JPH0471110A - Dielectric porcelain composition - Google Patents
Dielectric porcelain compositionInfo
- Publication number
- JPH0471110A JPH0471110A JP2183415A JP18341590A JPH0471110A JP H0471110 A JPH0471110 A JP H0471110A JP 2183415 A JP2183415 A JP 2183415A JP 18341590 A JP18341590 A JP 18341590A JP H0471110 A JPH0471110 A JP H0471110A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- dielectric
- barium
- mol
- dielectric constant
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 27
- 229910052573 porcelain Inorganic materials 0.000 title description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 22
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 21
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052788 barium Inorganic materials 0.000 claims abstract description 14
- 229940071182 stannate Drugs 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 7
- 229910001954 samarium oxide Inorganic materials 0.000 claims abstract description 7
- 229940075630 samarium oxide Drugs 0.000 claims abstract description 7
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 27
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910021523 barium zirconate Inorganic materials 0.000 abstract description 11
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 239000003985 ceramic capacitor Substances 0.000 description 16
- 238000005452 bending Methods 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は誘電体磁器組成物に関し、特にチタン酸バリ
ウムを主体とし、たとえばセラミックコンデンサなどに
用いられる誘電体磁器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dielectric ceramic composition, and more particularly to a dielectric ceramic composition containing barium titanate as a main ingredient and used, for example, in ceramic capacitors.
（従来技術）
従来より、磁器コンデンサに用いられる誘電体磁器組成
物として、チタン酸バリウムを主体とするものが数多く
知られている。チタン酸バリウムは、１２０℃付近にキ
ュリー点を持ち、１００００近い誘電率を示すが、それ
だけでは常温で高誘電率とはなり得ない。そこで、シフ
ター材とよばれるものを加え、キュリー点を常温に移動
させて常温で高誘電率を持たせている。このシフター材
としては、錫酸化物、ジルコニア酸化物、稀土類元素な
どが知られている。(Prior Art) Many dielectric ceramic compositions mainly containing barium titanate have been known for use in ceramic capacitors. Barium titanate has a Curie point near 120° C. and exhibits a dielectric constant of nearly 10,000, but this alone cannot provide a high dielectric constant at room temperature. Therefore, something called a shifter material is added to move the Curie point to room temperature, giving it a high dielectric constant at room temperature. Known examples of this shifter material include tin oxide, zirconia oxide, and rare earth elements.
このようなシフター材を利用したチタン酸バリウムを主
体とする磁器コンデンサとしては、単板型リード線付タ
イプのものが製造されてきた。ところが、近年積層化技
術が進歩し、また３０〜８０μｍ程度の誘電体グリーン
シートが容易に得られるようになった。そして、内部電
極で誘電体薄膜を挟持する形で複数層積層したいわゆる
積層セラミックコンデンサがエレクトロニクス業界に進
出し、従来の誘電体磁器組成物もこのような積層セラミ
ックコンデンサの材料として利用されるようになった。As a ceramic capacitor mainly made of barium titanate using such a shifter material, a single-plate type with a lead wire has been manufactured. However, in recent years, lamination technology has progressed, and dielectric green sheets with a thickness of about 30 to 80 μm can now be easily obtained. Then, so-called multilayer ceramic capacitors, in which multiple layers are laminated with a dielectric thin film sandwiched between internal electrodes, entered the electronics industry, and conventional dielectric ceramic compositions were also used as materials for such multilayer ceramic capacitors. became.
一方、最近の磁器コンデンサは小型化の傾向があり、特
に積層コンデンサにおいては、磁器誘電体層の厚みが１
０〜２０μｍというように薄層化する傾向にある。この
場合、１００〜１００００μｍの厚みを持つ単板型コン
デンサに比べて、１０倍以上の電界強度を受ける。した
がって、単板型コンデンサに比べて電圧依存性の小さい
組成物が要求されている。On the other hand, there is a trend toward miniaturization of recent ceramic capacitors, and especially in multilayer capacitors, the thickness of the ceramic dielectric layer is 1
There is a tendency for the layer to become thinner, such as 0 to 20 μm. In this case, the electric field strength is ten times or more greater than that of a single-plate capacitor having a thickness of 100 to 10,000 μm. Therefore, a composition that has less voltage dependence than that of single-plate capacitors is required.
