JP2654299B2 - Microwave dielectric porcelain composition - 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 ceramic composition used for a resonator material used in a microwave range of several GHz.

[0002]

2. Description of the Related Art In recent years, attempts have been made to use a dielectric material for a resonator or a filter used in a transceiver such as a satellite communication / broadcast, a mobile communication, or a mobile identification device using a microwave of several GHz. Has been done.

Conventionally, this type of dielectric porcelain material includes:
For example, JP-A-61-8806 (H01B 3/1)
2) BaO-TiO ₂ -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 /
° C, and sufficient characteristics were not obtained.

By the way, when forming a dielectric resonator,
Since the size of the resonator can be reduced as the material having a larger dielectric constant ε is used, a material having a larger dielectric constant ε is desired.

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

The temperature coefficient τ of such a dielectric porcelain composition
As a method of lowering f, the dielectric constant ε is as large as possible,
In addition, there is a method in which a material having a negative temperature coefficient τf is combined therewith. 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, generally, as the dielectric constant ε increases, the temperature coefficient τf increases toward the plus side, and a material having a large dielectric constant ε and a large temperature coefficient τf toward the negative side is not known.

[0008]

In view of the above, 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 ceramic composition having a large dielectric constant ε and a temperature coefficient τf of the resonance frequency close to zero using such a dielectric ceramic composition. It is.

[0011]

Means for Solving the Problems The dielectric ceramic composition for microwave according to the first invention of the present invention has a composition formula (A ¹⁺
_1/2 · B3 ⁺ _1/2 ) When expressed as TiO ₃ , A ¹⁺ is Li ¹⁺
However, any one of Nd3 ⁺ , Sm ³⁺ , Co ^{3+ and} Pr ³⁺ is selected as B ³⁺ .

Further, the present invention relates to (A ¹⁺ _1/2.
B ³⁺ _1/2 ) TiO ₃ , MgO, CoO, ZnO,
One of CaCO _{3 and} SrCO ₃ is appropriately selected and added.

Furthermore, the dielectric ceramic composition for microwave according to the second invention 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), Li ¹⁺ , A ′ as A ^1+
1+ as Na ¹⁺ is one in which Nd ³⁺ or Sm ³⁺ is selected as B ^3+.

Further, the dielectric ceramic composition for microwaves according to the third invention of the present invention has a 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⁺ .

Further, the dielectric ceramic composition for microwave according to the fourth invention 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⁺ .

Further, the dielectric ceramic composition for microwave according to the fifth invention 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%), where Nd ³⁺ or Sm ³⁺ is selected as B ³⁺ It is.

Further, the dielectric ceramic composition for microwaves according to the sixth invention 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⁺ Things.

[0018]

According to the first aspect of the present invention, (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⁺ _1/2 · B
³⁺ _1/2 ) MgO, CoO, ZnO, Ca for TiO ₃
The Q value is improved by adding one of CO _{3 and} SrCO ₃ .

The Li ₂ O—Na _{2 according} to the second aspect of the present invention.
O-Sm ₂ O ₃ dielectric ceramic composition -TiO ₂ as main components and _{Li 2 O-Na 2 O-} Nd 2 O 3 -TiO 2 dielectric ceramic composition mainly composed of a high dielectric constant And the temperature coefficient τf of the resonance frequency is small.

The Nd ₂ O ₃ —Li according to the third aspect of the present invention.
Dielectric composition containing ₂ O—Na ₂ O—Sm ₂ O ₃ —TiO ₂ as a main component 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.

The Li ₂ O—Ca according to the fourth aspect of the present invention.
O-Sm ₂ O ₃ -TiO ₂ dielectric ceramic composition as a main component and _{Li 2 O-CaO-Nd 2} O 3 -TiO 2 dielectric ceramic composition as a main component is and a high dielectric constant The temperature coefficient τf of the resonance frequency becomes small.

Further, as in the fifth and sixth aspects,
(Li _1/2 · B ³⁺ _1/2 ) TiO ₃ and a large dielectric constant ε,
And 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 temperature coefficient τf is small and the resonance frequency at a high dielectric constant can be obtained.

