JPS6348134B2 - - Google Patents
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- Publication number
- JPS6348134B2 JPS6348134B2 JP58096312A JP9631283A JPS6348134B2 JP S6348134 B2 JPS6348134 B2 JP S6348134B2 JP 58096312 A JP58096312 A JP 58096312A JP 9631283 A JP9631283 A JP 9631283A JP S6348134 B2 JPS6348134 B2 JP S6348134B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- composition
- dielectric constant
- dielectric
- mno
- 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
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- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
産業上の利用分野
本発明は焼成温度が低く、大きい誘電率を有し
温度特性に優れ、さらに誘電体損失の小さいセラ
ミツクコンデンサ用材料に関するものである。
従来例の構成とその問題点
セラミツクコンデンサ用の高誘電率材料として
はチタン酸バリウム系の材料が広く用いられてい
る。この系の材料が有している比誘電率は、その
温度特性と密接な関係にあり、JIS規格に定めら
れたＹ級Ｆ特性（誘電率の温度変化が−25〜85℃
の温度範囲で20℃の値を基準として＋30％、−80
％以内）を満たす材料としては比誘電率が10000
程度、Ｙ級Ｄ特性（前述の条件で＋20％、−30％
以内）を満たす材料では比誘電率が4000程度であ
る。このチタン酸バリウム系の材料は誘電体損失
tanδも低く、その他の諸特性も優れているが、そ
の焼成には1300〜1400℃という相当高い温度を必
要とする。そのため、この系の材料を積層セラミ
ツクコンデンサに用いるときには、内部電極とし
て高価な白金系の電極が必要となる。一方、900
℃前後の低温で焼成可能な材料として、Pb（Fe1/2
Nb1/2）O3−Pb（Fe2/3W1/3）O3系等の誘電体材料
が知られている。これらは室温の比誘電率が
10000〜20000と大きい値を有するが、その温度変
化率も大きく、前述のＹ級Ｄ特性を満たす材料は
知られていない。
民生用電子機器で使用されているコンデンサの
大半は、その温度特性としてＹ級Ｄ特性に相当す
るものであるため、900℃前後の温度で焼成可能
であり、温度特性の優れたコンデンサ材料が得ら
れるならば、その工業的価値は大である。
発明の目的
本発明は、焼成温度が850〜950℃と低く、チタ
ン酸バリウム系でＹ級Ｄ特性を満たす材料の比誘
電率と同等以上、すなわち4000以上の比誘電率を
有し、かつ−25゜〜85℃の温度範囲で誘電体損失
tanδが小さい磁器組成物を提供することを目的と
する。
発明の構成
本発明の誘電体磁器組成物は、Pb（Mg1/3
Nb2/3）x（Zn1/3Nb2/3）y（Fe2/3W1/3）zO3＋Ｗ重量％
MnO2の組成物においてｘ、ｙ、ｚが図に示す多
角形ABCDEの範囲内の組成にあり、さらに
MnO2を0.05〜１重量％含むことを特徴とする。
実施例の説明
原料として化学的に高純度のPbO、MgO、
Nb2O5、ZnO、Fe2O3、WO3、MnO2を下表の組
成に従つて秤量し、めのうの玉石と純水を加えて
ポリエチレンポツトで15時間混合し、乾燥した
後、750℃で２時間仮焼し、さらに前述のポツト
で15時間粉砕して乾燥させた。その後、ポリビニ
ルアルコール水溶液をバインダとして加え、直径
13mm、高さ10mmの円柱状に加圧成形し、バインダ
を焼却した後、マグネシア磁器容器に入れ、850
〜950℃で２時間焼成した。得られたPb（Mg1/3
Nb2/3）x（Zn1/3Nb2/3）y（Fe2/3W1/3）zO3＋Ｗ重量％
MnO2なる組成の磁器焼成物を厚さ１mmに切断
し、両面にCr−Auを蒸着して電極を形成し、20
℃の温度下での比誘電率εrと誘電正接tanδおよび
その温度変化を1KHz、1V／mmの電界で測定し
た。これらの結果を表に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a ceramic capacitor material that has a low firing temperature, a large dielectric constant, excellent temperature characteristics, and low dielectric loss. Conventional Structure and Problems Barium titanate-based materials are widely used as high dielectric constant materials for ceramic capacitors. The relative permittivity of this type of material is closely related to its temperature characteristics, and it is defined by the JIS standard Y class F characteristic (temperature change in dielectric constant of -25 to 85 degrees Celsius).
+30%, -80 based on the value of 20℃ in the temperature range of
%), the relative dielectric constant is 10000.
grade, Y class D characteristics (+20%, -30% under the above conditions)
Materials that satisfy (within) have a relative permittivity of approximately 4000. This barium titanate-based material has dielectric loss
It has a low tan δ and other excellent properties, but its firing requires a fairly high temperature of 1300 to 1400°C. Therefore, when this type of material is used in a multilayer ceramic capacitor, expensive platinum-based electrodes are required as internal electrodes. On the other hand, 900
Pb (Fe 1/2
Dielectric materials such as Nb 1/2 ) O 3 -Pb (Fe 2/3 W 1/3 ) O 3 are known. These have dielectric constants at room temperature of
Although it has a large value of 10,000 to 20,000, its temperature change rate is also large, and no material is known that satisfies the above-mentioned Y class D characteristics. Most capacitors used in consumer electronic devices have temperature characteristics equivalent to Class Y D characteristics, so they can be fired at temperatures around 900°C, making it possible to obtain capacitor materials with excellent temperature characteristics. If possible, its industrial value would be great. Purpose of the Invention The present invention has a low firing temperature of 850 to 950°C, a dielectric constant equal to or higher than that of a barium titanate-based material satisfying Y class D characteristics, that is, a dielectric constant of 4000 or higher, and - Dielectric loss in temperature range from 25° to 85°C
The object is to provide a porcelain composition with a small tan δ. Structure of the Invention The dielectric ceramic composition of the present invention contains Pb (Mg 1/3
Nb 2/3 ) x (Zn 1/3 Nb 2/3 ) y (Fe 2/3 W 1/3 ) z O 3 + W weight%
In the composition of MnO 2 , x, y, and z are within the range of the polygon ABCDE shown in the figure, and
It is characterized by containing 0.05 to 1% by weight of MnO2 . Description of Examples Chemically high-purity PbO, MgO,
Weigh Nb 2 O 5 , ZnO, Fe 2 O 3 , WO 3 , and MnO 2 according to the composition in the table below, add agate cobbles and pure water, mix in a polyethylene pot for 15 hours, dry, and then The mixture was calcined at ℃ for 2 hours, and then ground and dried in the pot described above for 15 hours. After that, polyvinyl alcohol aqueous solution was added as a binder, and the diameter
Pressure molded into a cylindrical shape of 13 mm and height 10 mm, incinerated the binder, placed in a magnesia porcelain container, and heated to 850
Baked at ~950°C for 2 hours. The obtained Pb(Mg 1/3
Nb 2/3 ) x (Zn 1/3 Nb 2/3 ) y (Fe 2/3 W 1/3 ) z O 3 + W weight%
A fired porcelain product with a composition of MnO 2 was cut to a thickness of 1 mm, and Cr-Au was vapor-deposited on both sides to form electrodes.
The relative dielectric constant εr, dielectric loss tangent tanδ, and their temperature changes at a temperature of ℃ were measured at 1 KHz and an electric field of 1 V/mm. These results are shown in the table.
【表】【table】
【表】
＊は本発明範囲外の比較例
表において、＊印を付した試料は本発明の範囲
外の試料である。本発明の範囲内の試料は全て−
25゜〜85℃の温度範囲で20℃の値を基準とする比
誘電率εrの変化率が−30％〜＋20％の範囲内であ
り、JIS規格に定められたＹ級Ｄ特性の温度変化
率を満足する。さらに、比誘電率εrはチタン酸バ
リウム系の材料と同等以上の4100〜6600を示し、
その誘電損失を表わすtanδも室温で１％以下、−
25〜85℃の温度範囲についてみても2.5％以下で
ある。組成式Pb（Mg1/3Nb2/3）x（Zn1/3Nb2/3）y
（Fe2/3W1/3）zO3（ただしｘ＋ｙ＋ｚ＝１）のｘ、
ｙ、ｚが図に示すＡ、Ｂ、Ｃ、Ｄ、Ｅの五点を頂
点とする多角形の領域外では、温度変化率がＹ級
Ｄ特性を満足しないので、本発明の範囲から除か
れる。また、MnO2の添加量が0.05重量％よりも
少ないと室温より高い温度下での損失が大きく、
tanδを表わして10％以上にも達し、コンデンサと
しては機能しなくなり、また、MnO2の添加量が
１重量％を越えるとやはり誘電体損失が大きくな
るので、本発明の範囲から除かれる。
発明の効果
以上述べてきたように、本発明による誘電体磁
器組成物によれば、比誘電率が大きく、また焼成
温度が低くてよいため、安価な内部電極材料を使
用した積層型セラミツクコンデンサを作製するこ
とができる。無論、その他のセラミツクコンデン
サに使用しても、大きな比誘電率、低い焼成温度
は非常に大きな長所となる。また、その温度特性
についても民生用電子機器に使用されているコン
デンサの大半を満足することができるので、本発
明の工業的価値は大きい。[Table] * indicates a comparative example outside the scope of the present invention In the table, samples marked with an asterisk (*) are samples outside the scope of the present invention. All samples within the scope of the invention-
In the temperature range of 25° to 85°C, the rate of change in relative dielectric constant ε r is within the range of -30% to +20% with respect to the value at 20°C, and the temperature is the Y class D characteristic specified in the JIS standard. Satisfy the rate of change. Furthermore, the relative permittivity ε r is 4100 to 6600, which is equal to or higher than that of barium titanate-based materials.