また、誘電体層が薄くなるに従って、セラミックの構造
的な欠陥が特性に反映されやすくなるので、結晶粒子の
大きさ゛（グレインサイズ）が均一でかつ微細であるこ
とと、空孔が少なくかつ小さいことが望まれる。In addition, as the dielectric layer becomes thinner, the structural defects of the ceramic are more likely to be reflected in the characteristics. It is hoped that
グレインサイズの小さいチタン酸バリウムを主体とした
誘電体磁器が、たとえば特願昭５６−１８０５９号、特
願昭５７−１６８０９号、特願昭５７−１０５９１９号
、特願昭５７−１９６４６９号などに開示されている。Dielectric porcelain mainly made of barium titanate with small grain size has been disclosed in Japanese Patent Application No. 56-18059, Japanese Patent Application No. 16809-1982, Japanese Patent Application No. 105919-1982, Japanese Patent Application No. 196469-1987, etc. Disclosed.
これらは、チタン酸バリウムに、酸化セリウムを加え、
あるいは酸化セリウムとジルコン酸バリウムを加え、あ
るいは酸化ネオジウムを加えることによって、チタン酸
バリウムのグレインサイズを小さくしたものである。These are made by adding cerium oxide to barium titanate.
Alternatively, the grain size of barium titanate is reduced by adding cerium oxide and barium zirconate, or by adding neodymium oxide.
（発明が解決しようとする課題）
グレインサイズの小さいこれらの誘電体磁器では、誘電
率が常温で最大１００００前後であり、グレインサイズ
の大きいものに比べると誘電率が小さく、積層コンデン
サを小型にした場合、大きい静電容量を得ることが困難
であった。さらに、誘電率の温度変化曲線が急峻である
ことも問題であった。(Problem to be solved by the invention) These dielectric ceramics with small grain sizes have a maximum dielectric constant of around 10,000 at room temperature, which is smaller than those with large grain sizes, making multilayer capacitors smaller. In this case, it was difficult to obtain a large capacitance. Another problem was that the temperature change curve of dielectric constant was steep.
それゆえに、この発明の主たる目的は、グレインサイズ
が小さく、大きい誘電率を有し、温度変化に対する誘電
率の変化が少なく、かつ電圧依存性の小さい誘電体磁器
を得ることができる誘電体磁器組成物を提供することで
ある。Therefore, the main object of the present invention is to provide a dielectric ceramic composition that can obtain a dielectric ceramic having a small grain size, a large dielectric constant, a small change in the permittivity with respect to temperature changes, and a small voltage dependence. It is about providing something.
本発明者は、誘電体磁器のグレインサイズが１〜３μｍ
と小さいときに誘電率が１００００に満たない原因を種
々検討した結果、主原料であるチタン酸バリウムの不純
物の種類とその含有量とが多い場合、その誘電率が大き
くならないことを見出した。The inventor has discovered that the grain size of dielectric porcelain is 1 to 3 μm.
As a result of various studies on the reasons why the dielectric constant is less than 10,000 when the barium titanate is small, it was found that the dielectric constant does not become large when the type and content of impurities in barium titanate, the main raw material, are large.
さらに、アルカリ金属酸化物の含有量が少ないチタン酸
バリウムにおいて、これに酸化ランタン、酸化セリウム
、酸化ネオジウム、酸化プラセオジウムおよび酸化サマ
リウムの中から選ばれる少なくとも１種類を加えること
によって、グレインサイズが小さくなりしかも大きい誘
電率を示すことを見出した。Furthermore, by adding at least one kind selected from lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, and samarium oxide to barium titanate, which has a low content of alkali metal oxides, the grain size can be reduced. Moreover, it was found that it exhibits a large dielectric constant.
また、ジルコン酸バリウム、錫酸バリウムおよび酸化チ
タンを加えることによって、誘電率の温度変化が小さく
電圧依存性の小さい誘電体磁器が得られることを見出し
た。Furthermore, it has been found that by adding barium zirconate, barium stannate, and titanium oxide, a dielectric ceramic whose dielectric constant changes little with temperature and whose voltage dependence is small can be obtained.
（課題を解決するための手段）
この発明は、不純物としてのアルカリ金属酸化物の含有
量が０．０３重量％以下のチタン酸バリウム１００モル
％に対して、酸化ランタン、酸化セリウム、酸化ネオジ
ウム、酸化プラセオジウムおよび酸化サマリウムの中か
ら選ばれる少なくとも１種１！［２，５〜５．０モル％
、ジルコン酸バリウムと錫酸バリウムとをＢ ａ （
Ｚ ｒ ｌ−ａ Ｓ ｎａ）Ｏ３ （ただし、０＜ａ≦
１，０）に換算して０５〜５．０モル％、および酸化チ
タンを１． ５〜６．０モル％含有した、誘電体磁器組
成物である。(Means for Solving the Problems) This invention provides that lanthanum oxide, cerium oxide, neodymium oxide, lanthanum oxide, cerium oxide, neodymium oxide, etc. At least one selected from praseodymium oxide and samarium oxide1! [2.5-5.0 mol%
, barium zirconate and barium stannate are B a (
Z r l-a S na) O3 (However, 0<a≦
05 to 5.0 mol% in terms of 1.0), and titanium oxide to 1.0% by mole. It is a dielectric ceramic composition containing 5 to 6.0 mol%.
