JPH0731931B2 - Thick film paste - Google Patents
Thick film pasteInfo
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- JPH0731931B2 JPH0731931B2 JP61080660A JP8066086A JPH0731931B2 JP H0731931 B2 JPH0731931 B2 JP H0731931B2 JP 61080660 A JP61080660 A JP 61080660A JP 8066086 A JP8066086 A JP 8066086A JP H0731931 B2 JPH0731931 B2 JP H0731931B2
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Description
【発明の詳細な説明】 Ｉ 発明の背景 技術分野 本発明は非酸化物絶縁基板をメタライズする際に用いら
れる厚膜ペーストに関する。Description: BACKGROUND OF THE INVENTION 1. Technical Field The present invention relates to thick film pastes used in metallizing non-oxide insulating substrates.
先行技術とその問題点 パラジウム−銀（Pd−Ag）ペーストは、アルミナ基板の
配線用や、チップコンデンサの外部電極（特公昭41−22
023号等）などに用いられており、従来、以下に示す３
種類に大別できる。Prior art and its problems Palladium-silver (Pd-Ag) paste is used for wiring of alumina substrates and external electrodes of chip capacitors (Japanese Patent Publication No.
No. 023), etc.
It can be roughly divided into types.
Pd−Agにガラスフリットを添加したもの。Glass frit added to Pd-Ag.
Pd−Agに金属酸化物を添加したもの。A metal oxide added to Pd-Ag.
この場合金属酸化物としてはCdO、CuO、V2O5などが用い
られる。In this case, CdO, CuO, V 2 O 5 or the like is used as the metal oxide.
ミックスボンドと称されるもので、上記のとの混
合物であるもの。It is called a mix bond and is a mixture with the above.
ところで、非酸化物系絶縁体、例えば窒化アルミニウム
焼結体は、窒化アルミニウムの熱伝導率がアルミナの10
倍と大きいため熱伝導性が良好で、しかも熱膨張率が小
さいことが知られている。このため、非酸化物系絶縁
体、例えば窒化アルミニウム焼結体を基板として用いる
ことにより上記の特性を生かすことができると考えられ
る。By the way, a non-oxide-based insulator, for example, an aluminum nitride sintered body, has a thermal conductivity of aluminum nitride 10
It is known that the thermal conductivity is good and the coefficient of thermal expansion is small because it is twice as large. Therefore, it is considered that the above characteristics can be utilized by using a non-oxide type insulator, for example, an aluminum nitride sintered body as a substrate.
しかし、非酸化物系絶縁体、例えば窒化アルミニウム焼
結体は金属とは接着しにくいという欠点がある。そして
その接着方法としては前記Pd−Ag等の金属ペーストを塗
布する厚膜法が通常用いられるが、このような基板では
接着強度が十分でないなど問題があり、何らかの改善が
必要である。However, a non-oxide type insulator, for example, an aluminum nitride sintered body has a drawback that it is difficult to adhere to a metal. A thick film method in which a metal paste such as Pd-Ag is applied is usually used as the bonding method, but there is a problem such as insufficient bonding strength with such a substrate, and some improvement is necessary.
II 発明の目的 本発明の目的は、窒化アルミニウム焼結体基板等の非酸
化物系絶縁基板との接着強度の信頼性を高めることがで
き、特に高温中での接着強度の劣化を抑制することが可
能な厚膜ペーストを提供することにある。II Object of the Invention The object of the present invention is to improve the reliability of the adhesive strength with a non-oxide insulating substrate such as an aluminum nitride sintered substrate, and particularly to suppress the deterioration of the adhesive strength at high temperatures. It is to provide a thick film paste capable of
III 発明の開示 このような目的は、下記の本発明によって達成される。III DISCLOSURE OF THE INVENTION Such an object is achieved by the present invention described below.
すなわち、本発明はパラジウムおよび銀を主成分とし、
さらにZnO−B2O3系のガラス成分と金属酸化物とを含有
し、非酸化物系絶縁基板のメタライズ用に用いられる厚
膜ペーストである。That is, the present invention is mainly composed of palladium and silver,
Further, it is a thick film paste containing a ZnO—B 2 O 3 based glass component and a metal oxide and used for metallizing a non-oxide insulating substrate.
