JPH0794020A - Composition for barium titanate semiconductor ceramic - Google Patents

Abstract

PURPOSE:To provide a useful ceramic composition by using the composition of specific quantity in at least one kind main component raw material of BaTiO3, CaTiO3, and PbTiO3 and in semiconductor agents of Na, Ta, Sb, W, and Y and in the compound of TiO2, Al2O3, SiO2, and Mn. CONSTITUTION:At least one kind oxide of Nb, Ta, Sb, W, and Y is used as a semiconductor agent for main component raw material of BaTiO3 of 62-90mol%, CaTi03 of 7-18mol%, and PbTiO3 of 3-20mol%, and an element is blended to a main component so as to be included by 0.18-0.30mol%. Moreover as an additive, a TiO2 of 0.3-1.0mol%, an Al2O3 of 0.1-2.0mol%, and a SiO2 of 2.0-5.0mol%, and as a Mn element, Manganese compound of 0.02-0.06mol% are to be contained. This composition is reduced to powder, and obtained powder is temporarily baked, then a binder is mixed to easily form barium titanate semicondutive ceramic via granulating, molding, and sintering. This constitution obtains ceramic excellent in a withstand voltage characteristic and having small resistivity at ordinary temperature and positive resistance temperature characteristic.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、耐電圧特性に優れ、且
つ常温における比抵抗の小さい、正の抵抗温度特性を有
するチタン酸バリウム系半導体磁器用組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barium titanate-based semiconductor porcelain composition having excellent withstand voltage characteristics, low specific resistance at room temperature, and positive resistance temperature characteristics.

【０００２】[0002]

【従来の技術】チタン酸バリウム系半導体磁器は、Ｂａ
ＴｉＯ₃ を主成分とし、希土類元素等を半導体化剤とし
て少量含有させた組成を有するものであり、キュリー点
を超えると著しい正の抵抗温度特性を示す特徴がある。
このキュリー点は、主成分であるＢａＴｉＯ₃ の特性に
より、ほゞ１２０℃付近にあるが、その用途に応じてＢ
ａの一部をＰｂで置換し、キュリー点を高温側へ移行さ
せたり、あるいはＢａの一部をＳｒで置換したり、Ｔｉ
の一部をＺｒまたはＳｎで置換して、キュリー点を低温
側へ移行させたりすることが知られている。この様なチ
タン酸バリウム系半導体磁器の耐電圧特性を向上させる
ために、Ｂａの一部をＣａで置換したり、又はＣａ及び
Ｐｂで置換したもの等が知られている。また、その製造
方法において、ＢａＣＯ₃ 、ＴｉＯ₂ を主原料とし、こ
れにＣａＣＯ₃ 、ＰｂＯ、ＺｒＯ₂ 、ＳｎＯ₂ 、ＳｒＣ
Ｏ₃ のうち一種以上、希土類元素等の半導体化剤、特性
改善の添加剤として必要に応じＭｎ化合物や、ＳｉＯ₂
を加え仮焼して、得られた粉体を微粉砕、成形の後、大
気中にて焼成することが知られている。2. Description of the Related Art Barium titanate-based semiconductor porcelain is made of Ba.
It has a composition containing TiO ₃ as a main component and a small amount of a rare earth element or the like as a semiconducting agent, and is characterized by exhibiting a remarkable positive resistance-temperature characteristic when it exceeds the Curie point.
The Curie point is around 120 ° C. due to the characteristics of the main component BaTiO ₃ , but depending on the application, B
A part of a is replaced with Pb to shift the Curie point to a high temperature side, or a part of Ba is replaced with Sr, Ti
It is known that a part of the is replaced with Zr or Sn to shift the Curie point to the low temperature side. In order to improve the withstand voltage characteristics of such a barium titanate-based semiconductor ceramic, it is known that a part of Ba is replaced with Ca, or Ca and Pb are replaced. In addition, in the manufacturing method thereof, BaCO ₃ and TiO ₂ are used as main raw materials, and CaCO ₃ , PbO, ZrO ₂ , SnO ₂ , and SrC are added to the main raw materials.
If necessary, one or more of O ₃ , a semiconductor agent such as a rare earth element, and an additive for improving characteristics, such as a Mn compound or SiO ₂
It is known that the resulting powder is finely pulverized and molded, and then fired in the air.