次に、この発明にかかる誘電体磁器組成物の組成範囲を
限定した理由について説明する。Next, the reason for limiting the composition range of the dielectric ceramic composition according to the present invention will be explained.
従来、工業的に大量に用いられるチタン酸バリウムは９
８．５〜９９．５％程度の純度であり、不純物としてＳ
ｒＯ，Ｃａｂ、ＭｇＯなどのアルカリ土類金属、Ｎａｚ
Ｏ，に、０などのアルカリ金属酸化物およびＡｌ２ｚ
Ｏｓ 、Ｓ ｉｏｚなどの粉砕混合操作に伴う混入物
を含有するのが一般的である。Conventionally, barium titanate, which is used in large quantities industrially, is 9
It has a purity of about 8.5 to 99.5%, and contains S as an impurity.
Alkaline earth metals such as rO, Cab, MgO, Naz
O, to alkali metal oxides such as 0 and Al2z
It generally contains contaminants associated with the grinding and mixing operation, such as Os and Sioz.
この発明は、これらチタン酸バリウム中の不純物のうち
、特にＮａ、Ｏ，に、Ｏなどのアルカリ金属酸化物の含
有量が一定限度を超えると、特性が劣化することを見出
したことによって考え出されたものである。This invention was conceived based on the discovery that among the impurities in barium titanate, when the content of alkali metal oxides such as Na, O, and O exceeds a certain limit, the properties deteriorate. It is what was done.
すなわち、この発明にかかる誘電体磁器組成物では、チ
タン酸バリウム中の不純物のうちアルカリ金属酸化物の
含有量が０．０３重量％以下にされる。なぜなら、その
含有量が０．０３重量％を超えると、誘電率が１０００
０以下と小さくなるためである。That is, in the dielectric ceramic composition according to the present invention, the content of alkali metal oxide among impurities in barium titanate is set to 0.03% by weight or less. This is because when its content exceeds 0.03% by weight, the dielectric constant becomes 1000.
This is because the value becomes smaller than 0.
また、この発明にかかる誘電体磁器組成物では、アルカ
リ金属酸化物の不純物としての含有量を００３重量％以
下にしたチタン酸バリウム１００モル％に対して、酸化
ランタン、酸化セリウム。In addition, in the dielectric ceramic composition according to the present invention, lanthanum oxide and cerium oxide are added to 100 mol% of barium titanate in which the content of alkali metal oxide as an impurity is 0.03% by weight or less.
酸化ネオジウム、酸化プラセオジウム、酸化サマリウム
の中から選ばれる少なくとも１種類が２゜５〜５．０モ
ル％含有される。これらの含有量が２．５モル％未満で
は、得られた磁器のグレインサイズが十分に小さくなら
ない。一方、これらの含有量が５．０モル％を超えると
、キュリー点が常温より低温に移動し、常温での誘電率
が小さくなるか、あるいは焼結性が悪くなる。At least one selected from neodymium oxide, praseodymium oxide, and samarium oxide is contained in an amount of 2.5 to 5.0 mol %. If the content is less than 2.5 mol%, the grain size of the resulting porcelain will not be sufficiently small. On the other hand, if the content exceeds 5.0 mol %, the Curie point moves to a lower temperature than room temperature, and the dielectric constant at room temperature decreases or the sinterability deteriorates.
このように、不純物としてのアルカリ金属酸化物の含有
量が０．０３重量％以下のチタン酸バリウム１００モル
％に対して、酸化ランタン、酸化セリウム、酸化ネオジ
ウム、酸化プラセオジウム、酸化サマリウムの中から選
ばれる少なくとも１種類を２．５〜５．０モル％含有す
れば、グレインサイズが小さく、しかも誘電率が１１０
００以上と大きい誘電体磁器を得ることができる。In this way, for 100 mol% of barium titanate with an alkali metal oxide content of 0.03% by weight or less as an impurity, a compound selected from lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, and samarium oxide is used. By containing 2.5 to 5.0 mol% of at least one type, the grain size is small and the dielectric constant is 110.
It is possible to obtain dielectric ceramic having a diameter of 0.00 or more.
