JPH0572082B2 - - Google Patents
Info
- Publication number
- JPH0572082B2 JPH0572082B2 JP1339566A JP33956689A JPH0572082B2 JP H0572082 B2 JPH0572082 B2 JP H0572082B2 JP 1339566 A JP1339566 A JP 1339566A JP 33956689 A JP33956689 A JP 33956689A JP H0572082 B2 JPH0572082 B2 JP H0572082B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- thick film
- thermistor
- transition metal
- film thermistor
- 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
- 239000011521 glass Substances 0.000 claims description 30
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Description
〔発明の目的〕
（産業上の利用分野）
本発明は、基板上の電極間にサンドイツチ形に
印刷形成される厚膜サーミスタ用の厚膜サーミス
タ組成物に関する。
（従来の技術）
従来の厚膜サーミスタ組成物としては、Mn、
Co、Fe、Niなどの遷移金属酸化物と導電性材料
としてのRuO2粉末と、さらにガラス粉末を混合
したものが知られている。
そして、この組成物は基板上の上下の電極間に
サーミスタ層として印刷、焼成により形成され、
サンドイツチ形厚膜サーミスタが形成されるもの
である。
（発明が解決しようとする課題）
しかるに上述のように得られた厚膜サーミスタ
や遷移金属酸化物を成形して焼結したデイスクタ
イプのサーミスタは、原材料に含まれる不純物の
影響や、空気中での酸化、焼成時の歪と結晶のよ
り安定な相への変化などにより、使用中に抵抗値
が変化してしまう現象がある。
このため、要求される特性によつては、表面を
ガラス層で覆つたり、製造工程の途中で150℃〜
200℃で10時間〜100時間エージングを行ない、抵
抗値を安定させる必要があつた。
しかしガラス層の被覆はまだしも、熱エージン
グは工程が途中で途切れ、工程の連続性、量産
性、製品の納期対応などに問題が発生し、また、
製造においても、エージングによる抵抗値変化を
考慮して初期抵抗値を設定しなければならないと
いう問題があつた。
本発明の目的は上記問題点に鑑み、厚膜サーミ
スタの抵抗値を安定化し製造工程の途中で熱エー
ジングを行う必要のない厚膜サーミスタ組成物を
提供するものである。
〔発明の構成〕
（課題を解決するための手段）
本発明の厚膜サーミスタ組成物は、Mn、Co、
Fe、Niの夫々の酸化物のうちから選ばれたサー
ミスタ特性を有する少なくとも２種の遷移金属酸
化物と、RuO2よりなる導電性物質と、ガラスに
前記サーミスタ特性を有する金属酸化物のうちの
少なくとも一種を溶融して含有させた遷移金属酸
化物融合ガラスよりなるガラス材とよりなるもの
である。
（作用）
本発明の厚膜サーミスタ組成物は、ガラスにサ
ーミスタ特性を有する遷移金属酸化物を溶融した
遷移金属酸化物融合ガラスよりなるガラス材が、
遷移金属のほぼ同じ熱膨脹係数となるため、厚膜
サーミスタを形成するためにサーミスタ組成物を
基板に印刷後の焼成時に、遷移金属酸化物とガラ
ス材との熱膨脹係数の差により歪を発生すること
がなく、得られた厚膜サーミスタが長時間の加熱
によつても抵抗値に変化を生じ難いものとなる。
（実施例）
本発明の一実施例を説明する。
Mn3O4：Co3O4：Fe3O4＝１：１：0.4の重量比
で固相反応させたサーミスタ特性を有する遷移金
属酸化物と市販のホウケイ酸鉛ガラス粉末を5wt
％：95wt％となるように秤量し自動混合機また
はボールミルにより充分に混合した。その後、こ
の混合粉末を白金ルツボに入れ1250℃で10分間溶
融した。溶融物を攪拌水中に滴下し遷移金属酸化
物融合ガラスよりなるガラス材を作成した。この
遷移金属酸化物融合ガラス材をさらに粉砕機、ボ
ールミルで粉砕し、325メツシユの篩にかけ、目
的とする遷移金属酸化物融合ガラスよりなるガラ
ス材粉末を得た。
次に、前記ガラス粉末に混合する以前のサーミ
スタ特性を有する遷移金属酸化物粉末53wt％と
RuO2粉末2wt％、前記遷移金属酸化物融合ガラ
スよりなるガラス材粉末45wt％を混合した。こ
こに有機ビヒクルとして8wt％のエチルセルロー
スを含むブチルカルビトールを混合物の30wt％
となるように加え、三本ロール等で充分に混合し
厚膜サーミスタペーストを作成した。得られた厚
膜サーミスタペーストを用い、第１図に示すよう
に、絶縁基板１上に上下に重ね合わされ対向する
電極２，２の面積0.25mm2間にサンドイツチ状に厚
膜サーミスタ層３を印刷、焼成して厚膜サーミス
タを得た。
この実施例で得られた厚膜サーミスタ（本発明
品）と従来の遷移金属酸化物とRuO2とガラスと
よりなる厚膜サーミスタ（従来品）の抵抗値、Ｂ
定数を表１に示す。
[Object of the Invention] (Industrial Application Field) The present invention relates to a thick film thermistor composition for a thick film thermistor that is printed and formed in the shape of a sandwich arch between electrodes on a substrate. (Prior art) Conventional thick film thermistor compositions include Mn,
A mixture of transition metal oxides such as Co, Fe, and Ni, RuO 2 powder as a conductive material, and glass powder is known. This composition is then printed and fired as a thermistor layer between the upper and lower electrodes on the substrate.
