JP4304279B2 - Method for producing ultrafine metal particles having an organic film formed on the surface - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000002923 metal particle Substances 0.000 title claims description 24
- 239000002184 metal Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000011882 ultra-fine particle Substances 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002887 superconductor Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 12
- 239000005642 Oleic acid Substances 0.000 description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910001111 Fine metal Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003595 mist Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 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
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
Description
本発明は、大気中でも酸化しにくい金属超微粒子の製造方法及び該製造方法に使用する製造装置に関する。 The present invention relates to a method for producing ultrafine metal particles that are difficult to oxidize in the atmosphere and a production apparatus used in the production method.
現在多くの電子機器の導線として、導電性ペーストが使用されている。このペーストの中には金属粒子が分散されており、ペーストの揮発成分を蒸発させることにより、任意の形状の導線が作製できる。現在、このペーストには直径２００ｎｍ程度の金属粒子が使用されているが電子部品の小型化の要求により、このペースト厚も薄膜化が求められ、ペースト中に分散される金属粒子の粒径を小さくすることが必要とされている。 Currently, conductive paste is used as a conductor of many electronic devices. Metal particles are dispersed in the paste, and a conductor having an arbitrary shape can be produced by evaporating the volatile components of the paste. Currently, metal particles having a diameter of about 200 nm are used in this paste, but due to the demand for downsizing of electronic components, the thickness of this paste is also required to be reduced, and the particle size of the metal particles dispersed in the paste is reduced. There is a need to do.
一方、金属粒子の粒径を小さくすると、比表面積が大きくなり、酸化速度が増大する。金属微粒子の表面が酸化されると導電性が低下するため、導電性ペーストに使用する金属微粒子は高価な不活性ガス中で保存する必要があり、金属微粒子の作製とその保存は困難であった。このため、金属微粒子の作製、ひいては電子部品の小型化への大きな障害となっていた。 On the other hand, when the particle size of the metal particles is reduced, the specific surface area is increased and the oxidation rate is increased. When the surface of the metal fine particles is oxidized, the conductivity is lowered. Therefore, it is necessary to store the metal fine particles used in the conductive paste in an expensive inert gas, and it is difficult to produce and store the metal fine particles. . For this reason, it has been a major obstacle to the production of metal fine particles and consequently to the miniaturization of electronic components.
このような問題点を解決するために、本発明者等は先に、有機物蒸気・ミスト中で金属細線をパルス通電加熱して、発生した金属蒸気を凝結させた直後に金属微粒子表面に有機物被膜を形成することにより有機物被覆金属超微粒子を作製する方法を提案した。（特許文献１、２参照）
この方法はエネルギー変換効率の高いパルス細線放電法を利用して超微粒子作製するものであるが、有機物蒸気・ミストを発生させるために、熱拡散によるエネルギー損失が大きいヒーターによって反応室を加熱して有機物を蒸発させる必要があった。このため、金属微粒子の製造に多大のエネルギーを必要とし、超微粒子製造コストを下げることが出来なかった。さらに、反応室内に有機物を均一に蒸発分散させることが必要となり、その製造装置の構成が複雑化し、製造装置自体も高価なものとなるという問題があった。 In this method, ultrafine particles are produced using the pulsed wire discharge method with high energy conversion efficiency. In order to generate organic vapor and mist, the reaction chamber is heated by a heater with a large energy loss due to thermal diffusion. It was necessary to evaporate the organics. For this reason, enormous energy was required for the production of metal fine particles, and the production cost of ultrafine particles could not be reduced. Furthermore, it is necessary to uniformly evaporate and disperse the organic substance in the reaction chamber, which complicates the configuration of the manufacturing apparatus and causes the manufacturing apparatus itself to be expensive.
したがって、本発明は上記従来技術の問題点を解消して、簡単な工程で外部加熱装置を必要とせずに、高いエネルギー効率で表面に有機物被膜が形成された、大気中でも酸化しにくい金属超微粒子を効率良く製造する方法、及び該方法に使用する安価で簡単な構成の製造装置を提供することを目的とする。 Therefore, the present invention solves the above-mentioned problems of the prior art, and does not require an external heating device in a simple process, and an organic coating film is formed on the surface with high energy efficiency, and is a metal ultrafine particle that is not easily oxidized in the atmosphere. It is an object of the present invention to provide a method for efficiently manufacturing a device and a manufacturing apparatus having a low-cost and simple configuration used in the method.
