JP2003300716A - Method for treatment of carbonaceous material and method for obtaining carbon nanotube dispersion and solution - Google Patents
Method for treatment of carbonaceous material and method for obtaining carbon nanotube dispersion and solutionInfo
- Publication number
- JP2003300716A JP2003300716A JP2002330395A JP2002330395A JP2003300716A JP 2003300716 A JP2003300716 A JP 2003300716A JP 2002330395 A JP2002330395 A JP 2002330395A JP 2002330395 A JP2002330395 A JP 2002330395A JP 2003300716 A JP2003300716 A JP 2003300716A
- Authority
- JP
- Japan
- Prior art keywords
- carbon nanotubes
- carbon nanotube
- carbon
- plasma
- liquid
- 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.)
- Granted
Links
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】炭素質材料の分散性が向上で
き、且つ、精製も可能な炭素質材料のプラズマ処理方法
であって、特にカーボンナノチューブを含有する炭素質
材料をプラズマ処理することで得られる、カーボンナノ
チューブ分散液、溶液、精製されたカーボンナノチュー
ブおよび組成物、ならびにこれらの製造方法に関する。TECHNICAL FIELD A plasma treatment method for a carbonaceous material capable of improving the dispersibility of the carbonaceous material and capable of being refined, which is particularly obtained by plasma treating a carbonaceous material containing carbon nanotubes. Carbon nanotube dispersions, solutions, purified carbon nanotubes and compositions, and methods for their production.
【０００２】カーボンナノチューブは、高い機械的強
度、高い導電性を有することから、燃料電池やリチウム
２次電池用負極材、樹脂や有機半導体との複合材料から
なる高強度樹脂、導電性樹脂、電磁波シールド材として
期待されており、さらに、Ｌ／Ｄ（長さ／直径の比）が
大きく、直径は数ｎｍであることから、走査型トンネル
顕微鏡用プローブ、電界電子放出源、ナノピンセットと
して期待されており、また、ナノサイズの空間を有する
ことから、吸着材料、医療用ナノカプセル、ＭＲＩ造影
剤として期待されている。Since carbon nanotubes have high mechanical strength and high conductivity, they are negative electrodes for fuel cells and lithium secondary batteries, high-strength resins made of composite materials with resins and organic semiconductors, conductive resins, electromagnetic waves. It is expected as a shield material, and has a large L / D (length / diameter ratio) and a diameter of several nm, so it is expected as a scanning tunneling microscope probe, field electron emission source, and nanotweezers. In addition, since it has a nano-sized space, it is expected as an adsorbent material, a medical nanocapsule, and an MRI contrast agent.
【０００３】[0003]
【従来の技術】カーボンナノチューブは、グラファイト
の１枚面を巻いて筒状にした形状を有しており、１層に
巻いたものを単層カーボンナノチューブ、２層に巻いた
ものを２層カーボンナノチューブ、多層に巻いたものを
多層カーボンナノチューブという。2. Description of the Related Art Carbon nanotubes have a shape in which one surface of graphite is rolled into a tubular shape. One layer is wound into a single-walled carbon nanotube, and two layers are wound into a double-walled carbon. Nanotubes, which are wound in multiple layers, are called multi-walled carbon nanotubes.
【０００４】カーボンナノチューブを例えば樹脂用充填
剤として使用する場合、カーボンナノチューブを最小限
添加して、添加効果を得るためには、カーボンナノチュ
ーブはお互いに絡まり合うことなく樹脂中に分散または
溶解していることが好ましい。薬剤輸送材料として用い
る場合、カーボンナノチューブが溶解した水溶液である
ことが好ましい。フィールドエミッションディスプレー
の電子源として使用する場合、カーボンナノチューブの
絡まり合った固まりの大きさが均一な方が、電子源の均
一性の制御が可能となり好ましい。しかし、通常、カー
ボンナノチューブは隣接するこれとは別のカーボンナノ
チューブと絡まり合った固まり状で得られる。この固ま
りの大きさは、通常均一でなく、大きさも大きくそのま
までは液中には分散または溶解しない。特にカーボンナ
ノチューブは疎水性であり、親水性溶媒には分散または
溶解しなかった。When the carbon nanotubes are used as a filler for resin, for example, the carbon nanotubes are dispersed or dissolved in the resin without being entangled with each other in order to add the carbon nanotubes to the minimum and obtain the effect of addition. Is preferred. When used as a drug transport material, it is preferably an aqueous solution in which carbon nanotubes are dissolved. When used as an electron source for a field emission display, it is preferable that the entangled mass of carbon nanotubes has a uniform size because the uniformity of the electron source can be controlled. However, the carbon nanotubes are usually obtained in the form of a lump that is entangled with another carbon nanotube adjacent to the carbon nanotube. The size of this lump is usually not uniform, and the size is large, and it does not disperse or dissolve in the liquid as it is. In particular, carbon nanotubes were hydrophobic and did not disperse or dissolve in hydrophilic solvents.
【０００５】また、カーボンナノチューブを複合材料と
して用いる場合、マトリクスとなる材料の種類によって
は、外表面に付着したアモルファスカーボンを除去した
り、外表面に官能基を付与したカーボンナノチューブを
用いることが、マトリクス材料との界面強度が向上でき
好ましい。合成後の粗カーボンナノチューブからアモル
ファスカーボン等の炭素不純物を除去する方法として、
例えば高温下で酸素と反応させる方法や、高温下で硝酸
や過マンガン酸カリウムを還流する方法（非特許文献１
参照）が提案されている。しかし、これらの方法はアモ
ルファスカーボン等の炭素不純物を除去すると同時にカ
ーボンナノチューブの構造をも破壊し、カーボンナノチ
ューブが消耗されるという問題があった。さらに、高温
下の条件では加熱や冷却の操作が必要となり、硝酸や過
マンガン酸カリウム等の溶媒を用いる方法（ウエット条
件処理）では洗浄や乾燥の操作が必要となり、操作が煩
雑になるという問題があった。また、カーボンナノチュ
ーブ外表面に官能基を導入する方法として、例えば高温
下でフッ素ガスと反応させる方法（非特許文献２参照）
が提案されている。しかし、反応に長時間を要するとい
う問題があった。つまり、カーボンナノチューブの構造
を大きく壊すことなく外表面に付着したアモルファスカ
ーボンを除去したり、低温かつドライ条件処理、短時間
で外表面に官能基を付与することは困難であり、特に、
層の数が少ない単層や２〜５層のカーボンナノチューブ
に対しては難易度が高かった。このように、従来、簡易
的な操作（低温かつドライ条件処理、短時間）で、カー
ボンナノチューブの分散性向上、精製、外表面への官能
基導入といった機能を同時に付与できる処理方法は皆無
であった。When carbon nanotubes are used as a composite material, amorphous carbon adhering to the outer surface may be removed or carbon nanotubes having a functional group attached to the outer surface may be used, depending on the type of the matrix material. This is preferable because the interface strength with the matrix material can be improved. As a method for removing carbon impurities such as amorphous carbon from the synthesized coarse carbon nanotubes,
For example, a method of reacting with oxygen at a high temperature or a method of refluxing nitric acid or potassium permanganate at a high temperature (Non-Patent Document 1
(See) is proposed. However, these methods have a problem in that carbon impurities such as amorphous carbon are removed, and at the same time, the structure of the carbon nanotube is destroyed and the carbon nanotube is consumed. Further, heating and cooling operations are required under high temperature conditions, and washing and drying operations are required in the method using a solvent such as nitric acid or potassium permanganate (wet condition treatment), which makes the operation complicated. was there. Further, as a method of introducing a functional group into the outer surface of the carbon nanotube, for example, a method of reacting with fluorine gas at high temperature (see Non-Patent Document 2).
