JP2000306704A - Zinc oxide varistor and manufacture thereof - Google Patents

Zinc oxide varistor and manufacture thereof

Info

Publication number
JP2000306704A
JP2000306704A JP11112051A JP11205199A JP2000306704A JP 2000306704 A JP2000306704 A JP 2000306704A JP 11112051 A JP11112051 A JP 11112051A JP 11205199 A JP11205199 A JP 11205199A JP 2000306704 A JP2000306704 A JP 2000306704A
Authority
JP
Japan
Prior art keywords
resistance layer
sintered body
zinc oxide
layer
main component
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
Application number
JP11112051A
Other languages
Japanese (ja)
Inventor
Katsuyuki Miyauchi
克行 宮内
Masaaki Katsumata
雅昭 勝又
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP11112051A priority Critical patent/JP2000306704A/en
Publication of JP2000306704A publication Critical patent/JP2000306704A/en
Pending legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide a zinc oxide varistor in which the surface of a sintered body does not deteriorated, when a high resistance layer is formed, and a manufacturing method of the varistor. SOLUTION: After a high-resistance agent paste, which contains water-based binder and at least Fe oxide and Si oxide, is spread uniformly on the side surface of a molded object whose main component is zinc oxide, baking is performed at 980 deg.C for 5 hours, and a sintered body 1, having a high resistance layer 2 as a lower layer, is obtained. A ceramic coating agent containing inorganic high molecular structure is spread uniformly on the high resistance layer 2 as the lower layer, and a high resistance layer 4 as an upper laver is formed by hydrolytic curing at 500 deg.C. Electrodes 4 are formed on the upper surface and the lower surface of the sintered body 1. The high resistance layer 2 as the low layer has Zn2SiO4 as main component and contains Zn7Sb2O12, having at least Fe solid solution as a subcomponent. The high resistance layer 3 as the upper layer has inorganic high molecular structure.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は主として避雷器等に
用いられる酸化亜鉛バリスタおよびその製造方法に関す
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 for lightning arresters and the like and a method for producing the same.

【０００２】[0002]

【従来の技術】近年の電力系統は送電コスト低減のため
に大容量化、高電圧化が進み、それに伴って避雷器につ
いても５００ｋＶ程度のものが実用化されている。それ
故に、避雷器に用いられる酸化亜鉛バリスタにも大容量
化、高性能化が求められる。2. Description of the Related Art In recent years, power systems have been increased in capacity and voltage in order to reduce transmission costs, and as a result, lightning arresters of about 500 kV have been put into practical use. Therefore, a zinc oxide varistor used for a lightning arrester is required to have a large capacity and high performance.

【０００３】従来の酸化亜鉛バリスタは、例えば特開平
２−７４０１号公報で示されているように、酸化亜鉛を
主成分とする円柱状の焼結体側面に無機系高分子構造を
有するセラミックコーティング剤を塗布し、３００℃程
度の低温で熱処理することにより高抵抗層を形成し、そ
の後の焼結体の上、下面に研磨後電極を形成したもので
あった。[0003] A conventional zinc oxide varistor is, for example, a ceramic coating having an inorganic polymer structure on the side surface of a cylindrical sintered body containing zinc oxide as a main component, as disclosed in Japanese Patent Application Laid-Open No. Hei 2-7401. A high-resistance layer was formed by applying an agent and heat-treating at a low temperature of about 300 ° C., and after polishing, electrodes were formed on the upper and lower surfaces of the sintered body.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、この無
機系高分子構造を有するセラミックコーティング剤は、
接着強度を大きくするために結合剤として強酸性のリン
酸化合物が多く用いられている。ここで、耐酸性が十分
でない焼結体に対してセラミックコーティング剤を塗布
した場合、焼結体の表面が劣化してしまい接着強度が大
きく低下してしまうという問題点を有していた。However, this ceramic coating agent having an inorganic polymer structure is
In order to increase the bonding strength, a strongly acidic phosphate compound is often used as a binder. Here, when a ceramic coating agent is applied to a sintered body having insufficient acid resistance, there is a problem that the surface of the sintered body is deteriorated and the adhesive strength is greatly reduced.

