JPH05275211A - Zinc oxide varistor and its manufacture and coating crystallized glass composite - Google Patents
Zinc oxide varistor and its manufacture and coating crystallized glass compositeInfo
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- JPH05275211A JPH05275211A JP4070748A JP7074892A JPH05275211A JP H05275211 A JPH05275211 A JP H05275211A JP 4070748 A JP4070748 A JP 4070748A JP 7074892 A JP7074892 A JP 7074892A JP H05275211 A JPH05275211 A JP H05275211A
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- glass
- crystallized glass
- zinc oxide
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は主として電力分野に用い
られる酸化亜鉛バリスタおよびその製造方法と、サーミ
スタ、バリスタなどの酸化物セラミックの被覆に用いら
れる結晶化ガラス組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc oxide varistor mainly used in the electric power field, a method for producing the same, and a crystallized glass composition used for coating an oxide ceramic such as a thermistor or a varistor.
【０００２】[0002]
【従来の技術】ＺｎＯを主成分とし、Ｂｉ2Ｏ3，Ｃｏ
Ｏ，Ｓｂ2Ｏ3，Ｃｒ2Ｏ3，ＭｎＯ2を始めとする種類の
金属酸化物を副成分とする酸化亜鉛バリスタは、大きな
サージ耐量と優れた電圧非直線性を有し、近年ギャップ
レスアレスタ用の素子として、従来のシリコンカーバイ
トバリスタにとって代わって広く利用されていることは
周知の通りである。2. Description of the Related Art ZnO as a main component and Bi 2 O 3 , Co
Zinc oxide varistor, which contains metal oxides such as O, Sb 2 O 3 , Cr 2 O 3 , and MnO 2 as a secondary component, has a large surge withstand capability and excellent voltage non-linearity. It is well known that the conventional silicon carbide varistor has been widely used as an element for the device.
【０００３】従来より、酸化亜鉛バリスタの製造方法と
して、例えば特開昭６２−１０１００２号公報などが開
示されているが、前記先行例の内容は以下の通りであ
る。Conventionally, as a method for producing a zinc oxide varistor, for example, Japanese Patent Application Laid-Open No. 62-101002 has been disclosed. The contents of the above-mentioned prior art are as follows.
【０００４】まず、主成分のＺｎＯに、Ｂｉ2Ｏ3，Ｓｂ
2Ｏ3，Ｃｒ2Ｏ3、ＣｏＯ、ＭｎＯ2などの金属酸化物を
それぞれ０．０１〜６．０モル％添加した原料粉を混
合、造粒し、この造粒粉を円柱状に加圧、形成し、電気
炉で１２００℃、６時間焼成する。First, ZnO as a main component is mixed with Bi 2 O 3 and Sb.
2 O 3, Cr 2 O 3 , CoO, a raw material powder of metal oxides such as MnO 2 were added respectively 0.01 to 6.0 mol% mixture, granulating, pressing the granulated powder into a cylindrical shape Formed, and fired in an electric furnace at 1200 ° C. for 6 hours.
【０００５】次に、得られた焼結体の側面に、ＰｂＯを
６０重量％含有するＰｂＯ系ガラスフリットを８０重量
％と、長石を２０重量％と、有機バインダーとからなる
ガラスペーストを、スクリーン印刷機で５〜５００mg／
cm2塗布した後、焼付処理を行う。このようにして得ら
れた素子の両端面を平面研磨し、アルミニウムのメタリ
コン電極を形成し、酸化亜鉛バリスタを得るものであ
る。Next, a glass paste containing 80% by weight of a PbO-based glass frit containing 60% by weight of PbO, 20% by weight of feldspar and an organic binder was screened on the side surface of the obtained sintered body. 5 to 500 mg / in printing machine
After applying cm 2, apply baking treatment. Both end faces of the element thus obtained are flat-polished to form aluminum metallikon electrodes to obtain a zinc oxide varistor.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、前記従
来の製造方法による酸化亜鉛バリスタは、スクリーン印
刷法を用いるため、側面ガラス層の厚みが均一に形成さ
れ、放電耐量特性のバラツキが小さいという長所を持つ
ものの、ＰｂＯ系ガラスフリットと長石のコンポジット
ガラスであるため、放電耐量特性が低く、またガラス焼
付処理時に電圧非直線性が低下し、課電寿命特性も悪化
するという欠点を有していた。However, since the zinc oxide varistor according to the above-mentioned conventional manufacturing method uses the screen printing method, the side glass layer is formed to have a uniform thickness, and the variations in discharge withstand voltage characteristics are small. However, since it is a composite glass of PbO-based glass frit and feldspar, it has the drawbacks of low discharge withstand characteristics, reduced voltage nonlinearity during glass baking treatment, and deteriorated voltage life characteristics.