A sandwich-type thick film thermistor is formed. (Problem to be solved by the invention) However, the thick-film thermistor obtained as described above and the disk-type thermistor formed by molding and sintering transition metal oxides are susceptible to the effects of impurities contained in the raw materials and to resistance in the air. There is a phenomenon in which the resistance value changes during use due to oxidation of the material, strain during firing, and change of the crystal to a more stable phase. For this reason, depending on the required characteristics, the surface may be covered with a glass layer, or the temperature may exceed 150°C during the manufacturing process.
It was necessary to stabilize the resistance value by aging at 200°C for 10 to 100 hours. However, although the glass layer is still coated, the thermal aging process is interrupted midway, causing problems with process continuity, mass production, and product delivery deadlines.
In manufacturing as well, there was a problem in that the initial resistance value had to be set in consideration of changes in resistance value due to aging. In view of the above problems, an object of the present invention is to provide a thick film thermistor composition that stabilizes the resistance value of the thick film thermistor and does not require thermal aging during the manufacturing process. [Structure of the Invention] (Means for Solving the Problems) The thick film thermistor composition of the present invention includes Mn, Co,
At least two types of transition metal oxides having thermistor characteristics selected from the respective oxides of Fe and Ni, a conductive substance made of RuO 2 , and a metal oxide having the thermistor characteristics selected from the glass. It is made of a glass material made of transition metal oxide fused glass containing at least one type of fused glass. (Function) In the thick film thermistor composition of the present invention, the glass material is made of transition metal oxide fused glass in which a transition metal oxide having thermistor properties is fused to glass.
Since transition metals have almost the same coefficient of thermal expansion, when the thermistor composition is printed on a substrate to form a thick film thermistor and then fired, distortion may occur due to the difference in coefficient of thermal expansion between the transition metal oxide and the glass material. Therefore, the resulting thick film thermistor is unlikely to change its resistance value even when heated for a long time. (Example) An example of the present invention will be described. Mn 3 O 4 :Co 3 O 4 :Fe 3 O 4 = 5 wt of commercially available lead borosilicate glass powder and a transition metal oxide having thermistor characteristics that were subjected to a solid phase reaction at a weight ratio of 1:1:0.4.
%: 95 wt%, and thoroughly mixed using an automatic mixer or ball mill. Thereafter, this mixed powder was placed in a platinum crucible and melted at 1250°C for 10 minutes. The melt was dropped into stirring water to create a glass material made of transition metal oxide fused glass. This transition metal oxide fused glass material was further pulverized using a crusher and a ball mill, and passed through a 325 mesh sieve to obtain the desired glass material powder made of transition metal oxide fused glass. Next, 53wt% of transition metal oxide powder having thermistor characteristics was added to the glass powder.
