JPH11310806A - Production of copper-silver composite powder for electrically conductive paste - Google Patents
Production of copper-silver composite powder for electrically conductive pasteInfo
- Publication number
- JPH11310806A JPH11310806A JP10118390A JP11839098A JPH11310806A JP H11310806 A JPH11310806 A JP H11310806A JP 10118390 A JP10118390 A JP 10118390A JP 11839098 A JP11839098 A JP 11839098A JP H11310806 A JPH11310806 A JP H11310806A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- copper
- silver
- weight
- conductive 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 176
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 92
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 66
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 46
- 238000010298 pulverizing process Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 40
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 28
- 239000000194 fatty acid Substances 0.000 claims abstract description 28
- 229930195729 fatty acid Natural products 0.000 claims abstract description 28
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 28
- 230000007935 neutral effect Effects 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 20
- 239000004332 silver Substances 0.000 abstract description 20
- 238000004438 BET method Methods 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000004925 Acrylic resin Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000007650 screen-printing Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 235000021313 oleic acid Nutrition 0.000 description 4
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 230000010485 coping Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電ペースト用銅
銀複合粉の製造方法に関するものである。The present invention relates to a method for producing a copper-silver composite powder for a conductive paste.
【０００２】[0002]
【従来の技術】一般にポリマー型導電ペーストと言え
ば、導電性金属粉である銅粉あるいは銀粉を合成樹脂バ
インダーに分散させたタイプが主流である。これら導電
ペーストはプリント基板のスルーホールや導電回路、電
極の接着剤、電磁波シールド用等に多量に使用されてい
る。しかし、銅粉を分散したものは安価であるが銀のよ
うな優れた導電性を得ることが難しく、また酸化により
導電性が悪化し易い。2. Description of the Related Art In general, a polymer type conductive paste is mainly of a type in which copper powder or silver powder, which is conductive metal powder, is dispersed in a synthetic resin binder. These conductive pastes are used in large quantities for through holes in printed circuit boards, conductive circuits, adhesives for electrodes, electromagnetic wave shielding, and the like. However, the one in which copper powder is dispersed is inexpensive, but it is difficult to obtain excellent conductivity like silver, and the conductivity is easily deteriorated by oxidation.
【０００３】これらの問題を解決するために「導電性銅
ペースト」（特許番号第２６５４０６７号公報）が提案
されているが、銅粉を還元しながらペースト化するもの
であり還元性樹脂を使用する必要が有る等多くの制約が
あり、一般の樹脂や用途に対応出来るものでない。銀粉
を使用したものは優れた導電性が得られるものの、高価
格でありマイグレーションの問題が発生し易い。これら
の理由で銅粉に銀メッキした銅粉「銀めっき銅粉」（特
開平９−２８２９３５号公報）、銀メッキ銅粉を分散し
たペースト「導電性接着剤」（特開平７−１３８５４９
号公報）等が提案されている。[0003] In order to solve these problems, "conductive copper paste" (Japanese Patent No. 2654067) has been proposed, but it is used to form a paste while reducing copper powder, and a reducing resin is used. There are many restrictions such as necessity, and it cannot be used for general resins and applications. Although the use of silver powder provides excellent conductivity, it is expensive and tends to cause migration problems. For these reasons, copper powder silver-plated on copper powder “silver-plated copper powder” (Japanese Patent Application Laid-Open No. 9-282935), and paste “conductive adhesive” in which silver-plated copper powder is dispersed (Japanese Patent Application Laid-Open No. 7-138549)
And the like have been proposed.
【０００４】しかし、銀メッキ銅粉はメッキ液の廃液の
処理、粒子径の細かい比表面積の大きな粉にメッキ処理
するのは難しい等の問題を有している。銅合金粉の粒子
表面への銀濃度を高くした銅銀合金粉を使用したペース
ト「はんだ付け可能な銅系導電性ペースト」（特公平７
−１０９７２４号公報）が提案されているが、不活性ガ
スアトマイズ法で製造した金属粉を使用しているためや
はり高価であり、粒子径の小さい粉末では表面近傍と内
部の銀濃度に差がなくなる傾向がある。さらにアトマイ
ズ法では導電ペーストに使用できるような細かい粉を製
造するのが難しい。最近では電子機器の小型化傾向によ
り、吹き付け塗装法あるいはロールコータ法、スクリー
ン印刷法による電磁波シールド用途では、より塗装し易
く、かつ薄い塗膜が必要となってきた。また、スクリー
ン印刷方法による導電回路やジャンパー線では、より細
線パターンに対応出来る導電ペーストが要求されてきて
いる。ディスペンサーによる導電接着剤用途も部品の小
型化により接着面積が微細化し、より細かい粒子を分散
した導電ペーストが必要になってきている。However, silver-plated copper powder has problems that it is difficult to treat a waste liquid of a plating solution and to plate a powder having a small particle diameter and a large specific surface area. “Solderable copper-based conductive paste” using copper-silver alloy powder with increased silver concentration on the surface of copper alloy powder particles
JP-A-109724) has been proposed, but it is still expensive because metal powder produced by an inert gas atomization method is used, and there is a tendency that there is no difference between the silver concentration in the vicinity of the surface and the silver concentration in the inside of a powder having a small particle diameter. There is. Further, it is difficult to produce a fine powder that can be used for a conductive paste by the atomizing method. Recently, due to the trend of miniaturization of electronic devices, it has become necessary to use a spray coating method, a roll coater method, and a screen printing method for electromagnetic wave shielding applications that require a thinner coating film that is easier to apply. In the case of a conductive circuit or a jumper wire formed by a screen printing method, a conductive paste capable of coping with a finer line pattern has been required. For conductive adhesive applications using dispensers, the bonding area has been reduced due to the downsizing of components, and a conductive paste in which finer particles are dispersed has become necessary.
【０００５】[0005]
【発明が解決しようとする課題】従来まで導電ペースト
用に使用されてきた金属粉は、銀粉が主である。それ
は、優れた導電性が容易に得られるとともに信頼性にお
いて安定した性能が得られるためである。しかし銀粉は
高価であるとともに、回路の線間が狭くなればなるほど
マイグレーションの問題が発生し易く、新しい導電性金
属粉が待たれていた。銅粉に銀をメッキしたものや、表
面の銀濃度を高くしたものなどが新規な導電性金属粉と
して提案されてきたが、いずれも製造法上粒子径の小さ
いものが出来ず、最近の電子機器の小型化に対応できな
いものであった。すなわち、銀粉は粒子径を細かくして
も、また機械的に片状加工しても酸化の問題がほとんど
ないため、通常ペーストに使用している銀粉の粒子径は
細かい物が多い。The metal powder which has hitherto been used for the conductive paste is mainly silver powder. This is because excellent conductivity is easily obtained and stable performance in reliability is obtained. However, silver powder is expensive and migration problems are more likely to occur as the lines between circuits become narrower, and new conductive metal powders have been awaited. Copper powder plated with silver and silver with a high silver concentration on the surface have been proposed as new conductive metal powders. It could not cope with downsizing of equipment. That is, even if the silver powder has a small particle diameter or is mechanically flaked, there is almost no problem of oxidation. Therefore, the silver powder usually used in the paste often has a small particle diameter.
【０００６】しかし、銀メッキ銅粉は、メッキする粒子
径を細かくすると均一にメッキが出来ず、さらに形状が
片状であると銅粉表面に付着している油脂や比表面積が
大きすぎるために、均一にメッキする事が非常に難しく
なる。これら製造上の理由から、工業的に銀メッキは荒
い粒子しか行われていない。銀メッキ銅粉と類似の形態
の細かい粉末、あるいは片状でも導電性が得られれば、
薄膜化、塗膜外観の平滑性など最近のペーストに要求さ
れる性能をかなりの部分で満足させることができ、銀粉
の代わりに使用出来る。しかし、これまで銀の効果を十
分に生かしたこの様な特性を有する粉末はまだ見いだせ
ていない。そこで、本発明者等はポリマー型導電ペース
ト用として最近の塗装・印刷技術に対応出来る銅銀粉の
製造方法について研究を重ねた結果、銅粉に酸化銀を機
械的に接合して、その後還元性雰囲気中で低温還元処理
すれば、銅粉の表面に銀を多く含有した、銀に近い導電
性能を示す、細かい銅銀複合粉が出来ることを見いだし
た。However, silver-plated copper powder cannot be uniformly plated if the particle diameter to be plated is small, and if the shape is flake-like, the fat or oil or the specific surface area adhering to the surface of the copper powder is too large. It is very difficult to plate uniformly. For these manufacturing reasons, silver plating is industrially performed with only coarse particles. If fine powder of similar form to silver-plated copper powder, or even flakes can obtain conductivity,
The performance required for recent pastes such as thinning and smoothness of the coating film appearance can be satisfied to a large extent, and can be used instead of silver powder. However, a powder having such characteristics, which makes full use of the effect of silver, has not been found yet. Accordingly, the present inventors have conducted research on a method of producing copper-silver powder capable of coping with recent coating and printing techniques for polymer-type conductive paste, and as a result, silver oxide was mechanically bonded to copper powder, and then reduced. It has been found that, when a low-temperature reduction treatment is performed in an atmosphere, a fine copper-silver composite powder containing a large amount of silver on the surface of the copper powder and having a conductive property close to that of silver can be formed.