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、これら
チタン酸バリウム系半導体磁器は、キュリー点を１４０
℃以上にした場合、１０Ω・ｃｍ以下の比抵抗において
耐電圧が１００Ｖ／ｍｍ以下であり、電気部品としての
応用範囲を制約し、小型化、且つ高い安全性を有する電
気部品への適応を困難としてものであった。However, these barium titanate-based semiconductor ceramics have a Curie point of 140.
When the temperature is higher than ℃, the withstand voltage is 100 V / mm or less at the specific resistance of 10 Ω · cm or less, which limits the application range as an electrical component and makes it difficult to apply it to an electrical component having a small size and high safety. It was as

【０００４】又その製造方法は、ＰｂＯを上記の様に仮
焼前に添加することで、ＢａＴｉＯ₃ への固溶を向上さ
せ、又ＰｂＴｉＯ₃ の仮焼後における添加よりも比抵抗
を低下させているが、その焼成工程において、ＰｂＯ蒸
気圧が高いため揮散し、組成の不均質化を招き易く、こ
のため、いかにＰｂＯ揮散を押えて焼成するかという技
術的な課題を有していた。本発明はかかる課題を解決す
べく、耐電圧特性に優れ、且つ比抵抗の小さい、しかも
Ｐｂ成分の仮焼前後の添加を問わず、比抵抗を大きく変
化させることのない正の抵抗温度特性を有するチタン酸
バリウム系半導体磁器を製造するための原料組成物を提
供することを目的とする。Further, in the manufacturing method thereof, PbO is added before calcination as described above to improve the solid solution in BaTiO ₃ and to lower the specific resistance as compared with the addition of PbTiO ₃ after calcination. However, in the firing step, since the PbO vapor pressure is high, it is likely to be volatilized to cause inhomogeneity of the composition. Therefore, there is a technical problem of how to suppress the volatilization of PbO for firing. In order to solve such a problem, the present invention provides a positive resistance temperature characteristic which is excellent in withstand voltage characteristics and has a small specific resistance, and which does not significantly change the specific resistance regardless of addition of the Pb component before and after calcination. It is an object of the present invention to provide a raw material composition for producing the barium titanate-based semiconductor ceramics.

【０００５】[0005]

【課題を解決するための手段】即ち本発明はチタン酸バ
リウム系化合物の主成分に半導体化剤を添加させたチタ
ン酸バリウム系半導体磁器用原料組成物において、主成
分はＢａＴｉＯ₃ ６２〜９０モル％、ＣａＴｉＯ₃
７〜１８モル％、ＰｂＴｉＯ₃ ３〜２０モル％なる組
成物、又は該組成物形成用原料組成物であり、半導体化
剤としてＮａ、Ｔａ、Ｓｂ、Ｗ、Ｙのうちの少なくとも
一種の元素の化合物を主成分１００モル％に対して元素
として０．１８〜０．３０モル％含有し、添加剤として
ＴｉＯ₂ を０．３〜１．０モル％、Ａｌ₂ Ｏ₃ を０．１
〜２．０モル％、ＳｉＯ₂ を２．０〜５．０モル％、マ
ンガン化合物をＭｎ元素として０．０２〜０．０６モル
％含有することを特徴とするチタン酸バリウム系半導体
磁器用原料組成物に関するものであり、この組成物を微
粉砕し、得られた微粉を仮焼後、バインダーを混合、造
粒、成形後焼結してチタン酸バリウム系半導体磁器を容
易に製造することができる。That is, the present invention relates to a barium titanate-based semiconductor porcelain raw material composition in which a semiconducting agent is added to the barium titanate-based compound as a main component, and the main component is BaTiO ₃ 62 to 90 mol. %, CaTiO ₃
7 to 18 mol%, PbTiO _{3 3 to} 20 mol%, or a raw material composition for forming the composition, wherein at least one element selected from Na, Ta, Sb, W and Y is used as a semiconducting agent. The compound contains 0.18 to 0.30 mol% as an element based on 100 mol% of the main component, 0.3 to 1.0 mol% of TiO ₂ and 0.1% of Al ₂ O ₃ as additives.
To 2.0 mol%, SiO ₂ 2.0 to 5.0 mol%, and manganese compound 0.02 to 0.06 mol% as Mn element, barium titanate-based semiconductor porcelain raw material It relates to a composition, and finely pulverizes the composition, calcining the obtained fine powder, mixing a binder, granulating, and sintering after molding to easily produce a barium titanate-based semiconductor porcelain. it can.

