JP3843767B2 - Method for manufacturing resistor paste and method for manufacturing thick film resistor - Google Patents
Method for manufacturing resistor paste and method for manufacturing thick film resistor Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、抵抗体ペーストの製造方法及び厚膜抵抗体の製造方法に関する。
【０００２】
【従来の技術】
抵抗体ペーストは、一般に、抵抗値を調整するため及び結合性を与えるためのガラス材料と、導電性材料と、ビヒクルとから主として構成されており、これを基板上に印刷した後、焼成することによって厚膜抵抗体が形成される。
【０００３】
従来より、多くの抵抗体ペーストは、ガラス材料として酸化鉛系のガラスを、導電性材料として酸化ルテニウム又はこの酸化ルテニウム及び鉛の化合物をそれぞれ用いており、従って鉛を含有したペーストとなっている。
【０００４】
こにように鉛を含有した抵抗体ペーストを使用することは、環境汚染の観点から望ましくないため、鉛フリーの厚膜抵抗体ペーストについて研究がなされており、提案がなされている（特開平８−２４３３４２号公報）。
【０００５】
【発明が解決しようとする課題】
しかしながら、このように導電性材料及びガラス材料を鉛フリーで構成した抵抗体ペーストは、シート抵抗値として１ＭΩ／□以上となる高抵抗値を有するものを製造し難いという問題を有している。このため、導電性材料とガラス材料との混合比を調整する、及び／又は金属酸化物等の添加物を多種、かつ多量に添加して抵抗値の増加を図ることが行われるが、充分に満足できる値まで抵抗値を上げることは難しかった。また、一般的に用いられている金属酸化物添加剤は、多種、多量に調整剤を用いるので均一に混合することが難しく、その結果、製造が困難であり、また、製品によって特性にばらつきの生じる可能性があった。
【０００６】
従って本発明の目的は、多種、多量の金属酸化物を添加しなくとも極めて高い抵抗値が得られる、鉛フリーの抵抗体ペーストの製造方法及び厚膜抵抗体の製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明によれば、ガラス組成物に、導電性を与えるための金属元素を含む第１の導電性材料をあらかじめ溶解させてガラス材料を得る工程と、ガラス材料と、上述の金属元素を含む第２の導電性材料と、ビヒクルとを混練する工程とを備えており、ガラス組成物及び第１及び第２の導電性材料は鉛を含まない抵抗体ペーストの製造方法、及びガラス組成物の一部分量に、導電性を与えるための金属元素を含む第１の導電性材料をあらかじめ溶解させてガラス材料を得る工程と、ガラス材料と、ガラス組成物の残りの分量と、上述の金属元素を含む第２の導電性材料と、ビヒクルとを混練する工程とを備えており、ガラス組成物及び第１及び第２の導電性材料は鉛を含まない抵抗体ペーストの製造方法、並びにこれらの方法によって製造した抵抗体ペーストを所望の形状にパターニングし、焼き付ける厚膜抵抗体の製造方法が提供される。
【０００８】
鉛フリーのガラス組成物及び導電性材料を用いる場合であっても、導電性を与えるための金属元素を含む導電性材料をガラス組成物にあらかじめ溶解してガラス材料を形成することによって、導電性材料の分散状態が変わり劇的に高い抵抗値を得ることができる。即ち、導電性を与えるための金属元素を含む導電性材料をあらかじめガラス中に入れてその金属元素を飽和させておくことにより、後の工程において同じ金属元素を含む導電性材料を混練してもその金属元素を含む化合物がガラス中に析出しないことから極めて高い抵抗値が得られるのである。このように、金属酸化剤を多種多量の添加しなくても充分に高い抵抗値を得ることができるので、製造が容易となりかつ製品毎に電気的特性がばらついて不安定となるような不都合が生じない。
【０００９】
あらかじめ溶解される第１の導電性材料の分量が、ガラス材料中にこの金属元素を含む化合物が析出する限界量以下の量であることが望ましい。
【００１０】
