ 2 O 3 -zTiO 2 ( where,
v + w + x + y + z = 100% mol), A ¹⁺
As Li ¹⁺ , A ′ ¹⁺ as Na ¹⁺ , and B ³⁺ as Sm ³⁺
And Nd ³⁺ or Pr ³⁺ is selected as B ′ ³⁺ .

Furthermore, the dielectric ceramic composition for microwaves according to the fourth aspect of the present invention has a composition formula wA ¹⁺ ₂ O-xCa.
_{^{O-yB 3+ 2 O 3 -zTiO}} 2 ( where, w + x + y + z =
100% mol), Li ¹⁺ is selected as A ^{1+ and} Sm ³⁺ or Nd ³⁺ is selected as B ³⁺ .

Furthermore, a dielectric ceramic composition for microwaves according to a fifth aspect of the present invention has a composition formula x · (Li _1/2 · B
³⁺ _1/2 ) TiO _3- (100-x) .CaTiO ₃ (where 0 mol% <x <100 mol%), Nd ³⁺ or Sm ³⁺ is selected as B ³⁺ Is.

Furthermore, the dielectric ceramic composition for microwaves according to the sixth aspect of the present invention has a composition formula of x · (Li _1/2 ·
^{_{B 3+ 1/2) TiO 3 - (}} 100-x) · (Na 1/2 · C 3+
_1/2) TiO ₃ (provided that when expressed in 0 mol% <x <100 mole%), Nd ³⁺ or Sm ³⁺ as B ³⁺ is, Nd ³⁺ or Sm ³⁺ is selected as the C ³⁺ It is something.

[0018]

[Function] According to the first invention described above (A ¹⁺ _1/2.
The dielectric ceramic composition represented by B ³⁺ _1/2 ) TiO ₃ has a large dielectric constant ε and a large negative temperature coefficient τf of the resonance frequency. And such (Li _1/2 · B ³⁺
_1/2 ) MgO, CoO, ZnO, CaC with respect to TiO ₃
The Q value is improved by adding O ₃ or SrCO ₃ .

Li ₂ O--Na _{2 according} to the second aspect of the invention
The dielectric ceramic composition containing O—Sm ₂ O ₃ —TiO ₂ as a main component and the dielectric ceramic composition containing Li ₂ O—Na ₂ O—Nd ₂ O ₃ —TiO ₂ as a main component have a high dielectric constant. In addition, the temperature coefficient τf of the resonance frequency is small.

Nd ₂ O ₃ -Li according to the third aspect of the present invention
₂ O-Na ₂ O-Sm ₂ O ₃ -TiO ₂ -based dielectric composition and Pr ₂ O ₃ -Li ₂ O-Na ₂ O-Sm ₂ O ₃
The dielectric ceramic composition containing —TiO ₂ as a main component has a high dielectric constant and a small temperature coefficient τf of the resonance frequency.

Li ₂ O--Ca according to the above-mentioned fourth invention
The dielectric ceramic composition containing O—Sm ₂ O ₃ —TiO ₂ as a main component and the dielectric ceramic composition containing Li ₂ O—CaO—Nd ₂ O ₃ —TiO ₂ as a main component have a high dielectric constant and The temperature coefficient τf of the resonance frequency is small.

Further, as in the above fifth and sixth inventions,
(Li _1/2 · B ³⁺ _1/2 ) TiO ₃ and a large dielectric constant ε,
Moreover, the temperature coefficient τf of the resonance frequency is large on the plus side (N
By combining a _1/2 · C ³⁺ _1/2 ) TiO ₃ or CaTiO ₃ , a dielectric ceramic material having a high dielectric constant and a small temperature coefficient τf of the resonance frequency can be obtained.

[0023]

EXAMPLE An example of the present invention will be described below.

The microwave porcelain composition of the first embodiment is
In the composition formula (A ¹⁺ _1/2 · B ³⁺ _1/2 ) TiO ₃ , Li ¹⁺ is A ^{1+ and} Nd ³⁺ , Sm ³⁺ , Co ³⁺ or Pr ³⁺ is B ^3+. Be selected.

First, the manufacturing method will be described. As raw materials, TiO ₂ , Li ₂ CO ₃ , Nd ₂ O ₃ , Sm
High-purity powders of ₂ O ₃ , Co ₂ O ₃ , and Pr ₆ O ₁₁ are weighed so as to have a predetermined mole fraction. As the raw material, for example, TiO ₂ is a high-purity grade manufactured by Toho Titanium Co., Ltd., and Li ₂ CO ₃ is a high-purity grade manufactured by High Purity Chemical Co., Ltd.
3N manufactured by Mitsui Kinzoku Co., Ltd. as N grade and Nd ₂ O ₃
Grade, Sm ₂ O ₃ as 3N grade manufactured by Mitsui Kinzoku Co., Ltd., Co ₂ O ₃ as reagent grade manufactured by Kojundo Chemical Co., Ltd., Pr ₆ O ₁₁ as 3N grade manufactured by Mitsui Metal Co., Ltd. , Used.