Is proposed. However, there is a problem that the reaction takes a long time. That is, it is difficult to remove the amorphous carbon adhering to the outer surface without significantly destroying the structure of the carbon nanotube, to treat the low temperature and dry conditions, and to impart a functional group to the outer surface in a short time.
The difficulty was high for single-walled carbon nanotubes with a small number of layers and for carbon nanotubes with 2-5 layers. As described above, conventionally, there is no treatment method capable of simultaneously imparting functions such as improving the dispersibility of carbon nanotubes, refining, and introducing a functional group to the outer surface by a simple operation (low temperature and dry condition treatment, short time). It was
【０００６】[0006]
【非特許文献１】斉藤弥八、坂東俊治、カーボンナノチ
ューブの基礎、株式会社コロナ社、ｐ５３[Non-Patent Document 1] Yahachi Saito, Shunji Bando, Fundamentals of Carbon Nanotubes, Corona Co., p53
【非特許文献２】イー・ティー・ミケルソン（E.T.Mick
elson）,ケミカル・フィジックス・レターズ（Chem.Phy
s.Lett.）,296,188(1998)[Non-Patent Document 2] ET Mickelson (ETMick
elson), Chemical Physics Letters (Chem.Phy
s. Lett.), 296,188 (1998)
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記のよう
な事情に鑑みなされたものであり、プラズマ処理したカ
ーボンナノチューブ、分散液、溶液および組成物ならび
にこれらの製造方法等の提供を目的とする。The present invention has been made in view of the above circumstances, and an object thereof is to provide plasma-treated carbon nanotubes, dispersions, solutions and compositions, and methods for producing these. To do.
【０００８】[0008]
【課題を解決するための手段】前記課題を達成するた
め、本発明は主として次のような構成をとる。In order to achieve the above object, the present invention mainly has the following configuration.
【０００９】すなわち、炭素質材料をプラズマで処理す
ることを特徴とする、炭素質材料の処理方法、炭素質材
料をプラズマで処理する際に、炭素質材料をかき混ぜる
ことを特徴とする処理方法である。特に、炭素質材料が
カーボンナノチューブを含有することを特徴とし、カー
ボンナノチューブが１〜５層であることを特徴とする。That is, a method of treating a carbonaceous material characterized by treating a carbonaceous material with plasma, and a treatment method characterized by stirring the carbonaceous material when treating the carbonaceous material with plasma. is there. In particular, the carbonaceous material is characterized by containing carbon nanotubes, and the carbon nanotubes are characterized by having 1 to 5 layers.
【００１０】さらに、上記プラズマ処理したカーボンナ
ノチューブを、液に分散させることを特徴とする、カー
ボンナノチューブ分散液を得る方法。液に分散させた
後、固液分離することを特徴とする、カーボンナノチュ
ーブ溶液を得る方法。液に分散させた後、分級すること
を特徴とするカーボンナノチューブの精製方法。カーボ
ンナノチューブ分散液、またはカーボンナノチューブ溶
液を、濃縮、乾燥することを特徴とする高濃度カーボン
ナノチューブ分散液、溶液及び粉末状カーボンナノチュ
ーブの製造方法。Further, a method of obtaining a carbon nanotube dispersion liquid, which comprises dispersing the plasma-treated carbon nanotubes in a liquid. A method for obtaining a carbon nanotube solution, which comprises solid-liquid separation after dispersing in a liquid. A method for purifying carbon nanotubes, which comprises classifying after dispersing in a liquid. A method for producing a high-concentration carbon nanotube dispersion, a solution, and a powdery carbon nanotube, which comprises concentrating and drying a carbon nanotube dispersion or a carbon nanotube solution.
【００１１】（１）カーボンナノチューブ合成工程、
（２）カーボンナノチューブプラズマ処理工程、（３）
カーボンナノチューブを液に分散する工程、（４）カー
ボンナノチューブを分級又は固液分離する工程の４つの
工程を有することを特徴とするカーボンナノチューブの
製造方法。(1) Carbon nanotube synthesis step,
(2) Carbon nanotube plasma treatment step, (3)
A method for producing a carbon nanotube, which comprises four steps of dispersing the carbon nanotube in a liquid and (4) classifying the carbon nanotube or solid-liquid separating.
【００１２】上記カーボンナノチューブと金属を含有す
る液を接触させることを特徴とする触媒組成物の製造方
法、上記カーボンナノチューブと有機化合物を含有する
液を接触させることを特徴とする有機化合物含有カーボ
ンナノチューブの製造方法、上記カーボンナノチューブ
を含有することを特徴とするコーティング用組成物の製
造方法である。A method for producing a catalyst composition, which comprises contacting the carbon nanotube with a liquid containing a metal, and contacting the carbon nanotube with a liquid containing an organic compound, the carbon nanotube containing an organic compound And a method for producing a coating composition containing the carbon nanotube.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
【００１４】本発明は、処理空間内に炭素質材料と処理
するガスを供給した状態で、高電圧を印可して発生する
プラズマにより、炭素質材料を処理する方法を特徴とす
る。The present invention is characterized by a method of treating a carbonaceous material with a plasma generated by applying a high voltage in a state where a carbonaceous material and a treatment gas are supplied into the treatment space.
【００１５】炭素質材料は、例えばカーボンナノチュー
ブ、フラーレン、活性炭、カーボンブラック、グラファ
イト、アモルファスカーボン、炭素繊維などを挙げるこ
とができる。なかでも、カーボンナノチューブの処理に
好ましく、１〜５層のカーボンナノチューブの処理に特
に好ましい。Examples of the carbonaceous material include carbon nanotube, fullerene, activated carbon, carbon black, graphite, amorphous carbon, carbon fiber and the like. Among them, it is preferable for the treatment of carbon nanotubes, and particularly preferable for the treatment of carbon nanotubes having 1 to 5 layers.
【００１６】プラズマ処理は、特に制限されないが例え
ば公知の低温プラズマ処理のことをいい、処理装置とし
ては、特に限定されるものではなく、公知の内部電極方
式または外部電極方式が使用されるが、電極の汚染のな
い点から外部電極方式が好ましい。処理圧力、電源周波
数、処理出力などの処理条件は特に限定されるものでは
なく目的に応じ好ましく選定すればよい。プラズマ発生
ガスとしては、特に限定されないが、有機、無機ガスが
目的に応じ単独あるいは混合されて用いられる。たとえ
ば、酸素、窒素、水素、アンモニア、メタン、エチレ
ン、４フッ化炭素などが挙げられる。The plasma treatment is not particularly limited, but refers to, for example, a known low temperature plasma treatment, and the treatment apparatus is not particularly limited, and a known internal electrode system or external electrode system is used. The external electrode method is preferable from the viewpoint of no contamination of the electrodes. Processing conditions such as processing pressure, power supply frequency, and processing output are not particularly limited and may be preferably selected according to the purpose. The plasma generating gas is not particularly limited, but organic and inorganic gases may be used alone or in combination depending on the purpose. For example, oxygen, nitrogen, hydrogen, ammonia, methane, ethylene, carbon tetrafluoride and the like can be mentioned.