【０００５】そこで本発明は、高抵抗層を形成しても焼
結体表面が劣化しない酸化亜鉛バリスタおよびその製造
方法を提供することを目的とするものである。Accordingly, an object of the present invention is to provide a zinc oxide varistor in which the surface of a sintered body does not deteriorate even when a high-resistance layer is formed, and a method for manufacturing the same.

【０００６】[0006]

【課題を解決するための手段】この目的を達成するため
に本発明の酸化亜鉛バリスタは、酸化亜鉛を主成分とす
る焼結体と、この焼結体の表面に所定の間隔を有するよ
うに形成した少なくとも二つの電極と、前記焼結体の表
面の前記電極非形成部分に設けた少なくとも二層からな
る高抵抗層とを備え、この高抵抗層の下層はＺｎ2Ｓｉ
Ｏ4を主成分とし副成分として少なくともＦｅが固溶し
たＺｎ7Ｓｂ2Ｏ12を含有するものであり、上層は無機系
高分子構造を有するものであり、下層高抵抗層を設ける
ことにより焼結体の表面の耐酸性が向上するので、無機
系高分子構造を有する高抵抗層を形成しても焼結体表面
が劣化することなく、上記目的を達成することができ
る。In order to achieve this object, a zinc oxide varistor according to the present invention comprises a sintered body containing zinc oxide as a main component and a sintered body having a predetermined spacing on the surface of the sintered body. At least two electrodes formed, and a high-resistance layer composed of at least two layers provided on the non-electrode-formed portion of the surface of the sintered body, and a lower layer of the high-resistance layer is Zn 2 Si
It contains O 4 as a main component and Zn 7 Sb 2 O 12 in which at least Fe is dissolved as a sub-component as an auxiliary component. The upper layer has an inorganic polymer structure, and is fired by providing a lower high resistance layer. Since the acid resistance of the surface of the sintered body is improved, the above object can be achieved without deteriorating the surface of the sintered body even if a high resistance layer having an inorganic polymer structure is formed.

【０００７】[0007]

【発明の実施の形態】本発明の請求項１に記載の発明
は、酸化亜鉛を主成分とする焼結体と、この焼結体の表
面に所定の間隔を有するように形成した少なくとも二つ
の電極と、前記焼結体の表面の前記電極非形成部分に設
けた少なくとも二層からなる高抵抗層とを備え、この高
抵抗層の下層はＺｎ2ＳｉＯ4を主成分とし副成分として
少なくともＦｅが固溶したＺｎ7Ｓｂ2Ｏ12を含有するも
のであり、上層は無機系高分子構造を有するものである
酸化亜鉛バリスタであり、高い絶縁性と安定した放電耐
量特性とを有するものである。BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is characterized in that a sintered body mainly composed of zinc oxide and at least two sintered bodies formed at predetermined intervals on the surface of the sintered body. An electrode and a high-resistance layer composed of at least two layers provided on the surface of the sintered body where the electrode is not formed. The lower layer of the high-resistance layer contains Zn 2 SiO 4 as a main component and at least Fe as a subcomponent. Contains Zn 7 Sb 2 O 12 as a solid solution, and the upper layer is a zinc oxide varistor having an inorganic polymer structure, which has high insulation properties and stable discharge withstand characteristics. .