IV 発明の具体的構成 以下、本発明の具体的構成について詳細に説明する。IV Specific Structure of the Invention Hereinafter, the specific structure of the present invention will be described in detail.
本発明の厚膜ペーストは、窒化アルミニウム（AlN）焼
結体基板等の非酸化物系絶縁基板上のメタライズに用い
るものである。The thick film paste of the present invention is used for metallization on a non-oxide insulating substrate such as an aluminum nitride (AlN) sintered body substrate.
具体的にはペーストを基板上に印刷し乾燥し焼成するこ
とによってメタライズ化して電極の形成や基板の接合を
行うものである。Specifically, the paste is printed on a substrate, dried and fired to be metallized to form electrodes and join substrates.
本発明の厚膜ペーストは、パラジウムPdおよび銀Agを主
成分とし、これにZnO−B2O3系のガラス成分と金属酸化
物とを含有する。The thick film paste of the present invention contains palladium Pd and silver Ag as main components, and also contains a ZnO—B 2 O 3 based glass component and a metal oxide.
そして、さらには金属酸化物を含有させるのがよい。And it is better to further contain a metal oxide.
この場合、金属水酸化物としては水酸化アルミニウム、
水酸化第二鉄、水酸化マグネシウム、水酸化カルシウ
ム、水酸化アルミニウム・マグネシウム複塩等が挙げら
れ、なかでも水酸化アルミニウムが好ましい。In this case, the metal hydroxide is aluminum hydroxide,
Examples thereof include ferric hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide / magnesium double salt, with aluminum hydroxide being preferred.
このような金属水酸化物、例えば水酸化アルミニウムを
含有したペーストを焼成した場合、最終的にAl2O3とH2O
になると推定されるが、水酸化アルミニウム中の水酸基
が活性化し、窒化アルミニウム焼結体と金属酸化物との
反応を促進していると考えられる。When a paste containing such a metal hydroxide, such as aluminum hydroxide, is fired, finally Al 2 O 3 and H 2 O
However, it is considered that the hydroxyl groups in aluminum hydroxide are activated and promote the reaction between the aluminum nitride sintered body and the metal oxide.
金属酸化物はPdおよびAg100重量部に対して１〜10重量
部、好ましくは２〜６重量部含ませるのがよい。The metal oxide is contained in an amount of 1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of Pd and Ag.
このような含量とするのは、１重量部未満では高温中で
の接着強度の劣化（半田エージング現象）に対する効果
が見られなくなり、10重量部をこえると、十分な接着強
度が得られなくなるからである。When the content is less than 1 part by weight, the effect on deterioration of the adhesive strength at high temperature (solder aging phenomenon) cannot be seen, and when it exceeds 10 parts by weight, sufficient adhesive strength cannot be obtained. Is.
金属酸化物は、通常0.01〜１μｍ程度の粒径とする。The metal oxide usually has a particle size of about 0.01 to 1 μm.
ガラス成分として用いられるZnO−B2O3系のガラスはPb
を含まないものである。Pbを含むガラスを添加すると厚
膜導体に発泡等が生じてしまう。ZnO-B 2 O 3 based glass which is used as a glass component Pb
It does not include. Addition of glass containing Pb causes foaming or the like in the thick film conductor.
ガラス成分は、PdおよびAg100重量部に対して１〜６重
量部、好ましくは２〜４重量部含ませるのがよい。The glass component is contained in an amount of 1 to 6 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of Pd and Ag.
このような含量とするのは、１重量部未満では接着強度
が十分でなくなり、６重量部をこえると厚膜導体の抵抗
値は急激に増加して半田付け性も悪くなってしまうから
である。The reason for this content is that if the amount is less than 1 part by weight, the adhesive strength becomes insufficient, and if it exceeds 6 parts by weight, the resistance value of the thick film conductor increases rapidly and the solderability deteriorates. .
金属酸化物としては、酸化バナジウム、酸化カドミウム
および酸化銅が挙げられ、このなかの少なくとも１種を
用いるのがよい。Examples of the metal oxide include vanadium oxide, cadmium oxide and copper oxide, and it is preferable to use at least one of them.