本発明者等は鋭意検討した結果、金属超微粒子の原料となる金属細線に有機物を直接塗布することによって、高いエネルギー効率で金属蒸気及び有機物蒸気・ミストを同時に発生させることができることを見出し、本発明を完成したものである。
すなわち、本発明は次の１〜３の構成をとるものである。
１．沸点が４００℃以下で、常温常圧で液体である有機物を塗布した金属細線に、０．１〜５０μｓの間パルス電流を通電することにより発生した蒸気を不活性気体中で凝結させることを特徴とする、平均粒径が５〜１００ｎｍで表面に有機物被膜を形成した金属超微粒子の製造方法。
２．金属細線がＮｉ、Ｃｕ、Ｓｎ、Ｂｉ、Ａｇ、Ｉｎからなる群から選択された１種又は２種以上の金属により構成されたものであることを特徴とする１に記載された金属超微粒子の製造方法。
３．有機物が鉱物油、炭素数１〜１８の脂肪族カルボン酸、炭素数１〜５の脂肪族低級アルコール、３−エチル−３−ヒドロキシメチルオキセタン、１，６−ヘキサンジオールジグリシジルエーテルから選択されたものであることを特徴とする１又は２に記載された金属超微粒子の製造方法。
As a result of intensive studies, the present inventors have found that by directly applying an organic substance to a fine metal wire that is a raw material of ultrafine metal particles, it is possible to simultaneously generate metal vapor and organic vapor / mist with high energy efficiency. The invention has been completed.
That is, this invention takes the structure of the following 1-3.
1. It is characterized in that vapor generated by applying a pulse current for 0.1 to 50μs to a thin metal wire coated with an organic substance that has a boiling point of 400 ° C. or less and is liquid at normal temperature and pressure is condensed in an inert gas. The manufacturing method of the metal ultrafine particle which formed the organic substance film in the surface with an average particle diameter of 5-100 nm.
2. 1. The ultrafine metal particles according to 1, wherein the fine metal wire is composed of one or more metals selected from the group consisting of Ni, Cu, Sn, Bi, Ag, and In. Production method.
3. The organic substance was selected from mineral oil, aliphatic carboxylic acid having 1 to 18 carbon atoms, aliphatic lower alcohol having 1 to 5 carbon atoms, 3-ethyl-3-hydroxymethyloxetane, and 1,6-hexanediol diglycidyl ether. metal ultrafine particles production method according to 1 or 2, characterized in that.
本発明の製造方法によれば、耐酸化性に優れた有機物被覆金属超微粒子を、外部加熱装置を必要とせずに高いエネルギー効率で安価に製造することができる。また、本発明の製造装置は、簡単な構成で装置の小型化、低コスト化を図り、有機物被覆金属超微粒子を安価に製造することができる。有機物蒸気・ミストを使用する従来の技術では、金属超微粒子の重量の２倍以上の重量の有機物を蒸発させる必要があったが、本発明では有機物の使用量を金属超微粒子の重量の０．２〜１．９倍程度の量に抑えることができるので、更なる低コスト化を可能とした。
本発明は、小型積層セラミックコンデンサーや、電解コンデンサー代替大容量積層セラミックコンデンサー等の、次世代電子機器用基盤部品の実用的生産の道を拓くものであり、極めて実用的価値の高いものである。
According to the production method of the present invention, it is possible to produce organic-coated metal ultrafine particles excellent in oxidation resistance at low cost with high energy efficiency without requiring an external heating device. In addition, the manufacturing apparatus of the present invention can reduce the size and cost of the apparatus with a simple configuration and can manufacture organic-coated metal ultrafine particles at low cost. In the conventional technique using the organic vapor / mist, it is necessary to evaporate an organic substance having a weight more than twice the weight of the ultrafine metal particles. Since the amount can be reduced to about 2 to 1.9 times, further cost reduction can be achieved.
The present invention opens up the path of practical production of base parts for next-generation electronic devices, such as small monolithic ceramic capacitors and large-capacity monolithic ceramic capacitors that replace electrolytic capacitors, and has extremely high practical value.
