JP2865927B2 - Method for producing dielectric porcelain composition - Google Patents
Method for producing dielectric porcelain compositionInfo
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- JP2865927B2 JP2865927B2 JP4025663A JP2566392A JP2865927B2 JP 2865927 B2 JP2865927 B2 JP 2865927B2 JP 4025663 A JP4025663 A JP 4025663A JP 2566392 A JP2566392 A JP 2566392A JP 2865927 B2 JP2865927 B2 JP 2865927B2
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Description
【０００１】[0001]
【産業上の利用分野】本発明は損失の小さな低誘電率の
誘電体磁器組成物及びその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition having low loss and a low dielectric constant, and a method for producing the same.
【０００２】[0002]
【従来の技術】損失の小さな低誘電率の誘電体磁器組成
物を誘電体層の材料に用いた磁器コンデンサは、一般
に、高周波回路におけるフィルター等に使用されてい
る。このような低誘電率の誘電体磁器組成物は一般的に
１２００〜１３００℃という高温で焼結されることが多
いので、これを積層磁器コンデンサの誘電体層の材料と
して使用する場合は、積層磁器コンデンサの内部電極の
材料にＰｔ，Ｐｄあるいはこれらの合金のような高融点
の金属を使う必要があった。2. Description of the Related Art A ceramic capacitor using a dielectric ceramic composition having a low loss and a low dielectric constant as a material of a dielectric layer is generally used for a filter in a high-frequency circuit. Since such a low dielectric constant dielectric porcelain composition is generally sintered at a high temperature of 1200 to 1300 ° C., when this is used as a material for a dielectric layer of a laminated porcelain capacitor, It has been necessary to use a high melting point metal such as Pt, Pd, or an alloy thereof as the material of the internal electrodes of the porcelain capacitor.
【０００３】[0003]
【発明が解決しようとする問題点】しかし、Ｐｔ，Ｐｄ
あるいはこれらの合金は電気伝導度が低く、これを内部
電極の材料として使用した積層磁器コンデンサを高周波
回路におけるフィルターに使用した場合は、損失が大き
くなり、Ｑが低下してしまうという欠点があった。この
ため、電気伝導度のより高いＡｇ，Ｃｕ等の金属を積層
磁器コンデンサの内部電極の材料として使用できるよう
に、１０００℃以下、好ましくは９００℃以下の温度の
焼成で緻密に焼結させることができ、しかも所望の電気
特性を備えている誘電体磁器組成物を開発する必要があ
った。However, Pt, Pd
Alternatively, these alloys have low electric conductivity, and when a laminated ceramic capacitor using this as a material of an internal electrode is used for a filter in a high-frequency circuit, there is a drawback that loss increases and Q decreases. . Therefore, in order to use a metal having a higher electric conductivity, such as Ag or Cu, as a material for the internal electrode of the laminated ceramic capacitor, it should be densely sintered by firing at a temperature of 1000 ° C. or less, preferably 900 ° C. or less. Therefore, it was necessary to develop a dielectric ceramic composition having the desired electrical characteristics.
【０００４】本発明の目的は、９００℃以下の温度の焼
成で緻密に焼結させることができ、しかも所望の電気特
性を備えている低誘電率の誘電体磁器組成物とその製造
方法を提供することにある。An object of the present invention is to provide a dielectric ceramic composition having a low dielectric constant, which can be densely sintered by firing at a temperature of 900 ° C. or less and which has desired electric characteristics, and a method for producing the same. Is to do.
【０００５】[0005]
【課題を解決するための手段】 本発明に係る誘電体磁
器組成物は、組成式：ａ（ｘＢａ−ｙＣａ−ｚＳｒ）Ｏ
−ｂＳｉＯ２−ｃ（ｍＨｆ−ｎＺｒ）Ｏ２−（ｄ／２）
Ａｌ２Ｏ３−ｅＴｉＯ２ で表わされる組成物を主成分とする焼結体からなるもの
である。Means for Solving the Problems The dielectric ceramic composition according to the present invention has a composition formula: a (xBa-yCa-zSr) O
-BSiO 2 -c (mHf-nZr) O 2 - (d / 2)
Al 2 O 3 -eTiO 2 And a sintered body mainly composed of the composition represented by
【０００６】ここで、５モル％≦ａ≦６０モル％とした
のは、ａが５モル％未満になったり、６０モル％を越え
たりすると、いずれの場合も、９００℃の温度の焼成で
緻密な焼結体が得られなくなるからである。また、１０
モル％≦ｂ≦７０モル％としたのは、ｂが１０モル％未
満になると組成物がガラス化せず、ｂが７０モル％を越
えると、９００℃の焼成で緻密な焼結体が得られなくな
るからである。Here, the reason that 5 mol% ≦ a ≦ 60 mol% is satisfied is that when a becomes less than 5 mol% or exceeds 60 mol%, in either case, firing at a temperature of 900 ° C. This is because a dense sintered body cannot be obtained. Also, 10
The reason that mol% ≦ b ≦ 70 mol% is that when b is less than 10 mol%, the composition does not vitrify, and when b exceeds 70 mol%, a dense sintered body is obtained by firing at 900 ° C. This is because it will not be possible.