【０００６】[0006]

【作用】次に本発明の原料組成物について述べる。主成
分は夫々６２〜９０モル％、７〜１８モル％、３〜２０
モル％のＢａＴｉＯ₃ 、ＣａＴｉＯ₃ 、ＰｂＴｉＯ₃ よ
りなる組成物、又は該組成物を形成し得る原料であるＢ
ａＣＯ₃ 、ＣａＣＯ₃ 、ＰｂＯ又はＰｂ₃ Ｏ₄ 、ＴｉＯ
₂ を焼成後，ＢａＴｉＯ₃ ６２〜９０モル％、ＣａＴ
ｉＯ₃ ７〜１８モル％、ＰｂＴｉＯ₃ ３〜２０モル
％なる組成物を生成するように混合する。ＢａＴｉＯ₃
を６２〜９０モル％としたのは、６２モル％未満では磁
器の比抵抗が大きくなり、９０モル％を超えると耐電圧
特性が著しく低下するからである。Next, the raw material composition of the present invention will be described. The main components are 62 to 90 mol%, 7 to 18 mol% and 3 to 20 respectively.
A composition comprising mol% of BaTiO ₃ , CaTiO ₃ , and PbTiO ₃ , or B which is a raw material capable of forming the composition
aCO ₃ , CaCO ₃ , PbO or Pb ₃ O ₄ , TiO
After firing ₂ , BaTiO ₃ 62-90 mol%, CaT
iO ₃ 7 to 18 mol%, and mixed to produce a PbTiO ₃ 3 to 20 mol% becomes the composition. BaTiO ₃
The content of 62 to 90 mol% is because if it is less than 62 mol%, the specific resistance of the porcelain becomes large, and if it exceeds 90 mol%, the withstand voltage characteristics are significantly deteriorated.

【０００７】又、ＣａＴｉＯ₃ を７〜１８モル％とした
のは、７モル％未満では特性改善の効果が認められず、
１８モル％を超えると比抵抗が大きくなるからである。
更に、ＰｂＴｉＯ₃ を３〜２０モル％としたのは、３モ
ル％未満では１４０℃以上のキュリー点が得られなく、
２０モル％を超えると比抵抗が大きくなるからである。Further, the CaTiO ₃ content is set to 7 to 18 mol% because the effect of improving the characteristics is not recognized when the content is less than 7 mol%.
This is because if it exceeds 18 mol%, the specific resistance increases.
Further, PbTiO _{3 is set} to ₃ to 20 mol%, because the Curie point of 140 ° C. or higher cannot be obtained if the PbTiO ₃ content is less than 3 mol%.
This is because if it exceeds 20 mol%, the specific resistance increases.

