JPH03176905A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JPH03176905A JPH03176905A JP31485889A JP31485889A JPH03176905A JP H03176905 A JPH03176905 A JP H03176905A JP 31485889 A JP31485889 A JP 31485889A JP 31485889 A JP31485889 A JP 31485889A JP H03176905 A JPH03176905 A JP H03176905A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- weight
- parts
- conductive paste
- weight part
- 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
- 239000000843 powder Substances 0.000 claims abstract description 72
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 229910003217 Ni3Si Inorganic materials 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、導電性ペース１〜に関し、詳しくは導電粉末
としてＣｕ粉末を用いた大気焼成可能な導電性ペースト
に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to conductive pastes 1 to 1, and specifically relates to a conductive paste that uses Cu powder as a conductive powder and can be fired in the atmosphere.
（従来の技術）
一般に、導電性ペーストは、導体回路、セラミックコン
デンサの電極、電磁波シールド材プラズマデイスプレー
の電極等に用いられ、特にＤＣ型プラズマデイスプレー
用の電極としての用途が有望視されている。(Prior Art) Generally, conductive paste is used for conductive circuits, ceramic capacitor electrodes, electromagnetic shielding materials, plasma display electrodes, etc., and its use as an electrode for DC-type plasma displays is particularly promising. There is.
例えばプラズマデイスプレーは、ガラス製のバックプレ
ート基板上に電極（陰極）をプリント形成する一方、カ
バープレートの側に陰極に対向させ透明電極を形成し、
両電極間に電圧を印加して放電させ発色させるものであ
り、これはＮｉ等の金属導電性ペーストをバックプレー
ト基板上にスクリーン印刷して厚膜形成し、その後これ
を乾燥した後、大気焼成して電極を形成する。For example, in a plasma display, an electrode (cathode) is printed on a glass back plate substrate, and a transparent electrode is formed on the cover plate side facing the cathode.
A voltage is applied between both electrodes to cause discharge and color development.This is done by screen printing a metal conductive paste such as Ni on the back plate substrate to form a thick film, then drying it and baking it in the air. to form an electrode.
この種の導電性ペーストにおいては、その製造時、大気
焼成して電極等を形成するときＮｉが酸化されて導電性
を消失しやすいので、従来のペースト組成中にＢを含有
させてＮｉの酸化を防止することが考えられている。そ
の−例が特公昭５５５１２８５号および特公昭６Ｃ）−
１６０４１号公報に開示されている。このうち前者のも
のはＮｉおよびＢを（Ｎｉａ Ｂ）ａ （Ｎｉ３Ｓｉ
）ｂの組成物の形で含有するものであり、後者のものは
Ｎｉ粉末中にＢ粉末を添加させた形態のもので、何れも
Ｂの選択的酸化反応によってＮｉの酸化反応を防止する
ものである。In this type of conductive paste, Ni is easily oxidized and loses its conductivity when it is baked in the air to form electrodes, etc. during production, so B is included in the conventional paste composition to oxidize the Ni. It is considered to prevent Examples are Special Publication No. 5551285 and Special Publication No. 6C)
It is disclosed in Japanese Patent No. 16041. Of these, the former is Ni and B (Nia B) a (Ni3Si
) It is contained in the form of the composition b, and the latter is in the form of B powder added to Ni powder, and both prevent the oxidation reaction of Ni by the selective oxidation reaction of B. It is.
（発明が解決しようとする課題）
しかしながら、これら従来の導電性ペーストは、その製
造法および特性の点で次のような問題を有している。(Problems to be Solved by the Invention) However, these conventional conductive pastes have the following problems in terms of their manufacturing method and characteristics.