【０００７】 また、９．２モル％≦ｃ≦３０モル％と
したのは、ｃが３０モル％を越えると、９００℃の焼成
で緻密な焼結体が得られなくなるからである。また、
２．３モル％≦ｄ≦３０モル％としたのは、ｄが３０モ
ル％を越えると、９００℃の焼成で緻密な焼結体が得ら
れなくなるからである。また、４．６モル％≦ｅ≦３０
モル％としたのは、ｅが３０モル％を越えると、９００
℃の焼成で緻密な焼結体が得られなくなるからである。The reason that 9.2 mol% ≦ c ≦ 30 mol% is that if c exceeds 30 mol%, a dense sintered body cannot be obtained by firing at 900 ° C. Also,
2.3 mol% ≦ d ≦ 30 mol% is because if d exceeds 30 mol%, a dense sintered body cannot be obtained by firing at 900 ° C. In addition, 4.6 mol% ≦ e ≦ 30
The reason for using mol% is that if e exceeds 30 mol%, 900%
This is because a dense sintered body cannot be obtained by firing at a temperature of ℃.
【０００８】以上説明したこの誘電体磁器組成物は、焼
成して酸化物となるＢａ，Ｃａ，Ｓｒ，Ｓｉ，Ｈｆ，Ｚ
ｒ，Ａｌ及びＴｉの各原料化合物の中の少なくともＢ
ａ，Ｃａ，Ｓｒ及びＳｉの各原料化合物を混合して加熱
溶融し、この溶融したものを急冷してガラス化し、この
ガラス化したものを微粉砕し、この微粉砕したものを含
めて全ての原料化合物の混合物を成形し、この成形した
ものを焼成する方法によって製造することができる。The above-described dielectric porcelain composition is obtained by firing Ba, Ca, Sr, Si, Hf, Z
At least B in each of the raw material compounds of r, Al and Ti
The raw material compounds of a, Ca, Sr and Si are mixed and melted by heating, the melted material is rapidly cooled to vitrify, and the vitrified material is finely pulverized. It can be produced by a method of molding a mixture of raw material compounds and firing the molded product.
【０００９】ここで、原料化合物としては、焼成して酸
化物となるＢａ，Ｃａ，Ｓｒ，Ｓｉ，Ｈｆ，Ｚｒ，Ａｌ
及びＴｉの各化合物を使用することができる。後述する
実施例では、原料化合物としてＢａＣＯ3 ，ＣａＣＯ
3 ，ＳｒＣＯ3 ，ＳｉＯ2 ，ＨｆＯ2 ，ＺｒＯ2 ，Ａｌ
2 Ｏ3 及びＴｉＯ2 を原料化合物として使用したが、加
熱によって酸化物となるものであればこれら以外の化合
物を使用できることはもちろんである。Here, as the raw material compound, Ba, Ca, Sr, Si, Hf, Zr, Al
And Ti can be used. In Examples described later, BaCO 3 , CaCO 3
3 , SrCO 3 , SiO 2 , HfO 2 , ZrO 2 , Al
Although 2 O 3 and TiO 2 were used as starting compounds, it goes without saying that other compounds can be used as long as they become oxides when heated.
【００１０】 また、各原料化合物は、式：ａ（ｘＢａ
−ｙＣａ−ｚＳｒ）Ｏ−ｂＳｉＯ２−ｃ（ｍＨｆ−ｎＺ
ｒ）Ｏ２−（ｄ／２）Ａｌ２Ｏ３−ｅＴｉＯ２ で表わされる割合で使用する。各原料化合物の割合の限
定理由は上述した誘電体磁器組成物の説明におけると全
く同様である。Further, each raw material compound has the formula: a (xBa
-YCa-zSr) O-bSiO 2 -c (mHf-nZ
r) O 2 - (d / 2) Al 2 O 3 -eTiO 2 Use at the rate represented by The reason for limiting the ratio of each raw material compound is exactly the same as in the description of the dielectric ceramic composition described above.
【００１１】更に、Ｈｆ，Ｚｒ，Ａｌ及びＴｉの各化合
物については、他の原料化合物とともにガラス化して使
用してもよいし、あるいはガラス化した他の原料化合物
に後から混合して使用してもよい。いずれの場合も所望
の誘電体磁器組成物を得ることができる。Further, the respective compounds of Hf, Zr, Al and Ti may be used after being vitrified together with other raw material compounds, or may be used after being mixed with other vitrified raw material compounds. Is also good. In any case, a desired dielectric porcelain composition can be obtained.