しかし−ながら、このような組成物では、温度変化に対
する誘電率の変化が大きくなり、ＪＩＳ規格のＦ特性な
どが満足されない。さらに、電圧依存性も大きくなり、
積層セラミックコンデンサにおいて、磁器誘電体層の薄
層化にとって好ましくない。However, in such a composition, the change in dielectric constant with respect to temperature change becomes large, and the F characteristic of the JIS standard is not satisfied. Furthermore, the voltage dependence increases,
In a multilayer ceramic capacitor, this is not preferable for reducing the thickness of the ceramic dielectric layer.
このような問題を解決するために、ジルコン酸バリウム
、錫酸バリウムが加えられ、ジルコン酸バリウム、錫酸
バリウムをＢａ （Ｚｒ、−、Ｓｎ。To solve this problem, barium zirconate and barium stannate are added, and barium zirconate and barium stannate are replaced by Ba(Zr,-,Sn).
）Ｏコ （ただし、Ｑ＜ａ≦１．０）に換算して０５〜
５．０モル％の範囲で添加することによってその効果が
大きくなる。) Oko (However, when converted to Q<a≦1.0) 05~
The effect becomes greater when it is added in an amount of 5.0 mol%.
それに対して、ジルコン酸バリウム、錫酸バリウムの含
有量が０．５モル％未満では、誘電率の温度特性が向上
せず、電圧依存性も大きい。一方、ジルコン酸バリウム
、錫酸バリウムの含有量が５０モル％を超えると、誘電
率の温度特性は向上するが、誘電率が低下する。On the other hand, if the content of barium zirconate or barium stannate is less than 0.5 mol %, the temperature characteristics of the dielectric constant are not improved and the voltage dependence is also large. On the other hand, if the content of barium zirconate or barium stannate exceeds 50 mol%, the temperature characteristics of the dielectric constant will improve, but the dielectric constant will decrease.
さらに、この発明にかかる誘電体磁器組成物では、酸化
チタンが１．５〜６．０モル％加えられる。酸化チタン
の含有量が１．５モル％未満では、焼結性が悪くなり、
焼成温度が高くなる。一方、酸化チタンの含有量が６．
０モル％を趙えると、室温および高温での絶縁抵抗が小
さくなる。Further, in the dielectric ceramic composition according to the present invention, 1.5 to 6.0 mol% of titanium oxide is added. If the content of titanium oxide is less than 1.5 mol%, sinterability will deteriorate,
Firing temperature increases. On the other hand, the content of titanium oxide is 6.
When the content is 0 mol%, the insulation resistance at room temperature and high temperature becomes small.
なお、この発明にかかる誘電体磁器組成物から誘電体磁
器を得るにあたって、還元防止側として微量のＭｎＣＯ
５、ＦｅｔＯ，などを添加しても、得られる磁器の特性
を損なうことがない。In addition, in obtaining dielectric ceramics from the dielectric ceramic composition according to the present invention, a trace amount of MnCO is added as a reduction prevention side.
5. Addition of FetO, etc. does not impair the properties of the resulting porcelain.
（発明の効果）
この発明によれば、グレインサイズが小さく、大きい誘
電率を有し、温度変化に対する誘電率の変化が少なく、
かつ電圧依存性の小さい誘電体磁器を得ることができる
。(Effects of the Invention) According to the present invention, the grain size is small and the dielectric constant is large, and the change in the dielectric constant with respect to temperature changes is small.
In addition, dielectric ceramics with low voltage dependence can be obtained.
この発明の上述の目的、その他の目的、特徴および利点
は、図面を参照して行う以下の実施例の詳細な説明から
一層明らかとなろう。The above objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings.
（実施例）
災施拠よ
原料として種々の純度のＢａＣＯ３とＴ ｉＯｚとを用
いて、これらをＢａＣＯ３とＴ ｉ Ｏｔとのモル比が
１．０００となるように秤量し、ジルコニア玉石を用い
たボールミルによって１６時時間式混合を行って、混合
物を得た。(Example) Using BaCO3 and TiOz of various purity as raw materials for disaster relief sites, these were weighed so that the molar ratio of BaCO3 and TiOt was 1.000, and zirconia cobblestone was used. Mixing was performed for 16 hours using a ball mill to obtain a mixture.
得られた混合物中の水分を蒸発した後、１１５０℃で２
時間保持して仮焼し、再びボールミルで平均粒径が２μ
ｍ以下になるまで粉砕した。このようにして、表１のＡ
、Ｂ、ＣおよびＤに示す純度の異なる４種類のチタン酸
バリウムを得た。After evaporating the water in the resulting mixture, it was heated at 1150°C for 2
Temporarily calcined for a period of time, then ball milled again to achieve an average particle size of 2μ.