2 wt % of RuO 2 powder and 45 wt % of the glass material powder made of the transition metal oxide fused glass were mixed. Here 30wt% of the mixture contains butyl carbitol with 8wt% ethylcellulose as the organic vehicle.
A thick film thermistor paste was prepared by adding the following ingredients and thoroughly mixing with a triple roll or the like. Using the obtained thick film thermistor paste, as shown in Fig. 1, a thick film thermistor layer 3 is printed in the shape of a sandwich arch on an insulating substrate 1 between two opposing electrodes 2, 2 , which have an area of 0.25 mm. , and fired to obtain a thick film thermistor. Resistance values of the thick film thermistor (product of the present invention) obtained in this example and the conventional thick film thermistor (conventional product) made of transition metal oxide, RuO 2 , and glass, B
The constants are shown in Table 1.
【表】
実施例で得られた厚膜サーミスタをガラスで被
覆し、600℃で焼成したときの抵抗値変化率を表
２に示す。[Table] Table 2 shows the rate of change in resistance value when the thick film thermistor obtained in the example was covered with glass and fired at 600°C.
本発明によれば、ガラス材としてガラスに遷移
金属酸化物を溶融して含有させた遷移金属融合ガ
ラスを配合したため、このガラス材の熱膨脹係数
が遷移金属酸化物の熱膨脹係数に近く、厚膜サー
ミスタ成形のための焼成時に歪を生じない。した
がつて得られた厚膜サーミスタを長時間加熱して
も抵抗値に変化を生じないから、製造工程途中で
エージングを行つたりする必要がなく、生産性を
向上させることができる。
According to the present invention, since a transition metal fused glass in which a transition metal oxide is melted and contained in glass is blended as a glass material, the coefficient of thermal expansion of this glass material is close to that of the transition metal oxide, and the thick film thermistor No distortion occurs during firing for molding. Therefore, even if the obtained thick film thermistor is heated for a long time, the resistance value does not change, so there is no need to perform aging during the manufacturing process, and productivity can be improved.
第１図は本発明の厚膜サーミスタ組成物によつ
て得られた厚膜サーミスタの断面図、第２図、第
３図は夫々実施例の組成物で得られた厚膜サーミ
スタと従来厚膜サーミスタとのガラス被覆をしな
いもの、ガラス被覆をしたものの抵抗−温度特性
図である。
FIG. 1 is a sectional view of a thick film thermistor obtained using the thick film thermistor composition of the present invention, and FIGS. 2 and 3 show a thick film thermistor obtained using the composition of the example and a conventional thick film It is a resistance-temperature characteristic diagram of a thermistor not coated with glass and a thermistor coated with glass.
Claims (1)
ら選ばれたサーミスタ特性を有する少なくとも２
種の遷移金属酸化物と、 RuO2よりなる導電性物質と、 ガラスに前記サーミスタ特性を有する金属酸化
物のうちの少なくとも一種を溶融して含有させた
遷移金属酸化物融合ガラスよりなるガラス材 とよりなることを特徴とする厚膜サーミスタ組成
物。[Claims] 1. At least 2 oxides having thermistor characteristics selected from oxides of Mn, Co, Fe, and Ni.
a conductive substance made of RuO 2 ; and a glass material made of transition metal oxide fused glass in which at least one of the metal oxides having the thermistor characteristics is melted and contained in the glass. A thick film thermistor composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339566A JPH03200302A (en) | 1989-12-27 | 1989-12-27 | Thick-film thermistor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339566A JPH03200302A (en) | 1989-12-27 | 1989-12-27 | Thick-film thermistor composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200302A JPH03200302A (en) | 1991-09-02 |
| JPH0572082B2 true JPH0572082B2 (en) | 1993-10-08 |
Family
ID=18328684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1339566A Granted JPH03200302A (en) | 1989-12-27 | 1989-12-27 | Thick-film thermistor composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03200302A (en) |
-
1989
- 1989-12-27 JP JP1339566A patent/JPH03200302A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03200302A (en) | 1991-09-02 |
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