【００１２】[0012]
実施例１及び比較例１ まず、表１の試料No.1-1の場合について説明する。Ｂａ
ＣＯ3 ，ＣａＣＯ3 ，ＳｒＣＯ3 ，ＳｉＯ2 ，ＨｆＯ
2 ，ＺｒＯ2 ，Ａｌ2 Ｏ3 及びＴｉＯ2 を、表１の試料
No.1-1に示すモル比で秤量し、これらを水とともにボー
ルミルに入れ、湿式で十分に撹拌混合して混合物を得
た。ここで、ＨｆＯ2 とＺｒＯ2 の比率はＨｆＯ2 ：Ｚ
ｒＯ2 ＝５：５とした。Example 1 and Comparative Example 1 First, the case of Sample No. 1-1 in Table 1 will be described. Ba
CO 3 , CaCO 3 , SrCO 3 , SiO 2 , HfO
2 , ZrO 2 , Al 2 O 3 and TiO 2 were converted to the samples shown in Table 1.
The mixture was weighed at the molar ratio shown in No. 1-1, put into a ball mill together with water, and sufficiently stirred and mixed by a wet method to obtain a mixture. Here, the ratio of HfO 2 and ZrO 2 is HfO 2: Z
rO 2 = 5: 5.
【００１３】次に、この混合物を乾燥した後、坩堝に入
れて１７００℃に加熱し、溶融した混合物を水中に滴下
して急冷し、ガラスを得た。そして、このガラスを粉砕
して、平均粒径１μｍ程度の微粉末とし、このガラス粉
末に有機バインダー（ＰＶＡ）を加えて十分に混合し、
１ton/cm2 の圧力で直径１０mm、厚み１mmの円板状の成
形体を作製した。Next, after drying this mixture, it was put into a crucible and heated to 1700 ° C., and the molten mixture was dropped into water and quenched to obtain glass. Then, the glass is pulverized to a fine powder having an average particle size of about 1 μm, and an organic binder (PVA) is added to the glass powder and mixed sufficiently.
At a pressure of 1 ton / cm 2, a disk-shaped compact having a diameter of 10 mm and a thickness of 1 mm was prepared.
【００１４】次に、この成形体を焼成炉に入れ、大気雰
囲気中において４００〜６００℃で１０時間保持して成
形体中の有機バインダーを燃焼除去させ、その後、炉内
温度を９００℃まで上昇させ、この温度で２時間保持さ
せて成形体を焼結させた。Next, the molded body is placed in a firing furnace, and kept at 400 to 600 ° C. for 10 hours in an air atmosphere to burn off the organic binder in the molded body. Thereafter, the furnace temperature is raised to 900 ° C. The molded body was kept at this temperature for 2 hours to sinter the molded body.
【００１５】次に、この焼結させた成形体の表裏面に銀
ペーストを塗布して焼き付け、直径７mmの銀電極を表裏
面に備えた測定用の試料を得た。そして、この試料の電
気特性（比誘電率εr 及びＱ）を、１ＭＨｚ，１Ｖｒｍ
ｓ，２０℃の条件で測定した。結果は表１の試料No.1-1
の電気特性の欄に示す通りとなった。Next, a silver paste was applied to the front and back surfaces of the sintered compact and baked to obtain a sample for measurement having silver electrodes having a diameter of 7 mm on the front and back surfaces. Then, the electrical characteristics (relative permittivity ε r and Q) of this sample were measured at 1 MHz and 1 Vrm.
s, measured at 20 ° C. The results are shown in Sample No. 1-1 in Table 1.
In the column of electrical characteristics.
【００１６】以上、No.1-1の試料の作製方法及びその電
気特性の測定方法について述べたが、試料No.1-2〜1-23
についても、組成を表１に示すように変化させた他は、
No.1-1の試料と全く同一の方法で試料を作製し、全く同
一の方法でその電気特性を測定した。結果は表１の電気
特性の欄に示す通りとなった。The method for preparing the sample No. 1-1 and the method for measuring the electric characteristics of the sample have been described above.
, Also except that the composition was changed as shown in Table 1,
A sample was prepared by exactly the same method as the sample of No. 1-1, and its electrical characteristics were measured by the exactly same method. The results were as shown in the column of electrical characteristics in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】次に、表１に示す結果について、各Noの試
料の組成及びその電気特性等を参照しながら説明する。
まず、試料No.1-1〜1-3 に示すように、ａが６０モル％
で、Ｂａの量が０〜６０モル％の範囲（０≦ｘ≦１）に
ある場合は所望の電気特性の組成物が得られる。また、
試料No.1-4〜1-6 に示すように、ａが６０モル％で、Ｃ
ａの量が０〜６０モル％の範囲（０≦ｙ≦１）にある場
合は所望の電気特性の組成物が得られる。更に、試料N
o.1-7〜1-9 に示すように、ａが６０モル％で、Ｓｒの
量が０〜６０モル％の範囲（０≦ｚ≦１）にある場合は
所望の電気特性の組成物が得られる。Next, the results shown in Table 1 will be described with reference to the composition of each No. sample and its electrical characteristics.
First, as shown in Sample Nos. 1-1 to 1-3, a was 60 mol%.