【０００７】本発明は前記従来の課題を解決するもの
で、高信頼性の酸化亜鉛バリスタおよびその製造方法、
さらに酸化物系セラミック一般に用いられる被覆用結晶
化ガラス組成物を提供することを目的とするものであ
る。The present invention solves the above-mentioned conventional problems by providing a highly reliable zinc oxide varistor and a method for manufacturing the same.
Furthermore, it is an object of the present invention to provide a crystallized glass composition for coating which is generally used for oxide ceramics.
【０００８】[0008]
【課題を解決するための手段】本発明では前記従来の課
題を解決するため、ＺｎＯを主成分とする焼結体の側面
に、少なくともＶ2Ｏ5を０．１〜５．０重量％含むＰｂ
Ｏ主成分とする結晶化ガラスからなる側面高抵抗層を有
する構成としたものである。また、前記焼結体の側面に
少なくともＶ2Ｏ5を０．１〜５．０重量％含むＰｂＯを
主成分とする結晶化ガラスと有機バインダーからなるガ
ラスペースを１０．０〜１００．０mg／cm2塗布し、４
５０〜６００℃の温度範囲にて焼付処理し、側面高抵抗
層を形成するものである。In order to solve the above-mentioned conventional problems, the present invention includes at least 0.1 to 5.0% by weight of V 2 O 5 on the side surface of a sintered body containing ZnO as a main component. Pb
The structure has a side surface high resistance layer made of crystallized glass containing O as a main component. Further, a glass pace composed of a crystallized glass containing PbO as a main component containing at least 0.1 to 5.0% by weight of V 2 O 5 and an organic binder is 10.0 to 100.0 mg / on the side surface of the sintered body. cm 2 applied, 4
The side surface high resistance layer is formed by baking in a temperature range of 50 to 600 ° C.
【０００９】さらに、側面高抵抗層用の、少なくともＶ
2Ｏ5を０．１〜５．０重量％含むＰｂＯ−ＺｎＯ−Ｂ2
Ｏ3−ＳｉＯ2−Ｖ2Ｏ5系の酸化物セラミック被覆用の結
晶化ガラス組成物を提供するものである。Furthermore, at least V for the lateral high-resistance layer is used.
Including 2 O 5 0.1 to 5.0 wt% PbO-ZnO-B 2
Provided is a crystallized glass composition for coating an O 3 —SiO 2 —V 2 O 5 -based oxide ceramic.
【００１０】[0010]
【作用】本発明によれば、ＰｂＯ−長石系コンポジット
ガラスに較べ、ＰｂＯを主成分とする結晶化ガラスは、
Ｖ2Ｏ5の添加により結晶化が促進され、ＳｉＯ2の添加
により被覆膜の強度が向上し、焼結体との密着性もよい
ため放電耐量特性に優れ、されに絶縁性も高いため、焼
付処理時の電圧非直線性の低下を最小限に抑えることが
可能となり、課電寿命特性にも優れた高信頼性の酸化亜
鉛バリスタを得ることができる。According to the present invention, compared to the PbO-feldspar composite glass, the crystallized glass containing PbO as the main component is
Crystallization is promoted by the addition of V 2 O 5 , the strength of the coating film is improved by the addition of SiO 2 , and the adhesiveness with the sintered body is also good, so the discharge withstand characteristic is excellent, and the insulating property is also high. In addition, it is possible to minimize the decrease in voltage nonlinearity during the baking process, and it is possible to obtain a highly reliable zinc oxide varistor that is excellent in the electric charge life characteristic.
【００１１】[0011]
【実施例】以下、本発明の酸化亜鉛バリスタおよびその
製造方法、さらに被覆用結晶化ガラス組成物について実
施例に基づき詳細に説明する。EXAMPLES The zinc oxide varistor of the present invention, the method for producing the same, and the crystallized glass composition for coating will be described in detail with reference to Examples.
