JPH05190020A - Dielectric porcelain composition and manufacture thereof - Google Patents
Dielectric porcelain composition and manufacture thereofInfo
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- JPH05190020A JPH05190020A JP4025661A JP2566192A JPH05190020A JP H05190020 A JPH05190020 A JP H05190020A JP 4025661 A JP4025661 A JP 4025661A JP 2566192 A JP2566192 A JP 2566192A JP H05190020 A JPH05190020 A JP H05190020A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は損失の小さな低誘電率
の誘電体磁器組成物と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 low dielectric constant dielectric ceramic composition having a small loss 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 for a dielectric layer is generally used for a filter or the like in a high frequency circuit. Since such a low dielectric constant dielectric ceramic composition is often sintered at a high temperature of 1200 to 1300 ° C., when it is used as a material of a dielectric layer of a multilayer ceramic capacitor, it is laminated. 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。Problems to be Solved by the Invention However, Pt, Pd
Alternatively, these alloys have low electric conductivity, and when a laminated ceramic capacitor using the same as a material for an internal electrode is used as a filter in a high frequency circuit, there is a drawback that the loss becomes large and the Q decreases. .. Therefore, it is necessary to sinter densely by firing at a temperature of 1000 ° C. or lower, preferably 900 ° C. or lower so that a metal such as Ag or Cu having higher electric conductivity can be used as a material for the internal electrode of the laminated ceramic capacitor. It was necessary to develop a dielectric porcelain composition capable of achieving the above and having 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 low-dielectric-constant dielectric ceramic composition which can be densely sintered by firing at a temperature of 900 ° C. or lower, and a method for producing the same. 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 −ｃＺｒＯ2 −（ｄ／２）Ａｌ2 Ｏ3 −ｅＴ
ｉＯ2 （但し、５モル％≦ａ≦６０モル％、ｘ＋ｙ＋ｚ＝１、
１０モル％≦ｂ≦７０モル％、０モル％＜ｃ≦３０モル
％、０モル％＜ｄ≦３０モル％、０モル％＜ｅ≦３０モ
ル％、ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１００モル％）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。The dielectric ceramic composition according to the present invention has a composition formula: a (xBa-yCa-zSr) O-.
bSiO 2 -cZrO 2 - (d / 2) Al 2 O 3 -eT
iO 2 (however, 5 mol% ≦ a ≦ 60 mol%, x + y + z = 1,
10 mol% ≦ b ≦ 70 mol%, 0 mol% <c ≦ 30 mol%, 0 mol% <d ≦ 30 mol%, 0 mol% <e ≦ 30 mol%, a + b + c + d + e = 100 mol%) It is made of a sintered body containing a substance as a main component.
【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, 5 mol% ≤ a ≤ 60 mol% means that when a is less than 5 mol% or exceeds 60 mol%, in both cases, firing at a temperature of 900 ° C is required. This is because a dense sintered body cannot be obtained. Also, 10
Mol% ≤ b ≤ 70 mol% means 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. Because you will not be able to.
【０００７】また、０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、０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、０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 for setting 0 mol% <c ≦ 30 mol% is that if c exceeds 30 mol%, a dense sintered body cannot be obtained by firing at 900 ° C. Also, 0 mol%
<D ≦ 30 mol%, because if d exceeds 30 mol%, a dense sintered body cannot be obtained by firing at 900 ° C. Further, the reason that 0 mol% <e ≦ 30 mol% is set is that if e exceeds 30 mol%, a dense sintered body cannot be obtained by firing at 900 ° C.
【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，Ｚｒ，Ａ
ｌ及びＴｉの各原料化合物の中の少なくともＢａ，Ｃ
ａ，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 ceramic composition is Ba, Ca, Sr, Si, Zr, A which becomes an oxide by firing.
at least Ba, C in the raw material compounds of 1 and Ti
Each raw material compound of a, Sr, and Si is mixed and heated and melted, the molten material is rapidly cooled to vitrify, the vitrified material is finely pulverized, and all raw material compounds including the finely pulverized material It can be manufactured by a method of molding the mixture of and molding 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，Ｚｒ，Ａｌ及びＴ
ｉ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 ，ＣａＣＯ3 ，Ｓｒ
ＣＯ3 ，ＳｉＯ2 ，ＺｒＯ2，Ａｌ2 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 compounds, Ba, Ca, Sr, Si, Zr, Al and T, which become oxides by firing, are used.
Each compound of i can be used. In the examples described below, BaCO 3 , CaCO 3 , and Sr were used as raw material compounds.