第１の導電性材料及び第２の導電性材料が、導電性を与えるための金属元素を共通に含む互いに異なる組成物であるか、又は同一の組成物であることも好ましい。
【００１１】
ガラス組成物が、Ｂ２Ｏ３及びＳｉＯ２の１種以上を主成分とするガラス組成物であることが好ましい。
【００１２】
ガラス組成物が、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、酸化リチウム、酸化ナトリウム、酸化カリウム、酸化リン、酸化銅、酸化バナジウム、酸化亜鉛、酸化マンガン及び酸化ビスマスの１種以上を含有していることも好ましい。
【００１３】
第１又は第２の導電性材料が、ＲｕＯ２又はＲｕの複合酸化物であることが好ましい。この場合、Ｒｕの複合酸化物が、ＣａＲｕＯ３、ＳｒＲｕＯ３、ＢａＲｕＯ３又はＢｉ２Ｒｕ２Ｏ７であってもよい。
【００１４】
第１又は第２の導電性材料が、Ｐｄ−Ａｇ合金、ＴａＮ、Ｔａ２Ｎ、ＬａＢ６、ＷＣ、ＭｏＳｉ２、ＴａＳｉ２、ＳｎＯ２又はＴａ２Ｏ５であることも好ましい。
【００１５】
【発明の実施の形態】
本発明の一実施形態においては、抵抗体ペーストは、鉛を含まないガラスフリットによるガラス組成物と、鉛を含まない導電粒子による導電性材料と、これらを媒体中に分散させるビヒクルとから生成される。
【００１６】
ガラスフリットは、鉛フリーであれば特にその組成に制限はないが、Ｂ２Ｏ３及びＳｉＯ２の１種以上を主成分とするガラスであることが好ましい。
【００１７】
このガラスは、珪酸ガラス、硼珪酸ガラス、珪酸カルシウムガラス、硼酸カルシウムガラス、硼珪酸カルシウムガラス、珪酸ストロンチウムガラス、硼酸ストロンチウムガラス、硼珪酸ストロンチウムガラス、珪酸バリウムガラス、硼酸バリウムガラス、硼珪酸バリウムガラス、珪酸マグネシウムガラス、硼酸マグネシウムガラス、硼珪酸マグネシウムガラス、珪酸リチウムガラス、硼酸リチウムガラス、硼珪酸リチウムガラス、珪酸ナトリウムガラス、硼酸ナトリウムガラス、硼珪酸ナトリウムガラス、珪酸カリウムガラス、硼酸カリウムガラス、硼珪酸カリウムガラス、珪酸リンガラス、硼酸リンガラス、硼珪酸リンガラス、珪酸銅ガラス、硼酸銅ガラス、硼珪酸銅ガラス、珪酸バナジウムガラス、硼酸バナジウムガラス、硼珪酸バナジウムガラス、珪酸亜鉛ガラス、硼酸亜鉛ガラス、硼珪酸亜鉛ガラス、珪酸マンガンガラス、硼酸マンガンガラス、硼珪酸マンガンガラス、珪酸ビスマスガラス、硼酸ビスマスガラス又は硼珪酸ビスマスガラスである。また、これらガラスを混合して使用しても良い。
【００１８】
この組成のガラスフリットは、焼成前は非晶質であり、焼成によって結晶化しても良い。
【００１９】
このガラスフリットの平均粒径は、特に制限はないが、スクリーン印刷性を考慮すれば、約５μｍ以下が好ましい。
【００２０】
導電粒子は、導電性を与えるための金属元素を含みかつ鉛フリーであれば特にその組成に制限はない。例えば、ＲｕＯ２、ＣａＲｕＯ３、ＳｒＲｕＯ３、ＢａＲｕＯ３、Ｂｉ２Ｒｕ２Ｏ７、Ｐｄ−Ａｇ合金、ＴａＮ、Ｔａ２Ｎ、ＬａＢ６、ＷＣ、ＭｏＳｉ２、ＴａＳｉ２、ＳｎＯ２又はＴａ２Ｏ５や他の導電性化合物、若しくは各種合金を用いることができる。特に、ＲｕＯ２及びＲｕの複合酸化物の１種以上を主成分とするものが好ましい。
【００２１】
導電粒子の平均粒径は、０．０５〜１．０μｍ程度であることがペースト中での粒子の分散を良好にして抵抗体ペーストの流動性を良好にする点及びノイズ特性の点で望ましい。
【００２２】
ビヒクルとしては、エチルセルロース、ポリビニルブチラール、メタクリル樹脂、ブチルメタアクリレート等のバインダと、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート、アセテート、トルエン、アルコール、キシレン等の溶剤とが用いられるが、その他各種の分散剤、活性剤、可塑剤等が用途に応じて適宜選択される。
【００２３】
また、必要に応じて遷移金属群の元素からなる酸化物、典型金属群の元素からなる酸化物等の各種金属酸化物をＴＣＲ調整剤又はその他の目的で添加しても良い。
【００２４】