【００１２】まず、ＺｎＯの粉末に合計量に対し、Ｂｉ
2Ｏ3 ０．５モル％，ＣＯ2Ｏ3 ０．５モル％，ＭｎＯ
2 ０．５モル％，Ｓｂ2Ｏ3 １．０モル％，Ｃｒ2Ｏ3
０．５モル％，ＮｉＯ ０．５モル％，ＳｉＯ2
０．５モル％を加え、純水、バインダー、分散剤ととも
に例えばボールミルにて充分に混合、粉砕した後、スプ
レードライヤーにて乾燥、造粒して原料粉を得た。この
原料粉を直径４０mm、厚さ３０mmの大きさに圧縮成形
し、５００℃以上の温度条件にて脱脂処理した。その
後、１１００〜１２５０℃の温度範囲で焼成し、焼結体
を得た。First, for the total amount of ZnO powder, Bi
2 O 3 0.5 mol%, CO 2 O 3 0.5 mol%, MnO
2 0.5 mol%, Sb 2 O 3 1.0 mol%, Cr 2 O 3
0.5 mol%, NiO 0.5 mol%, SiO 2
0.5 mol% was added, thoroughly mixed with pure water, a binder, and a dispersant by, for example, a ball mill, pulverized, dried with a spray dryer and granulated to obtain a raw material powder. This raw material powder was compression molded into a size of 40 mm in diameter and 30 mm in thickness, and degreased at a temperature of 500 ° C. or higher. Then, it baked in the temperature range of 1100-1250 degreeC, and obtained the sintered compact.
【００１３】一方、被覆用結晶化ガラスは、ＰｂＯ，Ｚ
ｎＯ，Ｂ2Ｏ3，ＳｉＯ2，Ｖ2Ｏ5を所定量秤量し、例え
ばボールミルにて混合、粉砕した後、白金ルツボにて１
０００〜１２００℃の温度条件で溶融し、急冷してガラ
ス化させた。このガラスを粗粉砕した後、ボールミルに
て微粉砕し、ガラスフリットを得た。なお、比較検討用
試料としてＰｂＯ ７０．０重量％，ＺｎＯ ２５．０
重量％，Ｂ2Ｏ3 ５．０重量％からなるガラスフリット
８０．０重量％と長石（長石はＫＡｌＳｉ3Ｏ8，ＮａＡ
ｌＳｉ3Ｏ8，ＣａＡｌ2Ｓｉ2Ｏ8の固溶体）２０．０重
量％からなるコンポジットガラスを同様の工程で作製し
た。On the other hand, the crystallized glass for coating is made of PbO, Z
A predetermined amount of nO, B 2 O 3 , SiO 2 , and V 2 O 5 is weighed, mixed and crushed by, for example, a ball mill, and then mixed with platinum crucible 1
It was melted under a temperature condition of 000 to 1200 ° C. and rapidly cooled to be vitrified. This glass was roughly crushed and then finely crushed with a ball mill to obtain a glass frit. As a sample for comparison, PbO 70.0 wt%, ZnO 25.0
80.0% by weight of glass frit composed of 5.0% by weight of B 2 O 3 and feldspar (feldspar is KAlSi 3 O 8 , NaA
A composite glass composed of 10.0% by weight of 1Si 3 O 8 and CaAl 2 Si 2 O 8 as a solid solution was prepared in the same process.
【００１４】以上のように作製したガラスフリットの、
組成およびガラス転移点（Ｔｇ）、線膨脹係数（α）お
よび結晶性を下記の（表１）に示した。Of the glass frit produced as described above,
The composition, glass transition point (Tg), linear expansion coefficient (α) and crystallinity are shown in the following (Table 1).
【００１５】なお、（表１）においてガラス転移点Ｔｇ
および線膨脹係数αは熱分析装置を用いて測定した。ま
た、結晶性は金属顕微鏡あるいは電子顕微鏡によりガラ
スの表面状態を観察し、結晶性の高い試料については○
印で、全く結晶の見られないものについては×印で表示
した。In Table 1, the glass transition point Tg
The linear expansion coefficient α was measured using a thermal analyzer. For crystallinity, observe the surface condition of glass with a metallographic microscope or electron microscope.
The mark indicates that no crystal was observed, and the mark indicates x.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（表１）よりＰｂＯの添加量が多い場合、
線膨脹係数（α）が高くなり、ＺｎＯの添加量が多い場
合、ガラス転移点（Ｔｇ）が低くなり結晶化しやすくな
る。また、Ｂ2Ｏ3の添加量が多い場合、ガラス転移点が
高くなり、添加量が１５．０重量％を超えた場合には結
晶化しにくくなる。さらに、ＳｉＯ2の添加量が多くな
るに従いガラス転移点は高くなる傾向があり、線膨脹係
数は低くなる傾向がある。そして、Ｖ2Ｏ5の添加量が増
加するに従いガラス転移点が下がりガラスの結晶化が進
行した。また、ＰｂＯ，Ｂ2Ｏ3が少ない系ではポーラス
なガラスとなり易かった。When the amount of PbO added is larger than that shown in Table 1,
When the coefficient of linear expansion (α) becomes high and the amount of ZnO added is large, the glass transition point (Tg) becomes low and crystallization becomes easy. Further, when the added amount of B 2 O 3 is large, the glass transition point becomes high, and when the added amount exceeds 15.0% by weight, crystallization becomes difficult. Furthermore, the glass transition point tends to increase and the linear expansion coefficient tends to decrease as the amount of SiO 2 added increases. Then, as the amount of V 2 O 5 added increased, the glass transition point decreased and crystallization of the glass proceeded. Further, in a system containing a small amount of PbO and B 2 O 3, it was easy to form a porous glass.