The tan δ, which represents the dielectric loss, is less than 1% at room temperature, -
Even in the temperature range of 25 to 85°C, it is less than 2.5%. Composition formula Pb (Mg 1/3 Nb 2/3 ) x (Zn 1/3 Nb 2/3 ) y
(Fe 2/3 W 1/3 ) x of z O 3 (x+y+z=1),
Outside the polygonal region where y and z have the five points A, B, C, D, and E shown in the figure as vertices, the temperature change rate does not satisfy the Y-class D characteristic and is therefore excluded from the scope of the present invention. . Furthermore, if the amount of MnO 2 added is less than 0.05% by weight, the loss will be large at temperatures higher than room temperature.
If the tan δ reaches 10% or more, it will no longer function as a capacitor, and if the amount of MnO 2 added exceeds 1% by weight, the dielectric loss will become large, so it is excluded from the scope of the present invention. Effects of the Invention As described above, the dielectric ceramic composition according to the present invention has a large dielectric constant and requires a low firing temperature, so that multilayer ceramic capacitors using inexpensive internal electrode materials can be used. It can be made. Of course, even when used in other ceramic capacitors, the large dielectric constant and low firing temperature are very significant advantages. Moreover, since the temperature characteristics can satisfy most of the capacitors used in consumer electronic devices, the present invention has great industrial value.
図はPb（Zn1/3Nb2/3）O3−Pb（Mg1/3Nb2/3）O3
−Pb（Fe2/3W1/3）O3三元系の組成図である。
The figure shows Pb(Zn 1/3 Nb 2/3 )O 3 −Pb(Mg 1/3 Nb 2/3 )O 3
-Pb(Fe2 /3W1 /3 ) O3 ternary system composition diagram.
Claims (1)
zO3系固溶体（ただし、ｘ＋ｙ＋ｚ＝１）の三元
系の組成図においてｘ、ｙ、ｚの値が下記点Ａ、
Ｂ、Ｃ、Ｄ、Ｅを頂点とする多角形の領域内の組
成物を主成分とし、さらに副成分としてMnO2を
0.05〜１重量％添加含有させたことを特徴とする
誘電体磁器組成物。 【表】[Claims] 1 Pb (Mg 1/3 Nb 2/3 ) x (Zn 1/3 Nb 2/3 ) y (Fe 2/3 W 1/3 )
In the composition diagram of the ternary system of z O 3 solid solution (x + y + z = 1), the values of x, y, and z are the following points A,
The composition within the polygonal region with vertices B, C, D, and E is the main component, and MnO 2 is further added as a subcomponent.
A dielectric ceramic composition characterized in that it contains 0.05 to 1% by weight. 【table】
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58096312A JPS59219804A (en) | 1983-05-30 | 1983-05-30 | Dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58096312A JPS59219804A (en) | 1983-05-30 | 1983-05-30 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59219804A JPS59219804A (en) | 1984-12-11 |
| JPS6348134B2 true JPS6348134B2 (en) | 1988-09-27 |
Family
ID=14161502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58096312A Granted JPS59219804A (en) | 1983-05-30 | 1983-05-30 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59219804A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6053408B2 (en) * | 1978-03-23 | 1985-11-26 | ニチコン株式会社 | Reduced semiconductor ceramic composition |
| JPS5767209A (en) * | 1980-10-15 | 1982-04-23 | Nippon Electric Co | Porcelain composition |
-
1983
- 1983-05-30 JP JP58096312A patent/JPS59219804A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59219804A (en) | 1984-12-11 |
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