JP3755847B2 - Thick film resistor paste - Google Patents
Thick film resistor paste Download PDFInfo
- Publication number
- JP3755847B2 JP3755847B2 JP14738597A JP14738597A JP3755847B2 JP 3755847 B2 JP3755847 B2 JP 3755847B2 JP 14738597 A JP14738597 A JP 14738597A JP 14738597 A JP14738597 A JP 14738597A JP 3755847 B2 JP3755847 B2 JP 3755847B2
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- paste
- film resistor
- glass frit
- resistor paste
- 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 - Lifetime
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Description
【０００１】
【産業上の分野】
この発明は、厚膜抵抗ペーストに関わり、特にファクシミリやバーコードプリンタ用等の厚膜型サーマルヘッドの発熱抵抗体を形成するに好適な厚膜抵抗ペーストに関する。
【０００２】
【従来の技術】
厚膜抵抗ペーストは、酸化ルテニウムやパイロクロール型ルテニウム複合酸化物等のルテニウム化合物の粉末と、その結合剤としてのガラスフリット、および必要に応じて種々の無機添加物とからなる無機混合粉末を有機ビヒクルに分散させて作成される。この種の厚膜抵抗ペーストは、アルミナやグレーズ基板等のセラミック基板上に印刷され、乾燥、焼成工程を経て厚膜抵抗体として形成される。
【０００３】
従来、厚膜型サーマルヘッドの発熱抵抗体形成用厚膜抵抗ペーストとしては、耐熱性重視の観点から、アルミナやジルコニア等の高耐熱性酸化物を添加すると共に、ガラスフリットとしてもＬａ2Ｏ3−Ｂ2Ｏ3−ＳｉＯ2−ＣａＯ−ＺｎＯ系のガラスを用いた厚膜抵抗ペーストが使用されてきた。
【０００４】
【発明が解決しようとする課題】
しかしながら、上記の例の抵抗ペーストを、印字の高密度化、高速化を図るため、高い印加電力で使用されるバーコードプリンタ用途の抵抗ペーストとして用いた場合、電力印加による抵抗値変化が大きくなるという問題が生じた。
そこでこの発明は、上記の問題点を解決し、従来品以上の耐電力特性を有する発熱抵抗体を形成できる厚膜抵抗ペーストを提供することを目的とする。
【０００５】
【課題を解決するための手段】
この発明の目的は、酸化ルテニウム粉末とガラスフリットとを主たる成分とする無機混合粉末を有機ビヒクルに分散させて成る厚膜抵抗ペーストにおいて、ガラスフリットとして、重量比率でＳｉＯ2を５０〜６０％、ＰｂＯを１５〜２０％、Ａｌ2Ｏ3を７〜１０％、ＣａＯを５〜１０％、Ｂ2Ｏ3を２〜７％、ＢａＯを２〜７％、及びＭｇＯを１〜５％の組成を有するものを用いたことを特徴とする厚膜抵抗ペーストによって達成される。
【０００６】
【発明の実施の形態】
この発明による厚膜抵抗ペーストを製造するに当たり、ルテニウム化合物としては、酸化ルテニウムを用いることが望ましく、ルテニウム化合物粉末及びガラスフリットの粒径は、１μｍ以下であることが望ましい。又、ガラスとしては、ボールミルで充分微粉砕したものを用いる事ができる。
【０００７】
ガラスフリットとして用いるガラス成分をこの発明の様に限定した理由は次の通りである。即ち、ＰｂＯは、１５重量％未満では軟化点が上がり過ぎてしまい、２０重量％を越えると耐熱性が低下する。Ｓｉ2Ｏ3は、ガラスのネットワークフォーマーとして機能するが、５０重量％未満では耐熱性が低下し、６０重量％を越えて配合すると軟化点が上昇し過ぎてしまう。Ａｌ2Ｏ3、ＣａＯ、Ｂ2Ｏ3、ＢａＯ、ＭｇＯはいずれも失透傾向を低下させ、耐熱性を向上させる働きがあり、上述の配合量の下限値未満ではこの効果が出にくく、上限値を超えて配合すると軟化点が上がってしまう。
又、有機ビヒクルとしては、エチルセルロースを有機溶剤に溶解したものを用いることが良好な印刷特性を得る上から求められる。有機溶剤は、エチルセルロース等の樹脂を溶解出来るものであれば良く、カルビトールアセテート、パインオイル、ターピネオール等が好ましく用いられる。溶剤の配合量は、抵抗ペーストの印刷特性にあわせて増減すれば良い。
【０００８】
【実施例】
ガラスフリットとしては、重量比率で、ＳｉＯ2を５５％、ＰｂＯを１７％、Ａｌ2Ｏ3を８．５％、ＣａＯを７．５％、Ｂ2Ｏ3を５．０％、ＢａＯを４．５％、及びＭｇＯを２．５％と成るように原料成分を混合し、１３００℃で溶解し、冷却後ボールミルを用いて平均粒径２μｍ以下に粉砕したものを用いた。
こうして得られたガラスフリット６１重量部を導電成分である平均粒径０．８μｍの二酸化ルテニウム粉末２２重量部及び高耐熱性酸化物としての平均粒径１μｍ以下の酸化ジルコニウム粉末１７重量部と共に、有機ビヒクル中に分散させて三本ロールミルを用いて混練してペースト化した。ここで、有機ビヒクルとしては、エチルセルロースをターピネオールに溶解した物を用いた。
ここで得た厚膜抵抗ペーストを２５０メッシュ、エマルジョン厚２０μｍのステンレススクリーンを用いて、あらかじめ金電極を形成したグレーズ基板（日本特殊陶業社製、品番ＧＳ３１）上に印刷し、オーブンで１２０℃１０分間乾燥後、コンベア式電気炉に入れて８００℃で焼成（ピーク時間１０分、入り口〜出口１時間）し、長さ２００μｍ、幅６２．５μｍの抵抗体素子が複数並んだ抵抗アレイを形成し、以下の評価を行った。
先ず、焼成膜厚を測定すると、６μｍ、素子１個当たりの抵抗値（ドット抵抗値）を測定すると９０６Ωであった。その後ステップストレステスト（ＳｔｅｐＳｔｒｅｓｓ Ｔｅｓｔ）を行った。この評価に当たっては、印加電力１ワットからスタートし、０．５ワットずつ上げていき、抵抗値が一旦マイナスヘシフトした後、再び上昇しプラスに転じた時の抵抗値変化率（最大ドリフト）及び更に電力印加を続けていき抵抗値がプラス１％に変化した時のワッテージ（破壊点）を測定すると、それぞれ、−１７．５％、１．６５ワットであった。
【０００９】
【比較例】
