JPS6161686B2 - - Google Patents
Info
- Publication number
- JPS6161686B2 JPS6161686B2 JP55153280A JP15328080A JPS6161686B2 JP S6161686 B2 JPS6161686 B2 JP S6161686B2 JP 55153280 A JP55153280 A JP 55153280A JP 15328080 A JP15328080 A JP 15328080A JP S6161686 B2 JPS6161686 B2 JP S6161686B2
- Authority
- JP
- Japan
- Prior art keywords
- firing
- firing container
- antimony oxide
- container
- lid
- 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.)
- Expired
Links
- 238000010304 firing Methods 0.000 claims description 107
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 43
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 238000001354 calcination Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- -1 Sb 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Description
【発明の詳細な説明】
本発明は、ガス化有機バインダの雰囲気中で非
直線抵抗体が焼成されないようにすることによつ
て、非直線抵抗体におけるその側面に状態良好に
して絶縁被膜を形成させるようにした電圧非直線
抵抗体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention forms an insulating film on the side surface of a non-linear resistor in good condition by preventing the non-linear resistor from being fired in an atmosphere of a gasified organic binder. The present invention relates to a method of manufacturing a voltage nonlinear resistor in which the voltage nonlinear resistor is made to
従来より酸化亜鉛ZnOを主成分とする酸化物非
直線抵抗体は非直線性が良好であるところから、
例えば避雷器用非直線抵抗体、即ち、特性要素と
して最適なものとなつているが、従来にあつては
その製造方法が適当でなかつたことから、最終的
に得られる非直線抵抗体のその側面には良好に絶
縁被膜が形成され得ないという欠点がある。 Conventionally, oxide nonlinear resistors mainly composed of zinc oxide, ZnO, have good nonlinearity, so
For example, non-linear resistors for lightning arresters, in other words, are ideal as a characteristic element, but since the manufacturing method was not suitable in the past, this aspect of the non-linear resistor finally obtained has the disadvantage that an insulating film cannot be formed satisfactorily.
一般に上記非直線抵抗体は例えば高純度酸化亜
鉛ZnO91mol％にSb2O3、Bi2O3、Co2O3、MnO2、
SiO2などを合計9mol％加えて混合、造粒、圧縮
成形した後特殊な雰囲気中で1000℃以上1400℃以
下の高温（電気的特性上からは1100℃〜1300℃が
適当であるとされている）下で焼成することによ
つて得られる。この場合での特殊雰囲気中での
（本）焼成は成形体としての非直線抵抗体を焼成
すると同時に、その側面に高抵抗絶縁被膜を形成
させるために必要なものとなつている。しかしな
がら、本焼成のために加熱温度を徐々に上昇せし
める一次焼成（仮焼）過程（この過程での800℃
〜1000℃の温度領域では非直線抵抗体は体積比で
40％程度収縮される）において、造粒過程で加え
られた有機バインダが熱分解され水分H2Oや酸化
炭素CO2、水素H2等の形で非直線抵抗体外部に放
出され、この放出されたガスが非直線抵抗体に作
用して悪影響を与えるというものである。ここに
いう悪影響とは具体的には放出ガスに含まれてい
る還元性ガスあるいは高温放出ガスより新たに生
成された還元性ガスが本来酸化物ある非直線抵抗
体を還元することによつて生じる不具合を指して
いる。また、一次焼成過程において有機バインダ
の熱分解が不十分であつてガスの放出が不十分で
ある場合には本焼成時にそれによる悪影響が現
れ、非直線抵抗体側面と形成された絶縁被膜との
間の密着性が良好でなく剥離し易かつたり、均一
性ある絶縁被膜が形成されないという不具合があ
る。 Generally, the above non-linear resistor is made of, for example, 91 mol% of high purity zinc oxide ZnO, Sb 2 O 3 , Bi 2 O 3 , Co 2 O 3 , MnO 2 ,
After adding a total of 9 mol% of SiO 2 etc., mixing, granulating, and compression molding, it is heated in a special atmosphere at a high temperature of 1000°C to 1400°C (1100°C to 1300°C is considered appropriate from the electrical characteristics standpoint). It is obtained by firing under In this case, the (main) firing in a special atmosphere is necessary in order to simultaneously sinter the nonlinear resistor as a molded body and form a high-resistance insulating film on its side surface. However, the primary firing (calcination) process in which the heating temperature is gradually raised for the main firing (800℃ in this process)
In the temperature range of ~1000℃, the nonlinear resistor has a volume ratio of
The organic binder added during the granulation process is thermally decomposed and released to the outside of the nonlinear resistor in the form of water H 2 O, carbon oxide CO 2 , hydrogen H 2 , etc. The resulting gas acts on the nonlinear resistor and has an adverse effect. Specifically, the negative effects mentioned here are caused by the reducing gas contained in the emitted gas or the reducing gas newly generated from the high temperature emitted gas reducing the nonlinear resistor, which is originally an oxide. Indicates a defect. Additionally, if the thermal decomposition of the organic binder is insufficient during the primary firing process and the release of gas is insufficient, this will have an adverse effect during the main firing, causing damage to the side surface of the nonlinear resistor and the formed insulating film. There are problems in that the adhesion between the two layers is not good and it is easy to peel off, and a uniform insulating film cannot be formed.
