JP2616220B2 - Porcelain composition - Google Patents
Porcelain compositionInfo
- Publication number
- JP2616220B2 JP2616220B2 JP2304153A JP30415390A JP2616220B2 JP 2616220 B2 JP2616220 B2 JP 2616220B2 JP 2304153 A JP2304153 A JP 2304153A JP 30415390 A JP30415390 A JP 30415390A JP 2616220 B2 JP2616220 B2 JP 2616220B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- porcelain composition
- dielectric constant
- temperature
- present
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は磁器組成物に関し、特に誘電率、絶縁抵抗が
高く、誘電損失が小さく、かつ1000℃以下の温度で焼結
可能な磁器組成物に関するものである。Description: TECHNICAL FIELD The present invention relates to a porcelain composition, and more particularly to a porcelain composition having a high dielectric constant, a high insulation resistance, a small dielectric loss, and which can be sintered at a temperature of 1000 ° C. or lower. It is about.
［従来の技術］ 従来、高誘電率系磁器組成物として、チタン酸バリウ
ム［BaTiO3］系がよく知られており、チタン酸カルシウ
ム［CaTiO3］、チタン酸鉛［PbTiO3］などを添加、置換
することにより、温度特性の改善を図っているが、焼結
温度が1300℃以上の高温であるため、積層セラミックコ
ンデンサに使用した場合、その内部電極には白金，パラ
ジウム等の高価な貴金属しか利用できなかった。[Prior art] Conventionally, barium titanate [BaTiO 3 ] is well known as a high dielectric constant porcelain composition, and calcium titanate [CaTiO 3 ], lead titanate [PbTiO 3 ], etc. are added. The temperature characteristics are improved by replacement, but since the sintering temperature is as high as 1300 ° C or more, when used for multilayer ceramic capacitors, only expensive noble metals such as platinum and palladium are used for the internal electrodes. Not available.
［発明が解決しようとする課題］ 従来の材料で温度変化率の小さい材料を実現した場
合、得られる誘電率はせいぜい2000程度にすぎず、コン
デンサ用の材料としては小さすぎる。近年、低温で焼結
し、かつ誘電率が高い材料として鉛系複合ペロブスカイ
ト化合物が報告されている。例えばマグネシウム・ニオ
ブ酸鉛［Pb（Mg1/3Nb2/3）O3］、チタン酸鉛［PbTi
O3］、ニッケル・ニオブ酸鉛［Pb（Ni1/3Nb2/3）O3］か
らなる３成分組成物は、誘電率を室温で20000以上と高
くすることが可能であることが報告されている。しかし
この３成分系では、誘電率の温度変化が大きく、かつ直
流バイアスを印加した時の容量の減少が大きいという問
題点がある。そのため実用上、その使用範囲が限られて
いた。[Problem to be Solved by the Invention] When a material having a small temperature change rate is realized by a conventional material, the obtained dielectric constant is only about 2000 at most, and is too small as a material for a capacitor. In recent years, a lead-based composite perovskite compound has been reported as a material which is sintered at a low temperature and has a high dielectric constant. For example, lead magnesium / niobate [Pb (Mg 1/3 Nb 2/3 ) O 3 ], lead titanate [PbTi
It has been reported that a three-component composition comprising O 3 ] and nickel nickel niobate [Pb (Ni 1/3 Nb 2/3 ) O 3 ] can have a dielectric constant as high as 20,000 or more at room temperature. Have been. However, this three-component system has a problem that the temperature change of the dielectric constant is large and the capacitance decreases greatly when a DC bias is applied. Therefore, the range of use has been practically limited.
本発明の目的は、上記の組成物の誘電率の温度特性を
改善し、かつ直流バイアス印加時の容量減少ができるだ
け小さい磁器組成物を提供することにある。An object of the present invention is to provide a porcelain composition which improves the temperature characteristics of the dielectric constant of the above composition and reduces the capacity when applying a DC bias as little as possible.
［課題を解決するための手段］ 本発明は、マグネシウム・タングステン酸鉛［Pb（Mg
1/2Ｗ1/2）O3］、チタン酸鉛［PbTiO3］および亜鉛・ニ
オブ酸鉛［Pb（Zn1/3Nb2/3）O3］からなる３成分系組成
物を［Pb（Mg1/2Ｗ1/2）O3］ｘ［PbTiO3］ｙ［Pb（Zn
1/3Nb2/3）O3］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）と表現し
たとき、以下の組成点 （ｘ＝0.40、ｙ＝0.20、ｚ＝0.40） （ｘ＝0.40、ｙ＝0.50、ｚ＝0.10） （ｘ＝0.20、ｙ＝0.20、ｚ＝0.60） を結ぶ線上、およびこの３点に囲まれる組成範囲内にあ
ることを特徴とし、かつｘ≠2z/3であることを特徴とす
る磁器組成物である。[Means for Solving the Problems] The present invention relates to a magnesium / lead tungstate [Pb (Mg
1/2 W 1/2 ) O 3 ], lead titanate [PbTiO 3 ] and zinc / niobate lead [Pb (Zn 1/3 Nb 2/3 ) O 3 ]. (Mg 1/2 W 1/2 ) O 3 ] x [PbTiO 3 ] y [Pb (Zn
When expressed as 1/3 Nb 2/3 ) O 3 ] z (where x + y + z = 1.0), the following composition points (x = 0.40, y = 0.20, z = 0.40) (x = 0.40, y = 0.50, z = 0.10) (x = 0.20, y = 0.20, z = 0.60) and within a composition range surrounded by these three points, and x ≠ 2z / 3. It is a porcelain composition.
本発明における組成範囲を表す３成分組成図は第１図
で表される。本発明に含まれる組成範囲は図の斜線で示
す範囲（但しｘ≠2z/3を満足する組成に限る。）、およ
びその境界線上である。なお、特公昭58−074569号公報
において、本発明における磁器組成物と同じ組成系であ
る［Pb（Mg1/2Ｗ1/2）O3］−［PbTiO3］−［Pb（Zn1/3N
b2/3）O3］が報告されているが、この組成系は、第１図
中、点々で示す領域である。本発明は特公昭58−074569
号公報で報告した組成範囲の磁器組成物に対して、誘電
率がさらに高くなっている点で改良された磁器組成物で
ある。The three-component composition diagram representing the composition range in the present invention is shown in FIG. The composition range included in the present invention is a range indicated by oblique lines in the figure (however, limited to a composition satisfying x ≠ 2z / 3) and a boundary thereof. In JP-B-58-074569, [Pb (Mg 1/2 W 1/2 ) O 3 ]-[PbTiO 3 ]-[Pb (Zn 1 / ) is the same composition system as the porcelain composition of the present invention. 3 N
b 2/3 ) O 3 ] has been reported, but this composition system is a region indicated by dots in FIG. The present invention relates to Japanese Patent Publication No. 58-074569.
This is a porcelain composition improved in that the dielectric constant is higher than that of the porcelain composition in the composition range reported in Japanese Patent Publication No.
［実施例］ 以下、本発明の実施例について詳細に説明する。[Examples] Hereinafter, examples of the present invention will be described in detail.
実施例１ 出発原料として酸化鉛（PbO）、酸化タングステン（W
O3）、酸化マグネシウム（MgO）、酸化ニオブ（Nb
2O5）、酸化亜鉛（ZnO）、酸化チタン（TiO2）を使用
し、第１表に示した配合比となるように各々秤量した。Example 1 Lead oxide (PbO), tungsten oxide (W
O 3 ), magnesium oxide (MgO), niobium oxide (Nb
2 O 5 ), zinc oxide (ZnO), and titanium oxide (TiO 2 ) were weighed so as to have the compounding ratios shown in Table 1.
次に秤量した各材料をボールミル中で湿式混合したの
ち、800〜850℃で仮焼を行い、この粉末をボールミルで
粉砕し、濾過、乾燥後、有機バインダを入れて整粒後プ
レスし、直径約16mm、厚さ約2mmの円板２枚と、直径約1
6mm、厚さ約10mmの円柱を作製した。Next, the weighed materials are wet-mixed in a ball mill, then calcined at 800 to 850 ° C., the powder is pulverized in a ball mill, filtered, dried, put in an organic binder, sized, and pressed. Approximately 16mm, thickness of about 2mm two discs, diameter of about 1
A cylinder having a thickness of 6 mm and a thickness of about 10 mm was produced.