【０００７】[0007]
【課題を解決するための手段】本発明に関する導電ペー
スト用銅銀複合粉の製造方法とは、銅粉に対して３〜５
０重量％の酸化銀を加え、粉砕機にて粉砕加工しながら
銅粉に酸化銀を接合せしめる。目的とする大きさまで粉
砕加工した後、還元性雰囲気中で１２０〜４００℃の温
度で還元処理する。その後篩などで、粒子径が100μｍ
以下になるように調整し，ＢＥＴ法比表面積値が２００
０ｃｍ2／ｇ以上の銅銀複合粉を得ることを特徴とする
ものである。銅粉に酸化銀を機械的に接合せしめた後
に、０．１〜２重量％の脂肪酸を混合被覆し、還元性雰
囲気中で１５０〜５００℃の温度で還元処理する方法
は、脂肪酸の存在により、還元処理中の粉末凝集防止の
効果が有る。還元処理時間が長く必要であり、脂肪酸が
多く残留しないように処理する必要が有るが、分散性の
良い比表面積の大きい、細かい銅銀複合粉を容易に製造
することが出来る。また、粉砕加工する粉末に対して１
重量％以下の脂肪酸を添加し、粉砕加工しながら機械的
に銅粉に酸化銀を接合せしめ、しかる後に還元性雰囲気
中で１５０〜５００℃の温度で還元処理すると、片状の
形状の導電ペースト用銅銀複合粉を容易に製造すること
が出来る。The method for producing a copper-silver composite powder for a conductive paste according to the present invention is as follows.
0% by weight of silver oxide is added, and silver oxide is bonded to the copper powder while being pulverized by a pulverizer. After pulverizing to a desired size, reduction treatment is performed at a temperature of 120 to 400 ° C. in a reducing atmosphere. Then, with a sieve or the like, the particle size is 100 μm
The BET specific surface area was adjusted to 200 or less.
A copper-silver composite powder of 0 cm 2 / g or more is obtained. A method of mechanically bonding silver oxide to copper powder, mixing and coating 0.1 to 2% by weight of a fatty acid, and performing a reduction treatment in a reducing atmosphere at a temperature of 150 to 500 ° C depends on the presence of the fatty acid. This has the effect of preventing powder agglomeration during the reduction treatment. Although a long reduction treatment time is required and it is necessary to perform treatment so that a large amount of fatty acid does not remain, a fine copper-silver composite powder having a good specific surface area with good dispersibility can be easily produced. In addition, 1
% By weight or less fatty acid is added, silver oxide is mechanically bonded to copper powder while pulverizing, and then reduced at a temperature of 150 to 500 ° C. in a reducing atmosphere. Copper-silver composite powder can be easily manufactured.
【０００８】[0008]
【発明の実施の形態】本発明の構成を詳しく説明すれば
次の通りである。本発明の出発原料である銅粉は、硫酸
銅の水溶液から電解法により析出した電解銅粉、水・ガ
ス・空気などで噴霧回収したアトマイズ銅粉、銅の酸化
物を高温還元した還元銅粉などが使用可能である。溶液
還元法などによって得られる細かい銅粉は、経済的にも
また本発明の効果の点からも好ましくない。酸化銀は、
例えば硝酸銀に水酸化ナトリウムを加え沈殿乾燥して得
られる、Ａｇ2Ｏで表示される黒い粉末である。一般に
市販されている酸化銀の粒子径は０．５〜２μｍと銅粉
に比較すると非常に細かい。同じような粒径でも銀粉だ
と、粉砕加工中に銀粉同士が凝集したり、銀粉自体が銅
粉よりも展延加工され大きな片状粉となるため、本発明
のような形態の銅銀複合粉とならない。銅粉に加える酸
化銀の量は、銅粉に対して３〜５０重量％が良い。３重
量％より少ないと銀粉に近い導電性や導電ペーストとし
ての信頼性が得られない。５０重量％よりも多いと、酸
化銀を銀に還元する時間が長くなり、銀粉とも価格的に
差がなくなり、またマイグレーションも少なくならず、
好ましくない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The construction of the present invention will be described in detail as follows. Copper powder, which is a starting material of the present invention, is an electrolytic copper powder precipitated by an electrolytic method from an aqueous solution of copper sulfate, an atomized copper powder spray-recovered with water, gas, air, or the like, and a reduced copper powder obtained by reducing copper oxide at a high temperature. Etc. can be used. Fine copper powder obtained by the solution reduction method or the like is not preferable from the viewpoint of economy and the effect of the present invention. Silver oxide is
For example, it is a black powder represented by Ag 2 O obtained by adding sodium hydroxide to silver nitrate and drying by precipitation. In general, the particle size of commercially available silver oxide is 0.5 to 2 μm, which is extremely fine as compared with copper powder. Even with the same particle size, if it is silver powder, the silver powder agglomerates during the pulverization process, or the silver powder itself is spread more than the copper powder and becomes a large flaky powder. Does not become powder. The amount of silver oxide added to the copper powder is preferably 3 to 50% by weight based on the copper powder. If it is less than 3% by weight, the conductivity close to that of silver powder and the reliability as a conductive paste cannot be obtained. If the content is more than 50% by weight, the time required to reduce silver oxide to silver becomes longer, the price does not differ from silver powder, and migration does not decrease.
Not preferred.
【０００９】粉砕加工しながら機械的に銅粉に酸化銀を
接合せしめる方法は、ボールミル、振動ミル、アジテー
タミル、デイスクミル、などの粉砕機を使用して、粉砕
機中で粉砕加工しながら銅粉に酸化銀を物理的に接合さ
せれば良い。粉砕機の種類や粉砕時間を調整する事によ
り、目的とする粒子径、目的とするＢＥＴ法比表面積値
を有する銅銀複合粉を製造することが出来る。銅粉に酸
化銀を接合させる工程において、脂肪酸は出来るだけ少
ない方がうまく接合させることが出来るので良い。しか
し、粉砕加工中に粉体が細かくなり凝集してきた場合や
出発原料が細かい時などには、粉砕加工する粉末に対し
て１重量％以下の脂肪酸を添加すれば良い。１重量％よ
り多いと銅粉に酸化銀がうまく接合出来ず、還元処理後
銅粉と銀粉が分離することが起こる。A method of mechanically bonding silver oxide to copper powder while pulverizing is performed by using a pulverizer such as a ball mill, a vibration mill, an agitator mill, and a disk mill while pulverizing copper in a pulverizer. The silver oxide may be physically bonded to the powder. By adjusting the type of the pulverizer and the pulverization time, a copper-silver composite powder having a target particle diameter and a target BET specific surface area can be produced. In the step of bonding silver oxide to the copper powder, it is preferable that the amount of fatty acid is as small as possible, because the bonding can be performed well. However, when the powder becomes fine and agglomerated during the pulverizing process or when the starting material is fine, the fatty acid may be added in an amount of 1% by weight or less based on the powder to be pulverized. If the amount is more than 1% by weight, silver oxide cannot be bonded to the copper powder well, and the copper powder and the silver powder are separated after the reduction treatment.
【００１０】一方、粉砕加工中に少量の脂肪酸を添加す
ることは、片状の銅銀複合粉を製造することが出来る。
銀が銅粉に分散した本発明の片状粉は全く新規な導電性
金属粉であり、平滑な塗膜や銀に近い導電性能が得られ
る。本発明の特徴の一つは、銅粉に酸化銀を粉砕加工し
て接合した粉体を低温で還元処理して、酸化銀を金属銀
にすることにある。しかし、還元処理中に酸化銀は隣の
粒子と凝集する傾向がある。特に粒子径が細かく、比表
面積が大きく、また銅粉の表面に酸化銀が多く存在すれ
ばするほど凝集が生じやすい。低温で長時間注意深く処
理する方法であれば還元処理中の凝集の問題はない。On the other hand, by adding a small amount of fatty acid during the pulverizing process, a flaky copper-silver composite powder can be produced.
