JPH03185701A - Thick film thermistor composition - Google Patents
Thick film thermistor compositionInfo
- Publication number
- JPH03185701A JPH03185701A JP1324424A JP32442489A JPH03185701A JP H03185701 A JPH03185701 A JP H03185701A JP 1324424 A JP1324424 A JP 1324424A JP 32442489 A JP32442489 A JP 32442489A JP H03185701 A JPH03185701 A JP H03185701A
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- film thermistor
- thermistor
- resistance
- conductive material
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004020 conductor Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は絶縁基板上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 printed on an insulating substrate.
（従来の技術） 従来の厚膜サーミスタ組成物としては、Ｍｎ。(Conventional technology) Conventional thick film thermistor compositions include Mn.
Ｃｏ５Ｆｃ５Ｎｉなどのサーミスタ特性を有する金属酸
化物と、導電材料としてのＲｕＯ２とさらにガラス粉末
を混合したものが知られている。A mixture of a metal oxide having thermistor characteristics such as Co5Fc5Ni, RuO2 as a conductive material, and glass powder is known.
そしてこの組成物を絶縁基板上に形成された第１の電極
上に一部を重ね合わせて印刷し、さらにこの上に第２の
電極を重ね合わせて形成したサンドイッチ形の厚膜サー
ミスタがある。このサンドイッチ形厚膜サーミスタは、
同一平面上の電極間にサーミスタ組成物を印刷したシー
ト状の厚膜サーミスタと比べて抵抗値を低くすることが
できる。しかし、このサンドイッチ形の厚膜サーミスタ
でも抵抗値は２にΩ程度が限度であり、それ以下の抵抗
値を出すには、サーミスタ特性を有する金属酸化物に、
更に直接ＣｕまたはＣ１１酸化物（以下、Ｃｕと略す）
を加えていた。There is a sandwich-type thick film thermistor in which this composition is printed by partially overlapping a first electrode formed on an insulating substrate, and a second electrode is further overlaid on this. This sandwich type thick film thermistor is
The resistance value can be lowered compared to a sheet-like thick film thermistor in which a thermistor composition is printed between electrodes on the same plane. However, even with this sandwich-type thick film thermistor, the resistance value is limited to about 2Ω, and in order to achieve a resistance value lower than that, a metal oxide with thermistor characteristics must be used.
Furthermore, directly Cu or C11 oxide (hereinafter abbreviated as Cu)
was added.
（発明が解決しようとする課題）
しかし、サーミスタ特性を有する金属酸化物に、Ｃｕを
直接添加した場合は、添加量に比例して抵抗値は下るが
、同時にＢ定数（抵抗値変化率を知る定数で一般にはＢ
＝２０００に〜５０００にである。）も低下してしまい
、高いＢ定数を有しながら低い抵抗値を得るのは困難で
あった。(Problem to be solved by the invention) However, when Cu is directly added to a metal oxide that has thermistor characteristics, the resistance value decreases in proportion to the amount added, but at the same time the B constant (the rate of change in resistance value) A constant, generally B
=2000 to 5000. ), and it was difficult to obtain a low resistance value while having a high B constant.
またＣｕは熱安定性に欠け、１２５℃、１００時間で＋
１０％〜＋１５％の抵抗値変化を起すという問題がある
。In addition, Cu lacks thermal stability, and after 100 hours at 125°C,
There is a problem in that the resistance value changes by 10% to +15%.
本発明は上述の問題点に鑑み、添加されたＣｕの耐熱変
化を抑え、高いＢ定数を有しながらも抵抗値を下げるこ
とができる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-mentioned problems, the present invention provides a thick film thermistor composition which can suppress the change in heat resistance of added Cu and can lower the resistance value while having a high B constant.
（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種の金属酸化物と、第１の導
電性物質としてのＲｕＯ２と、第２の導電性物質として
のＣｕまたはＣｕＯと２価の原子価を有する元素の化合
物とを混合焼結した複合酸化物と、ガラスとよりなるも
のである。(Means for Solving the Problems) The thick film thermistor composition of the present invention contains Mn, Co, Fe.
, at least two metal oxides having thermistor characteristics selected from the respective oxides of Ni, RuO2 as the first conductive substance, and Cu or CuO2 as the second conductive substance. It is made of a composite oxide mixed and sintered with a compound of an element having a valence, and glass.