ここで従来技術に係る焼成方法を説明すればこ
れは以下のようである。 Here, the firing method according to the prior art will be explained as follows.
即ち、第１図ａ，ｂは仮焼をほぼ密閉状態で行
なつた後、本焼成する場合を示す。第１図ａに示
す如く焼成容器（アルミナ質）１内底面に台座
（アルミナ質あるいは酸化亜鉛系焼結板等の耐熱
性セラミツク材）６、敷粉（アルミナ質または非
直線抵抗体の造粉末分あるいは仮焼非直線抵抗体
の破砕粉等）５を介し非直線抵抗体（成形体）３
を載置し、蓋（アルミナ質）４によつて焼成容器
１内部をほぼ密閉にした状態で仮焼するものであ
る。仮焼後は第１図ｂに示すように例えば焼成容
器１内側面に絶縁被膜形成用の塗布剤（アンチモ
ン酸化物Sb2O3、Sb2O4、Sb2O5のうち少なくと
も何れか１つを含むもの、あるいはそのものを主
成分とする化合物）２を塗布し、塗布剤２の乾燥
後は蓋４によつて焼成容器１を密閉にした状態で
非直線抵抗体（仮焼非直線抵抗体）３が本焼成さ
れるようにしたものである。尤も仮焼と本焼成を
第１図ｂに示す如くにした状態で同一焼成容器で
同時的に行なうようにすることも可能である。本
焼成時には塗布剤２中に含まれるアンチモン酸化
物が920℃付近より昇華し、1000℃以上では昇華
は非常に活発となり焼成容器内はアンチモン酸化
物の雰囲気となり、これが非直線抵抗体の側面に
作用することによつて側面には高抵抗絶縁被膜で
あるスピネル（Zn2.33Sb0.67O4）が形成されるもの
である。 That is, FIGS. 1a and 1b show the case where the main firing is performed after the calcination is performed in a substantially closed state. As shown in FIG. (or crushed powder of calcined nonlinear resistor, etc.) 5 through nonlinear resistor (molded body) 3
is placed and calcined with the inside of the firing container 1 substantially sealed with a lid (made of alumina) 4. After calcination, as shown in FIG. 1b, for example, a coating agent for forming an insulating film (at least one of antimony oxides Sb 2 O 3 , Sb 2 O 4 , and Sb 2 O 5 ) is applied to the inner surface of the firing container 1. After the coating agent 2 has dried, the firing container 1 is sealed with the lid 4, and the nonlinear resistor (calcined nonlinear resistor) 2 is applied. Body) 3 is subjected to final firing. Of course, it is also possible to carry out the calcination and main firing simultaneously in the same firing container in the state shown in FIG. 1b. During the main firing, the antimony oxide contained in coating agent 2 sublimates from around 920°C, and at temperatures above 1000°C, the sublimation becomes very active, creating an atmosphere of antimony oxide inside the firing container, which spreads onto the sides of the nonlinear resistor. As a result of this action, spinel (Zn 2 . 33 Sb 0 . 67 O 4 ), which is a high-resistance insulating film, is formed on the side surfaces.
