JPH06338219A - Conductive paste - Google Patents

Conductive paste

Info

Publication number
JPH06338219A
JPH06338219A JP12710093A JP12710093A JPH06338219A JP H06338219 A JPH06338219 A JP H06338219A JP 12710093 A JP12710093 A JP 12710093A JP 12710093 A JP12710093 A JP 12710093A JP H06338219 A JPH06338219 A JP H06338219A
Authority
JP
Japan
Prior art keywords
conductive paste
powder
resistance
holes
flake
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
Application number
JP12710093A
Other languages
Japanese (ja)
Inventor
秀次 ▲くわ▼島
Hideji Kuwajima
Shozo Yamana
章三 山名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Denko Materials Co Ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP12710093A priority Critical patent/JPH06338219A/en
Publication of JPH06338219A publication Critical patent/JPH06338219A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To prevent the short circuit between electrodes or between wirings even if an electric field is applied to it under high conductive and hot and humid atmosphere by containing specified ingredients in conductive paste. CONSTITUTION:Conductive paste contains flake-shaped silver powder, copper powder, ceramic powder, and a kind of nitrophenyl hydrazine. Hereby, high conductive paste, where the resistance of a through hole in a wiring board is low, can be gotten. Moreover, economical conductive paste, where the drop of insulation resistance between through holes after load test in humidity is low and further the quantity of used silver is mail, can be gotten by using flake-shaped silver powder, copper powder, and ceramic powder jointly.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は電気回路形成用の導電ペ
ーストに関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste for forming an electric circuit.

【0002】[0002]

【従来の技術】従来、プリント配線板、電子部品等の配
線導体を形成する方法として、導電性に優れた銀粉を含
有するペーストを塗布又は印刷して形成する方法が一般
的に知られている。
2. Description of the Related Art Conventionally, as a method for forming a wiring conductor of a printed wiring board, an electronic component or the like, a method of applying or printing a paste containing silver powder having excellent conductivity is generally known. .

【0003】[0003]

【発明が解決しようとする課題】銀粉を用いた導電ペー
ストは導電性が良好なことから印刷配線板、電子部品等
の配線導体や電極として使用されているが、これらは高
温多湿の雰囲気下で電界が印加されると、配線導体や電
極にマイグレーションと称する銀の電析が生じ電極間又
は配線間が短絡するという欠点が生じる。このマイグレ
ーションを防止するための方策はいくつか行われてお
り、導体の表面に防湿塗料を塗布するか又は導電ペース
トに窒素化合物などの腐食抑制剤を添加するなどの方策
が検討されているが十分な効果が得られるものではなか
った。
Since a conductive paste using silver powder has good conductivity, it is used as a wiring conductor or an electrode for printed wiring boards, electronic parts, etc., but these are used under a high temperature and high humidity atmosphere. When an electric field is applied, there is a drawback that a wiring conductor or an electrode is electro-deposited with silver called migration and a short circuit occurs between electrodes or between wirings. Several measures have been taken to prevent this migration, and measures such as applying a moisture-proof coating to the surface of the conductor or adding a corrosion inhibitor such as a nitrogen compound to the conductive paste have been studied, but it is sufficient. It was not possible to obtain such an effect.

【0004】また、導通抵抗の良好な導体を得るには銀
粉の配合量を多くしなければならず、銀粉が高価である
ことから導電ペーストも高価になるという欠点があっ
た。
Further, in order to obtain a conductor having good conduction resistance, it is necessary to increase the amount of silver powder blended, and the silver paste is expensive, so that the conductive paste is also expensive.

【0005】本発明はかかる欠点のない導電ペーストを
提供するものである。
The present invention provides a conductive paste that does not have such drawbacks.

【0006】[0006]

【課題を解決するための手段】本発明はフレーク状銀
粉、銅粉、セラミックス粉及びニトロフェニルヒドラジ
ン類を含む導電ペーストに関する。
The present invention relates to a conductive paste containing flaky silver powder, copper powder, ceramic powder and nitrophenylhydrazines.

