JPH1129801A - Conductive alloy powder, its production, conductive paste using the conductive alloy powder, and electronic equipment - Google Patents
Conductive alloy powder, its production, conductive paste using the conductive alloy powder, and electronic equipmentInfo
- Publication number
- JPH1129801A JPH1129801A JP9185570A JP18557097A JPH1129801A JP H1129801 A JPH1129801 A JP H1129801A JP 9185570 A JP9185570 A JP 9185570A JP 18557097 A JP18557097 A JP 18557097A JP H1129801 A JPH1129801 A JP H1129801A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- resin
- conductive
- conductive alloy
- nickel
- 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.)
- Withdrawn
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 107
- 239000000956 alloy Substances 0.000 title claims abstract description 107
- 239000000843 powder Substances 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001816 cooling Methods 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000004020 conductor Substances 0.000 claims abstract description 11
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 10
- 239000000057 synthetic resin Substances 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000006104 solid solution Substances 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 229920006305 unsaturated polyester Polymers 0.000 claims description 4
- 239000000113 methacrylic resin Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 229920001568 phenolic resin Polymers 0.000 abstract description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 abstract 3
- 238000010298 pulverizing process Methods 0.000 abstract 2
- 238000007712 rapid solidification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 238000010791 quenching Methods 0.000 description 18
- 230000000171 quenching effect Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 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
- -1 and the like Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅とニッケルから
構成される、高導電性および耐酸化性に優れた特性を有
する導電性合金粉末およびその製造方法ならびに該導電
性合金粉末を用いた導電ペーストと電子機器に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive alloy powder composed of copper and nickel and having high conductivity and excellent oxidation resistance, a method for producing the same, and a conductive method using the conductive alloy powder. It relates to pastes and electronic equipment.
【０００２】[0002]
【従来の技術】従来、メンブレンスイッチ、回路基板、
電子部品などの配線部または電極部を形成するのに使用
される導電性材料としては、銅粉末または銅基合金粉末
などの導電粒子と熱硬化性樹脂などのバインダーから成
るものが知られている。この場合、銅粉末または銅基合
金粉末の調製に用いられる銅は、通常９９．９％〜９
９．９９％の純度を有している。2. Description of the Related Art Conventionally, membrane switches, circuit boards,
As a conductive material used to form a wiring portion or an electrode portion of an electronic component, a conductive material such as a copper powder or a copper-based alloy powder and a binder made of a thermosetting resin or the like are known. . In this case, copper used for preparing copper powder or copper-based alloy powder is usually 99.9% to 99.9%.
It has a purity of 9.99%.
【０００３】[0003]
【発明が解決しようとする課題】しかし、銅は大気中に
おいて酸化しやすいという性質があり、銅基合金粉末を
導電粒子として含む導電性複合材料を使用していると、
含まれている銅が酸化するにつれ、抵抗値が徐々に上昇
していき、場合によっては導電性を示さなくなるという
問題があった。それに対して、銀の粉末から構成されて
いる導電粒子、あるいは金属粉の表面を銀でコーティン
グした導電粒子を用いた導電性複合材料が、実用上問題
なく使用できることが知られている。なぜなら、銀は銅
より酸化しにくく、長期使用においてもほとんど変化し
ないからである。しかし、銀は貴金属で高価であるとい
う問題があり、成分として貴金属である銀を含有しない
合金粉末で、大気中で長期間支障なく使用できるものは
今までには知られていなかった。However, copper has a property of being easily oxidized in the air, and if a conductive composite material containing copper-based alloy powder as conductive particles is used,
As the contained copper is oxidized, the resistance value gradually increases, and in some cases, there is a problem in that the material no longer exhibits conductivity. On the other hand, it is known that a conductive composite material using conductive particles composed of silver powder or conductive particles obtained by coating the surface of metal powder with silver can be used without any practical problem. This is because silver is less susceptible to oxidation than copper and hardly changes during long-term use. However, silver has a problem that it is a noble metal and is expensive, and there has been no known alloy powder containing no noble metal as a component that can be used in the atmosphere for a long time without any trouble.
【０００４】上記の点に鑑み本発明は、長期間使用して
も表面酸化膜の厚さを導電性に支障のない範囲に抑える
ことができる導電性合金粉末およびその製造方法を提供
すること、およびこの導電性合金粉末を成分として含有
する導電ペーストを提供することを目的とする。[0004] In view of the above, the present invention provides a conductive alloy powder capable of keeping the thickness of a surface oxide film within a range that does not affect conductivity even when used for a long period of time, and a method for producing the same. It is another object of the present invention to provide a conductive paste containing the conductive alloy powder as a component.
【０００５】[0005]
【課題を解決するための手段】本発明に係る導電性合金
粉末は銅とニッケルからなり、この導電性合金粉末中に
占めるニッケルの割合が５ないし２０重量％であり、ニ
ッケルが銅に固溶した組織を有し、平均粒径が４５μｍ
以下であり、かつ表面酸化膜の厚さが１ｎｍ以下である
ことを特徴とする。前記導電性合金粉末中に占めるニッ
ケルの割合は、５ないし２０重量％の範囲にあることが
好ましい。その理由は、前記導電性合金粉末中のニッケ
ルの割合が５％未満の場合は、酸化しやすい銅の比率が
多くなり、大気中における表面酸化膜の厚さが１ｎｍを
超えてしまい、耐環境性に劣るものとなるからである。
また、前記導電性合金粉末中のニッケルの割合が２０％
を超える場合は、ニッケル自体の固有抵抗値が高いた
め、この導電性合金粉末の固有抵抗値が高くなり、実際
の使用には適さないものとなるからである。The conductive alloy powder according to the present invention comprises copper and nickel. The proportion of nickel in the conductive alloy powder is 5 to 20% by weight, and nickel is dissolved in copper. Having an average grain size of 45 μm
Or less, and the thickness of the surface oxide film is 1 nm or less. The proportion of nickel in the conductive alloy powder is preferably in the range of 5 to 20% by weight. The reason is that, when the ratio of nickel in the conductive alloy powder is less than 5%, the ratio of copper which is easily oxidized increases, and the thickness of the surface oxide film in the air exceeds 1 nm, and the This is because it is inferior in sex.
The ratio of nickel in the conductive alloy powder is 20%.
If the value exceeds, the specific resistance value of nickel itself is high, so that the specific resistance value of this conductive alloy powder becomes high, which is not suitable for actual use.
