JPH0417304A - Porcelain composition for voltage-dependent nonlinear resistor use - Google Patents
Porcelain composition for voltage-dependent nonlinear resistor useInfo
- Publication number
- JPH0417304A JPH0417304A JP2122417A JP12241790A JPH0417304A JP H0417304 A JPH0417304 A JP H0417304A JP 2122417 A JP2122417 A JP 2122417A JP 12241790 A JP12241790 A JP 12241790A JP H0417304 A JPH0417304 A JP H0417304A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- cuo
- nonlinear resistor
- surge
- na2o
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 6
- 230000001419 dependent effect Effects 0.000 title abstract 2
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 8
- 229910052681 coesite Inorganic materials 0.000 abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract 4
- 239000000377 silicon dioxide Substances 0.000 abstract 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract 4
- 229910052682 stishovite Inorganic materials 0.000 abstract 4
- 229910052905 tridymite Inorganic materials 0.000 abstract 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 3
- 229910008593 TiyO3 Inorganic materials 0.000 abstract 2
- 230000007423 decrease Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical group [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 101100348017 Drosophila melanogaster Nazo gene Proteins 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は電圧非直線抵抗体用磁器組成物に関し、特に
、たとえば電子機器で発生する異常電圧、ノイズを吸収
もしくは除去するバリスタとして用いられる電圧非直線
抵抗体を得るための電圧非直線抵抗体用磁器組成物に関
する。Detailed Description of the Invention (Field of Industrial Application) This invention relates to a ceramic composition for voltage non-linear resistors, and in particular to voltage varistors used as varistors to absorb or remove abnormal voltages and noise generated in electronic equipment. The present invention relates to a ceramic composition for a voltage nonlinear resistor for obtaining a nonlinear resistor.
（従来技術）
従来、この種の磁器組成物からなる電圧非直線抵抗体に
は、粒界酸化型電圧非直線抵抗体と、チタン酸ストロン
チウムを主成分とする電圧非直線抵抗体とがあった。(Prior art) Conventionally, voltage nonlinear resistors made of this type of ceramic composition include grain boundary oxidation type voltage nonlinear resistors and voltage nonlinear resistors whose main component is strontium titanate. .
粒界酸化型電圧非直線抵抗体では、粒界を酸化すること
によってバリスタ特性を得ている。このように粒界を酸
化する方法としては、空気中で粒界を酸化する方法ある
いはＮａ、Ｏなどの酸化剤を粒界に拡散する方法が知ら
れている。In a grain boundary oxidation type voltage nonlinear resistor, varistor characteristics are obtained by oxidizing the grain boundaries. As a method for oxidizing grain boundaries in this manner, a method of oxidizing grain boundaries in air or a method of diffusing an oxidizing agent such as Na or O into grain boundaries is known.
また、チタン酸ストロンチウムを主成分とする電圧非直
線抵抗体は、異常電圧、ノイズを吸収するバリスタとし
ての機能のほかにコンデンサとしての機能を有している
。この種の材料としては、特開昭５８−１６５０４号公
報、特開昭５８−９１６０２号公報に開示されているよ
うに、５ｒＴｉ０．、あるいは５ｒｌ−、ＣａｘＴ ｉ
Ｏｘ （０゜０１≦ｘ≦０．５）を主成分とし、これ
に半導体化のための成分としてＮ ｂ ｚ Ｏｓ 、
Ｔ ａ ｚ ０５ 。Furthermore, a voltage nonlinear resistor whose main component is strontium titanate has a function as a capacitor in addition to a function as a varistor that absorbs abnormal voltage and noise. As this type of material, 5rTi0. , or 5rl-, CaxT i
Ox (0゜01≦x≦0.5) is the main component, and N b z Os is added as a component for semiconductor formation.
T az 05.
ＷＯｚ 、Ｌａｇ ０３．Ｃｅ０ｚ 、Ｎｄｚ Ｏｘ
＊ Ｙ２０３などの金属酸化物およびサージ劣化防止の
ためのＮａｚＯを含有したものがあった。WOz, Lag 03. Ce0z, NdzOx
*Some products contained metal oxides such as Y203 and NazO to prevent surge deterioration.