つぎに、本発明の好適な実施形態について図面を参照しながら説明するが、以下の具体例は本発明を限定するものではない。
図１は、本発明の有機物被覆金属超微粒子の製造装置の１例を示す模式図である。
この製造装置１は、不活性ガス供給装置２を備えた密閉可能な反応室３内に、有機物を塗布した金属細線４を保持する電極５を配置し、該電極５にコンデンサー６、及び電源７を接続すると共にギャップスイッチ９を設けたものである。そして、反応室３には生成した金属超微粒子を回収するためのフイルター８が設置されている。製造装置１を構成する各部材の寸法は任意に選択することができるが、例えば反応室３の体積としては、通常は１〜１０Ｌ程度とすることが好ましい。
Next, preferred embodiments of the present invention will be described with reference to the drawings, but the following specific examples do not limit the present invention.
FIG. 1 is a schematic view showing an example of an apparatus for producing organic coated metal ultrafine particles of the present invention.
In this
この製造装置１を使用して有機物被覆金属超微粒子を製造するには、反応室３内の電極５に有機物を塗布した金属細線４を保持させて、窒素、ヘリウム、アルゴン等の不活性気体を充填した後にコンデンサー６によりパルス電流を通電し、金属蒸気と有機物蒸気ミストを同時に発生させ、不活性気体中で金属超微粒子を凝結させることによって、表面に有機物被膜を形成した平均粒径が５〜１００ｎｍ程度の金属超微粒子を製造する。
有機物を塗布した金属細線には、あらかじめ電源７により０．１〜２０ＫＶ程度、好ましくは１〜１０ＫＶ程度に充電したコンデンサー６からパルス大電流を０．０１〜１００μｓ程度、好ましくは０．１〜５０μｓ程度通電するが、パルス電流の通電量、時間等は、金属或いは有機物の種類に応じて適宜選択することができる。
In order to produce organic matter-coated metal ultrafine particles using this
The fine metal wire coated with an organic substance is subjected to a pulse high current of about 0.01 to 100 μs, preferably 0.1 to 50 μs from a
金属細線を構成する好ましい金属としては、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｚｒ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｃｄ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｔｌ、Ｐｂ、Ｂｉ、Ｉｎ等が挙げられ、これらは金属単体又は２種以上の合金として使用することができる。
特に好ましい金属としては、Ｎｉ、Ｃｕ、Ｓｎ、Ｂｉ、Ａｇ、Ｉｎ等が挙げられる。
Preferred metals constituting the fine metal wires include Sc, Ti, V, Cr, Mn, Fe, Co, Zn, Y, Zr, Nb, Zr, Mo, Tc, Ru, Rh, Cd, Sn, Hf, Ta, W, Re, Os, Ir, Tl, Pb, Bi, In, etc. are mentioned, These can be used as a metal simple substance or 2 or more types of alloys.
Particularly preferable metals include Ni, Cu, Sn, Bi, Ag, In and the like.
金属細線に塗布する好ましい有機物としては沸点が４００℃以下で、常温常圧で液体である炭素数１〜１８の脂肪族カルボン酸、炭素数１〜５の脂肪族低級アルコール、３−エチル−３−ヒドロキシメチルオキセタン、１，６−ヘキサンジオールジグリシジルエーテル等が挙げられる。
特に有機物として沸点が４００℃以下で常温常圧で液体であるオレイン酸、スピンドル油のような鉱物油を使用した場合には、低粘度導電ペースト用として好適な有機物被覆金属超微粒子を作製することが可能となる。
Preferred organic substances to be applied to the fine metal wires are aliphatic carboxylic acids having 1 to 18 carbon atoms, aliphatic lower alcohols having 1 to 5 carbon atoms, and 3-ethyl-3 having a boiling point of 400 ° C. or lower and liquid at normal temperature and pressure. -Hydroxymethyloxetane, 1,6-hexanediol diglycidyl ether and the like.
In particular, when mineral oil such as oleic acid or spindle oil, which has a boiling point of 400 ° C. or lower and is liquid at room temperature and normal pressure, is used as an organic substance, organic coated metal ultrafine particles suitable for low-viscosity conductive pastes should be prepared. Is possible.