抵抗体ペーストは、導電性を与えるための金属元素を含む前述のごとき組成の導電粒子、即ち第１の導電性材料粉末を作成し、その第１の導電性材料粉末を前述のごとき組成のガラス粉末に混合して溶解し、再びガラス化してガラス粉末とし、このガラス粉末と、同じ金属元素を含む第２の導電性材料粉末とビヒクルとを混合及び混練して得られる。ガラス中に溶解させる第１の導電性材料粉末の分量は、この導電性を与えるための金属元素が飽和するだけの分量とし、ガラス材料としてできあがった時点で析出するほど多くは入れない。第１及び第２の導電性材料粉末の総分量は、ガラス材料の分量と共に所定の組成となるように調整される。
【００２５】
第１の導電性材料及び第２の導電性材料が、同一の導電性材料であっても良いが、導電性を与えるための金属元素を共通に含む互いに異なる導電性材料であっても良い。
【００２６】
第１の導電性材料粉末を溶解させたガラス粉末と溶解させてないガラス粉末を混合したガラス粉末と第２の導電性材料粉末とビヒクルとを混合及び混練して抵抗体ペーストを作成しても良い。また、ガラス中に溶解させる第１の導電性材料粉末は、上述したように既存のガラス粉末に加えて溶解させても良いが、ガラス粉末を作成時にＢ２Ｏ３、ＳｉＯ２等の酸化物を混合する際に加えて溶解させても良い。
【００２７】
基板上に厚膜抵抗体を形成するには、その基板上に抵抗体ペーストをスクリーン印刷し、８５０℃程度の温度で焼成すれば良い。基板は、アルミナ基板、ＡｌＮ基板、その他の単層基板、複合基板であっても良いし、多層基板であっても良い。厚膜抵抗体は、多層基板の外部のみならず内部に形成しても良い。
【００２８】
このように、導電性を与えるための金属元素を含む第１の導電性材料粉末をガラス粉末に混合して溶解し、再びガラス化したものと、同じ金属元素を含む第２の導電性材料粉末と、ビヒクルとを混練して得ているため、鉛フリーの抵抗体ペーストであっても、抵抗値が劇的に高くなる。このように、金属酸化剤を添加しなくとも充分高い抵抗値を得ることができるので、製造が容易でありかつ電気的特性に製品毎のばらつきがなくなり安定する。
【００２９】
【実施例】
以下具体的な実施例により本発明をより詳細に説明する。
【００３０】
第１の導電性材料を溶解させたガラス材料と第１の導電性材料を溶解させてないガラス材料とをそれぞれ用いて抵抗体ペースト試料をそれぞれ作成し、これらをアルミナ基板上に焼き付けて厚膜抵抗体を作成してシート抵抗値を測定した。
【００３１】
ガラス組成物としては硼珪酸亜鉛ガラスを使用し、第１の導電性材料としては導電性を与えるための金属元素Ｒｕを含むＲｕＯ２を、第２の導電性材料としては同じく導電性を与えるための金属元素Ｒｕを含むＣａＲｕＯ３又はＳｒＲｕＯ３をそれぞれ用いた。
【００３２】
第２の導電性材料の作成
ＣａＲｕＯ３となるように所定量のＣａＣＯ３粉末又はＣａ（ＯＨ）２粉末とＲｕＯ２粉末とを秤量し、ボールミルで混合して乾燥した。この混合によって得られた粉末を、５℃／ｍｉｎの速度で１２００℃まで昇温しその温度を５時間保持した後に５℃／ｍｉｎの速度で室温（２５℃）まで冷却することによって、ＣａＲｕＯ３化合物の粉末を得た。ＳｒＲｕＯ３についても同様な方法で、ＳｒＲｕＯ３化合物の粉末を得た。
【００３３】
ガラス組成物の作成
ＺｎＯ、Ｂ２Ｏ３、ＳｉＯ２の粉末を所定量秤量し、ボールミルで混合して乾燥した。この混合によって得られた粉末を、５℃／ｍｉｎの速度で１２００℃まで昇温しその温度を１時間保持した後に水中投下することによって急冷し、ガラス化した。得られたガラス化物をボールミルで粉砕し、ガラス粉末を得た。
【００３４】
第１の導電性材料を溶解したガラス材料の作成
上述のごとく形成したガラス組成物とＲｕＯ２とを所定量秤量し、ボールミルで混合して乾燥した。得られた粉末を、５℃／ｍｉｎの速度で１４００℃まで昇温しその温度を１時間保持した後に水中投下することによって急冷し、ガラス化した。得られたガラス化物をボールミルで粉砕し、ガラス粉末を得た。
【００３５】
抵抗体ペーストの作成
上述のごとく作成したＣａＲｕＯ３又はＳｒＲｕＯ３化合物の粉末と、第１の導電性材料を溶解したガラス粉末と、樹脂がエチルセルロース、溶剤がターピネオールでなる有機ビヒクルとを各組成となるように秤量し、３本ロールミルで混練することにより、抵抗体ペーストを得た。
【００３６】
厚膜抵抗体の作成及び抵抗値測定