【００１７】プラズマ処理によって、炭素質材料の分散
性、精製度が改良できる。この理由は現時点で明らかで
はないが、以下のように推察される。プラズマとは荷電
粒子を含む気体で、荷電粒子が炭素質物質と衝突するこ
とにより、炭素−炭素の結合が切れることによって処理
される。あるいは、炭化水素がデポジットされることに
より処理される。プラズマ処理により、炭素−炭素の結
合が切れた場合は、酸素と接触することにより、その部
分にカルボキシル基やカルボニル基、ヒドロキシル基等
などの官能基が生じると考えられる。The plasma treatment can improve the dispersibility and the degree of purification of the carbonaceous material. The reason for this is not clear at this point, but it is presumed as follows. Plasma is a gas containing charged particles and is processed by breaking the carbon-carbon bond when the charged particles collide with a carbonaceous material. Alternatively, it is processed by depositing hydrocarbons. When the carbon-carbon bond is broken by the plasma treatment, it is considered that a functional group such as a carboxyl group, a carbonyl group, a hydroxyl group, or the like is generated at that portion by contact with oxygen.
【００１８】本発明でのプラズマ処理は、プラズマ処理
の際に炭素質材料をかき混ぜることが好ましい。粉末状
の試料をプラズマ処理する場合、粉末全体にプラズマが
行き渡らない場合がある。鋭意検討した結果、プラズマ
処理の際に炭素質材料をかき混ぜることにより、炭素質
材料全体にプラズマ処理を行き渡らせることができるこ
とを見出した。本発明においてかき混ぜるとは、ひっく
り返したり、攪拌したりする事を言い、均一にプラズマ
処理を行うために、処理の際に処理する材料を動かすこ
とを言う。最も簡単には、プラズマ処理した後、一度取
り出してかき混ぜて、再度プラズマ処理にかける。好ま
しくは、かき混ぜながらプラズマ処理を行う。かき混ぜ
ながらプラズマ処理を行うプラズマ処理装置として、外
部電極方式を用いることが、かき混ぜる動作を装置に組
み込むための設計に自由度があり、且つ容易なことから
好ましい。In the plasma treatment of the present invention, it is preferable to stir the carbonaceous material during the plasma treatment. When a powdery sample is subjected to plasma treatment, the plasma may not spread throughout the powder. As a result of intensive studies, it was found that the plasma treatment can be spread over the entire carbonaceous material by stirring the carbonaceous material during the plasma treatment. In the present invention, "stirring" means turning over or stirring, and moving the material to be treated during the treatment in order to uniformly perform the plasma treatment. In the simplest case, after plasma treatment, it is taken out once, stirred, and subjected to plasma treatment again. Preferably, the plasma treatment is performed while stirring. It is preferable to use an external electrode system as a plasma processing apparatus that performs plasma processing while stirring, because there is a degree of freedom in designing the apparatus for incorporating the stirring operation into the apparatus, and it is easy.
【００１９】本発明は、特にカーボンナノチューブを含
有する炭素質材料をプラズマ処理することを特徴とす
る。カーボンナノチューブは、高い機械的強度、高い導
電性を有することから、燃料電池やリチウム２次電池用
負極材、樹脂や有機半導体との複合材料からなる高強度
樹脂、導電性樹脂、電磁波シールド材として期待されて
おり、さらに、Ｌ／Ｄ（長さ／直径の比）が大きく、直
径は数ｎｍであることから、走査型トンネル顕微鏡用プ
ローブ、電界電子放出源、ナノピンセットとして期待さ
れており、また、ナノサイズの空間を有することから、
吸着材料、医療用ナノカプセル、ＭＲＩ造影剤として期
待されている。The present invention is characterized in that a carbonaceous material containing carbon nanotubes is plasma-treated. Since carbon nanotubes have high mechanical strength and high conductivity, they are used as negative electrode materials for fuel cells and lithium secondary batteries, high-strength resins composed of resins and composite materials with organic semiconductors, conductive resins, electromagnetic wave shielding materials. It is expected, and since it has a large L / D (length / diameter ratio) and a diameter of several nm, it is expected as a scanning tunneling microscope probe, field electron emission source, and nanotweezers. Also, because it has a nano-sized space,
It is expected as an adsorbent material, a medical nanocapsule, and an MRI contrast agent.
【００２０】カーボンナノチューブの形態は、高分解能
透過型電子顕微鏡で調べることができる。グラファイト
の層は、透過型電子顕微鏡でまっすぐにはっきりと見え
るほど好ましいが、グラファイト層は乱れていても構わ
ない。グラファイト層が乱れたものは、カーボンナノフ
ァイバーと定義することがあるが、このようなカーボン
ナノファイバーも本発明においてはカーボンナノチュー
ブに含むものとする。カーボンナノチューブは、一般に
レーザーアブレーション法、アーク放電法、熱ＣＶＤ
法、プラズマＣＶＤ法、燃焼法などで製造できるが、ど
のような方法で製造したカーボンナノチューブでも構わ
ない。篠原らが報告しているようにゼオライトを触媒の
担体としてアセチレンを原料に熱ＣＶＤ法で作る方法
は、特に精製することなく、多少の熱分解炭素等の炭素
被覆はあるものの、純度が高く、良くグラファイト化さ
れたカーボンナノチューブが得られる点で特に好ましい
方法である(Chemical Physics Letters 303(1999) 117-
124)。このようなカーボンナノチューブを使えば、プラ
ズマ処理をするだけで、分散化させたり、精製できたり
するので非常に好ましい。The morphology of carbon nanotubes can be examined by a high resolution transmission electron microscope. The graphite layer is preferable so that it can be clearly seen straight under a transmission electron microscope, but the graphite layer may be disordered. The one in which the graphite layer is disturbed may be defined as a carbon nanofiber, and such a carbon nanofiber is also included in the carbon nanotube in the present invention. Carbon nanotubes are generally produced by laser ablation, arc discharge, thermal CVD.
Method, plasma CVD method, combustion method, or the like, but carbon nanotubes manufactured by any method may be used. As reported by Shinohara et al., The method of making acetylene as a raw material by a thermal CVD method using zeolite as a catalyst carrier has a high degree of purity, though there is some carbon coating such as pyrolytic carbon without any particular purification. It is a particularly preferred method in that well graphitized carbon nanotubes can be obtained (Chemical Physics Letters 303 (1999) 117-
124). It is very preferable to use such a carbon nanotube because it can be dispersed or purified by only plasma treatment.