A specific production example of the dielectric ceramic composition for microwaves of this embodiment using each of the above raw materials will be described.

First, TiO ₂ , Li ₂ CO ₃ and Nd ₂
As a molar fraction of high-purity powder of O ₃ , Sm ₂ O ₃ , Co ₂ O ₃ , and Pr ₆ O ₁₁ , TiO ₂ is 1 mol and Li ₂ CO ₃ is 1/4.
And moles, in the case of selecting the Nd ₂ O ₃ thereto, Nd ₂
When O ₃ is 1/4 mol and Sm ₂ O ₃ is selected, Sm ₂
When O ₃ is 1/4 mol and Co ₂ O ₃ is selected, Co ₂
When O ₃ is 1/4 mol and Pr ₆ O ₁₁ is selected, Pr is selected.
₆ O ₁₁ is 1/12 mol.

These raw material powders, 15φ nylon balls and ethyl alcohol were put in a nylon pot and blended under the following conditions and wet-mixed for 8 hours. Raw powder: Nylon ball: Ethyl alcohol = 100
g: 500g: 500cc

Next, this is dried at 120 ° C. for 24 hours. The dried product was crushed in an alumina mortar, and the crushed product was packed in a magnesia (MgO) boat for 900
Pre-sinter at ~ 1200 ° C, in this example 1150 ° C for 2 hours. Then, the pre-sintered product is crushed again in the mortar.

This coarsely crushed material is put into a nylon pot under the following conditions and wet-milled for 20 to 60 hours, and in this embodiment for 30 hours. Crushed product: Nylon ball: Ethyl alcohol = 100
g: 1000 g: 500 cc

Subsequently, the ground product is dried at 120 ° C. for 24 hours. Then, this powder is roughly crushed, and 3 g of a 10% solution of polyvinyl alcohol as a binder is mixed with 50 g of the powder in a mortar and granulated. The granulated product is dried at 100 ° C. for 5 hours.

Then, the dried product is classified using two kinds of sieves of 100 mesh (150 μm) and 200 mesh (75 μm), and only particles of 75 to 150 μm are taken out.

This classified powder is 2,000 to 3,000 K
A disk having a diameter of 10 mm and a thickness of 6 mm is press-molded at a pressure of g / cm ² , in this example, 2550 kg / cm ² .

Subsequently, this molded product was put into a baking boat made of alumina, a plate made of zirconia (ZrO ₂ ) was laid under the boat, and the temperature was raised at 150 ° C./H at 350 ° C. for 2 hours.
Baking is performed by holding at 600 ° C. for 2 hours and 1300 ° C. for 5 hours. So that the thickness of the fired product is half the diameter,
For example, double-side polishing is performed using polishing powder FO-800 # manufactured by Fujimi Polishing Industry. In addition, the polished object is again 1500 #
Polish both sides cleanly with water resistant paper. Then, the sample is completed by ultrasonically cleaning with acetone and finally drying at 100 ° C. for 2 hours.

The sample thus completed was subjected to a dielectric resonator method (Hacke-Coleman method) and a dielectric constant ε and Q value using a YHP 8510B network analyzer in the range of a measurement frequency of about 3 GH. Measure. Further, the temperature coefficient τf of the resonance frequency was calculated by the following equation by measuring the change in the resonance frequency between 20 ° C and 70 ° C by placing the measurement system in a constant temperature bath.

[0036]

[Equation 1] Here, F ₇₀ is the resonance frequency at 70 ° C., F ₂₀ is the resonance frequency at 20 ° C., and ΔT is the temperature difference.

Table 1 shows the measurement results obtained by changing A ¹⁺ and B ³⁺ variously.

[0038]

[Table 1]

In the table, sample numbers 5 to 7 marked with * are comparative examples outside the scope of the present invention. Although the combination as in the comparative example is sintered, the dielectric properties in the microwave region are poor and measurement becomes impossible.

On the other hand, as is clear from Table 1, (A ¹⁺
₁ / ^{2.B 3+} _1/2 ) TiO ₃ by selecting Li ¹⁺ as A ^{1+ and} Nd ³⁺ , Sm ³⁺ , Co ³⁺ or Pr ³⁺ as B ³⁺ A porcelain composition having a large dielectric constant ε and a large temperature coefficient τf of the resonance frequency on the negative side can be obtained.