９６％純度のアルミナ基板上に、Ａｇ−Ｐｄ導体ペーストを所定形状にスクリーン印刷して乾燥させた。Ａｇ−Ｐｄ導体ペーストにおけるＡｇは８５重量％、Ｐｄは１５重量％であった。このアルミナ基板を、ベルト炉に入れ、投入から排出まで１時間のパターンで焼き付けした。焼き付け温度は８５０℃、その温度の保持時間は１０分とした。
【００３７】
このようにして導体が形成されたアルミナ基板上に前述のごとく作成した抵抗体ペーストを所定形状にスクリーン印刷して乾燥させた。次いで、導体焼付けと同じ条件で抵抗体ペーストを焼き付け、厚膜抵抗体を得た。
【００３８】
この厚膜抵抗体の抵抗値を測定した。その測定結果を表１に示す。なお、表１の各試料における試料数は２４である。
【００３９】
【表１】
表1において、試料１〜６は第２の導電性材料としてＣａＲｕＯ３を用いた場合、試料７〜９は第２の導電性材料としてＳｒＲｕＯ３を用いた場合であり、試料１〜４、７及び８はガラス材料中に第１の導電性材料をあらかじめ溶解しない従来の製造方法によるもの、試料５、６及び９はガラス材料中に第１の導電性材料をあらかじめ溶解した本発明の製造方法によるものである。
【００４１】
第２の導電性材料としてＣａＲｕＯ３を用いた場合、従来技術の試料１〜４に比して、本発明による試料５及び６は３１〜５２ＭΩという劇的に高い抵抗値を有している。しかも、抵抗値のばらつきを表すＣＶ値（標準偏差／平均値）が１９〜２１と従来技術による試料の１／３と非常に小さい。なお、試料３は本発明のものより抵抗値が１桁低く、しかもばらつきが非常に大きい。
【００４２】
第２の導電性材料としてＳｒＲｕＯ３を用いた場合、従来技術の試料７に比して、本発明による試料９は３０ＭΩという劇的に高い抵抗値を有している。しかも、抵抗値のばらつきを表すＣＶ値（標準偏差／平均値）が２５と小さい。なお、試料８は金属酸化物を多量に入れることによりかなり高い抵抗値を示しているが、ばらつきが極めて大きい。
【００４３】
このように、鉛フリーの抵抗体ペーストであっても、導電性を与えるための金属元素を含む第１の導電性材料をガラス組成物にあらかじめ溶解してガラス材料を形成することによって、第１及び第２の導電性材料とガラス材料との比率を調整しなくても、また、金属酸化物等の添加物を多種、かつ多量に添加しなくても、特性のばらつきを抑えつつ極めて高い抵抗値を得られることが分かった。
【００４４】
以上述べた実施形態及び実施例は全て本発明を例示的に示すものであって限定的に示すものではなく、本発明は他の種々の変形態様及び変更態様で実施することができる。従って本発明の範囲は特許請求の範囲及びその均等範囲によってのみ規定されるものである。
【００４５】
【発明の効果】
以上詳細に説明したように本発明によれば、鉛フリーのガラス組成物及び導電性材料を用いる場合であっても、導電性を与えるための金属元素を含む導電性材料をガラス組成物にあらかじめ溶解してガラス材料を形成することによって、導電性材料の分散状態が変わり劇的に高い抵抗値を得ることができる。即ち、導電性を与えるための金属元素を含む導電性材料をあらかじめガラス中に入れてその金属元素を飽和させておくことにより、後の工程において同じ金属元素を含む導電性材料を混練してもその金属元素を含む化合物がガラス中に析出しないことから極めて高い抵抗値が得られるのである。このように、金属酸化剤を多種多量の添加しなくても充分に高い抵抗値を得ることができるので、製造が容易となりかつ製品毎に電気的特性がばらついて不安定となるような不都合が生じない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing a resistor paste and a method of manufacturing a thick film resistor.
[0002]
[Prior art]
In general, a resistor paste is mainly composed of a glass material for adjusting a resistance value and imparting bondability, a conductive material, and a vehicle, and is printed on a substrate and then fired. Thus, a thick film resistor is formed.
