JPH0589723A - Dielectric porcelain composition - Google Patents
Dielectric porcelain compositionInfo
- Publication number
- JPH0589723A JPH0589723A JP3274542A JP27454291A JPH0589723A JP H0589723 A JPH0589723 A JP H0589723A JP 3274542 A JP3274542 A JP 3274542A JP 27454291 A JP27454291 A JP 27454291A JP H0589723 A JPH0589723 A JP H0589723A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- basic component
- mol
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は平坦な温度特性を有する
高誘電率系の誘電体磁器組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high dielectric constant type dielectric ceramic composition having flat temperature characteristics.
【０００２】[0002]
【従来の技術】平坦な温度特性を有する高誘電率系の誘
電体磁器組成物としては、例えばチタン酸バリウム（Ｂ
ａＴｉＯ3 ）に錫酸ビスマスなどのビスマス酸化物を添
加したもの（例１）、チタン酸バリウム（ＢａＴｉ
Ｏ3）に五酸化ニオブ（Ｎｂ2 Ｏ5）と酸化コバルト（Ｃ
ｏＯやＣｏ2 Ｏ3 など）を添加したもの（例２）、チタ
ン酸バリウム（ＢａＴｉＯ3 ）に五酸化ニオブ（Ｎｂ2
Ｏ5 ）と希土類（Ｌａ，Ｎｄ，Ｄｙなど）の酸化物を添
加したもの（例３）などが知られている。2. Description of the Related Art As a dielectric ceramic composition of high dielectric constant having flat temperature characteristics, for example, barium titanate (B
aTiO 3 ) to which bismuth oxide such as bismuth stannate is added (Example 1), barium titanate (BaTi 3
O 3) to niobium pentoxide (Nb 2 O 5) and cobalt oxide (C
oO and Co, such as 2 O 3) obtained by adding (Example 2), niobium pentoxide, barium titanate (BaTiO 3) (Nb 2
It is known that O 5 ) and an oxide of a rare earth (La, Nd, Dy, etc.) are added (Example 3).
【０００３】ところで、近年、電子回路の高密度化に伴
い、積層磁器コンデンサを更に小型化・大容量化するこ
とが求められている。積層磁器コンデンサを小型化・大
容量化する方法としては、誘電体層を形成している誘電
体磁器組成物自体の比誘電率εs を高める以外に、誘電
体層を薄層化・多層化することが知られている。そこ
で、上記誘電体磁器組成物を用いた積層磁器コンデンサ
についても小型化・大容量化のために誘電体層の薄層化
・多層化が図られている。By the way, in recent years, with the increasing density of electronic circuits, it has been required to further reduce the size and capacity of laminated ceramic capacitors. To reduce the size and increase the capacity of laminated porcelain capacitors, in addition to increasing the relative permittivity ε s of the dielectric porcelain composition that forms the dielectric layer, the dielectric layer can be thinned or multilayered. Is known to do. Therefore, in order to reduce the size and increase the capacity of a laminated ceramic capacitor using the above-mentioned dielectric ceramic composition, the dielectric layer has been thinned / multilayered.
【０００４】[0004]
【発明が解決しようとする課題】しかし、例１の誘電体
磁器組成物は比誘電率εs 自体が１０００〜２０００と
かなり低いので、誘電体層を薄層化・多層化しても積層
磁器コンデンサの小型化・大容量化には限界があった。However, the dielectric ceramic composition of Example 1 has a relatively low relative permittivity ε s of 1000 to 2000, so that even if the dielectric layer is thinned or multilayered, a laminated ceramic capacitor is obtained. There was a limit to miniaturization and large capacity.
【０００５】また、例２、３の誘電体磁器組成物につい
ても、誘電体層の薄層化・多層化に伴なって、同一の電
圧を印加した場合に単位厚さ当りにかかる電界強度が大
きくなるので、誘電体層を薄層化・多層化し過ぎると積
層磁器コンデンサの誘電体損失（以下、ｔａｎδ）が悪
化し、静電容量の温度変化率（以下、ＴＣ）が悪化する
という問題点があった。Also, regarding the dielectric ceramic compositions of Examples 2 and 3, the electric field strength applied per unit thickness when the same voltage is applied is accompanied by the thinning and multilayering of the dielectric layers. Since it becomes large, the dielectric loss (hereinafter tan δ) of the laminated ceramic capacitor deteriorates if the dielectric layer is made too thin or multilayer, and the temperature change rate of capacitance (hereinafter TC) deteriorates. was there.
【０００６】本発明は積層磁器コンデンサの誘電体層の
一層当たりの厚みが１５μｍ以下になっても、２５℃に
おける比誘電率εs が４０００以上、−５５℃から１２
５℃の範囲におけるＴＣが±１５％以内、１５０℃で１
ｈｒ熱処理した後、１０００ｈｒ経過後の容量変化率が
３％以内、２５℃におけるｔａｎδが２．５％以内の誘
電体磁器組成物を提供することを目的とするものであ
る。According to the present invention, the relative dielectric constant ε s at 25 ° C. is 4000 or more, and the dielectric constant ε s at 25 ° C. is 12 to 15 ° C. even if the thickness of each dielectric layer of the laminated ceramic capacitor is 15 μm or less.
TC within ± 15% in the range of 5 ° C, 1 at 150 ° C
An object of the present invention is to provide a dielectric ceramic composition having a capacity change rate of 3% or less after 1000 hours of heat treatment for 3 hours and a tan δ at 25 ° C. of 2.5% or less.
【０００７】[0007]
【課題を解決するための手段】まず、本発明に係る誘電
体磁器組成物は基本成分と添加成分とからなり、基本成
分はＢａＴｉＯ3 −ＮｂＯ2.5 −ＮｉＯの三成分からな
り、添加成分は、ＣａＺｒＯ3 及び／又はＢａＺｒＯ
3 、Ｌｎ2 Ｏ3 （ＬｎはＧｄ，Ｓｍ及び／又はＮｄ）並
びにＭｎＯからなる。First, a dielectric ceramic composition according to the present invention comprises a basic component and an additive component, the basic component comprises three components of BaTiO 3 --NbO 2.5 --NiO, and the additive component is: CaZrO 3 and / or BaZrO
3 , Ln 2 O 3 (Ln is Gd, Sm and / or Nd) and MnO.