Next, the second embodiment will be described. Second
The porcelain composition of the example is B ^{3+ with} respect to the porcelain composition (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ obtained in the first example.
Is Nd ³⁺ or Pr ³⁺ , MgO, CoO or Zn
O is added by adding CaCO ₃ , SrCO ₃ or ZnO when B ³⁺ is Sm ³⁺ . (Li _1/2・
Ca based on 100 parts by weight of the main component of B ³⁺ _1/2 ) TiO _3.
A predetermined weight part of CO ₃ , SrCO ₃ or ZnO is added. Examples of the raw material of this additive include CaCO ₃ as a reagent grade manufactured by Kishida Chemical Co., Ltd., SrCO ₃ as a reagent grade manufactured by Kishida Chemical Co., Ltd., and ZnO as a 3N grade manufactured by High Purity Chemical Co., Ltd. Is used.

In the second embodiment, the measurement sample is prepared by
A predetermined amount of the above-mentioned additive is added to a material obtained by wet-mixing each raw material of the main component (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ and dry mixing is performed. After that, by the same method as in the first embodiment, calcination, molding and firing are performed to complete a measurement sample.

Tables 2 to 4 show the measurement results of the dielectric properties by the Hacky-Coleman method at the measurement frequency of about 3 GHz in the measurement samples prepared by changing the addition amount of each additive.

Table 2 shows the measurement results when MgO, CoO or ZnO was added to (Li _1/2 · Nd ³⁺ _1/2 ) TiO ₃ .

Table 3 shows the measurement results when CaCO ₃ , SrCO ₃ or ZnO was added to (Li _1/2 · Sm ³⁺ _1/2 ) TiO ₃ .

Table 4 shows the measurement results when MgO, CoO or ZnO was added to (Li _1/2 · Pr ³⁺ _1/2 ) TiO ₃ .

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

In the table, sample numbers 27 and 32 marked with *
-37.42.47.52 are comparative examples outside the scope of the present invention.

As is clear from Tables 2 to 4, addition of each additive improves the Q value. However, although the Q value increases as the added amount increases, the dielectric constant decreases. Therefore, the addition amount of each additive is (Li _1/2 · B ³⁺ _1/2 )
10 parts by weight or less is suitable for 100 parts by weight of TiO ₃ .

Next, a third embodiment will be described.

The microwave porcelain composition of the third embodiment is
'In ^{_{(1+ 2 O-B 3+ 2}} O 3 -TiO 2, Li 1+ as A ^1+, A composition formula A ^{1 +} · A)' Na ¹⁺ as ^1+, B ³⁺
Is selected as Nd ³⁺ . In the third embodiment, the raw materials are TiO ₂ , Li ₂ CO ₃ , Na ₂ CO ₃ and N.
Samples were prepared by using high-purity d ₂ O ₃ powder and changing the compounding ratio of each component in the same manner as in the first embodiment. Table 5 shows the dielectric characteristics of the produced sample measured by the Hacky-Coleman method at a measurement frequency of around 3 GHz. In the table, w, x,
y and z represent mole fractions, and w + x + y + z = 100 mol%.

[0054]

[Table 5]

As is clear from Table 5, the composition formula w · Li
₂ O-x / Na ₂ O-y / Nd ₂ O ₃ -z / TiO ₂ (w +
The dielectric ceramic composition represented by (x + y + z = 100 mol%) has a large dielectric constant ε, a small temperature coefficient τf of the resonance frequency, and a high Q value.

It is possible to set w, x, y and z in the following ranges. 0.0 mol% <w ≦ 17.0 mol% 0.0 mol% ≦ x ≦ 17.0 mol% 0.0 mol% <y ≦ 25.0 mol% 0.0 mol% <z ≦ 80.0 Mol%

Particularly, good dielectric properties can be obtained when w, x, y and z are set in the following ranges. 3.0 mol% ≦ w ≦ 15.0 mol% 3.0 mol% ≦ x ≦ 15.0 mol% 9.0 mol% ≦ y ≦ 25.0 mol% 0.0 mol% <z ≦ 80.0 Mol%

Next, a fourth embodiment will be described. The microwave porcelain composition of the fourth embodiment has the composition formula (A ¹⁺ · A ′).
¹⁺ ) ₂ O-B ³⁺ ₂ O ₃ -TiO _{2 and} Li as A ^1+
1+, Na ¹⁺ as A ^'1+, Sm ³⁺ is selected as B ^3+. In the fourth embodiment, TiO is used as a raw material.
Samples were prepared by using high-purity powders of ₂ , Li ₂ CO ₃ , Na ₂ CO ₃ , and Sm ₂ O ₃ and changing the compounding ratio of each component in the same manner as in the first embodiment. Tables 6 and 7 show the dielectric characteristics of the produced sample measured by the Hacky-Coleman method at a measurement frequency of around 3 GHz. In the table, w, x, y and z represent mole fractions, and w + x + y + z = 100 mol%.