[0003]
Conventionally, many resistor pastes use lead oxide glass as a glass material and ruthenium oxide or a compound of this ruthenium oxide and lead as a conductive material, and thus lead-containing pastes. .
[0004]
Since it is not desirable to use a resistor paste containing lead in this way from the viewpoint of environmental pollution, research has been conducted on a lead-free thick film resistor paste and a proposal has been made (Japanese Patent Laid-Open No. Hei 8). -243342).
[0005]
[Problems to be solved by the invention]
However, the resistor paste made of lead-free conductive material and glass material as described above has a problem that it is difficult to produce a sheet having a high resistance value of 1 MΩ / □ or more as a sheet resistance value. For this reason, the mixing ratio between the conductive material and the glass material is adjusted, and / or various kinds and a large amount of additives such as metal oxides are added to increase the resistance value. It was difficult to raise the resistance value to a satisfactory value. In addition, generally used metal oxide additives are used in a large amount and a large amount, so that it is difficult to mix uniformly. As a result, it is difficult to manufacture, and the characteristics vary depending on the product. Could have occurred.
[0006]
Accordingly, an object of the present invention is to provide a method for producing a lead-free resistor paste and a method for producing a thick film resistor, which can obtain extremely high resistance values without adding various and large amounts of metal oxides. .
[0007]
[Means for Solving the Problems]
According to the present invention, the first conductive material containing a metal element for imparting conductivity to the glass composition is preliminarily dissolved to obtain a glass material, the glass material, and the first metal element containing the metal element described above. And a step of kneading the conductive material and the vehicle, wherein the glass composition and the first and second conductive materials are a lead-free resistor paste manufacturing method, and a part of the glass composition. Including a step of previously dissolving a first conductive material containing a metal element for imparting conductivity to obtain a glass material, a glass material, a remaining amount of the glass composition, and the metal element described above A step of kneading the second conductive material and the vehicle, wherein the glass composition and the first and second conductive materials are a lead-free resistor paste manufacturing method, and by these methods Manufactured The body paste was patterned into a desired shape, the manufacturing method of the thick film resistor to burn is provided.
[0008]
Even when lead-free glass composition and conductive material are used, the conductive material containing the metal element for providing conductivity is dissolved in the glass composition in advance to form the glass material. The dispersion state of the material changes and a dramatically high resistance value can be obtained. That is, even if a conductive material containing the same metal element is kneaded in a later step, a conductive material containing a metal element for imparting conductivity is previously placed in glass and the metal element is saturated. Since the compound containing the metal element does not precipitate in the glass, a very high resistance value can be obtained. In this way, a sufficiently high resistance value can be obtained without adding a large amount of metal oxidizer, so that there is an inconvenience that the manufacturing becomes easy and the electrical characteristics vary from product to product and become unstable. Does not occur.
[0009]
It is desirable that the amount of the first conductive material dissolved in advance is an amount equal to or less than the limit amount in which the compound containing the metal element is precipitated in the glass material.
[0010]
It is also preferable that the first conductive material and the second conductive material are different compositions containing a metal element for imparting conductivity in common or the same composition.
[0011]
Glass composition is preferably a B 2 O 3 and glass compositions based on one or more SiO 2.
[0012]
The glass composition contains one or more of calcium oxide, strontium oxide, barium oxide, magnesium oxide, lithium oxide, sodium oxide, potassium oxide, phosphorus oxide, copper oxide, vanadium oxide, zinc oxide, manganese oxide, and bismuth oxide. It is also preferable.
[0013]
It is preferable that the first or second conductive material is RuO 2 or a composite oxide of Ru. In this case, the composite oxide of Ru may be CaRuO 3 , SrRuO 3 , BaRuO 3, or Bi 2 Ru 2 O 7 .
[0014]
It is also preferable that the first or second conductive material is a Pd—Ag alloy, TaN, Ta 2 N, LaB 6 , WC, MoSi 2 , TaSi 2 , SnO 2 or Ta 2 O 5 .
[0015]
DETAILED DESCRIPTION OF THE INVENTION
In one embodiment of the present invention, the resistor paste is produced from a glass composition with lead-free glass frit, a conductive material with lead-free conductive particles, and a vehicle in which they are dispersed in a medium. The
[0016]
The glass frit is not particularly limited as long as it is lead-free, but it is preferably a glass mainly composed of one or more of B 2 O 3 and SiO 2 .
