JP2841395B2 - Method for manufacturing NTC thermistor - Google Patents
Method for manufacturing NTC thermistorInfo
- Publication number
- JP2841395B2 JP2841395B2 JP63297911A JP29791188A JP2841395B2 JP 2841395 B2 JP2841395 B2 JP 2841395B2 JP 63297911 A JP63297911 A JP 63297911A JP 29791188 A JP29791188 A JP 29791188A JP 2841395 B2 JP2841395 B2 JP 2841395B2
- Authority
- JP
- Japan
- Prior art keywords
- ntc thermistor
- present
- resistance
- metal electrode
- hours
- 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 - Fee Related
Links
Landscapes
- Thermistors And Varistors (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はNTC（Negative Temperature Coefficient）
サーミスタに係り、特に高温使用下の抵抗変化率が小さ
いNTCサーミスタの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to NTC (Negative Temperature Coefficient).
The present invention relates to a thermistor, and more particularly, to a method for manufacturing an NTC thermistor having a small resistance change rate under high temperature use.
NTCサーミスタは温度上昇にともなってその抵抗値が
減少するため、例えば感温素子等に使用されている。NTC thermistors are used, for example, as temperature-sensitive elements, because their resistance decreases as the temperature rises.
一般にNTCサーミスタ組成物に、例えばAgなどの貴金
属電極を形成し、酸化性雰囲気で焼付けを行ってNTCサ
ーミスタ素子を製造している。Generally, an NTC thermistor element is manufactured by forming a noble metal electrode such as Ag on the NTC thermistor composition and baking it in an oxidizing atmosphere.
ところで、前記のような、NTCサーミスタ組成物にAg
などの貴金属電極を形成して酸化性雰囲気中で焼付けを
行うと、得られたNTCサーミスタ素子は120℃以上の高温
使用下における抵抗変化率が大きいという問題があっ
た。By the way, as described above, Ag is added to the NTC thermistor composition.
When a noble metal electrode is formed and baked in an oxidizing atmosphere, there is a problem that the obtained NTC thermistor element has a large resistance change rate when used at a high temperature of 120 ° C. or higher.
特にCuOを含有したNTCサーミスタ組成物はこの抵抗変
化率が非常に大きく、80℃以上での使用は不可能であっ
た。Particularly, the resistance change rate of the NTC thermistor composition containing CuO was extremely large, and it was impossible to use the composition at 80 ° C. or higher.
従って本発明の目的は前記の問題点を解決した、高温
の使用下における抵抗変化率の小さなNTCサーミスタを
提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an NTC thermistor which solves the above-mentioned problem and has a small resistance change rate under high temperature use.
このために本発明者等は鋭意研究の結果、Mn、Ni、C
o、Fe、Cu、Cr等の遷移金属酸化物の複数種類あるいは
これらにAl、Zrなどの金属酸化物を加えたものを主成分
とするNTCサーミスタ組成物に卑金属電極を塗布形成し
た後に、還元または中性雰囲気で、この塗布形成した卑
金属電極の焼付けを行ってNTCサーミスタを製造するこ
とにより、前記目的を達成したNTCサーミスタを提供で
きることを見出した。To this end, the present inventors have conducted intensive studies and found that Mn, Ni, C
o, Fe, Cu, a plurality of types of transition metal oxides such as Cr or Al, Zr and other metal oxides are added to the NTC thermistor composition as a main component, and a base metal electrode is coated and formed. Alternatively, the present inventor has found that an NTC thermistor that achieves the above object can be provided by producing an NTC thermistor by baking the base metal electrode coated and formed in a neutral atmosphere.
これにより120℃においても抵抗変化率が１％以下と
非常に低いものを得る。しかもCuOを含有するNTCサーミ
スタについても120℃における抵抗変化率を同様に非常
に低いものとすることができる。Thus, a very low resistance change rate of 1% or less even at 120 ° C. is obtained. Moreover, the resistance change rate at 120 ° C. of the NTC thermistor containing CuO can be similarly made extremely low.
本発明を実施例に基づいて詳細に説明する。 The present invention will be described in detail based on examples.
出発材料としてMnCO3、NiO、Co2O3、CuO、Fe2O3、Cr
O、ZrO2、Al2O3のように焼成後に各金属の酸化物になる
ものを、その焼成後に第１表の組成比になるように化学
天秤で選択的に秤量配合し、メディアとともにポットミ
ル中に入れて純水を加えて16時間湿式混合する。その後
脱水、乾燥し、乳鉢、乳棒で粉体にする。MnCO 3 , NiO, Co 2 O 3 , CuO, Fe 2 O 3 , Cr as starting materials
O, ZrO 2 , and Al 2 O 3 , which become oxides of each metal after firing, are selectively weighed and blended with an analytical balance so as to have the composition ratios shown in Table 1 after firing, and pot milled together with media. Add pure water and mix wet for 16 hours. After that, it is dehydrated, dried and made into powder with a mortar and pestle.
