JPS59214105A

JPS59214105A - Dielectric porcelain composition

Info

Publication number: JPS59214105A
Application number: JP58086936A
Authority: JP
Inventors: 州児伊藤
Original assignee: TDK Corp
Current assignee: TDK Corp
Priority date: 1983-05-18
Filing date: 1983-05-18
Publication date: 1984-12-04

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】産業上の利用分野本発明は、高安定度磁器コンデンサ材料として使用され
る誘電体磁器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to dielectric ceramic compositions used as high stability ceramic capacitor materials.

従来技術とその問題点高安定度磁器コンデンサ材料としては、従来から種々の
誘電体磁器組成物が公知である。これらの従来の誘電体
磁器組成物によって、例えば温度補償用積層磁器コンデ
ンサ等を製造する場合、Ａｇ−Ｐｄ合金等で形成される
内部電極に対する熱的悲影響を考えると、焼成温度をで
きるだけ低く抑えたい。ところが従来の誘電体磁器組成
物は、焼成温度が１３００〜１４００°Ｃ程度であり、
焼成温度をこれ以下にすると、誘電率が低下し、損失が
増え、誘電率の温度係数が大きくなり、満足な特性が得
られない。このため、例えば温度補償用積層磁器コンデ
ンサ等においては、特性の改善に限界を生じていた。Prior Art and its Problems Various dielectric ceramic compositions have been known as high stability ceramic capacitor materials. When manufacturing, for example, temperature-compensating multilayer ceramic capacitors using these conventional dielectric ceramic compositions, it is necessary to keep the firing temperature as low as possible, considering the negative thermal effects on the internal electrodes formed of Ag-Pd alloys, etc. sea bream. However, conventional dielectric ceramic compositions have a firing temperature of about 1300 to 1400°C;
If the firing temperature is lower than this, the dielectric constant decreases, loss increases, and the temperature coefficient of the dielectric constant increases, making it impossible to obtain satisfactory characteristics. For this reason, there has been a limit to the improvement of characteristics in, for example, temperature-compensating multilayer ceramic capacitors.

本発明の目的そこで本発明は上述する従来からの問題点を解決し、高
誘電率、低損失かつ誘電率の低温度係数を保ったままで
、焼成温度を２００〜３００℃程度も低下させ得るよう
にした焼結性の良好な誘電体磁器組成物を提供すること
を目的とする。Purpose of the Invention Therefore, the present invention solves the above-mentioned conventional problems, and makes it possible to lower the firing temperature by as much as 200 to 300°C while maintaining a high dielectric constant, low loss, and a low temperature coefficient of dielectric constant. The object of the present invention is to provide a dielectric ceramic composition with good sinterability.

本発明の構成上記目的を達成するため、本発明に係る誘電体磁器組成
物は、Ｘモル形ＢａＯ−Ｖモル％ＴｉＯλ−２モル％Ｎ
ｄ２Ｏ３の三成分系組成物において、Ｘ、ｙ及び２が５≦Ｘ≦２５５５≦ｙ≦８０１０≦２≦３０ｘ＋ｙ＋ｚ＝１００と表される組成物を主成分とし、副成分として、ａ重量
％ｐｂｏ　−ｂ重量％Ｂｉｚｌｈ　　　ｃ重量％ＳｉＯ
λ−８重量％ＺｎＯにおいて、ａ、ｂ、ｃ及びｄが０≦
ａ≦９５０≦ｂ≦９５５≦Ｃ≦２００≦ｄ≦２０ａ＋　　ｂ＋ｃ＋ｄ＝　　１　００と表される焼結助材を５重量％乃至２０重量％含有する
ことを特徴とする。Structure of the Present Invention In order to achieve the above object, the dielectric ceramic composition according to the present invention has an X molar type BaO-V mol%TiOλ-2 mol%N
In the ternary composition of d2O3, the main component is a composition in which X, y, and 2 are expressed as 5≦X≦25 55≦y≦80 10≦2≦30 x+y+z=100, and as a subcomponent, a weight %pbo-bwt%Bizlhcwt%SiO
In λ-8 wt% ZnO, a, b, c and d are 0≦
It is characterized by containing 5% by weight to 20% by weight of a sintering aid expressed as a≦95 0≦b≦95 5≦C≦20 0≦d≦20 a+b+c+d=100.