【０００６】前記導電性合金粉末は球状、偏平状、フレ
ーク状またはリン片状の形態を持ち、その平均粒径は、
４５μｍ以下であることが好ましく、３μｍないし２０
μｍであることがさらに好ましい。その理由は、平均粒
径が４５μｍを超える場合は、この導電性合金粉末を原
料に製造される導電ペーストでスクリーン印刷を行った
際に、ファインパターンの印刷が困難になるからであ
る。前記導電性合金粉末は、液体状態から１０4℃／秒
以上の冷却速度で凝固させることが好ましい。その理由
は、１０4℃／秒未満の冷却速度では凝固までの時間が
長くなり、この結果、表面酸化膜の厚さが１ｎｍを超え
てしまう。表面酸化膜の厚さが１ｎｍを超えてしまう
と、この導電性合金粉末の導電性が損なわれるからであ
る。[0006] The conductive alloy powder has a spherical, flat, flake, or flake shape, and the average particle size is
45 μm or less, preferably 3 μm to 20 μm.
More preferably, it is μm. The reason is that if the average particle size exceeds 45 μm, fine pattern printing becomes difficult when screen printing is performed with a conductive paste manufactured using this conductive alloy powder as a raw material. The conductive alloy powder is preferably solidified from a liquid state at a cooling rate of 10 4 ° C / sec or more. The reason is that at a cooling rate of less than 10 4 ° C / sec, the time until solidification becomes longer, and as a result, the thickness of the surface oxide film exceeds 1 nm. If the thickness of the surface oxide film exceeds 1 nm, the conductivity of the conductive alloy powder is impaired.
【０００７】前記導電性合金粉末は、溶湯ノズルから銅
とニッケルとからなる合金溶湯を流出させ、前記溶湯ノ
ズル下方に設置したガスノズルから噴出するガスによっ
て前記流出合金溶湯を分断するとともに一次冷却し、さ
らに大きな冷却速度の得られ難い大径液滴を、前記ガス
ノズルの下方に設置した回転冷却体に衝突させることに
より製造することができる。[0007] The conductive alloy powder flows out of a molten alloy made of copper and nickel from a molten metal nozzle, and separates and primary cools the molten metal with the gas jetted from a gas nozzle installed below the molten metal nozzle. It can be manufactured by colliding large-diameter droplets, for which it is difficult to obtain a higher cooling rate, with a rotary cooling member provided below the gas nozzle.
【０００８】こうして得られた導電性合金粉末と、この
合金粉末同士を結合させるバインダーとを主成分として
導電ペーストを調製することができる。この導電ペース
トは、導電性合金粉末１００重量部に対し、バインダー
が５ないし２５重量部添加されることが好ましい。その
理由は、導電性合金粉末１００重量部に対し、バインダ
ーが５重量部未満であると、導電性合金粉末の比率が高
すぎるため、得られた導電ペーストを印刷した際、塗膜
強度が低くなってしまうからである。逆に、バインダー
の量が２５重量部を超えると、導電ペーストを印刷して
得られた回路の導電性が低くなり、実用性に欠けるもの
になる。[0008] A conductive paste can be prepared using the conductive alloy powder thus obtained and a binder for binding the alloy powders as main components. The conductive paste is preferably added with 5 to 25 parts by weight of a binder based on 100 parts by weight of the conductive alloy powder. The reason is that, with respect to 100 parts by weight of the conductive alloy powder, if the binder is less than 5 parts by weight, the ratio of the conductive alloy powder is too high. It is because it becomes. On the other hand, when the amount of the binder exceeds 25 parts by weight, the conductivity of a circuit obtained by printing the conductive paste becomes low, and the circuit lacks practicality.
【０００９】前記バインダーはフェノール樹脂、エポキ
シ樹脂、メラミン樹脂、ウレタン樹脂、不飽和ポリエス
テル、ポリイミド、エチレンビニルアセテート樹脂、塩
化ビニル樹脂、酢酸セルロース、メタクリル樹脂、エチ
ルセルロース、ブタジエン樹脂、飽和ポリエステルおよ
びフッ素樹脂の群から選ばれた、少なくとも１つの合成
樹脂またはこの合成樹脂の変成樹脂であるか、またはこ
れら合成樹脂を２種以上混合してなる樹脂であることが
好ましい。このようなバインダーを使用することで、合
金粉末同士を強固に結合させることができる。こうして
得られた導電ペーストは、例えば導電性接着剤、プリン
ト回路形成導電体、電磁シールド塗膜、接点材料など、
電子機器の導体部などに適用することができる。The binder may be a phenolic resin, epoxy resin, melamine resin, urethane resin, unsaturated polyester, polyimide, ethylene vinyl acetate resin, vinyl chloride resin, cellulose acetate, methacrylic resin, ethylcellulose, butadiene resin, saturated polyester and fluororesin. It is preferably at least one synthetic resin selected from the group or a modified resin of this synthetic resin, or a resin obtained by mixing two or more of these synthetic resins. By using such a binder, the alloy powders can be strongly bonded to each other. The conductive paste thus obtained is, for example, a conductive adhesive, a printed circuit forming conductor, an electromagnetic shield coating, a contact material, etc.
The present invention can be applied to a conductor of an electronic device.
【００１０】[0010]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明の導電性合金粉末は、銅にニッケルが固溶
した組織と表面酸化膜が１ｎｍ以下であることを特徴と
している。このような組織を持つ導電性合金粉末は、原
料の合金溶湯を分断するとともに、これを１０4℃／秒
以上の冷却速度で急冷凝固させることにより得ることが
できる。このような冷却速度を達成するための方法の一
例として、二段液体急冷法が挙げられる。ここで、二段
液体急冷法について図１を用いて説明する。図１は、二
段液体急冷法に用いられる装置の概略構成図であり、図
中符号１は二段液体急冷装置、符号２はるつぼ、符号３
は熱電対、符号４はストッパー、符号５は溶湯ノズル、
符号６はガス噴射器、符号７はガス噴射口、符号８は回
転冷却体、符号９は合金溶湯である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The conductive alloy powder of the present invention is characterized in that a structure in which nickel is dissolved in copper and a surface oxide film is 1 nm or less. The conductive alloy powder having such a structure can be obtained by dividing the molten alloy as a raw material and rapidly solidifying the molten alloy at a cooling rate of 10 4 ° C / sec or more. One example of a method for achieving such a cooling rate is a two-stage liquid quenching method. Here, the two-stage liquid quenching method will be described with reference to FIG. FIG. 1 is a schematic configuration diagram of an apparatus used for a two-stage liquid quenching method, in which reference numeral 1 denotes a two-stage liquid quenching device, reference numeral 2 denotes a crucible, and reference numeral 3
Is a thermocouple, reference numeral 4 is a stopper, reference numeral 5 is a molten metal nozzle,
Reference numeral 6 denotes a gas injector, reference numeral 7 denotes a gas injection port, reference numeral 8 denotes a rotary cooling body, and reference numeral 9 denotes a molten alloy.
