JPH05144319A - Manufacture of dielectric ceramic composition - Google Patents
Manufacture of dielectric ceramic compositionInfo
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- JPH05144319A JPH05144319A JP3334106A JP33410691A JPH05144319A JP H05144319 A JPH05144319 A JP H05144319A JP 3334106 A JP3334106 A JP 3334106A JP 33410691 A JP33410691 A JP 33410691A JP H05144319 A JPH05144319 A JP H05144319A
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- organic solvent
- ceramic composition
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- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、誘電体磁器組成物に
関し、詳しくは、ニッケルなどの卑金属材料を内部電極
として用いる積層コンデンサ用の誘電体材料として好適
な非還元性誘電体磁器組成物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition, more specifically, a non-reducing dielectric ceramic composition suitable as a dielectric material for a laminated capacitor using a base metal material such as nickel as an internal electrode. It relates to a manufacturing method.
【０００２】[0002]
【従来の技術】ＢａＴｉＯ3系の誘電体材料は優れた誘
電特性を有していることから、積層コンデンサなどの種
々の用途に広く用いられている。しかし、従来のＢａＴ
ｉＯ3系の誘電体磁器材料は、中性または還元性の雰囲
気下で焼成すると、還元され、半導体化するという問題
点がある。したがって、焼成は酸化性の高酸素分圧下で
行うことが必要になるが、その場合、例えば、積層コン
デンサにおいてニッケル（Ｎｉ）などの卑金属材料を内
部電極として用いると、焼成工程で内部電極（ニッケ
ル）が酸化されてしまう。したがって、電極材料として
は、高温の焼成温度で溶融せず、かつ、酸化性雰囲気下
で焼成しても酸化されない、例えば、パラジウム（Ｐ
ｄ）や白金（Ｐｔ）などの貴金属を用いなければなら
ず、積層コンデンサのコストを増大させる大きな要因と
なっている。2. Description of the Related Art Since BaTiO 3 type dielectric materials have excellent dielectric properties, they are widely used in various applications such as multilayer capacitors. However, conventional BaT
The iO 3 -based dielectric ceramic material has a problem that it is reduced to a semiconductor when fired in a neutral or reducing atmosphere. Therefore, the firing needs to be performed under an oxidizing high oxygen partial pressure. In that case, for example, when a base metal material such as nickel (Ni) is used as the internal electrode in the multilayer capacitor, the internal electrode (nickel ) Will be oxidized. Therefore, the electrode material does not melt at a high firing temperature and is not oxidized even if fired in an oxidizing atmosphere. For example, palladium (P
Noble metals such as d) and platinum (Pt) must be used, which is a major factor in increasing the cost of the multilayer capacitor.
【０００３】そのため、焼成工程においてニッケルなど
の卑金属電極材料が酸化されることのない、酸素分圧の
低い中性または還元性の雰囲気下で焼成しても還元され
て半導体化することがなく、コンデンサ用の誘電体材料
として使用するのに十分な比抵抗と優れた誘電特性を有
する非還元性誘電体磁器材料に対する必要性が強く認識
されるに至っている。そして、これらの条件を満たすも
のとして、例えば、特開昭６２−２５６４２２号公報に
開示されたＢａＴｉＯ3−ＣａＺｒＯ3−ＭｎＯ−ＭｇＯ
系の材料や、特公昭６１−１４６１１号公報に開示され
たＢａＴｉＯ3−（Ｍｇ，Ｚｎ，Ｓｒ，Ｃａ）Ｏ−Ｂ2Ｏ
3−ＳｉＯ2系の材料などが提案されている。Therefore, the base metal electrode material such as nickel is not oxidized in the firing step, and is not reduced to be a semiconductor even if fired in a neutral or reducing atmosphere with a low oxygen partial pressure. It has been strongly recognized that there is a need for a non-reducing dielectric ceramic material having a specific resistance sufficient for use as a dielectric material for capacitors and excellent dielectric properties. And, as those satisfying these conditions, for example, BaTiO 3 —CaZrO 3 —MnO—MgO disclosed in JP-A-62-256422 is disclosed.
System material or, BaTiO 3 as disclosed in JP-B 61-14611 - (Mg, Zn, Sr , Ca) O-B 2 O
Materials such as 3- SiO 2 series have been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記特開昭６
２−２５６４２２号公報に開示されたＢａＴｉＯ3−Ｃ
ａＺｒＯ3−ＭｎＯ−ＭｇＯ系の非還元性誘電体磁器組
成物においては、ＣａＺｒＯ3や焼成過程で生成するＣ
ａＴｉＯ3がＭｎなどとともに二次相を形成する傾向が
あり、高温における信頼性が必ずしも十分ではないとい
う問題点がある。However, the above-mentioned Japanese Unexamined Patent Application Publication No.
BaTiO 3 -C disclosed in JP-A-2-256422
In the aZrO 3 —MnO—MgO-based non-reducing dielectric ceramic composition, CaZrO 3 and C generated in the firing process are used.