それからAl2O3厘鉢にこの原料を入れて800℃〜1000℃
で２時間仮焼する。次いでこれを粉砕し、ボールミルで
微粉砕後、脱水、乾燥し、この材料にバインダーとして
ポリビニールアルコール（PVA）を加え、乳鉢、乳棒で
顆粒に造粒した後、直径16mm、厚さ2.5mmの円板状に加
圧成型する。この加圧成型に際し2t/cm2の圧力を加え
る。Then put this raw material in Al 2 O 3 bowl, 800 ℃ ～ 1000 ℃
And calcine for 2 hours. Then, this is pulverized, finely pulverized by a ball mill, dehydrated and dried, polyvinyl alcohol (PVA) is added as a binder to the material, and the mixture is granulated into granules with a mortar and pestle. Press molding into a disk shape. During this pressure molding, a pressure of 2 t / cm 2 is applied.
そして大気中で600℃で２時間加熱してバインダーを
除脱した後に、大気中で1000℃〜1400℃の範囲で２時間
本焼成する。Then, after the binder is removed by heating at 600 ° C. for 2 hours in the air, the main baking is performed at 1000 ° C. to 1400 ° C. for 2 hours in the air.
このようにして得られた試料に、第１表に示す如く、
AgまたはCu、Niのペーストをスクリーン印刷で塗布して
電極を形成し、Agについては大気中で、Cu及びNiについ
てはN2雰囲気中で、500℃以上で10分間以上電極焼付け
を行った。As shown in Table 1, the sample thus obtained was
An electrode was formed by applying a paste of Ag, Cu, or Ni by screen printing, and the electrode was baked at 500 ° C. or more for 10 minutes or more in the air for Ag and in the N 2 atmosphere for Cu and Ni.
このようにして得られた、NTCサーミスタの各試料を
直流四端子法を用いて、ヒューレット・パッカー社製の
HP 3456Aという番号の測定器を使用して抵抗値を測定
した結果、第１表に示す通りのものが得られた。Each sample of the NTC thermistor obtained in this manner was manufactured by Hewlett-Packer Company using the DC four-terminal method.
As a result of measuring the resistance value using a measuring instrument of HP 3456A, the one shown in Table 1 was obtained.
なお、この第１表に示す如く、各試料をそれぞれ125
℃で100時間、500時間、1000時間の高温保管試験後に抵
抗値を測定して25℃での抵抗値との抵抗変化率（％）も
測定した結果、第１表の通りのものが得られた。 In addition, as shown in Table 1, each sample was
After 100 hours, 500 hours, and 1000 hours of high-temperature storage test at 100 ° C, the resistance was measured and the rate of change in resistance (%) from the resistance at 25 ° C was measured. Was.
また25℃での比抵抗換算は、25℃での抵抗値をR25と
したとき次式で算出する。The specific resistance Conversion at 25 ° C. calculates the resistance value at 25 ° C. the following equation when the R 25.
Ｂ定数は、25℃及び85℃の抵抗値をそれぞれR25、R85
とするとき、次式により換算算出する。 The B constant is obtained by connecting the resistance values at 25 ° C and 85 ° C to R 25 and R 85 , respectively.
Is calculated by the following equation.
第１表において○印が本発明によるものであり、×印
は本発明によらないものである。 In Table 1, ○ indicates that the present invention was applied, and X indicates that the present invention was not applied.
この第１表により明らかな如く、試料No.1、２、７、
８、13、14、19、20、25、28、31、34に示すように、本
発明によらないものは、125℃において1000時間保持後
の抵抗変化率がいずれも１％を大きくあるいは相当越え
ているが、本発明によるものは１％以下と小さいもので
あることがわかる。As is clear from Table 1, Sample Nos. 1, 2, 7,
As shown in 8, 13, 14, 19, 20, 25, 28, 31, and 34, those not according to the present invention have a resistance change rate after holding at 125 ° C. for 1000 hours larger or equivalent to 1% in all cases. It can be seen that the value according to the present invention is as small as 1% or less.
しかも試料No.9〜12、21〜24に示す如く、比抵抗の低
いCuの酸化物を含有する場合でも1000時間保管後の抵抗
変化率が１％以下となり120℃以上での使用が十分可能
である。In addition, as shown in Sample Nos. 9 to 12, 21 to 24, even when Cu oxide with low specific resistance is contained, the resistance change rate after storage for 1000 hours is 1% or less, and it can be used at 120 ° C or more. It is.
勿論、本発明のNTCサーミスタ素子の製造に際して
は、Mn、Ni、Co、Fe、Cu、Crといった遷移金属酸化物あ
るいはこれらにAl、Zrなどの金属酸化物のうち、必要な
特性を満たすように２〜４成分を主成分となるように選
択配合されるものであり、仮焼、粉砕、本焼成して得ら
れた粉末を加圧成型して卑金属電極を形成し、500℃以
上の還元性または中性雰囲気中で焼付けるものである。Of course, in the production of the NTC thermistor element of the present invention, Mn, Ni, Co, Fe, Cu, a transition metal oxide such as Cr or a metal oxide such as Al, Zr, to satisfy the required properties. 2 to 4 components are selected and blended to be the main component. The powder obtained by calcination, pulverization, and main calcination is pressure-formed to form a base metal electrode, which is reduced at 500 ° C or higher. Alternatively, baking is performed in a neutral atmosphere.
