JPH0945132A - Conducting paste - Google Patents
Conducting pasteInfo
- Publication number
- JPH0945132A JPH0945132A JP19029195A JP19029195A JPH0945132A JP H0945132 A JPH0945132 A JP H0945132A JP 19029195 A JP19029195 A JP 19029195A JP 19029195 A JP19029195 A JP 19029195A JP H0945132 A JPH0945132 A JP H0945132A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- composite layer
- silver composite
- resistance
- fine particles
- 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.)
- Granted
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 48
- 239000004332 silver Substances 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 abstract description 12
- 238000013508 migration Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000007747 plating Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000011246 composite particle Substances 0.000 abstract description 2
- 238000007772 electroless plating Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- DZCLVBQEPZQZNN-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1 DZCLVBQEPZQZNN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011889 copper foil 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
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気回路形成に適し
た導電ペーストに関する。TECHNICAL FIELD The present invention relates to a conductive paste suitable for forming an electric circuit.
【０００２】[0002]
【従来の技術】従来、プリント配線板、電子部品等の電
気回路（配線導体）を形成する方法として、電子材料、
１９９４年１０月号の４２〜４６頁に記載されているよ
うに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 of forming an electric circuit (wiring conductor) such as a printed wiring board or an electronic component, electronic materials,
A method of applying or printing a paste containing silver powder having excellent conductivity is generally known as described in October 1994, pages 42 to 46.
【０００３】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、電子部品等の電気回路や電極と
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、電気回路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回路間が短絡する
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含窒素化合物など
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
十分な効果の得られるものではなかった。Since the conductive paste using silver powder has good conductivity, it is used as an electric circuit or an electrode of a printed wiring board, an electronic component, etc. When an electric field is applied in a hot and humid atmosphere, these are used. However, there is a drawback in that electroplating of silver called migration occurs in an electric circuit or an electrode and a short circuit occurs between electrodes or between circuits. 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-containing compound to the conductive paste have been studied. It was not a sufficient effect.
【０００４】また、導通抵抗の良好な導体を得るには銀
粉の配合量を高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】[0005]
【発明が解決しようとする課題】請求項１記載の発明
は、マイグレーションが生ぜず、導電性に優れた導電ペ
ーストを提供するものである。請求項２記載の発明は、
請求項１記載の発明に加えて、さらに耐マイグレーショ
ン性に優れた導電ペーストを提供するものである。DISCLOSURE OF THE INVENTION The invention according to claim 1 provides a conductive paste which does not cause migration and is excellent in conductivity. The invention according to claim 2 is
In addition to the invention described in claim 1, a conductive paste further excellent in migration resistance is provided.
【０００６】[0006]
【課題を解決するための手段】本発明は、平均粒径が３
０μｍ以下の銅微粒子の表面に銀複合層が形成された導
電粉を含有してなる導電ペーストに関する。また、本発
明は、銀複合層が銀及びチタンを含む前記導電ペースト
に関する。The present invention has an average particle size of 3
The present invention relates to a conductive paste containing conductive powder in which a silver composite layer is formed on the surface of copper fine particles of 0 μm or less. The present invention also relates to the conductive paste, wherein the silver composite layer contains silver and titanium.