[0023]

An embodiment 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. Examples of this raw material include TiO ₂ as a high-purity grade manufactured by Toho Titanium Co., Ltd., and Li ₂ CO ₃ as a high-purity grade manufactured by High-Purity Chemical Co., Ltd.
N grade, as the Nd ₂ O _3, manufactured by Mitsui Mining & Smelting Co., Ltd. 3N
Grade, Sm ₂ O ₃ , 3N grade manufactured by Mitsui Kinzoku Co., Ltd .; Co ₂ O ₃ , reagent grade manufactured by Kojundo Chemical Co., Ltd .; Pr ₆ O ₁₁ , 3N grade manufactured by Mitsui Kinzoku Co., Ltd. , Is 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 , Nd ₂
The molar fraction of the high-purity powder of O ₃ , Sm ₂ O ₃ , Co ₂ O ₃ , and Pr ₆ O ₁₁ was 1 mol of TiO _{2 and} 1/4 of Li ₂ CO _3.
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
If the O ₃ selects a 1/4 mol, Co ₂ O ₃ is, Co ₂
When O ₃ is １ ／ mole and Pr ₆ O ₁₁ is selected, Pr
₆ O ₁₁ is 1/12 mol.

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

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

The crushed product is placed in a nylon pot under the following conditions and wet-pulverized for 20 to 60 hours, in this example, 30 hours. Crushed material: nylon ball: ethyl alcohol = 100
g: 1000 g: 500 cc

Subsequently, the pulverized material is dried at 120 ° C. for 24 hours. Then, this powder is roughly crushed, and a mortar is used to granulate by mixing 3% of a 10% solution of polyvinyl alcohol as a binder with 50 g of the powder. The granules are dried at 100 ° C. for 5 hours.

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

[0033] The classified powder is 2,000-3000K
At a pressure of g / cm ² , in this example, at a pressure of 2550 Kg / cm ² , the plate is pressed into a disk having a diameter of 10 mm and a thickness of 6 mm.

Subsequently, the molded product was placed in a firing boat made of alumina, and a plate made of zirconia (ZrO ₂ ) was laid under the boat, and the temperature was raised at a rate of 150 ° C./H at 350 ° C. for 2 hours.
Baking is carried out at 600 ° C. for 2 hours and at 1300 ° C. for 5 hours. So that the thickness of the fired product is half the diameter,
For example, both sides are polished using polishing powder FO-800 # manufactured by Fujimi Abrasive Industry. Further, the polished material is again subjected to 1500 #
Polish both sides neatly with waterproof paper. Thereafter, the sample is ultrasonically washed with acetone, and finally dried at 100 ° C. for 2 hours to complete a sample.

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

[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. In the combination as in the comparative example, sintering is performed, but the dielectric properties in the microwave region are poor and measurement becomes impossible.

On the other hand, as apparent from Table 1, (A ¹⁺
_In a composition of 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 negative temperature coefficient τf of the resonance frequency can be obtained.

Next, a 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 obtained by adding CaCO ₃ , SrCO ₃ or ZnO when B ³⁺ is Sm ³⁺ . (Li _1/2・
B ³⁺ _1/2 ) Ca based on 100 parts by weight of the main component of TiO ₃
CO ₃ , SrCO ₃ or ZnO is added in a predetermined weight part. As raw materials for this additive, for example, CaCO ₃ reagent grade manufactured by Kishida Chemical Co., Ltd., SrCO ₃ reagent grade manufactured by Kishida Chemical Co., Ltd., and ZnO 3N grade manufactured by Kojundo Chemical Co., Ltd. Is used.

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

Tables 2 to 4 show the measurement results of the dielectric properties of the test samples prepared with different amounts of each of the above-mentioned additives by the Hacki-Coleman method near the measurement frequency of 3 GHz.

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 and 52 are comparative examples outside the scope of the present invention.

As is clear from Tables 2 to 4, the Q value is improved by the addition of each additive. However, the Q value increases as the amount of addition increases, but the dielectric constant decreases. Therefore, the additive 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⁺ . According to the third embodiment, TiO ₂ , Li ₂ CO ₃ , Na ₂ CO ₃ , N
A sample was prepared by using a high purity powder of d ₂ O ₃ and changing the mixing ratio of each component in the same manner as in the first embodiment. Table 5 shows the dielectric properties of the fabricated sample measured at a measurement frequency of about 3 GHz using the Hacki-Coleman method. In the table, w, x,
y and z show a molar fraction, 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.