【００１８】次に、このガラスフリット８５重量％と、
有機バインダー（エチルセルロース、ブチルカルビトー
ルアセテートの混合物）１５重量％を、例えば三本ロー
ルミルにて充分に混合し、被覆用ガラスペーストを得
た。この被覆用ガラスペーストを、例えば曲面スクリー
ン印刷機にて１２５〜２５０メッシュのスクリーンを用
いて前記焼結体の側面に印刷した。Next, with 85% by weight of this glass frit,
15% by weight of an organic binder (a mixture of ethyl cellulose and butyl carbitol acetate) was sufficiently mixed with, for example, a three-roll mill to obtain a glass paste for coating. This coating glass paste was printed on the side surface of the sintered body using a screen of 125 to 250 mesh with a curved screen printer, for example.
【００１９】ここで、被覆用ガラスペーストの塗布量は
ペーストを塗布した後、１５０℃で３０分間乾燥して焼
結体の重量差から求めた。また、塗布量は被覆用ガラス
ペーストに有機バインダー、酢酸ｎ−ブチルを添加して
調整した。その後、３５０〜７００℃の温度条件にて被
覆用ガラスペーストの焼付処理を行い、焼結体に側面高
抵抗層を形成した。Here, the coating amount of the coating glass paste was obtained from the difference in weight of the sintered bodies after the paste was coated and dried at 150 ° C. for 30 minutes. The coating amount was adjusted by adding an organic binder and n-butyl acetate to the coating glass paste. Then, the glass paste for coating was baked under a temperature condition of 350 to 700 ° C. to form a side surface high resistance layer on the sintered body.
【００２０】次に、この焼結体の両端面を平面研磨し、
アルミニウムのメタリコン電極を形成し、酸化亜鉛バリ
スタを得た。Next, both end faces of this sintered body were flat-polished,
An aluminum metallikon electrode was formed to obtain a zinc oxide varistor.
【００２１】図１に、以上のようにして得られた本発明
による酸化亜鉛バリスタの断面図を示す。図１におい
て、１は酸化亜鉛を主成分とする焼結体、２は焼結体１
の両端面に形成された電極、３は焼結体１の側面に結晶
化ガラスを焼付処理して得られた側面高抵抗層である。FIG. 1 shows a sectional view of the zinc oxide varistor according to the present invention obtained as described above. In FIG. 1, 1 is a sintered body containing zinc oxide as a main component, and 2 is a sintered body 1.
Electrodes 3 formed on both end surfaces of the sintered body 1 are side surface high resistance layers obtained by baking crystallized glass on the side surfaces of the sintered body 1.
【００２２】次に、下記の（表２）に上記（表１）の被
覆用ガラスを用いて作成してた化亜鉛バリスタの外観、Next, the following (Table 2) shows the appearance of the zinc fluoride varistor prepared by using the above-mentioned glass for coating (Table 1),
【００２３】[0023]
【外１】 [Outer 1]
【００２４】放電耐量特性および課電寿命特性を示す。
ここで、被覆用ガラスペーストの塗布量は、５０mg／cm
2となるようペーストの粘度をコントロールした。ま
た、焼付処理条件は５５０℃、１時間である。ここで、
試料数は各ロットｎ＝５個である。The discharge withstanding characteristic and the charging life characteristic are shown.
Here, the coating amount of the glass paste for coating is 50 mg / cm.
The viscosity of the paste was controlled to be 2 . The baking treatment condition is 550 ° C. for 1 hour. here,
The number of samples is n = 5 for each lot.
【００２５】また[0025]
【００２６】[0026]
【外２】 [Outside 2]
【００２７】は直流定電流電源を用いて測定した。そし
て、放電耐量特性は４／１０μＳの衝撃電流を５分間隔
で同一方向に２回ずつ印加し、４０ｋＡよりステップア
ップし、外観の異常の有無を目視にて、必要な場合には
金属顕微鏡を用いて調べた。Was measured using a DC constant current power supply. As for the discharge withstand voltage characteristic, an impact current of 4/10 μS is applied twice in the same direction at intervals of 5 minutes, and the step is increased from 40 kA to visually check whether there is an abnormality in the appearance, and if necessary, use a metallurgical microscope. It was investigated using.