すなわち、前者の特公昭５５−５１２８５号公報に記載
のものの場合、（Ｎ １３Ｂ） ｓ （Ｎ １３Ｓｉ
）ｂの組成物を製造するにはＮｉにＢを添加して溶解し
凝固させた後粉砕する必要があり、このときＢの比重が
Ｎｉに比べて約１／４と軽いために均一な組成物の製造
が困難であり、しかも粉砕して粒状粉末にするために製
造コストが高くなるのに加えて、粉末形状は角ばった形
状となり、ペーストを基板上に印刷形成する際の印刷性
が悪い。That is, in the case of the former described in Japanese Patent Publication No. 55-51285, (N 13B) s (N 13Si
) To produce the composition b, it is necessary to add B to Ni, dissolve it, solidify it, and then crush it. At this time, since the specific gravity of B is about 1/4 lighter than Ni, a uniform composition is obtained. It is difficult to manufacture the product, and the manufacturing cost is high because it is crushed into granular powder, and the shape of the powder is angular, making it difficult to print the paste on a substrate. .
また後者の特公昭６０−１６０４１号に記載のものの場
合、Ｂが比較的多量に添加されるために（Ｂの添加量は
４〜５０％）、酸化生成したＢ２Ｏ３が表面にガラス状
に浮上し、これら多量のＢ２Ｏ３が不純物となって電気
抵抗値を増大させるという問題がある。Furthermore, in the case of the latter described in Japanese Patent Publication No. 60-16041, since a relatively large amount of B is added (the amount of B added is 4 to 50%), the oxidized B2O3 floats to the surface in a glassy state. There is a problem in that a large amount of B2O3 becomes an impurity and increases the electrical resistance value.
本発明は、このような問題点を解決するためになされた
もので、本発明が解決しようとする課題は、Ｎｉに代え
て相対的に安価なＣｕを用い、流動性、成形性、印刷性
に優れ、かつ比較的高温の７００℃付近にて大気焼成可
能で、導電性の高い導電性組成物を製造可能な導電性ペ
ーストを提供することにある。The present invention has been made to solve these problems, and the problem to be solved by the present invention is to use relatively inexpensive Cu instead of Ni, and improve fluidity, moldability, and printability. An object of the present invention is to provide a conductive paste that can be fired in the atmosphere at a relatively high temperature of around 700°C, and can produce a conductive composition with high conductivity.
（課題を解決するための手段）
本発明は、前記課題を解決するためになされたもので、
その要旨とするところは、Ｃｕ粉末、Ｂ粉末、Ｓｉ粉末
、Ｂ２Ｏ３粉末、ガラスフリットおよび有機ビヒクルよ
りなる導電性ペーストであって、その組成が、（イ）前
記Ｂ粉末は、Ｃｕ粉末とＢ粉末の合計重量１００重量部
に対し３．５〜３．９重量部、（ロ）前記Ｓｉ粉末は、
Ｃｕ粉末とＢ粉末の合計重量１００重量部に対し２．０
〜２０．０重量部、（ハ）前記Ｂ２Ｏ３粉末は、Ｃｕ粉
末とＢ粉末の合計重量１００重量部に対し２．０〜３０
．０重量部、（ニ）前記ガラスフリットは、Ｃｕ粉末と
Ｂ粉末の合計重量１００重量部に対し１０〜３０重量部
であることを特徴とする。(Means for Solving the Problems) The present invention has been made to solve the above problems, and
The gist of this is that it is a conductive paste consisting of Cu powder, B powder, Si powder, B2O3 powder, glass frit, and an organic vehicle, the composition of which is: (a) the B powder is composed of Cu powder and B powder; 3.5 to 3.9 parts by weight per 100 parts by weight of the total weight of (b) the Si powder,
2.0 per 100 parts by weight of the total weight of Cu powder and B powder
~20.0 parts by weight, (c) the B2O3 powder is 2.0 to 30 parts by weight per 100 parts by weight of the total weight of Cu powder and B powder
．． (d) The amount of the glass frit is 10 to 30 parts by weight based on 100 parts by weight of the total weight of Cu powder and B powder.