The flaky powder of the present invention in which silver is dispersed in copper powder is a completely novel conductive metal powder, and can provide a smooth coating film and a conductive property close to silver. One of the features of the present invention is that silver oxide is converted into metallic silver by subjecting a powder obtained by pulverizing silver oxide to copper powder to a reduction treatment at a low temperature. However, silver oxide tends to agglomerate with neighboring grains during the reduction treatment. In particular, the finer the particle diameter, the larger the specific surface area, and the more silver oxide is present on the surface of the copper powder, the more the aggregation tends to occur. There is no problem of agglomeration during the reduction treatment if the method is carried out carefully at a low temperature for a long time.
【００１１】しかし、工業的には還元処理の前に０．１
〜２重量％の脂肪酸を混合被覆すれば、脂肪酸を飛散す
るのに還元時間が少し長くなるが還元処理中の凝集を少
なくすることが出来る。脂肪酸を混合被覆する方法はミ
キサーなどの混合機で、脂肪酸と粉末を機械的に混合す
れば良い。本発明で使用する脂肪酸はラウリン酸、パル
ミチン酸、ステアリン酸、オレイン酸など高級脂肪酸が
良い。低級脂肪酸は粉砕加工後あるいは還元処理中に悪
臭が出るため好ましくない。還元性雰囲気は、水素、一
酸化炭素、天然ガス、アンモニア分解ガスなど還元性気
体を流す方法が良い。However, industrially, 0.1% is required before the reduction treatment.
If the fatty acid is mixed and coated with ２2% by weight, the reduction time is slightly longer for scattering the fatty acid, but the aggregation during the reduction treatment can be reduced. The fatty acid may be mixed and coated by mechanically mixing the fatty acid and the powder with a mixer such as a mixer. The fatty acids used in the present invention are preferably higher fatty acids such as lauric acid, palmitic acid, stearic acid and oleic acid. Lower fatty acids are not preferred because they give off a bad smell after the pulverization or during the reduction treatment. As the reducing atmosphere, a method of flowing a reducing gas such as hydrogen, carbon monoxide, natural gas, or ammonia decomposition gas is preferable.
【００１２】還元処理する温度は、理論的には銅粉に接
合した酸化銀が還元できる以上の温度であれば良い。そ
れは１００℃よりも高い温度であれば酸化銀は還元を開
始するが、導電ペースト用粉末としてはベースとなる銅
粉の表面酸化膜も少ない方がよく、また酸化銀も十分に
還元する必要がある。導電ペースト用複合粉として還元
条件を検討した結果、本発明の還元温度は１２０〜４０
０℃が良いことが判明した。それよりも低い温度である
と還元に非常に長時間かかるとともに、酸化銀の一部は
還元するが未還元の酸化銀や銅粉に多くの酸化膜が存在
し、本発明の目的とする優れた導電性を有する銅銀複合
粉が得られない。４００℃より高い温度であると還元処
理中に粉末が凝集するため、分散不良を起こすとともに
導電性も悪くなる。脂肪酸を粉砕加工後に混合被覆、あ
るいは粉砕加工中に少量添加した場合は、還元温度を少
し高くする必要がある。脂肪酸が存在する場合は１５０
〜５００℃で還元処理するのが好ましい。本発明の導電
ペースト用銅銀複合粉としては、脂肪酸の最終含有量は
少ない方が好ましい。脂肪酸が不純物として存在する
と、反応硬化するある種のエポキシ樹脂では硬化時間が
変化したり、塗膜物性を変化したり、また表面に残留し
た脂肪酸が導電性の悪化の原因にもなる。The temperature for the reduction treatment is theoretically sufficient as long as the silver oxide bonded to the copper powder can be reduced. If the temperature is higher than 100 ° C., silver oxide starts to be reduced, but as a conductive paste powder, it is better that the surface oxide film of the copper powder as a base is small, and it is necessary to sufficiently reduce silver oxide. is there. As a result of examining the reduction conditions for the composite powder for the conductive paste, the reduction temperature of the present invention was 120 to 40.
0 ° C. proved to be good. If the temperature is lower than that, it takes a very long time to reduce, and a part of silver oxide is reduced but many oxide films are present on unreduced silver oxide or copper powder, which is an object of the present invention. A copper-silver composite powder having poor conductivity cannot be obtained. If the temperature is higher than 400 ° C., the powder agglomerates during the reduction treatment, so that poor dispersion is caused and conductivity is deteriorated. If the fatty acid is mixed and coated after the pulverization, or if a small amount is added during the pulverization, it is necessary to raise the reduction temperature slightly. 150 if fatty acids are present
It is preferable to carry out the reduction treatment at ~ 500 ° C. The copper-silver composite powder for a conductive paste of the present invention preferably has a lower final fatty acid content. When a fatty acid is present as an impurity, the curing time of a certain type of epoxy resin that is reactively hardened, the physical properties of the coating film are changed, and the fatty acid remaining on the surface causes deterioration of conductivity.
【００１３】従って、出来るだけ脂肪酸は飛散し、残留
しないように還元条件を決める必要が有る。還元処理し
た銅銀複合粉は、粉砕加工中に展延加工された粗大粉
や、還元処理中に再凝集した粗大粉を多く含んでいる場
合がある。従って、還元処理後１００μｍで篩分する必
要がある。１００μｍよりも荒い粉が有るとペーストと
して使用した場合、スクリーンの目詰まりを生じる。篩
分方法は篩や風力分級機を使用すればよい。目的とする
ＢＥＴ法比表面積値を有する複合粉を得るためには、粉
砕機を選定し、粉砕加工時間等を調整すれば良い。優れ
た導電ペースト用複合粉としては比表面積値を２０００
ｃｍ2／ｇ以上にする必要がある。２０００ｃｍ2／ｇよ
りも小さい値だと、導電性やペーストの粘度特性などが
悪くなる。最近のスクリーン印刷法で使用する場合に要
求されている性能は、粒子径が４５μｍ以下であって、
ＢＥＴ法比表面積値は３０００ｃｍ2／ｇ以上の細かい
粉が好まれている。Therefore, it is necessary to determine the reducing conditions so that fatty acids are scattered as much as possible and do not remain. The copper-silver composite powder that has been subjected to the reduction treatment may contain a large amount of coarse powder that has been spread during the pulverization process or a large amount of coarse powder that has re-agglomerated during the reduction treatment. Therefore, it is necessary to sieve at 100 μm after the reduction treatment. If a powder having a coarseness of more than 100 μm is used as a paste, screen clogging occurs. The sieving method may use a sieve or an air classifier. In order to obtain a composite powder having the desired BET specific surface area, a pulverizer may be selected, and the pulverization time and the like may be adjusted. Excellent specific surface area value of 2000 for composite powder for conductive paste
cm 2 / g or more. If the value is less than 2000 cm 2 / g, the conductivity and the viscosity characteristics of the paste will be deteriorated. The performance required for use in recent screen printing methods is that the particle size is 45 μm or less,
Fine powder having a BET specific surface area of 3000 cm 2 / g or more is preferred.
【００１４】[0014]
【実施例】以下、実施例により本発明を具体的に説明す
るが、これにより本発明の範囲及び使用範囲が限定され
るものではない。EXAMPLES The present invention will be described below in detail with reference to examples, but the scope and use of the present invention are not limited thereby.
【００１５】（実施例１）平均粒子径２５μｍの樹枝状
形状の電解銅粉９７重量部に、平均粒子径１μｍの酸化
銀３重量部を計量・配合し振動ミルに投入した。スチー
ルボールを粉砕媒体として振動ミルで２時間粉砕加工し
た。その後、振動ミルから粉砕加工した粉末を取り出
し、水素雰囲気の還元炉で２００℃６０分間還元処理し
た。このようにして得た粉末を１５０メッシュの篩を用
いて、１００μｍ以下の粒子径に調整し、ＢＥＴ法比表
面積値４１００ｃｍ2／ｇの導電ペースト用銅銀複合粉
を製造した。このようにして製造した本発明の導電ペー
スト用銅銀複合粉の性能を確認するために、銅銀複合粉
７５重量部、アクリル樹脂２５重量部になるように混合
し、トルオールで希釈して導電ペーストを作成した。作
成したペーストをＡＢＳ樹脂板にロールコータ法で印刷
し膜厚２５μｍの塗膜を作成し、比抵抗値を測定した。
その結果１．５×１０ー4Ω・ｃｍの良好な導電性を示し
た。Example 1 3 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 97 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. Pulverization was performed for 2 hours by a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 200 ° C. for 60 minutes. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 4100 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured.
As a result, good conductivity of 1.5 × 10 −4 Ω · cm was exhibited.
