JPS62124164A - Resistance coating compound and resistance element formed from same - Google Patents
Resistance coating compound and resistance element formed from sameInfo
- Publication number
- JPS62124164A JPS62124164A JP60265250A JP26525085A JPS62124164A JP S62124164 A JPS62124164 A JP S62124164A JP 60265250 A JP60265250 A JP 60265250A JP 26525085 A JP26525085 A JP 26525085A JP S62124164 A JPS62124164 A JP S62124164A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- resistance
- glass
- coating compound
- lanthanum
- 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.)
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- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、特に中抵抗域から高抵抗域において優れた特
性を有する酸化ルテニウム−ガラス抵抗塗料及びこの抵
抗塗料を用いて製造された厚膜抵抗体に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a ruthenium oxide-glass resistance paint that has excellent properties, particularly in the medium to high resistance range, and a thick film resistor manufactured using this resistance paint. Regarding.
従来の技術
絶縁基板上に酸化ルテニウムとガラスとからなる抵抗被
膜を焼付形成した厚膜抵抗体は、酸化ルテニウムとガラ
スの比を変化させることにより数Ω/口〜数MΩ/口の
広い抵抗域にわたって所望の抵抗値が得られるため、従
来から広く使用されている。ところがこの組成物はガラ
ス含有量の増加に伴って、温度による抵抗変化率即ち抵
抗温度係数(以下TCPという)が負側にシフトしてい
くので、ガラスを多聞に配合する中〜高抵抗域において
負に大きなTCPを示ずようになり、又同時にノイズが
増大する。通常抵抗体は周囲温度によってその抵抗値が
変わらないこと、即ちTCPが0に近いことが望まれる
から、中〜高抵抗域において’T’ CRをOに近づけ
るため、種々のTCP調整剤を配合することが試みられ
ている。Conventional technology Thick film resistors, which are made by baking a resistive film made of ruthenium oxide and glass on an insulating substrate, have a wide resistance range from several Ω/mm to several MΩ/mm by changing the ratio of ruthenium oxide and glass. Since a desired resistance value can be obtained over a wide range, it has been widely used. However, as the glass content of this composition increases, the rate of change in resistance due to temperature, that is, the temperature coefficient of resistance (hereinafter referred to as TCP) shifts to the negative side. It no longer shows a large negative TCP, and at the same time noise increases. Normally, it is desired that the resistance value of a resistor does not change depending on the ambient temperature, that is, that the TCP is close to 0. Therefore, in order to bring the 'T' CR close to O in the medium to high resistance range, various TCP adjusters are mixed. An attempt is being made to do so.
例えば米国特許第3324049号には銅酸化物を添加
したり、銅酸化物を含有するガラスを使用することが記
載されているが、銅酸化物を配合するとTCPはOに近
づくものの、同時に抵抗値が低くなり、かつ電圧係数、
ノイズ、負荷特性など他の特性が悪化する。又英国特許
第1470497号にはコロイド状の△l OOHを添
加するとTCPが正方向に変化することが記載されでい
るが、この場合もやはり抵抗値が低下する。従って結果
的に、高抵抗域でTCPがOに近いものを得ることがで
きなかった。For example, U.S. Patent No. 3,324,049 describes adding copper oxide or using glass containing copper oxide, but when copper oxide is added, TCP approaches O, but at the same time the resistance value becomes lower, and the voltage coefficient,
Other characteristics such as noise and load characteristics deteriorate. British Patent No. 1,470,497 describes that addition of colloidal Δl OOH changes TCP in the positive direction, but in this case, the resistance value also decreases. Therefore, as a result, it was not possible to obtain a TCP close to O in the high resistance region.
発明が解決しようとする問題点
本発明者等は抵抗値の高い領域において、他の′上気特
性を悪化させることなく、又抵抗値を低下させることな
く、TCPを正の方向に変化させ0に近づけるための添
加剤を倹約し、ランタン酸化物、ネオジム酸化物、プラ
セオジム酸化物及びサマリウム酸化物が有効であること
を見出し、先に特開昭58−117264号、特開昭5
9−76401号を出願した。これらの添加剤は、TC
Rを正方向にシフトさせる優れた効果を有するものであ
る。本発明者等は更にTCPの改善について研究を重ね
た結果、この系にtA酸化物を添加することにより、更
に優れた1−CR改善効果が得られることを見出した。Problems to be Solved by the Invention The present inventors have developed a method for changing TCP in a positive direction in a region of high resistance without deteriorating other upper air characteristics or reducing resistance. In order to get closer to the above, we found that lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide were effective.