[0059]

[Table 6]

[0060]

[Table 7]

In the table, sample number 67 with * is a comparative example outside the scope of the present invention.

[0062] Table 6 and Table 7, the composition formula _{w · Li 2 O-x ·} Na 2 O-y · Sm 2 O 3 -z · TiO
_The dielectric ceramic composition represented by ₂ (w + x + y + z = 100 mol%) has a large dielectric constant ε, a small temperature coefficient τf of the resonance frequency, and a high Q value. In the measurement sample of sample number 67 lacking Li ₂ O, the temperature coefficient τ of the resonance frequency is
The absolute value of f is slightly larger.

It is possible to set w, x, y, z in the following ranges. 0.0 mol% <w ≦ 17.0 mol% 0.0 mol% ≦ x ≦ 17.0 mol% 0.0 mol% <y ≦ 25.0 mol% 0.0 mol% <z ≦ 80.0 Mol%

Particularly, good dielectric properties can be obtained when w, x, y and z are set in the following ranges. 0.0 mol% <w ≦ 15.0 mol% 0.0 mol% ≦ x ≦ 15.0 mol% 0.0 mol% <y ≦ 20.0 mol% 0.0 mol% <z ≦ 75.0 Mol%

Next, a fifth embodiment will be described. Fifth
The microwave porcelain composition of the example of is a composition formula (A ¹⁺
In _{^{A '1+) 2 O- (B}} 3+ · B' 3+) 2 O 3 -TiO 2, Li 1+ as A ¹⁺ is, Na ¹⁺ is as A ^'1+, B ³⁺
Sm ³⁺ is Nd ³⁺ is selected as B ^'3+ as.
In the fifth embodiment, the raw materials are TiO ₂ , Li ₂ CO
High-purity powders of ₃ , Na ₂ CO ₃ , Nd ₂ O ₃ , and SmO ₃ were used, and the compounding ratio of each component was changed in the same manner as in the first example. Table 8 shows the dielectric properties of the produced sample measured by the Hacky-Coleman method at a measurement frequency of around 3 GHz. In the table, v, w, x, y, z represent mole fractions, v
+ W + x + y + z = 100 mol%.

[0066]

[Table 8]

As is clear from Table 8, the composition formula is vN
_{d 2 O 3 -w · Li 2} O-x · Na 2 O-y · Sm 2 O 3 -z
The dielectric ceramic composition represented by TiO ₂ (v + w + x + y + z = 100 mol%) has a large dielectric constant ε, a small temperature coefficient τf of resonance frequency, and a high Q value.

The v, w, x, y, z can be set within the following ranges. 0.0 mol% <v ≦ 25.0 mol% 0.0 mol% <w ≦ 17.0 mol% 0.0 mol% ≦ x ≦ 17.0 mol% 0.0 mol% <y ≦ 25.0 Mol% 0.0 mol% <z ≦ 80.0 mol%

Particularly, when v, w, x, y, z are set in the following ranges, good dielectric characteristics can be obtained. 3.0 mol% ≤ v ≤ 7.0 mol% 3.0 mol% ≤ w ≤ 15.0 mol% 0.0 mol% ≤ x ≤ 7.0 mol% 0.0 mol% <y ≤ 16.0 Mol% 0.0 mol% <z ≦ 75.0 mol%

Next, a sixth embodiment will be described. Sixth
The microwave porcelain composition of the example of is a composition formula (A ¹⁺
In _{^{A '1+) 2 O- (B}} 3+ · B' 3+) 2 O 3 -TiO 2, Li 1+ as A ¹⁺ is, Na ¹⁺ is as A ^'1+, B ³⁺
Sm ³⁺ is Pr ³⁺ is selected as B ^'3+ as.
In the sixth embodiment, the raw materials are TiO ₂ and Li ₂ CO.
High-purity powders of ₃ , Na ₂ CO ₃ , Nd ₂ O ₃ , and Rr ₆ O ₁₁ were used, and the compounding ratio of each component was changed in the same manner as in the first example. Table 9 shows the dielectric properties of the produced sample measured by the Hacky-Coleman method at a measurement frequency of around 3 GHz. In the table, v, w, x, y, and z represent mole fractions,
v + w + x + y + z = 100 mol%.

[0071]

[Table 9]

As is clear from Table 9, the composition formula is v · P.
_{r 2 O 3 -w · Li 2} O-x · Na 2 O-y · Sm 2 O 3 -z
The dielectric ceramic composition represented by TiO ₂ (v + w + x + y + z = 100 mol%) has a large dielectric constant ε, a small temperature coefficient τf of the resonance frequency, and a high Q value.