（発明が解決しようとする課題）
しかしながら、粒界酸化型電圧非直線抵抗体において、
空気中で粒界を酸化する前者の方法では、バリスタ特性
が総体的に低く、一方、酸化剤を粒界に拡散する後者の
方法では、静電容量が大きいこと、非直線係数αが大き
いこと、あるいはサージ耐量が大きいことの何れかの特
性を満足させることができても、これらの特性のすべて
を１つの組成物で満足させることができなかった。(Problem to be solved by the invention) However, in the grain boundary oxidation type voltage nonlinear resistor,
The former method, in which the grain boundaries are oxidized in air, has poor varistor characteristics overall, while the latter method, in which the oxidizing agent is diffused into the grain boundaries, has a large capacitance and a large nonlinear coefficient α. Even if it is possible to satisfy any of the characteristics of , high surge resistance, or high surge resistance, it has not been possible to satisfy all of these characteristics with a single composition.
また、チタン酸ストロンチウムを主成分とする電圧非直
線抵抗体でも、大きな非直線係数αを得ながら、サージ
が印加されても非直線係数αおよびバリスタ電圧の劣化
の小さいものが得られないという欠点があった。In addition, even with a voltage nonlinear resistor whose main component is strontium titanate, although a large nonlinear coefficient α can be obtained, it is difficult to obtain a nonlinear coefficient α and a small deterioration of the varistor voltage even when a surge is applied. was there.
それゆえに、この発明の主たる目的は、高いバリスタ電
圧、大きい非直線係数αおよび高いサージ耐量を有する
電圧非直線抵抗体を得ることができる、電圧非直線抵抗
体用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 ceramic composition for a voltage nonlinear resistor, which can obtain a voltage nonlinear resistor having a high varistor voltage, a large nonlinear coefficient α, and a high surge resistance. be.
（課題を解決するための手段）
この発明にかかる電圧非直線抵抗体用磁器組成物は、（
Ｓ ｒ＋−、Ｃａｘ）Ｔ ｉｙ ０３ （ただし、０
≦ｘ≦０．２５．０．９９６≦ｙ≦１．００３）が９８
．０〜９９．９モル％と、Ｎｂ、Ｗ、Ｔａ、ｉｎあるい
は希土類元素の酸化物が０．１〜２．０モル％とからな
る半導体磁器に、Ｎａ２Ｏ，５ｉＯｔおよびＣｕＯ（０
＜Ｎａｚ ０，０＜Ｓ ｉＯｔ、０≦Ｃｕｂ）を合わせ
て０．０１〜１．０モル％含有されてなる、電圧非直線
抵抗体用磁器組成物である。(Means for solving the problem) The ceramic composition for a voltage nonlinear resistor according to the present invention has the following features:
S r+-, Cax) T iy 03 (However, 0
≦x≦0.25.0.996≦y≦1.003) is 98
．． Na2O, 5iOt and CuO(0
<Naz 0,0<S iOt, 0≦Cub) in a total of 0.01 to 1.0 mol%.
（発明の効果）
この発明によれば、高いバリスタ電圧、大きい非直線係
数αおよび高いサージ耐量を有する電圧非直線抵抗体を
得ることができる、電圧非直線抵抗体用磁器組成物を得
ることができる。(Effects of the Invention) According to the present invention, it is possible to obtain a ceramic composition for a voltage nonlinear resistor that can obtain a voltage nonlinear resistor having a high varistor voltage, a large nonlinear coefficient α, and a high surge withstand capacity. can.
この発明の上述の目的、その他の目的、特徴および利点
は、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 detailed description of the following embodiments.
