JPH10168503A - Composite powder with high electric conductivity - Google Patents
Composite powder with high electric conductivityInfo
- Publication number
- JPH10168503A JPH10168503A JP8329293A JP32929396A JPH10168503A JP H10168503 A JPH10168503 A JP H10168503A JP 8329293 A JP8329293 A JP 8329293A JP 32929396 A JP32929396 A JP 32929396A JP H10168503 A JPH10168503 A JP H10168503A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- alloy
- metal
- coating
- coated
- 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- Withdrawn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
- 239000000843 powder Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000000956 alloy Substances 0.000 claims abstract description 45
- 238000004544 sputter deposition Methods 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 7
- 229910001111 Fine metal Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910007570 Zn-Al Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 13
- 229910007565 Zn—Cu Inorganic materials 0.000 claims description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 4
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 8
- 229910020935 Sn-Sb Inorganic materials 0.000 abstract description 5
- 229910008757 Sn—Sb Inorganic materials 0.000 abstract description 5
- -1 plastic moldings Substances 0.000 abstract description 3
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- 239000002985 plastic film Substances 0.000 abstract description 2
- 229920006255 plastic film Polymers 0.000 abstract description 2
- 238000010137 moulding (plastic) Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 12
- 230000006837 decompression Effects 0.000 description 11
- 229910006404 SnO 2 Inorganic materials 0.000 description 8
- 229910001245 Sb alloy Inorganic materials 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004566 building material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、帯電防止用，ＥＭＩシ
ールド用等の塗料，プラスチック成形品，プラスチック
フィルム，合成繊維等に配合される高導電性粉末に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly conductive powder to be incorporated in paints for antistatic purposes, EMI shielding and the like, plastic molded articles, plastic films, synthetic fibers and the like.
【０００２】[0002]
【従来の技術】帯電防止用として使用される導電性粉末
には、カーボンブラック，黒鉛，炭素繊維等のカーボン
系粉末，ＳｎドープＩｎ2 Ｏ3 ，ＳｂドープＳｎＯ2 ，
ＡｌドープＺｎＯ等の無機半導体粉末，ＳｎドープＳｎ
Ｏ2 被覆ＴｉＯ2 ，ＳｎドープＳｎＯ2 被覆マイカ，Ｓ
ｂドープＳｎＯ2 被覆ＢａＳＯ4 等の無機半導体被覆複
合粉末がある。なかでも、安価で導電性がよいことから
カーボンブラックが最も使用されている。しかし、カー
ボンブラックを使用した導電性粉末では、黒色以外の色
をつけることが困難であった。特に、カーペット，カー
テン等の合成繊維や、壁紙，間仕切り等のプラスチック
スを帯電防止処理する際には、カーボンブラックと同等
の優れた導電性を示し、且つ着色が容易な白色系の微粉
末が要求されていた。そこで、前掲したような各種の無
機半導体粉末や無機半導体被覆複合粉末が開発されてき
た。2. Description of the Related Art Conductive powders used for antistatic purposes include carbon-based powders such as carbon black, graphite and carbon fiber, Sn-doped In 2 O 3 , Sb-doped SnO 2 , and the like.
Inorganic semiconductor powder such as Al-doped ZnO, Sn-doped Sn
O 2 coated TiO 2 , Sn doped SnO 2 coated mica, S
There is an inorganic semiconductor-coated composite powder such as b-doped SnO 2 -coated BaSO 4 . Among them, carbon black is most used because of its low cost and good conductivity. However, it has been difficult to give a color other than black with a conductive powder using carbon black. In particular, when performing antistatic treatment on synthetic fibers such as carpets and curtains, and plastics such as wallpaper and partition walls, white fine powder that exhibits excellent conductivity equivalent to carbon black and is easy to color is used. Had been requested. Therefore, various inorganic semiconductor powders and inorganic semiconductor-coated composite powders as described above have been developed.
【０００３】従来の無機半導体粉末や無機半導体被覆複
合粉末は、何れも白色系で、種々の着色が容易であるも
のの、無機半導体であることからカーボンブラックや金
属に比較すると導電性がかなり劣っている。他方、コン
ピュータやＯＡ機器の急速な普及に伴って、電磁波の悪
影響が大きな問題となってきている。この点では、単な
る帯電防止用としてではなく、ＥＭＩシールドも可能な
カーペット，カーテン，壁紙，間仕切り等の内装建材の
開発が検討され始めており、そのためにより優れた導電
性を示す白色系微粉末の開発が強く望まれている。ＥＭ
Ｉシールド用には、Ａｇ，Ｃｕ，Ｎｉ，Ａｌ，Ｚｎ等の
金属粉末やＡｇ被覆シリコーン樹脂，Ｃｕ被覆マイカ，
Ｎｉ被覆チタン酸カリウムウイスカ等の金属被覆複合粉
末が優れた導電性を示す粉末として一般に使用されてい
る。[0003] Conventional inorganic semiconductor powders and inorganic semiconductor-coated composite powders are all white and can be easily colored in various ways. However, since they are inorganic semiconductors, their conductivity is considerably inferior to carbon black and metals. I have. On the other hand, with the rapid spread of computers and OA equipment, the adverse effects of electromagnetic waves have become a major problem. In this regard, the development of interior building materials such as carpets, curtains, wallpapers, partitions, etc. that are not merely antistatic but also capable of EMI shielding has begun to be studied. Is strongly desired. EM
For I shielding, metal powder such as Ag, Cu, Ni, Al, Zn, etc., Ag-coated silicone resin, Cu-coated mica,
Metal-coated composite powders such as Ni-coated potassium titanate whiskers are generally used as powders having excellent conductivity.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これらの金属
被覆複合粉末は、優れた導電性を示すものの、粒径が１
０μｍを超える大きさであり、繊維径が３０μｍ以下で
あるカーペット，カーテン等の合成繊維の中にうまく練
り込むことができない。また、金属粉末は、使用中に表
面が酸化又は腐食すると導電性が低下する。他方、金属
被覆複合粉末として、シリコーン樹脂やマイカに金属を
コーティングして導電性を発現させる場合、従来の無電
解めっき等では粒子表面に均一で且つ薄くコーティング
することが困難なために、膜厚を厚くすることにより導
電性を確保している。しかし、比表面積が大きく且つ比
重の小さいこれらの粉末に比重の大きい金属をコーティ
ングすると、５０〜８０重量％もの大きな被覆量が必要
となり、製造コストの大幅な上昇を招く。本発明は、こ
のような問題を解消すべく案出されたものであり、金属
微粉末の表面にスパッタリング法で白色系合金を被覆す
ることにより、金属被覆量を可能な限り少なくして製造
コストを節減し、カーボンブラック，金属等と同レベル
の導電性を示し、粒径が小さく耐食性にも優れた高導電
性粉末を提供することを目的とする。However, these metal-coated composite powders exhibit excellent conductivity, but have a particle size of 1%.