【００１１】るつぼ２中には、熱電対３を内部に収納し
た筒状のストッパー４が設けられている。また、るつぼ
２には、図示しない加熱源が設けられている。さらに、
るつぼ２の底面の開口部には、溶湯ノズル５が取り付け
られていて、溶湯ノズル５は筒状のストッパー４の下端
壁４ａで塞がれている。前記溶湯ノズル５の下端部を囲
むようにガス噴射器６が設けられている。このガス噴射
器６には、図示しないガス供給源から窒素、アルゴンな
どの高圧ガスが供給されるようになっている。このガス
噴射器６は箱状の構造体であり、中央部は円筒状の挿入
部６ａで仕切られ、この挿入部６ａの下端部に、ガス噴
射器６の内部空間に開口するガスノズル７が形成されて
いて、この挿入部６ａの中に溶湯ノズル５が挿入され、
溶湯ノズル先端部周囲にガスノズル７が位置されてい
る。また、溶湯ノズル５の下方には、円錐駒状の回転冷
却体８が設けられている。The crucible 2 is provided with a cylindrical stopper 4 in which a thermocouple 3 is housed. Further, the crucible 2 is provided with a heating source (not shown). further,
A molten metal nozzle 5 is attached to an opening at the bottom of the crucible 2, and the molten metal nozzle 5 is closed by a lower end wall 4 a of a cylindrical stopper 4. A gas injector 6 is provided so as to surround the lower end of the melt nozzle 5. The gas injector 6 is supplied with a high-pressure gas such as nitrogen or argon from a gas supply source (not shown). The gas injector 6 is a box-shaped structure. The central portion is partitioned by a cylindrical insertion portion 6a, and a gas nozzle 7 that opens into the internal space of the gas injector 6 is formed at the lower end of the insertion portion 6a. The molten metal nozzle 5 is inserted into the insertion portion 6a,
A gas nozzle 7 is located around the tip of the molten metal nozzle. Below the molten metal nozzle 5, a conical-piece-shaped rotary cooling body 8 is provided.
【００１２】次に、二段液体急冷装置の使用方法につい
て説明する。最初に、所望の混合比の金属原料をるつぼ
２に入れ、高周波誘導加熱などの加熱手段により加熱し
て溶解し、合金溶湯９とする。次に、るつぼ２の開口部
を開き、合金溶湯９を溶湯ノズル５から滴下する。同時
に、高圧の不活性なガスを断熱膨張させて発生した高速
ガスをガス噴射器６に供給し、滴下された合金溶湯に向
かって、ガスノズル７から噴出することにより、合金溶
湯９を分断、冷却するとともに高速で下方に吹き付ける
（一次冷却）。分断された合金溶湯９のうち、慣性の小
さな小粒径液滴はガス流に乗り回転冷却体８を避けて飛
散し、１０4℃／秒以上の冷却速度で球状のまま凝固す
る。また熱容量が大きいためそのままでは上記冷却速度
の得られない大粒径粉末は、その慣性の大きさを利用し
回転冷却体８に衝突させ１０4℃／秒以上の冷却速度で
急冷凝固し、導電性合金粉末となる（二次冷却）。すな
わち、合金溶湯９は、ガスノズル７から噴出したガスに
より分断、冷却され、さらに冷却速度の得られ難い大粒
径液滴は回転冷却器８に吹き付けられることにより急冷
される。また、上記のような方法で、導電性合金粉末は
球状、偏平状、フレーク状あるいはリン片状の混合粉末
となり、本発明に好適な導電性合金粉末を製造すること
ができる。Next, a method of using the two-stage liquid quenching device will be described. First, a metal raw material having a desired mixing ratio is put in the crucible 2 and heated and melted by a heating means such as high-frequency induction heating to obtain a molten alloy 9. Next, the opening of the crucible 2 is opened, and the molten alloy 9 is dropped from the molten metal nozzle 5. At the same time, a high-speed gas generated by adiabatic expansion of a high-pressure inert gas is supplied to a gas injector 6 and jetted from a gas nozzle 7 toward a dropped alloy melt, thereby dividing and cooling the alloy melt 9. Spray downward at high speed (primary cooling). Among the divided alloy melts 9, small inertia droplets having small inertia ride on the gas flow and scatter around the rotary cooling body 8, and solidify in a spherical shape at a cooling rate of 10 4 ° C./sec or more. The large-diameter powder, which cannot be obtained as it is because of its large heat capacity, collides with the rotary cooling body 8 by utilizing its inertia and rapidly solidifies at a cooling rate of 10 4 ° C / sec or more. It becomes a functional alloy powder (secondary cooling). That is, the molten alloy 9 is divided and cooled by the gas ejected from the gas nozzle 7, and the large-diameter droplets, for which the cooling rate is difficult to obtain, are rapidly cooled by being sprayed onto the rotary cooler 8. In addition, the conductive alloy powder becomes a spherical, flat, flake-like, or flake-like mixed powder by the above-described method, and a conductive alloy powder suitable for the present invention can be produced.
【００１３】従来、導電性合金粉末を製造する方法に
は、高圧アトマイズ法があった。高圧アトマイズ法と
は、所望の組成の合金を加熱溶解した合金溶湯を滴下
し、これに向かってガスまたは水などの高速高圧流を噴
出することにより合金溶湯を分断し、球状に急冷凝固さ
せるという方法である。しかしながら、本方法で分断さ
れた液滴は１ないし７５μｍの粒度範囲を持っており、
１ないし２５μｍ粒径の液滴は１０4ないし１０5℃／秒
で急冷凝固できるが、２５μｍを超える粒径の液滴は１
０2ないし１０4℃／秒の冷却速度でしか凝固できなかっ
た。これに対し、本実施の形態で用いた二段液体急冷法
の特徴は、高冷却速度を得られ難い２５μｍを超える粒
径の液滴を、一次冷却途中で回転冷却体に衝突させるこ
とで１０4ないし１０5℃／秒で急冷凝固できる点にあ
る。これが従来の高圧アトマイズ法と顕著に異なる点で
あり、本方法はいずれの液滴粒径においても１０4ない
し１０5℃／秒で急冷凝固できる。Hitherto, as a method for producing a conductive alloy powder, there has been a high-pressure atomizing method. The high-pressure atomizing method is a method in which a molten alloy obtained by heating and melting an alloy having a desired composition is dropped, and a high-speed high-pressure flow such as gas or water is jetted toward the molten alloy to divide the molten alloy and rapidly solidify into a sphere. Is the way. However, droplets broken by this method have a particle size range of 1 to 75 μm,
Droplets having a particle size of 1 to 25 µm can be rapidly solidified at 10 4 to 10 5 ° C / sec.
Solidification was only possible at a cooling rate of from 0 2 to 10 4 ° C / sec. On the other hand, the feature of the two-stage liquid quenching method used in the present embodiment is that a droplet having a particle diameter of more than 25 μm, which is difficult to obtain a high cooling rate, is caused to collide with the rotary cooling body during the primary cooling. The point is that it can be rapidly cooled and solidified at 4 to 10 5 ° C / sec. This is a remarkable difference from the conventional high-pressure atomization method, and the present method can rapidly solidify at 10 4 to 10 5 ° C / sec at any droplet size.
【００１４】また、一般に高圧アトマイズ法により得ら
れる導電性合金粉末は球形を呈するが、本方法で調製さ
れる導電性合金粉末は、一部の液滴が回転冷却体８に高
速で衝突するために球状、扁平状、フレーク状あるいは
リン片状の混合粉末となる。球状の導電性合金粉末のみ
では、点でしか接触することができないため導電性の向
上は難しい。また、扁平状のみでも空隙ができるため接
触面積が小さく導電性の向上が難しい。球状および扁平
状の混合粉末では、偏平状粉末同士の空隙に球状粉末が
入り込み、この結果接触面積が大幅に増加し、導電性合
金粉末を導電ペーストとした場合に、導電性を向上させ
ることができる。In general, the conductive alloy powder obtained by the high-pressure atomization method has a spherical shape. However, the conductive alloy powder prepared by the present method has a problem that some droplets collide with the rotary cooling body 8 at high speed. It becomes a spherical, flat, flake, or flaky mixed powder. It is difficult to improve conductivity because only spherical conductive alloy powder can make contact only at points. Further, since a gap is formed only in the flat shape, the contact area is small, and it is difficult to improve the conductivity. In the spherical and flat mixed powder, the spherical powder enters the gaps between the flat powders, and as a result, the contact area is greatly increased, and when the conductive alloy powder is used as the conductive paste, the conductivity can be improved. it can.
【００１５】次に、本発明の導電性合金粉末を、二段液
体急冷法を用いて製造する条件について説明する。合金
溶湯９は、るつぼ２中で１１００ないし１５００℃に保
たれている。効果的に合金溶湯９を微粒液滴化する観点
から、断熱膨張させる前のガスの圧力は１０ｋｇ／ｃｍ
2以上必要であり、５０ｋｇ／ｃｍ2以上が好ましい。断
熱膨張させたガスの流速は、合金溶湯９との衝突位置に
おいて１００ｍ／秒以上必要であり、４００ｍ／秒以上
が好ましい。ここで使用するガスは、例えば窒素、アル
ゴン、へリウムおよびそれらの混合ガスなどの不活性な
ガスである。Next, conditions for producing the conductive alloy powder of the present invention by using the two-stage liquid quenching method will be described. The molten alloy 9 is kept at 1100 to 1500 ° C. in the crucible 2. From the viewpoint of effectively turning the molten alloy 9 into fine droplets, the gas pressure before adiabatic expansion is 10 kg / cm.
2 or more is required, and 50 kg / cm 2 or more is preferable. The flow rate of the adiabatic expanded gas is required to be 100 m / sec or more at the collision position with the molten alloy 9, and is preferably 400 m / sec or more. The gas used here is, for example, an inert gas such as nitrogen, argon, helium and a mixed gas thereof.
【００１６】回転冷却体８の素材は、熱伝導が良好かつ
熱容量の大きな銅、鉄などが適しており、合金液滴の衝
突する表面には、高い硬度および耐熱性を得るため各種
メッキ、蒸着膜などの表面処理を施しておくことが好ま
しい。また、回転冷却体８の形状は頂角４５度以上、１
８０度以下が好ましい。回転冷却体８表面から導電性合
金粉末を効果的に剥離、飛散させる観点から、その回転
周速度は２０ｍ／秒以上が好ましく、その表面温度は５
０℃以下に保つことが好ましい。The material of the rotary cooling body 8 is suitably copper, iron, or the like having good heat conductivity and large heat capacity. The surface on which the alloy droplet collides is subjected to various plating and vapor deposition to obtain high hardness and heat resistance. It is preferable to perform a surface treatment such as a film. Further, the shape of the rotary cooling body 8 has a vertex angle of 45 degrees or more,
80 degrees or less is preferable. From the viewpoint of effectively exfoliating and scattering the conductive alloy powder from the surface of the rotary cooling body 8, its rotational peripheral speed is preferably 20 m / sec or more, and its surface temperature is 5
It is preferable to keep the temperature at 0 ° C. or lower.
【００１７】次に本発明の導電性合金粉末を使用した導
電ペーストについて説明する。本発明において、導電ペ
ーストに使用される導電性合金粉末の平均粒径は４５μ
ｍ以下であることが好ましく、３μｍないし２０μｍの
範囲にあることがより好ましい。その理由は、前記導電
性合金粉末の平均粒径が４５μｍを越えると、これを原
料に製造される導電ペーストをスクリーン印刷に使用す
る時に、ファインパターンの印刷が困難になるためであ
る。導電性合金粉末の平均粒径が４５μｍ以下であれ
ば、これに有機バインダーなどを加えてインク、塗料、
ペーストなどに問題なく加工できる。Next, a conductive paste using the conductive alloy powder of the present invention will be described. In the present invention, the average particle size of the conductive alloy powder used for the conductive paste is 45 μm.
m, and more preferably in the range of 3 μm to 20 μm. The reason is that if the average particle size of the conductive alloy powder exceeds 45 μm, it becomes difficult to print a fine pattern when using a conductive paste produced from the powder as a raw material for screen printing. When the average particle size of the conductive alloy powder is 45 μm or less, an ink, a paint,
Can be processed into pastes without any problems.
【００１８】本発明の導電ペーストは、導電性合金粉末
１００重量部に対してバインダーの量が５ないし２５重
量部の範囲にあることが好ましい。その理由は、導電性
合金粉末１００重量部に対し、バインダーが５重量部未
満であると、導電性合金粉末の比率が高すぎるため、得
られた導電ペーストを印刷した際、塗膜強度が低くなっ
てしまうからである。逆に、バインダーの量が２５重量
部を超えると、導電ペーストを印刷して得られた回路の
導電性が低くなり、実用性に欠けるものとなる。The conductive paste of the present invention preferably has a binder amount in the range of 5 to 25 parts by weight based on 100 parts by weight of the conductive alloy powder. The reason is that, with respect to 100 parts by weight of the conductive alloy powder, if the binder is less than 5 parts by weight, the ratio of the conductive alloy powder is too high. It is because it becomes. Conversely, if the amount of the binder exceeds 25 parts by weight, the conductivity of the circuit obtained by printing the conductive paste becomes low, and the circuit becomes less practical.
【００１９】前記バインダーは、フェノール樹脂、エポ
キシ樹脂、メラミン樹脂、ウレタン樹脂、不飽和ポリエ
ステル、ポリイミド、エチレンビニルアセテート樹脂、
塩化ビニル樹脂、酢酸セルロース、メタクリル樹脂、エ
チルセルロース、ブタジエン樹脂、飽和ポリエステルお
よびフッ素樹脂の群から選ばれた、少なくとも１つの合
成樹脂またはこの合成樹脂の変成樹脂であるか、または
これら合成樹脂を２種以上混合してなる樹脂であること
が好ましい。この混合物は、例えば複数の成分が完全に
混じり合っている状態であっても、ある成分が他の成分
中に分散している状態であってもよい。前記バインダー
を使用する場合、一般的には導電ペーストを接着させた
い基板の材質によって使用するバインダーを選定する。
例えばフェノール基板に導電ペーストを塗布する場合、
バインダーとしては、フェノール樹脂、エポキシ樹脂、
メラミン樹脂、ウレタン樹脂、不飽和ポリエステル、ポ
リイミドなどやそれらの混合物を選定することが好まし
い。基板がポリエステルフィルムの場合は、飽和ポリエ
ステル、エチレンビニルアセテート樹脂、塩化ビニル樹
脂、酢酸セルロース、エチルセルロース、ブタジエン樹
脂、エポキシ樹脂などやそれらの混合物を選定すること
が好ましい。The binder includes a phenol resin, an epoxy resin, a melamine resin, a urethane resin, an unsaturated polyester, a polyimide, an ethylene vinyl acetate resin,
At least one synthetic resin selected from the group consisting of vinyl chloride resin, cellulose acetate, methacrylic resin, ethyl cellulose, butadiene resin, saturated polyester and fluororesin, or a modified resin of this synthetic resin, or two kinds of these synthetic resins It is preferable to use a resin obtained by mixing the above. This mixture may be, for example, a state in which a plurality of components are completely mixed, or a state in which one component is dispersed in another component. When using the binder, the binder to be used is generally selected according to the material of the substrate to which the conductive paste is to be bonded.
For example, when applying a conductive paste to a phenol substrate,
As the binder, phenolic resin, epoxy resin,
It is preferable to select melamine resin, urethane resin, unsaturated polyester, polyimide, and the like, and a mixture thereof. When the substrate is a polyester film, it is preferable to select a saturated polyester, an ethylene vinyl acetate resin, a vinyl chloride resin, a cellulose acetate, an ethyl cellulose, a butadiene resin, an epoxy resin, or a mixture thereof.
【００２０】本発明において、前記導電性合金粉末は、
前記バインダーおよび必要に応じて種々の材料を加え
て、ペースト、塗料、インクなどの状態に加工される。
例えば、あらかじめバインダーを溶媒に溶かし調製した
ビヒクルに前記導電性合金粉末を投入し、ボールミル、
三本ロールミルなどにより分散、混練させて前記ペース
トを調製することができる。前記ペースト調製工程のい
ずれかにおいて、ペーストの諸特性を改善する公知のレ
ベリング剤、消泡剤、チキソトロピック剤、沈降防止剤
などのうち、１種類もしくは２種類以上を添加、混合す
ることができる。このようにして得られた導電ペースト
は、導電性接着剤、プリント回路形成導電体、電磁シー
ルド塗膜、接点材料などとして、電子機器の導体部を構
成することができる。例えば、導電ペーストを、スクリ
ーン印刷などの公知の方法により絶縁基板に塗布し、バ
インダーの種類に応じた乾燥、例えば自然乾燥、加熱硬
化などにより固化させることで分散型導電体を得ること
ができる。In the present invention, the conductive alloy powder comprises:
The binder and various materials are added as necessary, and processed into a paste, paint, ink, or the like.
For example, the conductive alloy powder is put into a vehicle prepared by dissolving a binder in a solvent in advance, and a ball mill,
The paste can be prepared by dispersing and kneading with a three-roll mill or the like. In any of the paste preparation steps, one or more of a known leveling agent, antifoaming agent, thixotropic agent, anti-settling agent, etc., which improve various properties of the paste, can be added and mixed. . The conductive paste thus obtained can constitute a conductor of an electronic device as a conductive adhesive, a printed circuit forming conductor, an electromagnetic shield coating film, a contact material, and the like. For example, a dispersion-type conductor can be obtained by applying a conductive paste to an insulating substrate by a known method such as screen printing and solidifying by drying according to the type of binder, for example, natural drying, heat curing, or the like.
【００２１】[0021]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例のみに限定されるもので
はない。 （実施例１）純度９９．９７％の電解銅９５重量部と、
純度９９％のニッケル５重量部を原料として、図１に示
す二段液体急冷装置を使用し、平均粒径３０μｍの導電
性合金粉末を調製した。この時、原料はるつぼ中で１５
００℃に昇温して溶解、混合した。また、二段液体急冷
装置の回転体の回転速度は３０ｍ／秒、冷却速度は１０
5℃／秒であった。 （実施例２）純度９９．９７％の電解銅８０重量部と、
純度９９％のニッケル２０重量部を原料として、図１に
示す二段液体急冷装置を使用し、平均粒径２２μｍの導
電性合金粉末を調製した。この時、原料はるつぼ中で１
５００℃に昇温して溶解、混合した。また、二段液体急
冷装置の回転体の回転速度は３０ｍ／秒、冷却速度は１
０5℃／秒であった。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. (Example 1) 95 parts by weight of electrolytic copper having a purity of 99.97%;
Using 5 parts by weight of nickel having a purity of 99% as a raw material, a conductive alloy powder having an average particle diameter of 30 μm was prepared using a two-stage liquid quenching apparatus shown in FIG. At this time, the raw materials are placed in a crucible for 15
The temperature was raised to 00 ° C. to dissolve and mix. The rotating speed of the rotating body of the two-stage liquid quenching device was 30 m / sec, and the cooling speed was 10 m / s.
5 ° C./sec. (Example 2) 80 parts by weight of electrolytic copper having a purity of 99.97%,
Using 20 parts by weight of nickel having a purity of 99% as a raw material, a two-stage liquid quenching apparatus shown in FIG. 1 was used to prepare a conductive alloy powder having an average particle size of 22 μm. At this time, the raw material is
The temperature was raised to 500 ° C. to dissolve and mix. The rotating speed of the rotating body of the two-stage liquid quenching device was 30 m / sec, and the cooling speed was 1
0 5 ° C / sec.