The values of w, x, y, and z can be set 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%

In particular, when w, x, y, and z are set in the following ranges, good dielectric properties can be obtained. 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 a composition formula (A 1 ⁺ · A ′).
¹⁺ ) ₂ O—B ³⁺ ₂ O ₃ —TiO ₂ , where A ¹⁺ is Li
^1+, Na ¹⁺ as A ^'1+, Sm ³⁺ is selected as B ^3+. The fourth embodiment uses TiO 2 as a raw material.
_2. Samples were prepared using high-purity powders of Li ₂ CO ₃ , Na ₂ CO ₃ , and Sm ₂ O _{3 in} the same manner as in the first embodiment, changing the mixing ratio of each component. Tables 6 and 7 show the dielectric properties of the prepared samples measured at a measurement frequency of about 3 GHz using the Hacki-Coleman method. In addition, w, x, y, and z in a table | surface show a molar fraction, and w + x + y + z = 100 mol%.

[0059]

[Table 6]

[0060]

[Table 7]

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

As is clear from Tables 6 and 7, the composition formula w · Li ₂ Ox · Na ₂ Oy · 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 No. 67 lacking Li ₂ O, the temperature coefficient τ of the resonance frequency was
The absolute value of f is slightly larger.

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, when w, x, y, and z are set in the following ranges, good dielectric properties can be obtained. 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 embodiment of the present invention has 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 selected, and Nd ³⁺ is selected as B ′ ³⁺ .
The fifth embodiment uses TiO ₂ , Li ₂ CO
₃ , high purity powders of Na ₂ CO ₃ , Nd ₂ O ₃ and SmO ₃ were used, and the mixing ratio of each component was changed in the same manner as in the first embodiment. Table 8 shows the dielectric properties of the fabricated sample measured at a measurement frequency of around 3 GHz using the Hacki-Coleman method. In the table, v, w, x, y, and z indicate mole fractions, and v
+ W + x + y + z = 100 mol%.

[0066]

[Table 8]

As is clear from Table 8, the composition formula is v · N
_{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.

V, w, x, y, and z can be set in 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%

In particular, when v, w, x, y, and 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 embodiment of the present invention has 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 selected, and Pr ³⁺ is selected as B ′ ³⁺ .
In the sixth embodiment, TiO ₂ , Li ₂ CO
₃ , high purity powders of Na ₂ CO ₃ , Nd ₂ O ₃ and Rr ₆ O ₁₁ were used, and the mixing ratio of each component was changed in the same manner as in the first embodiment. Table 9 shows the dielectric properties of the fabricated sample measured at a measurement frequency of around 3 GHz using the Hacki-Coleman method. In the table, v, w, x, y, and z indicate 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.

V, w, x, y, z can be set 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, and z are set in the following ranges, good dielectric properties 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, a seventh embodiment will be described. Seventh
The microwave porcelain composition of the embodiment of the present invention has the 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⁺ as B ³⁺ . The seventh embodiment uses TiO ₂ , Li ₂ CO ₃ , CaC as raw materials.
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. The prepared sample was measured at a measurement frequency of 3GH using the Hacki-Coleman method.
Table 10 shows the dielectric properties measured near z. In the table, w, x, y, and z indicate mole fractions, and vw + x + y + z =
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%) has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency.
Have a small and high Q value.

In particular, when w, x, y, and z are set in the following ranges, good dielectric properties can be obtained. 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, an eighth embodiment will be described. 8th
The microwave porcelain composition of the embodiment of the present invention has the composition formula A ¹⁺ ₂ O−
CaO-(In _{^{B 3+ 2 O 3 -TiO 2,}} L as A ¹⁺
Nd ³⁺ is selected as i ¹⁺ as B ³⁺ . In the eighth embodiment, TiO ₂ , Li ₂ CO ₃ , 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. The prepared sample was measured at a measurement frequency of 3GH using the Hacki-Coleman method.
Table 11 shows the dielectric properties measured near z. In the table, w, x, y, and z indicate mole fractions, and vw + x + y + z =
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%) has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency.
Have a small and 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%

In particular, when w, x, y, and z are set in the following ranges, good dielectric characteristics can be obtained. 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. Ninth
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 first example described above, and has a large dielectric constant ε and a temperature coefficient τf of the resonance frequency. Is obtained by mixing a porcelain composition (Na _1/2 · C ³⁺ _1/2 ) TiO ₃ having a large positive 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.
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 using the Hacki-Coleman method.