【００１６】（実施例２）平均粒子径２５μｍの樹枝状
形状の電解銅粉９０重量部に、平均粒子径１μｍの酸化
銀１０重量部を計量・配合し振動ミルに投入した。スチ
ールボールを粉砕媒体として振動ミルで２時間粉砕加工
した。その後、振動ミルから粉砕加工した粉末を取り出
し、水素雰囲気の還元炉で２００℃６０分間還元処理し
た。このようにして得た粉末を１５０メッシュの篩を用
いて、１００μｍ以下の粒子径に調整し、ＢＥＴ法比表
面積値４５００ｃｍ2／ｇの導電ペースト用銅銀複合粉
を製造した。このようにして製造した本発明の導電ペー
スト用銅銀複合粉の性能を確認するために、銅銀複合粉
７５重量部、アクリル樹脂２５重量部になるように混合
し、トルオールで希釈して導電ペーストを作成した。作
成したペーストをＡＢＳ樹脂板にロールコータ法で印刷
し膜厚２５μｍの塗膜を作成し、比抵抗値を測定した。
その結果１．１×１０ー4Ω・ｃｍの良好な導電性を示し
た。Example 2 10 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 90 parts by weight of dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. Pulverization was performed for 2 hours by a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 200 ° C. for 60 minutes. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 4500 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured.
As a result, good conductivity of 1.1 × 10 −4 Ω · cm was exhibited.
【００１７】（実施例３）平均粒子径２５μｍの樹枝状
形状の電解銅粉８０重量部に、平均粒子径１μｍの酸化
銀２０重量部を計量・配合し振動ミルに投入した。スチ
ールボールを粉砕媒体として振動ミルで２時間粉砕加工
した。その後、振動ミルから粉砕加工した粉末を取り出
し、水素雰囲気の還元炉で２００℃８０分間還元処理し
た。このようにして得た粉末を１５０メッシュの篩を用
いて、１００μｍ以下の粒子径に調整し、ＢＥＴ法比表
面積値５０００ｃｍ2／ｇの導電ペースト用銅銀複合粉
を製造した。このようにして製造した本発明の導電ペー
スト用銅銀複合粉の性能を確認するために、銅銀複合粉
７５重量部、アクリル樹脂２５重量部になるように混合
し、トルオールで希釈して導電ペーストを作成した。作
成したペーストをＡＢＳ樹脂板にロールコータ法で印刷
し膜厚２５μｍの塗膜を作成し、比抵抗値を測定した。
その結果１．１×１０ー4Ω・ｃｍの良好な導電性を示し
た。Example 3 20 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. Pulverization was performed for 2 hours by a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced at 200 ° C. for 80 minutes in a reducing furnace in a hydrogen atmosphere. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 5000 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured.
As a result, good conductivity of 1.1 × 10 −4 Ω · cm was exhibited.
【００１８】（実施例４）平均粒子径２５μｍの樹枝状
形状の電解銅粉５０重量部に、平均粒子径１μｍの酸化
銀５０重量部を計量・配合し振動ミルに投入した。スチ
ールボールを粉砕媒体として振動ミルで２時間粉砕加工
した。その後、振動ミルから粉砕加工した粉末を取り出
し、水素雰囲気の還元炉で２００℃１６０分間還元処理
した。このようにして得た粉末を１５０メッシュの篩を
用いて、１００μｍ以下の粒子径に調整し、ＢＥＴ法比
表面積値７８００ｃｍ2／ｇの導電ペースト用銅銀複合
粉を製造した。このようにして製造した本発明の導電ペ
ースト用銅銀複合粉の性能を確認するために、銅銀複合
粉７５重量部、アクリル樹脂２５重量部になるように混
合し、トルオールで希釈して導電ペーストを作成した。
作成したペーストをＡＢＳ樹脂板にロールコータ法で印
刷し膜厚２５μｍの塗膜を作成し、比抵抗値を測定し
た。その結果０．８×１０ー4Ω・ｃｍの良好な導電性を
示した。Example 4 50 parts by weight of silver oxide having an average particle diameter of 1 μm were weighed and blended with 50 parts by weight of dendritic electrolytic copper powder having an average particle diameter of 25 μm, and then charged into a vibration mill. Pulverization was performed for 2 hours by a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced at 200 ° C. for 160 minutes in a reducing furnace in a hydrogen atmosphere. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 7,800 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created.
The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured. As a result, good conductivity of 0.8 × 10 −4 Ω · cm was exhibited.
【００１９】（実施例５）平均粒子径１５μｍの樹枝状
形状の電解銅粉９０重量部に、平均粒子径０．８μｍの
酸化銀１０重量部を計量・配合しアジテータミルに投入
した。スチールボールを粉砕媒体としてアジテータミル
で６時間粉砕加工した。その後、アジテータミルから粉
砕加工した粉末を取り出し、水素雰囲気の還元炉で還元
温度及び還元時間を変えて１２０℃１８０分間、１５０
℃１２０分、２００℃９０分、３００℃６０分、４００
℃６０分間還元処理した。このようにして得た粉末を３
２５メッシュの篩を用いて４５μｍ以下の粒子径に調整
した。 １２０℃１８０分間還元処理した粉末はＢＥＴ法比表面
積値７４００ｃｍ2／ｇ、 １５０℃１２０分間還元処理した粉末はＢＥＴ法比表面
積値７２００ｃｍ2／ｇ、 ２００℃９０分間還元処理した粉末はＢＥＴ法比表面積
値６４００ｃｍ2／ｇ、 ３００℃６０分間還元処理した粉末はＢＥＴ法比表面積
値５５００ｃｍ2／ｇ、 ４００℃６０分間還元処理した粉末はＢＥＴ法比表面積
値３２００ｃｍ2／ｇであった。このようにして製造し
た本発明の導電ペースト用銅銀複合粉の性能を確認する
ために、銅銀複合粉７５重量部、エポキシ樹脂１０重量
部、エチルカルビトール１５重量部及び硬化剤、反応促
進剤を適量添加し導電ペーストを作成した。作成したペ
ーストを２００メッシュのスクリーンを使用してスクリ
ーン印刷方法で塗膜を作成し、比抵抗値を測定した。そ
の結果１２０℃１８０分還元処理したものは１.０×１
０ー4Ω・ｃｍ、１５０℃１２０分還元処理したものは０.
８×１０ー4Ω・ｃｍ、２００℃９０分還元処理したもの
は０.８×１０ー4Ω・ｃｍ、３００℃６０分還元処理した
ものは １.０×１０ー4Ω・ｃｍ、４００℃６０分還元処
理したものは１.３×１０ー4Ω・ｃｍと、すべて良好な導
電性を示した。Example 5 10 parts by weight of silver oxide having an average particle diameter of 0.8 μm was weighed and blended with 90 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 15 μm and charged into an agitator mill. The steel balls were pulverized for 6 hours using an agitator mill as a pulverizing medium. Thereafter, the pulverized powder was taken out of the agitator mill, and reduced at a temperature of 120 ° C. for 180 minutes by changing the reduction temperature and the reduction time in a reducing furnace in a hydrogen atmosphere.
120 ° C, 200 ° C for 90 minutes, 300 ° C for 60 minutes, 400
Reduction treatment was performed at 60 ° C. for 60 minutes. The powder obtained in this way is 3
The particle size was adjusted to 45 μm or less using a 25-mesh sieve. The powder reduced at 120 ° C. for 180 minutes has a specific surface area value of 7400 cm 2 / g, the powder reduced at 150 ° C. for 120 minutes has a specific surface area value of 7200 cm 2 / g, and the powder reduced at 200 ° C. for 90 minutes has a BET specific ratio. The powder subjected to the reduction treatment at a surface area of 6400 cm 2 / g at 300 ° C. for 60 minutes had a BET specific surface area of 5500 cm 2 / g, and the powder subjected to the reduction treatment at 400 ° C. for 60 minutes had a BET specific surface area of 3200 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus produced, 75 parts by weight of a copper-silver composite powder, 10 parts by weight of an epoxy resin, 15 parts by weight of ethyl carbitol, a curing agent, a reaction accelerator An appropriate amount of the agent was added to prepare a conductive paste. Using the prepared paste, a coating film was formed by a screen printing method using a 200-mesh screen, and the specific resistance value was measured. As a result, the product reduced at 120 ° C. for 180 minutes was 1.0 × 1
0.4-4 Ω · cm, reduced at 150 ° C for 120 min.
8 × 10 over 4 Ω · cm, 200 ℃ 90 minutes reduction treated ones 0.8 × 10 over 4 Ω · cm, 300 ℃ 60 minutes those reduction treatment 1.0 × 10 over 4 Ω · cm, 400 ° C. 60 minutes those reduction treatment and 1.3 × 10 over 4 Ω · cm, all showed good conductivity.