It cannot be kneaded well into synthetic fibers such as carpets and curtains having a size exceeding 0 μm and a fiber diameter of 30 μm or less. In addition, the conductivity of the metal powder decreases when the surface is oxidized or corroded during use. On the other hand, when a metal is coated on a silicone resin or mica as a metal-coated composite powder to exhibit conductivity, it is difficult to coat the particle surface uniformly and thinly by conventional electroless plating or the like. The conductivity is ensured by increasing the thickness. However, if these powders having a large specific surface area and a small specific gravity are coated with a metal having a large specific gravity, a coating amount as large as 50 to 80% by weight is required, and the production cost is greatly increased. The present invention has been devised to solve such a problem. By coating the surface of a fine metal powder with a white alloy by a sputtering method, the amount of metal coating can be reduced as much as possible to reduce the manufacturing cost. It is an object of the present invention to provide a highly conductive powder exhibiting the same level of conductivity as carbon black, metal and the like, and having a small particle size and excellent corrosion resistance.
【０００５】[0005]
【課題を解決するための手段】本発明の高導電性複合粉
末は、その目的を達成するため、平均粒径０．１〜１０
μｍの金属微粉末をスパッタリング法により１〜１０重
量％の白色系合金で被覆していることを特徴とする。金
属微粉末には、Ｓｉ，Ｔｉ，Ｚｎ又はＡｌの１種又は２
種以上が使用される。白色系合金には、Ｉｎ−Ｓｎ合
金，Ｓｎ−Ｓｂ合金、Ｚｎ−Ａｌ合金又はＺｎ−Ｃｕ合
金が使用される。Means for Solving the Problems The highly conductive composite powder of the present invention has an average particle diameter of 0.1 to 10 in order to achieve the object.
It is characterized in that fine metal powder of μm is coated with 1 to 10% by weight of a white alloy by a sputtering method. The metal fine powder includes one or more of Si, Ti, Zn or Al.
More than seeds are used. As the white alloy, an In-Sn alloy, a Sn-Sb alloy, a Zn-Al alloy, or a Zn-Cu alloy is used.
【０００６】[0006]
【実施の形態】Ｓｉ，Ｔｉ等の金属粉末の表面は、通常
ＳｉＯ2 ，ＴｉＯ2 等の酸化皮膜で覆われている。この
金属粉末の表面に、スパッタリング法でＳｎ−Ｓｂ合金
を被覆すると、粉末表面にＳｂドープＳｉＯ2 層，Ｓｂ
ドープＴｉＯ2 層等の無機半導体層が形成される。同様
に、Ｚｎ粉末の表面は、ＺｎＯの酸化皮膜で覆われてい
るので、この表面にスパッタリング法でＩｎ−Ｓｎ合
金，Ｚｎ−Ａｌ合金又はＺｎ−Ｃｕ合金を被覆すると、
粉末表面にＩｎドープＺｎＯ層，ＡｌドープＺｎＯ層，
ＣｕドープＺｎＯ層等の無機半導体層が形成される。ま
た、Ａｌ2 Ｏ3 の酸化皮膜で覆われているＡｌ粉末の表
面にスパッタリング法でＩｎ−Ｓｎ合金又はＳｎ−Ｓｂ
合金を被覆すると、粉末表面にＳｎドープＡｌ2 Ｏ3 層
のような無機半導体層が形成される。金属粉末は、球
状，粒状，フレーク状，ウイスカ状の何れの形状でも良
いが、塗料，プラスチックス等に対する分散性からは球
状が最適である。粉末の平均粒径は、０．１〜１０μ
ｍ，より好ましくは１〜３μｍの範囲が適している。粒
径が０．１μｍに満たないと、粉末の表面積が大きくな
り、導電性を発現させるために必要な合金の被覆量が極
めて多くなり、結果としてコストを上昇させる。逆に１
０μｍを超える大粒径では、塗料やプラスチックスに混
合する際に分散状態が不均一になり易く、安定した導電
性が得られ難い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface of a metal powder such as Si or Ti is usually covered with an oxide film such as SiO 2 or TiO 2 . When the surface of this metal powder is coated with a Sn—Sb alloy by a sputtering method, an Sb-doped SiO 2 layer, Sb
An inorganic semiconductor layer such as a doped TiO 2 layer is formed. Similarly, since the surface of the Zn powder is covered with a ZnO oxide film, if this surface is coated with an In—Sn alloy, a Zn—Al alloy, or a Zn—Cu alloy by a sputtering method,
In-doped ZnO layer, Al-doped ZnO layer,
An inorganic semiconductor layer such as a Cu-doped ZnO layer is formed. In addition, an In-Sn alloy or Sn-Sb is formed on the surface of the Al powder covered with the oxide film of Al 2 O 3 by a sputtering method.