ガラスフリットとして、Ｌａ2Ｏ3を４０％、Ｂ2Ｏ3を３０％残部をＳｉＯ2−ＣａＯ−ＺｎＯ系からなるものを用い、実施例と同様にして抵抗ペーストを得て、評価してみると、ドット抵抗値は９２０Ω、ワッテージは１．３５ワット、最大ドリフトは−２０．５％、膜厚は６μｍであった。これらの結果と実施例の結果とをまとめると表１の様になる。
【００１０】
【表１】
この表からわかる通り、この発明によれば、ワッテージは約２２％、最大ドリフトは約１５％向上した。
【００１２】
【発明の効果】
以上述べた通り、この発明の厚膜抵抗ペーストは、ガラスフリットの組成を特定化することにより、絶縁基板上へ印刷して耐電力性に優れた発熱抵抗体を形成することが可能となり、高速かつ高密度印字可能なサーマルヘッドの作成に有益な材料を提供するものである。[0001]
[Industrial field]
The present invention relates to a thick film resistance paste, and more particularly to a thick film resistance paste suitable for forming a heating resistor of a thick film type thermal head for a facsimile or barcode printer.
[0002]
[Prior art]
Thick film resistor paste is an organic mixed powder consisting of ruthenium oxide powder such as ruthenium oxide and pyrochlore-type ruthenium composite oxide, glass frit as its binder, and various inorganic additives as required. Created in a distributed vehicle. This type of thick film resistor paste is printed on a ceramic substrate such as an alumina or glaze substrate, and is formed as a thick film resistor through a drying and firing process.
[0003]
Conventionally, as a thick film resistor paste for forming a heating resistor of a thick film type thermal head, from the viewpoint of emphasizing heat resistance, a high heat resistant oxide such as alumina or zirconia is added, and La 2 O 3 is also used as a glass frit. -B 2 O 3 -SiO 2 -CaO- ZnO -based glass thick film resistor paste using the have been used.
[0004]
[Problems to be solved by the invention]
However, when the resistance paste of the above example is used as a resistance paste for barcode printers that are used with high applied power in order to increase the density and speed of printing, the resistance value change due to power application increases. The problem that occurred.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a thick film resistance paste that can solve the above-described problems and can form a heating resistor having a power durability characteristic higher than that of conventional products.
[0005]
[Means for Solving the Problems]
The purpose of the present invention is a ruthenium oxide powder and a glass frit comprising the inorganic powder mixture dispersed in an organic vehicle as main components thick-film resistor paste, the glass frit, the SiO 2 by weight ratio 50% to 60%, PbO 15-20% of Al 2 O 3 7~10%, 5~10 % of CaO, B 2 O 3 2-7% 2-7% the BaO, and composition of 1-5% of MgO It is achieved by a thick film resistance paste characterized by using a material having the following.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In producing the thick film resistor paste according to the present invention, it is desirable to use ruthenium oxide as the ruthenium compound, and the particle diameters of the ruthenium compound powder and the glass frit are desirably 1 μm or less. Further, as the glass, a glass finely pulverized with a ball mill can be used.