【００２１】プラズマ処理によって、カーボンナノチュ
ーブの分散性が向上する理由は、以下の様に考えること
ができる。通常、カーボンナノチューブは、隣接するこ
れとは別のカーボンナノチューブと絡まり合った固まり
状で得られる。プラズマ処理によって、カーボンナノチ
ューブ外表面にカルボキシル基やカルボニル基、ヒドロ
キシル基等の官能基が付与でき、隣接するこれとは別の
カーボンナノチューブ外表面に存在するこれらの官能基
と反発し合うようになり、これまで絡まり合っていたカ
ーボンナノチューブがほぐれ、水などの液中に分散する
と考えられる。The reason why the dispersibility of carbon nanotubes is improved by the plasma treatment can be considered as follows. Usually, carbon nanotubes are obtained in the form of a lump that is entangled with another carbon nanotube adjacent thereto. By the plasma treatment, functional groups such as carboxyl group, carbonyl group and hydroxyl group can be added to the outer surface of the carbon nanotube, and the functional groups existing on the outer surface of the carbon nanotube different from the adjacent ones will repel each other. It is considered that the carbon nanotubes that have been entangled with each other until now are loosened and dispersed in a liquid such as water.
【００２２】特に本発明では、プラズマ処理によってカ
ーボンナノチューブ外表面にカルボキシル基やカルボニ
ル基、ヒドロキシル基が付与できる（実施例１３、比較
例２参照）。中でもヒドロキシル基が付与できることは
好ましい。その理由は、ヒドロキシル基（フェノール性
水酸基）は、カルボキシル基やカルボニル基に比べ、カ
ーボンナノチューブ外表面の構造変化を最小限に抑えた
状態で、カーボンナノチューブの分散性を向上できるた
めである。さらに、カーボンナノチューブ外表面のヒド
ロキシル基（フェノール性水酸基）を修飾して、新たな
官能基を導入したり、他の高分子化合物と結合させるこ
とが可能となる。本発明で、カーボンナノチューブ外表
面にヒドロキシル基が付与できる理由は明確にできてい
ないが、一つの要因として、プラズマ処理の際にカーボ
ンナノチューブをかき混ぜることで、カーボンナノチュ
ーブ外表面が全体的に、比較的マイルドに処理されるた
めではないかと考えている。Particularly in the present invention, a carboxyl group, a carbonyl group, or a hydroxyl group can be imparted to the outer surface of the carbon nanotube by plasma treatment (see Example 13 and Comparative Example 2). Above all, it is preferable that a hydroxyl group can be imparted. The reason is that the hydroxyl group (phenolic hydroxyl group) can improve the dispersibility of the carbon nanotubes in a state in which the structural change on the outer surface of the carbon nanotubes is suppressed to a minimum as compared with the carboxyl group and the carbonyl group. Further, it becomes possible to modify the hydroxyl group (phenolic hydroxyl group) on the outer surface of the carbon nanotube to introduce a new functional group or to bond with another polymer compound. In the present invention, the reason why the hydroxyl group can be imparted to the outer surface of the carbon nanotube has not been clarified, but one factor is that by stirring the carbon nanotube during the plasma treatment, the outer surface of the carbon nanotube is generally compared. I think that it is because it is processed mildly.
【００２３】プラズマ処理には、種々の処理があるがと
りわけ酸素ガスプラズマ処理が好ましい。その理由は、
通常カーボンナノチューブは、アモルファスカーボンな
どが表面に付着しており、そのアモルファスカーボンを
酸化して二酸化炭素にして除去することができ、カーボ
ンナノチューブの親水化などの修飾だけでなく、同時に
精製もできるからである。酸素ガスプラズマ処理の条件
は、装置、放電形態によって異なるが外部電極方式の場
合、圧力は５から１００Ｐａが好ましい。プラズマ処理
の条件によって、アモルファスカーボンのような熱分解
炭素被覆物は、取り除くことも出来れば適度に残すこと
も出来る。適度に残した方が、カーボンナノチューブ全
体の外表面積が大きくなり、樹脂との複合など複合材料
に用いた場合、樹脂との親和性が高くなり、好ましい場
合もある。There are various types of plasma treatment, but oxygen gas plasma treatment is particularly preferable. The reason is,
Usually, carbon nanotubes have amorphous carbon etc. attached to the surface, and it is possible to oxidize the amorphous carbon and remove it into carbon dioxide, and not only modification such as hydrophilization of carbon nanotubes but also purification at the same time Is. The conditions of the oxygen gas plasma treatment differ depending on the apparatus and discharge form, but in the case of the external electrode method, the pressure is preferably 5 to 100 Pa. Depending on the conditions of the plasma treatment, the pyrolytic carbon coating such as amorphous carbon can be removed or left appropriately. If left appropriately, the outer surface area of the entire carbon nanotube becomes large, and when used in a composite material such as a composite with a resin, the affinity with the resin becomes high, which may be preferable.
【００２４】本発明のプラズマ処理は、特に、層数の少
ないカーボンナノチューブに好ましく、１〜５層のカー
ボンナノチューブに好ましい。層数の少ないカーボンナ
ノチューブは、層数の多いカーボンナノチューブに比
べ、耐酸化性など耐久性が無く、例えば、酸化剤を用い
て酸化する方法、酸素ガス存在下で焼成する方法によっ
て、カーボンナノチューブの分散性、精製度を改良する
手段が知られているが、これらは酸化のコントロールが
難しく、層数の少ないカーボンナノチューブをすべて燃
やしてしまうなどの欠点がある。それに比較してプラズ
マ処理は、表面層のみをマイルドに処理できるので、層
数の少ないナノチューブの構造を破壊することなく、分
散性、精製度を改良できる。特に、カーボンナノチュー
ブに物質を付着させる表面処理だけでなく、カーボンナ
ノチューブの表面層を直接改質するような表面修飾をし
た１〜５層のカーボンナノチューブは皆無であり、本発
明は新規なそのようなカーボンナノチューブを提供す
る。表面に、付着させて表面処理する方法は付着した物
がはがれ落ちるなどの欠点があるが、直接カーボンナノ
チューブ表面を改質した物は強固な表面処理となり、樹
脂などと混合したときに好ましい。The plasma treatment of the present invention is particularly preferable for carbon nanotubes having a small number of layers, and is preferable for carbon nanotubes having 1 to 5 layers. Carbon nanotubes with a small number of layers are less durable than carbon nanotubes with a large number of layers, such as oxidation resistance. For example, by using a method of oxidizing with an oxidizing agent or a method of firing in the presence of oxygen gas, Means for improving dispersibility and purification degree are known, but these have drawbacks such as difficulty in controlling oxidation and burning all carbon nanotubes having a small number of layers. On the other hand, the plasma treatment can mildly treat only the surface layer, so that the dispersibility and the degree of purification can be improved without destroying the structure of the nanotube having a small number of layers. In particular, there is no 1 to 5 layers of carbon nanotubes which are not only surface-treated to attach a substance to the carbon nanotubes but also surface-modified to directly modify the surface layer of the carbon nanotubes. To provide excellent carbon nanotubes. The method of adhering to the surface and treating the surface has a drawback that the adhered material is peeled off, but the material obtained by directly modifying the surface of the carbon nanotube is a strong surface treatment and is preferable when mixed with a resin or the like.