【００２０】（実施例６）平均粒子径５５μｍの粒状形
状の空気アトマイズ銅粉８０重量部に、平均粒子径１μ
ｍの酸化銀２０重量部を計量・配合し振動ミルに投入し
た。スチールボールを粉砕媒体として振動ミルで１時間
粉砕加工し、銅粉表面に酸化銀を接合した。その後、振
動ミルから粉砕加工した粉末を取り出し、水素雰囲気の
還元炉で３００℃８０分間還元処理した。このようにし
て得た粉末を１５０メッシュの篩を用いて、１００μｍ
以下の粒子径に調整し、ＢＥＴ法比表面積値２０１０ｃ
ｍ2／ｇの導電ペースト用銅銀複合粉を製造した。この
ようにして製造した本発明の導電ペースト用銅銀複合粉
の性能を確認するために、銅銀複合粉７５重量部アクリ
ル樹脂２５重量部と、銅銀複合粉８０重量部アクリル樹
脂２０重量部になるように２種類の混合物を作成し、そ
の後トルオールで希釈して２種類の導電ペーストを作成
した。作成したペーストをＡＢＳ樹脂板にロールコータ
法で印刷し膜厚７０μｍの塗膜を作成し、比抵抗値を測
定した。その結果銅銀粉含有量７５重量部のペーストは
３.５×１０ー4Ω・ｃｍで有ったが、銅銀複合粉８０重量
部のペーストは０.７×１０ー4Ω・ｃｍと銀粉に近い良好
な導電性を示した。本発明の導電ペースト用銅銀複合粉
の断面を観察すると、表面層の大部分が銀で被覆され、
スルーホール用として好ましい形態の粉末であった。Example 6 An 80% by weight air-atomized copper powder having an average particle diameter of 55 μm was added to 80 parts by weight of an average particle diameter of 1 μm.
Then, 20 parts by weight of silver oxide was measured and blended and charged into a vibration mill. Using a steel ball as a crushing medium, crushing was performed for 1 hour by a vibration mill, and silver oxide was bonded to the surface of the copper powder. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 300 ° C. for 80 minutes. The powder thus obtained was passed through a 150-mesh sieve,
Adjust to the following particle size, BET specific surface area value 2010c
A copper / silver composite powder for conductive paste of m 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder, 25 parts by weight of an acrylic resin, 80 parts by weight of a copper-silver composite powder, and 20 parts by weight of an acrylic resin Were prepared, and then diluted with toluene to prepare two types of conductive pastes. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 70 μm, and the specific resistance value was measured. As a result, the paste having a copper-silver powder content of 75 parts by weight was 3.5 × 10 −4 Ω · cm, while the paste having a copper-silver composite powder of 80 parts by weight was 0.7 × 10 −4 Ω · cm and the silver powder was 0.7 × 10 −4 Ω · cm. And good conductivity close to. When observing the cross section of the copper-silver composite powder for the conductive paste of the present invention, most of the surface layer is covered with silver,
The powder was in a preferred form for through holes.
【００２１】（実施例７）平均粒子径５５μｍの粒状形
状の空気アトマイズ銅粉８０重量部に、平均粒子径１μ
ｍの酸化銀２０重量部を計量・配合し振動ミルに投入し
た。スチールボールを粉砕媒体として振動ミルで４時間
粉砕加工した。その後、振動ミルから粉砕加工した粉末
を取り出し、水素雰囲気の還元炉で３００℃８０分間還
元処理した。このようにして得た粉末を１５０メッシュ
の篩を用いて、１００μｍ以下の粒子径に調整し、ＢＥ
Ｔ法比表面積値４２００ｃｍ2/ｇの導電ペースト用銅銀
複合粉を製造した。このようにして製造した本発明の導
電ペースト用銅銀複合粉の性能を確認するために、銅銀
複合粉７５重量部、アクリル樹脂２５重量部になるよう
に混合し、トルオールで希釈して導電ペーストを作成し
た。作成したペーストをＡＢＳ樹脂板にロールコータ法
で印刷し膜厚７０μｍの塗膜を作成し、比抵抗値を測定
した。その結果１．５×１０ー4Ω・ｃｍの良好な導電性
を示した。本発明の導電ペースト用銅銀複合粉の断面を
観察すると、細かい粒子では明確にならなかったが、粗
い粒子については表面が銀で被覆されているものが多く
認められた。Example 7 An 80% by weight granular air atomized copper powder having an average particle size of 55 μm was added to an average particle size of 1 μm.
Then, 20 parts by weight of silver oxide was measured and blended and charged into a vibration mill. Pulverization was performed for 4 hours by a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 300 ° C. for 80 minutes. The powder thus obtained was adjusted to a particle size of 100 μm or less using a 150-mesh sieve.
A copper-silver composite powder for a conductive paste having a T method specific surface area of 4,200 cm 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 70 μm, and the specific resistance value was measured. As a result, good conductivity of 1.5 × 10 −4 Ω · cm was exhibited. When the cross section of the copper-silver composite powder for a conductive paste of the present invention was observed, fine particles were not clear, but many coarse particles whose surface was coated with silver were recognized.
【００２２】（実施例８）平均粒子径１５μｍの樹枝状
形状の電解銅粉９０重量部に、平均粒子径０．８μｍの
酸化銀１０重量部を計量・配合しアジテータミルに投入
した。スチールボールを粉砕媒体としてアジテータミル
で８時間粉砕加工した。その後、アジテータミルから粉
砕加工した粉末を取り出し、当該粉末に対して０.１重
量％のオレイン酸を加え、ミキサーにて脂肪酸を表面に
混合被覆した。その後、水素雰囲気の還元炉で１５０℃
１８０分間還元処理した。このようにして得た粉末を３
２５メッシュの篩を用いて４５μｍ以下の粒子径に調整
し、ＢＥＴ法比表面積値９４００ｃｍ2／ｇの導電ペー
スト用銅銀複合粉を製造した。このようにして製造した
本発明の導電ペースト用銅銀複合粉の性能を確認するた
めに、銅銀複合粉７５重量部、エポキシ樹脂１０重量
部、エチルカルビトール１５重量部及び硬化剤、反応促
進剤を適量添加し導電ペーストを作成した。作成したペ
ーストを２００メッシュのスクリーンを使用してスクリ
ーン印刷方法で塗膜を作成し、比抵抗値を測定した。そ
の結果０.８×１０ー4Ω・ｃｍの良好な導電性を示した。Example 8 90 parts by weight of dendritic copper powder having an average particle diameter of 15 μm was weighed and blended with 10 parts by weight of silver oxide having an average particle diameter of 0.8 μm, and then charged into an agitator mill. Pulverization was performed for 8 hours by an agitator mill using a steel ball as a pulverizing medium. Thereafter, the pulverized powder was taken out from the agitator mill, 0.1% by weight of oleic acid was added to the powder, and a fatty acid was mixed and coated on the surface with a mixer. Thereafter, 150 ° C. in a reducing furnace in a hydrogen atmosphere
The reduction treatment was performed for 180 minutes. The powder obtained in this way is 3
The particle diameter was adjusted to 45 μm or less using a 25-mesh sieve to produce a copper-silver composite powder for conductive paste having a BET specific surface area of 9400 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus produced, 75 parts by weight of a copper-silver composite powder, 10 parts by weight of an epoxy resin, 15 parts by weight of ethyl carbitol, a curing agent, a reaction accelerator An appropriate amount of the agent was added to prepare a conductive paste. Using the prepared paste, a coating film was formed by a screen printing method using a 200-mesh screen, and the specific resistance value was measured. As a result, good conductivity of 0.8 × 10 −4 Ω · cm was exhibited.
【００２３】（実施例９）平均粒子径１５μｍの樹枝状
形状の電解銅粉９０重量部に、平均粒子径０.８μｍの
酸化銀１０重量部を計量・配合しアジテータミルに投入
した。スチールボールを粉砕媒体としてアジテータミル
で８時間粉砕加工した。その後、アジテータミルから粉
砕加工した粉末を取り出し、当該粉末に対して０．５重
量％のパルミチン酸を加え、ミキサーにて脂肪酸を表面
に混合被覆した。その後、水素雰囲気の還元炉で３００
℃１００分間還元処理した。このようにして得た粉末を
３２５メッシュの篩を用いて４５μｍ以下の粒子径に調
整し、ＢＥＴ法比表面積値８２００ｃｍ2／ｇの導電ペ
ースト用銅銀複合粉を製造した。このようにして製造し
た本発明の導電ペースト用銅銀複合粉の性能を確認する
ために、銅銀複合粉７５重量部、エポキシ樹脂１０重量
部、エチルカルビトール１５重量部及び硬化剤、反応促
進剤を適量添加し導電ペーストを作成した。作成したペ
ーストを２００メッシュのスクリーンを使用してスクリ
ーン印刷方法で塗膜を作成し、比抵抗値を測定した。そ
の結果０.８×１０ー4Ω・ｃｍの良好な導電性を示した。Example 9 10 parts by weight of silver oxide having an average particle diameter of 0.8 μm was weighed and blended with 90 parts by weight of a dendritic copper powder having an average particle diameter of 15 μm and charged into an agitator mill. Pulverization was performed for 8 hours by an agitator mill using a steel ball as a pulverizing medium. Thereafter, the pulverized powder was taken out from the agitator mill, and 0.5% by weight of palmitic acid was added to the powder, and a fatty acid was mixed and coated on the surface with a mixer. After that, 300 hours in a reducing furnace in a hydrogen atmosphere.