Since aTiO 3 tends to form a secondary phase together with Mn and the like, there is a problem that reliability at high temperature is not always sufficient.
【０００５】また、特公昭６１−１４６１１号公報に開
示されたＢａＴｉＯ3−（Ｍｇ，Ｚｎ，Ｓｒ，Ｃａ）Ｏ
−Ｂ2Ｏ3−ＳｉＯ2系の非還元性誘電体磁器組成物は、
誘電率が低く、Ｐｄなどの貴金属を内部電極として使用
するような従来の誘電体磁器組成物と比較すると、誘電
特性が劣っているため、この誘電体磁器組成物を従来の
誘電体材料と置き換えた場合、コストを低減することは
できるとしても、コンデンサとしての性能に劣り、小型
大容量化を実現することができないという問題点があ
る。また、この誘電体磁器組成物の誘電率の温度変化率
は、２０℃における容量値を基準にして、−５５〜８５
℃の温度範囲では±１５％であるが、８５℃を越える高
温では、±１５％を大きく上回り、ＥＩＡに規定されて
いるＸ７Ｒ特性を大きく外れてしまうという問題点があ
る。Further, BaTiO 3- (Mg, Zn, Sr, Ca) O disclosed in Japanese Patent Publication No. 61-14611.
The -B 2 O 3 -SiO 2 non-reducing dielectric ceramic composition is
Since the dielectric property is inferior to the conventional dielectric ceramic composition having a low dielectric constant and using a noble metal such as Pd as an internal electrode, this dielectric ceramic composition is replaced with a conventional dielectric material. In this case, although the cost can be reduced, the performance as a capacitor is inferior, and there is a problem in that it cannot be realized in a small size and a large capacity. The temperature change rate of the dielectric constant of this dielectric ceramic composition is -55 to 85 with reference to the capacitance value at 20 ° C.
Although it is ± 15% in the temperature range of ° C, at a high temperature exceeding 85 ° C, it greatly exceeds ± 15%, and there is a problem that it largely deviates from the X7R characteristic specified by EIA.
【０００６】さらに、これらの誘電体磁器組成物を形成
する原料粉体の工業的混合方法としては、主成分である
ＢａＴｉＯ3粉体に、添加元素を構成する金属元素の酸
化物あるいは炭酸塩（粉体）を添加混合して分散させる
方法が用いられているが、この方法では添加した粉体を
ＢａＴｉＯ3粉体の表面に均一に付着させ固定すること
ができず、安定した特性を有する誘電体磁器組成物粉体
を得ることが困難であるという問題点がある。Further, as an industrial mixing method of raw material powders for forming these dielectric porcelain compositions, BaTiO 3 powder as a main component is mixed with oxides or carbonates of metal elements constituting additive elements ( Powder) is added and mixed to disperse the powder, but with this method, the added powder cannot be uniformly adhered and fixed on the surface of the BaTiO 3 powder, and the dielectric having stable characteristics is used. There is a problem that it is difficult to obtain a body porcelain composition powder.
【０００７】この発明は、上記問題点を解決するもので
あり、低酸素分圧下の還元性雰囲気中でも組織の半導体
化を生じさせることなく焼成することが可能で、誘電率
及び絶縁抵抗が高く、かつ、誘電率の温度変化率が広い
範囲において安定である非還元性誘電体磁器組成物の製
造方法を提供することを目的とする。The present invention solves the above-mentioned problems, and can be fired in a reducing atmosphere under a low oxygen partial pressure without causing the tissue to be semiconducting, and has a high dielectric constant and insulation resistance. Further, it is an object of the present invention to provide a method for producing a non-reducing dielectric ceramic composition, which has a stable rate of change in dielectric constant with temperature.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
に、この発明の誘電体磁器組成物の製造方法は、アルカ
リ金属酸化物の含有量が０．０４重量％未満のチタン酸
バリウム（ＢａＴｉＯ 3）粉体と、前記チタン酸バリウ
ム（ＢａＴｉＯ3）粉体１００モルに対して、 Ｄｙ2Ｏ3として ： ０．６０〜 ０．７２モル ＣｏＯとして ： １．２０〜 １．４４モル ＢａＯとして ： １．３７〜 １．５８モル ＮｉＯとして ： ０．６０〜 ０．７２モル ＭｎＯとして ： ０．３０〜 ０．３６モル ＭｇＯとして ： １．８０〜 ２．１６モル となる量のＤｙ，Ｃｏ，Ｂａ，Ｎｉ，Ｍｎ及びＭｇの有
機溶剤可溶の有機化合物と、全体に対して１．１３〜
１．３１重量％の、Ｌｉ−Ｂａ−Ｓｒ−Ｓｉ系酸化物ガ
ラス成分を構成する有機溶剤可溶の有機化合物とを配合
し、これに有機溶剤を添加混合した後、有機溶剤を除去
して前記有機化合物を前記チタン酸バリウム（ＢａＴｉ
Ｏ3）粉体表面に均一に担持させ、熱処理することを特
徴とする。[Means for Solving the Problems] To achieve the above object
The method for producing the dielectric ceramic composition of the present invention is
Titanic acid containing less than 0.04 wt% of remetal oxide
Barium (BaTiO 3) Powder and the above-mentioned barium titanate
Mu (BaTiO3) For 100 mol of powder, Dy2O3As: 0.60 to 0.72 mol As CoO: 1.20 to 1.44 mol As BaO: 1.37 to 1.58 mol As NiO: 0.60 to 0.72 mol As MnO: 0.30 0.36 mol As MgO: 1.80 to 2.16 mol of Dy, Co, Ba, Ni, Mn and Mg
Organic compound soluble in machine solvent and 1.13 to the whole
1.31% by weight of Li-Ba-Sr-Si-based oxide gas
Blended with organic compounds soluble in organic solvents that make up the lath component
After adding and mixing the organic solvent to this, remove the organic solvent
Then, the organic compound is added to the barium titanate (BaTi).