ところで既述したように非直線抵抗体を密閉状
態の下で仮焼することは好ましいものでないこと
は明らかであり、むしろ開放状態の下で仮焼する
のが望ましいと云える。第２図はそのための焼成
容器を示したものである。これによると、焼成容
器は焼成容器本体（アルミナ質）７と蓋（アルミ
ナ質）８とからなるが、焼成容器本体７の上部縁
には切欠９が設けられていることから、蓋８によ
つて焼成容器本体７内部を密閉状態にしようとし
ても密閉状態におくことは不可能であることが従
来のものと異なつている。即ち、非直線抵抗体
（成形体）は密閉状態で仮焼されなく、ガス化し
た有機バインダは化焼中切欠９より焼成容器本体
７外に飛散し得るものである。したがつて仮焼は
第２図に示す焼成容器により行なう一方、本焼成
は第１図(b)に示す如くにして行なうようにすれ
ば、非直線抵抗体の側面には状態良好にして高抵
抗絶縁被膜が形成されることになる。 By the way, as mentioned above, it is clear that it is not preferable to calcinate the non-linear resistor under a closed condition, and it can be said that it is rather desirable to calcinate the nonlinear resistor under an open condition. FIG. 2 shows a firing container for this purpose. According to this, the firing container consists of a firing container body (alumina) 7 and a lid (alumina) 8, and since a notch 9 is provided in the upper edge of the firing container body 7, the lid 8 The difference from the conventional method is that even if an attempt is made to make the inside of the firing container body 7 airtight, it is impossible to do so. That is, the non-linear resistor (molded body) is not calcined in a sealed state, and the gasified organic binder may be scattered outside the firing container main body 7 through the notch 9 during calcining. Therefore, if the calcination is performed in the firing container shown in Figure 2, and the main firing is performed as shown in Figure 1(b), the sides of the non-linear resistor will be in good condition and have a high temperature. A resistive insulation coating will be formed.
しかしながら、仮焼と本焼成とに別個に高価な
焼成容器を要するということは経済的ではないば
かりか、仮焼と本焼成が同時的に行ない得ないと
いう新たな問題が生じる。尚、第２図に示す焼成
容器を用い本焼成をも行なう場合は非直線抵抗体
よりBi2O3が飛散することから、最終的に得られ
る非直線抵抗体の電気的特性は良好ではなくな
る。 However, not only is it not economical to require separate expensive firing containers for calcination and main firing, but also a new problem arises in that calcination and main firing cannot be performed simultaneously. Note that if the firing container shown in Figure 2 is also used for main firing, Bi 2 O 3 will scatter from the nonlinear resistor, so the electrical characteristics of the final nonlinear resistor will not be good. .
本発明の目的は、非直線抵抗体の仮焼と本焼成
とにそれぞれの用途の焼成容器を用いることなく
同一焼成容器を以て同時的に化焼と本焼成とが行
ない得、しかも非直線抵抗体の側面には高抵抗絶
縁被膜が状態良好にして形成され得る非直線抵抗
体の製造方法を供するにある。 It is an object of the present invention to simultaneously perform calcination and main firing of a non-linear resistor in the same firing container without using separate firing containers for calcination and main firing of a non-linear resistor. Another aspect of the present invention is to provide a method for manufacturing a non-linear resistor in which a high-resistance insulating film can be formed in good condition.
この目的のため本発明は、蓋と焼成容器本体と
の間にアンチモン酸化物あるいはアンチモン酸化
物と主成分とした化合物を介在させ、この介在に
より焼成容器本体内部が外気と連通し得るように
された状態で非直線抵抗体を順次仮焼、本焼成す
るようにしたものである。焼成時にはアンチモン
酸化物あるいはそれを主成分とする化合物の量は
アンチモン酸化物の昇華により徐々に減るが、そ
れに伴れて蓋がその自重により徐々に下降して焼
成容器本体内部を本焼成時には密閉するようにす
るものである。 For this purpose, the present invention interposes antimony oxide or a compound mainly composed of antimony oxide between the lid and the firing container body, and this interposition allows the inside of the firing container body to communicate with the outside air. The non-linear resistor is sequentially calcined and then main fired in this state. During firing, the amount of antimony oxide or a compound containing antimony oxide as a main component gradually decreases due to sublimation of antimony oxide, but the lid gradually lowers due to its own weight and seals the inside of the firing container during main firing. It is intended to do so.
以下、本発明を第３図から第５図により説明す
る。 The present invention will be explained below with reference to FIGS. 3 to 5.
先ず第３図ａに示す実施態様より説明する。本
態様では円盤状の焼成容器底蓋（アルミナ質）１
１上に台座６、敷粉５を介し成形体（仮焼体でも
可）としての非直線抵抗体３を載置し、焼成容器
底蓋１１周縁部上にはまたリング状に成形された
アンチモン酸化物（アンチモン酸化物を主成分と
する化合物でもよく、また、Bi2O3、SiO2などを
含むものも可）１３を介し焼成容器筒（アルミナ
質）１０を載置するものとし、更に焼成容器筒１
０上端面にはリング状に成形されたアンチモン酸
化物１３を介し焼成容器上蓋（アルミナ質）１２
を載置した状態で仮焼、本焼成を行なわんとする
ものである。この場合アンチモン酸化物１３は粉
状であつても何等差し支えなく、必ずしも焼成容
器筒の上下に設ける必要はなく何れか一方で十分
である。 First, the embodiment shown in FIG. 3a will be explained. In this embodiment, a disc-shaped firing container bottom lid (alumina) 1
A non-linear resistor 3 as a molded body (a calcined body is also acceptable) is placed on top of the pedestal 6 and a bed powder 5, and an antimony molded in a ring shape is placed on the periphery of the bottom lid 11 of the firing container. A firing container cylinder (alumina) 10 is placed through an oxide (a compound containing antimony oxide as a main component, or one containing Bi 2 O 3 , SiO 2 , etc.) 13 , and Firing container cylinder 1
0 A firing container upper lid (alumina material) 12 is placed on the upper end surface via a ring-shaped antimony oxide 13.
The calcination and final firing are carried out with the material placed on the surface. In this case, there is no problem even if the antimony oxide 13 is in powder form, and it is not necessarily necessary to provide it on the top or bottom of the firing container cylinder, either one being sufficient.
そのような状態の下では少なくともアンチモン
酸化物１３と焼成容器筒１０との間、アンチモン
酸化物１３と焼成容器上蓋１２、焼成容器底蓋１
１との間には間隙が在することから、焼成容器内
部は外気と連通した状態にあると云える。よつて
この状態の下で焼成温度を徐々に上昇せしめ1000
℃〜1400℃の範囲内で焼成するようにすれば、間
隙を介してガス化有機バインダがアンチモン酸化
物の昇華点（920℃）迄に焼成容器外部に飛散し
得るものである。一方、アンチモン酸化物１３は
焼成に伴れその量は昇華により徐々に減少するこ
とになる。アンチモン酸化物１３が徐々に減少す
るということはまた焼成容器内部が徐々に密閉状
態に移行するということを示している。結果的に
は焼成容器内部が外気としや断された状態で焼成
が行われるものである。ただ、図示のようにして
焼成を行なう場合昇華したアンチモン酸化物はそ
の一部が焼成容器外部に逃げるから、固−気相反
応による非直線抵抗体３側面への絶縁被膜形成に
は十分寄与し得ない。よつて実際には焼成容器が
密閉された後であつてもその容器内部には固形あ
るいは粉状のアンチモン酸化物が残存しているべ
く、アンチモン酸化物１３の他にも適当量のアン
チモン酸化物を焼成前に予め焼成容器内部に配し
ておく必要があろう。 Under such conditions, at least the space between the antimony oxide 13 and the firing container tube 10, the antimony oxide 13 and the firing container top lid 12, and the firing container bottom lid 1
Since there is a gap between 1 and 1, it can be said that the inside of the firing container is in communication with the outside air. Under these conditions, the firing temperature was gradually increased to 1000℃.
If the firing is performed within the range of 1400°C to 1400°C, the gasified organic binder can be scattered to the outside of the firing container through the gaps up to the sublimation point of antimony oxide (920°C). On the other hand, the amount of antimony oxide 13 gradually decreases due to sublimation during firing. The gradual decrease in antimony oxide 13 also indicates that the inside of the firing container gradually becomes sealed. As a result, firing is performed in a state where the inside of the firing container is cut off from outside air. However, when firing is performed as shown in the figure, a portion of the sublimated antimony oxide escapes to the outside of the firing container, so it does not sufficiently contribute to the formation of an insulating film on the side surface of the nonlinear resistor 3 due to the solid-vapor phase reaction. I don't get it. Therefore, even after the firing container is sealed, solid or powdered antimony oxide remains inside the container, so in addition to antimony oxide 13, an appropriate amount of antimony oxide is added. It may be necessary to place the inside of the firing container in advance before firing.