【０００８】半導体化剤としてＮｂ₂ Ｏ₅ 、Ｔａ₂ Ｏ
₅ 、Ｓｂ₂ Ｏ₃ 、Ｓｂ₂ Ｏ₅ 、ＷＯ₃、Ｙ₂ Ｏ₃ 、Ｙ
（ＮＯ₃ ）₃ 等を用いる。Ｎｂ、Ｔａ、Ｓｂ、Ｗ、Ｙの
うち少なくとも一種の元素の化合物を、主成分１００モ
ル％に対して元素として前述のように０．１８〜０．３
０モル％を配合するが、この範囲において本発明の目的
としている磁器の比抵抗を小さくし、且つ耐電圧特性の
向上が実現できるからである。又、主成分１００モル％
に対し、添加剤としてＴｉＯ₂ を０．３〜１．０モル％
としたのは、０．３モル％未満では特性改善の効果が認
められず、１．０モル％を超えると比抵抗が大きくなる
からである。又、Ａｌ₂ Ｏ₃ を０．１〜２．０モル％と
したのは、０．１モル％未満では特性改善の効果が認め
られず、２．０モル％を超えると比抵抗が大きくなるか
らである。更に、ＳｉＯ₂ を２．０〜５．０モル％とし
たのは、２．０モル％未満では特性改善の効果が認めら
れず、又、比抵抗が大きくなり、５．０モル％を超える
と比抵抗が大きくなり、又、焼結体同志の融着が発生す
るからである。又ＭｎはＭｎＣＯ₃ 、Ｍｎ（ＮＯ₃ ）
₂ 、ＭｎＯ₂ 等が用いられるがそれらをＭｎとして０．
０２〜０．０６モル％としたのは、０．０２モル％未満
では特性改善の効果が認められず、又、比抵抗が大きく
なり、０．０６モル％を超えると比抵抗が大きくなるか
らである。Nb ₂ O ₅ and Ta ₂ O as semiconducting agents
₅ , Sb ₂ O ₃ , Sb ₂ O ₅ , WO ₃ , Y ₂ O ₃ , Y
(NO ₃ ) ₃ or the like is used. As described above, a compound of at least one element of Nb, Ta, Sb, W, and Y is used as an element with respect to 100 mol% of the main component as described above.
This is because 0 mol% is blended, but in this range, the specific resistance of the porcelain, which is the object of the present invention, can be reduced and the withstand voltage characteristics can be improved. Also, the main component is 100 mol%
In contrast, 0.3 to 1.0 mol% of TiO ₂ as an additive
The reason is that if it is less than 0.3 mol%, the effect of improving the characteristics is not recognized, and if it exceeds 1.0 mol%, the specific resistance increases. Further, Al ₂ O _{3 is set} to 0.1 to 2.0 mol% because the effect of improving the characteristics is not recognized when the content is less than 0.1 mol%, and the specific resistance increases when the content exceeds 2.0 mol%. Because. Further, the reason why the SiO ₂ content is 2.0 to 5.0 mol% is that when the content is less than 2.0 mol%, the effect of improving the characteristics is not recognized, and the specific resistance increases, and the content exceeds 5.0 mol%. This is because the specific resistance increases and fusion between the sintered bodies occurs. Mn is MnCO ₃ , Mn (NO ₃ )
₂ , MnO _{2 and the} like are used, but these are referred to as Mn and 0.
The range of 02 to 0.06 mol% is that the effect of improving the characteristics is not recognized when the content is less than 0.02 mol%, and the specific resistance increases, and the specific resistance increases when the content exceeds 0.06 mol%. Is.

【０００９】本発明のチタン酸バリウム系半導体磁器用
原料組成物より半導体磁器を製造するのは公知の方法で
よい。例えば全原料を粉砕し、粉砕物を混合し１１００
〜１２００℃程度で仮焼し、仮焼物を微粉砕し、バイン
ダーを加え、造粒し、成形して成形体を得る。次にこの
成形体を１２００〜１３００℃程度で焼結することによ
り、磁器を得る。ＰｂＴｉＯ₃ を生成させるためにＰｂ
Ｏ等の鉛酸化物を用いるが、従来の磁器の製造法におい
ては前述のように鉛酸化物の添加が仮焼前の場合は磁器
の比抵抗が、仮焼後の添加の場合に比して低下する反
面、焼成工程においてＰｂＯが揮発し、製品の組成の不
均質化を生じ易いという欠点があったが、本発明の組成
物においてはＰｂＯの添加が仮焼前と仮焼後のいずれに
おいても特に問題はないという特徴がある。A known method may be used to manufacture a semiconductor porcelain from the barium titanate-based semiconductor porcelain raw material composition of the present invention. For example, crush all raw materials and mix the crushed material
It is calcined at about 1200 ° C, the calcined product is finely pulverized, a binder is added, granulated, and molded to obtain a molded body. Next, this molded body is sintered at about 1200 to 1300 ° C. to obtain a porcelain. Pb to produce PbTiO ₃
Although lead oxides such as O are used, in the conventional manufacturing method of porcelain, as described above, the resistivity of the porcelain when the addition of lead oxide is before calcination is higher than that after the calcination. On the other hand, although PbO volatilizes during the firing process and the composition of the product is likely to be non-homogeneous, the composition of the present invention contains PbO either before calcination or after calcination. There is a feature that there is no particular problem in.