When the amount of Ba is in the range of 0 to 60 mol% (0 ≦ x ≦ 1), a composition having desired electric characteristics can be obtained. Also,
As shown in Sample Nos. 1-4 to 1-6, when a was 60 mol% and C
When the amount of a is in the range of 0 to 60 mol% (0 ≦ y ≦ 1), a composition having desired electric characteristics can be obtained. Furthermore, sample N
As shown in o.1-7 to 1-9, when a is 60 mol% and the amount of Sr is in the range of 0 to 60 mol% (0 ≦ z ≦ 1), the composition having desired electric properties is obtained. Is obtained.
【００１９】また、試料No.1-1〜1-11に示すように、ａ
が５〜６０モル％の場合は所望の電気特性の組成物が得
られるが、試料No.1-12 に示すように、ａが３モル％に
なるか、試料No.1-13 に示すように、ａが６５モル％に
なると、組成物が９００℃で焼結しなくなる。従って、
ａの適正範囲は５〜６０モル％である。As shown in Sample Nos. 1-1 to 1-11, a
Is 5 to 60 mol%, a composition having desired electric characteristics can be obtained. However, as shown in Sample No. 1-12, a becomes 3 mol% or as shown in Sample No. 1-13. When a becomes 65 mol%, the composition does not sinter at 900 ° C. Therefore,
The appropriate range for a is 5 to 60 mol%.
【００２０】次に、試料No.1-15,1-16に示すように、ｂ
が１０〜７０モル％の場合は所望の電気特性の組成物が
得られるが、試料No.1-14 に示すように、ｂが５モル％
になると組成物がガラス化せず、また、試料No.1-17 に
示すように、ｂが７５モル％になると、組成物が１７０
０℃で溶融しなくなる。従って、ｂの適正範囲は１０〜
７０モル％である。Next, as shown in Sample Nos. 1-15 and 1-16, b
Is 10 to 70 mol%, a composition having desired electric characteristics can be obtained. However, as shown in Sample No. 1-14, b is 5 mol%.
When b becomes 75 mol%, as shown in Sample No. 1-17, the composition does not vitrify.
No melting at 0 ° C. Therefore, the appropriate range of b is 10 to
70 mol%.
【００２１】次に、試料No.1-18 に示すように、ｃが３
０モル％の場合は所望の電気特性の組成物が得られる
が、試料No.1-19 に示すように、ｃが３５モル％になる
と、組成物が９００℃で焼結しなくなる。従って、ｃの
適正範囲は少なくとも３０モル％以下である。Next, as shown in Sample No. 1-18, c was 3
In the case of 0 mol%, a composition having desired electric characteristics can be obtained. However, as shown in Sample No. 1-19, when c becomes 35 mol%, the composition does not sinter at 900 ° C. Therefore, the appropriate range of c is at least 30 mol% or less.
【００２２】次に、試料No.1-20 に示すように、ｄが３
０モル％の場合は所望の電気特性の組成物が得られる
が、試料No.1-21 に示すように、ｄが３５モル％になる
と、組成物が９００℃で焼結しなくなる。従って、ｄの
適正範囲は少なくとも３０モル％以下である。Next, as shown in Sample No. 1-20, d was 3
In the case of 0 mol%, a composition having desired electrical characteristics can be obtained, but as shown in Sample No. 1-21, when d becomes 35 mol%, the composition does not sinter at 900 ° C. Therefore, the appropriate range of d is at least 30 mol% or less.
【００２３】次に、試料No.1-22 に示すように、ｅが３
０モル％の場合は所望の電気特性の組成物が得られる
が、試料No.1-23 に示すように、ｅが３５モル％になる
と、組成物が９００℃で焼結しなくなる。従って、ｅの
適正範囲は少なくとも３０モル％以下である。Next, as shown in Sample No. 1-22, e was 3
In the case of 0 mol%, a composition having desired electric characteristics can be obtained. However, as shown in Sample No. 1-23, when e becomes 35 mol%, the composition does not sinter at 900 ° C. Therefore, the appropriate range of e is at least 30 mol% or less.
【００２４】実施例２及び比較例２ 実施例１で使用したものと同様の原料化合物を、ＴｉＯ
2 を除き、表２に示す割合で秤量して混合し、実施例１
と同様に加熱溶融して急冷し、得られたガラスにＴｉＯ
2 を表２に示す割合で加え、これらを湿式で粉砕混合し
て混合物を得た。以後は、この混合物を用いて、実施例
１と同様の手順で測定用の試料を作製し、その電気特性
を測定した。結果は表２の電気特性の欄に示す通りとな
った。この結果によれば、実施例２及び比較例２のよう
にして製造した誘電体磁器組成物も実施例１及び比較例
１の場合と全く同様の傾向を示した。しかして、実施例
２及び比較例２ではＴｉＯ2 を他の原料化合物とともに
ガラス化しなくても実施例１及び比較例１の場合と同様
の結果が得られることがわかる。Example 2 and Comparative Example 2 The same starting compound as used in Example 1 was
2 except, were weighed and mixed in proportions shown in Table 2, Example 1
Heating and melting in the same manner as described above, and quenching,
2 were added at the ratios shown in Table 2, and these were pulverized and mixed by a wet method to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 2. According to the results, the dielectric ceramic compositions manufactured as in Example 2 and Comparative Example 2 showed exactly the same tendency as in Example 1 and Comparative Example 1. Thus, it can be seen that in Example 2 and Comparative Example 2, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying TiO 2 together with other raw material compounds.