本発明による導電性ペーストは、Ｃｕ粉末を主成分に用
いているので製造コストはＮｉ扮粉末用いた場合に比べ
安価なものとなり、またＢ粉末の含有量をＣｕ粉末とＢ
粉末の合計重量１００部に対し３．５〜３．９重量部の
範囲にしその分Ｃｕ粉末を多くしているため導電性が向
上する。したがって、プラズマデイスプレーの電極形成
に本発明を適用した場合に画像の鮮明度が良好となる。Since the conductive paste according to the present invention uses Cu powder as the main component, the manufacturing cost is lower than when using Ni powder, and the content of B powder is lower than that of Cu powder.
Since the Cu powder is increased by an amount corresponding to 3.5 to 3.9 parts by weight based on 100 parts of the total weight of the powder, the conductivity is improved. Therefore, when the present invention is applied to electrode formation of a plasma display, the image clarity becomes good.
Ｃｕ粉末の平均粒径は１〜３０μｍとするのが望ましく
、さらに好ましくは５〜２０７ｘ ｍの範囲にする。こ
れは、平均粒径１μｍ未満とすると、Ｃｕ粒子の表面積
が相対的に大きくなり、Ｃｕの酸化反応が促進されやす
く電気抵抗値が大きくなりやすいためであり、平均粒径
３０μｍ以下としたのけ、３０μｍを超えると導電性ペ
ーストの流動性が悪くなり、印刷性および充填性が低下
するからである。The average particle diameter of the Cu powder is desirably in the range of 1 to 30 μm, more preferably in the range of 5 to 207×m. This is because if the average particle size is less than 1 μm, the surface area of the Cu particles becomes relatively large, which tends to promote the oxidation reaction of Cu and increase the electrical resistance value. This is because if the thickness exceeds 30 μm, the fluidity of the conductive paste deteriorates, resulting in poor printability and filling properties.
Ｂ粉末を添加するのは、Ｃｕの酸化防止のためであり、
そのためにはＢ粉末とＣｕ粉末の合計重量１００重量部
に対しＢ粉末は少なくとも３．５重量部が必要であり、
３．９重量部を超えると、その分Ｃｕの含有量が低下し
抵抗値が高くなるので、Ｂ粉末は３．５〜３．９重量部
の範囲にする。The reason for adding B powder is to prevent Cu from oxidizing.
For this purpose, at least 3.5 parts by weight of B powder is required per 100 parts by weight of the total weight of B powder and Cu powder,
If it exceeds 3.9 parts by weight, the Cu content decreases and the resistance value increases accordingly, so the amount of B powder is set in the range of 3.5 to 3.9 parts by weight.
すなわち、Ｂは高温において後述するように選択的に酸
化されてＢ２０．になるが、このＢ２０−の融点は５７
７℃程度に低いため、Ｂ量が多いとベース１へを焼成温
度６００〜６２０ ”Ｃ程度で大気焼成したとき選択的
に酸化されたＢｉ Ｏ３が表面に浮上してキラキラ光っ
た状態となり、これが電極特性を低下させ、プラズマデ
イスプレーにおいて画像鮮明度を低下させる原因となる
。この画像鮮明度を低下させる境界域は、Ｂの添加量が
４゜０重量部であり、これより多いと電極表面へのＢ２
Ｏ３の浮上が顕著となって表面がキラキラ光った状態と
なるからである。反対にＢの添加量がこれより少ないと
電極表面におけるキラキラ感が消失し、Ｂ２Ｏ３の浮上
が認められず、プラズマデイスプレーの画像鮮明度が高
（なる。またＢの原料粉末形態は、アモルファス粉末で
あるのが望ましく、もしくは平均粒径５０μｍ以下の粉
末であるのが望ましい。平均粒径５０ Ｉｔ ｍを超え
ると、導電性ペーストの流動性、印刷性等が低下するた
めである。That is, B is selectively oxidized at high temperature as described below to become B20. However, the melting point of this B20- is 57
Since the temperature is about 7℃, if the amount of B is large, when base 1 is fired in the atmosphere at a firing temperature of about 600 to 620''C, selectively oxidized BiO3 floats to the surface and becomes sparkling. This causes deterioration of the electrode characteristics and decreases the image clarity in plasma displays.The boundary region where the image clarity decreases is when the amount of B added is 4.0 parts by weight, and if it is more than this, the electrode surface B2 to
This is because the floating of O3 becomes noticeable and the surface becomes sparkling. On the other hand, if the amount of B added is less than this, the glittering feeling on the electrode surface disappears, no floating of B2O3 is observed, and the image clarity of the plasma display becomes high (in addition, the raw material powder form of B is amorphous powder). or a powder having an average particle size of 50 μm or less, because if the average particle size exceeds 50 It m, the fluidity, printability, etc. of the conductive paste will deteriorate.