酸化バナジウムはPdおよびAg100重量部に対して0.2〜５
重量部、好ましくは0.5〜２重量部含ませるのがよい。Vanadium oxide is 0.2 to 5 relative to 100 parts by weight of Pd and Ag.
It is preferable to include 0.5 part by weight, preferably 0.5 to 2 parts by weight.
このような含量とするのは、0.2重量部未満では高温中
での接着強度の劣化が著しくなり、５重量部をこえると
パターンから基板への酸化バナジウムのしみ出しが顕著
となるからである。The reason for setting such a content is that if it is less than 0.2 parts by weight, the adhesive strength is significantly deteriorated at high temperature, and if it exceeds 5 parts by weight, vanadium oxide exudes from the pattern to the substrate remarkably.
また、金属酸化物に酸化カドミウムが含まれる場合は、
PdおよびAg100重量部に対して１〜10重量部、好ましく
は２〜５重量部とするのがよい。１重量部未満では接着
強度を増加させるのに効果がなくなり、10重量部をこえ
ると導体抵抗が大きくなるからである。When the metal oxide contains cadmium oxide,
The amount is preferably 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of Pd and Ag. This is because if it is less than 1 part by weight, the effect of increasing the adhesive strength is lost, and if it exceeds 10 parts by weight, the conductor resistance increases.
酸化銅が含まれる場合は、PdおよびAg100重量部に対し
て0.2〜５重量部、好ましくは0.5〜２重量部とするのが
よい。When copper oxide is contained, the amount is 0.2-5 parts by weight, preferably 0.5-2 parts by weight, based on 100 parts by weight of Pd and Ag.
0.2重量部未満では接着強度を増加させるのに効果がな
くなり、５重量部をこえると導体抵抗が大きくなるから
である。This is because if it is less than 0.2 parts by weight, it has no effect on increasing the adhesive strength, and if it exceeds 5 parts by weight, the conductor resistance increases.
金属酸化物は通常0.1〜５μｍ程度の粒径とする。The metal oxide usually has a particle size of about 0.1 to 5 μm.
なお、これらのうちでは、酸化バナジウムを必須成分と
するものが好ましく、これに酸化カドミウム、酸化銅の
うちの少なくとも一方、最も好ましくは両者を含むもの
がより好ましい。Of these, those containing vanadium oxide as an essential component are preferable, and those containing at least one of cadmium oxide and copper oxide, and most preferably both are more preferable.
主成分とするPdおよびAgは、通常、Pd−Ag合金として用
いるが、PdとAgの比率は、Pd10〜30重量％、Ag90〜70重
量％、好ましくはPd15〜25重量％、Ag85〜75重量％とす
るのがよい。Pd and Ag as the main components are usually used as Pd-Ag alloys, but the ratio of Pd and Ag is 10 to 30% by weight of Pd, 90 to 70% by weight of Ag, preferably 15 to 25% by weight of Pd and 85 to 75% by weight of Ag. It is good to set it as%.
このような比率とするのはAgが多すぎるとマイグレーシ
ョンや半田侵蝕性の問題が起こり、Pdが多すぎると半田
濡れ性が悪くなったり、導体抵抗が増大するからであ
る。The reason for this ratio is that too much Ag causes problems of migration and solder erosion, and too much Pd causes poor solder wettability and increases conductor resistance.
Pd−Ag合金は0.01〜10μｍ程度の粒径のものを用いる。The Pd-Ag alloy used has a grain size of about 0.01 to 10 μm.
溶剤としては、α−テルピネオール、ブチルカルビトー
ルアセテート（BCA）等が用いられ、溶剤はPdおよびAg1
00重量部に対して10〜300重量部含有される。As the solvent, α-terpineol, butyl carbitol acetate (BCA), etc. are used, and the solvent is Pd and Ag1.
It is contained in an amount of 10 to 300 parts by weight based on 00 parts by weight.
この他、ペースト中にはガラス成分の他に粘結剤として
エチルセルロース、ニトロセルロースなどの樹脂、界面
活性剤、腰切れ剤、レベリング剤等が含有されてもよ
い。In addition to the glass component, the paste may contain, as a binder, a resin such as ethyl cellulose or nitrocellulose, a surfactant, a waist breaker, and a leveling agent.