【０００７】[0007]
【発明の実施の形態】本発明における銅微粒子は主とし
て銅からなる微粒子で、平均粒径が３０μｍ以下、好ま
しくは１０μｍ以下とされ、３０μｍを超えると印刷性
が悪くなる。銅微粒子の形状は球形、りん片状、樹枝状
等のものが用いられ、このうち導電性を高くするにはり
ん片状又は樹枝状のものを用いることが好ましい。また
本発明における銀複合層とは、銀と他の金属とを含む、
合金層のことを意味し、銅微粒子の表面を被覆するため
に必要である。銀複合層は厚いほど導電性を高めやすい
がコストが高くなるので０．１〜１μｍ程度の厚さに被
覆すればよい。銀複合層は、例えば無電解めっき法、化
学還元法、置換めっき法、メカニカルアロイング法、メ
カノフュージョン法等の方法で銅微粒子の表面を被覆す
るようにして形成することができる。即ち、銅微粒子の
表面に、上記に示すような方法で銀複合層を形成するこ
とにより複合化することができる。銀複合層を形成する
金属はマイグレーションの抑制の点で銀とチタンを含む
複合粒子が好ましく、チタンの割合はマイグレーション
の抑制、導電性の向上の点で銀が９０〜９９．９重量％
に対しチタンが０．１〜１０重量％の範囲が好ましく、
銀が９５〜９９．５重量％に対しチタンが０．５〜５重
量％の範囲であればさらに好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The copper fine particles in the present invention are fine particles mainly made of copper and have an average particle diameter of 30 μm or less, preferably 10 μm or less, and when it exceeds 30 μm, the printability is deteriorated. The shape of the copper fine particles is spherical, scaly, dendritic, or the like. Among them, it is preferable to use scaly or dendritic ones to enhance conductivity. Further, the silver composite layer in the present invention contains silver and another metal,
It means an alloy layer and is necessary for coating the surface of the copper fine particles. The thicker the silver composite layer, the higher the conductivity, but the higher the cost. Therefore, the thickness of the silver composite layer may be about 0.1 to 1 μm. The silver composite layer can be formed by coating the surface of the copper fine particles by a method such as an electroless plating method, a chemical reduction method, a displacement plating method, a mechanical alloying method, or a mechanofusion method. That is, it is possible to form a composite by forming a silver composite layer on the surface of the copper fine particles by the method as described above. The metal forming the silver composite layer is preferably a composite particle containing silver and titanium from the viewpoint of suppressing migration, and the proportion of titanium is 90 to 99.9% by weight of silver from the viewpoint of suppressing migration and improving conductivity.
On the other hand, titanium is preferably in the range of 0.1 to 10% by weight,
It is more preferable that titanium is in the range of 0.5 to 5% by weight with respect to 95 to 99.5% by weight of silver.
【０００８】また平均粒径が３０μｍ以下の銅微粒子の
表面への銀複合層の被覆量は、導体の抵抗と経済性から
銀複合層が５〜３０重量％に対し銅微粒子が７０〜９５
重量％の範囲が好ましく、銀複合層が１０〜２５重量％
に対し銅微粒子が７５〜９０重量％の範囲であればさら
に好ましい。Further, the coating amount of the silver composite layer on the surface of the copper fine particles having an average particle size of 30 μm or less is 5 to 30% by weight of the silver composite layer and 70 to 95 of the copper fine particles due to the resistance and economy of the conductor.
The range of 10% by weight is preferable, and the silver composite layer is 10 to 25% by weight.
On the other hand, it is more preferable that the copper fine particles are in the range of 75 to 90% by weight.
【０００９】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、２エチル４メチルイミダゾー
ルなどの有機質の接着剤成分の硬化剤及び必要に応じて
テルピネオール、エチルカルビトール、カルビトールア
セテート、ブチルセロソルブ等の溶媒、ベンゾチアゾー
ル、ベンズイミダゾール等の腐食抑制剤、微小黒鉛粉末
などを含有する。接着剤成分及び溶媒の含有量は導電ペ
ーストに対して接着剤成分が１０〜２０重量％及び溶媒
が１０〜３５重量％の範囲であることが好ましい。また
平均粒径が３０μｍ以下の銅微粒子の表面に銀複合層が
形成された導電粉（以下銀複合層被覆銅微粒子とする）
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２０〜７５体積％であることが好ましく、３
０〜６５体積％であればさらに好ましい。本発明におい
て体積％とは各々の重量を密度で除して算出した体積ベ
ースの割合を示す。In addition to the above-mentioned materials, the conductive paste is a curing agent for an organic adhesive component such as liquid epoxy resin, phenol resin, unsaturated polyester resin, etc., and an organic adhesive component such as 2 ethyl 4-methylimidazole, and if necessary. It contains a solvent such as terpineol, ethyl carbitol, carbitol acetate and butyl cellosolve, a corrosion inhibitor such as benzothiazole and benzimidazole, and fine graphite powder. The content of the adhesive component and the solvent is preferably in the range of 10 to 20% by weight of the adhesive component and 10 to 35% by weight of the solvent with respect to the conductive paste. Conductive powder having a silver composite layer formed on the surface of copper fine particles having an average particle diameter of 30 μm or less (hereinafter referred to as silver composite layer-coated copper fine particles)
The content of is preferably 20 to 75% by volume from the resistance and economy of the conductor with respect to the solid content of the conductive paste.