When the alloy is coated, an inorganic semiconductor layer such as a Sn-doped Al 2 O 3 layer is formed on the powder surface. The metal powder may be in any of spherical, granular, flake, and whisker-like shapes, but the spherical shape is optimal from the viewpoint of dispersibility in paints, plastics, and the like. The average particle size of the powder is 0.1-10μ
m, more preferably in the range of 1 to 3 μm. If the particle size is less than 0.1 μm, the surface area of the powder becomes large, and the amount of the alloy coating required for exhibiting conductivity becomes extremely large, resulting in an increase in cost. Conversely 1
If the particle diameter is larger than 0 μm, the dispersion state tends to be non-uniform when mixed with paints or plastics, and it is difficult to obtain stable conductivity.
【０００７】コーティングに使用される白色系合金とし
ては、次の条件を満足する合金組成が好ましい。 （１）合金自体の導電性が良好なこと。 （２）合金皮膜の最表面に生成する酸化物膜も、導電性
が良好な無機半導体組成になっていること。 （３）スパッタリング法による被覆時に、金属微粉末表
面の酸化皮膜層にも導電性の良い無機半導体ドープ層が
形成されること。 これら条件を満足させるためには、金属微粉末を構成し
ている金属元素よりも価数が一つ多い金属元素を含む合
金を選択する必要がある。これにより、酸化皮膜及びド
ープ層を構成している結晶格子が酸素欠損状態になり、
余剰電子が発生して電気が流れ易くなる。このような合
金として、Ｉｎ−Ｓｎ合金，Ｓｎ−Ｓｂ合金，Ｚｎ−Ａ
ｌ合金，Ｚｎ−Ｃｕ合金等がある。[0007] As a white alloy used for coating, an alloy composition satisfying the following conditions is preferable. (1) The conductivity of the alloy itself is good. (2) The oxide film formed on the outermost surface of the alloy film has an inorganic semiconductor composition having good conductivity. (3) An inorganic semiconductor doped layer having good conductivity is formed on the oxide film layer on the surface of the metal fine powder during coating by the sputtering method. In order to satisfy these conditions, it is necessary to select an alloy containing a metal element having one more valence than the metal element constituting the metal fine powder. As a result, the crystal lattice constituting the oxide film and the doped layer becomes oxygen-deficient,
Excess electrons are generated, and electricity flows easily. Such alloys include In-Sn alloy, Sn-Sb alloy, Zn-A
1 alloy, Zn-Cu alloy and the like.
【０００８】白色系合金の被覆量は、１〜１０重量％，
好ましくは４〜７重量％の範囲が適している。被覆量が
１重量％に満たないと、粉末表面を連続した被覆で覆う
ことが困難になり、十分な導電性が得られない。逆に１
０重量％を超える被覆量では、導電性が良好であるもの
の、製造コストが高くなる。コーティング法としては、
スパッタリング法以外にイオンプレーティング法，真空
蒸着法等が考えられるが、本発明者等が開発した粉末ス
パッタリング法が最適である。粉末スパッタリング法で
白色系合金の被覆層を形成する場合、次のようなターゲ
ットが使用される。何れのターゲットを使用した場合で
も、各合金成分が均一に固溶した所定組成をもつ合金皮
膜が形成される。 （ａ）形成しようとする合金と平均組成は等しいが、単
相でない複数の結晶層からなるターゲットを焼結法又は
溶融法で作製したもの。 （ｂ）形成しようとする合金被覆の主成分からなる金属
板に合金化しようとする金属を埋め込んだ組合せターゲ
ット （ｃ）形成しようとする合金被覆の組成に応じて複数の
単一金属のターゲットを組み合わせたもの。The coating amount of the white alloy is 1 to 10% by weight,
Preferably, the range of 4 to 7% by weight is suitable. If the coating amount is less than 1% by weight, it becomes difficult to cover the powder surface with a continuous coating, and sufficient conductivity cannot be obtained. Conversely 1
When the coating amount exceeds 0% by weight, the conductivity is good, but the production cost is high. As a coating method,
In addition to the sputtering method, an ion plating method, a vacuum evaporation method and the like can be considered, but the powder sputtering method developed by the present inventors is the most suitable. When forming a coating layer of a white alloy by the powder sputtering method, the following targets are used. Whichever target is used, an alloy film having a predetermined composition in which each alloy component is uniformly dissolved is formed. (A) A target having the same average composition as the alloy to be formed but having a plurality of non-single-phase crystal layers produced by a sintering method or a melting method. (B) a combination target in which a metal to be alloyed is embedded in a metal plate composed mainly of an alloy coating to be formed; and (c) a plurality of single metal targets according to the composition of the alloy coating to be formed. The combination.
【０００９】金属微粉末表面への各種合金の被覆は、本
発明者等が開発した粉末スパッタリング装置が使用可能
である。たとえば、微粉末を入れた回転容器を回転させ
て流動層を形成し、金属をスパッタリングする装置（特
開平２−１５３０６８号公報），繰り返し行われる微粉
末の落下流に金属をスパッタリングする装置（特開昭６
２−２５０１７２号公報）等がある。図１に示す粉末ス
パッタリング装置においては、回転ドラム１を２本のロ
ール２で支持し、一方のロール２をモータ３で回転させ
る。回転ドラム１の内部には、２個のスパッタリング源
４が配置されており、投入した粉末原料５がスパッタリ
ングされる。For coating the surface of the metal fine powder with various alloys, a powder sputtering apparatus developed by the present inventors can be used. For example, a rotating vessel containing fine powder is rotated to form a fluidized bed, and metal is sputtered (Japanese Patent Application Laid-Open No. 2-153068). Kaisho 6
2-250172). In the powder sputtering apparatus shown in FIG. 1, a rotating drum 1 is supported by two rolls 2, and one of the rolls 2 is rotated by a motor 3. Inside the rotating drum 1, two sputtering sources 4 are arranged, and the charged powder material 5 is sputtered.