No. 9-76401 was filed. These additives are TC
This has an excellent effect of shifting R in the positive direction. As a result of further research into improving TCP, the present inventors found that an even more excellent 1-CR improvement effect could be obtained by adding tA oxide to this system.
問題点を解決するための手段
本発明は、(a )酸化ルテニウムと、(b)ガラスと
、(c)ランタン酸化物、ネオジム酸化物、プラセオジ
ム酸化物及びサマリウム酸化物からなる群より選ばれる
1種又は2種以上の酸化物と、(d )銅酸化物と、(
e)有機ビヒクルとからなる抵抗塗料である。Means for Solving the Problems The present invention provides a compound selected from the group consisting of (a) ruthenium oxide, (b) glass, and (c) lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide. a species or two or more oxides, (d) a copper oxide, and (
e) A resistive paint consisting of an organic vehicle.
又第2の発明は、絶縁基板上に、(a)l化ルテニウム
と、(b )ガラスと、(c)ランタン酸化物、ネオジ
ム酸化物、プラセオジム酸化物及びサマリウム酸化物か
らなる群より選ばれる1種又は2種以上の酸化物と、(
d )銅酸化物とからなる抵抗被膜を形成してなる厚膜
抵抗体である。Further, the second invention provides, on an insulating substrate, (a) ruthenium chloride, (b) glass, and (c) a material selected from the group consisting of lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide. One or more oxides and (
d) A thick film resistor formed by forming a resistive film made of copper oxide.
抵抗塗料中へのランタン酸化物、ネオジム酸化物、プラ
セオジム酸化物、サマリウム酸化物、銅酸化物の添加形
態は特に制限はなく、粉末の形でも、又予めガラスと共
に処理することによってガラス中に含有させて添加して
もよい。粉末を用いる場合は粒径10.um以下、特に
0.1〜24程度のものが好ましい。There are no particular restrictions on the form in which lanthanum oxide, neodymium oxide, praseodymium oxide, samarium oxide, and copper oxide are added to the resistance paint; they can be added in the form of powder, or they can be incorporated into glass by pre-processing with glass. It may also be added. When using powder, the particle size is 10. um or less, particularly about 0.1 to 24 um, is preferable.
添加1は要求される抵抗値や他の特性により適宜決定す
るが、酸化ルテニウムとガラスの合計100重晴機転対
し、ランタン酸化物、ネオジム酸化物、プラセオジム酸
化物、サマリウム酸化物は総計で0.05〜7重量部、
銅酸化物は0.1〜5fflfi1部の範囲が望ましい
。ランタン酸化物等が0.05重機部より少ないと充分
な効果が得られず、又7重量部を越えて使用すると、T
CPが逆に負側にシフトする傾向を示ずので好ましくな
い。Addition 1 is determined as appropriate depending on the required resistance value and other characteristics, but the total amount of ruthenium oxide and glass is 100%, and the total amount of lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide is 0.05%. ~7 parts by weight,
The copper oxide is desirably in a range of 0.1 to 5 fflfi1 part. If the amount of lanthanum oxide, etc. is less than 0.05 parts by weight, sufficient effects cannot be obtained, and if it is used in excess of 7 parts by weight,
This is not preferable because CP does not show a tendency to shift to the negative side.
銅酸化物は0.1重量部より少なりれば効果が充分でな
く、5重量部を越えるとノイズが増加し、又負伺特性が
悪化する傾向がある。銅酸化物は特に0.5〜3千埴部
の範囲で添加するのが最適である。If the amount of copper oxide is less than 0.1 parts by weight, the effect will not be sufficient, and if it exceeds 5 parts by weight, noise will increase and there is a tendency for negative feedback characteristics to deteriorate. It is especially optimal to add copper oxide in an amount of 0.5 to 3,000 parts.
本発明の抵抗塗料に用いる酸化ルテニウム、ガラス、有
機ビヒクルは通常抵抗塗料に使用されているものでよい
。酸化ルテニウムも又、予め処理してガラス中に含有さ
せた形で用いることができる。The ruthenium oxide, glass, and organic vehicle used in the resistive paint of the present invention may be those commonly used in resistive paints. Ruthenium oxide can also be used in a pretreated form incorporated into the glass.