第１表のデータは、これらの一部を示すものにすぎな
い。The data in Table 1 shows only some of these.
本発明によれば120℃以上の高温下で使用しても、そ
の抵抗変化率の非常に小さいNTCサーミスタ素子を簡単
な方法により提供することができる。According to the present invention, even when used at a high temperature of 120 ° C. or more, an NTC thermistor element having a very small resistance change rate can be provided by a simple method.
しかも、CuOを含有するものに対しても、このような
高温で使用可能なNTCサーミスタ素子を簡単な方法によ
り提供することができる。Moreover, it is possible to provide an NTC thermistor element that can be used at such a high temperature by using a simple method even for those containing CuO.
また卑金属電極を使用するので、貴金属電極のものに
比して安価なNTCサーミスタ素子を提供することができ
る。In addition, since the base metal electrode is used, an inexpensive NTC thermistor element can be provided as compared with a noble metal electrode.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 淀川 正忠 東京都中央区日本橋１丁目13番１号 テ ィーディーケイ株式会社内 (56)参考文献 特開 昭57−111004（ＪＰ，Ａ) 特開 昭63−119503（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masatada Yodogawa 1-1-13 Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation (56) References JP-A-57-111004 (JP, A) JP-A-63 -119503 (JP, A)
Claims (1)
物の複数種類あるいはこれらにAl、Zrなどの金属酸化物
を加えたものを主成分とするNTCサーミスタ組成物に卑
金属電極を塗布形成した後に、還元または中性雰囲気
で、この塗布形成した卑金属電極の焼付けを行うことを
特徴とするNTCサーミスタの製造方法。1. An NTC thermistor composition comprising as a main component a plurality of transition metal oxides such as Mn, Ni, Co, Fe, Cu, Cr and the like and a metal oxide such as Al and Zr added thereto. A method for manufacturing an NTC thermistor, characterized in that after coating and forming a base metal electrode, the coated and formed base metal electrode is baked in a reducing or neutral atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63297911A JP2841395B2 (en) | 1988-11-25 | 1988-11-25 | Method for manufacturing NTC thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63297911A JP2841395B2 (en) | 1988-11-25 | 1988-11-25 | Method for manufacturing NTC thermistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02143502A JPH02143502A (en) | 1990-06-01 |
| JP2841395B2 true JP2841395B2 (en) | 1998-12-24 |
Family
ID=17852688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63297911A Expired - Fee Related JP2841395B2 (en) | 1988-11-25 | 1988-11-25 | Method for manufacturing NTC thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841395B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319043A (en) * | 2014-10-10 | 2015-01-28 | 广州新莱福磁电有限公司 | Manufacturing method of negative-temperature-coefficient thermistor chip electrode |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0582310A (en) * | 1991-09-24 | 1993-04-02 | Tdk Corp | Composition for thermistor |
| JPH0582308A (en) * | 1991-09-24 | 1993-04-02 | Tdk Corp | Composition for thermistor |
| US5497139A (en) * | 1994-09-23 | 1996-03-05 | Matsushita Electric Industrial Co., Ltd. | Temperature sensor and its manufacturing method |
| US6099164A (en) * | 1995-06-07 | 2000-08-08 | Thermometrics, Inc. | Sensors incorporating nickel-manganese oxide single crystals |
| US6076965A (en) * | 1996-06-17 | 2000-06-20 | Therometrics, Inc. | Monocrystal of nickel-cobalt-manganese oxide having a cubic spinel structure, method of growth and sensor formed therefrom |
| US6125529A (en) * | 1996-06-17 | 2000-10-03 | Thermometrics, Inc. | Method of making wafer based sensors and wafer chip sensors |
| WO1998007656A1 (en) * | 1996-08-23 | 1998-02-26 | Thermometrics, Inc. | Growth of nickel-iron-manganese oxide single crystals |
| CN115073140B (en) * | 2022-06-08 | 2023-05-05 | 盐城工学院 | Preparation method of copper-containing negative temperature coefficient thermosensitive ceramic material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57111004A (en) * | 1980-12-26 | 1982-07-10 | Tdk Electronics Co Ltd | Voltage non-linear resistance element and method of producing same |
| JPS63119503A (en) * | 1986-11-07 | 1988-05-24 | 株式会社村田製作所 | Manufacture of thermistor |
-
1988
- 1988-11-25 JP JP63297911A patent/JP2841395B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319043A (en) * | 2014-10-10 | 2015-01-28 | 广州新莱福磁电有限公司 | Manufacturing method of negative-temperature-coefficient thermistor chip electrode |
| CN104319043B (en) * | 2014-10-10 | 2017-05-03 | 广州新莱福磁电有限公司 | Manufacturing method of negative-temperature-coefficient thermistor chip electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02143502A (en) | 1990-06-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |