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JPS63314802A - Thick film varistor - Google Patents

Thick film varistor

Info

Publication number
JPS63314802A
JPS63314802A JP62151750A JP15175087A JPS63314802A JP S63314802 A JPS63314802 A JP S63314802A JP 62151750 A JP62151750 A JP 62151750A JP 15175087 A JP15175087 A JP 15175087A JP S63314802 A JPS63314802 A JP S63314802A
Authority
JP
Japan
Prior art keywords
varistor
mixed
glass
zno
paste
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.)
Granted
Application number
JP62151750A
Other languages
Japanese (ja)
Other versions
JPH0412004B2 (en
Inventor
Masayuki Ishikawa
政幸 石川
Tei Taguchi
禎 田口
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.)
Nidec Instruments Corp
Original Assignee
Sankyo Seiki Manufacturing 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 Sankyo Seiki Manufacturing Co Ltd filed Critical Sankyo Seiki Manufacturing Co Ltd
Priority to JP62151750A priority Critical patent/JPS63314802A/en
Publication of JPS63314802A publication Critical patent/JPS63314802A/en
Publication of JPH0412004B2 publication Critical patent/JPH0412004B2/ja
Granted legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/1006Thick film varistors

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Abstract

PURPOSE:To obtain stable characteristics, by constituting a varistor film of conductive oxide powder in which two kinds of semiconductor oxide are mixed and sintered, and glass component composed of BaO, Ba2O3, and conductive oxide or two kinds of semiconductor oxide. CONSTITUTION:Zn-ferrite in which mixture powder of ZnO and Fe2O3 are sintered is turned into powder having a diameter of 10mum. In glass component, ZnO and Fe2O3 are previouly mixed, and B2O3 is added to dissolve sufficiently ZnO and Fe2O3. BaO is mixed to adjust the melting point of the glass. The Zn-ferrite powder particle and the glass frit powder particle produced in this manner, are mixed by a specified amount. Ethylene cellulose and B.C.A as solvent are added, and kneaded to obtain paste. On an alumina forsterite crystallized glass plate 1, a fired electrode 2 of Ag paste, varistor paste 3 and an upper electrode 4 are stacked. In this constitution, the Zn-paste does not dissolve into glass during firing, so that varistor characteristics is stabilized.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、厚膜バリスタに関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to a thick film varistor.

(従来の技術) 従来から、非直線的な電流−電圧特性を持っ2端子素子
で主に衝撃電圧の抑制や雑音吸収、温度補償等に用いら
れるものとして厚膜バリスタが知られている。
(Prior Art) Thick film varistors have been known as two-terminal devices with nonlinear current-voltage characteristics that are mainly used for suppressing shock voltage, absorbing noise, and compensating for temperature.

との厚膜バリスタとは絶縁基板上に焼成された銀等の電
極の上に、半導体結晶粒としてのZnOと該半導体結晶
粒の結合剤としてのガラスフリットとを空気中で焼成し
たバリスタ層を積層し、その上に銀電極等を焼成し、該
バリスタ層をサンドインチ状に挟持した構造のものであ
る。
A thick film varistor is a varistor layer in which ZnO as semiconductor crystal grains and glass frit as a binder for the semiconductor crystal grains are fired in air on an electrode made of silver or the like fired on an insulating substrate. It has a structure in which the varistor layer is laminated, a silver electrode etc. is fired on top of the varistor layer, and the varistor layer is sandwiched in a sandwich-like manner.

(発明が解決しようとする問題点) ところで、上記厚膜バリスタを構成するガラスフリット
中の酸化ホウ素(Bzoa)はZnO等の酸化物を溶解
する特性を有しており、よって上記ZnO等の半導体酸
化物とガラスフリットとを混合焼成すると、上述の如く
、酸化ホウ素(B 203 )が半導体酸化物を溶解し
てしまうので、そのバリスタ特性が極めて不安定になっ
てしまうという問題点があった・ 本発明の目的は、安定したバリスタ特性を発揮する厚膜
バリスタを提供することにある。
(Problems to be Solved by the Invention) By the way, boron oxide (Bzoa) in the glass frit constituting the thick film varistor has the property of dissolving oxides such as ZnO, and therefore, When oxide and glass frit are mixed and fired, as mentioned above, boron oxide (B 203 ) dissolves the semiconductor oxide, resulting in the problem that the varistor properties become extremely unstable. An object of the present invention is to provide a thick film varistor that exhibits stable varistor characteristics.