【００２５】１〜５層の細いカーボンナノチューブの処
理には、窒素プラズマが好ましい。酸素プラズマよりも
マイルドに処理が出来るため、カーボンナノチューブ自
体が燃え尽きて無くなることはない。窒素プラズマ処理
でも、処理後空気中にさらすことにより、窒素プラズマ
により、切られた結合は、空気中の酸素と反応して、カ
ルボキシル基やカルボニル基、ヒドロキシル基等にな
る。Nitrogen plasma is preferred for the treatment of 1 to 5 layers of thin carbon nanotubes. Since it can be processed milder than oxygen plasma, the carbon nanotube itself will not burn out and disappear. Even in the nitrogen plasma treatment, when exposed to air after the treatment, the bonds cleaved by the nitrogen plasma react with oxygen in the air to form carboxyl groups, carbonyl groups, hydroxyl groups and the like.
【００２６】本発明では、プラズマで処理したカーボン
ナノチューブを、液に分散させることでカーボンナノチ
ューブ分散液を製造することができる。本発明における
分散液とは、カーボンナノチューブが液中に分散して浮
遊し、あたかも外見上は一様に見える状態のものを言
う。特に一日以上静置した後も、液状部分の上層部まで
カーボンナノチューブが存在しているものを分散液とい
う。本発明では、溶媒の種類とカーボンナノチューブの
種類、これらの組合せを選択することで、一週間たって
も上層部に透明性を有する部分が現れない分散液を得る
ことができる。分散液は、後述するようなカーボンナノ
チューブが溶解したカーボンナノチューブ溶液を含んで
いてもかまわない。In the present invention, the carbon nanotube dispersion liquid can be produced by dispersing the carbon nanotubes treated with plasma in the liquid. The dispersion liquid in the present invention means a state in which carbon nanotubes are dispersed and suspended in the liquid and look as if they were uniform in appearance. In particular, a dispersion in which the carbon nanotubes are present in the upper layer of the liquid portion even after standing for one day or more is called a dispersion liquid. In the present invention, by selecting the type of solvent, the type of carbon nanotube, and the combination thereof, it is possible to obtain a dispersion liquid in which a transparent portion does not appear in the upper layer even after one week. The dispersion liquid may contain a carbon nanotube solution in which carbon nanotubes are dissolved as described below.
【００２７】プラズマ処理で表面修飾したカーボンナノ
チューブは、表面がお互いに反発しあうため、液中で超
音波処理を行うことにより、絡まり合っていたカーボン
ナノチューブがほぐれて分散することを助けると考えら
れる。超音波処理は、出力が大きいものほど良く、１０
Ｗ以上、好ましくは２０Ｗ以上、さらに好ましくは５０
Ｗ以上であることが好ましい。プラズマで処理したカー
ボンナノチューブを液中に分散させる方法は、超音波で
ある必要は無く、ホモジナイザーのような高速攪拌、ア
トライター、ボールミル等の機械的衝撃を加える攪拌で
もよい。もちろん、通常の攪拌でもかまわない。Since carbon nanotubes surface-modified by plasma treatment repel each other, it is considered that ultrasonic treatment in a liquid helps disentangle and disperse the entangled carbon nanotubes. . The higher the ultrasonic output, the better the ultrasonic treatment.
W or more, preferably 20 W or more, more preferably 50
It is preferably W or more. The method of dispersing the carbon nanotubes treated with plasma in the liquid does not need to be ultrasonic waves, and may be high-speed stirring such as with a homogenizer, or stirring with mechanical impact such as with an attritor or ball mill. Of course, normal stirring may be used.
【００２８】一旦、液中に分散した液は、一部カーボン
ナノチューブが溶解した溶液を含む。この分散液を固液
分離することによって、カーボンナノチューブ溶液を得
ることができる。本発明におけるカーボンナノチューブ
溶液とは、カーボンナノチューブが液中に分散した透明
性を有した液体であり、ろ紙を用いてろ過した場合には
ろ紙を通過し、遠心分離を行った場合には沈殿物がな
い、一般にコロイダル溶液と呼ばれる液状物質のものを
言う。コロイダル溶液は、コロイドの粒が液中に溶けて
いる（溶解している）状態と表現される。このため本発
明では、このカーボンナノチューブのコロイダル溶液
を、液中にカーボンナノチューブが溶解したカーボンナ
ノチューブ溶液と称する。The liquid once dispersed in the liquid contains a solution in which carbon nanotubes are partially dissolved. A carbon nanotube solution can be obtained by solid-liquid separating this dispersion. The carbon nanotube solution in the present invention is a transparent liquid in which carbon nanotubes are dispersed in a liquid, and when the solution is filtered using a filter paper, it passes through the filter paper, and when it is centrifuged, it precipitates. It refers to a liquid substance generally called a colloidal solution. The colloidal solution is described as a state in which colloidal particles are dissolved (dissolved) in the liquid. Therefore, in the present invention, this colloidal solution of carbon nanotubes is referred to as a carbon nanotube solution in which carbon nanotubes are dissolved.
【００２９】固液分離の方法としては、特に限定されな
いが、例えば遠心分離法や濾過法が利用できる。ろ過に
用いるろ紙は、ＪＩＳ Ｐ ３８０１ ２種における保
留粒子径５（μｍ）程度であることが好ましく、また、
遠心分離の条件としては遠心加速度は１５０００（×
ｇ）、より好ましくは１７０００（×ｇ）、処理時間は
１時間程度行うことが、透明性を有する高濃度のカーボ
ンナノチューブ溶液が得られることから好ましい。濾過
法の場合は濾紙を抜けて出てきた液が、遠心分離法の場
合上澄みがカーボンナノチューブ溶液である。The solid-liquid separation method is not particularly limited, but for example, a centrifugation method or a filtration method can be used. The filter paper used for filtration preferably has a retained particle size of about 5 (μm) according to JIS P 3801 type 2, and
Centrifugal acceleration is 15000 (×
g), more preferably 17,000 (× g), and a treatment time of about 1 hour is preferable because a highly concentrated carbon nanotube solution having transparency can be obtained. In the case of the filtration method, the liquid that comes out through the filter paper is the solution, and in the case of the centrifugation method, the supernatant is the carbon nanotube solution.
【００３０】本発明におけるカーボンナノチューブを分
散又は溶解させる液は、特に限定されないが、親水化処
理されたカーボンナノチューブの場合は親水溶媒に、疎
水化されたカーボンナノチューブは疎水性溶媒に分散、
溶解させることが好ましい。親水性溶媒としては、水、
メタノール、エタノール、プロパノール、イソプロパノ
ール、ブタノール等の１価アルコール、エチレングリコ
ール、プロピレングリコール、ブタンジオール等の２価
アルコール、グリセリンなどの３価アルコール、アセト
ン等のケトン類、蟻酸、酢酸、プロピオン酸などの酸、
テトラヒドロフラン等の環状エーテル、Ｎ−メチルピロ
リドン、ジメチルスルフォキサイド（ＤＭＳＯ）等の溶
媒が挙げられる。これらは、混合物でも良く、金属塩な
どの各種イオン、ポリマー、界面活性剤など、その溶媒
に溶解する他の物質が溶解していても良い。疎水性溶媒
は、ベンゼン、トルエン、キシレンなどの芳香族、ヘキ
サン、シクロヘキサン等の脂肪族炭化水素などが例とし
てあげられる。The liquid for dispersing or dissolving the carbon nanotubes in the present invention is not particularly limited, but in the case of hydrophilized carbon nanotubes, it is dispersed in a hydrophilic solvent, and hydrophobized carbon nanotubes are dispersed in a hydrophobic solvent.