More preferably, it is 0 to 65% by volume. In the present invention, the term “% by volume” indicates a volume-based ratio calculated by dividing each weight by the density.
【００１０】[0010]
【実施例】以下本発明の実施例を説明する。 実施例１ 平均粒径が６μｍで最大径が２０μｍの略球形銅微粒子
５００ｇを濃度１規定の塩酸中で３分間表面処理した。
ついでこの略球形銅微粒子を水洗した後、硝酸銀及びチ
タン微粉末を水２リットル中にそれぞれ１６０ｇ及び８
ｇを添加し、撹拌して分散化させながら水溶液をガスバ
ーナーで弱く加熱する置換めっき法により、銀を該銅微
粒子の表面に０．５μｍの厚さに銀めっきして銀複合層
被覆銅微粒子を得た。この銀複合層にはチタン微粉末が
１重量％含有していた。EXAMPLES Examples of the present invention will be described below. Example 1 500 g of substantially spherical copper fine particles having an average particle diameter of 6 μm and a maximum diameter of 20 μm were surface-treated in hydrochloric acid having a concentration of 1 N for 3 minutes.
Next, after washing the substantially spherical copper fine particles with water, 160 g and 8 g of silver nitrate and titanium fine powder were added in 2 liters of water, respectively.
silver is coated on the surface of the copper fine particles to a thickness of 0.5 μm by a displacement plating method in which an aqueous solution is heated weakly with a gas burner while adding g and stirring to disperse the silver composite layer-coated copper fine particles. Got This silver composite layer contained 1% by weight of titanium fine powder.
【００１１】一方、レゾール系フェノール樹脂（自家
製、非売品）８０ｇ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(株)製、商品名エピコート１０
０７）２０ｇにエチルカルビトール（試薬）１２０ｇを
加え均一に混合して樹脂組成物とし、これに上記で得た
銀複合層被覆銅微粒子を４４０ｇ加えて撹拌らいかい機
及び３本ロールで均一に混合分散して導電ペーストを得
た。なお銀複合層と銅微粒子の割合は、銀複合層が２０
重量％及び銅微粒子は８０重量％であった。また銀複合
層被覆銅微粒子は導電ペーストの固形分に対して３４体
積％含有していた。On the other hand, 80 g of resole phenolic resin (home-made, not for sale) and bisphenol A type epoxy resin (Yukaka Shell Epoxy Co., Ltd., trade name Epicoat 10)
07) 120 g of ethyl carbitol (reagent) was added to 20 g of the mixture and mixed uniformly to form a resin composition. To this was added 440 g of the silver composite layer-coated copper fine particles, and the mixture was stirred uniformly with a stirrer and a triple roll mill. A conductive paste was obtained by mixing and dispersing. The ratio of the silver composite layer and the copper fine particles is 20 in the silver composite layer.
The weight% and the copper fine particles were 80% by weight. Further, the silver composite layer-coated copper fine particles were contained in an amount of 34% by volume based on the solid content of the conductive paste.
【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(株)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。次いで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
２２ｍΩ／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℃３０分を１００サイクル行い、湿中負荷試験は４
０℃９０％ＲＨ中、隣り合うライン間に５０Ｖの電圧を
印加して１０００時間保持した。Next, using the conductive paste obtained above, a paper phenol copper clad laminate having a thickness of 1.6 mm and a through hole having a diameter of 0.8 mm (φ) (manufactured by Hitachi Chemical Co., Ltd., product 1 MCL-437F) was printed with the test pattern shown in FIG. 1 and the through hole 1 was filled with the test pattern and heated in the atmosphere at 60 ° C. for 30 minutes and then at 160 ° C. for 30 minutes to obtain a wiring board. . In FIG. 1, 2 is a paper phenol copper clad laminate. Then, 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 was 22 mΩ / 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 condition is 125 ° C. for 30 minutes.