【００１０】[0010]

【実施例】【Example】

〈実施例・比較例〉以下実施例、及び比較例によって本
発明を更に詳細に説明する。 実施例 １〜２７ 磁器の主成分でＢａＴｉＯ₃ 、ＣａＴｉＯ₃ 及びＰｂＴ
ｉＯ₃ 形成材料としてＢａＣＯ₃ 、ＣａＣＯ₃ 、Ｐｂ
Ｏ、ＴｉＯ₂ を、半導体化剤としてＮｂ₂ Ｏ₅ 、Ｔａ₂
Ｏ₅ 、Ｓｂ₂ Ｏ₃ 、ＷＯ₃ 、Ｙ₂ Ｏ₃ を、添加剤として
ＴｉＯ₂ 、Ａｌ₂Ｏ₃ 、ＳｉＯ₂ 、ＭｎＣＯ₃ を用い、
表１に示す組成の磁器が得られるような割合で配合し、
湿式微粉を混合して本発明の組成物を得た。<Examples and Comparative Examples> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. BaTiO ₃ main component in Example 1-27 porcelain, CaTiO ₃ and PbT
BaCO ₃ , CaCO ₃ , Pb as an iO ₃ forming material
O, TiO ₂ as Nb ₂ O ₅ , Ta ₂ as a semiconducting agent
O ₅ , Sb ₂ O ₃ , WO ₃ and Y ₂ O ₃ are used, and TiO ₂ , Al ₂ O ₃ , SiO ₂ and MnCO ₃ are used as additives.
Blended in such a ratio that a porcelain having the composition shown in Table 1 is obtained,
The wet fine powder was mixed to obtain the composition of the present invention.

【００１１】[0011]

【表１】 [Table 1]

【００１２】これを脱水、乾燥後、１１５０℃の温度で
３時間仮焼し、得られた仮焼物を、再び湿式微粉砕混合
し、脱水、乾燥後、バインダーを混ぜて造粒の後、成形
圧力を２０００ｋｇ／ｃｍ² で成形して円板状の成形体
を得た。これを１２５０℃の温度で１．５時間焼結さ
せ、直径２０．０ｍｍ、厚さ１．０ｍｍの半導体磁器を
得た。これによって得られた半導体磁器に銀電極を焼き
付け、測定試料を得た。得られた試料について常温（２
５℃）における比抵抗、キュリー点、及び耐電圧を測定
した。その結果を表２に示す。After dehydration and drying, this was calcined at a temperature of 1150 ° C. for 3 hours, the calcined product obtained was wet-pulverized and mixed again, dehydrated and dried, and then a binder was mixed and granulated, followed by molding. A pressure of 2000 kg / cm ² was applied to obtain a disk-shaped formed body. This was sintered at a temperature of 1250 ° C. for 1.5 hours to obtain a semiconductor ceramic having a diameter of 20.0 mm and a thickness of 1.0 mm. A silver electrode was baked on the semiconductor porcelain thus obtained to obtain a measurement sample. For the obtained sample, room temperature (2
The specific resistance, Curie point, and withstand voltage at 5 ° C.) were measured. The results are shown in Table 2.