(問題点を解決するための手段) 本発明の厚膜バリスタは上記目的を達成するために、2
種類の半導体酸化物を混合し、焼結してなる電気伝導性
酸化物の粉末粒子と、これを結合するための酸化バリウ
ム(BaO)と酸化ホウ素(B2O−)と上記電気伝導
性酸化物若しくは上記2種類の半導体酸化物とから成る
ガラス成分とでバリスタ膜が構成されていることを特徴
とする。
(Means for Solving the Problems) In order to achieve the above object, the thick film varistor of the present invention has two features.
Powder particles of electrically conductive oxide obtained by mixing and sintering different types of semiconductor oxides, barium oxide (BaO) and boron oxide (B2O-) for bonding the powder particles, and the electrically conductive oxide or The varistor film is characterized in that it is constituted by a glass component consisting of the above two types of semiconductor oxides.

(作  用) 本発明によれば、ガラス成分中に予め添加される、2種
類の半導体酸化物を混合して焼結してなる電気伝導性酸
化物、若しくは上記2種類の半導体酸化物は予めガラス
成分中の酸化ホウ素(B、O,)により充分溶解され、
新たに混合する2種類の半導体酸化物の焼結よりなる電
気伝導性酸化物の粉末粒子をほとんど溶解させないよう
に働く。
(Function) According to the present invention, the electrically conductive oxide formed by mixing and sintering two types of semiconductor oxides, or the above two types of semiconductor oxides, is added in advance to the glass component. It is sufficiently dissolved by boron oxide (B, O,) in the glass component,
It works so as to hardly dissolve the electrically conductive oxide powder particles formed by sintering two types of semiconductor oxides to be newly mixed.

(実施例) 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.

まず、2種類の半導体酸化物ZnOとFe2O3とを所
定の組成比、すなねち本実施例においては、21070
〜99重量%、Fe20330〜1重量%となるよう正
確に秤量し、該原料をボールミル等で混合し1mmφ〜
5mmφにした後乾燥し、その後1100〜1400℃
で0.5〜10時間焼成する。そしてこの焼結体、すな
わちZn−フェライトと称せられる電気伝導性酸化物を
粉砕機にかけて400メツシユ以下に微粉砕し、10μ
m前後の必要な粒径のみにふるい分ける。
First, two types of semiconductor oxides, ZnO and Fe2O3, are mixed at a predetermined composition ratio, that is, in this example, 21070
Weigh accurately so that the amounts are ~99% by weight and Fe20330 ~1% by weight, and mix the raw materials with a ball mill etc. to a size of 1 mmφ ~
After cutting to 5mmφ, dry and then heat at 1100~1400℃
Bake for 0.5 to 10 hours. Then, this sintered body, that is, an electrically conductive oxide called Zn-ferrite, was pulverized to 400 mesh or less using a pulverizer.
Sieve only the required particle size around m.

一方ガラス成分としてのガラスフリット粉末は、本実施
例においてはZnOとFe2O,とBaO及びB2O3
とで構成され、所定の組成比、すなわちZnO40〜1
0重量%、Fe、0310〜1重量%。
On the other hand, in this example, the glass frit powder as a glass component is ZnO, Fe2O, BaO, and B2O3.
and a predetermined composition ratio, that is, ZnO40~1
0% by weight, Fe, 0310-1% by weight.

Ba045〜IO重量%、B2o:150〜25重量%
になるよう計量混合され、1100℃以上の高温で溶融
された後、水中で急冷され、所要の粒径まで微粉砕され
生成される。ここで上記ZnOとFe2O,との組成比
は、前述のZn−フェライトを生成するZnOとFe、
O,との組成比、例えばZnOとFe2O,とが8:2
の割合であるならば、それと同じ割合となっている。こ
のように、本発明においては、ガラス成分中にZnOや
Fe2O3等の酸化物を予め混入しておき、B、O,が
ZnOやFe、03等を充分溶解し得るようにしている
。そして共に混入されるBaOは、ガラスの融点の調整
のために用いられている。
Ba045-IO weight%, B2o: 150-25 weight%
After being mixed and measured at a high temperature of 1100° C. or higher, it is rapidly cooled in water and pulverized to a desired particle size. Here, the composition ratio of ZnO and Fe2O is as follows:
For example, the composition ratio of ZnO and Fe2O is 8:2.
If the ratio is the same, then it is the same ratio. As described above, in the present invention, oxides such as ZnO and Fe2O3 are mixed in the glass component in advance so that B, O, and the like can sufficiently dissolve ZnO, Fe, 03, etc. BaO, which is also mixed in, is used to adjust the melting point of the glass.