【００２５】[0025]
【表２】 [Table 2]
【００２６】実施例３及び比較例３ 実施例１で使用したものと同様の原料化合物を、Ａｌ2
Ｏ3 を除き、表３に示す割合で秤量して混合し、実施例
１と同様に加熱溶融して急冷し、得られたガラスにＡｌ
2 Ｏ3 を表３に示す割合で加え、湿式で粉砕混合して混
合物を得た。以後は、この混合物を用いて、実施例１と
同様の手順で測定用の試料を作製し、その電気特性を測
定した。結果は表３の電気特性の欄に示す通りとなっ
た。この結果によれば、実施例３及び比較例３のように
して製造した誘電体磁器組成物も実施例１及び比較例１
の場合と全く同様の傾向を示した。しかして、実施例３
及び比較例３ではＡｌ2 Ｏ3 を他の原料化合物とともに
ガラス化しなくても実施例１及び比較例１の場合と同様
の結果が得られることがわかる。[0026] The same starting compound as used in Example 3 and Comparative Example 3 Example 1, Al 2
Except for O 3, they were weighed and mixed at the ratios shown in Table 3, heated and melted and quenched in the same manner as in Example 1 to obtain Al.
2 O 3 was added at the ratios shown in Table 3 and pulverized and mixed by a wet method to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 3. According to this result, the dielectric ceramic compositions manufactured as in Example 3 and Comparative Example 3 were also used in Example 1 and Comparative Example 1.
The same tendency as in the case of was shown. Thus, Embodiment 3
In Comparative Example 3, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying Al 2 O 3 together with other raw material compounds.
【００２７】[0027]
【表３】 [Table 3]
【００２８】実施例４及び比較例４ 実施例１で使用したものと同様の原料化合物を、ＨｆＯ
2 及びＺｒＯ2 を除き、表４に示す割合で秤量して混合
し、実施例１と同様に加熱溶融して急冷し、得られたガ
ラスにＨｆＯ2 及びＺｒＯ2 を表４に示す割合で加え、
湿式で粉砕混合して混合物を得た。以後は、この混合物
を用いて、実施例１と同様の手順で測定用の試料を作製
し、その電気特性を測定した。結果は表４の電気特性の
欄に示す通りとなった。この結果によれば、実施例４及
び比較例４のようにして製造した誘電体磁器組成物も実
施例１及び比較例１の場合と全く同様の傾向を示した。
しかして、実施例４及び比較例４ではＨｆＯ2 及びＺｒ
Ｏ2 を他の原料化合物とともにガラス化しなくても実施
例１及び比較例１の場合と同様の結果が得られることが
わかる。Example 4 and Comparative Example 4 The same starting compound as that used in Example 1 was prepared by using HfO
Except for 2 and ZrO 2, they were weighed and mixed at the ratios shown in Table 4, heated and melted and quenched in the same manner as in Example 1, and HfO 2 and ZrO 2 were added to the obtained glass at the ratios shown in Table 4. ,
The mixture was pulverized and mixed by a wet method to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 4. According to this result, the dielectric ceramic compositions manufactured as in Example 4 and Comparative Example 4 showed the same tendency as in Example 1 and Comparative Example 1.
Thus, in Example 4 and Comparative Example 4, HfO 2 and Zr
It can be seen that the same results as in Example 1 and Comparative Example 1 can be obtained even if O 2 is not vitrified with other raw material compounds.
【００２９】[0029]
【表４】 [Table 4]
【００３０】実施例５及び比較例５ 実施例１で使用したものと同様の原料化合物を、Ａｌ2
Ｏ3 及びＴｉＯ2 を除き、表５に示す割合で秤量して混
合し、実施例１と同様に加熱溶融して急冷し、得られた
ガラスにＡｌ2 Ｏ3 及びＴｉＯ2 を表５に示す割合で加
え、湿式で粉砕混合して混合物を得た。以後は、この混
合物を用いて、実施例１と同様の手順で測定用の試料を
作製し、その電気特性を測定した。結果は表５の電気特
性の欄に示す通りとなった。この結果によれば、実施例
５及び比較例５のようにして製造した誘電体磁器組成物
も実施例１及び比較例１の場合と全く同様の傾向を示し
た。しかして、実施例５及び比較例５ではＡｌ2 Ｏ3 及
びＴｉＯ2 を他の原料化合物とともにガラス化しなくて
も実施例１及び比較例１の場合と同様の結果が得られる
ことがわかる。Example 5 and Comparative Example 5 The same starting compound as used in Example 1 was prepared by using Al 2
Except for O 3 and TiO 2, they were weighed and mixed at the ratios shown in Table 5, heated and melted and quenched in the same manner as in Example 1, and Al 2 O 3 and TiO 2 were shown in Table 5 in the obtained glass The mixture was added at a ratio and wet-milled to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 5. According to the results, the dielectric ceramic compositions manufactured as in Example 5 and Comparative Example 5 showed the same tendency as in Example 1 and Comparative Example 1. Thus, it can be seen that in Example 5 and Comparative Example 5, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying Al 2 O 3 and TiO 2 together with other raw material compounds.