【００２８】ここで、表中の○印は所定電流を２回印加
した後、サンプルに全く異常が認められなかったことを
示し、△印は１〜２個に、×印は３〜５個に異常が認め
られたことを示している。さらに、課電寿命特性は周囲
温度１３０℃、課電率９５％（ＡＣ、ピーク値）の条件
で行い、漏れ電流が５ｍＡ（ピーク値）に至るまでの時
間を測定した。また、Here, in the table, ∘ indicates that no abnormalities were observed in the sample after the predetermined current was applied twice, Δ indicates 1 to 2 pieces, and x indicates 3 to 5 pieces. Indicates that an abnormality was found in the. Further, the life characteristics of charging were performed under conditions of an ambient temperature of 130 ° C. and a charging rate of 95% (AC, peak value), and the time until the leakage current reached 5 mA (peak value) was measured. Also,
【００２９】[0029]
【外３】 [Outside 3]
【００３０】課電寿命は５個の平均値で示している。以
上の試料数、The applied voltage life is shown as an average value of 5 pieces. Number of samples above,
【００３１】[0031]
【外４】 [Outside 4]
【００３２】放電耐量の試験方法、課電寿命特性の評価
方法については、特別の記載がない限り、以下の各実施
例についても同様とする。Unless otherwise specified, the discharge withstand voltage test method and the voltage application life characteristic evaluation method are the same for the following examples.
【００３３】[0033]
【表２】 [Table 2]
【００３４】（表１）および（表２）から、被覆用ガラ
スの線膨脹係数が６５×１０-7／℃より小さい場合（Ｇ
１，Ｇ５ガラス）はガラスが剥離し易くなり、９０×１
０-7／℃を超えた場合（Ｇ４ガラス）にはクラックが発
生し易くなることがわかる。これらクラックやガラス剥
離が発生した試料は、側面高抵抗層の絶縁性が悪いた
め、放電耐量特性が低いと考えられる。From (Table 1) and (Table 2), when the linear expansion coefficient of the coating glass is less than 65 × 10 −7 / ° C. (G
(1, G5 glass), the glass is easy to peel off, 90 × 1
It can be seen that when it exceeds 0 −7 / ° C. (G4 glass), cracks are likely to occur. It is considered that the samples in which cracks and glass peeling occurred have low discharge withstand characteristics because the side surface high resistance layer has poor insulation.
【００３５】また、被覆用ガラスの線膨脹係数が６５〜
９０×１０-7／℃の範囲であっても、結晶性の悪いガラ
ス（Ｇ８ガラス）についてはクラックが入りやすく、放
電耐量特性も低い。これは、結晶性ガラスの方が非結晶
性ガラスに較べ被覆膜の強度が高いためと考えられる。The linear expansion coefficient of the coating glass is 65 to
Even in the range of 90 × 10 −7 / ° C., glass having poor crystallinity (G8 glass) is likely to be cracked and has low discharge withstand characteristic. This is considered to be because the strength of the coating film of crystalline glass is higher than that of amorphous glass.
【００３６】また、ＺｎＯの添加は、酸化亜鉛バリスタ
の電気的諸特性、信頼性に大きな影響を及ぼさず、ガラ
スの物性中でもガラス転移点の低下に役立つ。また、先
行文献例であるＰｂＯ−ＺｎＯ−Ｂ2Ｏ3、長石のコンポ
ジットガラスを用いた場合、課電寿命特性は実用的なレ
ベルではあるが放電耐量特性が低いことがわかる。Further, the addition of ZnO has no great influence on the electrical characteristics and reliability of the zinc oxide varistor, and is useful for lowering the glass transition point among the physical properties of glass. Further, the prior art example in which PbO-ZnO-B 2 O 3 , in the case of using the composite glass feldspar, voltage application life characteristic is it can be seen that a lower discharge withstand current rating characteristic is a practical level.
【００３７】次に、Ｖ2Ｏ5の添加量について考察する。
まず、Ｖ2Ｏ5の添加量が０．１重量％以上の組成系にお
いてはいずれの組成系であっても電圧非直線性が向上
し、それにともない課電寿命特性も向上する。これは、
Ｖ2Ｏ5を０．１重量％以上添加することにより、ガラス
焼付処理時に焼結体側面にＶ2Ｏ5が若干拡散し、ＺｎＯ
粒子の抵抗が上昇するためであると考えられる。Next, the amount of V 2 O 5 added will be considered.