斯くの如くして生成されたZn−フェライト粉末粒子3
0〜80重量%とガラスフリット粉末粒子70〜20重
量%とを混合し、得られた固形分子にエチレンセルロー
スと溶剤としてのB、C,Aを加えて良く混練し、ペー
スト状にして、バリスタペーストとする。
Zn-ferrite powder particles 3 produced in this way
0 to 80% by weight and 70 to 20% by weight of glass frit powder particles are mixed, and ethylene cellulose and B, C, and A as solvents are added to the obtained solid molecules and kneaded well to form a paste. Make a paste.

一方、上記手順と平行して図に示される如く。Meanwhile, as shown in the figure in parallel with the above procedure.

アルミナフォルステライト結晶化ガラス等よりなる耐熱
性絶縁基板1上に、Ag、Au、Pt等よりなる導電ペ
ーストをスクリーン印刷法により印刷し、焼成(して下
部電極2として積層する。
A conductive paste made of Ag, Au, Pt, etc. is printed on a heat-resistant insulating substrate 1 made of alumina forsterite crystallized glass or the like by a screen printing method, and then fired (and laminated as a lower electrode 2).

そして該下部電極2上に前述したバリスタペーストをス
クリーン印刷法で印刷し、乾燥後700〜1000℃で
焼成して、バリスタ層3として積層する。
Then, the above-mentioned varistor paste is printed on the lower electrode 2 by a screen printing method, and after drying, it is fired at 700 to 1000° C. to form a varistor layer 3.

ここで従来だとガラス成分中のB20.が、Zn−フェ
ライトを構成するZnOやFe2O,を、その焼成時に
溶解してしまうわけであるが、本発明では前述のように
、ガラス成分中に予めZnOやFe2o3が添加されて
おり、B20.が該ZnOやFe、O,を予め充分溶解
しているので、新たにZn−フェライトを構成するZn
OやFe2O,を溶解することはない。
Here, in the conventional case, B20 in the glass component. However, ZnO and Fe2O, which constitute Zn-ferrite, are dissolved during firing, but in the present invention, as mentioned above, ZnO and Fe2O3 are added to the glass component in advance, and B20. Since the ZnO, Fe, and O are sufficiently dissolved in advance, the Zn that newly constitutes the Zn-ferrite is
It does not dissolve O or Fe2O.

その後前述と同様な方法により、バリスタ層3の上に上
部電極4を積層する。
Thereafter, the upper electrode 4 is laminated on the varistor layer 3 by the same method as described above.

このようにして得られた図に示されるようなサンドイン
チ型の厚膜バリスタ5は、前述の如く、その焼成時に電
気伝導性酸化物(Zn−フェライト)がガラス中にほと
んど溶融することがないので、安定したバリスタ特性を
有するようになる。
As mentioned above, in the sandwich-type thick film varistor 5 shown in the diagram obtained in this way, the electrically conductive oxide (Zn-ferrite) hardly melts into the glass during firing. Therefore, it has stable varistor characteristics.

因に本発明者の実験によると、Zn090重量%とFe
、0.10重量%とを上述のガラスフリット粉末粒子、
エチレンセルロース、 B、C,Aと混合して厚膜バリ
スタを形成し、1mA流れる時の電圧値E1.10mA
流れる時の電圧値E工。を計測し、電圧非直線指数αを
算出したところ、 E1=19.3V Eよ。=28.2V α=6 となり、バリスタ特性の優れた厚膜バリスタが
得られるということが実証された。
According to the inventor's experiments, 90% by weight of Zn0 and Fe
, 0.10% by weight of the glass frit powder particles described above,
Ethylene cellulose is mixed with B, C, and A to form a thick film varistor, and the voltage value when 1 mA flows is E1.10 mA.
Voltage value E when flowing. When we measured and calculated the voltage nonlinear index α, we found that E1=19.3V E. =28.2V α=6, and it was verified that a thick film varistor with excellent varistor characteristics could be obtained.