It is preferable to dissolve it. As the hydrophilic solvent, water,
Monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, trihydric alcohols such as glycerin, ketones such as acetone, formic acid, acetic acid, propionic acid, etc. acid,
Examples include cyclic ethers such as tetrahydrofuran, and solvents such as N-methylpyrrolidone and dimethylsulfoxide (DMSO). These may be a mixture, and various substances such as various ions such as metal salts, polymers and surfactants, which are soluble in the solvent, may be dissolved therein. Examples of the hydrophobic solvent include aromatics such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and cyclohexane.
【００３１】本発明は、下式で示される、カーボンナノ
チューブ外表面の炭素に対する酸性官能基の含有率が２
％以上であることが、カーボンナノチューブの分散性向
上に好適である。According to the present invention, the content of the acidic functional group with respect to the carbon on the outer surface of the carbon nanotube represented by the following formula is 2
% Or more is suitable for improving the dispersibility of carbon nanotubes.
【００３２】[0032]
【数１】 [Equation 1]
【００３３】Ａｃ：カーボンナノチューブ１ｇに含まれ
る酸性官能基のモル数
２πＲａ：カーボンナノチューブ平均外周（nm）
［（Ｒａ−Ｒｂ）／Ｒｋ］＋１：カーボンナノチューブ
平均層数
Ｒａ：カーボンナノチューブ平均外半径
Ｒｂ：カーボンナノチューブ平均内半径
Ｒｋ：カーボンナノチューブ層間距離
上式に示す分子のＡｃは、外表面に官能基を有するカー
ボンナノチューブ１ｇに含まれる酸性官能基のモル数で
ある。純度１００％のカーボンナノチューブを得ること
は困難であり、それを同定することも困難であるため、
ここで言うカーボンナノチューブとは５万倍の倍率で走
査型電子顕微鏡で見たときに繊維状の物質がその電子顕
微鏡の視野の中に８０％以上であるカーボン質材料であ
ればカーボンナノチューブと言って差し支えない。従っ
て、厳密に定義すればカーボンナノチューブ外表面だけ
に酸性官能基を有するのではなく、カーボンナノチュー
ブに付着した炭素、カーボンナノチューブに混在する炭
素粒子も含んだ状態で酸量を測定し、すべてカーボンナ
ノチューブの表面に酸性官能基があるとして計算したも
のである。外表面に官能基を有するカーボンナノチュー
ブとは、図１の模式図に示されるように、カーボンナノ
チューブ外表面に少なくとも１種類以上の官能基を有す
るカーボンナノチューブのことである。官能基の種類は
特に限定されないが、例えば、水酸基、カルボニル基、
カルボキシル基、ニトロ基、スルホン基、エーテル基、
などを挙げることができる。外表面に官能基を有するカ
ーボンナノチューブに含まれる酸性官能基のモル数の測
定には、水酸化ナトリウム水溶液を用いた中和滴定の測
定から計算によって求める。Ac: number of moles of acidic functional group contained in 1 g of carbon nanotube 2πRa: average circumference of carbon nanotube (nm) [(Ra-Rb) / Rk] +1: average number of carbon nanotube layers Ra: average outer radius of carbon nanotube Rb : Carbon nanotube average inner radius Rk: Carbon nanotube interlayer distance Ac of the molecule shown in the above formula is the number of moles of acidic functional groups contained in 1 g of carbon nanotubes having a functional group on the outer surface. It is difficult to obtain a carbon nanotube with a purity of 100%, and it is also difficult to identify it.
The carbon nanotubes referred to here are called carbon nanotubes if the fibrous substance is 80% or more in the field of view of the electron microscope when viewed with a scanning electron microscope at a magnification of 50,000 times. It doesn't matter. Therefore, if strictly defined, the amount of acid is measured not only by having the acidic functional group only on the outer surface of the carbon nanotubes but also by including the carbon attached to the carbon nanotubes and the carbon particles mixed in the carbon nanotubes. It is calculated as if there were acidic functional groups on the surface of. The carbon nanotube having a functional group on the outer surface is a carbon nanotube having at least one kind of functional group on the outer surface of the carbon nanotube, as shown in the schematic view of FIG. The type of functional group is not particularly limited, for example, a hydroxyl group, a carbonyl group,
Carboxyl group, nitro group, sulfone group, ether group,
And so on. The number of moles of the acidic functional group contained in the carbon nanotube having a functional group on the outer surface is calculated by the neutralization titration measurement using an aqueous sodium hydroxide solution.
【００３４】上式に示す分母は、カーボンナノチューブ
１ｇに含まれるカーボンナノチューブ外表面の炭素のモ
ル数である。カーボンナノチューブ平均外周を、カーボ
ンナノチューブ平均層数とカーボンナノチューブ平均円
周の乗算結果を用いて除算することで、カーボンナノチ
ューブ全体に対するカーボンナノチューブ外表面の炭素
率を求める。これに、カーボンナノチューブ１ｇを炭素
原子の原子量（１２ｇ／ｍｏｌ）で除算した結果（つま
り、カーボンナノチューブ１ｇ中に含まれる炭素原子の
モル数）を乗算することで、カーボンナノチューブ１ｇ
に含まれるカーボンナノチューブ外表面の炭素のモル数
を求める。The denominator shown in the above equation is the number of moles of carbon on the outer surface of the carbon nanotube contained in 1 g of the carbon nanotube. The carbon ratio of the outer surface of the carbon nanotubes to the entire carbon nanotubes is obtained by dividing the average outer circumference of the carbon nanotubes by using the multiplication result of the average number of carbon nanotube layers and the average circumference of the carbon nanotubes. 1 g of carbon nanotubes is divided by the atomic weight of carbon atoms (12 g / mol) (that is, the number of moles of carbon atoms contained in 1 g of carbon nanotubes) is multiplied to obtain 1 g of carbon nanotubes.
The number of moles of carbon on the outer surface of the carbon nanotube contained in is calculated.
【００３５】カーボンナノチューブ平均外半径Ｒａ、カ
ーボンナノチューブ平均内半径Ｒｂは図１に示すように
定義され、例えば、透過型電子顕微鏡（ＴＥＭ）観察結
果から、ひとつのカーボンナノチューブを重複して用い
ないルール適用して、任意に少なくとも１０点以上、好
ましくは２０点以上のカーボンナノチューブの外半径、
内半径を計測し、それぞれ平均値を計算することで求め
る。The average outer radius Ra of the carbon nanotubes and the average inner radius Rb of the carbon nanotubes are defined as shown in FIG. 1. For example, from the observation result of a transmission electron microscope (TEM), a rule that one carbon nanotube is not duplicated is used. And optionally, at least 10 or more, preferably 20 or more, outer radii of carbon nanotubes,
It is calculated by measuring the inner radius and calculating the average value.
【００３６】カーボンナノチューブ層間距離Ｒｋは、公
知の値である０．３４ｎｍを用いる。A known value of 0.34 nm is used for the carbon nanotube interlayer distance Rk.