Reduction treatment was performed at 100 ° C. for 100 minutes. The powder thus obtained was adjusted to a particle size of 45 μm or less using a 325-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 8,200 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus produced, 75 parts by weight of a copper-silver composite powder, 10 parts by weight of an epoxy resin, 15 parts by weight of ethyl carbitol, a curing agent, a reaction accelerator An appropriate amount of the agent was added to prepare a conductive paste. Using the prepared paste, a coating film was formed by a screen printing method using a 200-mesh screen, and the specific resistance value was measured. As a result, good conductivity of 0.8 × 10 −4 Ω · cm was exhibited.
【００２４】（実施例１０）平均粒子径１５μｍの樹枝
状形状の電解銅粉９０重量部に、平均粒子径０.８μｍ
の酸化銀１０重量部を計量・配合しアジテータミルに投
入した。スチールボールを粉砕媒体としてアジテータミ
ルで８時間粉砕加工した。その後、アジテータミルから
粉砕加工した粉末を取り出し、当該粉末に対して１.０
重量％のステアリン酸を加え、ミキサーにて脂肪酸を表
面に混合被覆した。その後、アンモニア分解ガス雰囲気
の還元炉で４００℃１２０分間還元処理した。このよう
にして得た粉末を３２５メッシュの篩を用いて４５μｍ
以下の粒子径に調整し、ＢＥＴ法比表面積値７１００ｃ
ｍ2／ｇの導電ペースト用銅銀複合粉を製造した。この
ようにして製造した本発明の導電ペースト用銅銀複合粉
の性能を確認するために、銅銀複合粉７５重量部、エポ
キシ樹脂１０重量部、エチルカルビトール１５重量部及
び硬化剤、反応促進剤を適量添加し導電ペーストを作成
した。作成したペーストを２００メッシュのスクリーン
を使用してスクリーン印刷方法で塗膜を作成し、比抵抗
値を測定した。その結果１.０×１０ー4Ω・ｃｍの良好な
導電性を示した。Example 10 90 parts by weight of a dendritic copper powder having an average particle diameter of 15 μm was added to an average particle diameter of 0.8 μm.
Was weighed and blended and charged into an agitator mill. Pulverization was performed for 8 hours by an agitator mill using a steel ball as a pulverizing medium. Thereafter, the pulverized powder was taken out of the agitator mill, and the powder was 1.0
The stearic acid was added in a ratio of wt%, and the fatty acid was mixed and coated on the surface with a mixer. Thereafter, a reduction treatment was performed at 400 ° C. for 120 minutes in a reduction furnace in an ammonia decomposition gas atmosphere. The powder thus obtained was subjected to 45 μm
Adjusted to the following particle size, BET specific surface area value 7100c
A copper / silver composite powder for conductive paste of m 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus produced, 75 parts by weight of a copper-silver composite powder, 10 parts by weight of an epoxy resin, 15 parts by weight of ethyl carbitol, a curing agent, a reaction accelerator An appropriate amount of the agent was added to prepare a conductive paste. Using the prepared paste, a coating film was formed by a screen printing method using a 200-mesh screen, and the specific resistance value was measured. As a result, good conductivity of 1.0 × 10 −4 Ω · cm was exhibited.
【００２５】（実施例１１）平均粒子径１５μｍの樹枝
状形状の電解銅粉９０重量部に、平均粒子径０．８μｍ
の酸化銀１０重量部を計量・配合しアジテータミルに投
入した。スチールボールを粉砕媒体としてアジテータミ
ルで８時間粉砕加工した。その後、アジテータミルから
粉砕加工した粉末を取り出し、当該粉末に対して２.０
重量％のステアリン酸を加え、ミキサーにて脂肪酸を表
面に混合被覆した。その後、アンモニア分解ガス雰囲気
の還元炉で５００℃９０分間還元処理した。このように
して得た粉末を３２５メッシュの篩を用いて４５μｍ以
下の粒子径に調整し、ＢＥＴ法比表面積値４３００ｃｍ
2／ｇの導電ペースト用銅銀複合粉を製造した。このよ
うにして製造した本発明の導電ペースト用銅銀複合粉の
性能を確認するために、銅銀複合粉７５重量部、エポキ
シ樹脂１０重量部、エチルカルビトール１５重量部及び
硬化剤、反応促進剤を適量添加し導電ペーストを作成し
た。作成したペーストを２００メッシュのスクリーンを
使用してスクリーン印刷方法で塗膜を作成し、比抵抗値
を測定した。その結果１.２×１０ー4Ω・ｃｍの良好な導
電性を示した。Example 11 90 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 15 μm was added to an average particle diameter of 0.8 μm.
Was weighed and blended and charged into an agitator mill. Pulverization was performed for 8 hours by an agitator mill using a steel ball as a pulverizing medium. Thereafter, the pulverized powder was taken out of the agitator mill, and the powder was 2.0
The stearic acid was added in a ratio of wt%, and the fatty acid was mixed and coated on the surface with a mixer. Thereafter, a reduction treatment was performed at 500 ° C. for 90 minutes in a reduction furnace in an ammonia decomposition gas atmosphere. The powder thus obtained was adjusted to a particle diameter of 45 μm or less using a 325 mesh sieve, and the BET specific surface area value was 4300 cm.
2 / g of a copper-silver composite powder for conductive paste was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus produced, 75 parts by weight of a copper-silver composite powder, 10 parts by weight of an epoxy resin, 15 parts by weight of ethyl carbitol, a curing agent, a reaction accelerator An appropriate amount of the agent was added to prepare a conductive paste. Using the prepared paste, a coating film was formed by a screen printing method using a 200-mesh screen, and the specific resistance value was measured. As a result, good conductivity of 1.2 × 10 −4 Ω · cm was exhibited.
【００２６】（実施例１２）平均粒子径２５μｍの樹枝
状形状の電解銅粉８０重量部に、平均粒子径１μｍの酸
化銀２０重量部を計量・配合し振動ミルに投入した。粉
砕助剤として、粉末に対して０.１重量％のオレイン酸
を振動ミル投入前にあらかじめ添加し、ミキサーで混合
した。スチールボールを粉砕媒体として振動ミルで３時
間粉砕加工した。その後、振動ミルから粉砕加工した粉
末を取り出し、水素雰囲気の還元炉で１５０℃１８０分
間還元処理した。このようにして得た粉末を１５０メッ
シュの篩を用いて、１００μｍ以下の粒子径に調整し、
ＢＥＴ法比表面積値６５００ｃｍ2／ｇの導電ペースト
用銅銀複合粉を製造した。このようにして製造した本発
明の導電ペースト用銅銀複合粉の性能を確認するため
に、銅銀複合粉７５重量部、アクリル樹脂２５重量部に
なるように混合し、トルオールで希釈して導電ペースト
を作成した。作成したペーストをＡＢＳ樹脂板にロール
コータ法で印刷し膜厚２５μｍの塗膜を作成し、比抵抗
値を測定した。その結果塗膜表面が平滑で、しかも１.
５×１０ー4Ω・ｃｍの良好な導電性を示した。粉末の形
状を顕微鏡で見ると、すべて薄く展延加工された片状粉
であった。Example 12 20 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. As a grinding aid, 0.1% by weight of oleic acid with respect to the powder was added in advance before putting into a vibration mill, and mixed with a mixer. Pulverization was performed for 3 hours with a vibration mill using steel balls as a pulverizing medium. Thereafter, the pulverized powder was taken out of the vibration mill and reduced in a reducing furnace in a hydrogen atmosphere at 150 ° C. for 180 minutes. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve,
A copper-silver composite powder for a conductive paste having a BET specific surface area of 6,500 cm 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured. As a result, the coating film surface is smooth and 1.
It exhibited good conductivity of 5 × 10 −4 Ω · cm. When the shapes of the powders were observed with a microscope, all of the powders were thinly spread flaky powders.