【００３１】[0031]
【表５】 [Table 5]
【００３２】実施例６及び比較例６ 実施例１で使用したものと同様の原料化合物を、ＨｆＯ
2 ，ＺｒＯ2 及びＴｉＯ2 を除き、表６に示す割合で秤
量して混合し、実施例１と同様に加熱溶融して急冷し、
得られたガラスにＨｆＯ2 ，ＺｒＯ2 及びＴｉＯ2 を表
６に示す割合で加え、湿式で粉砕混合して混合物を得
た。以後は、この混合物を用いて、実施例１と同様の手
順で測定用の試料を作製し、その電気特性を測定した。
結果は表６の電気特性の欄に示す通りとなった。この結
果によれば、実施例６及び比較例６のようにして製造し
た誘電体磁器組成物も実施例１及び比較例１の場合と全
く同様の傾向を示した。しかして、実施例６及び比較例
６ではＨｆＯ2 ，ＺｒＯ2 及びＴｉＯ2 を他の原料化合
物とともにガラス化しなくても実施例１及び比較例１の
場合と同様の結果が得られることがわかる。Example 6 and Comparative Example 6 The same starting compound as used in Example 1 was prepared by using HfO
Except for 2 , ZrO 2 and TiO 2, they were weighed and mixed at the ratios shown in Table 6, heated and melted and quenched as in Example 1,
HfO 2 , ZrO 2 and TiO 2 were added to the obtained glass at the ratios shown in Table 6, and the mixture was pulverized and mixed by a wet method to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured.
The results were as shown in the column of electrical characteristics in Table 6. According to this result, the dielectric ceramic compositions manufactured as in Example 6 and Comparative Example 6 showed the same tendency as in Example 1 and Comparative Example 1. Thus, it can be seen that in Example 6 and Comparative Example 6, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying HfO 2 , ZrO 2 and TiO 2 together with other raw material compounds.
【００３３】[0033]
【表６】 [Table 6]
【００３４】実施例７及び比較例７ 実施例１で使用したものと同様の原料化合物を、ＨｆＯ
2 ，ＺｒＯ2 及びＡｌ2 Ｏ3 を除き、表７に示す割合で
秤量して混合し、実施例１と同様に加熱溶融して急冷
し、得られたガラスにＨｆＯ2 ，ＺｒＯ2 及びＡｌ2 Ｏ
3 を表７に示す割合で加え、湿式で粉砕混合して混合物
を得た。以後は、この混合物を用いて、実施例１と同様
の手順で測定用の試料を作製し、その電気特性を測定し
た。結果は表７の電気特性の欄に示す通りとなった。こ
の結果によれば、実施例７及び比較例７のようにして製
造した誘電体磁器組成物も実施例１及び比較例１の場合
と全く同様の傾向を示した。しかして、実施例７及び比
較例７ではＨｆＯ2 ，ＺｒＯ2 及びＡｌ2 Ｏ3 を他の原
料化合物とともにガラス化しなくても実施例１及び比較
例１の場合と同様の結果が得られることがわかる。Example 7 and Comparative Example 7 The same starting compound as that used in Example 1 was prepared by using HfO
Except for ZrO 2 , ZrO 2 and Al 2 O 3, they were weighed and mixed at the ratios shown in Table 7, heated and melted and quenched in the same manner as in Example 1, and HfO 2 , ZrO 2 and Al 2 O 3 were added to the obtained glass. O
3 was added in the ratio shown in Table 7, and the mixture was pulverized and mixed by a wet method to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 7. According to this result, the dielectric ceramic compositions manufactured as in Example 7 and Comparative Example 7 showed the same tendency as in Example 1 and Comparative Example 1. Thus, in Example 7 and Comparative Example 7, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying HfO 2 , ZrO 2 and Al 2 O 3 together with other raw material compounds. Recognize.