【００１０】回転ドラム１の上方には、外周に加熱コイ
ル６を備えた減圧処理室７が配置されており、減圧処理
室７の底部がバルブ８を備えた供給管９を介して回転ド
ラム１に接続されている。供給管９は、バルブ８より下
側の部分でＡｒガス導入管１０が内部に挿入された二重
管構造になっており、側面から回転ドラム１の内部に挿
入され、先端が回転ドラム１の底部に延びている。ま
た、バルブ８より下側で供給管９に分岐管１１が取り付
けられており、分岐管１１の先端が流体ジェットミル１
２に接続されている。流体ジェットミル１２の出側は、
循環管１３を経て減圧処理室７の上部に接続されてい
る。分岐管１１，循環管１３にバルブ１４，１５が挿入
されており、循環管１３には固気分離装置１６が接続さ
れている。Above the rotary drum 1, a decompression processing chamber 7 provided with a heating coil 6 on the outer periphery is arranged, and the bottom of the decompression processing chamber 7 is connected to the rotation drum 1 It is connected to the. The supply pipe 9 has a double pipe structure in which an Ar gas introduction pipe 10 is inserted inside a portion below the valve 8, and is inserted into the inside of the rotary drum 1 from a side surface, and a tip of the rotary drum 1 is provided. Extends to the bottom. A branch pipe 11 is attached to the supply pipe 9 below the valve 8, and the tip of the branch pipe 11 is connected to the fluid jet mill 1.
2 are connected. The outlet side of the fluid jet mill 12 is
It is connected to the upper part of the decompression processing chamber 7 via the circulation pipe 13. Valves 14 and 15 are inserted into the branch pipe 11 and the circulation pipe 13, and a solid-gas separation device 16 is connected to the circulation pipe 13.
【００１１】回転ドラム１内でスパッタリングにより金
属被覆された微粉末５は、分岐管１１，循環管１３から
減圧処理室７に送られ、所定厚みの皮膜が形成されるま
でスパッタリング処理に繰り返し供される。所定の厚み
をもつ皮膜が形成された微粉末５は、固気分離装置１６
で回収される。白色系合金皮膜が形成された微粉末は、
不活性雰囲気中での加熱・拡散処理により無機半導体ド
ープ層を成長させても良い。たとえば、アルゴン，窒
素，水素等のガス雰囲気中で３００〜５００℃で約１時
間加熱・拡散処理すると、無機半導体ドープ層が厚く成
長し、導電性が一層よくなる。また、色調や導電性を調
整するため、塗料，プラスチック中への混合量を５０重
量％以下と少なくしたり、従来のカーボン系粉末，無機
半導体系粉末，無機半導体被覆複合粉末，金属粉末，金
属被覆複合粉末等の従来品と本発明品を任意の割合で使
用することもできる。The fine powder 5 metal-coated by sputtering in the rotary drum 1 is sent from the branch pipe 11 and the circulation pipe 13 to the decompression processing chamber 7 and repeatedly subjected to the sputtering process until a film having a predetermined thickness is formed. You. The fine powder 5 on which a film having a predetermined thickness is formed is supplied to a solid-gas separation device 16.
Collected at. The fine powder on which the white alloy film is formed
The inorganic semiconductor doped layer may be grown by a heating / diffusion treatment in an inert atmosphere. For example, when heating and diffusion treatment is performed at 300 to 500 ° C. for about 1 hour in a gas atmosphere of argon, nitrogen, hydrogen, or the like, the inorganic semiconductor doped layer grows thickly, and the conductivity is further improved. Further, in order to adjust the color tone and conductivity, the mixing amount in paints and plastics is reduced to 50% by weight or less, and conventional carbon-based powders, inorganic semiconductor-based powders, inorganic semiconductor-coated composite powders, metal powders, and metal powders are used. A conventional product such as a coated composite powder and the product of the present invention can be used in any ratio.
【００１２】[0012]
【作用】金属微粉末の表面に白色系合金を粉末スパッタ
リングすると、たとえば１〜１０重量％というごく少量
の被覆量でも粉末粒子の全表面をほぼ均一に覆うことが
でき、導電性の良好な粉末が得られる。これは、スパッ
タリング時にプラズマ状態まで励起された金属原子が粉
末粒子の表面に高速で衝突する現象を繰り返し、金属皮
膜形成用の核発生点ｂが極めて高い密度で形成されるこ
とに原因がある。他方、無電解めっき法で粉末表面に合
金層を形成しようとすると、図２に示すように粉末粒子
ａの表面を予めＰｄ等で活性化処理する必要がある。Ｐ
ｄの付着部分は、無電解めっき時に金属皮膜形成用核の
発生点ｂになる。付着密度は、Ｐｄの付着が物理現象で
あることから、スパッタリング法におけるプラズマ状態
に励起された金属原子の衝突密度に比較すると格段に低
い。そのため、導電性の発現には粉末粒子の表面全体を
連続した皮膜ｃで覆うことが必要であるため、５０重量
％以上という多量の金属で粉末粒子を被覆することが要
求される。When a white alloy is powder-sputtered on the surface of a fine metal powder, the entire surface of the powder particles can be almost uniformly covered even with a very small amount of, for example, 1 to 10% by weight. Is obtained. This is due to the fact that metal atoms excited to a plasma state at the time of sputtering repeatedly collide with the surface of the powder particles at a high speed, and nucleation points b for forming a metal film are formed at an extremely high density. On the other hand, when an alloy layer is to be formed on the powder surface by the electroless plating method, it is necessary to previously activate the surface of the powder particles a with Pd or the like as shown in FIG. P
The adhering portion of d becomes a generation point b of a nucleus for forming a metal film during electroless plating. Since the adhesion density of Pd is a physical phenomenon, the adhesion density is much lower than the collision density of metal atoms excited to a plasma state in the sputtering method. For this reason, it is necessary to cover the entire surface of the powder particles with a continuous film c in order to exhibit conductivity, and it is required to cover the powder particles with a large amount of metal of 50% by weight or more.