100 cycles of 65 ° C. for 30 minutes, 4 in humidity and medium load test
A voltage of 50 V was applied between adjacent lines in 0 ° C. 90% RH, and the voltage was held for 1000 hours.
【００１３】実施例２ 実施例１で得た樹脂組成物２２０ｇに実施例１で得た銀
複合層被覆銅微粒子を３９０ｇ加えた後、撹拌らいかい
機及び３本ロールで均一に混合して導電ペーストを得
た。以下実施例１と同様の工程を得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
２０ｍΩ／穴であり、スルーホール間の絶縁抵抗は１０
8Ω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。なお銀複合層中にはチタン微粉
末が１．５重量％含有していた。また銀複合層被覆銅微
粒子は導電ペーストの固形分に対して３０体積％含有し
ていた。Example 2 To 220 g of the resin composition obtained in Example 1, 390 g of the silver composite layer-coated copper fine particles obtained in Example 1 was added, and then uniformly mixed with a stirrer and a three-roll mill to conduct electricity. I got a paste. The same steps as those in Example 1 were obtained below to fabricate a wiring board and evaluate its characteristics. As a result, the resistance of the through holes is 20 mΩ / hole, and the insulation resistance between the through holes is 10 mΩ.
It was more than 8 Ω. As a result of a thermal shock test of the wiring board, the resistance of the through hole was 23 mΩ / hole,
As a result of the wet and medium load test, the insulation resistance between the through holes was 10 8 Ω or more. The fine silver powder was contained in the silver composite layer in an amount of 1.5% by weight. Further, the silver composite layer-coated copper fine particles were contained in an amount of 30% by volume based on the solid content of the conductive paste.
【００１４】実施例３ チタン微粉末を添加しない以外は実施例１のめっき法と
同様な方法で０．３μｍの厚さに銀めっきした銀被覆銅
微粒子８００ｇをチタン微粉末１０ｇ及びジルコニアボ
ールと共にボールミルに投入し、１００時間回転させて
均一に分散した後、振動ミルで１０時間処理して銀複合
層被覆銅微粒子８１０ｇを得た。この後実施例１で得た
樹脂組成物２２０ｇに上記の銀複合層被覆銅微粒子を７
８０ｇ加えた後、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１２ｍΩ／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１４ｍΩ／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。なお
この銀複合層中にはチタン５重量％含有しており、その
形状は振動ミルの処理でりん片状に変形していた。また
銀複合層と銅微粒子の割合は、銀複合層が１０重量％及
び銅微粒子は９０重量％であった。さらに銀複合層被覆
銅微粒子は導電ペーストの固形分に対して４７体積％含
有していた。Example 3 800 g of silver-coated copper fine particles silver-plated to a thickness of 0.3 μm by the same method as the plating method of Example 1 except that titanium fine powder was not added, together with 10 g of titanium fine powder and zirconia balls, were ball-milled. The mixture was placed in a flask and rotated for 100 hours to be uniformly dispersed, and then treated with a vibration mill for 10 hours to obtain 810 g of silver composite layer-coated copper fine particles. Thereafter, 220 g of the resin composition obtained in Example 1 was mixed with 7 g of the above-mentioned silver composite layer-coated copper fine particles.
After adding 80 g, the mixture was 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 12 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 14 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. The silver composite layer contained 5% by weight of titanium, and its shape was transformed into a scaly shape by treatment with a vibration mill. The ratio of the silver composite layer and the copper fine particles was 10% by weight for the silver composite layer and 90% by weight for the copper fine particles. Further, the silver composite layer-coated copper fine particles were contained in an amount of 47% by volume based on the solid content of the conductive paste.