次に本発明の組成範囲の試料を900〜1000℃の温度で
１時間焼成を行った。焼成した円板の上下面に600℃で
銀電極を焼き付け、デジタルLCRメータで周波数1kHz、
電圧1Vr.m.s、室温で容量と誘電損失を測定し、誘電率
および温度に対する誘電率の変化率を求めた。さらに50
Vの直流電圧を１分間印加した時の電流値を絶縁抵抗計
で測定して試料の比抵抗を求めた。Next, the sample in the composition range of the present invention was fired at a temperature of 900 to 1000 ° C. for 1 hour. Silver electrodes are baked at 600 ° C on the upper and lower surfaces of the baked disk, and the frequency is 1 kHz with a digital LCR meter.
The capacitance and the dielectric loss were measured at a voltage of 1 Vr.ms and room temperature, and the permittivity and the rate of change of the permittivity with respect to the temperature were obtained. 50 more
The current value when a DC voltage of V was applied for one minute was measured with an insulation resistance meter to determine the specific resistance of the sample.
このようにして得られた磁器の主成分［Pb（Mg1/2Ｗ
1/2）O3］ｘ［PbTiO3］ｙ［Pb（Zn1/3Nb2/3）O3］ｚの
配合比x,y,zおよび室温における誘電率、誘電損失およ
び−30℃、85℃における誘電率の変化率（20℃における
誘電率を基準）を第１表に示す。The main component of the porcelain thus obtained [Pb (Mg 1/2 W
1/2) O 3] x [PbTiO 3] y [Pb (Zn 1/3 Nb 2/3) O 3] mixing ratio of z x, y, z and dielectric constant at room temperature, the dielectric loss and -30 ° C., Table 1 shows the rate of change of the dielectric constant at 85 ° C. (based on the dielectric constant at 20 ° C.).
第１表からも明らかなように、［Pb（Mg1/2Ｗ1/2）
O3］−［PbTiO3］−［Pb（Zn1/3Nb2/3）O3］３成分系組
成物における本発明の組成範囲の磁器組成物は、高い誘
電率、比抵抗の値を有し、かつ誘電率の温度による変化
が小さく、EIA規格のY5U特性、およびY5T特性を満足す
ることが可能である。さらに本発明の磁器組成物は1000
℃以下の低い温度で焼結できるため、積層セラミックコ
ンデンサの内部電極に安価な銀・パラジウム合金を用い
ることができる。As is clear from Table 1, [Pb (Mg 1/2 W 1/2 )
The porcelain composition in the composition range of the present invention in the O 3 ]-[PbTiO 3 ]-[Pb (Zn 1/3 Nb 2/3 ) O 3 ] ternary composition has high dielectric constant and specific resistance. It has a small change in dielectric constant with temperature, and can satisfy the Y5U characteristics and the Y5T characteristics of the EIA standard. Further, the porcelain composition of the present invention is 1000
Since sintering can be performed at a low temperature of not more than ℃, an inexpensive silver / palladium alloy can be used for the internal electrodes of the multilayer ceramic capacitor.
実施例２ ［Pb（Mg1/2Ｗ1/2）O3］ｘ［PbTiO3］ｙ［Pb（Zn1/3N
b2/3）O3］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）３成分系磁器
組成物において、（x,y,z）＝（0.40,0.30,0.30）、
（0.30,0.20,0.50）となるように、酸化鉛、酸化マグネ
シウム、酸化タングステン、酸化チタン、、酸化亜鉛お
よび酸化ニオブを正確に秤量し、実施例１で示した方法
と同様な方法で誘電体粉末を合成した。 Example 2 [Pb (Mg 1/2 W 1/2 ) O 3 ] x [PbTiO 3 ] y [Pb (Zn 1/3 N
b 2/3 ) O 3 ] z (where x + y + z = 1.0) In a three-component porcelain composition, (x, y, z) = (0.40,0.30,0.30),
(0.30, 0.20, 0.50) Lead oxide, magnesium oxide, tungsten oxide, titanium oxide, zinc oxide, and niobium oxide were accurately weighed, and the dielectric material was obtained in the same manner as described in Example 1. A powder was synthesized.