【０００８】ここで、基本成分及び添加成分を得るため
の出発原料としては実施例で示した酸化物以外の酸化
物、炭酸塩、水酸化物等を使用してもよい。Here, oxides other than the oxides shown in the examples, carbonates, hydroxides and the like may be used as starting materials for obtaining the basic component and the additive component.
【０００９】次に、基本成分中において、ＢａＴｉＯ3
は９５．０〜９９．０ｍｏｌ％、ＮｂＯ2.5 は０．６〜
４．２ｍｏｌ％、ＮｉＯは０．２〜２．０ｍｏｌ％の割
合になっている。Next, in the basic component, BaTiO 3
95.0~99.0mol% is, NbO 2.5 is 0.6
The ratio of 4.2 mol% and NiO is 0.2 to 2.0 mol%.
【００１０】ＢａＴｉＯ3 の割合が９５．０〜９９．０
ｍｏｌ％であるとした理由は、ＢａＴｉＯ3 の割合が９
５．０ｍｏｌ％未満では比誘電率εs が４０００を下回
ったり、−５５℃〜１２５℃におけるＴＣが±１５％を
外れ、またＢａＴｉＯ3 の割合が９９．０ｍｏｌ％を越
えると２５℃におけるｔａｎδが２．５％を越えたり、
−５５℃〜１２５℃におけるＴＣが±１５％を外れてし
まうからである。The ratio of BaTiO 3 is 95.0 to 99.0.
The reason why it is mol% is that the ratio of BaTiO 3 is 9
If it is less than 5.0 mol%, the relative dielectric constant ε s is less than 4000, TC at −55 ° C. to 125 ° C. is out of ± 15%, and if the ratio of BaTiO 3 exceeds 99.0 mol%, tan δ at 25 ° C. Over 2.5%,
This is because the TC at −55 ° C. to 125 ° C. deviates from ± 15%.
【００１１】また、ＮｂＯ2.5 の割合が０．６〜４．２
ｍｏｌ％であるとした理由は、ＮｂＯ2.5 の割合が０．
６ｍｏｌ％未満では比誘電率εs が４０００を下回り、
ｔａｎδが２．５％を越え、−５５℃〜１２５℃におけ
るＴＣが±１５％を外れてしまい、またＮｂＯ2.5の割
合が４．２ｍｏｌ％を越えると比誘電率εs が４０００
を下回り、−５５℃〜１２５℃におけるＴＣが±１５％
を外れてしまうからである。Further, the ratio of NbO 2.5 is 0.6 to 4.2.
The reason why it is mol% is that the ratio of NbO 2.5 is 0.
If it is less than 6 mol%, the relative permittivity ε s is less than 4000,
tan δ exceeds 2.5%, TC at −55 ° C. to 125 ° C. deviates from ± 15%, and when the ratio of NbO 2.5 exceeds 4.2 mol%, the relative permittivity ε s is 4000.
And TC at -55 ° C to 125 ° C is ± 15%
Because it will be out of.
【００１２】また、ＮｉＯの割合が０．２〜２．０ｍｏ
ｌ％であるとした理由は、ＮｉＯの割合が０．２ｍｏｌ
％未満では比誘電率εs が４０００を下回り、ｔａｎδ
が２．５％を越えてしまい、またＮｉＯの割合が２．０
ｍｏｌ％を越えると比誘電率εs が４０００を下回って
しまうからである。Further, the proportion of NiO is 0.2 to 2.0 mo.
The reason why it is 1% is that the ratio of NiO is 0.2 mol.
%, The relative permittivity ε s is less than 4000, and tan δ
Exceeds 2.5%, and the NiO ratio is 2.0.
This is because the relative dielectric constant ε s falls below 4000 if it exceeds mol%.
【００１３】次に、添加成分について、ＣａＺｒＯ3 及
び／又はＢａＺｒＯ3 は基本成分１００重量部に対して
０．１５〜１．９０重量部の割合で含有され、Ｌｎ2 Ｏ
3 は基本成分１００重量部に対して０．０８〜０．３０
重量部の割合で含有され、ＭｎＯは基本成分１００重量
部に対して０．００７〜０．２０重量部の割合で含有さ
れている。Next, with respect to the additive components, CaZrO 3 and / or BaZrO 3 are contained in a proportion of 0.15 to 1.90 parts by weight relative to 100 parts by weight of the basic components, and Ln 2 O
3 is 0.08 to 0.30 with respect to 100 parts by weight of the basic component.
The MnO content is 0.007 to 0.20 parts by weight with respect to 100 parts by weight of the basic component.
【００１４】ここで、ＣａＺｒＯ3 及び／又はＢａＺｒ
Ｏ3 の含有割合を基本成分１００重量部に対して０．１
５〜１．９０重量部としたのは、ＣａＺｒＯ3 及び／又
はＢａＺｒＯ3 の含有割合が基本成分１００重量部に対
して０．１５重量部未満では比誘電率εs が４０００を
下回ったり、１０００時間後の容量変化率が３．０％を
越えてしまい、またＣａＺｒＯ3 及び／又はＢａＺｒＯ
3 の含有割合が基本成分１００重量部に対して１．９重
量部を越えるとＴＣが±１５％を外れてしまうからであ
る。尚、ＣａＺｒＯ3 とＢａＺｒＯ3 はほゞ同様の働き
をするので少なくともいずれか一方が含まれていればよ
い。Here, CaZrO 3 and / or BaZr
The content ratio of O 3 is 0.1 with respect to 100 parts by weight of the basic component.