【００１３】無電解めっき法とスパッタリング法とで皮
膜形成時の結晶成長が異なることも、粉末粒子の全表面
を被覆するのに必要な被覆量に差がある原因である。す
なわち、無電解めっき法等で単一金属を被覆する場合、
核の発生と成長時に結晶が粗大化し易い傾向にある。他
方、スパッタリング法により合金皮膜を形成する場合に
は、逆に核の発生と成長時に結晶が微細化し易い傾向に
ある。そのため、スパッタリング法によるとき、より少
量の金属で粉末粒子の全表面を覆うことができる。ま
た、無電解めっき法等でＡｇ，Ｃｕ，Ｎｉ等の単一金属
をコーティングする場合、経時変化によって皮膜表面に
酸化膜ｄが生成し、導電性が低下する。他方、スパッタ
リング法で形成した皮膜の最表面に生成する無機半導体
膜ｅは、自然にＩＴＯ，ＡＴＯ等の無機半導体組成にな
っているので導電性の低下がほとんどなく、しかも耐食
性の向上にも効果がある。更に、スパッタリング法によ
る皮膜形成時に、プラズマ状態まで励起された金属原子
が金属微粉末の表面にある酸化皮膜に高速で衝突する現
象を繰り返す。そのため、微粉末粒子の表面にも無機半
導体ドープ層ｆが形成される。このように無機半導体ド
ープ層ｆの形成があるため、単に無機半導体を微粉末表
面に被覆するよりも、本発明のように特定の白色系合金
を被覆する方が導電性の向上により効果的である。The difference in crystal growth during film formation between the electroless plating method and the sputtering method is also a cause of the difference in the amount of coating required to cover the entire surface of the powder particles. In other words, when coating a single metal by electroless plating, etc.,
Crystals tend to coarsen during nucleation and growth. On the other hand, when an alloy film is formed by a sputtering method, conversely, there is a tendency that nuclei are generated and crystals are easily refined during growth. Therefore, when the sputtering method is used, the entire surface of the powder particles can be covered with a smaller amount of metal. Further, when a single metal such as Ag, Cu, Ni or the like is coated by an electroless plating method or the like, an oxide film d is generated on the surface of the film due to a change with time, and the conductivity is reduced. On the other hand, since the inorganic semiconductor film e formed on the outermost surface of the film formed by the sputtering method naturally has an inorganic semiconductor composition such as ITO and ATO, there is almost no decrease in conductivity, and it is also effective in improving corrosion resistance. There is. Further, a phenomenon in which the metal atoms excited to the plasma state collide with the oxide film on the surface of the metal fine powder at a high speed during the film formation by the sputtering method is repeated. Therefore, the inorganic semiconductor doped layer f is also formed on the surface of the fine powder particles. Since the inorganic semiconductor doped layer f is formed in this manner, it is more effective to coat a specific white alloy as in the present invention than to simply coat the inorganic semiconductor on the surface of the fine powder, because the conductivity is improved. is there.
【００１４】[0014]
実施例１：図１の粉末スパッタリング装置を使用して、
Ｓｉ微粉末（高純度化学研究所株式会社製，平均粒径：
０．１μｍ）の表面に、次のように１重量％の９５％Ｓ
ｎ−５％Ｓｂ合金を被覆した。内径２００ｍｍ，軸方向
長さ２００ｍｍの回転ドラム１に、２個の９５％Ｓｎ−
５％Ｓｂ合金スパッタリング源４を配置した。スパッタ
リング源４としては、Ｓｎターゲット及びＳｂターゲッ
トを組み合わせて出力１．５ＫＷ，周波数１３．５６Ｍ
Ｈｚのマグネトロン型を使用した。回転ドラム１にＳｉ
微粉末５を１００ｇ投入し、減圧処理室７を３．０×１
０ -3Ｐａに減圧した後、Ａｒガス導入管１０からＡｒガ
スを１５ｃｍ3 ／分の流量で導入し、Ｓｉ微粉末５を分
岐管１１，流体ジェットミル１２及び循環管１３を経て
減圧処理室７に吸引移送した。そして、減圧処理室７で
加熱コイル６により２００℃に３０分間加熱して乾燥脱
ガスした。 Example 1: Using the powder sputtering apparatus of FIG.
Si fine powder (manufactured by Kojundo Chemical Laboratory Co., Ltd., average particle size:
0.1 μm) on 1% by weight of 95% S
An n-5% Sb alloy was coated. 200mm inside diameter, axial direction
Two 95% Sn- on a rotating drum 1 having a length of 200 mm
A 5% Sb alloy sputtering source 4 was provided. Spatter
The ring source 4 includes a Sn target and an Sb target.
Output 1.5KW, frequency 13.56M
Hz magnetron type was used. Rotating drum 1 with Si
100 g of the fine powder 5 was charged, and the reduced-pressure processing chamber 7 was 3.0 × 1
0 -3After the pressure has been reduced to Pa, Ar gas
15cmThree / Minute, and introduce Si fine powder 5
Via manifold 11, fluid jet mill 12, and circulation pipe 13
The liquid was sucked and transferred to the decompression processing chamber 7. And in the decompression processing chamber 7
Heat to 200 ° C for 30 minutes with heating coil 6 to dry and remove
Gas.