Ｓｉ粉末は、Ｃｕ粉末とＢ粉末の合計重量１００重量部
に対し２．０〜２０．０重量部の範囲にするのが望まし
い。Ｓｉ粉末を添加するのは、温度６００°Ｃ以上でガ
ラス質を形成しＣｕの酸化を効果的に抑制するためであ
り、そのためには少なくとも２．０重量部が必要となる
。また２０．０重量部を超えると、Ｓｉ酸化物がガラス
膜状となり絶縁体を構成しペーストの電気抵抗値が増大
するからである。Ｓｉ粉末の平均粒径ば、５０μｍ以下
にするのが望ましい。これは流動性、充填性および印刷
性等を向上させるためである。It is desirable that the amount of Si powder be in the range of 2.0 to 20.0 parts by weight based on 100 parts by weight of the total weight of Cu powder and B powder. The reason why Si powder is added is to form a glassy substance at a temperature of 600° C. or higher and effectively suppress oxidation of Cu, and for this purpose, at least 2.0 parts by weight is required. If the amount exceeds 20.0 parts by weight, the Si oxide becomes like a glass film and forms an insulator, increasing the electrical resistance of the paste. The average particle size of the Si powder is desirably 50 μm or less. This is to improve fluidity, filling properties, printability, etc.
Ｂ ２０ ａ粉末は、Ｃｕ粉末とＢ粉末の合計重量１０
０重量部に対し２．０〜３０．０重量部の範囲にするの
が望ましい。Ｂ２Ｏ３粉末を添加するのは、温度３００
〜５００℃の範囲でガラス質を形成しＣｕの酸化を効果
的に抑制するためであり、そのためには少な（とも２．
０重量部が必要となる。また３０．０重量部を超えると
、Ｂ２Ｏ３がガラス膜状となり絶縁体を構成しペースト
の電気抵抗値が増大するからである。Ｂ ２０３粉末の
平均粒径は、ペーストの流動性、充填性および印刷性等
を向上させるため５０μｍ以下にするのが望ましい。B 20 a powder has a total weight of Cu powder and B powder of 10
It is desirable that the amount is in the range of 2.0 to 30.0 parts by weight relative to 0 parts by weight. B2O3 powder is added at a temperature of 300
This is to form a glassy substance in the range of ~500°C and effectively suppress the oxidation of Cu, and for that purpose, it is necessary to use a small amount (both 2.
0 parts by weight are required. Moreover, if it exceeds 30.0 parts by weight, B2O3 becomes like a glass film and constitutes an insulator, increasing the electrical resistance value of the paste. The average particle size of the B 203 powder is desirably 50 μm or less in order to improve the fluidity, filling properties, printability, etc. of the paste.
ガラスフリットは、軟化点温度４００〜６００℃のもの
で、Ｃｕ粉末とＢ粉末の合計重量１００重量部に対し、
１０〜３０重量部の範囲にするのが望ましい。ガラスフ
リットは、焼成時に温度４００〜６００℃の範囲でガラ
スフリッ１−がガラス状化してＣｕ粉末の周囲に保護層
を形成しＣｕの酸化防止の役割を果たすからであり、そ
のためにはガラスフリットが１０重量部以上必要となる
。The glass frit has a softening point temperature of 400 to 600°C, and is
It is desirable that the amount is in the range of 10 to 30 parts by weight. This is because the glass frit becomes vitrified at a temperature in the range of 400 to 600°C during firing to form a protective layer around the Cu powder, which plays a role in preventing oxidation of the Cu. 10 parts by weight or more is required.