5 to 1.90 parts by weight means that when the content ratio of CaZrO 3 and / or BaZrO 3 is less than 0.15 parts by weight with respect to 100 parts by weight of the basic component, the relative dielectric constant ε s is less than 4000, or 1000 The capacity change rate after time exceeds 3.0%, and CaZrO 3 and / or BaZrO
This is because if the content ratio of 3 exceeds 1.9 parts by weight with respect to 100 parts by weight of the basic component, TC will deviate from ± 15%. It should be noted that CaZrO 3 and BaZrO 3 have almost the same functions, so at least one of them should be contained.
【００１５】また、Ｌｎ2 Ｏ3 の含有割合を基本成分１
００重量部に対して０．０８〜０．３０重量部としたの
は、Ｌｎ2 Ｏ3 の含有割合が基本成分１００重量部に対
して０．０８重量部未満では１０００時間後の容量変化
率が３％を越えたり、ＴＣが±１５％を外れてしまい、
またＬｎ2 Ｏ3 の含有割合が基本成分１００重量部に対
して０．３０重量部を越えると比誘電率εs が４０００
を下回ってしまうからである。Further, the content ratio of Ln 2 O 3 is set to the basic component 1
0.08 to 0.30 parts by weight with respect to 00 parts by weight means that when the content ratio of Ln 2 O 3 is less than 0.08 parts by weight with respect to 100 parts by weight of the basic component, the capacity change rate after 1000 hours Exceeds 3%, TC is out of ± 15%,
When the content ratio of Ln 2 O 3 exceeds 0.30 parts by weight with respect to 100 parts by weight of the basic component, the relative dielectric constant ε s is 4000.
Is less than.
【００１６】また、ＭｎＯの含有割合を基本成分１００
重量部に対して０．００７〜０．２０重量部としたの
は、ＭｎＯの含有割合が基本成分１００重量部に対して
０．００７重量部未満ではｔａｎδが２．５％を越えて
しまい、またＭｎＯの含有割合が基本成分１００重量部
に対して０．２重量部を越えるとＴＣが±１５％を外れ
たり、１０００ｈｒ後の容量変化率が３％を越えてしま
うからである。Further, the content ratio of MnO is 100
The amount of 0.007 to 0.20 parts by weight with respect to parts by weight means that tan δ exceeds 2.5% when the content ratio of MnO is less than 0.007 parts by weight with respect to 100 parts by weight of the basic component. Further, if the content ratio of MnO exceeds 0.2 parts by weight with respect to 100 parts by weight of the basic component, TC will deviate from ± 15%, and the capacity change rate after 1000 hours will exceed 3%.
【００１７】尚、本発明においては、誘電体磁器組成物
の中にＣｅＯ2 ，Ａｌ2 Ｏ3 ，ＳｉＯ2 などの焼結助剤
を、電気特性を悪化させない範囲で微量添加してもよ
い。In the present invention, a small amount of a sintering aid such as CeO 2 , Al 2 O 3 or SiO 2 may be added to the dielectric ceramic composition as long as the electrical characteristics are not deteriorated.
【００１８】[0018]
【実施例】まず、試料Ｎｏ．１の場合について説明す
る。 原料粉末の調製： 基本成分の原料として、純度９９．
９９％以上のチタン酸バリウム（ＢａＴｉＯ3 ）、五酸
化ニオブ（Ｎｂ2 Ｏ5 ）及び酸化ニッケル（ＮｉＯ）を
次の割合で秤量した。 ＢａＴｉＯ3 …９９４．７７５ｇ（９９．０ｍｏｌ％） Ｎｂ2 Ｏ3 …………４．５８１ｇ（Ｎｂで０．８ｍｏｌ
％） ＮｉＯ………………０．６４４ｇ（０．２ｍｏｌ％）EXAMPLES First, sample No. The case of 1 will be described. Preparation of raw material powder: Purity of 99.
99% or more of barium titanate (BaTiO 3 ), niobium pentoxide (Nb 2 O 5 ) and nickel oxide (NiO) were weighed in the following proportions. BaTiO 3 --- 994.775 g (99.0 mol%) Nb 2 O 3 --- 4.581 g (0.8 mol in Nb)
%) NiO ……………… 0.644g (0.2mol%)
【００１９】また、添加物の原料として、メタジルコニ
ウム酸カルシウム（ＣａＺｒＯ3 ）、酸化ガドリニウム
（Ｇｄ2 Ｏ3 ）及び酸化マンガン（ＭｎＯ）を、基本成
分１０００ｇに対して次の割合で秤量した。 ＣａＺｒＯ3 …７．６０ｇ Ｇｄ2 Ｏ3 ……１．５０ｇ ＭｎＯ…………０．５０ｇAs raw materials for the additives, calcium metazirconate (CaZrO 3 ), gadolinium oxide (Gd 2 O 3 ) and manganese oxide (MnO) were weighed in the following proportions with respect to 1000 g of the basic component. CaZrO 3 … 7.60 g Gd 2 O 3 …… 1.50 g MnO ………… 0.50 g
【００２０】そして、これら基本成分の原料及び添加成
分の原料を３リットルの水とともにボールミル中に入
れ、１５時間湿式混合し、この湿式混合した原料をボー
ルミルから取り出し、大気中において１５０℃で３時間
乾燥し、この乾燥した原料をらいかい器で粗粉砕し、原
料粉末を得た。Then, the raw materials of these basic components and the raw materials of the additive components are put in a ball mill together with 3 liters of water and wet-mixed for 15 hours. The wet-mixed raw materials are taken out of the ball mill and kept in air at 150 ° C. for 3 hours. After drying, the dried raw material was roughly pulverized with a raker to obtain a raw material powder.
【００２１】グリーンシートの形成： 次に、この原料
粉末に有機バインダーを１０重量％添加し、更に１００
重量％の溶媒を加え、ボールミルを用いて２４時間湿式
混合し、原料スラリーを得た。そして、この原料スラリ
ーを用い、リバースロールコータで１０〜３０μｍの厚
さのグリーンシートを複数枚形成した。Formation of green sheet: Next, 10% by weight of an organic binder was added to this raw material powder, and then 100
A wt% solvent was added, and wet mixing was performed for 24 hours using a ball mill to obtain a raw material slurry. Then, using this raw material slurry, a plurality of green sheets having a thickness of 10 to 30 μm were formed by a reverse roll coater.