[0017]
This glass is silicate glass, borosilicate glass, calcium silicate glass, calcium borate glass, calcium borosilicate glass, strontium silicate glass, strontium borate glass, strontium borosilicate glass, barium silicate glass, barium borosilicate glass, barium borosilicate glass, Magnesium silicate glass, magnesium borate glass, magnesium borosilicate glass, lithium silicate glass, lithium borate glass, lithium borosilicate glass, sodium silicate glass, sodium borate glass, sodium borosilicate glass, potassium silicate glass, potassium borate glass, potassium borosilicate Glass, phosphorous silicate glass, phosphorous borate glass, phosphorous borosilicate glass, copper silicate glass, copper borate glass, copper borosilicate glass, vanadium silicate glass, vanadium borate glass, borosilicate vanad Mugarasu a zinc silicate glass, zinc borate glass, borosilicate zinc glass, silicate manganese glass, borate manganese glass, borosilicate manganese glass, silicate bismuth glass, borate bismuth glass or borosilicate bismuth glass. Further, these glasses may be mixed and used.
[0018]
The glass frit having this composition is amorphous before firing and may be crystallized by firing.
[0019]
The average particle size of the glass frit is not particularly limited, but is preferably about 5 μm or less in view of screen printability.
[0020]
The conductive particles are not particularly limited in composition as long as they contain a metal element for imparting conductivity and are lead-free. For example, RuO 2, CaRuO 3, SrRuO 3, BaRuO 3, Bi 2 Ru 2 O 7, Pd-Ag alloy, TaN, Ta 2 N, LaB 6, WC, MoSi 2, TaSi 2, SnO 2 or Ta 2 O 5 And other conductive compounds or various alloys can be used. In particular, those containing at least one of RuO 2 and Ru composite oxide as a main component are preferable.
[0021]
The average particle diameter of the conductive particles is preferably about 0.05 to 1.0 μm from the viewpoint of good dispersion of the particles in the paste to improve the fluidity of the resistor paste and noise characteristics.
[0022]
As the vehicle, binders such as ethyl cellulose, polyvinyl butyral, methacrylic resin, butyl methacrylate, and solvents such as terpineol, butyl carbitol, butyl carbitol acetate, acetate, toluene, alcohol, xylene are used. A dispersant, an activator, a plasticizer, and the like are appropriately selected depending on the application.
[0023]
In addition, various metal oxides such as an oxide composed of an element of a transition metal group and an oxide composed of an element of a typical metal group may be added for a TCR adjuster or other purposes as necessary.
[0024]
The resistor paste is made of conductive particles having a composition as described above containing a metal element for imparting conductivity, that is, a first conductive material powder, and the first conductive material powder is made of glass having a composition as described above. It is obtained by mixing and dissolving in powder, vitrifying again to obtain glass powder, and mixing and kneading this glass powder, a second conductive material powder containing the same metal element, and a vehicle. The amount of the first conductive material powder to be dissolved in the glass is such an amount that the metal element for imparting conductivity is saturated, and not so much as to precipitate when the glass material is formed. The total amount of the first and second conductive material powders is adjusted so as to have a predetermined composition together with the amount of the glass material.
[0025]
The first conductive material and the second conductive material may be the same conductive material, but may be different conductive materials that commonly include a metal element for imparting conductivity.
[0026]
A resistor paste is prepared by mixing and kneading a glass powder in which a glass powder in which the first conductive material powder is dissolved and a glass powder in which the first conductive material powder is not dissolved is mixed, a second conductive material powder, and a vehicle. good. In addition, the first conductive material powder to be dissolved in the glass may be dissolved in addition to the existing glass powder as described above. However, an oxide such as B 2 O 3 or SiO 2 is used at the time of preparing the glass powder. May be added and dissolved when mixing.
[0027]
In order to form a thick film resistor on a substrate, a resistor paste may be screen printed on the substrate and fired at a temperature of about 850 ° C. The substrate may be an alumina substrate, an AlN substrate, another single layer substrate, a composite substrate, or a multilayer substrate. The thick film resistor may be formed inside as well as outside the multilayer substrate.
[0028]
Thus, the 1st electroconductive material powder containing the metal element for providing electroconductivity is mixed with glass powder, melt | dissolved, and it vitrifies again, and the 2nd electroconductive material powder containing the same metal element And the vehicle is kneaded, the resistance value is dramatically increased even with a lead-free resistor paste. Thus, since a sufficiently high resistance value can be obtained without adding a metal oxidizer, the manufacture is easy and there is no variation in the electrical characteristics between products, and the product is stable.