また上記実施例におけるガラスフリット粉末を、Zn−
フェライトとBaO及びB2O3とで構成し、その組成
比を、Zn−フェライト40〜10重量%。
Further, the glass frit powder in the above example was replaced with Zn-
It is composed of ferrite, BaO and B2O3, and the composition ratio thereof is 40 to 10% by weight of Zn-ferrite.

Ba045〜lO重量%、B2o350〜25重量%と
して該粉末を生成するようにしても良く、そのようにし
ても先の実施例と同様な効果が得られた。
The powder may be produced with Ba045 to 10% by weight and B2o350 to 25% by weight, and the same effect as in the previous example was obtained even in this case.

そしてここでも、上記ガラスフリット中のZn−フェラ
イトを構成するZnOとFe、03との組成比は、電気
伝導性酸化物として後に混合することになるZn−フェ
ライトのZnOとFe、O,との組成比と同じ割合とな
っている。
Also here, the composition ratio of ZnO and Fe, O, which constitute the Zn-ferrite in the glass frit, is the same as the composition ratio of ZnO and Fe, O, of the Zn-ferrite that will be mixed later as an electrically conductive oxide. The ratio is the same as the composition ratio.

ところで、上記実施例においては、N型半導体酸化物と
してのZn○とFe、O,とがら電気伝導性酸化物とし
てのZn−フェライトを生成する例を示しているが、次
に示すような安価なN型半導体酸化物、例えばTi20
.CrO2,MoO2T W O2+BaMo0.. 
CaMoO3,5rCr○、、CaCrO3等の中から
2種類を混合し焼結して電気伝導性酸化物を生成するよ
うにし、酸化バリウム(B a O)と酸化ホウ素(B
aO3)と該電気伝導性酸化物、若しくは該電気伝導性
酸化物を構成する2種類の半導体酸化物とより成るガラ
ス成分と混合、焼結することにより厚膜バリスタを構成
するようにしても勿論良い。
By the way, in the above example, Zn○ as an N-type semiconductor oxide and Fe, O, and Zn-ferrite as an electrically conductive oxide are produced, but an inexpensive method such as the one shown below is shown. N-type semiconductor oxide, e.g. Ti20
.. CrO2, MoO2T W O2+BaMo0. ..
Barium oxide (B a O) and boron oxide (B
Of course, a thick film varistor may be constructed by mixing and sintering a glass component consisting of aO3) and the electrically conductive oxide, or two types of semiconductor oxides constituting the electrically conductive oxide. good.

さらにまた、空気中で焼結するとその特性が発揮できな
い、P型半導体酸化物としてのCu2OとTiOとを不
活性ガス、例えば窒素若しくはアルゴン中で混合焼成し
、電気伝導性酸化物Cu2O−TiOを生成するように
し、酸化バリウム(BaO)と酸化ホウ素(B20.)
とCu20−TiO、若しくはCu2OとTiOとより
成るガラス成分と混合、焼結することにより厚膜バリス
タを構成するようにすることも可能である。
Furthermore, Cu2O and TiO, which are P-type semiconductor oxides that cannot exhibit their properties when sintered in air, are mixed and fired in an inert gas such as nitrogen or argon to form an electrically conductive oxide Cu2O-TiO. to produce barium oxide (BaO) and boron oxide (B20.)
It is also possible to form a thick film varistor by mixing and sintering with a glass component consisting of Cu2O-TiO or Cu2O and TiO.

なお、上記実施例の厚膜バリスタは、図に示される如く
サンドイッチ型であるが、プレーナー型にも適用できる
というのはいうまでもない。
The thick film varistor of the above embodiment is a sandwich type as shown in the figure, but it goes without saying that it can also be applied to a planar type.