【００３５】[0035]
【表７】 [Table 7]
【００３６】実施例８及び比較例８ 実施例１で使用したものと同様の原料化合物を、ＨｆＯ
2 ，ＺｒＯ2 ，Ａｌ2Ｏ3 及びＴｉＯ2 を除き、表８に
示す割合で秤量して混合し、実施例１と同様に加熱溶融
して急冷し、得られたガラスにＨｆＯ2 ，ＺｒＯ2 ，Ａ
ｌ2 Ｏ3 及びＴｉＯ2 を表８に示す割合で加え、湿式で
粉砕混合して混合物を得た。以後は、この混合物を用い
て、実施例１と同様の手順で測定用の試料を作製し、そ
の電気特性を測定した。結果は表８の電気特性の欄に示
す通りとなった。この結果によれば、実施例８及び比較
例８のようにして製造した誘電体磁器組成物も実施例１
及び比較例１の場合と全く同様の傾向を示した。しかし
て、実施例８及び比較例８ではＨｆＯ2 ，ＺｒＯ2 ，Ａ
ｌ2 Ｏ3 及びＴｉＯ2 を他の原料化合物とともにガラス
化しなくても実施例１及び比較例１の場合と同様の結果
が得られることがわかる。Example 8 and Comparative Example 8 The same starting compound as used in Example 1 was prepared by using HfO
Except for 2 , ZrO 2 , Al 2 O 3 and TiO 2, they were weighed and mixed at the ratios shown in Table 8, heated and melted and quenched in the same manner as in Example 1, and HfO 2 , ZrO 2 were added to the obtained glass. , A
l 2 O 3 and TiO 2 were added at the ratios shown in Table 8 and wet-milled to obtain a mixture. Thereafter, using this mixture, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 8. According to this result, the dielectric ceramic compositions manufactured as in Example 8 and Comparative Example 8 were also obtained in Example 1.
And the same tendency as in the case of Comparative Example 1. In Example 8 and Comparative Example 8, HfO 2 , ZrO 2 , A
It can be seen that the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying l 2 O 3 and TiO 2 together with other raw material compounds.
【００３７】[0037]
【表８】 [Table 8]
【００３８】実施例９及び比較例９ 実施例１で使用したものと同様の原料化合物を表９に示
す割合で秤量して混合し、実施例１と同様に加熱溶融し
て急冷し、ガラス粉末を得た。但し、ＨｆＯ2とＺｒＯ2
の比率はＨｆＯ2 ：ＺｒＯ2 ＝１：９とした。以後
は、このガラス粉末を用いて、実施例１と同様の手順で
測定用の試料を作製し、その電気特性を測定した。結果
は表９の電気特性の欄に示す通りとなった。この結果に
よれば、実施例９及び比較例９のようにして製造した誘
電体磁器組成物も実施例１及び比較例１の場合と全く同
様の傾向を示した。Example 9 and Comparative Example 9 The same starting compounds as those used in Example 1 were weighed at the ratios shown in Table 9, mixed, heated and melted and quenched as in Example 1 to obtain a glass powder. I got However, HfO 2 and ZrO 2
Was HfO 2 : ZrO 2 = 1: 9. Thereafter, using this glass powder, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 9. According to this result, the dielectric ceramic compositions manufactured as in Example 9 and Comparative Example 9 showed exactly the same tendency as those in Example 1 and Comparative Example 1.
【００３９】[0039]
【表９】 [Table 9]
【００４０】実施例１０及び比較例１０ 実施例１で使用したものと同様の原料化合物を表１０に
示す割合で秤量して混合し、実施例１と同様に加熱溶融
して急冷し、ガラス粉末を得た。但し、ＨｆＯ2 とＺｒ
Ｏ2 の比率はＨｆＯ2 ：ＺｒＯ2 ＝９：１とした。以後
は、このガラス粉末を用いて、実施例１と同様の手順で
測定用の試料を作製し、その電気特性を測定した。結果
は表１０の電気特性の欄に示す通りとなった。この結果
によれば、実施例１０及び比較例１０のようにして製造
した誘電体磁器組成物も実施例１及び比較例１の場合と
全く同様の傾向を示した。Example 10 and Comparative Example 10 The same starting compounds as those used in Example 1 were weighed and mixed at the ratios shown in Table 10, and heated and melted and quenched as in Example 1 to obtain a glass powder. I got However, HfO 2 and Zr
The ratio of O 2 was HfO 2 : ZrO 2 = 9: 1. Thereafter, using this glass powder, a sample for measurement was prepared in the same procedure as in Example 1, and its electrical characteristics were measured. The results were as shown in the column of electrical characteristics in Table 10. According to this result, the dielectric ceramic compositions manufactured as in Example 10 and Comparative Example 10 showed the same tendency as in Example 1 and Comparative Example 1.
【００４１】[0041]
【表１０】 [Table 10]
【００４２】[0042]
【発明の効果】 本発明によれば、従来よりも低い温度
の焼成で所望の電気的特性を有する低誘電率の誘電体磁
器組成物を得ることができるので、高周波用磁器コンデ
ンサの内部電極としてＡｇやＣｕのような電気伝導度の
良い、安価な材料を使用することができ、従って、従来
よりも更にＱの大きな電気的特性の優れた磁器コンデン
サを安価に提供することができるという効果がある。According to the present invention, a low dielectric constant dielectric ceramic composition having desired electrical characteristics can be obtained by firing at a lower temperature than in the prior art, so that it can be used as an internal electrode of a high frequency ceramic capacitor. An inexpensive material having good electric conductivity such as Ag or Cu can be used, and therefore, there is an effect that a ceramic capacitor having a larger Q and excellent electric characteristics can be provided at a low cost. is there.