（実施例）
別表に示す組成比（モル％）となるように、母材料であ
る５ｒＣＯｓ 、Ｔｉ０ｚ 、ＣａＯ１および半導体化
剤であるＥｒｇ Ｏｓ 、Ｎｂｚ Ｏｓ 、ＷＯｓ 、
Ｔａｔ Ｏｓ ＋ Ｉ ｎｚ Ｏｘ 、Ｙｚ’ Ｏｘ
の各原料粉末を秤量して湿式混合し、混合物を得た。得
られた混合物を乾燥した後、１１５０℃で２時間仮焼し
て仮焼物を得た０次いで、得られた仮焼物を粉砕後、そ
れに酢酸ビニル系樹脂を５重量％添加して造粒し、造粒
物を得た。得られた造粒粉を１ ｔｏｎ／ａｄの圧力
で直径１０ｍ、厚さ１．５ｆｌのベレット状に成形して
成形体を得た。(Example) The base materials 5rCOs, Ti0z, CaO1 and the semiconducting agents ErgOs, NbzOs, WOs,
TatOs + InzOx, Yz'Ox
The respective raw material powders were weighed and wet mixed to obtain a mixture. After drying the resulting mixture, it was calcined at 1150°C for 2 hours to obtain a calcined product.Next, the resulting calcined product was crushed and granulated by adding 5% by weight of vinyl acetate resin to it. , a granulated product was obtained. The obtained granulated powder was molded into a pellet shape with a diameter of 10 m and a thickness of 1.5 fl under a pressure of 1 ton/ad to obtain a molded body.
そして、この成形体を空気中で１０００℃で２時間焼成
した後、体積比でＨｚ ：Ｎ２ ＝ｌ ： １００の
混合ガス雰囲気中において１４５０ｔで２時間焼成して
半導体磁器を得た。Then, this molded body was fired in air at 1000° C. for 2 hours, and then fired at 1450 t for 2 hours in a mixed gas atmosphere with a volume ratio of Hz:N2=l:100 to obtain semiconductor porcelain.
それから、得られた半導体磁器に、ＮａｔＯ。Then, NatO was applied to the obtained semiconductor porcelain.
Ｓｉｎ、およびＣｕＯの酸化剤を表に示す割合で添加し
て、１２００℃で２時間熱処理を行って、磁器ユニット
を得た。このようにして得られた磁器ユニフトの対向面
に銀電極を形成して電圧非直線抵抗体素子を得た。Oxidizing agents such as Sin and CuO were added in the proportions shown in the table, and heat treatment was performed at 1200° C. for 2 hours to obtain a ceramic unit. Silver electrodes were formed on the opposing surfaces of the ceramic unit thus obtained to obtain a voltage nonlinear resistor element.
そして、電圧非直線抵抗体素子のバリスタ電圧Ｖ＋−ａ
（Ｖ） 、非直線係数α、バリスタ電圧の変化率Δ
Ｖｌ−Ａ （％）および非直線係数の変化率Δα（％
）などの電気的特性を調べた。この場合、電圧非直線抵
抗体素子に１ｍＡの電流を流してバリスタ電圧Ｖ＋−Ａ
（Ｖ）を測定し、５０００Ａ／−のサージ電流を印加
してバリスタ電圧のｉ化率ΔＶ＋−ａ （％）と非直
線係数の変化率Δα（％）とを測定した。そして、それ
らの測定結果を、表に示した。Then, the varistor voltage V+-a of the voltage nonlinear resistor element
(V), nonlinear coefficient α, rate of change of varistor voltage Δ
Vl-A (%) and rate of change of nonlinear coefficient Δα (%
) and other electrical properties were investigated. In this case, by passing a current of 1 mA through the voltage nonlinear resistor element, the varistor voltage V+-A
(V), and a surge current of 5000 A/- was applied to measure the i conversion rate ΔV+-a (%) of the varistor voltage and the rate of change Δα (%) of the nonlinear coefficient. The measurement results are shown in the table.
なお、表中の試料番号に＊印の付したものはこの発明の
範囲外である。Note that sample numbers marked with * in the table are outside the scope of this invention.
次に、この発明にかかる電圧非直線抵抗体用磁器組成物
の各成分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 each component of the ceramic composition for a voltage nonlinear resistor according to the present invention will be explained.