本発明の抵抗には、その伯必要に応じ、種々の特性改善
の目的C従来から普通に使用されている金属酸化物添加
剤、例えばアルミナ、シリカ、酸化チタン、酸化ニオブ
、酸化バナジウム、酸化鉛、酸化錫等を配合してもよい
。The resistor of the present invention may contain metal oxide additives commonly used in the past, such as alumina, silica, titanium oxide, niobium oxide, vanadium oxide, and lead oxide, to improve various properties as necessary. , tin oxide, etc. may be blended.
本発明の塗料は絶縁基板上に印刷し、乾燥した後、70
0℃〜900℃程度で焼成して厚膜抵抗体を得る。The paint of the present invention is printed on an insulating substrate and dried for 70 minutes.
A thick film resistor is obtained by firing at about 0°C to 900°C.
負に大きいTCRを有する中〜高抵抗域の酸化ルテニウ
ム−ガラス抵抗にランタン酸化物、ネオジム酸化物、プ
ラセオジム酸化物及びサマリウム酸化物からなる群より
選ばれる1種又は2種以上の酸化物と、銅酸化物とを併
せて添加することにより、抵抗値を低下させることなく
T CPが大幅に改善され、高抵抗側においても温度
による抵抗値変化の少ない、極めて漬れた抵抗体が19
られる。One or more oxides selected from the group consisting of lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide for medium to high resistance range ruthenium oxide-glass resistance having a large negative TCR; By adding copper oxide together, the T CP is significantly improved without reducing the resistance value, and even on the high resistance side, an extremely immersed resistor with little change in resistance value due to temperature is produced.
It will be done.
又高温におけるTCPと低温にあけるTCPの差が小さ
く、広い温度範囲で安定した特性を示す。Furthermore, the difference between TCP at high temperature and TCP at low temperature is small, and exhibits stable characteristics over a wide temperature range.
又、!1酸化物を単独で添加した場合のようにノイズや
負荷特性が悪化せず、レーザトリミング性も良好である
。or,! Noise and load characteristics are not deteriorated unlike when monooxide is added alone, and laser trimming properties are also good.
実施例
以下実施例により本弁明を説明するが、本発明はこれに
限定されるものではない。EXAMPLES The present invention will be explained by examples below, but the present invention is not limited thereto.
表1に実施例1〜3、比較例1〜6の抵抗組成及び試験
結果を併せて示す。比較のためほぼ同等の抵抗値の実施
例と比較例をまとめて示した。尚比較例1.3.5は添
加剤を配合しないものであり、比較例2.4.6はラン
タン酸化物のみを添加した例である。Table 1 shows the resistance compositions and test results of Examples 1 to 3 and Comparative Examples 1 to 6. For comparison, Examples and Comparative Examples with almost the same resistance values are shown together. Comparative Example 1.3.5 does not contain any additives, and Comparative Example 2.4.6 contains only lanthanum oxide.
6例において、表1の各成分を混合し、有機ビヒクル4
5重宿部と共にロール混線を行い、均一にlI)散させ
て抵抗塗料とした。使用したガラスは平均粒径約3バの
Ill 11M #S’r−カルシウムーアルミニウム
ガラスである。ランタン酸化物、銅酸化物はいづ゛れし
1μm以下のt′J)末を用い、又酸化ルミニウムは比
表面積23m2/(lの粉末を用いた。行別ビヒクルは
中小でエチルセルロー2フ、5部、テルピネオール32
.5部、及びジブチルフタレート5.0部の均一混合物
である。In 6 cases, each component in Table 1 was mixed and the organic vehicle 4
Roll mixing was performed with the 5-layered part, and the mixture was uniformly dispersed to obtain a resistance paint. The glass used was Ill 11M #S'r-calcium-aluminum glass with an average particle size of about 3 bar. For lanthanum oxide and copper oxide, powders with t'J) of less than 1 μm were used, and for aluminum oxide, powders with a specific surface area of 23 m2/(l) were used. Part 5, Terpineol 32
.. 5 parts of dibutyl phthalate and 5.0 parts of dibutyl phthalate.