【0007】本発明におけるフレーク状銀粉はその形状
を限定するものではないが、アスペクト比は大略3以上
あることが好ましく、10以上であればさらに好まし
い。また、その粒径は長径が20μm以下が好ましく、
10μm以下であれば印刷性を低下させないのでさらに
好ましい。銅粉はその粒径が小さいほど好ましく、例え
ば20μm以下が好ましく、10μm以下であればフレ
ーク状銀粉の粒間に均一分散させやすいのでさらに好ま
しい。
The shape of the flake silver powder in the present invention is not limited, but the aspect ratio is preferably about 3 or more, more preferably 10 or more. In addition, the particle size is preferably such that the major axis is 20 μm or less,
If it is 10 μm or less, the printability is not deteriorated, which is more preferable. The smaller the particle diameter of the copper powder is, the more preferable it is.

【0008】セラミックス粉はその形状を限定するもの
ではないが、その粒径は長径10μm以下が好ましく、
5μm以下であればさらに好ましい。また、セラミック
ス粉の種類については特に制限はないがアルミナ粉を用
いることが好ましい。さらにフレーク状銀粉、銅粉及び
セラミックス粉の使用方法は、それぞれ個々に添加して
も良いが、予めフレーク状銀粉、銅粉及びセラミックス
粉をボールミル等で均一に混合したのち添加すればフレ
ーク状銀粉の分散性が良いので好ましい。ニトロフェニ
ルヒドラジン類としては、3−ニトロヒドラジン及び
3,5−ジニトロフェニルヒドラジンの一種又はこれら
の混合物を用いることが好ましい。ニトロフェニルヒド
ラジン類の量は導電ペーストの固形分に対してマイグレ
ーションの防止と経済性から0.05〜2.0重量%が
好ましい。
The shape of the ceramic powder is not limited, but the particle diameter is preferably 10 μm or less in the major axis,
It is more preferably 5 μm or less. The type of ceramic powder is not particularly limited, but alumina powder is preferably used. Further, the flake-shaped silver powder, the copper powder and the ceramic powder may be added individually. Is preferable because it has good dispersibility. As the nitrophenylhydrazines, it is preferable to use one of 3-nitrohydrazine and 3,5-dinitrophenylhydrazine or a mixture thereof. The amount of nitrophenylhydrazines is preferably 0.05 to 2.0% by weight from the standpoint of migration prevention and economy with respect to the solid content of the conductive paste.

【0009】フレーク状銀粉と銅粉の比率は導体の抵抗
とマイグレーションの防止の点から体積比で5:1〜
1:5(フレーク状銀粉:銅粉)であることが好まし
い。またフレーク状銀粉及び銅粉とセラミックス粉の比
率は導体の抵抗とマイグレーション防止の点から体積比
で5:1〜1:5(フレーク状銀粉及び銅粉:セラミッ
クス粉)であることが好ましい。
The flake-shaped silver powder and the copper powder have a volume ratio of 5: 1 to 1 in terms of resistance of the conductor and prevention of migration.
It is preferably 1: 5 (flake silver powder: copper powder). The ratio of the flake silver powder and copper powder to the ceramic powder is preferably 5: 1 to 1: 5 (flake silver powder and copper powder: ceramic powder) in terms of volume resistance and resistance of the conductor.

【0010】導電ペーストは上記の材料以外に液状のエ
ポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂
等の有機質の接着剤成分及び必要に応じてテルビネオー
ル、エチルカルビトール、カルビトールアセテート等の
溶媒、微小黒鉛粉末などを含有する。フレーク状銀粉、
銅粉及びセラミックス粉の含有量は導電ペーストの固形
分に対して導体の抵抗と経済性から20〜60重量%で
あることが好ましく、30〜60重量%であることがさ
らに好ましい。
In addition to the above materials, the conductive paste is an organic adhesive component such as liquid epoxy resin, phenol resin, unsaturated polyester resin and the like, if necessary, a solvent such as terbineol, ethyl carbitol, carbitol acetate, and fine graphite. Contains powder and the like. Flaky silver powder,
The content of the copper powder and the ceramic powder is preferably 20 to 60% by weight, and more preferably 30 to 60% by weight from the viewpoint of the resistance and economy of the conductor with respect to the solid content of the conductive paste.