【００１３】[0013]

【表２】 [Table 2]

【００１４】比較例 １〜２０ 本発明組成外の磁器を実施例１と同様に表３に示すよう
に製造し、同様に測定試料を作成した。Comparative Examples 1 to 20 Porcelains having a composition other than the composition of the present invention were manufactured as shown in Table 3 in the same manner as in Example 1, and measurement samples were similarly prepared.

【００１５】[0015]

【表３】 [Table 3]

【００１６】測定試料について実施例１と同様に比抵
抗、キュリー点及び耐電圧を測定した。その結果を表４
に示す。The specific resistance, Curie point and withstand voltage of the measurement sample were measured in the same manner as in Example 1. The results are shown in Table 4.
Shown in.

【００１７】[0017]

【表４】 [Table 4]

【００１８】実施例 ２８〜３６ 磁器の主成分であるＢａＴｉＯ₃ 及びＣａＴｉＯ₃ 、形
成材料としてＢａＣＯ₃ 、ＣａＣＯ₃ 、ＴｉＯ₂ を、半
導体化剤としてＮｂ₂ Ｏ₅ 、Ｔａ₂ Ｏ₅ 、Ｓｂ ₂ Ｏ₃ 、
ＷＯ₃ 、Ｙ₂ Ｏ₃ を用い、磁器中におけるＢａＴｉＯ
₃ 、ＣａＴｉＯ₃、半導化剤が第５表に示す組成になる
ような割合で配合し、湿式微粉砕して本発明の組成物を
得た。これを脱水、乾燥後、１１５０℃の温度で３時間
仮焼し、得られた仮焼物に、磁器中におけるＰｂＴｉＯ
₃ 、添加剤が表５に示す組成になるように、ＰｂＴｉＯ
₃ 、ＴｉＯ₂ 、Ａｌ₂ Ｏ₃ 、ＳｉＯ₂ 、ＭｎＣＯ₃ を配
合し、再び湿式微粉砕混合し、脱水、乾燥後、バインダ
ーを混ぜ以後実施例１と同様にして測定試料を作成し、
得られた試料について同様に比抵抗、キュリー点、及び
耐電圧を測定した。その結果を表６に示す。Examples 28 to 36 BaTiO 3 which is the main component of porcelain₃ And CaTiO₃ ,form
BaCO as a material₃ , CaCO₃ , TiO₂ Half
Nb as a conductor₂ O_Five , Ta₂ O_Five , Sb ₂ O₃ ,
WO₃ , Y₂ O₃ Using BaTiO 3 in porcelain
₃ , CaTiO₃, The semi-conducting agent has the composition shown in Table 5.
The composition of the present invention is blended in such a ratio and pulverized in a wet manner.
Obtained. After dehydrating and drying this, the temperature is 1150 ° C for 3 hours.
After calcination, the obtained calcination product was added with PbTiO 3 in porcelain.
₃ , So that the additives have the composition shown in Table 5, PbTiO 3
₃ , TiO₂ , Al₂ O₃ , SiO₂ , MnCO₃ Distribute
Weld, finely pulverize and mix again, dehydrate, dry, and then binder
After that, a measurement sample was prepared in the same manner as in Example 1,
The specific resistance, Curie point, and
The withstand voltage was measured. The results are shown in Table 6.

【００１９】[0019]

【表５】 [Table 5]

【００２０】[0020]

【表６】 [Table 6]

【００２１】比較例 ２１〜２５ 本発明組成外の磁器を実施例２８と同様に表７に示すよ
うに製造し、同様に測定試料を得た。Comparative Examples 21 to 25 Porcelain having a composition other than the composition of the present invention was manufactured as shown in Table 7 in the same manner as in Example 28, and a measurement sample was similarly obtained.

【００２２】[0022]

【表７】 [Table 7]

【００２３】測定試料について実施例２８と同様に比抵
抗、キュリー点及び耐電圧を測定した。その結果を表８
に示す。The specific resistance, Curie point and withstand voltage of the measurement sample were measured in the same manner as in Example 28. The results are shown in Table 8
Shown in.