ガラスフリットが多過ぎると、ガラス膜状の絶縁物を作
り易く、導電性が低下するから、３０重量部以内にする
。If there is too much glass frit, it is easy to form a glass film-like insulator and the conductivity decreases, so the amount is limited to 30 parts by weight or less.
有機ビヒクルは、導電性ペーストの流動性を確保するた
めに加えるものである。The organic vehicle is added to ensure the fluidity of the conductive paste.
前述した組成の導電性ペーストは、大気中つまり酸化性
雰囲気中で焼成可能である。また温度は最高７００℃付
近の温度で焼成可能である。The conductive paste having the composition described above can be fired in the air, that is, in an oxidizing atmosphere. Further, firing can be performed at a maximum temperature of around 700°C.
次に、前記導電性ペーストが大気焼成されるとき、前記
各種の添加物によりＣｕの酸化がどのように防止される
のかについて第１図に基づいて説明する。第１図中の矢
印で示す範囲の添加物は、主としてその温度範囲にて酸
化防止効果が働くことを示している。Next, how the oxidation of Cu is prevented by the various additives when the conductive paste is fired in the atmosphere will be explained based on FIG. 1. The additives in the range indicated by the arrows in FIG. 1 show that their antioxidant effect mainly occurs within that temperature range.
予備焼成後の焼成時、温度を室温から次第に上昇してい
（と、まず常温から約３５０℃までの範囲は、有機ビヒ
クルがＣｕの酸化を防止する。そして３００℃から３５
０℃の範囲においては、有機ビヒクルによるＣｕ酸化防
止が働くとともに、Ｂ２Ｏ３粉末がガラス質に変化する
ことに伴いＣＵの周囲にガラス質層を作ってＣｕの酸化
が防止サレル。３５０℃から４００℃の範囲になると、
Ｂ２Ｏ３のガラス質化によりＣｕの酸化が防止さレル。During firing after pre-firing, the temperature is gradually raised from room temperature (first, from room temperature to about 350°C, the organic vehicle prevents Cu oxidation, and then from 300°C to 350°C
In the temperature range of 0°C, the organic vehicle acts to prevent Cu from oxidizing, and as the B2O3 powder changes to glassy, a glassy layer is formed around the Cu to prevent Cu from oxidizing. When the temperature ranges from 350℃ to 400℃,
Vitrification of B2O3 prevents Cu oxidation.
４００℃から５５０℃の範囲になると、さらにガラスフ
リットがホウケイ酸ガラスを造ることによりＣｕの酸化
が防止される。５５０ ”Ｃを超えると選択的にＢが酸
化されるのに伴いＣｕの酸化が抑制される。６００℃（
”ｌ近においてはこのＢの働きが顕著に作用し、Ｃｕの
酸化が効果的に抑制される。６５０℃を超え７００ ’
Ｃ付近ではＳＬが酸化され易（これに伴いＣｕの酸化が
抑制される。When the temperature ranges from 400° C. to 550° C., the glass frit further forms borosilicate glass, thereby preventing Cu from oxidizing. When the temperature exceeds 550"C, B is selectively oxidized and the oxidation of Cu is suppressed. At 600"C (
At temperatures close to 650°C and 700°C, the effect of B is significant and the oxidation of Cu is effectively suppressed.
SL is easily oxidized near C (accompanying this, oxidation of Cu is suppressed).