O3) The feature is that it is uniformly supported on the powder surface and heat-treated.
To collect.
【０００９】すなわち、この発明の誘電体磁器組成物の
製造方法においては、ＢａＴｉＯ3粉体表面のシェルを
構成する元素及びガラス成分を構成する元素（すなわ
ち、添加元素）は、有機溶剤可溶な有機化合物の形で配
合され、添加された有機溶剤に溶解し、さらに有機溶剤
が除去された後均一な状態でＢａＴｉＯ3粉体（ＢａＴ
ｉＯ3コア）表面に付着する。そして、これを熱処理す
ることにより得られる誘電体磁器組成物は、不純物の含
有量が極めて少ない高純度のＢａＴｉＯ3が用いられて
おり、ＢａＴｉＯ3１００モルに対してＤｙ2Ｏ3０．６
０〜０．７２モル及びＣｏＯ１．２０〜１．４４モルが
固溶され、さらに、Ｂａ側を構成する成分とＴｉ側を構
成する成分のモル比を補正するためのＢａＯ１．３７〜
１．５８モルと、ＭｇＯ１．８０〜２．１６モル、Ｎｉ
Ｏ０．６０〜０．７２モルが添加され、また、還元防止
剤としてＭｎＯ０．３０〜０．３６モルと、焼結助剤と
して全体の１．１３〜１．３１重量％のＬｉ−Ｂａ−Ｓ
ｒ−Ｓｉ系酸化物ガラス成分とが添加されていることか
ら、誘電特性が向上し、誘電率の温度特性がよりフラッ
トに改善されるとともに絶縁抵抗値が向上する。That is, in the method for producing a dielectric ceramic composition of the present invention, the element constituting the shell of the BaTiO 3 powder surface and the element constituting the glass component (that is, the additional element) are soluble in an organic solvent. It is blended in the form of an organic compound, dissolved in the added organic solvent, and after the organic solvent is removed, the BaTiO 3 powder (BaT 3
iO 3 core) Adhere to the surface. The dielectric ceramic composition obtained by heat treating this, the content of impurities has very little pure BaTiO 3 of is used, Dy 2 O 3 0.6 with respect to BaTiO 3 100 moles
0 to 0.72 mol and CoO 1.20 to 1.44 mol are solid-dissolved, and BaO 1.37 to correct the molar ratio of the component forming the Ba side and the component forming the Ti side.
1.58 mol, MgO 1.80 to 2.16 mol, Ni
O of 0.60 to 0.72 mol was added, MnO of 0.30 to 0.36 mol as a reduction inhibitor, and 1.13 to 1.31 wt% of Li-Ba-S as a sintering aid.
Since the r-Si-based oxide glass component is added, the dielectric characteristics are improved, the temperature characteristics of the dielectric constant are improved more flatly, and the insulation resistance value is improved.
【００１０】この発明の誘電体磁器組成物の製造方法に
おいて、各成分を限定した理由を以下に説明する。The reason why each component is limited in the method for producing a dielectric ceramic composition of the present invention will be described below.
【００１１】まず、ＢａＴｉＯ3をアルカリ金属酸化物
の含有量が０．０４重量％未満のＢａＴｉＯ3に限定し
たのは、アルカリ金属酸化物の含有量が０．０４重量％
を越えると、誘電率の低下が生じ、添加元素の割合など
の他の条件を変えても所望の誘電特性を有する誘電体磁
器組成物を得ることが困難なためである。[0011] First, the a BaTiO 3 content of alkali metal oxides has been limited to BaTiO 3 of less than 0.04 wt%, the content of alkali metal oxide is 0.04 wt%
This is because if the value exceeds 1.0, the dielectric constant is lowered, and it is difficult to obtain a dielectric ceramic composition having desired dielectric properties even if other conditions such as the ratio of the additive element are changed.