First, in the composition system in which the added amount of V 2 O 5 is 0.1% by weight or more, the voltage non-linearity is improved in any composition system, and accordingly, the life span characteristic is also improved. this is,
By adding V 2 O 5 in an amount of 0.1% by weight or more, V 2 O 5 is slightly diffused on the side surface of the sintered body during the glass baking treatment, and ZnO
It is considered that this is because the resistance of the particles increases.
【００３８】一方、Ｖ2Ｏ5の添加量が５．０重量％より
多い場合、放電耐量特性が低い。これは、焼付処理時の
ガラスの流動性が悪いため、ポーラスになり易いためで
あると考えられる。従って、酸化亜鉛バリスタの側面高
抵抗層用のＰｂＯ−ＺｎＯ−Ｂ2Ｏ3−ＳｉＯ2−Ｖ2Ｏ5
系結晶化ガラスにおいて、少なくともＶ2Ｏ5を０．１〜
５．０重量％含む組成系であることが必要条件である。On the other hand, when the added amount of V 2 O 5 is more than 5.0% by weight, the discharge withstand characteristic is low. It is considered that this is because the flowability of the glass during the baking process is poor and the glass tends to become porous. Accordingly, PbO-ZnO-B 2 for side high-resistance layer of a zinc oxide varistor O 3 -SiO 2 -V 2 O 5
In the crystallized glass, at least V 2 O 5 is 0.1 to
It is a necessary condition that the composition system contains 5.0% by weight.
【００３９】以上の結果より、被覆用結晶化ガラスの組
成は、ＰｂＯが５５．０〜７５．０重量％、ＺｎＯが１
０．０〜３０．０重量％、Ｂ2Ｏ3が５．０〜１０．０重
量％、ＳｉＯ2が０〜１５．０重量％、Ｖ2Ｏ5が０．１
〜５．０重量％の範囲が最適であることがわかる。ま
た、酸化亜鉛バリスタの側面高抵抗層用としては、線膨
脹係数が６５〜９０×１０-7／℃の範囲内であることが
必要である。From the above results, the composition of the crystallized glass for coating is 55.0 to 75.0% by weight of PbO and 1% of ZnO.
0.0-30.0 wt%, B 2 O 3 5.0-10.0 wt%, SiO 2 0-15.0 wt%, V 2 O 5 0.1
It can be seen that the range of up to 5.0% by weight is optimal. Further, for the side surface high resistance layer of the zinc oxide varistor, it is necessary that the coefficient of linear expansion be within the range of 65 to 90 × 10 -7 / ° C.
【００４０】次に、本発明例である（表１）のＧ１６ガ
ラスを用いてガラスペーストの塗布量を検討した。この
結果を下記の（表３）に示した。この際、ガラスペース
トの塗布量は１．０〜３００．０mg／cm2で、ペースト
の粘度および塗布回数でコントロールした。この時、塗
布量が１０．０mg／cm2より少ない場合、被覆膜の強度
が低いため、また塗布量が１００．０mg／cm2より多い
場合にはガラスに流れが発生したり、ピンホールが発生
し易いため、放電耐量特性が悪い。従って、ガラスペー
ストの塗布量は１０．０〜１００．０mg／cm2の範囲が
最適であることがわかる。Next, the coating amount of the glass paste was examined using the G16 glass of the present invention (Table 1). The results are shown in (Table 3) below. At this time, the coating amount of the glass paste was 1.0 to 300.0 mg / cm 2 , and was controlled by the viscosity of the paste and the number of coatings. At this time, when the coating amount is less than 10.0 mg / cm 2 , the strength of the coating film is low, and when the coating amount is more than 100.0 mg / cm 2, glass flows or pinholes occur. Is likely to occur, resulting in poor discharge withstand characteristics. Therefore, it is understood that the optimum application amount of the glass paste is in the range of 10.0 to 100.0 mg / cm 2 .
【００４１】[0041]
【表３】 [Table 3]
【００４２】次に、本発明例である（表１）のＧ１６ガ
ラスを用いてガラスペーストの焼付処理条件を検討し
た。この結果を下記の（表４）に示した。この際、ガラ
スペーストの塗布量は５０．０mg／cm2となるよう粘度
をコントロールした。また、ガラスペーストの焼付処理
は３５０〜７００℃の温度範囲にて保持時間を１時間と
し空気中で行った。Next, the conditions for baking the glass paste were examined using the G16 glass of the present invention (Table 1). The results are shown in (Table 4) below. At this time, the viscosity was controlled so that the coating amount of the glass paste was 50.0 mg / cm 2 . Further, the baking treatment of the glass paste was performed in the air in the temperature range of 350 to 700 ° C. for a holding time of 1 hour.