It is possible to set v, w, x, y, z in the following ranges. 0.0 mol% <v ≦ 7.0 mol% 0.0 mol% <w ≦ 15.0 mol% 0.0 mol% ≦ x ≦ 7.0 mol% 0.0 mol% <y ≦ 16.0 Mol% 0.0 mol% <z ≦ 75.0 mol%

Particularly, when v, w, x, y, z are set in the following ranges, good dielectric characteristics can be obtained. 3.0 mol% ≤ v ≤ 7.0 mol% 3.0 mol% ≤ w ≤ 15.0 mol% 3.0 mol% ≤ x ≤ 7.0 mol% 9.0 mol% ≤ y ≤ 16.0 Mol% 65.0 mol% ≦ z ≦ 75.0 mol%

Next, the seventh embodiment will be described. 7th
The microwave porcelain composition of the example of is a composition formula A ¹⁺ ₂ O-
In _{^{CaO-B 3+ 2 O 3 -TiO}} 2, Li as A ¹⁺
Sm ³⁺ is selected as ¹⁺ is B ³⁺ . In the seventh embodiment, the raw materials are TiO ₂ , Li ₂ CO ₃ , and CaC.
High-purity powders of O ₃ and Sm ₂ O ₃ were used, and the mixing ratio of each component was changed in the same manner as in the first embodiment. Measurement frequency of the prepared sample using the Hacke-Coleman method 3 GHz
Table 10 shows the dielectric properties measured near z. In the table, w, x, y, and z represent mole fractions, and vw + x + y + z =
It is 100 mol%.

[0076]

[Table 10]

As is clear from Table 10, the composition formula is w.
_{Li 2 O-x · CaO-} y · Sm 2 O 3 -z · TiO 2 (w
+ X + y + z = 100 mol%), the dielectric ceramic composition has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency.
Is small and has a high Q value.

Particularly, good dielectric properties can be obtained when w, x, y, z are set in the following ranges. 0.0 mol% <w ≦ 25.0 mol% 0.0 mol% ≦ x <50.0 mol% 0.0 mol% <y ≦ 20.0 mol% 0.0 mol% <z ≦ 80.0 Mol%

Next, the eighth embodiment will be described. 8th
The microwave porcelain composition of the example of is a composition formula A ¹⁺ ₂ O-
CaO-(In _{^{B 3+ 2 O 3 -TiO 2,}} L as A ¹⁺
i ¹⁺ is selected as B ³⁺ and Nd ³⁺ is selected. In the eighth embodiment, the raw materials are TiO ₂ , Li ₂ CO ₃ , and CaC.
High-purity powders of O ₃ and Nd ₂ O ₃ were used, and the mixing ratio of each component was changed in the same manner as in the first embodiment. Measurement frequency of the prepared sample using the Hacke-Coleman method 3 GHz
Table 11 shows the dielectric properties measured near z. In the table, w, x, y, and z represent mole fractions, and vw + x + y + z =
It is 100 mol%.

[0080]

[Table 11]

As is clear from Table 11, the composition formula is w.
_{Li 2 O-x · CaO-} y · Nd 2 O 3 -z · TiO 2 (w
+ X + y + z = 100 mol%), the dielectric ceramic composition has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency.
Is small and has a high Q value.

W, x, y, z can be set in the following ranges. 0.0 mol% <w ≦ 25.0 mol% 0.0 mol% ≦ x <50.0 mol% 0.0 mol% <y ≦ 20.0 mol% 0.0 mol% <z ≦ 80.0 Mol%

Particularly, good dielectric properties can be obtained when w, x, y, z are set in the following ranges. 0.0 mol% <w ≦ 20.0 mol% 0.0 mol% ≦ x <50.0 mol% 0.0 mol% <y ≦ 20.0 mol% 50.0 mol% ≦ z ≦ 80.0 Mol%

Next, a ninth embodiment will be described. 9th
The porcelain composition of the example is the same as the porcelain composition (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ obtained in the above-mentioned first example, and has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency. Is obtained by mixing a large porcelain composition (Na _1/2 · C ³⁺ _1/2 ) TiO ₃ on the plus side. At this time, Nd ³⁺ or Sm ³⁺ is selected as B ³⁺ , and Nd ³⁺ or Sm ³⁺ is similarly selected as C ³⁺ .

A sample was prepared in the same manner as in the first embodiment,
Using the Hacky-Coleman method, the dielectric constant ε, the Q value, and the temperature coefficient τf of the resonance frequency were measured near the measurement frequency of 3 GHz.