【００１５】次いで、回転ドラム１の雰囲気をＡｒガス
で完全に置換した後、減圧処理室７のＳｉ微粉末５を供
給管９から回転ドラム１に落下させ、回転ドラム１を５
ｒｐｍの速度で回転させながら３．０×１０-3Ｐａの減
圧雰囲気下でスパッタリング源４からスパッタリングし
た。スパッタリングを１０分間継続した後、減圧処理室
７を減圧にすると共にＡｒガス導入管１０からＡｒガス
を導入し、Ｓｉ微粉末５を流体ジェットミル１２経由で
減圧処理室７に吸引返送し、スパッタリング中に塊状化
されたＳｉ微粉末５をできるだけ個々の粒子にほぐし
た。減圧処理室７に返送されたＳｉ微粉末５には、０．
１重量％の９５％Ｓｎ−５％Ｓｂ合金が被覆されてい
た。このスパッタリングを１０回繰り返すことにより、
１重量％のＳｎ−５％Ｓｂ合金被覆を形成した後、固気
分離装置１６から回収した。Next, after completely replacing the atmosphere of the rotary drum 1 with Ar gas, the Si fine powder 5 in the decompression processing chamber 7 is dropped from the supply pipe 9 onto the rotary drum 1, and the rotary drum 1
Sputtering was performed from the sputtering source 4 under a reduced pressure atmosphere of 3.0 × 10 −3 Pa while rotating at a speed of rpm. After the sputtering is continued for 10 minutes, the pressure in the decompression processing chamber 7 is reduced, and Ar gas is introduced from the Ar gas introduction pipe 10. The Si fine powder 5 is sucked and returned to the decompression processing chamber 7 via the fluid jet mill 12, and sputtering is performed. The Si fine powder 5 agglomerated therein was loosened as much as possible into individual particles. The Si fine powder 5 returned to the decompression processing chamber 7 contains 0.1.
1% by weight of a 95% Sn-5% Sb alloy was coated. By repeating this sputtering 10 times,
After forming a 1 wt% Sn-5% Sb alloy coating, it was recovered from the solid-gas separator 16.
【００１６】実施例２，３：実施例１と同様の手順で、
Ｓｉ粉末（高純度化学研究所株式会社製，平均粒径：
０．１μｍ）の表面に５重量％及び１０重量％の９５％
Ｓｎ−５％Ｓｂ合金被覆を形成した。 実施例４〜６：実施例１と同様の手順で、Ｔｉ粉末（高
純度化学研究所株式会社製，平均粒径：１０．０μｍ）
の表面に１重量％，５重量％及び１０重量％の９０％Ｓ
ｎ−１０％Ｓｂ合金被覆を形成した。 実施例７〜９：実施例１と同様の手順で、Ｚｎ粉末（東
邦亜鉛株式会社製，平均粒径：４．０μｍ）の表面に１
重量％，５重量％及び１０重量％の９０％Ｉｎ−１０％
Ｓｎ合金被覆を形成した。Embodiments 2 and 3: By the same procedure as in Embodiment 1,
Si powder (manufactured by Kojundo Chemical Laboratory Co., Ltd., average particle size:
95% of 5% and 10% by weight on the surface of 0.1 μm)
An Sn-5% Sb alloy coating was formed. Examples 4 to 6: In the same procedure as in Example 1, Ti powder (manufactured by Kojundo Chemical Laboratory Co., Ltd., average particle size: 10.0 μm)
1%, 5% and 10% by weight of 90% S
An n-10% Sb alloy coating was formed. Examples 7 to 9: In the same procedure as in Example 1, 1 was added to the surface of Zn powder (manufactured by Toho Zinc Co., Ltd., average particle size: 4.0 μm).
90% In-10% by weight, 5% and 10% by weight
A Sn alloy coating was formed.
【００１７】実施例１０〜１２：実施例１と同様の手順
で、Ｚｎ粉末（東邦亜鉛株式会社製，平均粒径：４．０
μｍ）の表面に１重量％，５重量％及び１０重量％の９
０％Ｚｎ−１０％Ａｌ合金被覆を形成した。 実施例１３〜１５：実施例１と同様の手順で、Ｚｎ粉末
（東邦亜鉛株式会社製，平均粒径：４．０μｍ）の表面
に１重量％，５重量％及び１０重量％の８０％Ｚｎ−２
０％Ｃｕ合金被覆を形成した。 実施例１６〜１８：実施例１と同様の手順で、Ａｌ粉末
（東洋アルミニウム株式会社製，平均粒径：１０．０μ
ｍ）の表面に１重量％，５重量％及び１０重量％の８０
％Ｓｎ−２０％Ｓｂ合金被覆を形成した。 比較例１〜５：市販品である１０％ＳｂドープＳｎＯ2
を２５重量％被覆したＴｉＯ2 粉末（三菱マテリアル株
式会社製，平均粒径：０．２μｍ）及び１０％Ｓｂドー
プＳｎＯ2 を３０重量％被覆したＢａＳＯ4 粉末（三井
金属株式会社製，平均粒径：０．４μｍ）等の無機半導
体被覆複合粉末、１０％ＳｎドープＳｎＯ2 粉末（三菱
マテリアル株式会社製，平均粒径：０．０２μｍ），５
％ＳｎドープＩｎ2 Ｏ3粉末（三菱マテリアル株式会社
製，平均粒径：０．０１μｍ）及び５％ＡｌドープＺｎ
Ｏ粉末（白水化学株式会社製，平均粒径：１．５μｍ）
等の無機半導体粉末を使用した。Examples 10 to 12: In the same procedure as in Example 1, Zn powder (manufactured by Toho Zinc Co., Ltd., average particle size: 4.0)
1%, 5% and 10% by weight of 9
A 0% Zn-10% Al alloy coating was formed. Examples 13 to 15: 1%, 5% and 10% by weight of 80% Zn were added to the surface of Zn powder (manufactured by Toho Zinc Co., Ltd., average particle size: 4.0 μm) in the same procedure as in Example 1. -2
A 0% Cu alloy coating was formed. Examples 16 to 18: In the same procedure as in Example 1, Al powder (manufactured by Toyo Aluminum Co., Ltd., average particle size: 10.0 μm)
m) of 1%, 5% and 10% by weight of 80
% Sn-20% Sb alloy coating was formed. Comparative Examples 1 to 5: Commercially available 10% Sb-doped SnO 2
25 wt% coated TiO 2 powder (Mitsubishi Materials Corporation, average particle diameter: 0.2 [mu] m) and 10% Sb doped BaSO 4 powder SnO 2 were coated 30 wt% (manufactured by Mitsui Mining & Smelting Co., Ltd., average particle size : 0.4 μm), 10% Sn-doped SnO 2 powder (Mitsubishi Materials Corporation, average particle size: 0.02 μm), 5
% Sn-doped In 2 O 3 powder (Mitsubishi Materials Corporation, average particle size: 0.01 μm) and 5% Al-doped Zn
O powder (manufactured by Hakusui Chemical Co., Ltd., average particle size: 1.5 μm)
And the like.