CO 3 , SiO 2 , ZrO 2 , Al 2 O 3 and TiO 2
Although the above was used as a raw material compound, 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 −ｃＺｒＯ2 −（ｄ／
２）Ａｌ2 Ｏ3 −ｅＴｉＯ2 （但し、５モル％≦ａ≦６０モル％、ｘ＋ｙ＋ｚ＝１、
１０モル％≦ｂ≦７０モル％、０モル％＜ｃ≦３０モル
％、０モル％＜ｄ≦３０モル％、０モル％＜ｅ≦３０モ
ル％、ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１００モル％）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 -cZrO 2 - (d /
2) Al 2 O 3 -eTiO 2 (however, 5 mol% ≦ a ≦ 60 mol%, x + y + z = 1,
10 mol% ≦ b ≦ 70 mol%, 0 mol% <c ≦ 30 mol%, 0 mol% <d ≦ 30 mol%, 0 mol% <e ≦ 30 mol%, a + b + c + d + e = 100 mol%) Used in. The reason for limiting the proportion of each raw material compound is exactly the same as in the above description of the dielectric ceramic composition.
【００１１】更に、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, each compound of Zr, Al and Ti may be used after vitrification together with other raw material compounds, or may be mixed with other vitrified raw material compounds later and used. . In any case, the desired dielectric ceramic 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 ，ＺｒＯ
2 ，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。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 , ZrO
2 , Al 2 O 3 and TiO 2 were weighed in the molar ratios shown in Sample No. 1-1 of Table 1, and these were put in a ball mill together with water, and sufficiently stirred and mixed by a wet method to obtain a mixture.
【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 rapidly cooled to obtain glass. Then, this glass is pulverized into 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,
A disk-shaped molded body having a diameter of 10 mm and a thickness of 1 mm was produced at a pressure of 1 ton / cm 2 .
【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 in the air atmosphere at 400 to 600 ° C. for 10 hours to burn and remove the organic binder in the molded body, after which the furnace temperature is raised to 900 ° C. Then, the molded body was sintered by holding this temperature for 2 hours.
【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 this sintered compact and baked to obtain a measurement sample having silver electrodes with a diameter of 7 mm on the front and back surfaces. The electrical characteristics (relative permittivity ε r and Q) of this sample are 1 MHz, 1 Vrm.
It was measured under the conditions of s and 20 ° C. The result is sample No.1-1 in Table 1.
The electrical characteristics are shown in the column.
【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 electrical characteristics thereof have been described above. Sample Nos. 1-2 to 1-23
Also, except that the composition was changed as shown in Table 1,
A sample was prepared by the same method as the sample No. 1-1, and its electrical characteristics were measured by the same method. The results are 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 No.1-1 to 1-3, a is 60 mol%
Then, 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, a is 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. In addition, 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), a composition having desired electrical characteristics 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。Further, as shown in Sample Nos. 1-1 to 1-11, a
When the content is 5 to 60 mol%, a composition having desired electrical characteristics can be obtained, but as shown in sample No. 1-12, a becomes 3 mol% or as shown in sample No. 1-13. Moreover, when a is 65 mol%, the composition does not sinter at 900 ° C. Therefore,
The appropriate range of 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
When the content is 10 to 70 mol%, a composition having desired electrical characteristics can be obtained, but as shown in Sample No. 1-14, b is 5 mol%.
The composition did not vitrify, and as shown in Sample No. 1-17, when b was 75 mol%, the composition was 170%.
It no longer melts at 0 ° C. Therefore, the proper range of b is 10
It is 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 is 3
In the case of 0 mol%, a composition having desired electric characteristics can be obtained, but 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 is 3
In the case of 0 mol%, a composition having desired electric characteristics can be obtained, but as shown in sample No. 1-21, when d is 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 is 3
In the case of 0 mol%, a composition having desired electric characteristics can be obtained, but 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 A raw material compound similar to that used in Example 1 was added to TiO 2.
2 except, were weighed and mixed in proportions shown in Table 2, Example 1
In the same manner as above, heat melting, quenching, and quenching
2 was added at a ratio shown in Table 2, and these were pulverized and mixed by a wet method to obtain a mixture. After that, 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 are as shown in the column of electrical characteristics in Table 2. According to this result, the dielectric ceramic compositions produced as in Example 2 and Comparative Example 2 also showed the same tendency as in Example 1 and Comparative Example 1. Therefore, 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。Example 3 and Comparative Example 3 A raw material compound similar to that used in Example 1 was used as Al 2
The O 3, except, were weighed and mixed in proportions shown in Table 3, and quenched by heating and melting in the same manner as in Example 1, the resulting glass Al
2 O 3 was added at a ratio shown in Table 3 and pulverized and mixed by a wet method to obtain a mixture. After that, 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 are as shown in the column of electrical characteristics in Table 3. According to this result, the dielectric ceramic composition produced as in Example 3 and Comparative Example 3 was also used in Example 1 and Comparative Example 1.