【0011】[0011]

【実施例】以下本発明の実施例を説明する。 実施例1 ビスフェノールA型エポキシ樹脂(油化シェルエポキシ
製、商品名エピコート834)60重量部及びビスフェ
ノールA型エポキシ樹脂(油化シェルエポキシ製、商品
名エピコート828)40重量部を予め加温溶解させ、
次いで室温に冷却した後2エチル4メチルイミダゾール
(四国化成製)5重量部、3−ニトロフェニルヒドラジ
ン(和光純薬製、試薬)1重量部、エチルカルビトール
(和光純薬製、試薬)20重量部及びブチルセロソルブ
(和光純薬製、試薬)20重量部を加えて均一に混合し
て樹脂組成物とし、この樹脂組成物146gにフレーク
状銀粉(徳力化学研究所製、商品名TCG−1)を11
0g、銅粉(福田金属箔粉製、商品名SPC4−8)を
40g及び平均粒径が0.4μmのアルミナ粉(住友化
学製、商品名AES−12)を35g加えて撹拌らいか
い機及び3本ロールで均一に分散して導電ペーストを得
た。
EXAMPLES Examples of the present invention will be described below. Example 1 60 parts by weight of bisphenol A type epoxy resin (Oilized shell epoxy, trade name Epicoat 834) and 40 parts by weight of bisphenol A type epoxy resin (Oilized shell epoxy, trade name Epicoat 828) were dissolved by heating in advance. ,
Then, after cooling to room temperature, 5 parts by weight of 2 ethyl 4-methyl imidazole (manufactured by Shikoku Kasei), 1 part by weight of 3-nitrophenylhydrazine (manufactured by Wako Pure Chemical Industries, reagent), 20 parts by weight of ethylcarbitol (manufactured by Wako Pure Chemical Industries, reagent) Part and butyl cellosolve (manufactured by Wako Pure Chemical Industries, reagent) 20 parts by weight are added and uniformly mixed to obtain a resin composition. 146 g of this resin composition is mixed with flake silver powder (manufactured by Tokuriki Kagaku Kenkyusho, trade name TCG-1). 11
0 g, 40 g of copper powder (manufactured by Fukuda Metal Foil Powder, trade name SPC4-8) and 35 g of alumina powder having an average particle size of 0.4 μm (manufactured by Sumitomo Chemical Co., Ltd., trade name AES-12), and a stirring mixer and An electrically conductive paste was obtained by uniformly dispersing it with three rolls.

【0012】次に上記で得た導電ペーストで厚さが1.
6mmで直径が0.8mm(φ)のスルーホールを形成
した紙フェノール銅張積層板(日立化成工業製、商品名
MCL−437F)に図1に示すテストパターンを印刷
すると共にこれをスルーホール1に充てんしたものを大
気中で60℃30分さらに160℃30分の条件で加熱
処理して配線板を得た。なお図1において2は紙フェノ
ール銅張積層板である。次に得られた配線板の抵抗を測
定した。その結果銅箔の抵抗を除いたスルーホール1の
抵抗は21mΩ/穴であり、隣り合うスルーホール間の
絶縁抵抗は108Ω以上であった。該配線板の冷熱衝撃
試験を実施した結果、スルーホール1の抵抗は25mΩ
/穴であった。また該配線板の湿中負荷試験を実施した
結果、スルーホール間の絶縁抵抗は108Ω以上であっ
た。なお、冷熱試験条件は125℃30分〜−65℃3
0分を100サイクル行い、湿中負荷試験は40℃90
%RH中、隣あうライン間に50Vの電圧を印加して1
000時間保持した。
Next, the conductive paste obtained above has a thickness of 1.
The test pattern shown in FIG. 1 is printed on a paper phenol copper clad laminate (Hitachi Chemical Co., Ltd., trade name MCL-437F) in which a through hole having a diameter of 6 mm and a diameter of 0.8 mm (φ) is formed. The wiring board was obtained by heat-treating the material filled in the above in the atmosphere under the conditions of 60 ° C. for 30 minutes and 160 ° C. for 30 minutes. In FIG. 1, 2 is a paper phenol copper clad laminate. Next, the resistance of the obtained wiring board was measured. As a result, the resistance of the through hole 1 excluding the resistance of the copper foil was 21 mΩ / hole, and the insulation resistance between adjacent through holes was 10 8 Ω or more. As a result of the thermal shock test of the wiring board, the resistance of the through hole 1 is 25 mΩ.
/ It was a hole. Moreover, as a result of performing a wet and medium load test on the wiring board, the insulation resistance between the through holes was 10 8 Ω or more. The cold heat test conditions are 125 ° C. 30 minutes to −65 ° C. 3
100 cycles of 0 minutes, 90 ° C for humidity and medium load test
Apply a voltage of 50V between adjacent lines during% RH to set 1
Hold for 000 hours.