【００２２】（比較例１）純度９９．９７％の電解銅９
７重量部と、純度９９％のニッケル３重量部を原料とし
て、図１に示す二段液体急冷装置を使用し、平均粒径５
０μｍの導電性合金粉末を調製した。この時、原料はる
つぼ中で１５００℃に昇温して溶解、混合した。また、
二段液体急冷装置の回転体の回転速度は３０ｍ／秒、冷
却速度は１０5℃／秒であった。 （比較例２）純度９９．９７％の電解銅７５重量部と、
純度９９％のニッケル２５重量部を原料として、図１に
示す二段液体急冷装置を使用し、平均粒径４０μｍの導
電性合金粉末を調製した。この時、原料はるつぼ中で１
５００℃に昇温して溶解、混合した。また、二段液体急
冷装置の回転体の回転速度は３０ｍ／秒、冷却速度は１
０5℃／秒であった。Comparative Example 1 Electrolytic copper 9 having a purity of 99.97%
Using 7 parts by weight and 3 parts by weight of nickel having a purity of 99% as raw materials, a two-stage liquid quenching apparatus shown in FIG.
A 0 μm conductive alloy powder was prepared. At this time, the raw materials were heated to 1500 ° C. in a crucible and dissolved and mixed. Also,
The rotating speed of the rotating body of the two-stage liquid quenching device was 30 m / sec, and the cooling speed was 10 5 ° C / sec. (Comparative Example 2) 75 parts by weight of electrolytic copper having a purity of 99.97%,
Using 25 parts by weight of nickel having a purity of 99% as a raw material, a conductive alloy powder having an average particle diameter of 40 μm was prepared using a two-stage liquid quenching apparatus shown in FIG. At this time, the raw material is
The temperature was raised to 500 ° C. to dissolve and mix. The rotating speed of the rotating body of the two-stage liquid quenching device was 30 m / sec, and the cooling speed was 1
0 5 ° C / sec.
【００２３】実施例１と比較例１で得られた導電性合金
粉末を大気中に１日放置した後、それぞれの表面酸化膜
の厚さをオージェ電子分析装置（ＡＥＳ）により下記の
方法で測定した。 装置：アルバック・ファイ製５９０Ａ 試料の固定：Ｉｎ箔に導電性合金粉末を埋め込み固定 加速電圧：５ｋＶ 試料電流：２０ｎＡ 傾斜：４５度 エッチング条件：Ａｒイオンを２ｋＶで加速して試料表
面よりエッチングAfter the conductive alloy powders obtained in Example 1 and Comparative Example 1 were left in the air for one day, the thickness of each surface oxide film was measured by an Auger electron analyzer (AES) by the following method. did. Apparatus: 590A made by ULVAC-PHI Sample fixation: Conductive alloy powder embedded and fixed in In foil Acceleration voltage: 5 kV Sample current: 20 nA Incline: 45 degrees Etching condition: Etching from the sample surface by accelerating Ar ions at 2 kV
【００２４】上記条件にてエッチングを行い、それぞれ
の導電性合金粉末の、酸素の原子分率の深さ方向の情報
を得た。通常、合金の表面ほど酸素分率が高く、内部に
進むに従い酸素分率は滅少していく。本測定において
は、酸素分率が導電性合金粉末内部の酸素溶存量と一致
する深さを表面酸化膜厚さと規定した。Ｓｉ０2のエッ
チング速度（約７．５ｎｍ／分）を用いて、導電性合金
粉末の表面酸化膜厚さを算出した。実施例１では、表面
酸化膜厚さは０．７ｎｍと計算された。ところが、比較
例１では、表面酸化膜厚さは２．５ｎｍと計算された。
このことから、導電性合金粉末中のニッケルの割合が５
％未満の場合は、大気中における表面酸化膜の厚さが１
ｎｍを超えてしまい、耐環境性に劣るものとなることが
わかった。Etching was performed under the above conditions, and information on the atomic fraction of oxygen in the depth direction of each conductive alloy powder was obtained. Usually, the oxygen content is higher at the surface of the alloy, and the oxygen content decreases as it goes inside. In this measurement, the depth at which the oxygen content coincided with the amount of oxygen dissolved in the conductive alloy powder was defined as the surface oxide film thickness. The surface oxide film thickness of the conductive alloy powder was calculated using the etching rate of SiO 2 (about 7.5 nm / min). In Example 1, the surface oxide film thickness was calculated to be 0.7 nm. However, in Comparative Example 1, the surface oxide film thickness was calculated to be 2.5 nm.
From this, the ratio of nickel in the conductive alloy powder was 5%.
%, The thickness of the surface oxide film in the atmosphere is 1
It was found that the average particle diameter exceeded nm, resulting in poor environmental resistance.
【００２５】次に、実施例２および比較例２で得られた
導電性合金粉末を原料とする導電ペーストの比抵抗を比
較した。フェノール樹脂に対して、実施例２および比較
例２で得られた導電性合金粉末を体積割合で４５％混入
して混練し、２種類の導電ペーストを製造した。この
時、溶剤は、ターピネオール、ベンジルアルコール、カ
ルビトールの３種類を１：２：２の割合で混合したもの
を使用した。得られた導電ペーストをスクリーン印刷
後、加熱硬化させた皮膜について比抵抗を測定したとこ
ろ、実施例２の導電性合金粉末から製造した導電ペース
トからなる皮膜では、２×１０-3Ωｃｍであったのに対
し、比較例２の導電性合金粉末から製造した導電ペース
トからなる皮膜では、１．５×１０-2Ωｃｍであった。
これにより、導電性合金粉末中のニッケルの割合が２０
％を超える場合は、この導電性合金粉末を用いて製造し
た導電ペーストの比抵抗が高くなり、実際の使用には適
さないものとなることがわかった。また、実施例２の導
電性合金粉末を用いて製造した導電ペーストからなる皮
膜について、８０℃、１０００時間の耐熱試験および６
０℃、湿度９０％、１０００時間の耐湿試験における抵
抗率の変化は、それぞれ３０％以下、５０％以下であっ
た。上記の試験結果を表１にまとめる。Next, the specific resistance of the conductive paste obtained from the conductive alloy powder obtained in Example 2 and Comparative Example 2 was compared. The conductive alloy powders obtained in Example 2 and Comparative Example 2 were mixed in a volume ratio of 45% with the phenol resin and kneaded to produce two types of conductive paste. At this time, the solvent used was a mixture of three kinds of terpineol, benzyl alcohol and carbitol at a ratio of 1: 2: 2. After screen printing of the obtained conductive paste, the specific resistance of the heat-cured film was measured. As a result, it was 2 × 10 −3 Ωcm for the film made of the conductive paste manufactured from the conductive alloy powder of Example 2. On the other hand, the film made of the conductive paste produced from the conductive alloy powder of Comparative Example 2 had a value of 1.5 × 10 −2 Ωcm.