【００３７】上記のようにして、カーボンナノチューブ
外表面の炭素に対する酸性官能基の含有率を求めるわけ
であるが、その概略を記すと、走査型電子顕微鏡（また
は透過型電子顕微鏡）で見たときに、顕微鏡の視野中に
繊維状物質（カーボンナノチューブ）を含む（好ましく
は繊維状物質を１０％以上、より好ましくは５０％以
上、さらに好ましくは８０％以上含む）カーボン質材料
を用いて、水酸化ナトリウム水溶液を用いた中和滴定の
値と、透過型電子顕微鏡（ＴＥＭ）ＴＥＭ観察結果から
求めたカーボンナノチューブ平均外半径、平均内半径の
値を前記式に代入し、カーボンナノチューブ外表面の炭
素に対する酸性官能基の含有率を求めることになる。後
述の実施例２（走査型電子顕微鏡での繊維状物質の確
認）、実施例１４（中和滴定）、実施例１５（透過型電
子顕微鏡写真からのカーボンナノチューブ直径計算）、
実施例１６（酸性官能基含有率の計算）参照。The content of the acidic functional group with respect to the carbon on the outer surface of the carbon nanotube is determined as described above. The outline thereof is as follows: when viewed with a scanning electron microscope (or a transmission electron microscope). In addition, a carbonaceous material containing a fibrous substance (carbon nanotube) in the field of view of the microscope (preferably containing 10% or more of fibrous substance, more preferably 50% or more, still more preferably 80% or more) is used. By substituting the values of the neutralization titration using an aqueous solution of sodium oxide, the average outer radius of the carbon nanotubes and the values of the average inner radius obtained from the TEM observation results of the transmission electron microscope (TEM), the carbon on the outer surface of the carbon nanotubes was substituted. The content of the acidic functional group with respect to Example 2 (confirmation of fibrous substance with a scanning electron microscope), Example 14 (neutralization titration), Example 15 (calculation of carbon nanotube diameter from transmission electron micrograph) described later,
See Example 16 (calculation of acidic functional group content).
【００３８】前記式で示される、カーボンナノチューブ
外表面の炭素に対する酸性官能基の含有率は２％以上、
好ましくは４％以上、さらに好ましくは８％以上である
ことが好ましい。２％より小さいと、液中への分散性が
悪化する。The content of the acidic functional group represented by the above formula with respect to the carbon on the outer surface of the carbon nanotube is 2% or more,
It is preferably 4% or more, more preferably 8% or more. If it is less than 2%, the dispersibility in the liquid deteriorates.
【００３９】また、前記式を満たすカーボンナノチュー
ブの官能基を、化学反応などの手法をもちいてさらに修
飾して用いてもかまわない。Further, the functional group of the carbon nanotube satisfying the above formula may be further modified and used by using a method such as a chemical reaction.
【００４０】前記式で求められるカーボンナノチューブ
外表面の炭素に対する酸性官能基含有率が２％以上であ
るカーボンナノチューブは、親水性溶媒に分散又は溶解
し、カーボンナノチューブの分散液、溶液になる。親水
性溶媒の中でも、取り扱い上の安全性や、コストの面か
ら、水が最も好ましい。Carbon nanotubes having an acidic functional group content of 2% or more with respect to carbon on the outer surface of the carbon nanotubes calculated by the above formula are dispersed or dissolved in a hydrophilic solvent to form a carbon nanotube dispersion liquid or solution. Among the hydrophilic solvents, water is most preferable from the viewpoint of handling safety and cost.
【００４１】本発明は、プラズマ処理したカーボンナノ
チューブを液に分散させた後、分級することを特徴とす
る精製カーボンナノチューブ溶液の製造方法も含む。プ
ラズマで処理したカーボンナノチューブを液に分散させ
たものは、カーボンナノチューブの固まりの大きさによ
って沈降速度が変わってくる。その性質を利用して、カ
ーボンナノチューブを遠心分離、フィルトレーション等
で固まりの大きさで分級する事が可能である。また、カ
ーボンナノチューブの製造に触媒を用いた場合、触媒部
分を含んでいるカーボンナノチューブと含んでいないカ
ーボンナノチューブの比重の違いを利用して遠心分離で
分級することも可能で、触媒を除去する精製も可能であ
る。このように、分級して固まりの大きさを均一にした
カーボンナノチューブは、フィールドエミッションディ
スプレーの電子源や、各種電極触媒としてコーティング
する場合に有用である。The present invention also includes a method for producing a purified carbon nanotube solution, which is characterized in that plasma-treated carbon nanotubes are dispersed in a liquid and then classified. When the carbon nanotubes treated with plasma are dispersed in a liquid, the sedimentation speed changes depending on the size of the aggregate of carbon nanotubes. By utilizing this property, it is possible to classify carbon nanotubes by the size of a lump by centrifugation, filtration or the like. Further, when a catalyst is used for the production of carbon nanotubes, it is also possible to perform classification by centrifugation by utilizing the difference in specific gravity between carbon nanotubes containing a catalyst portion and carbon nanotubes not containing a catalyst portion. Is also possible. In this way, the carbon nanotubes that have been classified to make the size of the aggregates uniform are useful for coating as an electron source for field emission displays and various electrode catalysts.
【００４２】本発明は、上記の方法で得られたカーボン
ナノチューブ分散液、またはカーボンナノチューブ溶液
を濃縮および／または乾燥することを特徴とする高濃度
カーボンナノチューブ分散液、溶液および粉末状カーボ
ンナノチューブの製造方法も含む。分散液から分級した
分散液や溶液を濃縮することによって高濃度のカーボン
ナノチューブ分散液や溶液が得られ、乾燥すれば粉末が
得られる。このようにして得られた粉末は、カーボンナ
ノチューブの絡まり方や固まり径が制御されているので
好ましい。濃縮や乾燥の方法は、通常の加熱による溶媒
の除去、真空排気による溶媒除去、凍結乾燥など従来公
知のすべての方法が利用できる。The present invention is directed to the production of a high-concentration carbon nanotube dispersion, a solution and a powdery carbon nanotube, characterized by concentrating and / or drying the carbon nanotube dispersion or the carbon nanotube solution obtained by the above method. Including methods. A high concentration carbon nanotube dispersion or solution is obtained by concentrating the dispersion or solution classified from the dispersion, and a powder is obtained by drying. The powder thus obtained is preferable because the entanglement of the carbon nanotubes and the solidified diameter are controlled. As the concentration and drying methods, all conventionally known methods such as removal of the solvent by ordinary heating, removal of the solvent by evacuation and freeze-drying can be used.