[0029]
【Example】
Hereinafter, the present invention will be described in more detail with reference to specific examples.
[0030]
Resistor paste samples are respectively prepared using a glass material in which the first conductive material is dissolved and a glass material in which the first conductive material is not dissolved, and these are pasted on an alumina substrate to form a thick film. A resistor was prepared and the sheet resistance value was measured.
[0031]
Zinc borosilicate glass is used as the glass composition, RuO 2 containing a metal element Ru for imparting conductivity is used as the first conductive material, and conductivity is also given as the second conductive material. CaRuO 3 or SrRuO 3 containing the metal element Ru was used.
[0032]
Preparation of Second Conductive Material A predetermined amount of CaCO 3 powder or Ca (OH) 2 powder and RuO 2 powder were weighed so as to be CaRuO 3 , mixed with a ball mill and dried. The powder obtained by this mixing was heated to 1200 ° C. at a rate of 5 ° C./min, maintained at that temperature for 5 hours, and then cooled to room temperature (25 ° C.) at a rate of 5 ° C./min, whereby CaRuO 3 A compound powder was obtained. A SrRuO 3 compound powder was obtained in the same manner for SrRuO 3 .
[0033]
Preparation of Glass Composition A predetermined amount of ZnO, B 2 O 3 and SiO 2 powders were weighed, mixed with a ball mill and dried. The powder obtained by this mixing was heated to 1200 ° C. at a rate of 5 ° C./min, held at that temperature for 1 hour, and then rapidly cooled by dropping into water to be vitrified. The obtained vitrified product was pulverized with a ball mill to obtain glass powder.
[0034]
Preparation of glass material in which first conductive material was dissolved A predetermined amount of the glass composition formed as described above and RuO 2 were weighed, mixed with a ball mill, and dried. The obtained powder was heated to 1400 ° C. at a rate of 5 ° C./min, held at that temperature for 1 hour, and then rapidly cooled by dropping into water to be vitrified. The obtained vitrified product was pulverized with a ball mill to obtain glass powder.
[0035]
Preparation of resistor paste A CaRuO 3 or SrRuO 3 compound powder prepared as described above, a glass powder in which a first conductive material is dissolved, an organic vehicle in which the resin is ethyl cellulose and the solvent is terpineol. A resistor paste was obtained by weighing each composition so as to be kneaded with a three-roll mill.
[0036]
Preparation of Thick Film Resistor and Measurement of Resistance Value An Ag—Pd conductor paste was screen printed in a predetermined shape on an alumina substrate having a purity of 96% and dried. Ag in the Ag-Pd conductor paste was 85% by weight and Pd was 15% by weight. This alumina substrate was placed in a belt furnace and baked in a pattern of 1 hour from charging to discharging. The baking temperature was 850 ° C., and the temperature holding time was 10 minutes.
[0037]
The resistor paste prepared as described above was screen-printed in a predetermined shape and dried on the alumina substrate thus formed with the conductor. Next, the resistor paste was baked under the same conditions as the conductor baking to obtain a thick film resistor.
[0038]
The resistance value of this thick film resistor was measured. The measurement results are shown in Table 1. The number of samples in each sample in Table 1 is 24.
[0039]
[Table 1]
In Table 1, Samples 1 to 6 are cases where CaRuO 3 is used as the second conductive material, Samples 7 to 9 are cases where SrRuO 3 is used as the second conductive material, and Samples 1 to 4, 7 And 8 are based on the conventional manufacturing method in which the first conductive material is not previously dissolved in the glass material, and Samples 5, 6 and 9 are the manufacturing method of the present invention in which the first conductive material is previously dissolved in the glass material. Is due to.
[0041]
When CaRuO 3 is used as the second conductive material, Samples 5 and 6 according to the present invention have dramatically higher resistance values of 31 to 52 MΩ compared to Samples 1 to 4 of the prior art. In addition, the CV value (standard deviation / average value) representing the variation in the resistance value is 19 to 21, which is 1/3 that of the conventional sample. Sample 3 has a resistance value that is an order of magnitude lower than that of the present invention, and the variation is very large.
[0042]
When SrRuO 3 is used as the second conductive material, the sample 9 according to the present invention has a dramatically higher resistance value of 30 MΩ than the sample 7 of the prior art. Moreover, the CV value (standard deviation / average value) representing the variation in resistance value is as small as 25. Sample 8 shows a considerably high resistance value by adding a large amount of metal oxide, but the variation is extremely large.