このようにして作成したペーストを以後Pd−Agペースト
とよぶ。The paste prepared in this way is hereinafter referred to as Pd-Ag paste.
このようなPd−Agペーストは、基板にスクリーン印刷等
によって印刷される。Such a Pd-Ag paste is printed on the substrate by screen printing or the like.
そして、印刷した後、乾燥し、焼成する。焼成は空気中
で行なう。Then, after printing, it is dried and fired. Firing is performed in air.
また、温度は、800〜1000℃、より好ましくは850〜950
℃とするのがよい。The temperature is 800 to 1000 ° C, more preferably 850 to 950.
It is good to set it to ℃.
800℃未満では、ペースト中の金属粉末の焼結が十分に
行われず、電極膜の強度が小さくなり、1000℃をこえる
とPd−Ag合金の融点をこえて、電極が溶けてしまうから
である。If the temperature is lower than 800 ° C, the metal powder in the paste will not be sufficiently sintered and the strength of the electrode film will be reduced, and if it exceeds 1000 ° C, the melting point of the Pd-Ag alloy will be exceeded and the electrode will melt. .
焼成のピーク時間は２〜60分、より好ましくは５〜15分
とするのがよい。The peak time of firing is 2 to 60 minutes, more preferably 5 to 15 minutes.
本発明に用いるAlN焼結体は、先に出願された特願昭59
−215971号、同59−265852号、同59−265853号、同59−
265854号、同59−265855号、同59−265856号等に記載さ
れているような方法により得られる。この場合AlN粉末
に焼結剤（CaB6等）を0.01〜10wt％添加して混合した
後、成形体とし、この成形体を非酸化性雰囲気中で焼成
することが好ましい。The AlN sintered body used in the present invention is based on Japanese Patent Application No.
-215971, 59-265852, 59-265853, 59-
No. 265854, No. 59-265855, No. 59-265856 and the like. In this case, it is preferable to add 0.01 to 10 wt% of a sintering agent (CaB 6 or the like) to the AlN powder, mix them, and then form a molded body, and fire this molded body in a non-oxidizing atmosphere.
なお、本発明のPd−Agペーストは、窒化アルミニウムに
限らず、窒化ケイ素、炭化ケイ素に対しても有効であ
る。The Pd-Ag paste of the present invention is effective not only for aluminum nitride but also for silicon nitride and silicon carbide.
Ｖ 発明の具体的作用効果 本発明によれば、パラジウムおよび銀を主成分とし、こ
れにZnO−B2O3系のガラス成分と金属酸化物とを含有さ
せているため、窒化アルミニウム焼結体基板等の非酸化
物系絶縁基板との接着強度の信頼性を高めることがで
き、特に高温中での接着強度の劣化を抑制することが可
能な厚膜ペーストが得られる。V Specific Actions and Effects of the Invention According to the present invention, the main components are palladium and silver, and the glass component of ZnO—B 2 O 3 system and the metal oxide are contained therein. It is possible to obtain a thick film paste that can improve the reliability of the adhesive strength with a non-oxide insulating substrate such as a substrate and can suppress the deterioration of the adhesive strength particularly at high temperatures.
VI 発明の具体的実施例 以下、本発明の具体的実施例を示し、本発明の効果をさ
らに詳細に説明する。VI Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown to explain the effects of the present invention in more detail.
実施例 平均粒子径が５μｍのAlN粉末に、平均粒径10μｍのCaB
6粉末を0.1重量％添加し混合した。次に、この混合物を
室温で約1000Kg/cm2の圧力を加えて成形体とした。Example AlN powder having an average particle diameter of 5 μm, CaB having an average particle diameter of 10 μm
0.1% by weight of 6 powders were added and mixed. Next, this mixture was applied with a pressure of about 1000 Kg / cm 2 at room temperature to obtain a molded body.
その後、成形体をN2気流中で1750℃まで昇温し、1750℃
で１時間保持した後、放冷した。After that, the temperature of the molded body was raised to 1750 ° C in a N 2 stream,
After holding for 1 hour, it was left to cool.