得られた抵抗塗料を、Ag−Pd系厚膜導体で端子電極
を形成したアルミナ長板上に1 mm X 1 mmの
パターンにスクリーン印刷した後、乾燥し、次いでベル
ト炉によりピーク温度850℃で]0分間焼成し、厚膜
抵抗体を製造した。The obtained resistance paint was screen printed in a 1 mm x 1 mm pattern on a long alumina plate on which terminal electrodes were formed using Ag-Pd thick film conductors, dried, and then heated in a belt furnace at a peak temperature of 850°C. ] A thick film resistor was manufactured by firing for 0 minutes.
それぞれの抵抗体について抵抗値、+25℃〜+125
℃の温度範囲におけるTCR(H−TCR)及び−50
°C−+25℃の温度範囲におけるTCP(c−TCP
)を測定し、結果を表1に示した。Resistance value for each resistor, +25℃~+125
TCR (H-TCR) and -50 in the temperature range of °C
TCP (c-TCP) in the temperature range °C-+25 °C
) was measured and the results are shown in Table 1.
−表1
(表中「部」はずべて重量品を表わず。)表1から明ら
かなように、本発明の抵抗体は、従来のものに比べてT
CR特竹が格段に優れている。-Table 1 (None of the "parts" in the table indicates heavy items.) As is clear from Table 1, the resistor of the present invention has a T
CR Tokutake is far superior.
次に表2に示した組成の実施例4〜5、及び比較例7〜
10について、同様にして抵抗体を製造し、抵抗値、H
−T CP、ノイズの他、耐パルス特性、耐電圧特性、
耐熱性、及び耐湿負荷4命特性を調べ、結果を表2に示
した。比較例7.9は添加剤を配合しないものであり、
比較例8.10は銅酸化物のみを添加した例である。Next, Examples 4 to 5 and Comparative Examples 7 to 7 have the compositions shown in Table 2.
Regarding No. 10, a resistor was manufactured in the same manner, and the resistance value, H
-T CP, noise, pulse resistance characteristics, voltage resistance characteristics,
The heat resistance and humidity load resistance characteristics were investigated, and the results are shown in Table 2. Comparative Example 7.9 does not contain additives,
Comparative Example 8.10 is an example in which only copper oxide was added.
各種試験は次のようにして行った。Various tests were conducted as follows.
耐パルス特性(断続過負荷試験):115定洛電圧の2
.5倍の電圧(但し最大400V)を1秒印加し、25
秒間隔をあけて又1秒印加する操作を1万サイクル繰返
した後の抵抗値変化率(%)を測定した。Pulse resistance characteristics (intermittent overload test): 2 of 115 constant voltage
.. Apply 5 times the voltage (maximum 400V) for 1 second,
The rate of change in resistance value (%) was measured after repeating 10,000 cycles of applying the voltage for 1 second at intervals of seconds.
耐電圧特性(短時間過負荷試験): 115定格電圧の
2.5倍の電圧(但し最大400V)を5秒印加した後
の抵抗飴変化率(%)を調べた。Withstanding voltage characteristics (short-time overload test): The rate of change in resistance (%) after applying a voltage 2.5 times the 115 rated voltage (maximum 400 V) for 5 seconds was examined.
耐熱性:150℃の温度に1000時間放首し、抵抗値
変化率(%)を調べた。Heat resistance: The product was exposed to a temperature of 150° C. for 1000 hours, and the rate of change in resistance value (%) was examined.
耐湿負荷寿命特性:95%RH165°Cの高湿雰囲気
中、115定格電圧の2.5倍の電圧(但し最大200
V)を90分印加し、30分間隔をあけて又90分印加
する操作を1000時間の間繰返した後、抵抗値変化率
(%)を調べた。Humidity load life characteristics: 95% RH In a high humidity atmosphere of 165°C, a voltage 2.5 times the rated voltage of 115 (however, a maximum of 200
After repeating the operation of applying V) for 90 minutes and then applying it again for 90 minutes at 30-minute intervals for 1000 hours, the rate of change in resistance value (%) was examined.
(以下余白)
表2
(表中「部」はすべて11部を表わす。)表2から、銅
酸化物のみを添加した抵抗体はTCPは改善されるもの
の、他の電気特性が極めて悪くなっているのに対し、本
発明では優れた安定性を有していることが明らかである
。(Left below) Table 2 (All "parts" in the table represent 11 parts.) From Table 2, it can be seen that although the TCP was improved in the resistor to which only copper oxide was added, other electrical properties were extremely poor. In contrast, it is clear that the present invention has excellent stability.