【0013】実施例2 実施例1で得た樹脂組成物146gに実施例1で用いた
フレーク状銀粉を200g、銅粉を100g及びアルミ
ナ粉を60g加えて実施例1と同様の方法で均一に混合
分散して導電ペーストを得た。以下実施例1と同様の工
程を経て配線板を作製してその特性を評価した。その結
果、スルーホールの抵抗は19mΩ/穴であり、スルー
ホール間の絶縁抵抗は108Ω以上であった。また該配
線板の冷熱衝撃試験を実施した結果、スルーホールの抵
抗は23mΩ/穴であり、湿中負荷試験の結果では、ス
ルーホール間の絶縁抵抗は108Ω以上であった。
Example 2 To 146 g of the resin composition obtained in Example 1, 200 g of the flake silver powder used in Example 1, 100 g of copper powder and 60 g of alumina powder were added and homogenized in the same manner as in Example 1. A conductive paste was obtained by mixing and dispersing. A wiring board was manufactured through the same steps as in Example 1 and the characteristics thereof were evaluated. As a result, the resistance of the through holes was 19 mΩ / hole, and the insulation resistance between the through holes was 10 8 Ω or more. As a result of a thermal shock test of the wiring board, the resistance of the through holes was 23 mΩ / hole, and the result of the wet and medium load test showed that the insulation resistance between the through holes was 10 8 Ω or more.

【0014】実施例3 実施例1で得た樹脂組成物146gに実施例1で用いた
フレーク状銀粉を800g、銅粉を300g及びアルミ
ナ粉を70g加えて実施例1と同様の方法で均一に混合
分散して導電ペーストを得た。以下実施例1と同様の工
程を経て配線板を作製してその特性を評価した。その結
果、スルーホールの抵抗は19mΩ/穴であり、スルー
ホール間の絶縁抵抗は108Ω以上であった。また該配
線板の冷熱衝撃試験を実施した結果、スルーホールの抵
抗は22mΩ/穴であり、湿中負荷試験の結果では、ス
ルーホール間の絶縁抵抗は108Ω以上であった。
Example 3 To 146 g of the resin composition obtained in Example 1, 800 g of the flake silver powder used in Example 1, 300 g of copper powder and 70 g of alumina powder were added, and the same procedure as in Example 1 was performed. A conductive paste was obtained by mixing and dispersing. A wiring board was manufactured through the same steps as in Example 1 and the characteristics thereof were evaluated. As a result, the resistance of the through holes was 19 mΩ / hole, and the insulation resistance between the through holes was 10 8 Ω or more. As a result of the thermal shock test of the wiring board, the resistance of the through holes was 22 mΩ / hole, and the result of the wet and medium load test showed that the insulation resistance between the through holes was 10 8 Ω or more.