(発明の効果) 以上のように本発明によれば、ガラス成分中に予め添加
される。2種類の半導体酸化物を混合して焼結してなる
電気伝導性酸化物、若しくは上記2種類の半導体酸化物
が予めガラス成分中の酸化ホウ素(B203)により充
分溶解され、新たに混合する2種類の半導体酸化物の焼
結よりなる電気伝導性酸化物の粉末粒子をほとんど溶解
させないようにし得るので、安定したバリスタ特性を有
する厚膜バリスタを提供することが可能となる。
(Effects of the Invention) As described above, according to the present invention, it is added in advance to the glass component. An electrically conductive oxide formed by mixing and sintering two types of semiconductor oxides, or two types of semiconductor oxides that are sufficiently dissolved in advance with boron oxide (B203) in the glass component and then newly mixed. Since powder particles of an electrically conductive oxide made of sintered semiconductor oxides of various types can be hardly dissolved, it is possible to provide a thick film varistor having stable varistor characteristics.

【図面の簡単な説明】[Brief explanation of the drawing]

図は本発明の一実施例を示す厚膜バリスタの概略断面図
である。 3・・・バリスタ膜、5・・・厚膜バリスタ手続ネ市正
書(方式) 昭和62年?月 1日 1、事件の表示 昭和62年特許願第151750号 2、発明の名称 厚膜バリスタ 3、補正をする者 事件との関係 特許出願人 名    称 (223)株式会社三協精機製作所4、
代 理 人 住 所 東京都世田谷区経堂4丁目5番4号6、補正の
対象 明細書の「発明の詳細な説明」の9 7、補正の内容
The figure is a schematic cross-sectional view of a thick film varistor showing one embodiment of the present invention. 3...Varistor film, 5...Thick film varistor procedure manual (method) 1986? Month 1, 1, Display of the case Patent Application No. 151750 of 1988 2, Name of the invention Thick film varistor 3, Person making the amendment Relationship to the case Patent applicant name (223) Sankyo Seiki Seisakusho Co., Ltd. 4,
Agent Address: 4-5-4-6, Kyodo, Setagaya-ku, Tokyo, 9-7, “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment

Claims (1)

【特許請求の範囲】[Claims] 2種類の半導体酸化物を混合し、焼結してなる電気伝導
性酸化物の粉末粒子と、これを結合するための酸化バリ
ウム(BaO)と酸化ホウ素(B_2O_3)と上記電
気伝導性酸化物若しくは上記2種類の半導体酸化物とか
ら成るガラス成分とでバリスタ膜が構成されていること
を特徴とする厚膜バリスタ。
Electrically conductive oxide powder particles formed by mixing and sintering two types of semiconductor oxides, barium oxide (BaO) and boron oxide (B_2O_3) for bonding the particles, and the above-mentioned electrically conductive oxides or A thick film varistor characterized in that the varistor film is constituted by a glass component comprising the above two types of semiconductor oxides.
JP62151750A 1987-06-18 1987-06-18 Thick film varistor Granted JPS63314802A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62151750A JPS63314802A (en) 1987-06-18 1987-06-18 Thick film varistor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62151750A JPS63314802A (en) 1987-06-18 1987-06-18 Thick film varistor

Publications (2)

Publication Number Publication Date
JPS63314802A true JPS63314802A (en) 1988-12-22
JPH0412004B2 JPH0412004B2 (en) 1992-03-03

Family

ID=15525469

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62151750A Granted JPS63314802A (en) 1987-06-18 1987-06-18 Thick film varistor

Country Status (1)

Country Link
JP (1) JPS63314802A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008530815A (en) * 2005-02-21 2008-08-07 エレクトロニクス アンド テレコミュニケーションズ リサーチ インスチチュート Electrical and electronic system protection circuit using abrupt metal-insulator transition element and electrical and electronic system including the circuit
JP2008533736A (en) * 2005-03-18 2008-08-21 エレクトロニクス アンド テレコミュニケーションズ リサーチ インスチチュート Low voltage noise prevention circuit using abrupt metal-insulator transition element

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008530815A (en) * 2005-02-21 2008-08-07 エレクトロニクス アンド テレコミュニケーションズ リサーチ インスチチュート Electrical and electronic system protection circuit using abrupt metal-insulator transition element and electrical and electronic system including the circuit
JP2008533736A (en) * 2005-03-18 2008-08-21 エレクトロニクス アンド テレコミュニケーションズ リサーチ インスチチュート Low voltage noise prevention circuit using abrupt metal-insulator transition element

Also Published As

Publication number Publication date
JPH0412004B2 (en) 1992-03-03

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