第３図ｂは第２の実施態様を示したものであ
る。先の実施態様ではアンチモン酸化物はリング
状とされたが、本実施態様では接極的に間隙を設
けるべく焼成容器上蓋１２と焼成容器筒１０との
間、焼成容器筒１０と焼成容器底蓋１１との間に
それぞれピース状のアンチモン酸化物１４を分散
介在させたものである。このようにすれば、ガス
化有機バインダを放出するための間隙１５が接極
的に設けられることになるものである。間隙１５
が接極的に設けられることを除けば事情は先の実
施態様とほぼ同様である。 FIG. 3b shows a second embodiment. In the previous embodiment, the antimony oxide was ring-shaped, but in this embodiment, in order to provide a positive gap, there is a gap between the firing container top lid 12 and the firing container cylinder 10, and between the firing container cylinder 10 and the firing container bottom lid. Piece-shaped antimony oxide 14 is dispersed between each of the two parts 11 and 11. In this way, the gap 15 for releasing the gasified organic binder will be provided in a positive manner. Gap 15
The situation is almost the same as in the previous embodiment, except that is provided positively.
最後に第４図ａ，ｂにより第３の実施態様を説
明する。 Finally, the third embodiment will be explained with reference to FIGS. 4a and 4b.
本実施態様では焼成容器は焼成容器本体に蓋が
嵌合されることによつてその内部は密閉状態にお
かれるようにするが、嵌合の程度を予めアンチモ
ン酸化物の介在によつて浅くしておき、アンチモ
ン酸化物が焼成温度の上昇によつて昇華する程に
その嵌合程度を深くするとともに、嵌合が深くな
るに伴れて外部と焼成容器内部とを徐々にしや断
するようにして焼成を行なわんとするものであ
る。 In this embodiment, the inside of the firing container is sealed by fitting the lid onto the firing container body, but the extent of the fitting is made shallow in advance by intervening antimony oxide. Then, the depth of the fit is made so deep that the antimony oxide sublimes as the firing temperature rises, and as the fit becomes deeper, the outside and the inside of the firing vessel are gradually cut off. The purpose is to perform the firing process.
本実施態様では図示の如く焼成容器は直方状と
され（これはさしたる問題ではない）、焼成容器
内部は焼成容器本体１６に蓋１７が外側より嵌合
されることによつて密閉されるが蓋１７の焼成容
器本体１６への嵌合の深さを浅くしておき、それ
によつて蓋１７の下部内側面２１と焼成容器本体
１６の外側面との間に形成される空スペースにア
ンチモン酸化物２２を介在させるものである。こ
のアンチモン酸化物２２に対応する焼成容器本体
１６側面に穴１８を穿つているのはその空スペー
スにアンチモン酸化物２２を収容させるためであ
る。また蓋１７側面には焼成容器本体１６の上端
面に一致する高さ位置から上方向に一定長さ穴１
９を穿つようにするものである。更に必要に応じ
蓋１７の下部内側面に溝２０を形成し、この溝２
０には、溝２０に対向する焼成容器本体１６側面
に穿たれた穴１８を介しアンチモン酸化物２２を
収容せしめるものである。 In this embodiment, the firing container is rectangular as shown in the figure (this is not a big problem), and the inside of the firing container is sealed by fitting the lid 17 to the firing container body 16 from the outside. 17 into the firing container body 16 is made shallow, thereby filling the empty space formed between the lower inner surface 21 of the lid 17 and the outer surface of the firing container body 16 with antimony oxide. 22 is interposed therebetween. The reason why a hole 18 is bored in the side surface of the firing container body 16 corresponding to the antimony oxide 22 is to accommodate the antimony oxide 22 in the empty space. In addition, a hole 1 of a certain length extends upward from a height position corresponding to the upper end surface of the firing container body 16 on the side surface of the lid 17.
This is to make it look like a 9. Furthermore, if necessary, a groove 20 is formed on the inner surface of the lower part of the lid 17, and this groove 2
0, the antimony oxide 22 is accommodated through a hole 18 bored in the side surface of the firing container body 16 facing the groove 20.