【００１８】実施例１〜１８で得られた試料及び比較例
１〜５の試料の合計２３サンプルについて、以下に示す
条件で導電性を測定した。粉末の比抵抗の測定に際して
は、試料粉末を２００ｋｇ／ｃｍ2 の圧力で成形し、直
径２５ｍｍ，厚み１０ｍｍの円柱形状の圧粉体を作製し
た。そして、圧粉体の両端に抵抗計を接続し、直流比抵
抗を測定した。塗装板の表面電気抵抗の測定に際して
は、各試料粉末１００ｇをアクリル塗料ベース（関西ペ
イント株式会社製 Ｎo.２０２６，樹脂含有量：４０重
量％）２５０ｇの中に投入し、８００ｍｌのステンレス
鋼製容器中で撹拌翼を２，０００ｒｐｍで１時間回転さ
せることにより分散した。得られたアクリル塗料を、ド
クターブレードを用いて乾燥塗膜厚みで約３０μｍとな
るように１ｍｍ厚の透明アクリル板上に塗布し、常温で
乾燥することにより塗装板を作製した。この塗装板につ
いて、表面電気抵抗を測定した。表１の測定結果にみら
れるように、本発明に従った実施例１〜１８では、少な
い被覆量でも良好な導電性を呈する白色粉末が得られて
いる。これに対し、比較例１，２の粉末では、必要な導
電性を得るために被覆量を多くすることが必要であっ
た。また、比較例３〜５の粉末では、導電性そのものが
低い値を示した。Conductivity was measured on the samples obtained in Examples 1 to 18 and the samples of Comparative Examples 1 to 5 in total under a condition shown below. In measuring the specific resistance of the powder, the sample powder was molded at a pressure of 200 kg / cm 2 to produce a cylindrical green compact having a diameter of 25 mm and a thickness of 10 mm. Then, a resistance meter was connected to both ends of the green compact, and the DC specific resistance was measured. When measuring the surface electric resistance of the coated plate, 100 g of each sample powder was put into 250 g of an acrylic paint base (Kansai Paint Co., Ltd., No. 2026, resin content: 40% by weight), and an 800 ml stainless steel container The dispersion was performed by rotating the stirring blade at 2,000 rpm for 1 hour in the inside. The obtained acrylic paint was applied on a transparent acrylic plate having a thickness of 1 mm so as to have a dry coating thickness of about 30 μm using a doctor blade, and dried at normal temperature to prepare a coated plate. The surface electric resistance of this coated plate was measured. As can be seen from the measurement results in Table 1, in Examples 1 to 18 according to the present invention, a white powder exhibiting good conductivity was obtained even with a small coating amount. On the other hand, in the powders of Comparative Examples 1 and 2, it was necessary to increase the coating amount in order to obtain the required conductivity. In the powders of Comparative Examples 3 to 5, the conductivity itself showed a low value.
【００１９】 [0019]
【００２０】[0020]
【発明の効果】以上に説明したように、本発明の高導電
性複合粉末は、金属微粉末にスパッタリング法で白色系
合金をコーティングしているため、ＳｎドープＳｎＯ2
被覆ＴｉＯ2 粉末，ＳｂドープＳｎＯ2 被覆ＢａＳＯ4
粉末等の無機半導体被覆複合粉末に比較すると導電性が
はるかに優れており、カーボンブラックや金属粉末に匹
敵する導電性を呈する。しかも、灰白色であることか
ら、種々の着色が容易に行われる。そのため、高性能の
帯電防止用導電性粉末として、外装建材，内装建材，家
電製品，自動車，船舶，繊維等の広範囲の分野で使用さ
れる。また、ＥＭＩシールドが可能なカーペット，カー
テン，間仕切り等の内装建材，液晶ディスプレイ用塗装
タイプの透明導電膜，自動車の後部窓ガラスの霜取りヒ
ータ用等の高導電膜等としても使用可能である。As described above, according to the present invention, highly conductive composite powder of the present invention, since the coated white alloy by sputtering metal micropowder, Sn-doped SnO 2
Coated TiO 2 powder, Sb-doped SnO 2 coated BaSO 4
Compared with inorganic semiconductor-coated composite powders such as powders, the conductivity is far superior and exhibits conductivity comparable to carbon black or metal powder. Moreover, since it is grayish white, various colorings are easily performed. Therefore, it is used as a high-performance antistatic conductive powder in a wide range of fields such as exterior building materials, interior building materials, home appliances, automobiles, ships, and fibers. It can also be used as interior building materials such as carpets, curtains, partitions, etc., capable of EMI shielding, as a transparent conductive film of a paint type for liquid crystal displays, and as a high conductive film for a defrost heater on a rear window glass of an automobile.