このようにして作製したAlN焼結体の基板（たて25mm、
横25mm、厚さ0.635mm）にAg−Pd金属粉末［Ag:Pd＝85:1
5（重量比）］100重量部に対して表１に示すような割合
で各添加物を加えた。The substrate of the AlN sintered body produced in this way (25 mm vertical,
25mm width, thickness 0.635mm) Ag-Pd metal powder [Ag: Pd = 85: 1
5 (weight ratio)] 100 parts by weight of each additive was added at a ratio shown in Table 1.
なお、Ag−Pdおよび表１に示す添加物に、エチルセルロ
ースとα−テルピネオールを所定粘度となるまでに約30
重量部添加した。In addition, Ag-Pd and the additives shown in Table 1 were mixed with ethyl cellulose and α-terpineol in about 30 times to reach a predetermined viscosity.
Parts by weight was added.
ペーストを5mmピッチで縦、横３か所ずつ計９か所に2mm
×2mm、厚さ10〜15μｍのパターニングを施し、エマル
ジョン厚20μｍ、250メッシュのスクリーンに印刷を施
し、その後乾燥した。これを空気中、850℃で10分間
（出し入れまでの合計時間60分）焼成した。The paste is 5mm pitch, 2mm vertically and 3 laterally in 9 places in total.
The patterning was performed with a size of 2 mm and a thickness of 10 to 15 μm, printing was performed on a screen of 250 mesh having an emulsion thickness of 20 μm, and then dried. This was fired in air at 850 ° C. for 10 minutes (total time before putting in and taking out was 60 minutes).
以上のようにして試料１〜14（表１）を作製し、接着強
度試験を行った。Samples 1 to 14 (Table 1) were prepared as described above, and an adhesive strength test was conducted.
接着強度試験はデュポン社の剥離試験に準じた。The adhesive strength test was based on the peel test of DuPont.
この場合、これらの試料のPd−Ag膜は上述のように、縦
2mm、横2mm、厚さ10〜15μｍとした。In this case, the Pd-Ag films of these samples were
The width was 2 mm, the width was 2 mm, and the thickness was 10 to 15 μm.
＜接着強度試験＞ 被着したPd−Ag膜の横方向に直径0.8mmの銅線をのば
し、Pd−Ag膜に重なる部分について半田付けし、その半
田付けの終わる一端からのびた銅線をPd−Ag膜被着面に
ほぼ垂直でかつPd−Ag膜を剥離する方向に引っ張り試験
機を用いて引っ張り、剥離した時の荷重を読んだ。この
値を初期値とする。<Adhesive strength test> A copper wire having a diameter of 0.8 mm is extended in the lateral direction of the adhered Pd-Ag film, and a portion overlapping with the Pd-Ag film is soldered. The load at the time of peeling was read by using a tensile tester to pull the Pd-Ag film in a direction substantially perpendicular to the surface on which the Ag film was adhered and in the direction of peeling. This value is the initial value.
また、試料を表１の括弧内に示す時間150℃に保った上
記の試験を行った。Further, the above test was carried out by keeping the sample at 150 ° C. for the time shown in parentheses in Table 1.
これらの結果を表１に示す。The results are shown in Table 1.
なお、本発明の試料No.4〜No.13において、Pbを含有し
ないZnO−B2O3系のガラス成分にかえて、PbO−SiO2−B2
O3−Al2O3系のガラス成分を用いたところ、本発明の試
料No.4〜No.13と異なり、Pd−Ag膜に発泡が生じた。 In Samples No. 4 to No. 13 of the present invention, PbO-SiO 2 -B 2 was used instead of Pb-free ZnO-B 2 O 3 -based glass component.
When a glass component of O 3 —Al 2 O 3 system was used, foaming occurred in the Pd—Ag film, unlike Samples No. 4 to No. 13 of the present invention.
以上より、本発明の効果は明らかである。From the above, the effect of the present invention is clear.