Tables 12 and 13 show the measurement results. 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.
₃ (C ³⁺ : Nd ³⁺ , Sm ³⁺ ), a dielectric constant ε, and a ceramic composition (Li _1/2 · B ³⁺ _1/2 ) TiO with a large temperature coefficient τf of the resonance frequency on the minus side ₃ (B ³⁺ : Nd ³⁺ , S
By mixing with m ³⁺ ), a ceramic 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 mixing ratio of (Li _1/2 · Sm _1/2 ) TiO ₃ and (Na _1/2 · Sm _1/2 ) TiO _3. It is a characteristic view showing a curve. Thus, by changing the mixing ratio, porcelain compositions having various characteristics can be obtained.

The porcelain compositions of the ninth embodiment shown in Tables 12 and 13 correspond to 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 positive side.
・ Nd _1/2 ) TiO ₃ or (Na _1/2・ Sm _1/2 ) TiO ₃
Are obtained by mixing Ti as each raw material
When the same porcelain composition as in the ninth embodiment is produced using high purity powders of O ₂ , LiCO ₃ , Na ₂ CO ₃ , Sm ₂ O ₃ and Nd ₂ O ₃ , the mixing ratio of the porcelain composition is shown in Table 14. As shown in Table 16 below, 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 numbers in parentheses of the sample numbers 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 plus 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 porcelain 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 Hacki-Coleman method at a measurement frequency of 3 GHz.
It is a result measured near z. Note that a and c in Table 17 are the same as in Tables 12 and 13.

[0097]

[Table 17]

Table 17 shows 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
FIG. 2 (B ³⁺ = Nd ³⁺ ) and FIG. 3 show characteristic curves of the dielectric constant ε and the temperature coefficient τf of the resonance frequency with respect to the mixing ratio with O ₃ .
(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,
A tenth embodiment using aTiO ₃ will be described.

The porcelain composition of the tenth embodiment shown in Table 17 is the same as the porcelain composition (Li _1/2 ) obtained in the first embodiment.
・ Nd _1/2 ) TiO ₃ or (Li _1/2・ Sm _1/2 ) TiO ₃
And CaTiO ₃ . Using these as raw materials, TiO ₂ , LiCO ₃ , Sm ₂ O ₃ , Nd ₂ O
₃ , the respective compounding ratios in the case of using high purity powder of CaCO ₃ are as shown in Tables 17 and 18. Identical. In Tables 18 to 19, the numbers in parentheses for the sample numbers 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 to 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, according to the second aspect of the present invention, Li
Dielectric porcelain composition containing ₂ O—Na ₂ O—Sm ₂ O ₃ —TiO ₂ as a main component 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, according to the third aspect of the present invention, the Nd
_{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.

Further, according to the fourth aspect of the present invention, Li
_The dielectric ceramic composition mainly composed of ₂ O—CaO—Sm ₂ O ₃ —TiO ₂ and the dielectric ceramic composition mainly composed of Li ₂ O—CaO—Nd ₂ O ₃ —TiO ₂ have a high dielectric constant. And the temperature coefficient τf of the resonance frequency is small.

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

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of (Li _1/2 · Sm _1/2 ) TiO ₃ and (N
a _1/2 · Sm _1/2 ) Dielectric constant ε to compounding ratio with TiO ₃
FIG. 7 is a characteristic diagram showing a characteristic curve of a temperature coefficient τf of the resonance frequency.

FIG. 2 shows (Li _1/2 .Nd _1/2 ) TiO ₃ and Ca of the present invention.
FIG. 7 is a characteristic diagram showing characteristic curves of a dielectric constant ε and a temperature coefficient τf of a resonance frequency with respect to a mixing ratio with TiO ₃ .

FIG. 3 shows (Li ₁ / 2.Sm _1/2 ) TiO ₃ and Ca of the present invention.
FIG. 7 is a characteristic diagram showing characteristic curves of a dielectric constant ε and a temperature coefficient τf of a resonance frequency with respect to a mixing ratio with TiO ₃ .