The measurement results are shown in Tables 12 and 13. A, b, c and d in the table are as follows. a: (Li _1/2 · Nd _1/2 ) TiO ₃ b: (Na _1/2 ·
Nd _1/2 ) TiO ₃ c: (Li _1/2 · Sm _1/2 ) TiO ₃ d: (Na _1/2 ·
Sm _1/2 ) TiO ₃

[0087]

[Table 12]

[0088]

[Table 13]

As can be seen from Tables 12 and 13, a porcelain composition (Na _1/2 · C ³⁺ _1/2 ) TiO having a large dielectric constant ε and a large temperature coefficient τf of the resonance frequency on the positive side is obtained.
₃ (C ³⁺ : Nd ³⁺ , Sm ³⁺ ) and a large dielectric constant ε, and the temperature coefficient τf of the resonance frequency is large on the negative side. Porcelain composition (Li _1/2 · B ³⁺ _1/2 ) TiO 2 ₃ (B ³⁺ : Nd ³⁺ , S
By mixing with m ³⁺ ), a porcelain composition having a large dielectric constant and a small temperature coefficient τf of the resonance frequency can be obtained.

FIG. 1 shows the characteristics of the dielectric constant ε and the temperature coefficient τf of the resonance frequency with respect to the compounding ratio of (Li _1/2 · Sm _1/2 ) TiO ₃ and (Na _1/2 · Sm _1/2 ) TiO _3. It is a characteristic view which shows a curve. Thus, by changing the compounding ratio, porcelain compositions having various characteristics can be obtained.

The porcelain compositions of the ninth embodiment shown in Tables 12 and 13 are the porcelain compositions (Li _1/2 · Nd _1/2 ) TiO ₃ or (Li) obtained in the first embodiment. _1/2 / S
m _1/2 ) TiO ₃ and a ceramic composition (Na _1/2) having a large dielectric constant ε and a large temperature coefficient τf of the resonance frequency on the plus side.
・ Nd _1/2 ) TiO ₃ or (Na _1/2 · Sm _1/2 ) TiO ₃
Is obtained by mixing. Ti as each raw material
A high-purity powder of O ₂ , LiCO ₃ , Na ₂ CO ₃ , Sm ₂ O ₃ , and Nd ₂ O ₃ was used to prepare the same porcelain composition as in the ninth example. Through Table 16, the dielectric properties of the porcelain compositions formed with these compounding ratios are the same as those of the samples shown in Tables 12 and 13.
In Tables 14 to 16, the sample numbers in parentheses correspond to the samples shown in Tables 11 and 12.

[0092]

[Table 14]

[0093]

[Table 15]

[0094]

[Table 16]

Next, as a porcelain composition having a large dielectric constant ε and a large temperature coefficient τf of the resonance frequency on the positive side, C
A tenth embodiment using aTiO ₃ will be described.

Table 17 shows the composition formula (Li _1/2 · B ³⁺ _1/2 ) Ti.
A dielectric ceramic sample in which B ³⁺ is Nd ³⁺ or Sm ³⁺ in O ₃ -CaTiO ₃ was prepared in the same manner as in the first embodiment, and its dielectric characteristics were measured by the Hacky-Coleman method at a frequency of 3GH.
It is the result measured near z. Incidentally, a and c in Table 17 are the same as those in Tables 12 and 13.

[0097]

[Table 17]

From Table 17, it can be seen that a dielectric ceramic composition having a large dielectric constant exceeding 100 and a small temperature coefficient τf can be obtained.

(Li _1/2 · B ³⁺ _1/2 ) TiO ₃ and CaTi
The characteristic curves of the dielectric constant ε and the temperature coefficient τf of the resonance frequency with respect to the composition ratio with O ₃ are shown in FIG. 2 (B ³⁺ = Nd ³⁺ ) and FIG.
(B ³⁺ = Sm ³⁺ )

Next, as a porcelain composition having a large dielectric constant ε and a large temperature coefficient τf of the resonance frequency on the plus side, C
A tenth embodiment using aTiO ₃ will be described.

The porcelain composition of the tenth embodiment shown in Table 17 is the porcelain composition (Li _1/2 obtained in the above-mentioned first embodiment).
・ Nd _1/2 ) TiO ₃ or (Li _1/2 · Sm _1/2 ) TiO ₃
And CaTiO ₃ are mixed. Using these as raw materials, TiO ₂ , LiCO ₃ , Sm ₂ O ₃ , Nd ₂ O
The respective compounding ratios of the high-purity powders of ₃ and CaCO ₃ are as shown in Tables 17 to 18, and the dielectric properties of the porcelain composition formed with these compounding ratios are the same as those of the samples shown in Table 17. It is the same. In Tables 18 to 19, the sample numbers in parentheses correspond to the samples shown in Table 17.

[0102]

[Table 18]

[0103]

[Table 19]

[0104]

As described above, the dielectric ceramic composition represented by (A ¹⁺ _1/2 · B ³⁺ _1/2 ) TiO _{3 according} to the first invention of the present invention has a dielectric constant of ε is large, and the temperature coefficient τf of the resonance frequency is large at a negative value. And, for such (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ , Mg
The Q value is improved by adding O, CoO, ZnO, CaCO ₃ or SrCO ₃ .