これらペースト中の添加物つまり有機ビヒクル、Ｂ２Ｏ
３，ガラスフリット、Ｂ、Ｓｉが、それぞ ０
れ所定の温度域において効果的にＣｕの酸化防止を図る
。これにより、大気中の比較的高温の７００″Ｃ付近に
おいても、酸化抑制効果が顕著に作用し導電性を保持し
つつ焼成可能になる。The additives in these pastes, namely the organic vehicle, B2O
3. Glass frit, B, and Si each effectively prevent Cu from oxidizing in a predetermined temperature range. As a result, even at a relatively high temperature of around 700''C in the atmosphere, the oxidation suppressing effect works significantly and it becomes possible to sinter while maintaining conductivity.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
導電性ペーストの原料としては、平均粒径１０゜４μｍ
の球状Ｃｕ扮粉末、アモルファスＢ粉末と、アモルファ
スＳｉ粉末ど、平均粒径５０μｍ以下のＢ２Ｏ３粉末と
、これにガラスフリットを加え、さらに有機ビヒクルと
してエチルセルロースをテルピネオールに溶解したもの
を使用した。これらを３本ロールミルを用いて混練した
後、＃２００スクリーンを用いて線幅０．５ｍｍＸ長さ
１００ｍｍの線をアルミナ基板上に印刷した。これを１
２０℃で１０分乾燥した後、６００〜８００℃で１５〜
２０分大気焼成した。焼成後の膜厚の平均値は５０μｍ
であった。As a raw material for conductive paste, the average particle size is 10°4 μm.
Spherical Cu powder, amorphous B powder, amorphous Si powder, etc., B2O3 powder with an average particle size of 50 μm or less, glass frit was added to this, and ethyl cellulose dissolved in terpineol was used as an organic vehicle. After kneading these using a three-roll mill, lines with a line width of 0.5 mm and a length of 100 mm were printed on an alumina substrate using a #200 screen. This is 1
After drying at 20℃ for 10 minutes, drying at 600-800℃ for 15~
It was baked in the air for 20 minutes. The average film thickness after firing is 50μm
Met.
得られた焼成部の表面状態を観察し、その焼成部の色相
から表面酸化状態を観察したところ、焼成部の色相は第
１表に示す通りであった。焼成部の比抵抗値について測
定したところ、その結果は第１表に示すとおりであった
。When the surface condition of the obtained fired part was observed and the surface oxidation state was observed from the hue of the fired part, the hue of the fired part was as shown in Table 1. When the specific resistance value of the fired part was measured, the results were as shown in Table 1.
（以下、余白。）
１
第１表において、実施例１〜９においては、焼成部の比
抵抗が１５Ｘ］Ｏ−’Ωｃｍ以下となり、導電性が高い
値となった。(The following is a blank space.) 1 In Table 1, in Examples 1 to 9, the specific resistance of the fired part was 15X]O-'Ωcm or less, and the conductivity was a high value.
これに対し、比較例１および比較例２はＳｔを含まず本
発明のＳｉの範囲から逸脱するものであり、比較例３は
Ｂ２Ｏ３を含有しない等の理由により、比抵抗値が極め
て大きいかあるいは測定不能（５００ｃｍより抵抗大）
という結果となった。On the other hand, Comparative Examples 1 and 2 do not contain St and deviate from the Si range of the present invention, and Comparative Example 3 does not contain B2O3, so the specific resistance value is extremely high or Unmeasurable (resistance greater than 500cm)
The result was.
また比較例４および比較例５は、それぞれ焼成温度が７
５０℃、８００℃と高温であったこと等により比抵抗値
が大となった。これは、高温において酸化が過度に促進
されたものと推定される。Furthermore, in Comparative Example 4 and Comparative Example 5, the firing temperature was 7.
The specific resistance value was large due to the high temperatures of 50°C and 800°C. This is presumed to be because oxidation was excessively accelerated at high temperatures.
（発明の効果）
以上説明したように、本発明の導電性ペーストによれば
、流動性、充填性、印刷性が良好なペーストであり、比
較的高温にて大気焼成時の酸化防止効果が適正に働くの
で、得られる導電体は電気抵抗値が小さいだけでな（、
基板との同時焼成が可能になり、極めて簡単な生産」−
程により良好な導電性をもつ導電体が得られるという効
果がある。(Effects of the Invention) As explained above, the conductive paste of the present invention has good fluidity, fillability, and printability, and has an appropriate oxidation prevention effect during air firing at relatively high temperatures. Therefore, the resulting conductor not only has a small electrical resistance value (,
It is now possible to fire simultaneously with the substrate, making production extremely simple.