It was pulverized until it was less than m. In this way, A in Table 1
Four types of barium titanate having different purity shown in , B, C and D were obtained.
そして、このチタン酸バリウム１００モル％に対して、
表２に示すように、酸化ランタン（ＬａｔＯり、酸化セ
リウム（Ｃｅ Ｏ□）、酸化ネオジウム（Ｎ ａｚ ０
３ ） 、酸化プロセオジウム（Ｐｒ６０＋＋）＊酸化
サマリウム（Ｓｍｚ ０３ ）、ジルコン酸バリウム（
ＢａＺｒＯ５）、錫酸バリウム（ＢａＳｎＯｓ）、酸化
チタン（Ｔ ｉＯｘ’）などを秤量し、酢酸ビニルバイ
ンダを加えて１６時時間式混合して混合物を得た。この
混合物を乾燥、造粒後２０００ｋｇ／−の圧力で直径１
０鴎、厚さ０．５ｍの円板に成形した。この円板を、表
３に示す温度で２時間焼成し、円板状の磁器を得た。And, for this barium titanate 100 mol%,
As shown in Table 2, lanthanum oxide (LatO), cerium oxide (CeO□), neodymium oxide (N az 0
3), Proseodymium oxide (Pr60++) *Samarium oxide (Smz 03), Barium zirconate (
BaZrO5), barium stannate (BaSnOs), titanium oxide (T iOx'), etc. were weighed, a vinyl acetate binder was added, and the mixture was mixed for 16 hours to obtain a mixture. After drying and granulating this mixture, the diameter of
It was molded into a disc with a thickness of 0.5 m. This disk was fired for 2 hours at the temperature shown in Table 3 to obtain a disk-shaped porcelain.
この磁器表面を電子顕微鏡を用いて２０００倍で観察し
、グレインサイズを測定した。The surface of this porcelain was observed using an electron microscope at a magnification of 2000 times, and the grain size was measured.
得られた磁器の両生面に銀電極を焼き付けて測定試料（
コンデンサ）とし、その室温での誘電率ε、誘電損失ｔ
ａｎδ（％）および温度変化に対する静電容量の変化率
を測定した。また、１００Ｖ／ｗｍ、１ｋｔｌｚの交流
電圧を印加し、誘電損失ｔａｎδ（％）を測定した。さ
らに、絶縁抵抗を測定するために、室温および１２５℃
で、絶縁抵抗計を用いて１００Ｖの電圧を２分間印加し
て比抵抗ρ（Ωｅｌｌ）を測定した。A measurement sample (
capacitor), its dielectric constant ε and dielectric loss t at room temperature are
anδ (%) and the rate of change in capacitance with respect to temperature change were measured. Further, an AC voltage of 100 V/wm and 1 ktlz was applied to measure the dielectric loss tan δ (%). Furthermore, to measure the insulation resistance, the
Then, a voltage of 100 V was applied for 2 minutes using an insulation resistance meter to measure the specific resistance ρ (Ωell).
なお、誘電率εおよび誘電損失ｔａｎδは、温度２５℃
１周波数１ｋｌ（ｚで測定した。また、温度変化に対す
る静電容量の変化率については、２０℃での静電容量を
基準とした一２５℃および８５℃での静電容量の変化率
（ΔＣ／ Ｃｔ。）を示した。Note that the dielectric constant ε and dielectric loss tan δ are determined at a temperature of 25°C.
The rate of change in capacitance with respect to temperature change is determined by the rate of change in capacitance at 25°C and 85°C (ΔC) based on the capacitance at 20°C. /Ct.).
これらの測定結果を表３に示した。The results of these measurements are shown in Table 3.
次に、表１２表２および表３に示す結果に基づいて、こ
の発明にかかる誘電体磁器組成物の組成範囲を限定した
理由について説明す７る。Next, based on the results shown in Table 12 and Table 3, the reason for limiting the composition range of the dielectric ceramic composition according to the present invention will be explained.
試料番号１および２のように、酸化ランタン。Lanthanum oxide, as in sample numbers 1 and 2.
酸化セリウム、酸化ネオジウム、酸化プラセオジウム、
酸化サマリウムなどの含有量が２．５モル％より少ない
場合、誘電率が小さくなるかまたはグレインサイズが３
μｍより大きくなってしまう。Cerium oxide, neodymium oxide, praseodymium oxide,
If the content of samarium oxide etc. is less than 2.5 mol%, the dielectric constant will be small or the grain size will be 3.
It becomes larger than μm.
一方、試料番号１３および１４のように、これらの含有
量が５モル％より多い場合、誘電率が小さくなったり、
焼成温度が高くなる。On the other hand, when the content is more than 5 mol%, as in sample numbers 13 and 14, the dielectric constant becomes small,
Firing temperature increases.
試料番号１５のように、ジルコン酸バリウムおよび錫酸
バリウムの含有量が０．５モル％より少ない場合、静電
容量の変化率が一８０％を超えてしまい好ましくない。When the content of barium zirconate and barium stannate is less than 0.5 mol %, as in sample number 15, the rate of change in capacitance exceeds 180%, which is not preferable.
一方、試料番号１６のように、ジルコン酸バリウムおよ
び錫酸バリウムの含有量が５．０モル％より多い場合、
静電容量の変化率は小さいが、誘電率が大幅に減少して
しまう。On the other hand, when the content of barium zirconate and barium stannate is more than 5.0 mol%, as in sample number 16,
Although the rate of change in capacitance is small, the dielectric constant decreases significantly.
また、試料番号１７のように、錫酸バリウムが全く含ま
れない場合、１００Ｖ／ｍの交流電圧を印加したときの
誘電損失が大きくなって好ましくない。Moreover, when barium stannate is not included at all, as in sample number 17, the dielectric loss increases when an AC voltage of 100 V/m is applied, which is not preferable.
試料番号１８および１９のように、アルカリ金属酸化物
の含有量が多いチタン酸バリウム原料ＣＤを用いた場合
、誘電率が小さくなる。When a barium titanate raw material CD containing a large amount of alkali metal oxide is used, as in sample numbers 18 and 19, the dielectric constant becomes small.
試料番号２０のように、酸化チタンの含有量が１．５モ
ル％より少ない場合、焼成温度が高くなる。一方、試料
番号２１のように、酸化チタンの含有量が６．０モル％
より多い場合、室温および高温での絶縁抵抗が小さくな
って好ましくない。When the content of titanium oxide is less than 1.5 mol%, as in sample number 20, the firing temperature becomes high. On the other hand, like sample number 21, the content of titanium oxide is 6.0 mol%
If the amount is larger than this, the insulation resistance at room temperature and high temperature becomes low, which is not preferable.
それに対して、この発明の範囲内の誘電体磁器組成物を
用いた試料（試料番号３〜１２参照）では、いずれも、
磁器の焼結体のグレインサイズが１〜３μｍと小さく、
誘電率が１１０００以上と大きく、また１００Ｖ／ｓｌ
ｌの交流電圧を印加したときの誘電損失が３．０％以内
と小さい。しかも、２０℃を基準にした一２５℃および
８５℃での静電容量の変化率が一８０％以内であり、Ｊ
ＩＳ規格のＦ特性を満足する。また、室温での比抵抗が
１０１３Ω口以上、高温での比抵抗が１０１０Ωａ以上
と大きい。On the other hand, in all samples using dielectric ceramic compositions within the scope of this invention (see sample numbers 3 to 12),
The grain size of the porcelain sintered body is as small as 1 to 3 μm,
It has a large dielectric constant of 11,000 or more, and has a high dielectric constant of 100V/sl.
The dielectric loss when applying an AC voltage of 1 is small, within 3.0%. Moreover, the rate of change in capacitance at -25°C and 85°C with 20°C as a reference is within 180%, and J
Satisfies the F characteristics of the IS standard. Further, the specific resistance at room temperature is 1013Ω or more, and the specific resistance at high temperature is 1010Ωa or more.
失施斑Ｉ
表２の試料番号１１の組成となるように秤量した原料に
、有機バインダ、分散剤、消泡剤の混合水溶液を１５重
量％添加し、５０重量％の水とともにボールミルで粉砕
、混合して原料スラリを得た。この原料スラリを用いて
、ドクターブレード法によって２２μｍのセラミックグ
リーンシートを作製した。このセラミックグリーンシー
ト上に、スクリーン印刷法によって内部電極用のパラジ
ウムペーストを印刷した。印刷したパラジウムペースト
が互いに対向するように、複数のセラミックグリーンシ
ートを積層し、熱圧着して積層体を得た。Mottling loss I To the raw material weighed to have the composition of sample number 11 in Table 2, 15% by weight of a mixed aqueous solution of an organic binder, dispersant, and antifoaming agent was added, and ground with 50% by weight of water in a ball mill. A raw material slurry was obtained by mixing. Using this raw material slurry, a 22 μm ceramic green sheet was produced by a doctor blade method. Palladium paste for internal electrodes was printed on this ceramic green sheet by screen printing. A plurality of ceramic green sheets were laminated so that the printed palladium pastes faced each other, and thermocompression bonded to obtain a laminate.