Further, Li according to the second invention of the present invention
₂ O-Na ₂ O-Sm ₂ O ₃ -TiO ₂ -based dielectric ceramic composition and Li ₂ O-Na ₂ O-Nd ₂ O ₃ -TiO _2
The dielectric ceramic composition containing ₂ as a main component has a high dielectric constant and a small temperature coefficient τf of the resonance frequency.

Further, Nd according to the third invention of the present invention.
_{2 O 3 -Li 2 O-Na} 2 O-Sm 2 O 3 -TiO 2 as main components dielectric composition and _{Pr 2 O 3 -Li 2 O-} Na 2 O
The dielectric ceramic composition containing —Sm ₂ O ₃ —TiO ₂ as a main component has a high dielectric constant and a small temperature coefficient τf of the resonance frequency.

The Li according to the fourth aspect of the present invention
_The dielectric ceramic composition containing ₂ O-CaO-Sm ₂ O ₃ -TiO ₂ as a main component and the dielectric ceramic composition containing Li ₂ O-CaO-Nd ₂ O ₃ -TiO ₂ as a main component have a high dielectric constant. And the temperature coefficient τf of the resonance frequency is small.

Further, as in the fifth and sixth inventions of the present invention, (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ has a large dielectric constant ε and the temperature coefficient τf of the resonance frequency is large. By combining large (Na _1/2 · C ³⁺ _1/2 ) TiO ₃ or CaTiO ₃ on the positive side, a dielectric ceramic material having a high dielectric constant and a small temperature coefficient τf at the resonance frequency can be obtained.

[Brief description of drawings]

FIG. 1 shows (Li _1/2 · Sm _1/2 ) TiO ₃ and (N
a ₁ / 2.Sm _1/2 ) Dielectric constant ε with respect to the compounding ratio with TiO ₃
FIG. 6 is a characteristic diagram showing a characteristic curve of a temperature coefficient τf of a resonance frequency.

FIG. 2 shows (Li _1/2 · Nd _1/2 ) TiO ₃ and Ca of the present invention.
It is a characteristic diagram showing the characteristic curve of the temperature coefficient τf of the dielectric constant ε and the resonance frequency for the compounding ratio of the TiO _3.

FIG. 3 shows (Li _1/2 · Sm _1/2 ) TiO ₃ and Ca of the present invention.
It is a characteristic diagram showing the characteristic curve of the temperature coefficient τf of the dielectric constant ε and the resonance frequency for the compounding ratio of the TiO _3.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 3-104458 (32) Priority date Hei 3 (1991) May 9 (33) Priority claim country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 3-111913 (32) Priority Date No. 3 (1991) May 16 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-218872 (32) Priority Hihei 3 (1991) August 29 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-303293 (32) Priority Day Hei 3 (1991) November 19 (33) ) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 3-323237 (32) Priority date Hei 3 (1991) December 6 (33) Priority claiming country Japan (JP) (72) Inventor Yasuhiko Okamoto 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. (72) Inventor Juichi Takahashi 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. Inside the company (72) Kenichi Shibata 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. Inside the company (72) Inventor Kazuhiko Kuroki 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd.

Claims (15)