【００４３】また、本発明によれば、従来よりも低い温
度の焼成で所望の電気的特性を有する誘電体磁器組成物
を得ることができるので、誘電体磁器組成物を焼結させ
るためのエネルギーコストを低下させることができ、従
って、従来よりも安価な磁器コンデンサを提供すること
ができるという効果がある。Further, according to the present invention, a dielectric ceramic composition having desired electrical characteristics can be obtained by firing at a lower temperature than in the prior art, so that energy for sintering the dielectric ceramic composition can be obtained. The cost can be reduced, and therefore, there is an effect that a porcelain capacitor which is less expensive than the conventional one can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 成田 直人 東京都台東区上野６丁目16番20号 太陽 誘電株式会社内 (72)発明者 水野 洋一 東京都台東区上野６丁目16番20号 太陽 誘電株式会社内 (72)発明者 増田 淳 東京都台東区上野６丁目16番20号 太陽 誘電株式会社内 (56)参考文献 特開 平１−102808（ＪＰ，Ａ) 特開 昭49−59298（ＪＰ，Ａ) 特公 昭43−2441（ＪＰ，Ｂ１) （株）東京化学同人「化学大辞典」 （1989年10月20日）Ｐ．1795 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoto Narita 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Yuden Co., Ltd. (72) Yoichi Mizuno 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Yuden (72) Inventor Jun Masuda 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Yuden Co., Ltd. (56) References JP-A-1-102808 (JP, A) JP-A-49-59298 (JP) , A) Tokiko Sho 43-2441 (JP, B1) Tokyo Chemical Industry Co., Ltd., “Chemical Encyclopedia” (October 20, 1989) 1795
Claims (2)
Ｏ−ｂＳｉＯ２−ｃ（ｍＨｆ−ｎＺｒ）Ｏ２−（ｄ／
２）Ａｌ２Ｏ３−ｅＴｉＯ２ で表わされる組成物を主成分とする焼結体からなること
を特徴とする誘電体磁器組成物。1. Composition formula: a (xBa-yCa-zSr)
O-bSiO 2 -c (mHf- nZr) O 2 - (d /
2) Al 2 O 3 -eTiO 2 A dielectric ceramic composition comprising a sintered body containing a composition represented by the following formula as a main component:
ｒ，Ｓｉ，Ｈｆ，Ｚｒ，Ａｌ及びＴｉの各原料化合物の
中の少なくともＢａ，Ｃａ，Ｓｒ及びｓｉの各原料化合
物を混合して加熱溶融する工程と、この溶融したものを
急冷してガラス化する工程と、このガラス化したものを
微粉砕する工程と、この微粉砕したものを含めて全ての
原料化合物の混合物を成形する工程と、この成形したも
のを焼成する工程とを備え、 前記各原料化合物が、式：ａ（ｘＢａ−ｙＣａ−ｚＳ
ｒ）Ｏ−ｂＳｉＯ２−ｃ（ｍＨｆ−ｎＺｒ）Ｏ２−（ｄ
／２）Ａｌ２Ｏ３−ｅＴｉＯ２ で表わされる割合になっていることを特徴とする誘電体
磁器組成物の製造方法。2. Ba, Ca, S which becomes an oxide by firing
a step of mixing at least Ba, Ca, Sr and si starting compounds among the starting compounds of r, Si, Hf, Zr, Al and Ti and heating and melting, and quenching and vitrifying the melted one; And a step of finely pulverizing the vitrified material, a step of molding a mixture of all the raw material compounds including the finely pulverized substance, and a step of firing the molded substance. The starting compound has the formula: a (xBa-yCa-zS
r) O-bSiO 2 -c ( mHf-nZr) O 2 - (d
/ 2) Al 2 O 3 -eTiO 2 A method for producing a dielectric porcelain composition, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025663A JP2865927B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025663A JP2865927B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05190017A JPH05190017A (en) | 1993-07-30 |
| JP2865927B2 true JP2865927B2 (en) | 1999-03-08 |
Family
ID=12172041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4025663A Expired - Fee Related JP2865927B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2865927B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4959298A (en) * | 1972-10-12 | 1974-06-08 | ||
| JPH01102808A (en) * | 1987-10-14 | 1989-04-20 | Murata Mfg Co Ltd | Dielectric porcelain compound for temperature compensation |
-
1992
- 1992-01-16 JP JP4025663A patent/JP2865927B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| （株）東京化学同人「化学大辞典」（１９８９年１０月２０日）Ｐ．１７９５ |
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| Publication number | Publication date |
|---|---|
| JPH05190017A (en) | 1993-07-30 |
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