【００４３】この結果、４５０℃より低温で焼付処理を
行った場合、ガラスペーストが充分に溶融しないため放
電耐量特性が低く、６００℃より高温で焼付処理を行っ
た場合、電圧比が著しく低下し、課電寿命特性が悪化す
る。従って、ガラスペーストの焼付処理条件は４５０〜
６００℃の温度範囲が最適であることがわかる。As a result, when the baking treatment is carried out at a temperature lower than 450 ° C., the glass paste is not sufficiently melted so that the discharge withstand characteristic is low, and when the baking treatment is carried out at a temperature higher than 600 ° C., the voltage ratio is remarkably lowered. , The charging life characteristic deteriorates. Therefore, the baking treatment condition of the glass paste is 450-
It can be seen that the temperature range of 600 ° C. is optimum.
【００４４】[0044]
【表４】 [Table 4]
【００４５】なお、本実施例ではＰｂＯ−ＺｎＯ−Ｂ2
Ｏ3−Ｖ2Ｏ5、ＰｂＯ−ＺｎＯ−Ｂ2Ｏ3−ＳｉＯ2−Ｖ2
Ｏ5の４および５成分系の被覆用結晶化ガラスについて
述べたが、第６成分として、さらにガラスの結晶化を促
進する微量添加物、例えばＡｌ 2Ｏ3，ＳｎＯ2などを添
加しても本発明の効果に変わりはない。In this embodiment, PbO-ZnO-B is used.2
O3-V2OFive, PbO-ZnO-B2O3-SiO2-V2
OFiveCrystallized Glass for Coating of 4 and 5 Component Systems
As mentioned above, as the sixth component, it promotes further crystallization of glass.
Advancing trace additives such as Al 2O3, SnO2Etc.
Even if added, the effect of the present invention does not change.
【００４６】また、ガラス転移点を低下させる物質とし
て、前記実施例ではＺｎＯを用いたが、これはその他の
物質で置き換えることもできるのはもちろんである。Further, ZnO was used as the substance for lowering the glass transition point in the above embodiment, but it is needless to say that it can be replaced with other substances.
【００４７】さらに、本実施例では、酸化物セラミック
の代表例として、酸化亜鉛バリスタに本発明のＰｂＯ−
ＺｎＯ−Ｂ2Ｏ3−ＳｉＯ2−Ｖ2Ｏ5系の被覆用結晶化ガ
ラスを用いたが、チタン酸ストロンチウム系のバリス
タ、チタン酸バリウム系のコンデンサや正特性サーミス
タ、金属酸化物系の負特性サーミスタなど、いずれの酸
化物セラミックにも全く同様に適用できるものである。Further, in this embodiment, as a typical example of oxide ceramics, zinc oxide varistor is used in the PbO-type of the present invention.
ZnO—B 2 O 3 —SiO 2 —V 2 O 5 based crystallized glass for coating was used, but strontium titanate varistor, barium titanate based capacitors and positive temperature coefficient thermistors, and metal oxide negative electrodes were used. It can be applied to any oxide ceramic such as a characteristic thermistor.
【００４８】[0048]
【発明の効果】以上のように本発明によれば、酸化亜鉛
を主成分とする焼結体の側面に少なくともＶ2Ｏ5を０．
１〜５．０重量％含むＰｂＯ−ＺｎＯ−Ｂ2Ｏ3−ＳｉＯ
2−Ｖ2Ｏ5系の酸化物セラミック被覆用の結晶化ガラス
を４５０〜６００℃の温度条件で焼付処理することによ
り、放電耐量特性、課電寿命特性の優れた酸化亜鉛バリ
スタを得ることができる。As described above, according to the present invention, at least V 2 O 5 is added to the side surface of the sintered body containing zinc oxide as a main component.
PbO-ZnO-B 2 O 3 -SiO containing 1 to 5.0 wt%
By baking at a temperature of 2 -V 2 O 5 based oxide crystallized glass ceramic coating of the 450 to 600 ° C., discharge withstand current rating characteristics, is possible to obtain an excellent ZnO varistor voltage application life characteristics it can.
【図１】本発明の製造方法ならびに本発明の被覆用結晶
化ガラスを適用した一実施例による酸化亜鉛バリスタの
断面図FIG. 1 is a sectional view of a zinc oxide varistor according to an embodiment to which the manufacturing method of the present invention and the coated crystallized glass of the present invention are applied.