この発明で主成分として用いる（Ｓｒ、−、ＣａＸ ）
Ｔ ｉｙ Ｏ２において、Ｃａの量すなわちＸを０≦
ｘ≦０．２５とするのは、Ｘが０．２５を趙えると、サ
ージ耐量が低下して好ましくないためである。(Sr, -, CaX) used as the main component in this invention
In T iy O2, the amount of Ca, that is, X, is 0≦
The reason for setting x≦0.25 is that if X exceeds 0.25, the surge resistance decreases, which is not preferable.
また、（Ｓ ｒｌ−＊ Ｃａｘ ）Ｔ ｉｙ Ｏ３にお
イテ、ＴｉＯ量すなわちｙを０．９９６〜１．００３の
範囲とするのは、ｙが０．９９６〜１．０００未満の範
囲ではサージ耐量が改善され、一方、ｙが１．０００〜
１．００３の範囲では特性が安定し、ばらつきが小さ（
なるという効果が得られるからである。Also, regarding (Srl-*Cax)T iy O3, the reason why the amount of TiO, that is, y, is set in the range of 0.996 to 1.003 is because the surge resistance is limited when y is in the range of 0.996 to less than 1.000. is improved, while y is 1.000~
In the range of 1.003, the characteristics are stable and the variation is small (
This is because the effect of becoming
さらに、半導体化剤としてのＮｂ、Ｗ、Ｔａ。Furthermore, Nb, W, and Ta as semiconducting agents.
Ｉｎ、Ｙあるいは希土類元素の酸化物の置を０゜１〜２
．０モル％とするのは、これらの酸化物が０モル％では
バリスタ特性を示さず、２．０モル％を超えるとサージ
耐量が低下するからである。The position of In, Y or rare earth element oxide is 0°1~2
．． The reason why the content of these oxides is 0 mol % is that 0 mol % of these oxides does not exhibit varistor properties, and when it exceeds 2.0 mol %, the surge resistance decreases.
また、酸化剤としてのＮａ、Ｏ，ＳｉＯ，およびＣｕＯ
（０＜Ｎａｇ Ｏ，Ｏ＜５ｉＣｈ 、Ｏ≦ＣＵＯ）の合
計が０．０１モル％未満では非直線係数が小さく、その
合計が１．００モル％を超えるとサージ耐量が低下する
。Also, Na, O, SiO, and CuO as oxidizing agents
If the sum of (0<Nag O, O<5iCh, O≦CUO) is less than 0.01 mol%, the nonlinear coefficient is small, and if the sum exceeds 1.00 mol%, the surge resistance decreases.
それに対して、この発明にかかる電圧非直線抵抗体用磁
器組成物を用いれば、高いバリスタ電圧、大きい非直線
係数αおよび高いサージ耐量を有する電圧非直線抵抗体
を得ることができる。On the other hand, by using the ceramic composition for a voltage nonlinear resistor according to the present invention, a voltage nonlinear resistor having a high varistor voltage, a large nonlinear coefficient α, and a high surge resistance can be obtained.
上述の実施例では、たとえば、５０００Ａ／ｃｄのサー
ジ電圧印加後のサージ耐量に優れ、非直線係数αがα＞
１５と大きい電圧非直線抵抗体を得ることができた。In the above embodiment, for example, the surge resistance after applying a surge voltage of 5000 A/cd is excellent, and the nonlinear coefficient α is α>
We were able to obtain a voltage nonlinear resistor with a high voltage of 15.
また、Ｎａｚ ＯおよびＳｉｎ、を酸化剤として用いた
場合、非直線係数αおよびサージ耐量が現状の１．５倍
程度に向上し、安定性に優れる。Furthermore, when Naz O and Sin are used as oxidizing agents, the nonlinear coefficient α and the surge resistance are improved to about 1.5 times the current level, and the stability is excellent.