（実施例１）
図１に示す内容積が１Ｌの反応室３を有する製造装置１を用いて、表面にオレイン酸を０．１ｍｍの厚さで塗布した直径０．２５ｍｍ、長さ２５ｍｍの銅線を電極５に保持させ、不活性ガス供給装置２から窒素ガスを充填して反応室内の圧力を１００ｋＰａとした。ついで、あらかじめ電源７で５．２ｋＶに充電しておいた容量１０μＦのコンデンサー６に電極５を接続し、パルス大電流放電によってオレイン酸塗布銅線４を加熱・蒸発させた。プラズマの冷却によって作製した有機物被膜銅超微粒子は、フイルター８を介して脱気することにより回収した。
Example 1
Using a
図２に回収した銅超微粒子の透過型電子顕微鏡明視野像を示す。１０−３０ｎｍの球形粒子が濃いコントラストを示し、そのまわりを薄いコントラストの物質が取り巻いているのが分かる。また、図３にこの銅超微粒子のエネルギー分散型エックス線分析結果を示す。この図３のピークの中で、Ｍｏピークはサンプル保持用グリッドから発した特性Ｘ線で、試料から発したものではない。この他にはＣｕとＣのピークが見られることから、超微粒子はＣｕとＣを含むことが分かる。
そして、図４に超微粒子をアセトンに沈降させた後、上澄み液を取りだして揮発成分を乾燥させた後測定した赤外吸収スペクトルを示す。また、オレイン酸のスペクトルも同図に示す。このスペクトルの対比から超微粒子中にはオレイン酸が含まれていることが分かる。
FIG. 2 shows a transmission electron microscope bright field image of the collected copper ultrafine particles. It can be seen that 10-30 nm spherical particles show a strong contrast and a thin contrast material surrounds them. FIG. 3 shows the result of energy dispersion X-ray analysis of the copper ultrafine particles. Among the peaks in FIG. 3, the Mo peak is a characteristic X-ray emitted from the sample holding grid and is not emitted from the sample. In addition, since Cu and C peaks are observed, it can be seen that the ultrafine particles contain Cu and C.
FIG. 4 shows an infrared absorption spectrum measured after the ultrafine particles are precipitated in acetone, and then the supernatant liquid is taken out and the volatile components are dried. The spectrum of oleic acid is also shown in the figure. From the comparison of the spectra, it can be seen that oleic acid is contained in the ultrafine particles.
さらに、図５に作製後１４日間室温大気中に保持した銅超微粒子のＸ線回折図形を示す。また、同図内に、オレイン酸を塗布しない銅細線を用いて作製し同期間室温大気中に保持した銅超微粒子のＸ線回折図形も示す。オレイン酸塗布銅細線を用いた超微粒子には、１４日後も酸化物が生成していないが、オレイン酸塗布していない銅細線を用いた場合、酸化物が生成した。これらの結果より、オレイン酸塗布銅細線を用いて作製された銅超微粒子では、原料となる銅線中に含まれるオレイン酸が銅超微粒子を被覆し、耐酸化性を向上させることによって１４日間銅超微粒子の酸化を抑えたことが判明した。 Further, FIG. 5 shows an X-ray diffraction pattern of copper ultrafine particles kept in the room temperature atmosphere for 14 days after the production. Also shown in the figure is an X-ray diffraction pattern of ultrafine copper particles prepared using copper fine wires not coated with oleic acid and held in the atmosphere for the same period. In the ultrafine particles using the oleic acid-coated copper fine wire, no oxide was formed even after 14 days, but when a copper fine wire not coated with oleic acid was used, an oxide was produced. From these results, in the copper ultrafine particles produced using the oleic acid-coated copper fine wires, the oleic acid contained in the raw copper wire covers the copper ultrafine particles and improves the oxidation resistance for 14 days. It was found that the oxidation of copper ultrafine particles was suppressed.
（実施例２）
実施例１において、金属超微粒子の原料となるオレイン酸を塗布した銅線に代えて、石油系真空ポンプオイル（沸点２００℃の鉱油油）を塗布した直径１ｍｍのＳｎ線を使用した以外は、実施例１と同様にして有機物被覆金属超微粒子を製造した。
得られた超微粒子は、室温大気中で２月以上酸化物を生成せずに安定に保存することができた。
(Example 2)
In Example 1, instead of using a copper wire coated with oleic acid as a raw material for ultrafine metal particles, a Sn wire having a diameter of 1 mm coated with petroleum-based vacuum pump oil (mineral oil oil having a boiling point of 200 ° C.) was used. Organic coated ultrafine metal particles were produced in the same manner as in Example 1.