１ 焼結体 ２ 電極 ３ 側面高抵抗層 1 Sintered body 2 Electrode 3 Side high resistance layer
Claims (6)
タ特性を有する焼結体の側面に、少なくとも酸化バナジ
ウムをＶ2Ｏ5の形に換算して０．１〜５．０重量％含む
ＰｂＯを主成分とする結晶化ガラスからなる側面高抵抗
層を有する酸化亜鉛バリスタ。1. At least 0.1% by weight of vanadium oxide in the form of V 2 O 5 on the side surface of a sintered body containing zinc oxide as a main component and having varistor characteristics by itself. A zinc oxide varistor having a lateral high-resistance layer made of crystallized glass containing PbO as a main component.
Ｖ2Ｏ5系結晶化ガラスからなる請求項１記載の酸化亜鉛
バリスタ。2. A side high-resistance layer is PbO-ZnO-B 2 O 3 -
The zinc oxide varistor according to claim 1, which is made of V 2 O 5 type crystallized glass.
ＳｉＯ2−Ｖ2Ｏ5系結晶化ガラスからなる請求項１記載
の酸化亜鉛バリスタ。3. The lateral high-resistance layer comprises PbO—ZnO—B 2 O 3 —
Zinc oxide varistor according to claim 1, wherein comprising a SiO 2 -V 2 O 5 based crystallized glass.
タ特性を有する焼結体の側面に、少なくとも酸化バナジ
ウムをＶ2Ｏ5の形に換算して０．１〜５．０重量％含む
ＰｂＯを主成分とする結晶化ガラスと有機物からなるガ
ラスペーストを１０．０〜１００．０mg／cm2塗布し、
４５０〜６００℃の温度範囲にて焼付処理する酸化亜鉛
バリスタの製造方法。4. 0.1 to 5.0% by weight of at least vanadium oxide in the form of V 2 O 5 on the side surface of the sintered body having zinc oxide as a main component and the sintered body itself having varistor characteristics. A glass paste composed of crystallized glass containing PbO as a main component and an organic substance is applied in an amount of 10.0 to 100.0 mg / cm 2 ,
A method for producing a zinc oxide varistor, which comprises performing a baking process in a temperature range of 450 to 600 ° C.
囲にある結晶化ガラスを用い請求項４記載の酸化亜鉛バ
リスタの製造方法。5. The method for producing a zinc oxide varistor according to claim 4, wherein crystallized glass having a coefficient of linear expansion of 65 to 90 × 10 −7 / ° C. is used.
Ｏ １０．０〜３０．０重量％，Ｂ2Ｏ3 ５．０〜１
５．０重量％，ＳｉＯ2 ０〜１５．０重量％，Ｖ2Ｏ5
０．１〜５．０重量％からなる被覆用結晶化ガラス組
成物。6. PbO 55.0 to 75.0% by weight, Zn
O 10.0-30.0% by weight, B 2 O 3 5.0-1
5.0% by weight, SiO 2 0 to 15.0% by weight, V 2 O 5
A crystallized glass composition for coating comprising 0.1 to 5.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4070748A JP3003374B2 (en) | 1992-03-27 | 1992-03-27 | Zinc oxide varistor, method for producing the same, and crystallized glass composition for coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4070748A JP3003374B2 (en) | 1992-03-27 | 1992-03-27 | Zinc oxide varistor, method for producing the same, and crystallized glass composition for coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05275211A true JPH05275211A (en) | 1993-10-22 |
| JP3003374B2 JP3003374B2 (en) | 2000-01-24 |
Family
ID=13440448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4070748A Expired - Lifetime JP3003374B2 (en) | 1992-03-27 | 1992-03-27 | Zinc oxide varistor, method for producing the same, and crystallized glass composition for coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3003374B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816894A (en) * | 1987-01-29 | 1989-03-28 | Seiko Instruments & Electronics Ltd. | Semiconductor variable capacitance element |
| EP0709863A1 (en) * | 1994-10-28 | 1996-05-01 | Hitachi, Ltd. | Voltage non-linear resistor and fabricating method |
| US6110569A (en) * | 1997-10-16 | 2000-08-29 | Tdk Corporation | Conductive paste and non-reciprocal device using the same |
-
1992
- 1992-03-27 JP JP4070748A patent/JP3003374B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816894A (en) * | 1987-01-29 | 1989-03-28 | Seiko Instruments & Electronics Ltd. | Semiconductor variable capacitance element |
| EP0709863A1 (en) * | 1994-10-28 | 1996-05-01 | Hitachi, Ltd. | Voltage non-linear resistor and fabricating method |
| US5610570A (en) * | 1994-10-28 | 1997-03-11 | Hitachi, Ltd. | Voltage non-linear resistor and fabricating method thereof |
| US6110569A (en) * | 1997-10-16 | 2000-08-29 | Tdk Corporation | Conductive paste and non-reciprocal device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3003374B2 (en) | 2000-01-24 |
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