（作用）
本発明の厚膜サーミスタ組成物は、サーミスタ特性を有
する金属酸化物と、ＲｕＯ２よりなる第１の導電性物質
とガラスとよりなる厚膜サーミスタ材料にさらに第２の
導電性物質として、ＣｕまたはＣｕＯと２価の原子価を
有する元素の化合物を混合焼結した複合酸化物を添加し
たことによりＣｕを直接添加した場合のようにＢ定数を
低下させたり、熱による抵抗値変化率を増大させるよう
なことがなく厚膜サーミスタの抵抗値を低下させるもの
である。(Function) The thick film thermistor composition of the present invention comprises a metal oxide having thermistor characteristics, a thick film thermistor material made of a first conductive substance made of RuO2, and glass, and further comprising a metal oxide having thermistor properties as a second conductive substance. By adding a composite oxide made by mixing and sintering a compound of Cu or CuO and a divalent element, it is possible to lower the B constant and reduce the rate of change in resistance value due to heat, unlike when Cu is directly added. This reduces the resistance value of the thick film thermistor without increasing it.
（実施例）
ＣｕＯと２価の原子価を有する元素の化合物としてのＣ
ｕＯを重量比で１＝１になるように秤量し、自動混合機
またはボールミルにより充分に混合する。（ボールミル
を使う場合は、ＣｕＯは水と反応するためブチルカルピ
トールアセテートなどを用いる）混合粉末を磁性ルツボ
に入れ、１０００℃で２時間固相反応をさせて焼結した
第２の導電性物質としての複合酸化物とし、その後この
複合酸化物を粉砕機またはボールミルにかけ粉末にする
。(Example) C as a compound of CuO and a divalent element
Weigh uO so that the weight ratio is 1=1, and mix thoroughly using an automatic mixer or ball mill. (When using a ball mill, use butylcarpitol acetate, etc., as CuO reacts with water.) The mixed powder is placed in a magnetic crucible, and a solid phase reaction is performed at 1000°C for 2 hours to sinter the second conductive material. After that, this composite oxide is processed into a powder by a crusher or a ball mill.
次にＭｎ、 ０４ 、Ｃｏ３Ｏ４、Ｆｅ、 ０４を
ｌ：１Ｇ、２の重量比で固相反応させて得た金属酸化物
粉末３９ｗｔ％、第１の導電性物質としてのＲｕＯ２粉
末８ｖ１％、ホウケイ酸鉛ガラス粉末４０ｗ１％、前記
Ｃｕ−Ｃａ複合酸化物粉末１３Ｗ（％を混合して混合物
とする。ここに有機ビヒクルとして８ｗ１％のエチルセ
ルロースを含むブチルカルピトールを前記混合物の３Ｇ
ｗｔ９６となる様に加え、３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、図に示すように、基板１上に対
向面積０．２５ｍｍ２となるように上下に対向して形成
される電極２．２間に膜厚５０＋＋ｍとなるようにサン
ドイッチ形に厚膜サーミスタ体３を印刷、焼成により形
成し厚膜サーミスタを得た。Next, 39wt% of metal oxide powder obtained by solid phase reaction of Mn, 04, Co3O4, Fe, 04 at a weight ratio of 1:1G, 2, 8v1% of RuO2 powder as the first conductive substance, and borosilicate. A mixture is prepared by mixing 40w1% of lead glass powder and 13W (%) of the Cu-Ca composite oxide powder.As an organic vehicle, butyl calpitol containing 8w1% of ethyl cellulose is added to 3G of the mixture.
In addition, a thick film thermistor paste was prepared by thoroughly mixing with a three-roll roll or the like to obtain wt96. Using the obtained thick film thermistor paste, as shown in the figure, a film thickness of 50++ m was formed between the electrodes 2 and 2, which are formed vertically facing each other on the substrate 1 so that the opposing area is 0.25 mm2. A thick film thermistor body 3 was formed in a sandwich shape by printing and firing to obtain a thick film thermistor.
得られた厚膜サーミスタの抵抗値１００Ω、Ｂ定数２５
５０に、１２５℃、５００時間加熱の抵抗値変化率＋ｔ
、ｏｇ％できわめて安定した特性であった。The obtained thick film thermistor had a resistance value of 100Ω and a B constant of 25.
50, resistance value change rate +t of heating at 125°C for 500 hours
, og%, the properties were extremely stable.
別表に、従来の厚膜サーミスタ試料１．２．３と本発明
の複合酸化物を添加した厚膜サーミスタ試料１．２．３
．４．５の抵抗値、Ｂ定数、１２５℃ミ５００時間の抵
抗値変化率を示す。In the attached table, a conventional thick film thermistor sample 1.2.3 and a thick film thermistor sample 1.2.3 added with the composite oxide of the present invention are shown.
．． It shows a resistance value of 4.5, a B constant, and a resistance change rate after 500 hours at 125°C.
表において実施例１〜３のＣｕ−Ｃｌは、ＣｕＯとＣＩ
Ｏをｌ：１で混合して焼結し粉砕した複合酸化物の粉末
、実施例４．５のＣｕ−３ｒはＣｕＯとＳｒＯを１：１
で混合して焼結し粉砕した複合酸化物の粉末を示す。In the table, Cu-Cl in Examples 1 to 3 is CuO and CI
Cu-3r in Example 4.5, which is a composite oxide powder obtained by mixing O in a ratio of 1:1, sintering and pulverizing, is a mixture of CuO and SrO in a ratio of 1:1.