The obtained ultrafine particles could be stably stored in the air at room temperature without generating oxides for more than two months.
（実施例３）
実施例１において、金属超微粒子の原料となる金属細線として、Ｓｎ：Ａｇ：Ｃｕが９７：２：１の合金からなる細線の表面に３−エチル−３−ヒドロキシメチルオキセタンを塗布した直径１ｍｍの細線を使用した以外は、実施例１と同様にして有機物被覆金属超微粒子を製造した。
得られた超微粒子は、室温大気中で１月以上酸化物を生成せずに安定に保存することができた。
(Example 3)
In Example 1, as a metal fine wire used as a raw material for ultrafine metal particles, 3-ethyl-3-hydroxymethyloxetane was applied to the surface of a fine wire made of an alloy of Sn: Ag: Cu of 97: 2: 1. Organic coated metal ultrafine particles were produced in the same manner as in Example 1 except that fine wires were used.
The obtained ultrafine particles could be stably stored in the air at room temperature without generating oxides for more than one month.
（実施例４）
実施例１において、金属超微粒子の原料となる金属細線としてＳｎ：Ｉｎが７０：３０の合金からなる細線の表面にイソプロピルアルコールを塗布した直径０．５ｍｍの細線を使用した以外は、実施例１と同様にして有機物被覆金属超微粒子を製造した。
得られた超微粒子は、室温大気中で２月以上酸化物を生成せずに安定に保存することができた。
(Example 4)
In Example 1, except that a thin wire having a diameter of 0.5 mm in which isopropyl alcohol was applied to the surface of a thin wire made of an alloy of Sn: In 70:30 was used as a thin metal wire used as a raw material for ultrafine metal particles, Example 1 Organic coated metal ultrafine particles were produced in the same manner as described above.
The obtained ultrafine particles could be stably stored in the air at room temperature without generating oxides for more than two months.
（実施例５）
実施例１において、金属超微粒子の原料となる金属細線として、Ｓｎ：Ｂｉが７０：３０の合金からなる細線の表面に１，６−ヘキサンジオールジクリシジルエーテルを塗布した直径１ｍｍの細線を使用した以外は、実施例１と同様にして有機物被覆金属超微粒子を製造した。
得られた超微粒子は、室温大気中で１月以上酸化物を生成せずに安定に保存することができた。
(Example 5)
In Example 1, a thin wire having a diameter of 1 mm in which 1,6-hexanediol diglycidyl ether was applied to the surface of a thin wire made of an alloy of Sn: Bi of 70:30 was used as a thin metal wire used as a raw material for ultrafine metal particles. Except for the above, organic-coated metal ultrafine particles were produced in the same manner as in Example 1.
The obtained ultrafine particles could be stably stored in the air at room temperature without generating oxides for more than one month.
（比較例１）
実施例２において、金属超微粒子の原料となる金属細線として、石油系真空ポンプオイルを塗布していない直径１ｍｍのＳｎ線を使用した以外は、実施例２と同様にして金属超微粒子を製造した。
得られた超微粒子は、製造装置から取り出した時点で酸化され、導電性が低いものであった。
(Comparative Example 1)
In Example 2, ultrafine metal particles were produced in the same manner as in Example 2 except that a 1 mm diameter Sn wire not coated with petroleum-based vacuum pump oil was used as the fine metal wire used as the raw material for ultrafine metal particles. .
The obtained ultrafine particles were oxidized when taken out from the production apparatus, and had low conductivity.
特許文献１、２に記載された有機物蒸気・ミストを使用する従来の技術では、金属超微粒子の重量の２倍以上の重量の有機物を蒸発させる必要があった。これに対して、本発明の方法によれば有機物の使用量を金属超微粒子の重量の０．２〜１．９倍程度の量に抑えることができるので、有機物被覆を形成した金属超微粒子をさらに低コストで製造することが可能となる。
In the conventional technique using the organic vapor / mist described in
１ 有機物被覆金属超微粒子の製造装置
２ 不活性ガス供給装置
３ 反応室
４ 有機物塗布金属細線
５ 電極
６ コンデンサー
７ 電源
８ フイルター
９ ギャップスイッチ
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| CN102161094B (en) * | 2011-04-02 | 2012-12-19 | 三祥新材股份有限公司 | Method for avoiding surface oxidation of metal in core-spun yarn |
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