【００１２】また、Ｄｙ2Ｏ3の添加量を０．６０〜０．
７２モルとしたのは、主成分であるＢａＴｉＯ3１００
モルに対してＤｙ2Ｏ3の添加量が０．６０モル未満の場
合には誘電率の低下が生じるとともに、低温での容量温
度変化率が大きく（−）側に外れてしまい、また、添加
量が０．７２モルを越えると高温部における容量温度変
化率が大きく（＋）側に外れてしまうことによる。Further, the addition amount of Dy 2 O 3 is 0.60 to 0.
72 mol was selected as the main component of BaTiO 3 100.
When the amount of Dy 2 O 3 added is less than 0.60 mol per mol, the dielectric constant decreases, and at the same time, the rate of change in capacity-temperature at low temperatures largely deviates to the (-) side. This is because when the amount exceeds 0.72 mol, the rate of change in the capacity temperature at the high temperature portion is large and the value deviates to the (+) side.
【００１３】ＣｏＯの添加量を１．２０〜１．４４モル
としたのは、ＢａＴｉＯ3１００モルに対してＣｏＯの
添加量が１．２０モル未満の場合には、高温部での容量
温度変化率が大きく（＋）側に外れてしまい、また、添
加量が１．４４モルを越えると誘電率の低下が生じると
ともに低温部での容量温度変化率が大きく（−）側に外
れてしまうことによる。The amount of CoO added is set to 1.20 to 1.44 mol, because the amount of CoO added is less than 1.20 mol relative to 100 mol of BaTiO 3 , the capacity-temperature change at a high temperature portion. The rate is greatly deviated to the (+) side, and if the addition amount exceeds 1.44 mol, the dielectric constant is lowered and the rate of change in capacity temperature at the low temperature part is greatly deviated to the (-) side. by.
【００１４】また、Ｄｙ2Ｏ3及びＣｏＯの添加量を上記
のように限定したのは、Ｄｙ2Ｏ3とＣｏＯの合計量が
１．８０モル未満の場合にはＤｙ2Ｏ3及びＣｏＯの添加
効果が不十分になり、キュリー温度付近の高温における
容量温度変化率が大きく（＋）側に外れてしまい、ま
た、Ｄｙ2Ｏ3及びＣｏＯの合計量が２．１６モルを越え
るとＤｙ2Ｏ3及びＣｏＯの構成比率が大きくなり、絶縁
抵抗及び誘電率の低下が著しくなることにもよる。Further, the addition amount of Dy 2 O 3 and CoO were limited as described above, when the total amount of Dy 2 O 3 and CoO is less than 1.80 mol of Dy 2 O 3 and CoO The effect of addition becomes insufficient, the rate of change in capacity-temperature at high temperatures near the Curie temperature is largely deviated to the (+) side, and when the total amount of Dy 2 O 3 and CoO exceeds 2.16 mol, Dy 2 This is also due to the fact that the composition ratio of O 3 and CoO becomes large, and the insulation resistance and the dielectric constant significantly decrease.
【００１５】ＢａＯの添加量を１．３７〜１．５８モル
としたのは、ＢａＴｉＯ3１００モルに対してＢａＯの
添加量が１．３７モル未満の場合には焼成中に組織が半
導体化して絶縁抵抗値が低下し、また、添加量が１．５
８モルを越えると焼結性が悪くなることによる。The amount of BaO added is set to 1.37 to 1.58 mol. The reason is that when the amount of BaO added is less than 1.37 mol per 100 mol of BaTiO 3 , the structure becomes a semiconductor during firing. Insulation resistance decreases, and the addition amount is 1.5
This is because if the amount exceeds 8 moles, the sinterability deteriorates.
【００１６】ＭｇＯの添加量を１．８０〜２．１６モル
としたのは、ＢａＴｉＯ3１００モルに対してＭｇＯの
添加量が１．８０モル未満になると容量温度変化率をフ
ラットにする効果がなくなり、特に低温側で（−）側に
外れる傾向があるとともに、絶縁抵抗値向上の効果がな
くなり、また、添加量が２．１６モルを越えた場合に
は、誘電率及び絶縁抵抗値が低下することによる。The amount of MgO added is set to 1.80 to 2.16 mol, because the amount of MgO added is less than 1.80 mol with respect to 100 mol of BaTiO 3 , which has the effect of flattening the rate of change in capacity-temperature. In particular, there is a tendency to deviate to the (-) side at low temperature side, the effect of improving the insulation resistance value disappears, and when the addition amount exceeds 2.16 moles, the dielectric constant and insulation resistance value decrease. By doing.