【００２２】内部電極の印刷： 次に、スクリーン印刷
機を用いて各グリーンシートの一方の面にＰｄペースト
からなる５０個の内部電極パターン（１個の内部電極パ
ターンは長さ１４ｍｍ×幅７ｍｍ）を印刷形成した。Printing of internal electrodes: Next, using a screen printing machine, 50 internal electrode patterns made of Pd paste were formed on one surface of each green sheet (one internal electrode pattern was 14 mm long and 7 mm wide). Was printed.
【００２３】積層チップの形成： 次に、内部電極パタ
ーンの乾燥後、内部電極パターンを上にして、グリーン
シートを１０枚積層した。この際、隣り合うグリーンシ
ートの内部電極パターンはその長手方向に半分程ずれる
ようにした。そして、積層させたグリーンシートの上下
に厚さ３０μｍのグリーンシートをカバーシートとして
５枚ずつ積層した。更に、この積層物を金型に入れて熱
圧着させた。そして、この熱圧着により得られた積層物
を格子状に裁断し、５０個の積層チップを得た。Formation of Laminated Chip: Next, after drying the internal electrode pattern, 10 green sheets were laminated with the internal electrode pattern facing upward. At this time, the internal electrode patterns of the adjacent green sheets were displaced by about half in the longitudinal direction. Then, five green sheets each having a thickness of 30 μm were stacked as a cover sheet above and below the stacked green sheets. Further, this laminate was placed in a mold and thermocompression bonded. Then, the laminate obtained by this thermocompression bonding was cut into a lattice shape to obtain 50 laminated chips.
【００２４】積層チップの焼成： 積層チップを焼成炉
に入れ、大気雰囲気下で、２０℃／ｈｒの速度で３００
℃まで昇温させながら加熱し、この温度で３時間保持さ
せて積層チップ内の有機バインダーを分解燃焼させ、２
５０℃／ｈｒの速度で１２８０℃まで昇温させながら加
熱し、この温度で２時間保持させて十分緻密化させ、１
５０℃／ｈｒの速度で降温させ、室温まで冷却した。Firing of laminated chips: The laminated chips are put in a firing furnace and placed in an air atmosphere at a rate of 20 ° C./hr for 300 times.
While heating up to ℃, it is heated at this temperature for 3 hours to decompose and burn the organic binder in the laminated chip.
Heat at a rate of 50 ° C./hr while raising the temperature to 1280 ° C., hold at this temperature for 2 hours to sufficiently densify, and
The temperature was lowered at a rate of 50 ° C./hr and cooled to room temperature.
【００２５】外部電極の形成： この積層チップの両方
の端部（裁断によって内部電極の端部が露出している部
分）にＡｇペーストを塗布し、これを約８００℃で焼き
付けて外部電極とし、積層磁器コンデンサを作成した。Formation of External Electrodes: Ag paste is applied to both ends of the laminated chip (portions where the ends of the internal electrodes are exposed by cutting), and the paste is baked at about 800 ° C. to form external electrodes. A laminated porcelain capacitor was created.
【００２６】電気特性の測定： 次に、このようにして
形成した積層磁器コンデンサについて、誘電体層の比誘
電率εs 、２５℃におけるｔａｎδ、ＴＣ及び１０００
時間後の容量変化率ΔＣを測定したところ、比誘電率ε
s が４２００、ｔａｎδが１．９０％、ＴＣのΔＣmax
が＋１０．４％、ΔＣmin が−１３．３％、容量変化率
ΔＣが２．８％であった。なお、電気特性は次の要領で
測定した。Measurement of electrical characteristics: Next, regarding the laminated ceramic capacitor thus formed, the relative dielectric constant ε s of the dielectric layer, tan δ at 25 ° C., TC and 1000
When the capacity change rate ΔC after time was measured, the relative permittivity ε
s is 4200, tan δ is 1.90%, and ΔC max of TC
Was + 10.4%, ΔC min was −13.3%, and the capacity change rate ΔC was 2.8%. The electrical characteristics were measured as follows.
【００２７】(1) 比誘電率εs 温度２５℃、周波数１ｋＨｚ、電圧（実効値）１．０Ｖ
の条件で積層磁器コンデンサの静電容量を測定し、この
測定値、内部電極の有効交差面積及び電極間距離とから
計算で求めた。(1) Specific permittivity ε s Temperature 25 ° C., frequency 1 kHz, voltage (effective value) 1.0 V
The electrostatic capacitance of the laminated ceramic capacitor was measured under the conditions of, and calculated from the measured value, the effective intersection area of the internal electrodes, and the distance between the electrodes.
【００２８】(2) ｔａｎδ 比誘電率εs の測定と同一条件にて測定した。(2) tan δ The relative permittivity ε s was measured under the same conditions.
【００２９】(3) 静電容量の温度特性 恒温槽の中に試料である積層磁器コンデンサを入れ、−
５５℃，−２５℃，０℃，２０℃，２５℃，４０℃，６
０℃，８５℃，１０５℃，１２５℃の各温度において周
波数１ｋＨＺ、電圧１．０Ｖ（実効値）の条件で静電容
量を測定し、２５℃の時の静電容量Ｃに対する変化率を
求め、この変化率の最大値ΔＣmax 及びこの変化率の最
小値ΔＣmin を求めた。(3) Temperature characteristics of capacitance Capacitance of a laminated ceramic capacitor as a sample in a constant temperature bath,
55 ° C, -25 ° C, 0 ° C, 20 ° C, 25 ° C, 40 ° C, 6
At each temperature of 0 ℃, 85 ℃, 105 ℃, and 125 ℃, the capacitance is measured under the condition of frequency 1kHz and voltage 1.0V (effective value), and the rate of change with respect to the capacitance C at 25 ℃ is obtained. The maximum value ΔC max of this change rate and the minimum value ΔC min of this change rate were determined.