かかる組成の誘電体磁器組成物は、高話・電率、低損失
かつ誘電率の低温度係数を保持したままで、焼成温度を
１１００°Ｃ前後と、従来より２００〜３００℃も低く
することができ、例えば７０重量％Ａｇ−３０重量％Ｐ
ｄ合金を内部電極とする温度補償用積層チップコンデン
サを製造するのに好適な誘電体磁器組成物が得られるこ
とが解った。A dielectric ceramic composition having such a composition can be fired at a firing temperature of around 1100°C, which is 200 to 300°C lower than conventional methods, while maintaining high electrical conductivity, low loss, and a low temperature coefficient of dielectric constant. For example, 70% Ag-30% P
It has been found that a dielectric ceramic composition suitable for manufacturing a temperature-compensating multilayer chip capacitor using a d-alloy as an internal electrode can be obtained.

以下実施例により、本発明の内容を具体的に説明する。The content of the present invention will be specifically explained below with reference to Examples.

実施例本発明の誘電体磁器組成物を得る出発原料として、Ｂａ
ＣＯ３，ＴｉＯ２、Ｎｄ、−ＯＢ、　ＰｂＯ、Ｂｉ２Ｏ
５、５ｉＯ１、ＺｎＯの各粉末を用いた。なおここで用
いた原料粉末は、９５％Ｎｄｚ　ＯＢ　を除いて、何れ
も純度９８％以上のものを使用した。Examples As a starting material for obtaining the dielectric ceramic composition of the present invention, Ba
CO3, TiO2, Nd, -OB, PbO, Bi2O
5, 5iO1, and ZnO powders were used. Note that all of the raw material powders used here had a purity of 98% or higher, except for 95% Ndz OB .

次に主成分となるＢａＺＯ３、Ｔｉ０ｚ、ＮｄｚＯｓ　
ノ各粉末を表１の組成範囲となるように秤量し、これを
ボールミル中で４昆合処理した。次に濾過乾燥させて、
直径６０１、高さ５０ｍｍの円柱状に加圧成形した後、
１１５０°Ｃ乃至１２５０°Ｃの温度条件で、２時間、
空気中で仮焼を行ない、粉砕した。Next, the main components are BaZO3, Ti0z, and NdzOs.
Each powder was weighed so as to have the composition range shown in Table 1, and subjected to four-combining treatment in a ball mill. Then filter and dry
After pressure molding into a cylindrical shape with a diameter of 601 mm and a height of 50 mm,
2 hours at a temperature of 1150°C to 1250°C.
It was calcined in air and pulverized.

一方、焼結助材であるＰｂＯ、ｓｉ、ｏ３、Ｓ＋　Ｏｌ
　、ＺｎＯを表１の組成範囲となるように秤量し、これ
を前δ東生成分粉砕粉末に加え、ボールミル中で混自合処理した。次に濾過乾燥させて、直径１６．５ｆｆ１
ｍの円板に加圧成形した後、１０５０°Ｃ乃至１１５０
°Ｃの温度条件で２時間焼成した。このようにして得ら
れた誘電体磁器の両面に銀電極を焼付けて磁器コンデン
サとした。この磁器コンデンサはＮ００２〜Ｎ０．１０
として表１に示しである。次にこれらの磁器コンデンサ
試料の誘電率ε、誘電損失ｔａｎ　δ及び誘電率の温度
係数ｐｐｍ／’Ｃを、−５５℃から＋１２５°Ｃの温度
範囲、周波数ＩＭΩの条件で測定した。イη・られた結
果の内、代表的な例を表１に示しである。なお、表１に
おいてＮＯ，１の試料はＢａＣＯ３、ＴｉＯ２、Ｎｄ２
０ａだけの組成に成る誘電体磁器組成物によって製造さ
れた磁器コンデンサであり、本発明に対する比較例であ
る。On the other hand, sintering aids PbO, si, o3, S+Ol
, ZnO were weighed to have the composition range shown in Table 1, added to the pulverized powder of the previous δ Tosei component, and mixed in a ball mill. Next, it is filtered and dried, and the diameter is 16.5ff1.
After pressure forming into a disc of 1050°C to 1150°C
It was baked for 2 hours at a temperature of °C. Silver electrodes were baked on both sides of the dielectric ceramic thus obtained to produce a ceramic capacitor. This ceramic capacitor is N002~N0.10
As shown in Table 1. Next, the dielectric constant ε, dielectric loss tan δ, and temperature coefficient of dielectric constant ppm/'C of these ceramic capacitor samples were measured under the conditions of a temperature range of -55°C to +125°C and a frequency of IMΩ. Table 1 shows typical examples of the results obtained. In addition, in Table 1, the samples of NO, 1 are BaCO3, TiO2, Nd2
This is a ceramic capacitor manufactured using a dielectric ceramic composition having a composition of only 0a, and is a comparative example to the present invention.

