JPH03200302A - Thick-film thermistor composition - Google Patents
Thick-film thermistor compositionInfo
- Publication number
- JPH03200302A JPH03200302A JP1339566A JP33956689A JPH03200302A JP H03200302 A JPH03200302 A JP H03200302A JP 1339566 A JP1339566 A JP 1339566A JP 33956689 A JP33956689 A JP 33956689A JP H03200302 A JPH03200302 A JP H03200302A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- glass
- thermistor
- thick film
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 37
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract 2
- 229910052748 manganese Inorganic materials 0.000 claims abstract 2
- 229910052759 nickel Inorganic materials 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 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
- 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
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 238000003878 thermal aging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔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ッチ形に印刷形成
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。DETAILED DESCRIPTION OF THE INVENTION [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 in a sandwich form between electrodes on a substrate.
（従来の技術）
従来の厚膜サーミスタ組成物としては、ＭｌｌｌＣｏＳ
ＦｅＳＮｉなどの遷移金属酸化物と導電材料としてのＲ
ｕｂ２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。(Prior art) As a conventional thick film thermistor composition, MlllCoS
Transition metal oxides such as FeSNi and R as a conductive material
A mixture of ub2 powder and glass powder is known.
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、サンドイッチ形
厚膜サーミスタが形成されるものである。Then, this composition is formed as a thermistor layer between upper and lower electrodes on a substrate by printing and baking to form a sandwich type thick film thermistor.
（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ィ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。(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 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.
このため、要求される特性によっては、表面をガラス層
で覆ったり、製造工程の途中で１５０℃〜２００℃で１
０時間〜１００時間エージングを行ない、抵抗値を安定
させる必要があった。For this reason, depending on the required characteristics, the surface may be covered with a glass layer or heated at 150°C to 200°C during the manufacturing process.
It was necessary to perform aging for 0 to 100 hours to stabilize the resistance value.
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った。However, even though the glass layer is still coated, the heat aging process is interrupted midway, causing problems with process continuity, mass production, and product delivery deadlines.Furthermore, during manufacturing, changes in resistance due to aging must be taken into account. There was a problem in that the initial resistance value had to be set.
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。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.
（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、Ｍｎ５Ｃｏ、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、ＲｕＯ
□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。(Means for Solving the Problems) The thick film thermistor composition of the present invention includes Mn5Co, Fe,
At least two transition metal oxides having thermistor characteristics selected from among the respective oxides of Ni, and RuO
□ and a glass material made of transition metal oxide fused glass, which is made by melting and containing at least one of the metal oxides having the thermistor characteristics in the glass.
（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、遷移金属とほぼ同じ熱
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る歪を発生す
ることがなく、得られた厚膜サーミスタが長時間の加熱
によっても抵抗値に変化を生じ難いものとなる。(Function) The thick film thermistor composition of the present invention has a glass material made of transition metal oxide fused glass in which a transition metal oxide having thermistor properties is melted into glass, and has a coefficient of thermal expansion almost the same as that of the transition metal. During firing after printing the thermistor composition on a substrate to form a film thermistor, distortion due to the difference in thermal expansion coefficient between the transition metal oxide and the glass material does not occur, and the obtained thick film thermistor can last for a long time. Even when heated, the resistance value hardly changes.
（実施例） 本発明の一実施例を説明する。(Example) An embodiment of the present invention will be described.
Ｍｎ３Ｏ４： Ｃｏ３ｏ４： Ｆｅ：＋０４＝ 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５ｗｆ％：９５ｖｆ％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。溶融物を撹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自材を作成した。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。Mn3O4: Co3o4: Fe:+04=1:
A transition metal oxide having thermistor characteristics that was subjected to a solid phase reaction in a weight ratio of 1:0.4 and a commercially available lead borosilicate glass powder were weighed to give a ratio of 5wf%:95vf% and thoroughly mixed using an automatic mixer or ball mill. Mixed. 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.
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５３Ｗ１％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４５Ｗ１％を混合した。Next, 53W1% of transition metal oxide powder having thermistor characteristics before being mixed with the glass powder, 2wt% of RUO2 powder, and 1% of glass material powder made of the transition metal oxide fused glass 45W were mixed.
ここに有機ビヒクルとして３ｖｔ％のエチルセルロース
を含むブチルカルピトールを混合物の３０１１％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
間にサンドイッ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。Butylcarpitol containing 3vt% of ethyl cellulose was added as an organic vehicle to the mixture to give a concentration of 3011%, and the mixture was sufficiently mixed using a triple roll or the like to prepare a thick film thermistor paste. Using the obtained thick film thermistor paste, as shown in FIG.
A thick film thermistor layer 3 was printed in sandwich form between them and fired to obtain a thick film thermistor.
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
。Table 1 shows the resistance values and B constants of the thick film thermistor obtained in this example (product of the present invention) and the conventional thick film thermistor made of transition metal oxide, RuO2, and glass (conventional product).
表 １
実施例で得られた厚膜サーミスタをガラスで被覆し、６
００℃で焼成したときの抵抗値変化率を表２に示す。Table 1 The thick film thermistor obtained in the example was covered with glass, and 6
Table 2 shows the rate of change in resistance value when fired at 00°C.
表１、表２より遷移金属酸化物融合ガラスが配合された
本発明品を使用した厚膜サーミスタは、同じＢ定数を有
しながら、抵抗値を約１７％低くできた。As shown in Tables 1 and 2, the thick film thermistor using the product of the present invention containing transition metal oxide fused glass had the same B constant but had a resistance value lowered by about 17%.
また表１に示す本発明品を使用した厚膜サーミスタと従
来品との１５０℃、１０００Ｈｔの耐熱変化率を第２図
に示した。Further, the rate of change in heat resistance at 150° C. and 1000 Ht between the thick film thermistor using the product of the present invention shown in Table 1 and the conventional product is shown in FIG.
表２に示す本発明品を使用した厚膜サーミスタと従来品
との１５０℃、１０００Ｈｒの耐熱変化率を第３図に示
す。FIG. 3 shows the rate of change in heat resistance at 150° C. and 1000 hours between the thick film thermistor using the inventive product shown in Table 2 and the conventional product.
第２図、第３図より本発明品を使用した厚膜サーミスタ
は１５０℃耐熱変化も殆んどないことがわかる。It can be seen from FIGS. 2 and 3 that the thick film thermistor using the product of the present invention has almost no change in heat resistance at 150°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。したがっ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っ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って得られ
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 cross-sectional view of a thick film thermistor obtained using the thick film thermistor composition of the present invention, and FIGS. FIG. 3 is a resistance-temperature characteristic diagram of a non-glass-coated product and a glass-covered product.
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、 ＲｕＯ＿２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。(1) At least two types of transition metal oxides having thermistor characteristics selected from oxides of Mn, Co, Fe, and Ni, a conductive substance made of RuO_2, and glass having the thermistor characteristics. 1. A thick film thermistor composition comprising a glass material made of transition metal oxide fused glass containing melted at least one kind of metal oxide.
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 true JPH03200302A (en) | 1991-09-02 |
| JPH0572082B2 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 |
|---|---|
| JPH0572082B2 (en) | 1993-10-08 |
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