得られた誘電体粉末を有機溶媒中に分散させ、有機バ
インダと混練してスラリーを作製し、スラリーを通常の
ドクターブレード法を用いて40μｍの厚さに成膜した。
さらに通常のスクリーン印刷法で内部電極ペーストを印
刷し、所定の形状に打ち抜いた後、積層、熱プレスを行
って得た積層体を一定の形状に切断してコンデンサのグ
リーンチップを作製した。グリーンチップを所定の温度
条件で脱バインダ、焼成を行い、さらに銀ペーストを用
いて外部電極を被着、形成した。The obtained dielectric powder was dispersed in an organic solvent, kneaded with an organic binder to prepare a slurry, and the slurry was formed into a film having a thickness of 40 μm using a normal doctor blade method.
Further, the internal electrode paste was printed by a normal screen printing method, punched into a predetermined shape, and then laminated and hot-pressed, and the obtained laminate was cut into a predetermined shape to produce a capacitor green chip. The green chip was subjected to binder removal and firing under a predetermined temperature condition, and an external electrode was attached and formed using a silver paste.
コンデンサにデジタルマルチメータで０〜50Vの電流
バイアスを印加した状態でデジタルLCRメータを用いて1
KHz、1Vr.m.s.の交流で、室温でコンデンサの容量を測
定した。測定結果を第２図に示した。図中、Ａは（x,y,
z）＝（0.30,0.20,0.50）の組成物を、Ｂは（x,y,z）＝
（0.40,0.30,0.30）の組成物を示す。Use a digital LCR meter while applying a current bias of 0 to 50 V to the capacitor with a digital multimeter.
The capacity of the capacitor was measured at room temperature with an alternating current of 1 Hz and KHz. The measurement results are shown in FIG. In the figure, A is (x, y,
z) = (0.30,0.20,0.50) composition, B is (x, y, z) =
(0.40, 0.30, 0.30).
比較例 ［Pb（Mg1/3Nb2/3）O3］ｘ［PbTiO3］ｙ［Pb（Ni1/3N
b2/3）O3］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）で示される３
成分系磁器組成物において、ｘ＝0.20,y＝0.20,z＝0.60
となるような組成物を用いて、実施例２で示した方法で
コンデンサを作製し、同様の方法で直流バイアス印加時
の容量を測定した。測定結果を実施例２の結果と共に第
２図に示した。Comparative Example [Pb (Mg 1/3 Nb 2/3 ) O 3 ] x [PbTiO 3 ] y [Pb (Ni 1/3 N
b 2/3) O 3] 3 represented by z (provided that x + y + z = 1.0)
In the component-based porcelain composition, x = 0.20, y = 0.20, z = 0.60
Using such a composition, a capacitor was produced by the method shown in Example 2, and the capacitance when a DC bias was applied was measured in the same manner. FIG. 2 shows the measurement results together with the results of Example 2.
第２図に示したように、比較例で示した組成の磁器組
成物を用いたコンデンサは直流バイアス印加時の容量減
少が著しいのに対して、本発明の磁器組成物を用いたコ
ンデンサは直流バイアス印加時の容量減少が小さいこと
がわかる。As shown in FIG. 2, the capacitor using the porcelain composition having the composition shown in the comparative example has a remarkable decrease in capacity when a DC bias is applied, whereas the capacitor using the porcelain composition of the present invention has a direct current. It can be seen that the capacitance decrease during bias application is small.
なお、本発明の範囲外の組成では、キュリー点が室温
から高温側や低温側に片寄りすぎて容量の温度特性が悪
くなる、誘電損失が大きくなる、あるいは比抵抗が小さ
くなるという弊害が現れるためコンデンサ用の磁器組成
物としては適さない。In addition, in a composition outside the range of the present invention, the Curie point deviates too much from the room temperature to the high temperature side or the low temperature side to deteriorate the temperature characteristics of the capacitor, increase the dielectric loss, or reduce the specific resistance. Therefore, it is not suitable as a porcelain composition for capacitors.
［発明の効果］ 本発明の磁器組成物は、誘電率が高く、温度による誘
電率の変化も小さく、かつ直流バイアス印加時の容量減
少が小さい。また良好な誘電損失の値を持ち、低い温度
で焼結が可能である。したがって温度特性の優れた積層
セラミックコンデンサを製造することが可能であり、か
つコンデンサの内部電極に安価な銀−パラジウムを用い
ることができる。[Effect of the Invention] The porcelain composition of the present invention has a high dielectric constant, a small change in the dielectric constant with temperature, and a small decrease in capacity when a DC bias is applied. In addition, it has a good dielectric loss value and can be sintered at a low temperature. Therefore, a multilayer ceramic capacitor having excellent temperature characteristics can be manufactured, and inexpensive silver-palladium can be used for the internal electrodes of the capacitor.
さらに直流バイアス印加時の容量減少が小さいため、
スイッチング電極など直流バイアスを印加した条件で使
用される積層セラミックコンデンサ用の磁器組成物とし
て用いることが可能である。Furthermore, since the capacity decrease when DC bias is applied is small,
It can be used as a porcelain composition for a multilayer ceramic capacitor used under conditions where a DC bias is applied, such as a switching electrode.
第１図は本発明の組成範囲を示す３成分組成図、第２図
は本発明の組成物を用いた積層セラミックコンデンサの
一例の直流バイアス印加時の容量変化率を積層セラミッ
クコンデンサの１層当たりの直流電界強度に対してプロ
ットした図である。FIG. 1 is a three-component composition diagram showing the composition range of the present invention, and FIG. 2 is a graph showing an example of a multilayer ceramic capacitor using the composition of the present invention. FIG. 5 is a diagram plotted against the DC electric field intensity of FIG.
Claims (1)
1/2Ｗ1/2）O3］、チタン酸鉛［PbTiO3］および亜鉛・ニ
オブ酸鉛［Pb（Zn1/3Nb2/3）O3］からなる３成分系組成
物を［Pb（Mg1/2Ｗ1/2）O3］ｘ［PbTiO3］ｙ［Pb（Zn
1/3Nb2/3）O3］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）と表現し
たとき、以下の組成点 （ｘ＝0.40、ｙ＝0.20、ｚ＝0.40） （ｘ＝0.40、ｙ＝0.50、ｚ＝0.10） （ｘ＝0.20、ｙ＝0.20、ｚ＝0.60） を結ぶ線上、およびこの３点に囲まれる組成範囲内にあ
ることを特徴とし、かつｘ≠2z/3であることを特徴とす
る磁器組成物。Claims: 1. Magnesium lead tungstate [Pb (Mg
1/2 W 1/2 ) O 3 ], lead titanate [PbTiO 3 ] and zinc / niobate lead [Pb (Zn 1/3 Nb 2/3 ) O 3 ]. (Mg 1/2 W 1/2 ) O 3 ] x [PbTiO 3 ] y [Pb (Zn
When expressed as 1/3 Nb 2/3 ) O 3 ] z (where x + y + z = 1.0), the following composition points (x = 0.40, y = 0.20, z = 0.40) (x = 0.40, y = 0.50, z = 0.10) (x = 0.20, y = 0.20, z = 0.60) and within a composition range surrounded by these three points, and x ≠ 2z / 3. Porcelain composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2304153A JP2616220B2 (en) | 1990-11-13 | 1990-11-13 | Porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2304153A JP2616220B2 (en) | 1990-11-13 | 1990-11-13 | Porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04182344A JPH04182344A (en) | 1992-06-29 |
| JP2616220B2 true JP2616220B2 (en) | 1997-06-04 |
Family
ID=17929695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2304153A Expired - Fee Related JP2616220B2 (en) | 1990-11-13 | 1990-11-13 | Porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2616220B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874569A (en) * | 1981-09-30 | 1983-05-06 | 日本電気株式会社 | Ceramic composition |
| JPH068205B2 (en) * | 1985-10-02 | 1994-02-02 | 松下電器産業株式会社 | Dielectric porcelain composition |
| JPH0664931B2 (en) * | 1985-11-14 | 1994-08-22 | 株式会社村田製作所 | Dielectric porcelain composition |
| JP2719594B2 (en) * | 1988-04-29 | 1998-02-25 | ティーディーケイ株式会社 | High dielectric constant porcelain composition |
-
1990
- 1990-11-13 JP JP2304153A patent/JP2616220B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04182344A (en) | 1992-06-29 |
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