【０００８】請求項２に記載の発明は、酸化亜鉛を主成
分とし副成分としてＳｂ化合物を含有した成形体の側面
に水系バインダー溶液と少なくともＦｅ酸化物及びＳｉ
酸化物を含む高抵抗剤ペーストを塗布する第１の工程
と、次に前記成形体を最高温度９３０〜９８０℃の温度
範囲で熱処理し側面に下層高抵抗層を有する焼結体を得
る第２の工程と、次いで前記下層の高抵抗層の表面に無
機系高分子構造を有する上層の高抵抗層を形成する第３
の工程と、その後前記焼結体の表面に電極を形成する第
４の工程とを備えた酸化亜鉛バリスタの製造方法であ
り、下層の高抵抗層を設けることにより、焼結体の表面
の耐酸性が向上するので、無機系高分子構造を有する上
層の高抵抗層を形成しても焼結体の表面が劣化すること
なく、高い絶縁性と安定した放電耐量特性とを有する酸
化亜鉛バリスタを得ることができる。According to a second aspect of the present invention, an aqueous binder solution and at least Fe oxide and Si are provided on the side surface of a molded body containing zinc oxide as a main component and an Sb compound as an auxiliary component.
A first step of applying a high-resistance paste containing an oxide; and a second step of heat-treating the molded body at a maximum temperature of 930 to 980 ° C. to obtain a sintered body having a lower high-resistance layer on a side surface. And forming an upper high-resistance layer having an inorganic polymer structure on the surface of the lower high-resistance layer.
And a fourth step of thereafter forming an electrode on the surface of the sintered body. A method of manufacturing a zinc oxide varistor, comprising: The zinc oxide varistor has high insulation and stable discharge withstand characteristics without deteriorating the surface of the sintered body even if an upper high-resistance layer having an inorganic polymer structure is formed because the property is improved. Obtainable.

【０００９】（実施の形態１）図１は本実施の形態にお
ける酸化亜鉛バリスタの断面図であり、１は焼結体、２
は下層の高抵抗層、３は上層の高抵抗層、４は電極であ
る。(Embodiment 1) FIG. 1 is a sectional view of a zinc oxide varistor according to the present embodiment.
Denotes a lower high resistance layer, 3 denotes an upper high resistance layer, and 4 denotes an electrode.

【００１０】以下本実施の形態における酸化亜鉛バリス
タの製造方法について説明する。Hereinafter, a method of manufacturing a zinc oxide varistor according to the present embodiment will be described.

【００１１】まず、酸化亜鉛を主成分とし、副成分とし
てビスマス、コバルト、ニッケル、ケイ素などの化合物
を添加した原料粉末に純水、バインダ、分散剤を加え、
ボールミルにて十分混合してスラリーを得た。次にこの
スラリーをスプレードライヤーを用いて、噴霧乾燥、造
粒し、平均粒径１００〜２００μmの造粒粉を得た。次
いでこの造粒粉を４００ｋｇ／ｃｍ2の圧力で成形体を
得た。その後のこの成形体の側面に水系バインダーと、
少なくともＦｅ酸化物とＳｉ酸化物を含む高抵抗剤ペー
ストをローラー塗布にて均一に塗布した後、９８０℃で
５時間焼成し、下層の高抵抗層２を有する焼結体１を得
た。First, pure water, a binder, and a dispersant are added to a raw material powder containing zinc oxide as a main component and compounds such as bismuth, cobalt, nickel, and silicon as auxiliary components,
The slurry was sufficiently mixed with a ball mill to obtain a slurry. Next, this slurry was spray-dried and granulated using a spray drier to obtain granulated powder having an average particle diameter of 100 to 200 μm. Next, a compact was obtained from the granulated powder at a pressure of 400 kg / cm 2 . Aqueous binder on the side of this molded body after that,
After uniformly applying a high-resistance agent paste containing at least an Fe oxide and a Si oxide by roller application, it was baked at 980 ° C. for 5 hours to obtain a sintered body 1 having a lower high-resistance layer 2.

【００１２】この下層の高抵抗層２は、Ｚｎ2ＳｉＯ4を
主成分とし、副成分として少なくともＦｅが固溶したＺ
ｎ7Ｓｂ2Ｏ12を含有するものである。The lower high-resistance layer 2 contains Zn 2 SiO 4 as a main component and a Z component in which at least Fe is dissolved as a sub-component.
It contains n 7 Sb 2 O 12 .