【0015】比較例1 実施例1で得た樹脂組成物146gに実施例1で用いた
フレーク状銀粉を1000g加えて実施例1と同様の方
法で均一に混合分散して導電ペーストを得た。以下実施
例1と同様の工程を経て配線板を作製してその特性を評
価した。その結果、スルーホールの抵抗は22mΩ/穴
であり、スルーホール間の絶縁抵抗は108Ω以上であ
った。また該配線板の冷熱衝撃試験を実施した結果、ス
ルーホールの抵抗は28mΩ/穴であり、湿中負荷試験
の結果では、スルーホール間の絶縁抵抗は配線板5枚の
うち1枚107Ω台に低下しているものがあった。
Comparative Example 1 To 146 g of the resin composition obtained in Example 1, 1000 g of the flake silver powder used in Example 1 was added and uniformly mixed and dispersed in the same manner as in Example 1 to obtain a conductive paste. A wiring board was manufactured through the same steps as in Example 1 and the characteristics thereof were evaluated. As a result, the resistance of the through holes was 22 mΩ / hole, and the insulation resistance between the through holes was 10 8 Ω or more. As a result of a thermal shock test of the wiring board, the resistance of the through hole was 28 mΩ / hole, and the result of the wet and medium load test showed that the insulation resistance between the through holes was 10 7 Ω per one of the five wiring boards. There was something that was falling on the table.

【0016】[0016]

【発明の効果】本発明になる導電ペーストは配線板にお
けるスルーホールの抵抗が低い高導電性のペーストであ
り、また湿中負荷試験後におけるスルーホール間の絶縁
抵抗の低下が小さく、さらにフレーク状銀粉、銅粉及び
セラミックス粉を併用することにより銀の使用量を少な
くできるなど経済的にも優れた導電ペーストである。
EFFECT OF THE INVENTION The conductive paste according to the present invention is a highly conductive paste having a low resistance of through holes in a wiring board, has a small decrease in insulation resistance between through holes after a humidity and medium load test, and has a flaky shape. By using silver powder, copper powder, and ceramics powder together, the amount of silver used can be reduced, which is an economically superior conductive paste.

【図面の簡単な説明】[Brief description of drawings]

【図1】紙フェノール銅張積層板に導電ペーストを印刷
すると共にスルーホールに充てんした状態を示す平面図
である。
FIG. 1 is a plan view showing a state in which a conductive paste is printed on a paper phenol copper clad laminate and the through holes are filled.

【符号の説明】[Explanation of symbols]

1 スルーホール 2 紙フェノール銅張積層板 1 Through hole 2 Paper phenol copper clad laminate

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 フレーク状銀粉、銅粉、セラミックス粉
及びニトロフェニルヒドラジン類を含む導電ペースト。
1. A conductive paste containing flaky silver powder, copper powder, ceramics powder and nitrophenylhydrazines.
JP12710093A 1993-05-28 1993-05-28 Conductive paste Pending JPH06338219A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12710093A JPH06338219A (en) 1993-05-28 1993-05-28 Conductive paste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12710093A JPH06338219A (en) 1993-05-28 1993-05-28 Conductive paste

Publications (1)

Publication Number Publication Date
JPH06338219A true JPH06338219A (en) 1994-12-06

Family

ID=14951598

Family Applications (1)

Application Number Title Priority Date Filing Date
JP12710093A Pending JPH06338219A (en) 1993-05-28 1993-05-28 Conductive paste

Country Status (1)

Country Link
JP (1) JPH06338219A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1032038A3 (en) * 1999-02-12 2002-07-24 National Starch and Chemical Investment Holding Corporation Conductive and resitive material with electrical stability for use in electronics devices
EP1231248A1 (en) * 2001-02-13 2002-08-14 National Starch and Chemical Investment Holding Corporation Conductive and resistive materials with electrical stability for use in electronics devices
WO2002089152A1 (en) * 2001-04-25 2002-11-07 National Starch And Chemical Investment Holding Corporation Conductive materials with electrical stability for use in electronics devices

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1032038A3 (en) * 1999-02-12 2002-07-24 National Starch and Chemical Investment Holding Corporation Conductive and resitive material with electrical stability for use in electronics devices
EP1231248A1 (en) * 2001-02-13 2002-08-14 National Starch and Chemical Investment Holding Corporation Conductive and resistive materials with electrical stability for use in electronics devices
WO2002089152A1 (en) * 2001-04-25 2002-11-07 National Starch And Chemical Investment Holding Corporation Conductive materials with electrical stability for use in electronics devices

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