 ──────────────────────────────────────────────────続 き Continuation of the front page (31) Priority claim number Japanese Patent Application No. 3-111913 (32) Priority date Hei 3 (1991) May 16 (33) Priority claim country Japan (JP) (31) Priority Claim No. 3-218872 (32) Priority date Hei 3 (1991) August 29 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-303293 (32) Priority (3) Priority claiming country Japan (JP) (31) Priority claim 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 2-18-18 Keihanhondori, Moriguchi City Inside Sanyo Electric Co., Ltd. (72) Inventor Juichi Takahashi 2-18-18 Keihanhondori, Moriguchi City Sanyo Electric Co., Ltd. (72) Inventor Kenichi Shibata 2-18 Keihanhondori, Moriguchi City Sanyo Electric Co., Ltd. (72) Inventor Black Kazuhiko Ki 2-18-18 Keihanhondori, Moriguchi City Sanyo Electric Co., Ltd.

Claims (15)

(57) [Claims] The composition formula is represented by (A ¹⁺ _1/2 · B ³⁺ _1/2 ) TiO ₃ , wherein A ¹⁺ is Li ¹⁺
In and, B ³⁺ is ^{Nd3 +, Sm3 +, Co3 +} , Pr3 + or is one microwave dielectric ceramic composition within the. 2. A dielectric ceramic composition having a composition formula represented by (Li ¹⁺ _1/2 · Nd ³⁺ _1/2 ) TiO ₃ , wherein (Li ¹⁺ _1/2 · Nd ^{3 +} _{1 / 2} ) A dielectric ceramic composition for microwaves, wherein one of MgO, CoO and ZnO is added in an amount of 10 parts by weight or less to 100 parts by weight of TiO ₃ . _3. A dielectric ceramic composition having a composition formula represented by (Li ¹⁺ _1/2 · Sm ³⁺ _1/2 ) TiO ₃ , wherein (Li ¹⁺ _1/2 · Sm ^{3 +} _{1 / 2} ) A dielectric ceramic composition for microwaves, in which any one of CaCO ₃ , SrCO _{3 and} ZnO is added in an amount of 10 parts by weight or less to 100 parts by weight of TiO ₃ . 4. A dielectric ceramic composition having a composition formula represented by (Li ¹⁺ _1/2 · Pr ³⁺ _1/2 ) TiO ₃ , wherein (Li ¹⁺ _1/2 · Pr ^{3 +} _{1 / 2} ) A dielectric ceramic composition for microwaves, wherein one of MgO, CoO and ZnO is added in an amount of 10 parts by weight or less based on 100 parts by weight of TiO ₃ . 5. The composition formula: ^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⁺ , B ³⁺ is Nd
A microwave dielectric porcelain composition of 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 the molar ratio is in a range of 0.0 mol ≤ x ≤ 17.0 mol% 0.0 mol <y ≤ 25.0 mol% 0.0 mol <z ≤ 80.0 mol%. Dielectric porcelain composition. 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. 6. The microwave according to claim 5, wherein the molar ratio is 0.0 mol ≦ x ≦ 17.0 mol% 0.0 mol <y ≦ 20.0 mol% 0.0 mol <z ≦ 75.0 mol%. Dielectric porcelain composition. 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
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, 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 dielectric material for microwave according to claim 8, wherein 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⁺ , 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 microwave according to claim 8, wherein 0.0 mol <z ≦ 75.0 mol%. 11. The composition formula is: w · A 1 ⁺ ₂ ^Ox · CaO-y · B ³⁺ ₂ O ₃ -z · TiO ₂
(However, w + x + y + z = 100% mol)
^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 are 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 microwave according to claim 11, wherein ≤ 80.0 mol%. 13. A ¹⁺ is Li ¹⁺ , B ³⁺ is Nd ³⁺ ,
w, x, y, z are 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 microwave according to claim 11, wherein ≤ 80.0 mol%. 14. The composition formula: 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 represented by aTiO ₃ (where 0 mol% x <x ≦ 100 mol%), wherein B ³⁺ is Nd ³⁺ or Sm ³⁺ .