JP2009138305A - Conductive nanofiber - Google Patents
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- JP2009138305A JP2009138305A JP2007317779A JP2007317779A JP2009138305A JP 2009138305 A JP2009138305 A JP 2009138305A JP 2007317779 A JP2007317779 A JP 2007317779A JP 2007317779 A JP2007317779 A JP 2007317779A JP 2009138305 A JP2009138305 A JP 2009138305A
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本願発明は、ナノファイバーに関し、更に詳しくは、イオン注入された優れた導電性を有するナノファイバーに関する。 The present invention relates to a nanofiber, and more particularly to a nanofiber having excellent conductivity that is ion-implanted.
近年、サブミクロンスケールの直径を持つファイバーを簡単に作製できる技術として、エレクトロスピニング法が注目されている。この方法は、高分子溶液に高電圧を印加することによって溶液をスプレーし、ファイバーを形成させるものである。ファイバーの太さは、印加電圧、溶液濃度およびスプレーの飛散距離に依存する。 In recent years, the electrospinning method has attracted attention as a technique for easily producing a fiber having a diameter of a submicron scale. In this method, a high voltage is applied to the polymer solution to spray the solution to form fibers. The thickness of the fiber depends on the applied voltage, the solution concentration and the spray distance.
これまでの研究から、工業用熱可塑性ポリマー、生分解性ポリマー、ポリマーブレンド、そして、無機化合物を混入した複合材のファイバーがエレクトロスピニング法によって紡糸されている。ここ数年では、アルミナ、酸化ジルコニウム、酸化チタン、チタン酸ジルコン酸鉛等のセラミックスナノファイバーの作製例が盛んに報告されてもいる。通常、エレクトロスピニング法においては、溶媒に材料を溶解した溶液を紡糸材料として用いている。 From previous studies, industrial thermoplastic polymers, biodegradable polymers, polymer blends, and composite fibers mixed with inorganic compounds have been spun by electrospinning. In recent years, production examples of ceramic nanofibers such as alumina, zirconium oxide, titanium oxide, and lead zirconate titanate have been actively reported. Usually, in the electrospinning method, a solution in which a material is dissolved in a solvent is used as a spinning material.
このエレクトロスピニング法により、例えば、各種形状の穴を有する電極を回転させてファイバーの配向をそろえるようにすること、糸巻き状のものをコレクタに、もしくは紡糸開始点とコレクタとの間に配置してナノファイバーを巻き取り配向性の不織布を得ること、紡糸開始点を２つ設定し２層構造や混合したファイバーを作製すること等が報告されている。 By this electrospinning method, for example, by rotating an electrode having holes of various shapes so as to align the orientation of the fiber, a bobbin-shaped object is arranged in the collector or between the spinning start point and the collector. It has been reported that a nanofiber is wound up to obtain a non-woven fabric with orientation and that two spinning start points are set to produce a two-layer structure or a mixed fiber.
このような進展が見られるエレクトロスピニング法によれば、基板上に連続的にファイバーを作製することによって、立体的な網目をもつ３次元構造の薄膜が得られることや、機能性薄膜を３次元構造にすることで、新しい特性の発見や機能の向上が期待できる。また、この手法では膜を布のように厚くすることが可能で、サブミクロンの網目をもつ不織布を作製することができる。この不織布は様々な新機能を有する布として、宇宙服や防護服などへの応用のほか、人工皮膚や人工臓器などへの応用が研究されている。 According to the electrospinning method in which such progress is observed, a thin film having a three-dimensional network can be obtained by continuously producing fibers on a substrate, and a functional thin film can be formed in three dimensions. The structure can be expected to discover new properties and improve functions. In addition, in this method, the film can be made thick like a cloth, and a non-woven fabric having a submicron mesh can be produced. This non-woven fabric has various new functions and has been studied for application to space suits and protective clothing as well as artificial skin and organs.
しかしながら、高分子からなるナノファイバーは、エレクトロスピニング法により比較的容易に作製することができるものの、得られたナノファイバー不織布は、材料となった高分子の特性のみを反映するものでそれ以上の機能は望めないのが実情であった（特許文献１参照）。
本願発明は、以上のような背景から、従来技術の問題点を解消し、材料となった高分子の特性のみを反映するものでなく、エレクトロスピニング法により作製されるナノファイバーにこれまでにない機能性を持たせることのできる新しいナノファイバーとその製造方法を提供することを課題としている。 The present invention eliminates the problems of the prior art from the background as described above, and does not reflect only the characteristics of the polymer used as a material, and has never existed in a nanofiber produced by an electrospinning method. It is an object to provide a new nanofiber that can be provided with functionality and a manufacturing method thereof.