【００１３】次にこの焼結体１の側面の下層の高抵抗層
２上に、スプレーガンにてセラミックコーティング剤を
均一になるよう塗布した後、５００℃で加水分解硬化さ
せて上層の高抵抗層４を形成した。このセラミックコー
ティング剤は、無機高分子構造を有するＡｌ2Ｏ3または
ＳｉＯ2の少なくともいずれか一方を主成分とし、Ａｌ
ＰＯ4を１．０〜２５．０モル％含むセラミック材料で
形成したものである。Next, a ceramic coating agent is uniformly applied on the lower high-resistance layer 2 on the side surface of the sintered body 1 with a spray gun, and then hydrolyzed and hardened at 500 ° C. to form a high-resistance upper layer. Layer 4 was formed. This ceramic coating agent contains at least one of Al 2 O 3 or SiO 2 having an inorganic polymer structure as a main component,
PO 4 and is obtained by forming a ceramic material comprising 1.0 to 25.0 mol%.

【００１４】その後、次いで焼結体１の上、下面を平面
研磨してアルミニウムの溶射により電極４を形成し、図
１に示す酸化亜鉛バリスタを得た。Thereafter, the upper and lower surfaces of the sintered body 1 were polished flat to form electrodes 4 by spraying aluminum to obtain a zinc oxide varistor shown in FIG.

【００１５】以下本発明のポイントについて記載する。The points of the present invention will be described below.

【００１６】（１）下層の高抵抗層２を形成するための
高抵抗剤ペースト中にＦｅを含有させることにより、１
０００℃以下の低温においても焼結体１との反応性が高
く、焼結体１の側面に耐酸性がある下層の高抵抗層２を
形成できるのである。(1) By adding Fe to the high-resistance agent paste for forming the lower high-resistance layer 2, 1
Even at a low temperature of 000 ° C. or less, the reactivity with the sintered body 1 is high, and the lower high-resistance layer 2 having acid resistance can be formed on the side surface of the sintered body 1.

【００１７】（２）下層の高抵抗層２を形成するための
高抵抗剤ペースト中の金属成分としては、鉄をＦｅ2Ｏ3
の形に換算して１０〜４０モル％、ビスマスをＢｉ2Ｏ3
の形に換算して１〜２０モル％、残部がＳｉＯ2である
ことが望ましい。(2) Iron is Fe 2 O 3 as a metal component in the high-resistance paste for forming the lower high-resistance layer 2.
Bismuth is Bi 2 O 3
It is desirable that the content is 1 to 20 mol% in terms of the formula, and the balance is SiO 2 .

【００１８】（３）成形体を最高温度９３０〜９８０℃
と１０００℃以下で熱処理焼成しても、焼結体１を得る
ことができると同時に下層の高抵抗層２を形成できるこ
とは、焼成エネルギーの削減や焼成プロセスの熱効率の
向上などに効果がある。(3) The molded product is heated to a maximum temperature of 930 to 980 ° C.
The fact that the sintered body 1 can be obtained and the lower high resistance layer 2 can be formed at the same time even when heat-treated and fired at a temperature of 1000 ° C. or lower are effective in reducing the firing energy and improving the thermal efficiency of the firing process.

【００１９】（４）下層の高抵抗層２は成形体の側面に
均一に塗布するために、高抵抗剤ペーストには水系バイ
ンダー溶液を用いることが望ましい。しかしながら、水
系バインダー溶液を用いるために下層の高抵抗層２の厚
みは大きくすることは難しいが、下層の高抵抗層２の厚
みは小さくても均一に側面に形成できれば、上層の高抵
抗層３を形成する際に十分な耐酸性を実現できる。(4) In order to uniformly apply the lower high resistance layer 2 to the side surface of the molded product, it is desirable to use an aqueous binder solution for the high resistance paste. However, it is difficult to increase the thickness of the lower high-resistance layer 2 due to the use of the aqueous binder solution. When forming, sufficient acid resistance can be realized.