The same tendency as in the above case was exhibited. Then, Example 3
Also, it is understood that 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、ＺｒＯ
2 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ＺｒＯ
2 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ＺｒＯ2 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 A raw material compound similar to that used in Example 1 was used as ZrO 2.
Except for 2 , the mixture was weighed and mixed at a ratio shown in Table 4, and
In the same manner as above, heat melting, quenching, and cooling the obtained glass with ZrO
2 was added at the ratio shown in Table 4 and pulverized and mixed by a wet method to obtain a mixture. After that, 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 are as shown in the electrical characteristics column of Table 4. According to this result, the dielectric ceramic compositions produced as in Example 4 and Comparative Example 4 also showed the same tendency as in Example 1 and Comparative Example 1. Therefore, it is understood that in Example 4 and Comparative Example 4, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying ZrO 2 together 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 A raw material compound similar to that used in Example 1 was used as Al 2
Except O 3 and TiO 2, they are weighed and mixed in the proportions shown in Table 5, heated and melted and quenched similarly to Example 1, and Al 2 O 3 and TiO 2 are shown in Table 5 in the obtained glass. The mixture was added in a ratio and pulverized and mixed by a wet method to obtain a mixture. After that, 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 are as shown in the column of electrical characteristics in Table 5. According to these results, the dielectric ceramic compositions produced as in Example 5 and Comparative Example 5 also showed the same tendency as in Example 1 and Comparative Example 1. Therefore, 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、ＺｒＯ
2 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ＺｒＯ2 及びＴｉ
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 6 and Comparative Example 6 A raw material compound similar to that used in Example 1 was used as ZrO 2.
Except for 2 and TiO 2, they were weighed and mixed in the ratios shown in Table 6, heated and melted and quenched similarly to Example 1, and ZrO 2 and TiO 2 were added to the obtained glass in the ratios shown in Table 6. ,
A wet mixture was pulverized and mixed to obtain a mixture. After that, 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 are as shown in the column of electrical characteristics in Table 6. According to these results, the dielectric ceramic compositions produced as in Example 6 and Comparative Example 6 also showed the same tendency as in Example 1 and Comparative Example 1.
Therefore, in Example 6 and Comparative Example 6, ZrO 2 and Ti
It can be seen that the same results as in the case of Example 1 and Comparative Example 1 can be obtained without vitrifying O 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、ＺｒＯ
2 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ＺｒＯ2 及びＡｌ2 Ｏ3 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 A raw material compound similar to that used in Example 1 was used as ZrO 2.
Except for 2 and Al 2 O 3, they were weighed and mixed in the proportions shown in Table 7, heated and melted and quenched in the same manner as in Example 1, and ZrO 2 and Al 2 O 3 were added to the obtained glass in Table 7. The mixture was added in the proportions shown and pulverized and mixed by a wet method to obtain a mixture. After that, 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 are shown in the column of electrical characteristics in Table 7. According to these results, the dielectric ceramic compositions produced as in Example 7 and Comparative Example 7 also showed the same tendency as in Example 1 and Comparative Example 1. Therefore, in Example 7 and Comparative Example 7, it is understood that the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying ZrO 2 and Al 2 O 3 together with other raw material compounds.
【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、ＺｒＯ
2 ，Ａｌ2 Ｏ3 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ＺｒＯ2 ，Ａｌ2 Ｏ3 及びＴｉＯ
2 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ＺｒＯ2 ，Ａｌ2Ｏ3 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 A raw material compound similar to that used in Example 1 was used as ZrO 2.
2 , Al 2 O 3 and TiO 2 were removed, and they were weighed and mixed in the proportions shown in Table 8, heated and melted and quenched in the same manner as in Example 1, and the obtained glass was ZrO 2 , Al 2 O 3 and TiO
2 was added at the ratio shown in Table 8 and pulverized and mixed by a wet method to obtain a mixture. After that, 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 are shown in the column of electrical characteristics in Table 8. According to this result, the dielectric ceramic compositions produced as in Example 8 and Comparative Example 8 also showed the same tendency as in Example 1 and Comparative Example 1. Therefore, in Example 8 and Comparative Example 8, the same results as in Example 1 and Comparative Example 1 can be obtained without vitrifying ZrO 2 , Al 2 O 3 and TiO 2 together with other raw material compounds. Recognize.
【００３７】[0037]
【表８】 [Table 8]
【００３８】[0038]
【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, it is possible to obtain a dielectric ceramic composition having a low dielectric constant having desired electric characteristics by firing at a temperature lower than conventional ones, and therefore, as an internal electrode of a high frequency ceramic capacitor. It is possible to use an inexpensive material having a good electric conductivity such as Ag or Cu, and therefore, it is possible to provide a porcelain capacitor having more excellent electrical characteristics than before, at a low cost.