【００３０】(4) １０００時間後の容量変化率ΔＣ 試料である積層磁器コンデンサに１５０℃の熱処理を１
時間施した時の静電容量Ｃ1 とそれから１０００時間後
の静電容量Ｃ2 を測定し、次式により１０００時間後の
容量変化率ΔＣを算出した。 ΔＣ＝〔（Ｃ2 −Ｃ1 ）／Ｃ1 〕×１００（％）(4) Capacitance change rate after 1000 hours ΔC A heat treatment at 150 ° C. was applied to a laminated ceramic capacitor as a sample.
The electrostatic capacity C 1 when applied for a time and the electrostatic capacity C 2 1000 hours after that were measured, and the capacity change rate ΔC after 1000 hours was calculated by the following formula. ΔC = [(C 2 −C 1 ) / C 1 ] × 100 (%)
【００３１】以上、試料Ｎｏ．１の場合について説明し
たが、試料Ｎｏ２〜４７についても基本成分及び添加成
分の組成を表１に示すように変えた他は試料Ｎｏ．１と
全く同一の方法で積層磁器コンデンサを作製し、同一の
方法で電気特性を測定した。結果は表１に示す通りとな
った。As described above, the sample No. Although the case of Sample No. 1 has been described, Sample Nos. 2 to 47 are the same except that the compositions of the basic component and the additive component are changed as shown in Table 1. A laminated ceramic capacitor was manufactured by the same method as that of No. 1, and the electrical characteristics were measured by the same method. The results are shown in Table 1.
【００３２】尚、表１の基本成分の欄の数値の単位はモ
ル％、添加成分の欄の数値の単位は基本成分１００重量
部に対する重量部である。添加成分の欄におけるＣＺは
ＣａＺｒＯ3 の略、ＣＢはＢａＺｒＯ3 の略である。肉
厚ｔの欄の数値（μｍ）は誘電体層一層当たりの平均肉
厚である。また試料Ｎｏに※印を付けた試料は比較例で
ある。The unit of the numerical value in the column of the basic component in Table 1 is mol% and the unit of the numerical value in the column of the added component is parts by weight based on 100 parts by weight of the basic component. In the column of additive components, CZ is an abbreviation for CaZrO 3 and CB is an abbreviation for BaZrO 3 . The numerical value (μm) in the column of wall thickness t is the average wall thickness per dielectric layer. The sample marked with * is a comparative example.
【００３３】[0033]
【表１(1) 】 [Table 1 (1)]
【００３４】[0034]
【表１(2) 】 [Table 1 (2)]
【００３５】[0035]
【表１(3) 】 [Table 1 (3)]
【００３６】次に、表１(1) 〜表１(3) の結果について
検討する。まず、ＢａＴｉＯ3 の割合が、試料Ｎｏ．
１，４に示すように９９．０ｍｏｌ％の場合は所望の電
気特性のものが得られるが、ＢａＴｉＯ3 の割合が、試
料Ｎｏ．５に示すように９９．１ｍｏｌ％の場合は、２
５℃におけるｔａｎδが２．５％よりも大きくなり、−
５５℃〜１２５℃における静電容量の２５℃を基準とし
た変化率の最小値が−１５％を下回ってしまい、所望の
電気特性のものを得ることができない。従って、ＢａＴ
ｉＯ3 の割合の上限値は９９．０ｍｏｌ％ということに
なる。Next, the results of Tables 1 (1) to 1 (3) will be examined. First, the ratio of BaTiO 3 is the same as sample No.
As shown in Nos. 1 and 4, when 99.0 mol% is obtained, desired electrical characteristics are obtained, but the ratio of BaTiO 3 is the same as that of sample No. As shown in 5, when 99.1 mol%, 2
Tan δ at 5 ° C becomes larger than 2.5%,
The minimum value of the rate of change of the capacitance between 55 ° C. and 125 ° C. with reference to 25 ° C. is less than −15%, and it is not possible to obtain the desired electrical characteristics. Therefore, BaT
The upper limit of the ratio of iO 3 is 99.0 mol%.
【００３７】また、ＢａＴｉＯ3 の割合が、試料Ｎｏ．
２，３に示すように９５．０ｍｏｌ％の場合は所望の電
気特性のものが得られるが、ＢａＴｉＯ3 の割合が、試
料Ｎｏ．６に示すように９４．９ｍｏｌ％の場合は誘電
率εs が４０００を下回り、−５５℃〜１２５℃におけ
る静電容量の２５℃を基準とした変化率の最小値が−１
５％を下回ってしまう。従って、ＢａＴｉＯ3 の割合の
下限値は９５．０ｍｏｌ％ということになる。The proportion of BaTiO 3 is the same as that of sample No.
As shown in Nos. 2 and 3, when 95.0 mol% is obtained, desired electric characteristics are obtained, but the ratio of BaTiO 3 is the same as that of Sample No. As shown in 6, when the dielectric constant ε s is less than 4000 in the case of 94.9 mol%, the minimum value of the change rate of the electrostatic capacitance at −55 ° C. to 125 ° C. based on 25 ° C. is −1.
It will be below 5%. Therefore, the lower limit of the ratio of BaTiO 3 is 95.0 mol%.
【００３８】また、Ｎｂ2 Ｏ5 の割合が、試料Ｎｏ．２
に示すように４．２ｍｏｌ％の場合は所望の電気特性の
ものが得られるが、ＮｂＯ2.5 の割合が、試料Ｎｏ．８
に示すように４．３ｍｏｌ％の場合は誘電率εs が４０
００を下回り、−５５℃〜１２５℃における静電容量の
２５℃を基準とした変化率の最小値が−１５％を大きく
下回ってしまう。従って、Ｎｂ2 Ｏ5 の割合の上限値は
４．２ｍｏｌ％ということになる。The ratio of Nb 2 O 5 is the same as that of sample No. Two
As shown in Fig. 4, when 4.2 mol% is obtained, desired electrical characteristics can be obtained, but the ratio of NbO 2.5 is about No. 8
As shown in, when the dielectric constant is 4.3 mol%, the dielectric constant ε s is 40
00, and the minimum value of the rate of change of the electrostatic capacitance at -55 ° C to 125 ° C with reference to 25 ° C is much lower than -15%. Therefore, the upper limit of the ratio of Nb 2 O 5 is 4.2 mol%.