[Claims] 1. The composition formula is represented by (A ¹⁺ ₁ / ^{2.B 3+} _1/2 ) TiO ₃ , wherein A ¹⁺ is Li ^1+.
And B ³⁺ is Nd ³⁺ , Sm ³⁺ , Co ³⁺ , Pr ³⁺ , a dielectric ceramic composition for microwaves. 2. A dielectric ceramic composition represented by the formula: (Li _1/2 · Nd ³⁺ _1/2 ) TiO ₃ wherein (Li _1/2 · Nd ³⁺ _1/2 ) TiO ₃ A dielectric ceramic composition for microwaves, which is obtained by adding 10 parts by weight or less of MgO, CoO or ZnO to 100 parts by weight. _3. A dielectric ceramic composition represented by a composition formula of (Li _1/2 .Sm _1/2 ) TiO ₃ , wherein (Li ¹⁺ _1/2 .Sm ³⁺ _1/2 ) TiO ₃ A dielectric ceramic composition for microwaves, wherein 10 parts by weight or less of CaCO ₃ , SrCO ₃ or ZnO is added to 100 parts by weight. 4. A dielectric ceramic composition represented by a composition formula of (Li _1/2 .Pr _1/2 ) TiO ₃ , wherein (Li _1/2 .Nd ³⁺ _1/2 ) TiO ₃ 100 wt. A dielectric ceramic composition for microwaves, wherein MgO, CoO or ZnO is added in an amount of 10 parts by weight or less with respect to 10 parts by weight. 5. The composition formula is w · A ¹⁺ ₂ O−x · A ′ 1 ⁺ ₂ O−y · B ³⁺ ₂ O ₃ −z · Ti.
O ₂ (however, w + x + y + z = 100% mol), A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na ¹⁺ , and B ³⁺ is Nd.
^A dielectric ceramic composition for microwaves, which is ³⁺ or Sm ³⁺ . 6. A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na ¹⁺ , B ³⁺ is Nd ³⁺ , and w, x, y, z are 0.0 mol <w ≦ 17.0. The microwave according to claim 5, wherein mol% is 0.0 mol ≤ x ≤ 17.0 mol% 0.0 mol <y ≤ 25.0 mol% 0.0 mol <z ≤ 80.0 mol%. Dielectric porcelain composition for use. 7. A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na ¹⁺ , B ³⁺ is Sm ³⁺ , and w, x, y, z are 0.0 mol <w ≦ 17.0. The microwave according to claim 5, wherein the mol% is in the range of 0.0 mol ≦ x ≦ 17.0 mol% 0.0 mol <y ≦ 20.0 mol% 0.0 mol <z ≦ 75.0 mol%. Dielectric porcelain composition for use. 8. The composition _{^{formula, v · B '3+ 2 O}} 3 -w · A 1+ 2 O-x · A' 1+ 2 O-y · B
_{^{3+ 2 O 3 -z · TiO 2}} ( where, v + w + x + y + z = 1
00% mol), A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na,
B ³⁺ is a Sm ^3+, B ^'3+ is Nd ³⁺ or microwave dielectric ceramic composition is Pr ^3+. 9. A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na, and B ³⁺ is S.
m ³⁺ and B ′ ³⁺ are Nd ³⁺ , and v, w, x, y and z are 0.0 mol <v ≦ 25.0 mol% 0.0 mol <w ≦ 17.0 mol% 0 9. The microwave dielectric material according to claim 8, wherein the range is 0.0 mol ≦ x ≦ 17.0 mol% 0.0 mol <y ≦ 25.0 mol% 0.0 mol <z ≦ 80.0 mol%. Porcelain composition. 10. A ¹⁺ is Li ¹⁺ , A ′ ¹⁺ is Na ¹⁺ , B ³⁺
Is Sm ³⁺ , B ′ ³⁺ is Pr ³⁺ , and v, w, x, y, z
0.0 mol <v ≦ 7.0 mol% 0.0 mol <w ≦ 15.0 mol% 0.0 mol ≦ x ≦ 7.0 mol% 0.0 mol <y ≦ 16.0 mol% 0 9. The dielectric ceramic composition for microwaves according to claim 8, wherein the range is 0.0 mol <z ≦ 75.0 mol%. 11. The composition _{^{formula, w · A 1+ 2 O-}} x · CaO-y · B 3+ 2 O 3 -z · TiO 2
(However, w + x + y + z = 100% mol), A
^A dielectric ceramic composition for microwaves, wherein ¹⁺ is Li ¹⁺ and B ³⁺ is Sm ³⁺ or Nd ³⁺ . 12. A ¹⁺ is Li ¹⁺ , B ³⁺ is Sm ³⁺ ,
w, x, y, z is 0.0 mol <w ≦ 25.0 mol% 0.0 mol ≦ x <50.0 mol% 0.0 mol <y ≦ 20.0 mol% 0.0 mol <z The dielectric ceramic composition for microwaves according to claim 11, wherein the range is ≦ 80.0 mol%. 13. A ¹⁺ is Li ¹⁺ , B ³⁺ is Nd ³⁺ ,
w, x, y, z is 0.0 mol <w ≦ 25.0 mol% 0.0 mol ≦ x <50.0 mol% 0.0 mol <y ≦ 20.0 mol% 0.0 mol <z The dielectric ceramic composition for microwaves according to claim 11, wherein the range is ≦ 80.0 mol%. 14. The composition formula is x · (Li _1/2 · B ³⁺ _1/2 ) TiO ₃ — (100-x)
(Na _1/2 · C ³⁺ _1/2 ) TiO ₃ (however, 0 mol% x <x
≦ 100 mol%), B ³⁺ is Nd ³⁺ or Sm ³⁺ , and C ³⁺ is N
A dielectric ceramic composition for microwaves, which is d ³⁺ or Sm ³⁺ . 15. The composition formula is x. (Li _1/2 ^{.B 3+} _1/2 ) TiO _3- (100-x) C.
A dielectric ceramic composition for microwaves, which is represented by aTiO ₃ (however, 0 mol% x <x ≦ 100 mol%), and B ³⁺ is Nd ³⁺ or Sm ³⁺ .