【００２７】（実施例１３）平均粒子径２５μｍの樹枝
状形状の電解銅粉８０重量部に、平均粒子径１μｍの酸
化銀２０重量部を計量・配合し振動ミルに投入した。粉
砕助剤として、粉末に対して０．２重量％のパルミチン
酸を振動ミル投入前にあらかじめ添加し、ミキサーで混
合した。スチールボールを粉砕媒体として振動ミルで３
時間粉砕加工した。その後、振動ミルから粉砕加工した
粉末を取り出し、水素雰囲気の還元炉で３００℃８０分
間還元処理した。このようにして得た粉末を１５０メッ
シュの篩を用いて、１００μｍ以下の粒子径に調整し、
ＢＥＴ法比表面積値６８００ｃｍ2／ｇの導電ペースト
用銅銀複合粉を製造した。このようにして製造した本発
明の導電ペースト用銅銀複合粉の性能を確認するため
に、銅銀複合粉７５重量部、アクリル樹脂２５重量部に
なるように混合し、トルオールで希釈して導電ペースト
を作成した。作成したペーストをＡＢＳ樹脂板にロール
コータ法で印刷し膜厚２５μｍの塗膜を作成し、比抵抗
値を測定した。その結果塗膜表面が平滑で、しかも１.
５×１０ー4Ω・ｃｍの良好な導電性を示した。粉末の形
状を顕微鏡で見ると、すべて薄く展延加工された片状粉
であった。Example 13 20 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. As a grinding aid, 0.2% by weight of palmitic acid with respect to the powder was added before the addition to the vibration mill, and mixed with a mixer. 3 with a vibration mill using steel balls as grinding media
Crushed for hours. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 300 ° C. for 80 minutes. The powder thus obtained was adjusted to a particle diameter of 100 μm or less using a 150-mesh sieve,
A copper-silver composite powder for a conductive paste having a BET specific surface area of 6,800 cm 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm, and the specific resistance value was measured. As a result, the coating film surface is smooth and 1.
It exhibited good conductivity of 5 × 10 −4 Ω · cm. When the shapes of the powders were observed with a microscope, all of the powders were thinly spread flaky powders.
【００２８】（実施例１４）平均粒子径２５μｍの樹枝
状形状の電解銅粉８０重量部に、平均粒子径１μｍの酸
化銀２０重量部を計量・配合し振動ミルに投入した。ス
チールボールを粉砕媒体として振動ミルで１時間粉砕加
工した後、粉砕助剤として粉末に対して０.５重量％の
ステアリン酸を添加しさらに３時間粉砕加工した。その
後、振動ミルから粉砕加工した粉末を取り出し、水素雰
囲気の還元炉で３００℃１２０分間還元処理した。この
ようにして得た粉末を１５０メッシュの篩を用いて、１
００μｍ以下の粒子径に調整し、ＢＥＴ法比表面積値９
３００ｃｍ2／ｇの導電ペースト用銅銀複合粉を製造し
た。このようにして製造した本発明の導電ペースト用銅
銀複合粉の性能を確認するために、銅銀複合粉７５重量
部、アクリル樹脂２５重量部になるように混合し、トル
オールで希釈して導電ペーストを作成した。作成したペ
ーストをＡＢＳ樹脂板にロールコータ法で印刷し膜厚２
５μｍの塗膜を作成し、比抵抗値を測定した。その結果
塗膜表面が平滑で、しかも１.４×１０ー4Ω・ｃｍの良好
な導電性を示した。Example 14 20 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. After grinding with a vibration mill for 1 hour using a steel ball as a grinding medium, 0.5% by weight of stearic acid with respect to the powder was added as a grinding aid, and grinding was further performed for 3 hours. Thereafter, the pulverized powder was taken out of the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 300 ° C. for 120 minutes. The powder thus obtained was passed through a 150-mesh sieve,
The particle size was adjusted to be not more than 00 μm, and the BET specific surface area was 9
A copper-silver composite powder for a conductive paste of 300 cm 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste is printed on an ABS resin plate by a roll coater method, and the film thickness is 2
A coating film of 5 μm was formed, and the specific resistance value was measured. As a result, the coating film surface was smooth and showed good conductivity of 1.4 × 10 −4 Ω · cm.
【００２９】（実施例１５）平均粒子径２５μｍの樹枝
状形状の電解銅粉８０重量部に、平均粒子径１μｍの酸
化銀２０重量部を計量・配合し振動ミルに投入した。ス
チールボールを粉砕媒体として振動ミルで１時間粉砕加
工した。その後粉砕助剤として粉末に対して０.２重量
％のステアリン酸を１時間毎に添加し、６時間まで粉砕
加工した。その後、振動ミルから粉砕加工した粉末を取
り出し、水素雰囲気の還元炉で２５０℃１８０分間還元
処理した。このようにして得た粉末を１５０メッシュの
篩を用いて、１００μｍ以下の粒子径に調整し、ＢＥＴ
法比表面積値１２５００ｃｍ2／ｇの導電ペースト用銅
銀複合粉を製造した。このようにして製造した本発明の
導電ペースト用銅銀複合粉の性能を確認するために、銅
銀複合粉７５重量部、アクリル樹脂２５重量部になるよ
うに混合し、トルオールで希釈して導電ペーストを作成
した。作成したペーストをＡＢＳ樹脂板にロールコータ
法で印刷し膜厚１５μｍの塗膜を作成し、比抵抗値を測
定した。その結果塗膜表面が緻密でしかも平滑で、１.
７×１０ー4Ω・ｃｍの良好な導電性を示した。Example 15 20 parts by weight of silver oxide having an average particle diameter of 1 μm were weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. Pulverization was performed for 1 hour by a vibration mill using steel balls as a pulverizing medium. Thereafter, as a grinding aid, stearic acid of 0.2% by weight based on the powder was added every hour, and pulverization was performed for up to 6 hours. Thereafter, the pulverized powder was taken out from the vibration mill, and reduced in a reducing furnace in a hydrogen atmosphere at 250 ° C. for 180 minutes. The powder thus obtained was adjusted to a particle size of 100 μm or less using a 150-mesh sieve,
A copper-silver composite powder for a conductive paste having a specific surface area of 12,500 cm 2 / g was produced. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste was printed on an ABS resin plate by a roll coater method to form a film having a thickness of 15 μm, and the specific resistance was measured. As a result, the coating film surface is dense and smooth, and 1.
Good conductivity of 7 × 10 −4 Ω · cm was exhibited.
【００３０】（実施例１６）平均粒子径２５μｍの樹枝
状形状の電解銅粉８０重量部に、平均粒子径１μｍの酸
化銀２０重量部を計量・配合し振動ミルに投入した。ス
チールボールを粉砕媒体として振動ミルで１０分間粉砕
加工した。その後粉砕助剤として粉末に対して０.５重
量％のオレイン酸を添加し、３時間粉砕加工した。その
後、振動ミルから粉砕加工した粉末を取り出し、粉末に
対して１.５重量％のステアリン酸を加えミキサーで混
合被覆した。しかる後に、水素雰囲気の還元炉で５００
℃９０分間還元処理した。このようにして得た粉末を１
５０メッシュの篩を用いて、１００μｍ以下の粒子径に
調整し、ＢＥＴ法比表面積値４８００ｃｍ2／ｇの導電
ペースト用銅銀複合粉を製造した。このようにして製造
した本発明の導電ペースト用銅銀複合粉の性能を確認す
るために、銅銀複合粉７５重量部、アクリル樹脂２５重
量部になるように混合し、トルオールで希釈して導電ペ
ーストを作成した。作成したペーストをＡＢＳ樹脂板に
ロールコータ法で印刷し膜厚２５μｍの塗膜を作成し、
比抵抗値を測定した。その結果１．５×１０ー4Ω・ｃｍ
の良好な導電性を示した。塗膜外観も平滑で、粉末の形
状も片状で、かつ凝集物も非常に少なかった。Example 16 20 parts by weight of silver oxide having an average particle diameter of 1 μm was weighed and blended with 80 parts by weight of a dendritic electrolytic copper powder having an average particle diameter of 25 μm and charged into a vibration mill. Pulverization was performed for 10 minutes by a vibration mill using steel balls as a pulverizing medium. Thereafter, 0.5% by weight of oleic acid was added to the powder as a grinding aid, and the mixture was ground for 3 hours. Thereafter, the pulverized powder was taken out from the vibration mill, and 1.5% by weight of stearic acid was added to the powder and mixed and coated with a mixer. After that, in a hydrogen atmosphere reducing furnace,
Reduction treatment was performed at 90 ° C. for 90 minutes. The powder thus obtained is
The particle diameter was adjusted to 100 μm or less using a 50-mesh sieve to produce a copper-silver composite powder for a conductive paste having a BET specific surface area of 4,800 cm 2 / g. In order to confirm the performance of the copper-silver composite powder for a conductive paste of the present invention thus manufactured, 75 parts by weight of a copper-silver composite powder and 25 parts by weight of an acrylic resin were mixed and diluted with toluene to obtain a conductive powder. Paste created. The prepared paste is printed on an ABS resin plate by a roll coater method to form a coating film having a thickness of 25 μm.