得られた積層体を１３２０℃で２時間焼成して焼結体を
得た。得られた焼結体の両端面に銀ペーストを塗布し、
空気中において８００℃で焼き付け、内部電極と電気的
に接続された外部電極を形成した。このようにして、積
層セラミックコンデンサを得た。この積層セラミックコ
ンデンサの寸法は、次に示す通りである。The obtained laminate was fired at 1320° C. for 2 hours to obtain a sintered body. Apply silver paste to both end faces of the obtained sintered body,
Baking was performed at 800° C. in air to form an external electrode electrically connected to the internal electrode. In this way, a multilayer ceramic capacitor was obtained. The dimensions of this multilayer ceramic capacitor are as shown below.
外形寸法 幅：１．６日
長さ：３．２鶴
厚さ：１．２ｍ
セラミック厚さ８１３μｍ
有効誘電体層数：１９
１層あたりの対向電極面積：２．０ｆｉ”得られた積層
セラミックコンデンサの試料について、温度２５℃にお
ける１ ｋｈ、 １ ｖｒａ＊での静電容量Ｃ（ｎＦ
）および誘電損失ｔａｎδ（％）を測定した。また、２
５Ｖの直流電圧を２分間印加して、絶縁抵抗ＩＲ（Ω）
を測定した。また、２０℃での静電容量を基準とした一
２５℃および８５℃での静電容量変化率ΔＣ／ Ｃｚ。External dimensions Width: 1.6 day Length: 3.2 Thickness: 1.2 m Ceramic thickness: 813 μm Effective number of dielectric layers: 19 Opposing electrode area per layer: 2.0 fi” The obtained multilayer ceramic capacitor For the sample, the capacitance C (nF
) and dielectric loss tan δ (%) were measured. Also, 2
Apply 5V DC voltage for 2 minutes to measure insulation resistance IR (Ω)
was measured. Also, the capacitance change rate ΔC/Cz at -25°C and 85°C based on the capacitance at 20°C.
（％）を測定した。さらに、直流破壊電圧値ＢＤＶ （
Ｖ）と抗折強度とを測定した。(%) was measured. Furthermore, the DC breakdown voltage value BDV (
V) and bending strength were measured.
なお、抗折強度は、第１図に示す抗折強度測定装置１０
を用いて測定した。第１図において、１２は試料である
被試験積層セラミックコンデンサであり、１４は試料保
持台である。試料保持台１４上に置かれたコンデンサ１
２は、加圧ピン１６によって加圧される。そして、加圧
された圧力が、置き釘付テンションゲージ１８によって
表示される。この試験に際して、試料保持台１４の治具
のスパンは２１ｎとした。Note that the bending strength is measured using a bending strength measuring device 10 shown in FIG.
Measured using In FIG. 1, 12 is a sample of a multilayer ceramic capacitor to be tested, and 14 is a sample holder. Capacitor 1 placed on sample holder 14
2 is pressurized by a pressure pin 16. Then, the applied pressure is displayed by the tension gauge 18 with a set nail. In this test, the span of the jig for the sample holding table 14 was set to 21n.
比較例として、ＢａＴｉ０：＋ １００モル％に対し
て、ＢａＺｒＯｓ １Ｂ、５モル％、ＣａＺｒ０．８．
９モル％を添加し、上述と同様の方法によって積層セラ
ミックコンデンサを作製した。そして、この比較例につ
いて、上述の各特性を測定した。As a comparative example, BaZrOs 1B, 5 mol%, CaZr0.8.
A multilayer ceramic capacitor was fabricated by adding 9 mol % and using the same method as described above. The above-mentioned characteristics were then measured for this comparative example.
また、それぞれの積層セラミックコンデンサの表面を電
子顕微鏡で２０００倍で観察し、グレインサイズを測定
した。以上の結果を表４に示した。In addition, the surface of each multilayer ceramic capacitor was observed with an electron microscope at a magnification of 2000 times, and the grain size was measured. The above results are shown in Table 4.
表４かられかるように、この発明の組成を有する材料で
作製した積層セラミックコンデンサは、比較例に比べて
グレインサイズが小さく、誘電損失が小さい。また、こ
の発明の材料で作製した積層セラミックコンデンサは、
比較例に比べて、２倍程度の絶縁破壊電圧および抗折強
度を有する。As can be seen from Table 4, the multilayer ceramic capacitor made of the material having the composition of the present invention has a smaller grain size and a smaller dielectric loss than the comparative example. Furthermore, the multilayer ceramic capacitor manufactured using the material of this invention is
It has about twice the dielectric breakdown voltage and bending strength as the comparative example.