【００３９】また、Ｎｂ2 Ｏ5 の割合が、試料Ｎｏ．４
に示すように０．６ｍｏｌ％の場合は所望の電気特性の
ものが得られるが、ＮｂＯ2.5 の割合が、試料Ｎｏ．７
に示すように０．５ｍｏｌ％の場合はＴｃの最小値が−
１５％を下回り、誘電率εsが４０００を下回ってしま
う。従って、Ｎｂ2 Ｏ5 の割合の下限値は０．６ｍｏｌ
％ということになる。The proportion of Nb 2 O 5 was the same as that of sample No. Four
As shown in FIG. 6, when the content is 0.6 mol%, desired electrical characteristics are obtained, but the ratio of NbO 2.5 is equal to that of sample No. 7
As shown in, the minimum Tc value is −0.5 mol%.
It falls below 15%, and the dielectric constant ε s falls below 4000. Therefore, the lower limit of the ratio of Nb 2 O 5 is 0.6 mol.
%It turns out that.
【００４０】また、ＮｉＯの割合が、試料Ｎｏ．３に示
すように２．０ｍｏｌ％の場合は所望の電気特性のもの
が得られるが、ＮｉＯの割合が、試料Ｎｏ．１０に示す
ように２．１ｍｏｌ％の場合は比誘電率εs が４０００
を下回ってしまう。従って、ＮｉＯの割合の上限値は
２．０ｍｏｌ％ということになる。The proportion of NiO was the same as that of sample No. As shown in FIG. 3, when 2.0 mol%, desired electrical characteristics are obtained, but the proportion of NiO is the same as that of sample No. As shown in 10, the relative permittivity ε s is 4000 at 2.1 mol%.
Less than. Therefore, the upper limit of the proportion of NiO is 2.0 mol%.
【００４１】また、ＮｉＯの割合が、試料Ｎｏ．１に示
すように０．２ｍｏｌ％の場合は所望の電気特性のもの
が得られるが、ＮｉＯの割合が、試料Ｎｏ．９に示すよ
うに０．１ｍｏｌ％の場合はｔａｎδが２．５％を越
え、誘電率εs が４０００を下回ってしまう。従って、
ＮｉＯの割合の下限値は０．２ｍｏｌ％ということにな
る。The proportion of NiO was the same as that of sample No. As shown in FIG. 1, when the content is 0.2 mol%, the desired electrical characteristics are obtained, but the proportion of NiO is the same as that of sample No. As shown in FIG. 9, when 0.1 mol%, tan δ exceeds 2.5%, and the dielectric constant ε s falls below 4000. Therefore,
The lower limit of the proportion of NiO is 0.2 mol%.
【００４２】また、ＣａＺｒＯ3 の添加量が、試料Ｎ
ｏ．２１に示すように１．９重量部の場合は所望の電気
特性を得ることができるが、ＣａＺｒＯ3 の添加量が、
試料Ｎｏ．２２に示すように１．９６重量部の場合はＴ
Ｃが−１５％を下回ってしまう。従って、ＣａＺｒＯ3
又はＢａＺｒＯ3 の添加量の上限値は基本成分１００重
量部に対して１．９重量部ということになる。Further, the amount of CaZrO 3 added was the same as that of sample N
o. As shown in 21, when 1.9 parts by weight, desired electrical characteristics can be obtained, but the amount of CaZrO 3 added is
Sample No. In the case of 1.96 parts by weight as shown in 22,
C falls below -15%. Therefore, CaZrO 3
Alternatively, the upper limit of the amount of BaZrO 3 added is 1.9 parts by weight with respect to 100 parts by weight of the basic component.
【００４３】また、ＣａＺｒＯ3 の添加量が、試料Ｎ
ｏ．１７に示すように基本成分１００重量部に対して
０．１５重量部の場合は所望の電気特性を得ることがで
きるが、ＣａＺｒＯ3 又はＢａＺｒＯ3 の添加量が、試
料Ｎｏ．１６に示すように零の場合は１０００ｈｒ後の
容量変化率が３．０％を越えてしまう。従って、ＣａＺ
ｒＯ3 又はＢａＺｒＯ3 の添加量の下限値は基本成分１
００重量部に対して０．１５重量部ということになる。The amount of CaZrO 3 added was the
o. As shown in 17, when 0.15 parts by weight is used with respect to 100 parts by weight of the basic component, desired electrical characteristics can be obtained, but the addition amount of CaZrO 3 or BaZrO 3 is the same as that of sample No. As shown in 16, in the case of zero, the capacity change rate after 1000 hours exceeds 3.0%. Therefore, CaZ
The lower limit of the addition amount of rO 3 or BaZrO 3 is the basic component 1
This means 0.15 parts by weight with respect to 00 parts by weight.
【００４４】尚、試料Ｎｏ．１１〜１５で示すようにＣ
ａＺｒＯ3 とＢａＺｒＯ3 とはほゞ同様の働きをしてい
る。従って、ＣａＺｒＯ3 とＢａＺｒＯ3 のうちの少な
くとも一方が基本成分１００重量部に対して０．１５〜
１．９重量部含まれていれば、所望の電気特性を得るこ
とができる。Sample No. C as shown by 11 to 15
aZrO 3 and BaZrO 3 have almost the same functions. Therefore, at least one of CaZrO 3 and BaZrO 3 is 0.15 to 100 parts by weight of the basic component.
If the content is 1.9 parts by weight, desired electrical characteristics can be obtained.