したがつて、成形体としての非直線抵抗体３を
収容せしめた図示の状態より焼成温度を徐々に上
昇せしめるようにすれば、空スペースに収容され
たアンチモン酸化物２２は溝２０内に収容された
アンチモン酸化物ともども昇華により徐々にその
量が減少するところとなり、それに伴れて蓋１７
が自重により徐々に下降し嵌合が深くなつていく
わけである。よつて予め空スペースの上下方向に
おける長さ穴１９のそれよりも大であるようにし
ておけば、仮焼時にはガス化有機バインダが穴１
９を介して外部に逃げ得、また本焼成が行なわれ
る時分には穴１９は焼成容器本体１６側面によつ
て閉塞され、この密閉状態ではアンチモン酸化物
２２による昇華アンチモン酸化物の雰囲気中で本
焼成が行ない得るものである。本施態様による場
合も先の２つの実施態様と同様な効果が得られる
ことは勿論であり、焼成容器内部には必要に応じ
アンチモン酸化物を他に配することも可である。
尚、本実施態様において非直線抵抗体３の側面に
特に均一な絶縁被膜を形成させる必要がある場合
は、第５図に示す如く穴２４が多数穿たれてなる
板材（アルミナ質）２３を用い、穴１８を囲むよ
うにすればよい。穴１８からの昇華アンチモン酸
化物は適当に板材２３によつて拡散された状態で
非直線抵抗体３側面と固−気相反応するところと
なるわけである。 Therefore, if the firing temperature is gradually increased from the illustrated state in which the nonlinear resistor 3 as a molded body is accommodated, the antimony oxide 22 accommodated in the empty space will be accommodated in the groove 20. The amount of antimony oxide and antimony oxide gradually decreases due to sublimation, and as a result, the amount of antimony oxide
gradually descends due to its own weight, and the fit becomes deeper. Therefore, if the length in the vertical direction of the empty space is set in advance to be larger than that of the hole 19, the gasified organic binder can be inserted into the hole 1 during calcination.
The hole 19 can escape to the outside through the antimony oxide 22, and when the main firing is performed, the hole 19 is closed by the side surface of the firing container main body 16, and in this sealed state, the antimony oxide sublimated by the antimony oxide 22. Main firing can be performed. It goes without saying that the same effects as in the previous two embodiments can be obtained in this embodiment, and other antimony oxides can be placed inside the firing container as required.
In this embodiment, if it is necessary to form a particularly uniform insulating film on the side surface of the non-linear resistor 3, a plate material (alumina) 23 having a large number of holes 24 as shown in FIG. 5 may be used. , so as to surround the hole 18. The sublimated antimony oxide from the hole 18 is appropriately diffused by the plate 23 and reacts with the side surface of the nonlinear resistor 3 in a solid-vapor phase.
本発明は以上のようなものであるが、本発明は
複数の非直線抵抗体の側面に同時に絶縁被膜を形
成させる場合にも有効である。例えば複数の非直
線抵抗体が収容された焼成容器を上下方向に多段
に積み上げて焼成する場合には、その積上にアン
チモン酸化物を介在させるものである。最上段に
位置する焼成容器に対してはその上蓋との間にア
ンチモン酸化物を介在させるわけである。 Although the present invention is as described above, the present invention is also effective when forming insulating coatings on the side surfaces of a plurality of nonlinear resistors at the same time. For example, when baking containers containing a plurality of nonlinear resistors are stacked vertically in multiple stages and fired, antimony oxide is interposed between the stacks. Antimony oxide is interposed between the upper lid of the firing container located at the uppermost stage.
尚、アンチモン酸化物中に予めBi2O3を含ませ
ておく場合は焼成中非直線抵抗体からのBi2O3の
飛散を防止することが可能である。 Note that if Bi 2 O 3 is included in the antimony oxide in advance, it is possible to prevent Bi 2 O 3 from scattering from the nonlinear resistor during firing.
以上説明したように本発明による場合、焼成容
器内に収容された成形体としての非直線抵抗体は
仮焼時その内部からのガス化有機バインダが焼成
容器外部に放出されつつ仮焼され、また、本焼成
時には密閉された状態で、しかもガス化有機バイ
ンダの存しない雰囲気中で焼成されるから、その
側面には高抵抗絶縁被膜が状態良好にして形成さ
れ、特性上良好なものが得られるという効果があ
る。しかも、本発明はその実施が容易であるとと
もに、経済的であることは以上の説明より明らか
である。 As explained above, according to the present invention, the non-linear resistor as a molded body housed in the firing container is calcined while the gasified organic binder from inside is discharged to the outside of the firing container, and During the main firing, it is fired in a sealed state and in an atmosphere free of gasified organic binders, so a high-resistance insulating film is formed on the side surface in good condition, resulting in good properties. There is an effect. Moreover, it is clear from the above description that the present invention is easy to implement and economical.