酸化剤としてさらにＣｕＯを加えた場合、静電容量が、
Ｎａｚ ＯとＳｉｎｇとを酸化剤として用いた場合の約
２倍となる。この静電容量は、酸化剤としてのＣｕＯの
添加量によってコントロールすることができる。When CuO is further added as an oxidizing agent, the capacitance becomes
This is approximately twice as much as when Naz O and Sing are used as oxidizing agents. This capacitance can be controlled by the amount of CuO added as an oxidizing agent.
特許出願人 株式会社 村田製作所
代理人 弁理士 岡 １） 全 啓
手続主甫正書帽発）
平成２年０５月２８日
平成２年５月１０日付出願の特許層
２、発明の名称
電圧非直線抵抗体用磁器組成物
３、補正をする者
事件との関係 特許出願人
住 所 京都府長岡京市天神二丁目２６番１０号名 称
（６２３）株式会社 打出製作所代表者 村 １
） 昭
４、代 理 人 畢５４１ ！！大阪（０６） ２５２
−６８８８ （代）住 所 大阪市中央区南本町４丁目
２番２１号８、補正の内容
（１）明細書第４頁第１９行目の「よび利点は、行う以
下の」を、「よび利点は、以下の」に訂正する。Patent applicant Murata Manufacturing Co., Ltd. Patent attorney Oka 1) Zenkei procedure chief Ho Seishobu) May 28, 1990 Patent layer 2 of the application dated May 10, 1990, name of the invention Voltage non-linearity Porcelain Composition for Resistor 3, Relationship with the Amendment Person Case Patent Applicant Address 2-26-10 Tenjin, Nagaokakyo City, Kyoto Name (623) Uchide Seisakusho Co., Ltd. Representative Village 1
) 4th year of Showa, agent Bi 541! ! Osaka (06) 252
-6888 Address: No. 8, 4-2-21 Minamihonmachi, Chuo-ku, Osaka, Contents of the amendment (1) On page 4, line 19 of the specification, “and the following” has been replaced with “and the following”. The advantages are corrected below.
（２）明細書第７頁第１１行目のｒｌｎ、Ｙあるいは」
を、ｒＩｎあるいはＪに訂正する。(2) rln, Y or "on page 7, line 11 of the specification"
Correct it to rIn or J.
（３）明細書の発明の詳細な説明中で、実施例の説明の
中に記載の表を、本書添付の表と差し替える。(3) In the detailed description of the invention in the specification, the table described in the description of the examples is replaced with the table attached to this document.
以上 自発補正that's all spontaneous correction
Claims (1)
、０≦ｘ≦０．２５、０．９９６≦ｙ≦１．００３）が
９８．０〜９９．９モル％と、Ｎｂ，Ｗ，Ｔａ，Ｉｎあ
るいは希土類元素の酸化物が０．１〜２．０モル％とか
らなる半導体磁器に、Ｎａ＿２Ｏ、ＳｉＯ＿２およびＣ
ｕＯ（０＜Ｎａ＿２Ｏ、０＜ＳｉＯ＿２、０≦ＣｕＯ）
を合わせて０．０１〜１．０モル％含有されてなる、電
圧非直線抵抗体用磁器組成物。(Sr_1_-_xCa_x)Ti_yO_3 (0≦x≦0.25, 0.996≦y≦1.003) is 98.0 to 99.9 mol%, and Nb, W, Ta, In or rare earth elements Na_2O, SiO_2 and C
uO (0<Na_2O, 0<SiO_2, 0≦CuO)
A ceramic composition for a voltage nonlinear resistor, which contains 0.01 to 1.0 mol% of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122417A JPH0417304A (en) | 1990-05-10 | 1990-05-10 | Porcelain composition for voltage-dependent nonlinear resistor use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122417A JPH0417304A (en) | 1990-05-10 | 1990-05-10 | Porcelain composition for voltage-dependent nonlinear resistor use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0417304A true JPH0417304A (en) | 1992-01-22 |
Family
ID=14835310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2122417A Pending JPH0417304A (en) | 1990-05-10 | 1990-05-10 | Porcelain composition for voltage-dependent nonlinear resistor use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0417304A (en) |
-
1990
- 1990-05-10 JP JP2122417A patent/JPH0417304A/en active Pending
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