【００４５】また、Ｇｄの添加量が、試料Ｎｏ．２８に
示すように０．３０重量部の場合は所望の電気特性を得
ることができるが、Ｇｄの添加量が、試料Ｎｏ．２９に
示すように０．３２重量部の場合は比誘電率εs が４０
００を下回ってしまう。従って、Ｇｄの添加量の上限値
は０．３０重量部ということになる。The amount of Gd added was the same as that of sample No. As shown in FIG. 28, when 0.30 parts by weight, desired electrical characteristics can be obtained, but the addition amount of Gd is the same as that of sample No. 29, in the case of 0.32 parts by weight, the relative permittivity ε s is 40
It will be less than 00. Therefore, the upper limit of the amount of Gd added is 0.30 parts by weight.
【００４６】また、Ｇｄ2 Ｏ3 の添加量が、試料Ｎｏ．
２３に示すように零の場合にはＴＣが−１５％を下回
り、容量変化率が３％を越えてしまうが、Ｇｄ2 Ｏ3 の
添加量が、試料Ｎｏ．２４に示すように基本成分１００
重量部に対して０．０８重量部の場合は所望の電気特性
を得ることができる。従って、Ｇｄ2 Ｏ3 の添加量の下
限値は基本成分１００重量部に対してＧｄで０．０８重
量部ということになる。なお、Ｎｄ，Ｓｍについてもほ
ゞ同様の傾向を示した。The addition amount of Gd 2 O 3 was the same as that of sample No.
In the case of zero, as shown in 23 TC is below -15%, the capacity change rate exceeds 3%, the added amount of Gd 2 O 3 is, Sample No. 100 as shown in 24
When the content is 0.08 parts by weight with respect to the parts by weight, desired electrical characteristics can be obtained. Therefore, the lower limit of the amount of Gd 2 O 3 added is 0.08 part by weight of Gd with respect to 100 parts by weight of the basic component. Incidentally, Nd and Sm showed almost the same tendency.
【００４７】また、ＭｎＯの添加量が、試料Ｎｏ．３５
に示すように０．２０重量部の場合は所望の電気特性の
ものを得ることができるが、ＭｎＯの添加量が、試料Ｎ
ｏ．３６に示すように０．２１重量部の場合はＴｃが−
１５％を下回り、熱処理して１０００ｈｒ経過後の容量
変化率が３％を越えてしまう。従って、ＭｎＯの上限値
は基本成分１００重量部に対して０．２０重量部という
ことになる。The amount of MnO added was the same as the sample No. 35
As shown in Fig. 10, when 0.20 parts by weight, desired electrical characteristics can be obtained, but the amount of MnO added is
o. As shown in 36, when Tc is 0.21 parts by weight, Tc is-.
If it is less than 15% and heat treated for 1000 hours, the capacity change rate exceeds 3%. Therefore, the upper limit of MnO is 0.20 parts by weight with respect to 100 parts by weight of the basic component.
【００４８】また、ＭｎＯの添加量が、試料Ｎｏ．３１
に示すように基本成分１００重量部に対して０．００７
重量部の場合は所望の電気特性を得ることができるが、
ＭｎＯの添加量が、試料Ｎｏ．３０に示すように零の場
合は、２５℃におけるｔａｎδが２．５％を越えてしま
う。従って、ＭｎＯの下限値は基本成分１００重量部に
対して０．００７重量部ということになる。The amount of MnO added was the same as that of sample No. 31
As shown in, 0.007 is added to 100 parts by weight of the basic component.
In the case of parts by weight, desired electrical characteristics can be obtained,
The addition amount of MnO was the same as that of sample No. As shown in 30, when it is zero, tan δ at 25 ° C. exceeds 2.5%. Therefore, the lower limit of MnO is 0.007 parts by weight with respect to 100 parts by weight of the basic component.
【００４９】また、本発明の組成範囲に入らない誘電体
磁器組成物では、試料Ｎｏ．３７〜３９及び４３，４４
に示すように、誘電体層の厚さが１５μｍ以下になる
と、ｔａｎδが２．５％を越え、ＴＣが±１５％の範囲
から外れてしまうが、本発明の組成範囲に入る誘電体磁
器組成物では、試料Ｎｏ．４１，４２，４６，４７に示
すように誘電体層の厚さが１５μｍ以下になっても所望
の電気特性のものが得られている。Further, in the dielectric ceramic composition which does not fall within the composition range of the present invention, sample No. 37-39 and 43,44
As shown in FIG. 5, when the thickness of the dielectric layer is 15 μm or less, tan δ exceeds 2.5% and TC is out of the range of ± 15%. However, the dielectric ceramic composition within the composition range of the present invention. Sample No. As shown by 41, 42, 46 and 47, desired electric characteristics are obtained even when the thickness of the dielectric layer is 15 μm or less.
【００５０】なお、上記実施例では内部電極用の導電性
ペーストとしてＡｇペーストを使用したが、焼成温度に
応じてＡｇ／Ｐｄペーストを用いることもできる。焼成
温度が上記実施例のように１２８０℃の場合、Ａｇ／Ｐ
ｄペーストとしてはＡｇ／Ｐｄ＝３０／７０の組成のも
のが好ましい。Although the Ag paste is used as the conductive paste for the internal electrodes in the above embodiment, an Ag / Pd paste may be used depending on the firing temperature. When the firing temperature is 1280 ° C. as in the above example, Ag / P
It is preferable that the d paste has a composition of Ag / Pd = 30/70.
【００５１】[0051]
【発明の効果】本発明によれば誘電体層の一層当たりの
厚みが１５μｍより小さくなっても、２５℃における比
誘電率が４０００以上、−５５℃〜１２５℃の範囲にお
ける２５℃を基準にした静電容量の温度変化率が±１５
％以内、１０００時間後の容量変化率が３％以内、２５
℃におけるｔａｎδが２．５％以内の特性を有する誘電
体磁器組成物が得られる。According to the present invention, even if the thickness of each dielectric layer is less than 15 μm, the relative dielectric constant at 25 ° C. is 4000 or more, and the relative dielectric constant is 25 ° C. in the range of −55 ° C. to 125 ° C. The temperature change rate of the electrostatic capacity is ± 15
%, Capacity change rate after 1000 hours is 3% or less, 25
A dielectric ceramic composition having a tan δ at 2.5 ° C. of 2.5% or less is obtained.