（以−ド余白）表１を見ると明らかなように、比較例たる試料Ｎ０１１
は誘電性はある程度の値を示しているが、焼成温度を１
３６０°Ｃの高い値に保つ必要がある。(Additional blank space) As is clear from Table 1, sample N011, which is a comparative example,
shows a certain level of dielectric property, but when the firing temperature is increased to 1
It is necessary to maintain the temperature at a high value of 360°C.

これに対して、焼結助材としてＰｂＯ、Ｂｉ２Ｏ３、Ｓ
ｉ　０２　　、　ＺｎＯを含有せしめた本発明に係る誘
電体磁器組成物によって製造された試料ＮＯ２〜１０は
、焼成温度が１１００−１１４０℃と、比較例より２０
０〜３００　’Ｏ程度も低いにも拘わらず、誘電率が高
く、誘電損失ｔａｎδが０．０１と非常に小さく、しか
も誘電率の温度係数も低い値を示している。On the other hand, as sintering aids PbO, Bi2O3, S
Samples NO2 to 10 manufactured using the dielectric ceramic composition according to the present invention containing i 02 and ZnO had a firing temperature of 1100-1140°C, which was 20°C compared to the comparative example.
Although it is as low as 0 to 300'O, it has a high dielectric constant, a very small dielectric loss tan δ of 0.01, and a low temperature coefficient of dielectric constant.

このような低焼成温度で優れた誘電性及び温度特性を示
す範囲は、７モル％ＢａＯ−’１モル％ＴｉＯλ−Ｚモ
ル％Ｎｄえ０！の三成分系組成物において、ｘ、ｙ及Ｕ
’　ｚが、５≦Ｘ≦２５５５≦ｙ≦８０１０≦Ｚ≦３０）（＋ｙ＋Ｚ＝１００と表される組成範囲内にあり、かつ副成分と［で、ａ重
量％ｐｂｏ　−ｂ重量％Ｂｉ２０３−ｃ重量％５ｉ０２
　　ｄ　爪部％ＺｎＯにおいて、ａ、ｂ、Ｃ及びｄが０≦ａ≦９５０≦ｂ≦９５５≦Ｃ≦２００≦ｄ≦２０ａ　＋　　ｂ　＋　ｃ　＋　ｄ　＝　　ｌ　　ＯＯと表
される焼結助材を、５重量％乃至２０重量％含有する組
成物に限定される。The range that exhibits excellent dielectric properties and temperature characteristics at such a low firing temperature is 7 mol%BaO-'1 mol%TiOλ-Z mol%Nde0! In the ternary composition of x, y and U
'z is within the composition range expressed as 5≦X≦25 55≦y≦80 10≦Z≦30) (+y+Z=100, and the subcomponents and -c weight%5i02
d In the nail part % ZnO, a, b, C and d are 0≦a≦95 0≦b≦95 5≦C≦20 0≦d≦20 a + b + c + d = l OO The composition is limited to a composition containing 5% to 20% by weight of the binder.