【００１７】また、ＮｉＯの添加量を０．６０〜０．７
２モルとしたのは、ＢａＴｉＯ3１００モルに対してＮ
ｉＯの添加量が０．６０モル未満になると容量温度変化
率をフラットにする効果がなくなるばかりでなく、絶縁
抵抗値を向上させる効果がなくなり、また、添加量が
０．７２モルを越えた場合には、誘電率及び絶縁抵抗値
が低下することによる。The amount of NiO added is 0.60 to 0.7.
2 moles means that N is based on 100 moles of BaTiO 3.
When the added amount of iO is less than 0.60 mol, not only the effect of flattening the capacity-temperature change rate disappears but also the effect of improving the insulation resistance value disappears, and when the added amount exceeds 0.72 mol. This is because the dielectric constant and the insulation resistance value decrease.
【００１８】ＭｎＯの添加量を０．３０〜０．３６モル
としたのは、ＢａＴｉＯ3１００モルに対してＭｎＯの
添加量が０．３０モル未満になると組織の耐還元性向上
の効果が小さくなり、組織が半導体化して絶縁抵抗値が
著しく低下し、また、添加量が０．３６モルを越えた場
合には、絶縁抵抗値、特に高温における絶縁抵抗値が著
しく低下することによる。The amount of MnO added is set to 0.30 to 0.36 mol. The reason is that if the amount of MnO added is less than 0.30 mol per 100 mol of BaTiO 3 , the effect of improving the reduction resistance of the structure is small. This is because the structure becomes a semiconductor and the insulation resistance value is remarkably lowered, and when the addition amount exceeds 0.36 mol, the insulation resistance value, particularly the insulation resistance value at high temperature is remarkably decreased.
【００１９】さらに、焼結助剤のＬｉ−Ｂａ−Ｓｒ−Ｓ
ｉ系酸化物ガラスの添加量を１．１３〜１．３１重量％
としたのは、１．１３重量％未満では焼結温度を低下さ
せる効果及び耐還元性を向上させる効果が不十分にな
り、また、１．３１重量％を越えると誘電率が低下する
ことによる。Further, the sintering aid Li-Ba-Sr-S is used.
Addition amount of i-type oxide glass is 1.13 to 1.31% by weight
The reason is that if it is less than 1.13% by weight, the effect of lowering the sintering temperature and the effect of improving the reduction resistance become insufficient, and if it exceeds 1.31% by weight, the dielectric constant lowers. ..
【００２０】なお、上記添加元素（Ｌｉ−Ｂａ−Ｓｒ−
Ｓｉ系酸化物ガラス成分を含む）は、有機溶剤可溶な有
機（金属）化合物の形で配合され、添加された有機溶剤
に溶解し、さらに有機溶剤が除去された後に均一な状態
でＢａＴｉＯ3粉体表面に付着するため、ＢａＴｉＯ3コ
ア表面上にシェル及びガラス成分を構成する各添加元素
を均一にコーティングすることが可能になるとともに、
これを熱処理することによりＢａＴｉＯ3粉体表面に均
一なシェル及びガラス相を形成することができる。The above-mentioned additive element (Li-Ba-Sr-
(Including the Si-based oxide glass component) is blended in the form of an organic solvent-soluble organic (metal) compound, dissolved in the added organic solvent, and after the organic solvent is removed, BaTiO 3 in a uniform state. Since it adheres to the powder surface, it becomes possible to uniformly coat each additive element constituting the shell and the glass component on the BaTiO 3 core surface.
By heat treating this, a uniform shell and glass phase can be formed on the surface of the BaTiO 3 powder.
【００２１】上述のように、この発明の誘電体磁器組成
物の製造方法によると、従来の方法と比較して、より効
果的に添加元素をＢａＴｉＯ3粉体表面に均一に付着さ
せることが可能になり、少ない添加量でＢａＴｉＯ3粉
体表面に均一なシェルを形成することができるため、電
気特性を悪化させる要因となる添加元素の添加割合を減
少させることにより、誘電特性や絶縁特性などの電気特
性に優れ、かつ、焼結性にも優れた誘電体磁器組成物を
確実に製造することができる。As described above, according to the method for producing the dielectric ceramic composition of the present invention, the additive element can be more effectively and uniformly attached to the surface of the BaTiO 3 powder as compared with the conventional method. Since it is possible to form a uniform shell on the surface of the BaTiO 3 powder with a small addition amount, the addition ratio of the additional element that causes the deterioration of the electrical characteristics can be reduced to improve the dielectric characteristics and the insulation characteristics. It is possible to reliably produce a dielectric ceramic composition having excellent electrical characteristics and excellent sinterability.
【００２２】なお、Ｃｏを含有する有機化合物として
は、例えば、Ｃｏ（ＯＣ3Ｈ7）2，Ｃｏ（ＯＣ4Ｈ9）2な
どのアルコキシド、オクチル酸コバルト、ナフテン酸コ
バルトなどの脂肪酸塩、アセチルアセトナート化合物な
どを挙げることができる。Examples of organic compounds containing Co include alkoxides such as Co (OC 3 H 7 ) 2 and Co (OC 4 H 9 ) 2 , fatty acid salts such as cobalt octylate and cobalt naphthenate, and acetyl. An acetonate compound etc. can be mentioned.