【００３９】また、この発明によれば、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, it is possible to obtain a dielectric ceramic composition having desired electric characteristics by firing at a lower temperature than conventional ones, and therefore, the energy for sintering the dielectric ceramic composition can be obtained. Cost can be reduced,
Therefore, there is an effect that it is possible to provide a porcelain capacitor that is less expensive than conventional ones.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｇ 4/12 ３５８ 7135−5Ｅ (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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number for FI Technical indication H01G 4/12 358 7135-5E (72) Inventor Yoichi Mizuno 6-16-20 Ueno, Taito-ku, Tokyo No. Taiyo Induction Co., Ltd. (72) Inventor Atsushi Masuda No. 16-20 Ueno, Taito-ku, Tokyo Tokyo Induction Co., Ltd.
Claims (2)
Ｏ−ｂＳｉＯ2 −ｃＺｒＯ2 −（ｄ／２）Ａｌ2 Ｏ3 −
ｅＴｉＯ2 （但し、５モル％≦ａ≦６０モル％、 ｘ＋ｙ＋ｚ＝１、 １０モル％≦ｂ≦７０モル％、 ０モル％＜ｃ≦３０モル％、 ０モル％＜ｄ≦３０モル％、 ０モル％＜ｅ≦３０モル％、 ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１００モル％）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. A composition formula: a (xBa-yCa-zSr)
O-bSiO 2 -cZrO 2 - ( d / 2) Al 2 O 3 -
eTiO 2 (however, 5 mol% ≦ a ≦ 60 mol%, x + y + z = 1, 10 mol% ≦ b ≦ 70 mol%, 0 mol% <c ≦ 30 mol%, 0 mol% <d ≦ 30 mol%, 0 Mol% <e ≤ 30 mol%, a + b + c + d + e = 100 mol%) consisting of a sintered body containing a composition as a main component.
ｒ，Ｓｉ，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 −ｃＺｒＯ2 −（ｄ／２）Ａｌ2 Ｏ
3 −ｅＴｉＯ2 （但し、５モル％≦ａ≦６０モル％、 ｘ＋ｙ＋ｚ＝１、 １０モル％≦ｂ≦７０モル％、 ０モル％＜ｃ≦３０モル％、 ０モル％＜ｄ≦３０モル％、 ０モル％＜ｅ≦３０モル％、 ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１００モル％）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 and heating and melting at least each of the raw material compounds of Ba, Ca, Sr, and Si among the raw material compounds of r, Si, Zr, Al, and Ti, and a step of rapidly cooling the molten material to vitrify And a step of finely pulverizing the vitrified material, a step of molding a mixture of all raw material compounds including the finely ground material, and a step of firing the shaped material, each raw material compound Has the formula: a (xBa-yCa-zS
r) O-bSiO 2 -cZrO 2 - (d / 2) Al 2 O
3- eTiO 2 (however, 5 mol% ≦ a ≦ 60 mol%, x + y + z = 1, 10 mol% ≦ b ≦ 70 mol%, 0 mol% <c ≦ 30 mol%, 0 mol% <d ≦ 30 mol% , 0 mol% <e ≦ 30 mol%, a + b + c + d + e = 100 mol%), the method for producing a dielectric ceramic composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025661A JP2865925B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025661A JP2865925B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05190020A true JPH05190020A (en) | 1993-07-30 |
| JP2865925B2 JP2865925B2 (en) | 1999-03-08 |
Family
ID=12171991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4025661A Expired - Fee Related JP2865925B2 (en) | 1992-01-16 | 1992-01-16 | Method for producing dielectric porcelain composition |
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| Country | Link |
|---|---|
| JP (1) | JP2865925B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5639698A (en) * | 1993-02-15 | 1997-06-17 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
| US6997985B1 (en) * | 1993-02-15 | 2006-02-14 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01102808A (en) * | 1987-10-14 | 1989-04-20 | Murata Mfg Co Ltd | Dielectric porcelain compound for temperature compensation |
-
1992
- 1992-01-16 JP JP4025661A patent/JP2865925B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01102808A (en) * | 1987-10-14 | 1989-04-20 | Murata Mfg Co Ltd | Dielectric porcelain compound for temperature compensation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5639698A (en) * | 1993-02-15 | 1997-06-17 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
| US5897347A (en) * | 1993-02-15 | 1999-04-27 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
| US6084247A (en) * | 1993-02-15 | 2000-07-04 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device having a catalyst enhanced crystallized layer |
| US6997985B1 (en) * | 1993-02-15 | 2006-02-14 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor, semiconductor device, and method for fabricating the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2865925B2 (en) | 1999-03-08 |
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