効果
以上の通り、本発明の厚膜抵抗体はTCP調整剤として
ランタン酸化物等の酸化物と銅酸化物を(71用するこ
とにより中抵抗域から高抵抗域において大幅にT C+
1が改善される。即ち温度による抵抗変化率を極めて小
さい値に維持し得るものである。しかもノイズも小さく
、安定な電気特性を有しており、又レーデ1〜リミング
性も良好であって実用上極めて優れたものである。Effects As described above, the thick film resistor of the present invention significantly improves T C+ in the medium to high resistance range by using oxides such as lanthanum oxide and copper oxide (71) as TCP regulators.
1 is improved. That is, the rate of change in resistance due to temperature can be maintained at an extremely small value. In addition, it has low noise, stable electrical characteristics, and good Lede 1 to rimming properties, making it extremely excellent in practical use.
特に本発明は、酸化ルテニウムとガラスの中吊比が35
:65〜5:95、抵抗値にしておよそ10にΩ/口〜
10MΩ/口の抵抗体を製3m する場合に極めて有効
である。In particular, in the present invention, the hollow ratio of ruthenium oxide and glass is 35.
:65~5:95, resistance value is approximately 10Ω/mouth~
It is extremely effective when manufacturing a 3 m long resistor with a resistance of 10 MΩ/hole.
尚、実施例ではランタン酸化物と銅酸化物の組合ぜのみ
を扱ったが、ランタン以外の酸化物、即ちネオジム酸化
物、ブラセAジム酸化物、サマリウム酸化物又はそれら
の組合Uでも同様の効果を秦する。又酸化物成分を粉末
の形で添加するのではなく、ガラス中に含有させた形ぐ
添加しても結果は全く同様であった。In addition, although only the combination of lanthanum oxide and copper oxide was used in the examples, similar effects can be obtained with oxides other than lanthanum, such as neodymium oxide, braze A-dim oxide, samarium oxide, or their combination U. to Qin. Furthermore, the results were exactly the same even when the oxide component was added in the form of inclusion in the glass instead of in the form of a powder.
Claims (1)
酸化物及びサマリウム酸化物からなる群より選ばれる1
種又は2種以上の酸化物と、 (d)銅酸化物と、 (c)有機ビヒクル とからなる抵抗塗料。 2 絶縁基板上に、 (a)酸化ルテニウムと、 (b)ガラスと、 (c)ランタン酸化物、ネオジム酸化物、プラセオジム
酸化物及びサマリウム酸化物からなる群より選ばれる1
種又は2種以上の酸化物と、 (d)銅酸化物 とからなる抵抗被膜を形成してなる厚膜抵抗体。[Scope of Claims] 1 (a) ruthenium oxide; (b) glass; (c) 1 selected from the group consisting of lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide.
A resistive paint comprising: a species or two or more oxides; (d) a copper oxide; and (c) an organic vehicle. 2 On an insulating substrate, (a) ruthenium oxide, (b) glass, and (c) 1 selected from the group consisting of lanthanum oxide, neodymium oxide, praseodymium oxide, and samarium oxide.
A thick film resistor comprising a resistive film formed of a copper oxide or a copper oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60265250A JPS62124164A (en) | 1985-11-26 | 1985-11-26 | Resistance coating compound and resistance element formed from same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60265250A JPS62124164A (en) | 1985-11-26 | 1985-11-26 | Resistance coating compound and resistance element formed from same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62124164A true JPS62124164A (en) | 1987-06-05 |
JPH0212990B2 JPH0212990B2 (en) | 1990-04-03 |
Family
ID=17414615
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60265250A Granted JPS62124164A (en) | 1985-11-26 | 1985-11-26 | Resistance coating compound and resistance element formed from same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62124164A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5533786A (en) * | 1978-06-29 | 1980-03-10 | Price Edison A | Ceiling embedded luminaire |
JPS58117264A (en) * | 1981-12-29 | 1983-07-12 | Shoei Kagaku Kogyo Kk | Resistance paint and resistor formed therefrom |
-
1985
- 1985-11-26 JP JP60265250A patent/JPS62124164A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5533786A (en) * | 1978-06-29 | 1980-03-10 | Price Edison A | Ceiling embedded luminaire |
JPS58117264A (en) * | 1981-12-29 | 1983-07-12 | Shoei Kagaku Kogyo Kk | Resistance paint and resistor formed therefrom |
Also Published As
Publication number | Publication date |
---|---|
JPH0212990B2 (en) | 1990-04-03 |
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