第１図ａ，ｂは、従来技術に係る焼成方法を説
明するための図、第２図は、従来技術に係る焼成
方法の実施に際して使用される仮焼用焼成容器の
説明図、第３図ａ，ｂは、それぞれ本発明に直接
係る第１、第２の実施態様での焼成方法を説明す
るための図、第４図ａ，ｂは、本発明に直接係る
第３の実施態様での焼成方法を説明するための焼
成容器一部省略、正縦断面図と焼成容器一部省略
側面図、第５図は、第３の実施態様に関し更に好
ましい態様を示す焼成容器一部省略・正縦面図で
ある。
３……非直線抵抗体、１０……焼成容器筒、１
１……焼成容器底蓋、１２……焼成容器上蓋、１
３，１４，２２……アンチモン酸化物、１６……
焼成容器本体、１７……蓋、１８，１９……穴。
Figures 1a and b are diagrams for explaining the firing method according to the prior art, Figure 2 is an explanatory diagram of a firing container for calcination used when carrying out the firing method according to the prior art, and Figure 3 Figures a and b are diagrams for explaining the firing method in the first and second embodiments directly related to the present invention, respectively, and Figures 4a and b are diagrams for explaining the firing method in the third embodiment directly related to the present invention. A partially omitted normal vertical cross-sectional view of the baking vessel and a partially omitted side view of the baking vessel for explaining the firing method, and FIG. It is a front view. 3... Non-linear resistor, 10... Firing container cylinder, 1
1...Bottom lid of baking container, 12...Top lid of baking container, 1
3,14,22... antimony oxide, 16...
Firing container body, 17...lid, 18, 19...holes.
Claims (1)
ト、マンガン、アンチモン等の酸化物を微量加え
て混合、有機バインダによる造粒、圧縮成形、焼
成することによつて電圧非直線抵抗素子を得る製
造方法において、焼成容器内に収容された成形体
を焼成する際、予め焼成容器蓋と焼成容器本体と
の間に適当な態様でアンチモン酸化物あるいは該
酸化物を主成分とする化合物を介在させて焼成容
器内部を外気と連通し得る状態におき、該状態で
焼成温度を徐々に上昇せしめるに従い焼成容器内
部をガス化有機バインダを焼成容器外部に放出し
ながら徐々に密閉状態に移行せしめるようにな
し、ガス化有機バインダが放出後の、焼成容器内
部が密閉された状態でのアンチモン酸化物雰囲気
中で本焼成を行なうようにしたことを特徴とする
電圧非直線抵抗体の製造方法。1. A manufacturing method for obtaining a voltage nonlinear resistance element by adding a trace amount of oxides such as bismuth, cobalt, manganese, antimony, etc. to high-purity zinc oxide as the main component, mixing, granulating with an organic binder, compression molding, and firing. When firing the compact housed in the firing container, antimony oxide or a compound containing the oxide as a main component is interposed between the lid of the firing container and the main body of the firing container in advance. The inside of the firing container is placed in a state where it can communicate with the outside air, and as the firing temperature is gradually increased in this state, the inside of the firing container is gradually brought into a closed state while releasing the gasified organic binder to the outside of the firing container, A method for manufacturing a voltage nonlinear resistor, characterized in that after the gasified organic binder is released, main firing is performed in an antimony oxide atmosphere with the inside of the firing container sealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55153280A JPS5778105A (en) | 1980-10-31 | 1980-10-31 | Method of producing voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55153280A JPS5778105A (en) | 1980-10-31 | 1980-10-31 | Method of producing voltage nonlinear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5778105A JPS5778105A (en) | 1982-05-15 |
| JPS6161686B2 true JPS6161686B2 (en) | 1986-12-26 |
Family
ID=15559011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55153280A Granted JPS5778105A (en) | 1980-10-31 | 1980-10-31 | Method of producing voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5778105A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187909A (en) * | 1981-05-14 | 1982-11-18 | Meidensha Electric Mfg Co Ltd | Method of producing zinc oxide nonlinear resistance element former |
| JPS6422004A (en) * | 1987-07-17 | 1989-01-25 | Matsushita Electric Industrial Co Ltd | Manufacture of varistor |
| JPS6422005A (en) * | 1987-07-17 | 1989-01-25 | Matsushita Electric Industrial Co Ltd | Manufacture of varistor |
-
1980
- 1980-10-31 JP JP55153280A patent/JPS5778105A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5778105A (en) | 1982-05-15 |
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