【００２０】[0020]

【発明の効果】以上本発明によると、下層の高抵抗層を
設けることにより焼結体の表面の耐酸性が向上するの
で、無機系高分子構造を有する上層の高抵抗層を形成し
ても焼結体の表面が劣化することなく、高い絶縁性と安
定した放電耐量特性とを有する酸化亜鉛バリスタを提供
することができる。As described above, according to the present invention, by providing the lower high resistance layer, the acid resistance of the surface of the sintered body is improved, so that the upper high resistance layer having an inorganic polymer structure can be formed. It is possible to provide a zinc oxide varistor having high insulation properties and stable discharge withstand characteristics without deterioration of the surface of the sintered body.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の一実施の形態における酸化亜鉛バリス
タの断面図FIG. 1 is a cross-sectional view of a zinc oxide varistor according to an embodiment of the present invention.

【符号の説明】[Explanation of symbols]

１ 焼結体 ２ 下層の高抵抗層 ３ 上層の高抵抗層 ４ 電極 DESCRIPTION OF SYMBOLS 1 Sintered body 2 Lower high resistance layer 3 Upper high resistance layer 4 Electrode

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 酸化亜鉛を主成分とする焼結体と、この
焼結体の表面に所定の間隔を有するように形成した少な
くとも二つの電極と、前記焼結体の表面の前記電極非形
成部分に設けた少なくとも二層からなる高抵抗層とを備
え、この高抵抗層の下層はＺｎ2ＳｉＯ4を主成分とし副
成分として少なくともＦｅが固溶したＺｎ7Ｓｂ2Ｏ12を
含有するものであり、上層は無機系高分子構造を有する
ものである酸化亜鉛バリスタ。1. A sintered body containing zinc oxide as a main component, at least two electrodes formed on the surface of the sintered body so as to have a predetermined interval, and the electrode non-formation on the surface of the sintered body. A high-resistance layer composed of at least two layers provided in a portion thereof, and a lower layer of the high-resistance layer containing Zn 2 SiO 4 as a main component and containing Zn 7 Sb 2 O 12 containing at least Fe as a solid solution as a sub-component. Wherein the upper layer is a zinc oxide varistor having an inorganic polymer structure. 【請求項２】 酸化亜鉛を主成分とし副成分としてＳｂ
化合物を含有した成形体の側面に水系バインダー溶液と
少なくともＦｅ酸化物及びＳｉ酸化物を含む高抵抗剤ペ
ーストを塗布する第１の工程と、次に前記成形体を最高
温度９３０〜９８０℃の温度範囲で熱処理し側面に下層
高抵抗層を有する焼結体を得る第２の工程と、次いで前
記下層の高抵抗層の表面に無機系高分子構造を有する上
層の高抵抗層を形成する第３の工程と、その後前記焼結
体の表面に電極を形成する第４の工程とを備えた酸化亜
鉛バリスタの製造方法。2. Sb as a main component containing zinc oxide as a main component
A first step of applying a water-based binder solution and a high-resistance paste containing at least Fe oxide and Si oxide to the side surface of the molded article containing the compound, and then heating the molded article at a maximum temperature of 930 to 980 ° C. A second step of performing a heat treatment in the range to obtain a sintered body having a lower high-resistance layer on the side surface; and forming a third high-resistance layer having an inorganic polymer structure on the surface of the lower high-resistance layer. And a fourth step of forming an electrode on the surface of the sintered body thereafter.
JP11112051A 1999-04-20 1999-04-20 Zinc oxide varistor and manufacture thereof Pending JP2000306704A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP11112051A JP2000306704A (en) 1999-04-20 1999-04-20 Zinc oxide varistor and manufacture thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP11112051A JP2000306704A (en) 1999-04-20 1999-04-20 Zinc oxide varistor and manufacture thereof

Publications (1)

Publication Number Publication Date
JP2000306704A true JP2000306704A (en) 2000-11-02

Family

ID=14576806

Family Applications (1)

Application Number Title Priority Date Filing Date
JP11112051A Pending JP2000306704A (en) 1999-04-20 1999-04-20 Zinc oxide varistor and manufacture thereof

Country Status (1)

Country Link
JP (1) JP2000306704A (en)

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