特に、本願発明の課題は、優れた導電性を有する高分子ナノファイバーを提供することにある。 In particular, an object of the present invention is to provide a polymer nanofiber having excellent conductivity.
本願発明は、エレクトロスピニング法により形成された高分子ナノファイバーに導電性を与えるために、該ナノファイバーにイオンを照射することにより、上記課題を解決した。 The present invention has solved the above problems by irradiating the nanofibers with ions in order to impart conductivity to the polymer nanofibers formed by the electrospinning method.
上記高分子としては、ポリイミド（ＰＩ）、ポリスチレン（ＰＳ）、ポリカーボネイト（ＰＣ）、ポリビニルクロライド（ＰＶＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリアミド（ＰＡ）、ポリウレタン（ＰＵ）、ポリビニルアルコール（ＰＶＡ）、ポリ乳酸（ＰＬＡ）、ポリエチレングリコール（ＰＥＧ）等およびこれらの混合体が挙げられる。 Examples of the polymer include polyimide (PI), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyamide (PA), polyurethane (PU), polyvinyl alcohol (PVA), poly Examples thereof include lactic acid (PLA), polyethylene glycol (PEG), and the like, and mixtures thereof.
照射するイオンとしては、ヘリウム、ネオン、アルゴン、酸素、窒素、クリプトン又は金属等が挙げられる。 Examples of ions to be irradiated include helium, neon, argon, oxygen, nitrogen, krypton, and metal.
本願発明は、エレクトロスピニング法により形成された高分子ナノファイバーにイオンを照射することにより、該ナノファイバーに有効な導電性を与えることができた。 The present invention was able to impart effective conductivity to the nanofibers by irradiating the polymer nanofibers formed by the electrospinning method with ions.
以下に、本願発明を実施するための最良の形態を示す。 The best mode for carrying out the present invention will be described below.
図１に示すように、エレクトロスピニング法の装置は、先の尖ったプラス電極（キャピラリー）と、平面状のマイナス(アース)電極で構成されている。両電極間には高電圧が印加されており、キャピラリーを出た電荷を帯びた溶融ポリマーまたはポリマー溶解液は、電界中をマイナス電極に向かって吸い寄せられる。このとき、ポリマーが低分子だとスプレー状になり、高分子だと複数に分かれた繊維がマイナス電極に向かって吸い寄せられ、電極上で薄い繊維の層を形成する。 As shown in FIG. 1, the electrospinning apparatus is composed of a pointed plus electrode (capillary) and a flat minus (ground) electrode. A high voltage is applied between the electrodes, and the charged molten polymer or polymer solution exiting the capillary is sucked toward the negative electrode in the electric field. At this time, when the polymer is a low molecule, the polymer is sprayed, and when the polymer is a polymer, a plurality of divided fibers are sucked toward the minus electrode to form a thin fiber layer on the electrode.
イオン注入による処理深さをシュミレーションソフトであるTrimより算出した。その結果、ヘリウム、ネオン、アルゴンではそれぞれイオンの潜り込み深さは１５４０ｎｍ、６２５ｎｍ、３８０ｎｍであり、これらの処理深さにナノファイバー直径を制御した。まず、１５４０ｎｍの直径のナノファイバーを作製するため、ポリイミド溶液の濃度を１９０ｍｇ／ｍＬに調整し、送液速度２．４ｍＬ／ｈ、印加電圧１５ｋＶと設定した。６２５ｎｍの直径のナノファイバーを作製するため、ポリイミド溶液の濃度を１７０ｍｇ／ｍＬに調整し、送液速度０．２４ｍＬ／ｈ、印加電圧１０ｋＶと設定した。３８０ｎｍの直径のナノファイバーを作製するため、ポリイミド溶液の濃度を１２０ｍｇ／ｍＬに調整し、送液速度０．２４ｍＬ／ｈ、印加電圧１５ｋＶと設定した。すべての条件において、紡糸開始点とコレクタ間の距離を１０ｃｍと設定した。コレクタには両端をアルミホイルで覆ったガラス板を用いた。このような条件でエレクトロスピニングによるナノファイバーの作製を行い、一晩、真空乾燥した。 The treatment depth by ion implantation was calculated from Trim, which is simulation software. As a result, helium, neon, and argon had ion penetration depths of 1540 nm, 625 nm, and 380 nm, respectively, and the nanofiber diameter was controlled to these treatment depths. First, in order to produce nanofibers having a diameter of 1540 nm, the concentration of the polyimide solution was adjusted to 190 mg / mL, and the liquid feeding speed was set to 2.4 mL / h and the applied voltage was 15 kV. In order to produce a nanofiber having a diameter of 625 nm, the concentration of the polyimide solution was adjusted to 170 mg / mL, and the liquid feeding speed was set to 0.24 mL / h and the applied voltage was set to 10 kV. In order to produce a nanofiber having a diameter of 380 nm, the concentration of the polyimide solution was adjusted to 120 mg / mL, the liquid feeding speed was set to 0.24 mL / h, and the applied voltage was set to 15 kV. In all conditions, the distance between the spinning start point and the collector was set to 10 cm. A glass plate with both ends covered with aluminum foil was used as the collector. Under such conditions, nanofibers were produced by electrospinning, and vacuum-dried overnight.