【００２３】また、Ｄｙ，Ｂａ，Ｍｎ，Ｎｉ，Ｍｇ，Ｌ
ｉ，Ｓｒを含有する有機化合物としても、同様に、アル
コキシド、オクチル酸塩、ナフテン酸塩などの脂肪酸
塩、アセチルアセトナート化合物などを挙げることがで
きる。Dy, Ba, Mn, Ni, Mg, L
Similarly, examples of the organic compound containing i, Sr include fatty acid salts such as alkoxide, octylate, and naphthenate, and acetylacetonate compounds.
【００２４】また、Ｓｉを含有する有機化合物として
は、例えば、Ｓｉ（ＯＣ2Ｈ5）4などのアルコキシド、
シロキサン、シラン化合物などを挙げることができる。The organic compound containing Si includes, for example, alkoxides such as Si (OC 2 H 5 ) 4 ,
Examples thereof include siloxane and silane compounds.
【００２５】さらに、上述のような添加元素の有機化合
物を溶解するために添加する有機溶剤としては、ベンゼ
ン、トルエン、キシレンその他、添加元素の有機化合物
を溶解することができる種々の溶剤を用いることが可能
であり、１種類の有機溶剤を単独で用いてもよく、２種
類以上を混合したものを用いてもよい。Further, as the organic solvent added to dissolve the organic compound of the additional element as described above, benzene, toluene, xylene, and other various solvents capable of dissolving the organic compound of the additional element are used. It is also possible to use one type of organic solvent alone or a mixture of two or more types.
【００２６】[0026]
【実施例】以下に、この発明の実施例を比較例とともに
示して、発明の特徴をさらに詳しく説明する。EXAMPLES The features of the present invention will be described in more detail below by showing examples of the present invention together with comparative examples.
【００２７】ＢａＴｉＯ3粉体５０ｇに対して、表１に
示す割合になるように、各添加元素の有機溶剤可溶の有
機化合物（ナフテン酸コバルト、オクチル酸バリウム、
オクチル酸ジスプロシウム、オクチル酸マグネシウム、
マンガンアセチルアセトナート、ナフテン酸リチウム、
オクチル酸ニッケル、エチルシリケート、オクチル酸ス
トロンチウム）を正確に秤量して添加配合する。The relative BaTiO 3 powder 50 g, so that the ratio shown in Table 1, the organic compound in the organic solvent-soluble in the additive elements (cobalt naphthenate, barium octylate,
Dysprosium octylate, magnesium octylate,
Manganese acetylacetonate, lithium naphthenate,
Nickel octylate, ethyl silicate, strontium octylate) are accurately weighed and added.
【００２８】[0028]
【表１】 [Table 1]
【００２９】なお、表１において＊印を付した実験No.
１０〜２４はこの発明の範囲外の比較例の配合割合を示
すものであり、また、＊印を付した実験No.２５は従来
の誘電体磁器組成物（従来例）の配合割合を示してい
る。Experiment Nos. Marked with * in Table 1
10 to 24 show the compounding ratios of the comparative examples outside the scope of the present invention, and Experiment No. 25 marked with * shows the compounding ratios of the conventional dielectric ceramic composition (conventional example). There is.
【００３０】次いで、これに、トルエン（有機溶剤）２
５mlを添加するとともに、部分安定化ジルコニア玉石
（直径５mm）１５０ｇを加えて１６時間混合分散処理を
行う。その後、ＢａＴｉＯ3粉体１００重量部に対して
７．５重量部のアクリル樹脂系のバインダと、２．５重
量部のジオクチルフタレートを添加してさらに５時間混
合分散処理を行う。Then, to this, toluene (organic solvent) 2
While adding 5 ml, 150 g of partially stabilized zirconia cobblestone (diameter 5 mm) is added and mixed and dispersed for 16 hours. Then, 7.5 parts by weight of an acrylic resin-based binder and 2.5 parts by weight of dioctyl phthalate are added to 100 parts by weight of BaTiO 3 powder, and mixed and dispersed for another 5 hours.
【００３１】それから、上記のようにして調製した原料
スラリーを脱気した後、ドクターブレード法により厚さ
４０μmのシートを作成する。そして、このシートを所
定の形状に打ち抜き、複数枚積層して圧着し、厚さ１mm
の単板を作成する。なお、原料スラリーから単板が製造
される過程で有機溶剤が除去され添加成分がＢａＴｉＯ
3粉体表面に均一に担持される。そして、この単板を５m
m角のチップにカットし、Ｈ2／Ｎ2の体積比が３／１０
００の還元性雰囲気ガス気流中において１２７０℃で３
時間焼成して焼結体を得た。それから、この焼結体の表
裏両主面にＡｇ電極を焼き付け、これを試料として電気
特性を測定し、各試料の電気特性を評価した。表２に各
試料についての電気特性の測定結果を示す。Then, the raw material slurry prepared as described above is degassed, and then a sheet having a thickness of 40 μm is prepared by the doctor blade method. Then, this sheet is punched into a predetermined shape, a plurality of sheets are laminated and pressure-bonded, and the thickness is 1 mm.