【００２４】[0024]

【表８】 [Table 8]

【００２５】尚前記の比抵抗、キュリー点、耐電圧は次
のようにして求めた。「比抵抗」は、２５℃における抵
抗値Ｒをデジタルマルチメータを用いて測定し、表面積
をＳ、厚さをｔとした時、式ρ＝Ｒ×Ｓ／ｔにより求め
た。「キュリー点」はデジタルマルチメータを用い、試
料の抵抗値が最小となる値の２倍の抵抗値に達した時の
温度である。「耐電圧」は試料に直流電圧を印加し、そ
の電圧を徐々に上昇していった時に、試料の抵抗値が最
大になる時の電圧を、試料の厚みで割った値である。The specific resistance, Curie point, and withstand voltage were determined as follows. The “specific resistance” was obtained by measuring the resistance value R at 25 ° C. using a digital multimeter, and assuming that the surface area is S and the thickness is t, the formula ρ = R × S / t. The “Curie point” is the temperature when the resistance value of the sample reaches a resistance value twice the minimum value using a digital multimeter. The “withstand voltage” is a value obtained by dividing the voltage when the resistance value of the sample becomes maximum when the DC voltage is applied to the sample and the voltage is gradually increased by the thickness of the sample.

【００２６】[0026]

【発明の効果】本発明の組成物により１４０℃以上のキ
ュリー点を有し、耐電圧特性に優れ（１００Ｖ／ｍｍ以
上）、且つ比抵抗の小さい（１０Ω・ｃｍ以下）、しか
もＰｂ成分の仮焼前後の添加を問わず、比抵抗を大きく
変化させることのない正の抵抗温度特性を有するチタン
酸バリウム系半導体磁器を提供することができる。そし
て前記磁器は温度制御、又は電流制御等の種々の用途に
広く用いることができる。The composition of the present invention has a Curie point of 140 ° C. or higher, excellent withstand voltage characteristics (100 V / mm or higher), low specific resistance (10 Ω · cm or lower), and a temporary Pb component. It is possible to provide a barium titanate-based semiconductor ceramic having a positive resistance-temperature characteristic that does not significantly change the specific resistance regardless of whether it is added before or after firing. The porcelain can be widely used for various purposes such as temperature control or current control.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁶ 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｇ 4/12 ４１５ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location H01G 4/12 415

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 チタン酸バリウム系化合物の主成分に半
導体化剤を添加させたチタン酸バリウム系半導体磁器用
原料組成物において、 主成分はＢａＴｉＯ₃ ６２〜９０モル％、ＣａＴｉＯ
₃ ７〜１８モル％、ＰｂＴｉＯ₃ ３〜２０モル％な
る組成物、又は該組成物形成用原料組成物であり、 半導体化剤としてＮａ、Ｔａ、Ｓｂ、Ｗ、Ｙのうちの少
なくとも一種の元素の化合物を主成分１００モル％に対
して元素として０．１８〜０．３０モル％含有し、添加
剤としてＴｉＯ₂ を０．３〜１．０モル％、Ａｌ₂ Ｏ₃
を０．１〜２．０モル％、ＳｉＯ₂ を２．０〜５．０モ
ル％、マンガン化合物をＭｎ元素として０．０２〜０．
０６モル％含有することを特徴とするチタン酸バリウム
系半導体磁器用原料組成物。1. A barium titanate-based semiconductor porcelain raw material composition comprising a barium titanate-based compound and a semiconducting agent added thereto, wherein the main components are BaTiO ₃ 62 to 90 mol%, and CaTiO _{3.
3 to} 18 mol%, PbTiO _{3 3 to} 20 mol%, or a raw material composition for forming the composition, wherein at least one element selected from Na, Ta, Sb, W, and Y as a semiconducting agent. 0.18 to 0.30 mol% as an element based on 100 mol% of the main component, 0.3 to 1.0 mol% of TiO ₂ as an additive, and Al ₂ O ₃
Of 0.1 to 2.0 mol%, SiO ₂ of 2.0 to 5.0 mol%, and manganese compound of 0.02 to 0.
A raw material composition for barium titanate-based semiconductor porcelain, characterized by containing 06 mol%.