上記真空乾燥したナノファイバーに対して、ヘリウム、ネオンおよびアルゴンイオンを３とおりの照射量で照射した。その結果を以下の表１に示す。照射前のナノファイバーの面抵抗は、非常に高く測定不可能であったが、イオン照射することにより、導電性が下記の表に示されるように向上した。
また、図２に、含フッ素ポリイミド（６ＦＤＡ−６ＦＡＰ）のアルゴンを照射した場合と、照射していない場合のラマンスペクトルを示す。 In addition, FIG. 2 shows Raman spectra when the fluorine-containing polyimide (6FDA-6FAP) is irradiated with argon and when it is not irradiated.
図２から、材料が炭素化されたことを示している。まだカーボンナノチューブのような高いグラファイト構造は形成されていないが、今後そのような構造の形成を企画している。
FIG. 2 shows that the material has been carbonized. A high graphite structure such as carbon nanotubes has not yet been formed, but the formation of such a structure is planned in the future.
本願発明に係る導電性ナノファイバーは、導電率が高いので、帯電防止剤、電磁シールド、電池の電極材料、気体拡散電極、スーパーキャパシタ電極又は線材化の技術がさらに進歩すれば半導体の配線等に利用することができる。 Since the conductive nanofiber according to the present invention has high conductivity, if the technology of antistatic agent, electromagnetic shield, battery electrode material, gas diffusion electrode, supercapacitor electrode or wire is further advanced, it can be used for semiconductor wiring, etc. Can be used.
Claims (8)
導電性部材をエレクトロスピニング装置の電極基板上に配置する行程、
高電圧の印加された高分子を該装置のキャピラリーから該部材に向けてスプレーする行程、
該部材上にナノファイバーを形成する工程及び
該ナノファイバーにイオンを照射する工程を有することを特徴とする導電性ナノファイバーの製造方法。 A method for producing conductive nanofibers, comprising:
The step of placing the conductive member on the electrode substrate of the electrospinning device;
Spraying a polymer to which a high voltage is applied from the capillary of the apparatus toward the member;
A method for producing conductive nanofibers, comprising: forming nanofibers on the member; and irradiating the nanofibers with ions.
6. The conductive nanofiber according to claim 5, wherein the ion is neon or argon.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57138A (en) * | 1980-03-13 | 1982-01-05 | Inst Za Yadreni Izsledvaniya | Polymer surface dressing method |
| JPS6350569A (en) * | 1986-08-20 | 1988-03-03 | 尾池工業株式会社 | Conductive cloth like article |
| JPH04153367A (en) * | 1990-10-16 | 1992-05-26 | Kanebo Ltd | Electrically conductive fiber |
| JP2005276642A (en) * | 2004-03-25 | 2005-10-06 | Japan Science & Technology Agency | Electrolyte membrane electrode assembly produced by ion implantation |
| WO2005123995A1 (en) * | 2004-06-17 | 2005-12-29 | Korea Research Institute Of Chemical Technology | Filament bundle type nano fiber and manufacturing method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57138A (en) * | 1980-03-13 | 1982-01-05 | Inst Za Yadreni Izsledvaniya | Polymer surface dressing method |
| JPS6350569A (en) * | 1986-08-20 | 1988-03-03 | 尾池工業株式会社 | Conductive cloth like article |
| JPH04153367A (en) * | 1990-10-16 | 1992-05-26 | Kanebo Ltd | Electrically conductive fiber |
| JP2005276642A (en) * | 2004-03-25 | 2005-10-06 | Japan Science & Technology Agency | Electrolyte membrane electrode assembly produced by ion implantation |
| WO2005123995A1 (en) * | 2004-06-17 | 2005-12-29 | Korea Research Institute Of Chemical Technology | Filament bundle type nano fiber and manufacturing method thereof |
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