【図１】 本発明で使用する粉末スパッタリング装置FIG. 1 is a powder sputtering apparatus used in the present invention.
【図２】 スパッタリング法で合金皮膜を設けた導電性
粉末と従来の無電解めっきで金属皮膜を設けた導電性粉
末の相違を説明するための図FIG. 2 is a diagram for explaining a difference between a conductive powder provided with an alloy film by a sputtering method and a conductive powder provided with a metal film by conventional electroless plating.
ａ：微粉末粒子 ｂ：皮膜形成用核の発生点 ｃ：
連続皮膜 ｄ：酸化皮膜膜 ｅ：無機半導体膜
ｆ：無機半導体ドープ層 １：回転ドラム ２：ロール ３：モータ ４：
スパッタリング源 ５：粉末原料（金属微粉末） ６：加熱コイル
７：減圧処理室 ８：バルブ ９：供給管 １０：Ａｒガス導入管
１１：分岐管 １２：流体ジェットミル １３：循環管 １４，１
５：バルブ １６：固気分離装置a: fine powder particles b: generation point of nuclei for film formation c:
Continuous film d: Oxide film e: Inorganic semiconductor film
f: inorganic semiconductor doped layer 1: rotating drum 2: roll 3: motor 4:
Sputtering source 5: Powder raw material (metal fine powder) 6: Heating coil
7: Decompression processing chamber 8: Valve 9: Supply pipe 10: Ar gas introduction pipe
11: Branch pipe 12: Fluid jet mill 13: Circulation pipe 14, 1
5: Valve 16: Solid-gas separation device
Claims (3)
をスパッタリング法により１〜１０重量％の白色系合金
で被覆している高導電性複合粉末。1. A highly conductive composite powder obtained by coating a fine metal powder having an average particle size of 0.1 to 10 μm with a white alloy of 1 to 10% by weight by a sputtering method.
の１種又は２種以上である請求項１記載の高導電性複合
粉末。2. The method according to claim 1, wherein the metal fine powder is Si, Ti, Zn or Al.
The highly conductive composite powder according to claim 1, which is one or more of the following.
ｂ合金，Ｚｎ−Ａｌ合金又はＺｎ−Ｃｕ合金である請求
項１記載の高導電性複合粉末。3. The white alloy is an In—Sn alloy, Sn—S
The highly conductive composite powder according to claim 1, which is a b alloy, a Zn-Al alloy, or a Zn-Cu alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8329293A JPH10168503A (en) | 1996-12-10 | 1996-12-10 | Composite powder with high electric conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8329293A JPH10168503A (en) | 1996-12-10 | 1996-12-10 | Composite powder with high electric conductivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10168503A true JPH10168503A (en) | 1998-06-23 |
Family
ID=18219850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8329293A Withdrawn JPH10168503A (en) | 1996-12-10 | 1996-12-10 | Composite powder with high electric conductivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10168503A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005256063A (en) * | 2004-03-10 | 2005-09-22 | Ulvac Japan Ltd | Water collapsible al composite material, al film and al powder composed of the material, method for manufacturing the same, and constitution member for deposition chamber, and method for recovering deposition material |
| JP2008137077A (en) * | 2006-11-13 | 2008-06-19 | Sulzer Metco Us Inc | Material and method of manufacture of solder joint with high thermal conductivity and high electrical conductivity |
| JP6376266B1 (en) * | 2017-10-24 | 2018-08-22 | 千住金属工業株式会社 | Nuclear material, solder joint and bump electrode forming method |
-
1996
- 1996-12-10 JP JP8329293A patent/JPH10168503A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005256063A (en) * | 2004-03-10 | 2005-09-22 | Ulvac Japan Ltd | Water collapsible al composite material, al film and al powder composed of the material, method for manufacturing the same, and constitution member for deposition chamber, and method for recovering deposition material |
| JP4653406B2 (en) * | 2004-03-10 | 2011-03-16 | 株式会社アルバック | Water-disintegrating Al composite material, water-disintegrating Al sprayed film, method for producing water-disintegrating Al powder, film forming chamber component, and method for recovering film forming material |
| US7951463B2 (en) | 2004-03-10 | 2011-05-31 | Ulvac, Inc. | Water collapsible aluminum film |
| KR101235999B1 (en) * | 2004-03-10 | 2013-02-21 | 가부시키가이샤 알박 | Al COMPOSITE MATERIAL BEING CRUMBLED WITH WATER, Al FILM AND Al POWDER COMPRISING THE MATERIAL AND METHODS FOR PREPARATION THEREOF, CONSTITUTIONAL MEMBER FOR FILM-FORMING CHAMBER METHOD FOR RECOVERING FILM-FORMING MATERIAL |
| JP2008137077A (en) * | 2006-11-13 | 2008-06-19 | Sulzer Metco Us Inc | Material and method of manufacture of solder joint with high thermal conductivity and high electrical conductivity |
| JP2013144314A (en) * | 2006-11-13 | 2013-07-25 | Sulzer Metco Us Inc | Material and method for producing solder joint with high thermal conductivity and high electrical conductivity |
| JP6376266B1 (en) * | 2017-10-24 | 2018-08-22 | 千住金属工業株式会社 | Nuclear material, solder joint and bump electrode forming method |
| KR20190045846A (en) * | 2017-10-24 | 2019-05-03 | 센주긴조쿠고교 가부시키가이샤 | Nuclear material and solder joint and bump electrode forming method |
| TWI664298B (en) * | 2017-10-24 | 2019-07-01 | 日商千住金屬工業股份有限公司 | Core material, welding joint and formation method of bump electrode |
| CN109693054B (en) * | 2017-10-24 | 2020-02-28 | 千住金属工业株式会社 | Core material, solder joint and bump electrode forming method |
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