Create a veneer. The organic solvent was removed during the process of manufacturing the veneer from the raw material slurry, and the additive component was BaTiO 3.
3 Uniformly supported on the powder surface. And this veneer is 5m
Cut into m-square chips and the volume ratio of H 2 / N 2 is 3/10
3 at 1270 ° C in a reducing atmosphere gas flow of 00
It was fired for a time to obtain a sintered body. Then, Ag electrodes were baked on both the front and back main surfaces of this sintered body, and the electrical characteristics were measured using this as a sample, and the electrical characteristics of each sample were evaluated. Table 2 shows the measurement results of the electrical characteristics of each sample.
【００３２】[0032]
【表２】 [Table 2]
【００３３】表２に示すように、この発明の製造方法に
よって製造された誘電体磁器組成物は、いずれも、絶縁
抵抗がlogＩＲで１２（すなわち、１０12Ω・cm）以上
であり、誘電率も２５００以上と十分に高く、さらに、
高い誘電率を有しているにも拘らず静電容量の温度変化
率（ＴＣ）は、−５５〜１２５℃の範囲において、ＥＩ
Ａに規定されるＸ７Ｒ特性を満足していた。さらに、ta
nδも１．１％以下と小さく優れた誘電特性を有してい
ることがわかる。As shown in Table 2, each of the dielectric ceramic compositions produced by the production method of the present invention has an insulation resistance of 12 (ie, 10 12 Ω · cm) or more in log IR and a dielectric constant. Is 2,500 or more, which is sufficiently high.
Despite having a high dielectric constant, the temperature change rate (TC) of the capacitance is EI in the range of -55 to 125 ° C.
The X7R characteristics specified in A were satisfied. Furthermore, ta
It can be seen that nδ is as small as 1.1% or less and has excellent dielectric properties.
【００３４】なお、上記実施例においては、調整した原
料スラリーをシート状に成形し、所定の形状に打ち抜い
て積層し、圧着した後、これを焼成した場合について説
明したが、原料スラリーを乾燥させ、粉体原料として利
用することも可能である。In the above example, the adjusted raw material slurry was formed into a sheet, punched into a predetermined shape, laminated, pressure-bonded, and then fired, but the raw material slurry was dried. It can also be used as a powder raw material.
【００３５】[0035]
【発明の効果】上述のように、この発明の誘電体磁器組
成物の製造方法は、高純度のチタン酸バリウム（ＢａＴ
ｉＯ3）粉体と、添加元素の有機溶剤可溶の有機化合物
（Ｌｉ−Ｂａ−Ｓｒ−Ｓｉ系酸化物ガラス成分を含む）
を所定の割合で配合し、これに有機溶剤を添加混合し
て、ＢａＴｉＯ3粉体表面に有機化合物を均一に担持さ
せた後、所定の条件下で熱処理するようにしているた
め、絶縁抵抗がlogＩＲで１２以上で、誘電率が２５０
０以上と高く、かつ、静電容量の温度変化率（ＴＣ）が
ＥＩＡに規定されるＸ７Ｒ特性を満足し、しかもtanδ
の小さい（１．１％以下）誘電体磁器組成物を、特に複
雑な工程を必要とすることなく、また、比較的低い温度
（例えば、１２７０℃）で焼成することにより確実に製
造することができる。As described above, the method for producing a dielectric ceramic composition according to the present invention can be applied to high-purity barium titanate (BaT).
iO 3 ) powder and an organic solvent-soluble organic compound of an additional element (including a Li—Ba—Sr—Si-based oxide glass component)
Is mixed at a predetermined ratio, and an organic solvent is added to and mixed with this to uniformly support the organic compound on the surface of the BaTiO 3 powder, and heat treatment is performed under predetermined conditions. LogIR of 12 or more, dielectric constant of 250
It is as high as 0 or higher, and the temperature change rate (TC) of the capacitance satisfies the X7R characteristics specified by EIA, and tan δ
It is possible to reliably manufacture a small dielectric ceramic composition (1.1% or less) by firing at a relatively low temperature (for example, 1270 ° C.) without requiring a particularly complicated process. it can.
【００３６】また、この発明の製造方法により製造され
る誘電体磁器組成物を、例えば、積層コンデンサの誘電
体材料として用いることにより、Ｐｔなどの貴金属材料
に代えて、Ｎｉなどの卑金属材料を内部電極として用い
ることが可能になり、コンデンサとしての特性を低下さ
せることなく大幅なコストダウンを図ることが可能にな
る。Further, by using the dielectric ceramic composition manufactured by the manufacturing method of the present invention as a dielectric material of a laminated capacitor, for example, a noble metal material such as Pt is replaced with a base metal material such as Ni. It can be used as an electrode, and a significant cost reduction can be achieved without deteriorating the characteristics as a capacitor.