Claims (1)
分はＢａＴｉＯ3−ＮｂＯ2.5 −ＮｉＯの三成分からな
り、添加成分は、ＣａＺｒＯ3 及び／又はＢａＺｒＯ
3 、Ｌｎ2 Ｏ3 （ＬｎはＧｄ，Ｓｍ及び／又はＮｄ）並
びにＭｎＯからなり、 基本成分中において、ＢａＴｉＯ3 は９５．０〜９９．
０ｍｏｌ％、ＮｂＯ2. 5 は０．６〜４．２ｍｏｌ％、Ｎ
ｉＯは０．２〜２．０ｍｏｌ％の割合になっており、 ＣａＺｒＯ3 及び／又はＢａＺｒＯ3 は基本成分１００
重量部に対して０．１５〜１．９０重量部の割合で含ま
れ、Ｌｎ2 Ｏ3 は基本成分１００重量部に対して０．０
８〜０．３０重量部の割合で含まれ、ＭｎＯは基本成分
１００重量部に対して０．００７〜０．２０重量部の割
合で含まれている誘電体磁器組成物。1. A basic component and an additive component, the basic component comprises three components of BaTiO 3 —NbO 2.5 —NiO, and the additive component is CaZrO 3 and / or BaZrO.
3 , Ln 2 O 3 (Ln is Gd, Sm and / or Nd) and MnO, and BaTiO 3 is 95.0 to 99.
0mol%, NbO 2. 5 is 0.6~4.2mol%, N
The ratio of iO is 0.2 to 2.0 mol%, and CaZrO 3 and / or BaZrO 3 is 100% of the basic component.
It is contained in a proportion of 0.15 to 1.90 parts by weight with respect to parts by weight, and Ln 2 O 3 is 0.0 to 100 parts by weight of the basic component.
A dielectric ceramic composition in which the MnO content is 8 to 0.30 parts by weight, and MnO is 0.007 to 0.20 parts by weight with respect to 100 parts by weight of the basic component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3274542A JPH0589723A (en) | 1991-09-26 | 1991-09-26 | Dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3274542A JPH0589723A (en) | 1991-09-26 | 1991-09-26 | Dielectric porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0589723A true JPH0589723A (en) | 1993-04-09 |
Family
ID=17543168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3274542A Pending JPH0589723A (en) | 1991-09-26 | 1991-09-26 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0589723A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982004487A1 (en) * | 1981-06-12 | 1982-12-23 | Tokuyama Keiichi | Power source for automotive electronic equipment |
| JP2016113355A (en) * | 2014-12-16 | 2016-06-23 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor including the same |
| KR20180038429A (en) * | 2018-04-02 | 2018-04-16 | 삼성전기주식회사 | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0536308A (en) * | 1991-07-30 | 1993-02-12 | Tdk Corp | High permittivity dielectric ceramic composition |
-
1991
- 1991-09-26 JP JP3274542A patent/JPH0589723A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0536308A (en) * | 1991-07-30 | 1993-02-12 | Tdk Corp | High permittivity dielectric ceramic composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982004487A1 (en) * | 1981-06-12 | 1982-12-23 | Tokuyama Keiichi | Power source for automotive electronic equipment |
| JP2016113355A (en) * | 2014-12-16 | 2016-06-23 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor including the same |
| KR20160073243A (en) * | 2014-12-16 | 2016-06-24 | 삼성전기주식회사 | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor comprising the same |
| KR20180038429A (en) * | 2018-04-02 | 2018-04-16 | 삼성전기주식회사 | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor comprising the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100631995B1 (en) | Dielectric ceramic compositions for low temperature sintering and multilayer ceramic condenser using the same | |
| KR100278416B1 (en) | Dielectric Ceramic, Method for Producing the Same, Laminated Ceramic Electronic Element, and Method for Producing the Same | |
| EP1767507B1 (en) | Dielectric ceramic composition and laminated ceramic capacitor | |
| JP3568030B2 (en) | Method for producing dielectric ceramic composition and method for producing electronic component containing dielectric layer | |
| KR100414331B1 (en) | Nonreducing dielectric ceramic and monolithic ceramic capacitor using the same | |
| JP3878778B2 (en) | Dielectric porcelain composition and electronic component | |
| KR101274331B1 (en) | Electronic part and process for producing the same | |
| JP3503568B2 (en) | Non-reducing dielectric ceramic and multilayer ceramic capacitor using the same | |
| JPH08295559A (en) | Dielectric porcelain composition | |
| US20120075768A1 (en) | Dielectric ceramic composition and manufacturing method thereof, and ceramic electronic device | |
| JP6089770B2 (en) | Dielectric porcelain composition and electronic component | |
| JP2004214539A (en) | Dielectric ceramic and laminated ceramic capacitor | |
| JP2005022891A (en) | Dielectric porcelain and laminated electronic component | |
| KR100859264B1 (en) | Dielectric ceramic and multilayer ceramic capacitor | |
| KR100859058B1 (en) | Laminated electronic component and method for manufacturing the same | |
| JP2010208905A (en) | Method for manufacturing dielectric ceramic, dielectric ceramic, method for manufacturing laminated ceramic capacitor and the laminated ceramic capacitor | |
| JP2007261913A (en) | Dielectric porcelain composition, electronic part and multilayer ceramic capacitor | |
| JP2005187296A (en) | Dielectric ceramic composition and multilayer ceramic capacitor | |
| JP7262640B2 (en) | ceramic capacitor | |
| JP4614656B2 (en) | Dielectric porcelain, multilayer electronic component, and method of manufacturing multilayer electronic component | |
| JP3678072B2 (en) | Dielectric ceramic composition and multilayer ceramic component | |
| JP3250923B2 (en) | Dielectric porcelain composition | |
| JP3634930B2 (en) | Dielectric porcelain composition | |
| JP4487476B2 (en) | Dielectric porcelain composition and electronic component | |
| JP5167591B2 (en) | Electronic component, dielectric ceramic composition and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 19960416 |