The specific resistance value was measured. As a result 1.5 × 10 over 4 Ω · cm
Showed good conductivity. The appearance of the coating film was smooth, the shape of the powder was flaky, and the amount of aggregates was very small.
【００３１】[0031]
【発明の効果】本発明の方法によって得られる導電ペー
スト用銅銀複合粉は、従来の銀メッキ銅粉と異なり、粒
子径が細かくても、また片状形状でも銀粉に近い優れた
導電性能が得られ、しかも工業的に安価に製造出来る物
である。具体的な産業への利用方法としては、吹き付け
塗装法あるいはロールコータ法、スクリーン印刷法によ
る電磁波シールド用途では、比表面積が大きい粉末であ
るため非常に塗装し易く、しかも片状粉では塗膜表面が
平滑となり、かつ塗膜厚も薄く出来るようになった。ス
クリーン印刷方法による導電回路やジャンパー線では、
粒子径が小さく比表面積が大きいことはペースト中の単
位体積あたりの導電粒子の個数が増えることになり、印
刷方向や厚さ方向での導電性能のばらつきが無くなり、
安定した塗膜の形成が可能となった。The copper-silver composite powder for conductive paste obtained by the method of the present invention, unlike conventional silver-plated copper powder, has excellent conductive properties close to silver powder even if the particle diameter is small and even in a flaky shape. It can be obtained and can be manufactured industrially at low cost. As a specific industrial application method, in the application of electromagnetic wave shielding by spray coating method, roll coater method, screen printing method, it is very easy to paint because the powder has a large specific surface area. Became smooth and the thickness of the coating film became thinner. For conductive circuits and jumper wires by screen printing,
When the particle diameter is small and the specific surface area is large, the number of conductive particles per unit volume in the paste increases, and there is no variation in conductive performance in the printing direction or thickness direction,
A stable coating film can be formed.
【００３２】このように塗装性や印刷性が向上するばか
りか、塗膜表面の平滑性がはんだ付け性向上や、極細線
が必要なファインパターン用にも銀粉と同じような使用
ができるようになった。その他スルーホール用やディス
ペンサー用にも対応できるものとなった。もちろん本発
明の粉末は銅銀複合粉であるため、銀粉と比較するとマ
イグレーション発生の問題も少ない。このような導電ペ
ースト用銅銀複合粉が提供出来ることは、安価な導電ペ
ーストが製造出来るようになり、その使用範囲が広が
り、本発明の産業上への利用性は非常に大きいといえ
る。As described above, not only the paintability and printability are improved, but also the smoothness of the coating film surface is improved so that the solderability is improved, and it can be used in the same manner as silver powder even for fine patterns requiring extra fine lines. became. In addition, it can be used for through holes and dispensers. Of course, since the powder of the present invention is a copper-silver composite powder, there is less problem of occurrence of migration as compared with silver powder. Providing such a copper-silver composite powder for a conductive paste makes it possible to produce an inexpensive conductive paste, expands its use range, and can be said to have a very large industrial applicability of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｂ 1/00 Ｈ０１Ｂ 1/00 Ｚ 1/22 1/22 Ａ Ｈ０５Ｋ 1/09 Ｈ０５Ｋ 1/09 Ａ 9/00 9/00 Ｗ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01B 1/00 H01B 1/00 Z 1/22 1/22 A H05K 1/09 H05K 1/09 A 9/00 9/00 W
Claims (5)
機械的に銅粉に酸化銀を接合せしめて、しかる後に還元
性雰囲気中で１２０〜４００℃の温度で還元処理するこ
とを特徴とする導電ペースト用銅銀複合粉の製造方法。1. A method comprising adding silver oxide to copper powder, mechanically bonding the silver oxide to the copper powder while pulverizing, and then subjecting the copper powder to a reduction treatment at a temperature of 120 to 400 ° C. in a reducing atmosphere. Of producing a copper-silver composite powder for a conductive paste.
械的に銅粉に酸化銀を接合せしめ、次いで粉砕加工した
当該粉末に対して０．１〜２重量％の脂肪酸を混合被覆
し、しかる後に還元性雰囲気中で１５０〜５００℃の温
度で還元処理することを特徴とする導電ペースト用銅銀
複合粉の製造方法。2. Silver oxide is added to copper powder, silver oxide is mechanically bonded to copper powder while pulverizing, and then 0.1 to 2% by weight of fatty acid is mixed and coated on the pulverized powder. And a reduction treatment in a reducing atmosphere at a temperature of 150 to 500 ° C. after that.
に対して１重量％以下の脂肪酸を添加しながら粉砕加工
して、機械的に銅粉に酸化銀を接合せしめ、しかる後に
還元性雰囲気中で１５０〜５００℃の温度で還元処理す
ることを特徴とする導電ペースト用銅銀複合粉の製造方
法。3. Addition of silver oxide to copper powder, pulverization while adding 1% by weight or less of fatty acid to the powder to be pulverized, mechanically bond the silver oxide to the copper powder, and then reduce. A method for producing a copper-silver composite powder for a conductive paste, comprising performing a reduction treatment at a temperature of 150 to 500 ° C. in a neutral atmosphere.
化銀量が、銅粉に対して３〜５０重量％であることを特
徴とする導電ペースト用銅銀複合粉の製造方法。4. A method for producing a copper-silver composite powder for a conductive paste, wherein the amount of silver oxide according to claim 1, 2 or 3 is 3 to 50% by weight based on the copper powder. .
電ペースト用銅銀複合粉の粒子径が１００μｍ以下で、
ＢＥＴ法比表面積値が２０００ｃｍ2／ｇ以上であるこ
とを特徴とする導電ペースト用銅銀複合粉の製造方法。5. The copper-silver composite powder for a conductive paste according to claim 1, 2 or 3, having a particle size of 100 μm or less,
A method for producing a copper-silver composite powder for a conductive paste, wherein the BET specific surface area value is 2000 cm 2 / g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10118390A JPH11310806A (en) | 1998-04-28 | 1998-04-28 | Production of copper-silver composite powder for electrically conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10118390A JPH11310806A (en) | 1998-04-28 | 1998-04-28 | Production of copper-silver composite powder for electrically conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11310806A true JPH11310806A (en) | 1999-11-09 |
Family
ID=14735506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10118390A Pending JPH11310806A (en) | 1998-04-28 | 1998-04-28 | Production of copper-silver composite powder for electrically conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11310806A (en) |
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| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
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1998
- 1998-04-28 JP JP10118390A patent/JPH11310806A/en active Pending
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| JP2006120716A (en) * | 2004-10-19 | 2006-05-11 | Rohm Co Ltd | Semiconductor device |
| JP4567410B2 (en) * | 2004-10-19 | 2010-10-20 | ローム株式会社 | Semiconductor device |
| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
| JP2007100155A (en) * | 2005-10-03 | 2007-04-19 | Mitsui Mining & Smelting Co Ltd | Silver nanoparticle-adhered silver-copper composite powder and method for producing the silver nanoparticle-adhered silver-copper composite powder |
| KR101301634B1 (en) * | 2005-10-03 | 2013-08-29 | 미쓰이 긴조꾸 고교 가부시키가이샤 | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
| JP4666663B2 (en) * | 2007-11-30 | 2011-04-06 | 三井金属鉱業株式会社 | Silver compound-coated copper powder, method for producing the silver compound-coated copper powder, storage method for the silver compound-coated copper powder, and conductive paste using the silver compound-coated copper powder |
| JP2008106368A (en) * | 2007-11-30 | 2008-05-08 | Mitsui Mining & Smelting Co Ltd | Silver compound-coated copper powder, method for producing the silver compound-coated copper powder, method for storing the silver compound-coated copper powder and conductive paste using the silver compound-coated copper powder |
| JP5124691B1 (en) * | 2012-03-21 | 2013-01-23 | 有限会社 ナプラ | Conductive fine powder, conductive paste and electronic parts |
| US20180376593A1 (en) * | 2014-04-01 | 2018-12-27 | Korea Electronics Technology Institute | Ink composition for light sintering, wiring board using same and manufacturing method therefor |
| US20180376592A1 (en) * | 2014-04-01 | 2018-12-27 | Korea Electronics Technology Institute | Ink composition for light sintering, wiring board using same and manufacturing method therefor |
| US10477681B2 (en) * | 2014-04-01 | 2019-11-12 | Korea Electronics Technology Institute | Ink composition for light sintering, wiring board using same and manufacturing method therefor |
| US10477680B2 (en) * | 2014-04-01 | 2019-11-12 | Korea Electronics Technology Institute | Ink composition for light sintering, wiring board using same and manufacturing method therefor |
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