[0043]
As described above, even in the case of a lead-free resistor paste, the first conductive material containing the metal element for imparting conductivity is dissolved in the glass composition in advance to form the glass material. Even without adjusting the ratio between the second conductive material and the glass material, and without adding various and large amounts of additives such as metal oxides, extremely high resistance while suppressing variation in characteristics. It turns out that the value can be obtained.
[0044]
The above-described embodiments and examples are all illustrative and do not limit the present invention, and the present invention can be implemented in various other modifications and changes. Therefore, the scope of the present invention is defined only by the claims and their equivalents.
[0045]
【The invention's effect】
As described above in detail, according to the present invention, even when a lead-free glass composition and a conductive material are used, a conductive material containing a metal element for imparting conductivity is added to the glass composition in advance. By melting and forming a glass material, the dispersion state of the conductive material changes and a dramatically high resistance value can be obtained. That is, even if a conductive material containing the same metal element is kneaded in a later step, a conductive material containing a metal element for imparting conductivity is previously placed in glass and the metal element is saturated. Since the compound containing the metal element does not precipitate in the glass, a very high resistance value can be obtained. In this way, a sufficiently high resistance value can be obtained without adding a large amount of metal oxidizer, so that there is an inconvenience that the manufacturing becomes easy and the electrical characteristics vary from product to product and become unstable. Does not occur.
Claims (11)
前記ガラス材料と、前記金属元素を含む第２の導電性材料と、ビヒクルとを混練する工程とを備えており、
前記ガラス組成物及び前記第１及び第２の導電性材料は鉛を含まないことを特徴とする抵抗体ペーストの製造方法。A step of preliminarily dissolving a first conductive material containing a metal element for imparting conductivity to the glass composition to obtain a glass material;
A step of kneading the glass material, the second conductive material containing the metal element, and a vehicle;
The method for producing a resistor paste, wherein the glass composition and the first and second conductive materials do not contain lead.
前記ガラス材料と、前記ガラス組成物の残りの分量と、前記金属元素を含む第２の導電性材料と、ビヒクルとを混練する工程とを備えており、
前記ガラス組成物及び前記第１及び第２の導電性材料は鉛を含まないことを特徴とする抵抗体ペーストの製造方法。A step of preliminarily dissolving a first conductive material containing a metal element for imparting conductivity in a part of the glass composition to obtain a glass material;
Kneading the glass material, the remaining amount of the glass composition, the second conductive material containing the metal element, and a vehicle,
The method for producing a resistor paste, wherein the glass composition and the first and second conductive materials do not contain lead.
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| JP2001184792A JP3843767B2 (en) | 2001-06-19 | 2001-06-19 | Method for manufacturing resistor paste and method for manufacturing thick film resistor |
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| JP2001184792A JP3843767B2 (en) | 2001-06-19 | 2001-06-19 | Method for manufacturing resistor paste and method for manufacturing thick film resistor |
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| JP3630144B2 (en) * | 2002-02-28 | 2005-03-16 | 小島化学薬品株式会社 | Resistor |
| EP1480233A4 (en) * | 2002-02-28 | 2009-01-14 | Kojima Chemicals Co Ltd | Resistor |
| JP3579836B2 (en) * | 2002-02-28 | 2004-10-20 | 小島化学薬品株式会社 | Fixed resistor |
| JP5115949B2 (en) * | 2006-12-27 | 2013-01-09 | 国立大学法人 名古屋工業大学 | Conductive material and resistor paste |
| EP2106195B1 (en) * | 2008-03-28 | 2010-05-05 | Braun GmbH | Heating element with temperature sensor |
| KR101166709B1 (en) | 2010-10-27 | 2012-07-19 | (주) 케이엠씨 테크놀러지 | Manufacturing method of paste composite for resistor, thick film resistor and manufacturing method of the resistor |
| JP2018014211A (en) * | 2016-07-20 | 2018-01-25 | 住友金属鉱山株式会社 | Resistance paste and resistive element prepared from the resistance paste |
| JP6931455B2 (en) | 2017-02-17 | 2021-09-08 | 住友金属鉱山株式会社 | A composition for a resistor, a resistor paste containing the same, and a thick film resistor using the same. |
| CN107197544A (en) * | 2017-05-03 | 2017-09-22 | 陶志斌 | Inorganic non-metallic far infrared graphite resistive film, its preparation method and application |
| JP7251068B2 (en) | 2018-07-31 | 2023-04-04 | 住友金属鉱山株式会社 | Composition for thick film resistor, paste for thick film resistor, and thick film resistor |
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