なお、この実施例では、予めＢａＴｉＯ３，ＢａＺ ｒ
Ｏｘ 、Ｂ ａ Ｓ ｎ ０３を作製したのち、所定量
秤量して混合したが、この方法に限定されるものではな
く、予めアルカリ金属酸化物の含有量の少ないＢａＣ０
，、Ｔｉｃ）ｇ 、Ｚｒ０ｔ、５ｎＯ８の各原料を用い
て所望の組成比となるように配合し、所定の温度で仮焼
することによりＢａ（Ｔ１１−Ｘ−Ｖ Ｚ ｒ ｘ Ｓ
ｎｙ ） ０３を作製しても、同等の特性が得られる
。In this example, BaTiO3, BaZ r
After preparing Ox, B a S n 03, a predetermined amount was weighed and mixed. However, the method is not limited to this method.
,,Tic)g, Zr0t, and 5nO8 to obtain a desired composition ratio, and calcined at a predetermined temperature to produce Ba(T11-X-V Zr x S
Even if ny) 03 is produced, equivalent characteristics can be obtained.
第１図は試料の抗折強度を測定するための抗折強度測定
装置を示す図解図である。
図において、１０は抗折強度測定装置、１２は被試験積
層セラミックコンデンサ、１４は試料保持台、１６は加
圧ビン、１８は置き釘付テンションゲージである。
特許出願人 株式会社 村田製作所
代理人 弁理士 岡 １） 全 啓FIG. 1 is an illustrative diagram showing a bending strength measuring device for measuring the bending strength of a sample. In the figure, 10 is a bending strength measuring device, 12 is a multilayer ceramic capacitor to be tested, 14 is a sample holder, 16 is a pressure bottle, and 18 is a tension gauge with a set nail. Patent applicant Murata Manufacturing Co., Ltd. Representative Patent attorney Oka 1) Kei Zen
Claims (1)
３重量％以下のチタン酸バリウム１００モル％に対して
、 酸化ランタン、酸化セリウム、酸化ネオジウム、酸化プ
ラセオジウムおよび酸化サマリウムの中から選ばれる少
なくとも１種を２．５〜５．０モル％、 ジルコン酸バリウムと錫酸バリウムとをＢａ（Ｚｒ＿１
＿−＿ａＳｎ＿ａ）Ｏ＿３（ただし、０＜ａ≦１．０）
に換算して０．５〜５．０モル％、および酸化チタンを
１．５〜６．０モル％含有した、誘電体磁器組成物。[Claims] The content of alkali metal oxide as an impurity is 0.0.
2.5 to 5.0 mol% of at least one selected from lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, and samarium oxide to 100 mol% of barium titanate of 3% by weight or less, and zirconate. Barium and barium stannate are combined with Ba(Zr_1
____aSn_a)O_3 (however, 0<a≦1.0)
A dielectric ceramic composition containing 0.5 to 5.0 mol% of titanium oxide and 1.5 to 6.0 mol% of titanium oxide.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2183415A JP2508374B2 (en) | 1990-07-10 | 1990-07-10 | Dielectric porcelain composition |
| DE69116753T DE69116753T2 (en) | 1990-07-10 | 1991-07-09 | Dielectric ceramic compositions and manufacturing process of dielectric ceramics |
| US07/727,425 US5130281A (en) | 1990-07-10 | 1991-07-09 | Dielectric ceramic compositions and manufacturing method of dielectric ceramics |
| CA002046496A CA2046496C (en) | 1990-07-10 | 1991-07-09 | Dielectric ceramic compositions and manufacturing method of dielectric ceramics |
| EP91111441A EP0466122B1 (en) | 1990-07-10 | 1991-07-09 | Dielectric ceramic compositions and manufacturing method of dielectric ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2183415A JP2508374B2 (en) | 1990-07-10 | 1990-07-10 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0471110A true JPH0471110A (en) | 1992-03-05 |
| JP2508374B2 JP2508374B2 (en) | 1996-06-19 |
Family
ID=16135382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2183415A Expired - Lifetime JP2508374B2 (en) | 1990-07-10 | 1990-07-10 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2508374B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5144110A (en) * | 1974-10-11 | 1976-04-15 | Yoshiaki Nakamura | |
| JPS59154703A (en) * | 1983-02-20 | 1984-09-03 | 株式会社村田製作所 | High dielectric constant porcelain composition |
-
1990
- 1990-07-10 JP JP2183415A patent/JP2508374B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5144110A (en) * | 1974-10-11 | 1976-04-15 | Yoshiaki Nakamura | |
| JPS59154703A (en) * | 1983-02-20 | 1984-09-03 | 株式会社村田製作所 | High dielectric constant porcelain composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2508374B2 (en) | 1996-06-19 |
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