This has the effect that a conductor with better conductivity can be obtained as the temperature increases.
第１図は導電性ペーストに添加する各種添加物の酸化防
止効果を説明するための説明図である。FIG. 1 is an explanatory diagram for explaining the antioxidant effects of various additives added to the conductive paste.
Claims (1)
スフリットおよび有機ビヒクルよりなる導電性ペースト
であって、その組成が、 （イ）前記Ｂ粉末は、Ｃｕ粉末とＢ粉末の合計重量１０
０重量部に対し３．５〜３．９重量部、（ロ）前記Ｓｉ
粉末は、Ｃｕ粉末とＢ粉末の合計重量１００重量部に対
し２．０〜２０．０重量部、（ハ）前記Ｂ＿２Ｏ＿３粉
末は、Ｃｕ粉末とＢ粉末の合計重量１００重量部に対し
２．０〜３０．０重量部、 （ニ）前記ガラスフリットは、Ｃｕ粉末とＢ粉末の合計
重量１００重量部に対し１０〜３０重量部であることを
特徴とする導電性ペースト。[Claims] A conductive paste consisting of Cu powder, B powder, Si powder, B_2O_3 powder, glass frit, and an organic vehicle, the composition of which is: (a) the B powder is a combination of Cu powder and B powder; Total weight 10
3.5 to 3.9 parts by weight relative to 0 parts by weight, (b) the above Si
The powder is 2.0 to 20.0 parts by weight per 100 parts by weight of the total weight of Cu powder and B powder, and (c) the B_2O_3 powder is 2.0 parts by weight per 100 parts by weight of the total weight of Cu powder and B powder. ~30.0 parts by weight, (iv) A conductive paste characterized in that the glass frit is present in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total weight of Cu powder and B powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31485889A JPH03176905A (en) | 1989-12-04 | 1989-12-04 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31485889A JPH03176905A (en) | 1989-12-04 | 1989-12-04 | Conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03176905A true JPH03176905A (en) | 1991-07-31 |
Family
ID=18058466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31485889A Pending JPH03176905A (en) | 1989-12-04 | 1989-12-04 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03176905A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06349316A (en) * | 1993-06-11 | 1994-12-22 | Tdk Corp | Conductive paste |
| JP2011029113A (en) * | 2009-07-29 | 2011-02-10 | Jsr Corp | Photosensitive black paste, and method of forming bus electrode black layer |
| JP2015011979A (en) * | 2013-07-02 | 2015-01-19 | 大研化学工業株式会社 | Conductive paste for atmospheric firing, and method for manufacturing the same |
| JP2017535024A (en) * | 2014-08-28 | 2017-11-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Copper-containing conductive paste and electrode made from copper-containing conductive paste |
| US10672922B2 (en) | 2014-08-28 | 2020-06-02 | Dupont Electronics, Inc. | Solar cells with copper electrodes |
-
1989
- 1989-12-04 JP JP31485889A patent/JPH03176905A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06349316A (en) * | 1993-06-11 | 1994-12-22 | Tdk Corp | Conductive paste |
| JP2011029113A (en) * | 2009-07-29 | 2011-02-10 | Jsr Corp | Photosensitive black paste, and method of forming bus electrode black layer |
| JP2015011979A (en) * | 2013-07-02 | 2015-01-19 | 大研化学工業株式会社 | Conductive paste for atmospheric firing, and method for manufacturing the same |
| JP2017535024A (en) * | 2014-08-28 | 2017-11-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Copper-containing conductive paste and electrode made from copper-containing conductive paste |
| US10325693B2 (en) | 2014-08-28 | 2019-06-18 | E I Du Pont De Nemours And Company | Copper-containing conductive pastes and electrodes made therefrom |
| US10672922B2 (en) | 2014-08-28 | 2020-06-02 | Dupont Electronics, Inc. | Solar cells with copper electrodes |
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