As a result, the ratio of nickel in the conductive alloy powder becomes 20%.
%, It was found that the specific resistance of the conductive paste produced using this conductive alloy powder was high, which was not suitable for actual use. In addition, a film made of a conductive paste manufactured using the conductive alloy powder of Example 2 was subjected to a heat resistance test at 80 ° C. for 1000 hours,
The changes in resistivity in the humidity resistance test at 0 ° C., 90% humidity, and 1000 hours were 30% or less and 50% or less, respectively. Table 1 summarizes the above test results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】次に、本発明の導電ペーストを電子機器に
適用した例について述べる。実施例２で製造した合金粉
末とフェノール樹脂を、重量比で９０：１０の割合で混
合した。この混合物１に対してカルビトールを０．１な
いし０．２の割合で加えて粘度調整することにより、印
刷用ペーストを製造した。この印刷用ペーストを、スク
リーン印刷機を用いてポリエステルフィルム２２上に印
刷、焼成することにより、図２に示すノートブック型パ
ーソナルコンピューター用のポインティングデバイス用
回路基板２１を得た。この印刷された回路パターン２３
の抵抗率は２×１０-3Ωｃｍであり、８０℃、５００時
間の耐熱試験および６０℃、湿度９０％、５００時間の
耐湿試験における抵抗率の変化は、２５％、４２％であ
った。Next, an example in which the conductive paste of the present invention is applied to an electronic device will be described. The alloy powder produced in Example 2 and the phenol resin were mixed at a weight ratio of 90:10. A printing paste was prepared by adding carbitol to this mixture 1 at a ratio of 0.1 to 0.2 and adjusting the viscosity. The printing paste was printed on a polyester film 22 using a screen printing machine and baked to obtain a pointing device circuit board 21 for a notebook personal computer shown in FIG. This printed circuit pattern 23
Has a resistivity of 2 × 10 −3 Ωcm, and changes in resistivity in a heat resistance test at 80 ° C. for 500 hours and a humidity resistance test at 60 ° C., humidity of 90% and 500 hours are 25% and 42%.
【００２８】得られたポインティングデバイス用回路基
板２１上の回路パターン２３に、集積回路２４、コンデ
ンサ２５、抵抗器２６、コネクタ２７、ダイオードアレ
イ２８、電解コンデンサ２９をハンダ付けした。図３
は、集積回路２４を回路パターン２３にハンダ付けした
部分の拡大側面図である。ポリエステルフィルム２２上
の回路パターン２３のハンダ付け部分に、あらかじめハ
ンダ付け用ペースト３０を印刷しておき、この上に集積
回路２４のリード端子３１を乗せ、ハンダ３２で固定し
た。その他の部品においても同様の方法でハンダ付けを
行うことで、ノートブック型パーソナルコンピューター
用のポインティングデバイス用回路が得られた。An integrated circuit 24, a capacitor 25, a resistor 26, a connector 27, a diode array 28, and an electrolytic capacitor 29 were soldered to a circuit pattern 23 on the obtained pointing device circuit board 21. FIG.
FIG. 3 is an enlarged side view of a portion where the integrated circuit 24 is soldered to the circuit pattern 23. The soldering paste 30 was printed in advance on the soldered portion of the circuit pattern 23 on the polyester film 22, and the lead terminals 31 of the integrated circuit 24 were placed thereon and fixed with the solder 32. By soldering other parts in the same manner, a pointing device circuit for a notebook personal computer was obtained.
【００２９】[0029]
【発明の効果】上述のごとく、本発明の導電性合金粉末
は銅とニッケルからなり、この導電性合金粉末中に占め
るニッケルの割合が５ないし２０重量％であり、ニッケ
ルが銅に固溶した組織を有し、前記合金粉末の平均粒径
が４５μｍ以下であり、かつ表面酸化膜の厚さが１ｎｍ
以下であるという特徴を有する。この導電性合金粉末
は、大気中で酸化しにくく、長期安定性に優れている。
このような導電性合金粉末は、合金溶湯をガスにより分
断するとともに一次冷却し、生成した合金液滴を回転冷
却体に衝突させることにより二次冷却するとともに偏平
固化させる、二段液体急冷法により得ることができる。As described above, the conductive alloy powder of the present invention comprises copper and nickel. The proportion of nickel in the conductive alloy powder is 5 to 20% by weight, and nickel is dissolved in copper. The alloy powder has an average particle size of 45 μm or less, and the thickness of the surface oxide film is 1 nm.
It has the following features. This conductive alloy powder is hardly oxidized in the air and has excellent long-term stability.
Such a conductive alloy powder is divided into two parts by a two-stage liquid quenching method, in which the molten alloy is divided by gas and primary cooled, and the produced alloy droplets are secondarily cooled and flattened by colliding with a rotating cooling body. Obtainable.
【００３０】前記導電性合金粉末とバインダーを主成分
として作成した導電ペーストは、使用初期の段階から長
期にわたり導電性が良好である。さらに、本発明の導電
ペーストを電子機器に適用すると、導電性接着剤、プリ
ント回路形成導電体、電磁シールド塗膜、接点材料な
ど、抵抗率が低く、耐熱性、耐湿性に優れた電子機器の
導体部を得ることができる。The conductive paste prepared using the conductive alloy powder and the binder as main components has good conductivity for a long period of time from the initial stage of use. Furthermore, when the conductive paste of the present invention is applied to electronic equipment, conductive adhesives, printed circuit forming conductors, electromagnetic shielding coatings, contact materials, etc., have low resistivity, and have excellent heat resistance and moisture resistance. A conductor can be obtained.
【図１】 二段急冷法に用いられる装置の概略構成図。FIG. 1 is a schematic configuration diagram of an apparatus used for a two-stage quenching method.
【図２】 本発明の導電ペーストを電子機器に適用して
得られた回路図。FIG. 2 is a circuit diagram obtained by applying the conductive paste of the present invention to an electronic device.
【図３】 集積回路２４を回路パターン２３にハンダ付
けした部分の拡大側面図。FIG. 3 is an enlarged side view of a portion where the integrated circuit 24 is soldered to the circuit pattern 23.