[0007]
The reason why the glass components used as the glass frit are limited as in the present invention is as follows. That is, when PbO is less than 15% by weight, the softening point is excessively increased, and when it exceeds 20% by weight, the heat resistance is lowered. Si 2 O 3 functions as a glass network former, but if it is less than 50% by weight, the heat resistance is lowered, and if it exceeds 60% by weight, the softening point is too high. Al 2 O 3 , CaO, B 2 O 3 , BaO and MgO all have a function of reducing the devitrification tendency and improving the heat resistance. If it exceeds this value, the softening point will increase.
Further, as an organic vehicle, use of a solution obtained by dissolving ethyl cellulose in an organic solvent is required for obtaining good printing characteristics. The organic solvent is not particularly limited as long as it can dissolve a resin such as ethyl cellulose, and carbitol acetate, pine oil, terpineol and the like are preferably used. The blending amount of the solvent may be increased or decreased in accordance with the printing characteristics of the resistance paste.
[0008]
【Example】
The glass frit is composed of 55% SiO 2 , 17% PbO, 8.5% Al 2 O 3 , 7.5% CaO, 5.0% B 2 O 3 , and 4% BaO by weight ratio. The raw material components were mixed so as to be 0.5% and MgO to 2.5%, dissolved at 1300 ° C., cooled, and pulverized to an average particle size of 2 μm or less using a ball mill.
61 parts by weight of the glass frit thus obtained was combined with 22 parts by weight of ruthenium dioxide powder having an average particle diameter of 0.8 μm as a conductive component and 17 parts by weight of zirconium oxide powder having an average particle diameter of 1 μm or less as a high heat-resistant oxide. It was dispersed in a vehicle and kneaded using a three-roll mill to form a paste. Here, the organic vehicle used was a solution in which ethylcellulose was dissolved in terpineol.
The thick film resistance paste obtained here was printed on a glaze substrate (product number GS31, manufactured by Nippon Special Ceramics Co., Ltd.) on which a gold electrode was formed in advance using a 250 mesh stainless steel screen having an emulsion thickness of 20 μm. After drying for a minute, place in a conveyor-type electric furnace and fire at 800 ° C. (peak time 10 minutes, entrance to exit 1 hour) to form a resistor array with a plurality of resistor elements 200 μm long and 62.5 μm wide The following evaluation was performed.
First, the fired film thickness was measured to be 6 μm, and the resistance value per element (dot resistance value) was measured to be 906Ω. Thereafter, a step stress test was performed. In this evaluation, start with an applied power of 1 watt, increase it by 0.5 watts, once the resistance value has shifted to minus, then rise again and turn to plus, and the resistance value change rate (maximum drift) and further When the wattage (destruction point) when the resistance value was changed to plus 1% while continuing the power application was measured, they were -17.5% and 1.65 watts, respectively.
[0009]
[Comparative example]
Using glass frit made of 40% La 2 O 3 and 30% B 2 O 3 with the balance made of SiO 2 —CaO—ZnO, a resistance paste was obtained in the same manner as in the examples and evaluated. The dot resistance value was 920Ω, the wattage was 1.35 watts, the maximum drift was −20.5%, and the film thickness was 6 μm. Table 1 summarizes these results and the results of the examples.
[0010]
[Table 1]
As can be seen from this table, according to the present invention, the wattage is improved by about 22% and the maximum drift is improved by about 15%.
[0012]
【The invention's effect】
As described above, the thick film resistor paste of the present invention can be printed on an insulating substrate by specifying the composition of the glass frit to form a heating resistor having excellent power resistance, and high speed. In addition, the present invention provides a material useful for producing a thermal head capable of high-density printing.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14738597A JP3755847B2 (en) | 1997-06-05 | 1997-06-05 | Thick film resistor paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14738597A JP3755847B2 (en) | 1997-06-05 | 1997-06-05 | Thick film resistor paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10335108A JPH10335108A (en) | 1998-12-18 |
| JP3755847B2 true JP3755847B2 (en) | 2006-03-15 |
Family
ID=15429068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14738597A Expired - Lifetime JP3755847B2 (en) | 1997-06-05 | 1997-06-05 | Thick film resistor paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3755847B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1339258A4 (en) * | 2000-12-01 | 2005-07-20 | Ibiden Co Ltd | Ceramic heater, and ceramic heater resistor paste |
| JP5662361B2 (en) * | 2012-02-09 | 2015-01-28 | 京都エレックス株式会社 | Resistor paste for ceramic substrate heater and ceramic substrate heater |
-
1997
- 1997-06-05 JP JP14738597A patent/JP3755847B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10335108A (en) | 1998-12-18 |
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