ｘ、ｙ、ｚの値が上記範囲外になると、誘電率が小さく
なるか、誘電損失が大きくなるか或いは誘電率の温度特
性が大きくなって、実用性を失う。If the values of x, y, and z are outside the above ranges, the dielectric constant becomes small, the dielectric loss becomes large, or the temperature characteristic of the dielectric constant becomes large, and practicality is lost.

次にａ、ｂ、Ｃ，ｄの値が上記範囲外になると、焼成温
度が高くなり、本発明の目的に合致しなくなる。また焼
結助材の含有量が５重量％以下になると、焼成温度が高
くなり、２０重量％以上になると誘電損失が大きくなる
か、或いは誘電率の温度係数が大きくなって実用性を失
う。Next, if the values of a, b, C, and d are outside the above ranges, the firing temperature will become high and the object of the present invention will not be met. Further, if the content of the sintering aid is less than 5% by weight, the firing temperature will be high, and if it is more than 20% by weight, the dielectric loss will increase or the temperature coefficient of the dielectric constant will increase, making it impractical.

本発明の効果以北述べたように、本発明に係る誘電体磁器組成物は、
Ｘモル形Ｂａ０−ｙモル形Ｔｉ０２−ｚモル形Ｎｄ２Ｏ
！ｌ　の三成分系組成物において、ｘ、ｙ及び２を限定
された所定の値に選足した組成物を主成分とし、これに
副成分として、ａ重量％ｐｂｏ　−ｂ重量％Ｂｉ２０Ｂ
−ｃ重量％５ｉ０２ｄ重量％ＺｎＯにおいて、ａ、ｂ、
ｃ及びｄを所定の値に限定した焼結助材を、５重量％乃
至２０重量％含有させたことを特徴とするから、高誘電
率、低損失かつ誘電率の低温度係数を保ったままで、焼
成温度を２００〜３００°Ｃ程度も低下させ得るように
した焼結性の良好な誘電体磁器組成物を提供することが
できる。As described above, the dielectric ceramic composition according to the present invention has the following effects:
X molar form Ba0-y molar form Ti02-z molar form Nd2O
! In the ternary composition of l, the main component is a composition in which x, y, and 2 are selected to a limited predetermined value, and as a subcomponent, a weight % pbo - b weight % Bi20B
-c wt% 5i02d wt% ZnO, a, b,
Since it is characterized by containing 5% to 20% by weight of sintering aids that limit c and d to predetermined values, it maintains high dielectric constant, low loss, and low temperature coefficient of dielectric constant. , it is possible to provide a dielectric ceramic composition with good sinterability and which can lower the firing temperature by as much as 200 to 300°C.

Claims

【特許請求の範囲】[Claims]

（１）　Ｘモル形Ｂａ０−７モル％Ｔｉ０２−ｚモル形
Ｎｄ、　０３　の三成分系組成物において、ｘ、ｙ及び
２が、５≦Ｘ≦２５５５≦ｙ≦８０１Ｏ≦２≦３０ｘ＋ｙ＋ｚ−１ｏ。と表される組成物を主成分とし、副成分として、ａ重量
％ｐｂｏ−ｂｚ−量％Ｂｉ、　（ｈ　−ｃ　重量％５ｉ
（ｂ　−ｄ取量％ＺｎＯにおいて、ａ、ｂ、ｃ及びｄが
Ｏ≦ａ≦９５０≦ｂ≦９５５≦Ｃ≦２００≦ｄ≦２０ａ＋ｂ＋ｃ＋ｄ＝１０−０と表される焼結助材を５重量％乃至２０重量％含有する
ことを特徴とする誘電体磁器組成物。(1) In a ternary composition of X molar form Ba0-7 mol% Ti02-z molar form Nd, -1o. The main component is a composition expressed as , and the subcomponents are a weight % pbo-bz- amount % Bi, (h - c weight % 5i
(In the b - d amount of ZnO, a, b, c and d are expressed as O≦a≦95 0≦b≦95 5≦C≦20 0≦d≦20 a+b+c+d=10−0 A dielectric ceramic composition characterized by containing 5% to 20% by weight of a material.