１ 二段急冷装置 ２ るつぼ ３ 熱電対 ４ ストッパー ５ ノズル ６ ガス噴射器 ７ ガス噴射口 ８ 回転冷却体 ９ 金属溶湯 DESCRIPTION OF SYMBOLS 1 Two-stage quenching device 2 Crucible 3 Thermocouple 4 Stopper 5 Nozzle 6 Gas injector 7 Gas injection port 8 Rotary cooling body 9 Metal melt
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西山 信行 東京都中央区八重洲１丁目９番９号 帝国 ピストンリング株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobuyuki Nishiyama 1-9-9 Yaesu, Chuo-ku, Tokyo Imperial Piston Ring Co., Ltd.
Claims (5)
あって、該導電性合金粉末中に占めるニッケルの割合が
５ないし２０重量％であり、ニッケルが銅に固溶した組
織を有し、前記導電性合金粉末の平均粒径が４５μｍ以
下であり、かつ表面酸化膜の厚さが１ｎｍ以下であるこ
とを特徴とする導電性合金粉末。1. A conductive alloy powder comprising copper and nickel, wherein the proportion of nickel in the conductive alloy powder is 5 to 20% by weight, and the structure has a solid solution of nickel in copper; The conductive alloy powder, wherein the average particle size of the conductive alloy powder is 45 μm or less, and the thickness of the surface oxide film is 1 nm or less.
合金溶湯を流出させ、前記溶湯ノズル下方に設置したガ
スノズルから噴出するガスによって前記流出合金溶湯を
分断するとともに一次冷却し、さらに液滴を前記ガスノ
ズルの下方に設置した回転冷却体に衝突させることによ
って、１０4℃／秒以上の冷却速度で凝固させ、表面酸
化膜の厚さを１ｎｍ以下に抑えた球状および偏平状の混
合粉末を生成したことを特徴とする導電性合金粉末の製
造方法。2. An alloy melt composed of copper and nickel is caused to flow out of a melt nozzle, and the melted alloy melt is divided and primarily cooled by gas ejected from a gas nozzle provided below the melt nozzle, and the droplet is further cooled. By colliding with a rotary cooling member installed below the gas nozzle, the solidified material was solidified at a cooling rate of 10 4 ° C / sec or more, thereby producing a spherical and flat mixed powder in which the thickness of the surface oxide film was suppressed to 1 nm or less. A method for producing a conductive alloy powder, comprising:
量部に対し、バインダーを５ないし２５重量部添加した
ことを特徴とする導電ペースト。3. A conductive paste, characterized in that 5 to 25 parts by weight of a binder is added to 100 parts by weight of the conductive alloy powder according to claim 1.
キシ樹脂、メラミン樹脂、ウレタン樹脂、不飽和ポリエ
ステル、ポリイミド、エチレンビニルアセテート樹脂、
塩化ビニル樹脂、酢酸セルロース、メタクリル樹脂、エ
チルセルロース、ブタジエン樹脂、飽和ポリエステルお
よびフッ素樹脂の群から選ばれた、少なくとも１つの合
成樹脂または該合成樹脂の変成樹脂であるか、またはこ
れら合成樹脂を２種以上混合してなる樹脂であることを
特徴とする請求項３記載の導電ペースト。4. The binder according to claim 1, wherein the binder is a phenol resin, an epoxy resin, a melamine resin, a urethane resin, an unsaturated polyester, a polyimide, an ethylene vinyl acetate resin,
At least one synthetic resin selected from the group consisting of vinyl chloride resin, cellulose acetate, methacrylic resin, ethyl cellulose, butadiene resin, saturated polyester and fluororesin, or a modified resin of the synthetic resin, or two kinds of these synthetic resins 4. The conductive paste according to claim 3, which is a resin obtained by mixing the above.
した導体部を備えたことを特徴とする電子機器。5. An electronic device comprising a conductor portion formed of the conductive paste according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9185570A JPH1129801A (en) | 1997-07-10 | 1997-07-10 | Conductive alloy powder, its production, conductive paste using the conductive alloy powder, and electronic equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9185570A JPH1129801A (en) | 1997-07-10 | 1997-07-10 | Conductive alloy powder, its production, conductive paste using the conductive alloy powder, and electronic equipment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1129801A true JPH1129801A (en) | 1999-02-02 |
Family
ID=16173127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9185570A Withdrawn JPH1129801A (en) | 1997-07-10 | 1997-07-10 | Conductive alloy powder, its production, conductive paste using the conductive alloy powder, and electronic equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1129801A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060551A3 (en) * | 2000-02-18 | 2002-06-20 | Canadian Electronics Powders C | Nickel powder for use as electrodes in base metal electrode multilayered ceramic capacitors |
| CN102092714A (en) * | 2011-01-12 | 2011-06-15 | 株洲弗拉德科技有限公司 | Fine grain casting tungsten carbide continuous production furnace |
| KR101333342B1 (en) * | 2012-02-21 | 2013-11-28 | (주)이그잭스 | Method of forming a metal powder and method of manufacturing a conductive paste using the same |
| JP2014091842A (en) * | 2012-11-01 | 2014-05-19 | Dowa Electronics Materials Co Ltd | Method of manufacturing silver coating copper alloy powder |
-
1997
- 1997-07-10 JP JP9185570A patent/JPH1129801A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060551A3 (en) * | 2000-02-18 | 2002-06-20 | Canadian Electronics Powders C | Nickel powder for use as electrodes in base metal electrode multilayered ceramic capacitors |
| JP2003522835A (en) * | 2000-02-18 | 2003-07-29 | カナディアン・エレクトロニクス・パウダーズ・コーポレーション | Nickel powder for use as electrode of base metal electrode multilayer ceramic capacitor |
| US7520914B2 (en) | 2000-02-18 | 2009-04-21 | Canadian Electronic Powders Corporation | Nickel powder for use as electrodes in base metal electrode multilayered ceramic capacitors |
| JP4986356B2 (en) * | 2000-02-18 | 2012-07-25 | カナディアン・エレクトロニクス・パウダーズ・コーポレーション | Method for producing nickel powder |
| CN102092714A (en) * | 2011-01-12 | 2011-06-15 | 株洲弗拉德科技有限公司 | Fine grain casting tungsten carbide continuous production furnace |
| KR101333342B1 (en) * | 2012-02-21 | 2013-11-28 | (주)이그잭스 | Method of forming a metal powder and method of manufacturing a conductive paste using the same |
| JP2014091842A (en) * | 2012-11-01 | 2014-05-19 | Dowa Electronics Materials Co Ltd | Method of manufacturing silver coating copper alloy powder |
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