Claims (12)
ZnO−B2O3系のガラス成分と金属水酸化物とを含有し、
非酸化物系絶縁基板のメタライズ用に用いられる厚膜ペ
ースト。1. A main component of palladium and silver,
Containing a metal hydroxide glass component ZnO-B 2 O 3 system,
Thick film paste used for metallization of non-oxide insulating substrates.
特許請求の範囲第１項に記載の厚膜ペースト。2. The thick film paste according to claim 1, wherein the metal hydroxide is aluminum hydroxide.
囲第１項または第２項に記載の厚膜ペースト。3. The thick film paste according to claim 1, further comprising a metal oxide.
求の範囲第１項ないし第３項のいずれかに記載の厚膜ペ
ースト。4. The thick film paste according to any one of claims 1 to 3, wherein the metal oxide contains vanadium oxide.
求の範囲第１項ないし第４項のいずれかに記載の厚膜ペ
ースト。5. The thick film paste according to any one of claims 1 to 4, wherein the metal oxide contains cadmium oxide.
第１項ないし第５項のいずれかに記載の厚膜ペースト。6. The thick film paste according to any one of claims 1 to 5, wherein the metal oxide contains copper oxide.
部に対して１〜10重量部含まれる特許請求の範囲第１項
ないし第６項のいずれかに記載の厚膜ペースト。7. The thick film paste according to any one of claims 1 to 6, wherein the metal oxide is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of palladium and silver.
部に対して１〜６重量部含まれる特許請求の範囲第１項
ないし第７項のいずれかに記載の厚膜ペースト。8. The thick film paste according to any one of claims 1 to 7, wherein the glass component is contained in an amount of 1 to 6 parts by weight with respect to 100 parts by weight of palladium and silver.
重量部に対して0.2〜５重量部含まれる特許請求の範囲
第１項ないし第８項のいずれかに記載の厚膜ペースト。9. Vanadium oxide is palladium and silver 100.
The thick film paste according to any one of claims 1 to 8, which is contained in an amount of 0.2 to 5 parts by weight with respect to parts by weight.
0重量部に対して１〜10重量部含まれる特許請求の範囲
第１項ないし第９項のいずれかに記載の厚膜ペースト。10. Cadmium oxide is palladium and silver 10.
The thick film paste according to any one of claims 1 to 9, which is contained in an amount of 1 to 10 parts by weight with respect to 0 parts by weight.
に対して0.2〜５重量部含まれる特許請求の範囲第１項
ないし第10項のいずれかに記載の厚膜ペースト。11. The thick film paste according to claim 1, wherein copper oxide is contained in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of palladium and silver.
焼結体基板である特許請求の範囲第１項ないし第11項の
いずれかに記載の厚膜ペースト。12. The thick film paste according to any one of claims 1 to 11, wherein the non-oxide insulating substrate is a sintered aluminum oxide substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61080660A JPH0731931B2 (en) | 1986-04-08 | 1986-04-08 | Thick film paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61080660A JPH0731931B2 (en) | 1986-04-08 | 1986-04-08 | Thick film paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62237605A JPS62237605A (en) | 1987-10-17 |
| JPH0731931B2 true JPH0731931B2 (en) | 1995-04-10 |
Family
ID=13724515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61080660A Expired - Lifetime JPH0731931B2 (en) | 1986-04-08 | 1986-04-08 | Thick film paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0731931B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0294667A (en) * | 1988-09-30 | 1990-04-05 | Kyocera Corp | Photoelectric conversion device |
| FR2652226B1 (en) * | 1989-09-19 | 1991-10-25 | Alsthom Gec | PROCESS FOR PRODUCING CONDUCTIVE TRACKS FOR HYBRID CIRCUITS, IN PARTICULAR FOR HYBRID POWER CIRCUITS. |
| DE602006021767D1 (en) * | 2005-10-20 | 2011-06-16 | Toyo Aluminium Kk | PASTE COMPOSITION AND SOLAR BATTERY ELEMENT THEREWITH |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55107701A (en) * | 1979-02-14 | 1980-08-19 | Noritake Co Ltd | Palladium powder and production of palladium-powder-contained paste and palladium powder |
-
1986
- 1986-04-08 JP JP61080660A patent/JPH0731931B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62237605A (en) | 1987-10-17 |
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