This shows the composite oxide powder mixed, sintered, and ground.
なお、以上の実施例では、第２の導電性物質のＣｕ源と
してのＣｌｌ０を用いたが他のＣｕ化合物でもよい。ま
た、２価の原子価を有する元素の化合物としてはＣｒＯ
の他に、ＳｒＯ、ＢａＯなどの酸化物または炭酸塩を用
いることもできる。In the above embodiments, Cll0 was used as the Cu source of the second conductive substance, but other Cu compounds may be used. In addition, as a compound of an element having a divalent valence, CrO
In addition, oxides or carbonates such as SrO and BaO can also be used.
この表より従来の厚膜サーミスタに比べて本発明の組成
物を用いて形成した厚膜サーミスタは低抵抗で高いＢ定
数を有し、さらに熱に対して抵抗値変化率が少いことが
わかる。From this table, it can be seen that the thick film thermistor formed using the composition of the present invention has lower resistance and higher B constant than the conventional thick film thermistor, and also has a smaller rate of change in resistance value with respect to heat. .
本発明によれば、サーミスタ特性を有する金属酸化物、
第２の導電材料としてのＲ１１０２とガラスよりなる厚
膜サーミスタ材料に、さらに第２の導電材料としてＣｕ
またはＣｕＯと、２価の原子価を有する元素の化合物と
の複合酸化物を添加したため抵抗値を低下させることが
でき、Ｃｕを直接添加した場合のようにＢ定数を低下さ
せたり、耐熱安定外に欠けるようなことがなく、低低抗
でＢ定数が高く、軌に対する抵抗値変化率の少ない厚膜
サーミスタを得ることができる。According to the present invention, a metal oxide having thermistor properties,
A thick film thermistor material made of R1102 and glass as a second conductive material, and Cu as a second conductive material.
Or, by adding a composite oxide of CuO and a compound of divalent elements, it is possible to lower the resistance value, and as with the direct addition of Cu, the B constant may be lowered or the heat resistance becomes unstable. It is possible to obtain a thick-film thermistor that does not lack in properties, has a low resistance, a high B constant, and a small rate of change in resistance value with respect to the track.
また、第１、第２の導電材料を配合したから、夫々の添
加景を変化させることにより幅の広い抵抗ｆ直とＢ定数
の組合わせが可能になる。Furthermore, since the first and second conductive materials are blended, a wide range of combinations of resistance f constant and B constant can be made by changing the respective additive factors.
図は本発明の厚膜サーミスタ組代物を用いて形成された
厚膜サーミスタの縦断正面間である。The figure is a longitudinal cross-sectional view of a thick film thermistor formed using the thick film thermistor composite of the present invention.
Claims (1)
ら選ばれたサーミスタ特性を有する少なくとも２種の金
属酸化物と、 第１の導電性物質としてのＲｕＯ＿２と、 第２の導電性物質としてのＣｕまたはＣｕＯと２価の原
子価を有する元素の化合物とを混合焼結した複合酸化物
と、 ガラス 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 metal oxides having thermistor characteristics selected from oxides of Mn, Co, Fe, and Ni, RuO_2 as a first conductive substance, and a second conductive substance. A thick film thermistor composition comprising a composite oxide obtained by mixing and sintering Cu or CuO as a substance and a compound of an element having a divalent valence, and glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1324424A JPH03185701A (en) | 1989-12-14 | 1989-12-14 | Thick film thermistor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1324424A JPH03185701A (en) | 1989-12-14 | 1989-12-14 | Thick film thermistor composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03185701A true JPH03185701A (en) | 1991-08-13 |
Family
ID=18165644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1324424A Pending JPH03185701A (en) | 1989-12-14 | 1989-12-14 | Thick film thermistor composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03185701A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002270402A (en) * | 2001-03-09 | 2002-09-20 | Rohm Co Ltd | Chip resistor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54115799A (en) * | 1978-03-01 | 1979-09-08 | Hitachi Ltd | Thermistor composition |
| JPS54119695A (en) * | 1978-03-08 | 1979-09-17 | Hitachi Ltd | Composite material for thick film thermistor |
-
1989
- 1989-12-14 JP JP1324424A patent/JPH03185701A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54115799A (en) * | 1978-03-01 | 1979-09-08 | Hitachi Ltd | Thermistor composition |
| JPS54119695A (en) * | 1978-03-08 | 1979-09-17 | Hitachi Ltd | Composite material for thick film thermistor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002270402A (en) * | 2001-03-09 | 2002-09-20 | Rohm Co Ltd | Chip resistor |
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