【００１５】比較例１ 実施例１で得た樹脂組成物２２０ｇにフレーク状の銀粉
（徳力化学研究所製、商品名ＴＣＧ−１）を３８０ｇ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１５ｍΩ／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１７ｍΩ／
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４枚が１０6Ω以下に低下
していた。Comparative Example 1 To 220 g of the resin composition obtained in Example 1 was added 380 g of flake-shaped silver powder (TCG-1 manufactured by Tokuriki Kagaku Kenkyusho), and the mixture was uniformly mixed and dispersed in the same manner as in Example 1. A conductive paste was obtained. 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 15 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 17 mΩ /
According to the results of the humidity and medium load test, the insulation resistance between the through holes was reduced to 10 6 Ω or less in four of the five wiring boards.
【００１６】比較例２ 実施例１で得た樹脂組成物２２０重量部に実施例３で得
た銀被覆微粒子を３５０ｇ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１８ｍΩ／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１９ｍΩ／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３枚が１０6Ω以下に低下していた。Comparative Example 2 To 220 parts by weight of the resin composition obtained in Example 1, 350 g of the silver-coated fine particles obtained in Example 3 was added and uniformly mixed and dispersed in the same manner as in Example 1 to obtain a conductive paste. It was 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 18 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 hole was 19 mΩ / hole. According to the result of the wet and medium load test, the insulation resistance between the through holes was 10 6 for 3 out of 5 wiring boards. It was below Ω.
【００１７】[0017]
【発明の効果】請求項１における導電ペーストは、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、また高価な銀の配合量を少
なくすことができるので耐マイグレーション性を改善で
きるなど経済的にも優れた導電ペーストである。請求項
２における導電ペーストは、請求項１における導電ペー
ストの効果を奏し、さらに耐マイグレーション性に優れ
る。The conductive paste according to claim 1 is a highly conductive paste having a low resistance of through holes in a wiring board, a decrease in insulation resistance between through holes after a humidity and medium load test is small, and it is expensive. The conductive paste is economically excellent in that the migration resistance can be improved because the blending amount of silver can be reduced. The conductive paste according to claim 2 has the effect of the conductive paste according to claim 1, and is further excellent in migration resistance.
【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】 １ スルーホール ２ 紙フェノール銅張積層板[Explanation of symbols] 1 Through hole 2 Paper phenol copper clad laminate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/09 7511−4Ｅ Ｈ０５Ｋ 1/09 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication H05K 1/09 7511-4E H05K 1/09 A
Claims (2)
面に銀複合層が形成された導電粉を含有してなる導電ペ
ースト。1. A conductive paste containing a conductive powder having a silver composite layer formed on the surface of copper fine particles having an average particle diameter of 30 μm or less.
記載の導電ペースト。2. The silver composite layer comprises silver and titanium.
The conductive paste described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19029195A JP3596563B2 (en) | 1995-07-26 | 1995-07-26 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19029195A JP3596563B2 (en) | 1995-07-26 | 1995-07-26 | Conductive paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0945132A true JPH0945132A (en) | 1997-02-14 |
| JP3596563B2 JP3596563B2 (en) | 2004-12-02 |
Family
ID=16255732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19029195A Expired - Lifetime JP3596563B2 (en) | 1995-07-26 | 1995-07-26 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3596563B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7169330B2 (en) | 2004-02-25 | 2007-01-30 | E. I. Du Pont De Nemours And Company | Composition of conductive paste |
| CN108202873A (en) * | 2016-12-20 | 2018-06-26 | 波音公司 | For the conductive fastening system of composite construction |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11137014B2 (en) | 2019-01-08 | 2021-10-05 | The Boeing Company | Conductive fastening system and method for improved EME performance |
-
1995
- 1995-07-26 JP JP19029195A patent/JP3596563B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7169330B2 (en) | 2004-02-25 | 2007-01-30 | E. I. Du Pont De Nemours And Company | Composition of conductive paste |
| CN108202873A (en) * | 2016-12-20 | 2018-06-26 | 波音公司 | For the conductive fastening system of composite construction |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3596563B2 (en) | 2004-12-02 |
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