Claims (1)
重量％未満のチタン酸バリウム（ＢａＴｉＯ3）粉体
と、前記チタン酸バリウム（ＢａＴｉＯ3）粉体１００
モルに対して、 Ｄｙ2Ｏ3として ： ０．６０〜 ０．７２モル ＣｏＯとして ： １．２０〜 １．４４モル ＢａＯとして ： １．３７〜 １．５８モル ＮｉＯとして ： ０．６０〜 ０．７２モル ＭｎＯとして ： ０．３０〜 ０．３６モル ＭｇＯとして ： １．８０〜 ２．１６モル となる量のＤｙ，Ｃｏ，Ｂａ，Ｎｉ，Ｍｎ及びＭｇの有
機溶剤可溶の有機化合物と、全体に対して１．１３〜
１．３１重量％の、Ｌｉ−Ｂａ−Ｓｒ−Ｓｉ系酸化物ガ
ラス成分を構成する有機溶剤可溶の有機化合物とを配合
し、これに有機溶剤を添加混合した後、有機溶剤を除去
して前記有機化合物を前記チタン酸バリウム（ＢａＴｉ
Ｏ3）粉体表面に均一に担持させ、熱処理することを特
徴とする誘電体磁器組成物の製造方法。1. The content of alkali metal oxide is 0.04.
Barium titanate (BaTiO 3 ) powder of less than wt% and the barium titanate (BaTiO 3 ) powder 100
As moles of Dy 2 O 3 , 0.60 to 0.72 moles, as CoO: 1.20 to 1.44 moles, as BaO: 1.37 to 1.58 moles, as NiO: 0.60 to 0. 72 moles MnO: 0.30 to 0.36 moles MgO: 1.80 to 2.16 moles of Dy, Co, Ba, Ni, Mn and Mg organic solvent soluble organic compounds, For 1.13 ~
1.31% by weight of a Li-Ba-Sr-Si-based oxide glass component was mixed with an organic solvent-soluble organic compound, and an organic solvent was added to and mixed with this compound, and then the organic solvent was removed. The organic compound is added to the barium titanate (BaTi).
O 3 ) A method for producing a dielectric ceramic composition, which comprises uniformly supporting on a powder surface and heat-treating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03334106A JP3125386B2 (en) | 1991-11-21 | 1991-11-21 | Method for producing dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03334106A JP3125386B2 (en) | 1991-11-21 | 1991-11-21 | Method for producing dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05144319A true JPH05144319A (en) | 1993-06-11 |
| JP3125386B2 JP3125386B2 (en) | 2001-01-15 |
Family
ID=18273595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03334106A Expired - Lifetime JP3125386B2 (en) | 1991-11-21 | 1991-11-21 | Method for producing dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3125386B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0769719A (en) * | 1993-08-31 | 1995-03-14 | Fuji Elelctrochem Co Ltd | Production of low-temperature sintering dielectric porcelain |
| EP0737655A1 (en) * | 1995-04-12 | 1996-10-16 | Murata Manufacturing Co., Ltd. | Non-reduced dielectric ceramic compositions |
| JP2003007135A (en) * | 2001-06-22 | 2003-01-10 | Jsr Corp | Composition for forming dielectrics, composition for forming photo-sensitized dielectrics, dielectrics, and electronic part component |
| US6824873B2 (en) | 2001-06-22 | 2004-11-30 | Murata Manufacturing Co., Ltd. | Modified raw ceramic powder suitable for a monolithic ceramic electronic component |
| JP2007250995A (en) * | 2006-03-17 | 2007-09-27 | Kyocera Corp | Electronic component and method for manufacturing same |
-
1991
- 1991-11-21 JP JP03334106A patent/JP3125386B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0769719A (en) * | 1993-08-31 | 1995-03-14 | Fuji Elelctrochem Co Ltd | Production of low-temperature sintering dielectric porcelain |
| EP0737655A1 (en) * | 1995-04-12 | 1996-10-16 | Murata Manufacturing Co., Ltd. | Non-reduced dielectric ceramic compositions |
| JP2003007135A (en) * | 2001-06-22 | 2003-01-10 | Jsr Corp | Composition for forming dielectrics, composition for forming photo-sensitized dielectrics, dielectrics, and electronic part component |
| US6824873B2 (en) | 2001-06-22 | 2004-11-30 | Murata Manufacturing Co., Ltd. | Modified raw ceramic powder suitable for a monolithic ceramic electronic component |
| JP2007250995A (en) * | 2006-03-17 | 2007-09-27 | Kyocera Corp | Electronic component and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3125386B2 (en) | 2001-01-15 |
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