【００４３】本発明では、好ましくは（１）カーボンナ
ノチューブ合成工程、（２）カーボンナノチューブをプ
ラズマ処理する工程、（３）カーボンナノチューブを液
に分散する工程、（４）カーボンナノチューブを分級又
は固液分離する工程の４つの工程によりカーボンナノチ
ューブを製造する。従来、カーボンナノチューブの合成
方法は数多く提案されている。多くのカーボンナノチュ
ーブは絡まり合った固まり状で得られる。しかしなが
ら、実用化を考えた場合、カーボンナノチューブは、分
散していた方が良く、不純物と分離されていた方が好ま
しい。種々の精製方法が提案されているが、通常は強酸
やフッ酸を使用するという厳しい条件を使うものであ
る。また、今まで分散したカーボンナノチューブを効率
よく連続生産するプロセスは提案されていない。本発明
者らは、プラズマ処理によりカーボンナノチューブが液
中に良く分散することを見出し、その分散液が分級によ
って、溶液部分、微分散部分、触媒付着部分に分けるこ
とができることを見出した。In the present invention, preferably, (1) carbon nanotube synthesizing step, (2) carbon nanotube plasma treating step, (3) carbon nanotube dispersing step, (4) carbon nanotube classifying or solid-liquid step Carbon nanotubes are manufactured by four steps of separating. Conventionally, many methods for synthesizing carbon nanotubes have been proposed. Many carbon nanotubes are obtained in the form of entangled masses. However, from the viewpoint of practical application, it is preferable that the carbon nanotubes are dispersed, and it is preferable that they are separated from impurities. Although various refining methods have been proposed, usually, the severe conditions of using strong acid or hydrofluoric acid are used. Moreover, no process has been proposed so far for efficiently and continuously producing dispersed carbon nanotubes. The present inventors have found that the carbon nanotubes are well dispersed in the liquid by the plasma treatment, and found that the dispersion liquid can be divided into a solution portion, a fine dispersion portion, and a catalyst adhering portion by classification.
【００４４】本発明において、第一工程のカーボンナノ
チューブ合成工程とは、どのような方法でも良い。公知
のあらゆる技術が利用できる。レーザーアブレーション
法、アーク放電法、熱ＣＶＤ法、プラズマＣＶＤ法、燃
焼法などが挙げられる。工程をスムーズに進めるために
は、気相で連続生産できる熱ＣＶＤ法が好ましい。熱Ｃ
ＶＤ法は、６００℃から１２００℃の高温で触媒と炭素
源を接触させる方法で触媒を連続的に供給すれば連続的
にカーボンナノチューブを回収することができる。In the present invention, the carbon nanotube synthesizing step of the first step may be any method. Any known technique can be used. A laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method, a combustion method and the like can be mentioned. In order to proceed the process smoothly, a thermal CVD method that allows continuous production in a vapor phase is preferable. Heat C
The VD method is a method in which a catalyst and a carbon source are brought into contact with each other at a high temperature of 600 ° C. to 1200 ° C., and carbon nanotubes can be continuously recovered by continuously supplying the catalyst.
【００４５】第２工程は、プラズマ処理工程であり、こ
の工程は前述したとおりである。酸素ガスプラズマ処理
が好ましい。粉末のカーボンナノチューブを連続的に処
理できるプラズマ装置が好ましい。例えば、粉末のカー
ボンナノチューブを連続的（断続的でもよい）に供給
し、さらに、かき混ぜながらプラズマ処理を行うプラズ
マ処理装置として、外部電極方式を用いることが、装置
設計に自由度があり、且つ容易なことから好ましい。The second step is a plasma treatment step, and this step is as described above. Oxygen gas plasma treatment is preferred. A plasma device capable of continuously processing powdered carbon nanotubes is preferred. For example, the external electrode method is used as a plasma processing apparatus that continuously supplies powdered carbon nanotubes (may be intermittent) and performs plasma processing while stirring. Therefore, it is preferable.
【００４６】第３工程の分散工程は、プラズマ処理され
たカーボンナノチューブを液中に分散させる工程であ
る。分散させる方法は特に限定されないが、例えば、超
音波処理は、出力が大きいものほど良く、１０Ｗ以上、
好ましくは２０Ｗ以上、さらに好ましくは５０Ｗ以上で
あることが好ましい。ホモジナイザー（処理圧力は３Ｍ
Ｐａ以上が好ましい）のような高速攪拌、アトライター
（回転数は１００ｒｐｍ以上が好ましい）、ボールミル
（ボールの衝撃は１Ｇ以上が好ましい）等の機械的衝撃
を加える攪拌でもよい。もちろん、通常の攪拌でもかま
わない。The dispersion step of the third step is a step of dispersing the plasma-treated carbon nanotubes in the liquid. The method of dispersing is not particularly limited, but for example, the ultrasonic treatment is better as the output is larger, and 10 W or more,
It is preferably 20 W or more, more preferably 50 W or more. Homogenizer (Processing pressure is 3M
High-speed stirring such as Pa or higher), attritor (rotation speed is preferably 100 rpm or higher), mechanical agitation such as a ball mill (ball impact is preferably 1 G or higher) may be used. Of course, normal stirring may be used.
【００４７】第４の工程は、分散されたカーボンナノチ
ューブ分散液を分級又は固液分離する工程である。その
方法は特に限定されないが、例えばフィルトレーション
や遠心分離が適用できる。分級や固液分離によって、分
離された固体部分は、再度第３の工程に戻して、再分散
させて、再度第４の工程で溶液を回収することもでき
る。また、第４の工程で分級又は固液分離された、分散
度の低い部分は、乾燥した後、再度第２の工程に戻して
プラズマ処理をすることも行われる。また、第４の工程
で回収された最も比重の重い触媒を含有するカーボンナ
ノチューブは、空気中で焼成するなどしてカーボンナノ
チューブを除去して、触媒を第一の工程に戻すこともで
きる。The fourth step is a step of classifying or solid-liquid separating the dispersed carbon nanotube dispersion liquid. The method is not particularly limited, but filtration or centrifugation can be applied, for example. The solid portion separated by classification or solid-liquid separation can be returned to the third step again, redispersed, and the solution can be recovered again in the fourth step. Further, the portion having a low degree of dispersion, which has been classified or solid-liquid separated in the fourth step, may be dried and then returned to the second step for plasma treatment. Further, the carbon nanotubes containing the catalyst having the highest specific gravity recovered in the fourth step can be removed in the first step by firing the carbon nanotubes to remove the carbon nanotubes.
【００４８】本発明では、次の２つの工程を有すること
を特徴とする触媒組成物の製造方法によって優れた触媒
組成物を製造することができる。（１）カーボンナノチ
ューブをプラズマ処理する工程と、（２）プラズマ処理
後のカーボンナノチューブを金属を含有する液と接触す
る工程である。具体的な製造方法としては、プラズマ処
理したカーボンナノチューブを金属を含有する水溶液に
加え、この水溶液を撹拌することで触媒組成物を得るこ
とができる。さらに、上記液体状態の触媒組成物は、乾
燥させて溶媒を取り除き、固体状態とすることもでき
る。本発明の触媒組成物についての詳細を以下に記す。In the present invention, an excellent catalyst composition can be produced by the method for producing a catalyst composition characterized by comprising the following two steps. (1) a step of plasma-treating the carbon nanotubes; and (2) a step of contacting the carbon nanotubes after the plasma treatment with a liquid containing a metal. As a specific manufacturing method, the catalyst composition can be obtained by adding plasma-treated carbon nanotubes to an aqueous solution containing a metal and stirring the aqueous solution. Further, the liquid-state catalyst composition can be dried to remove the solvent to give a solid state. The details of the catalyst composition of the present invention are described below.
【００４９】本発明における親水性のカーボンナノチュ
ーブは、水に分散するので触媒担体として好ましく使用
できる。通常触媒成分である金属は、金属塩の水溶液の
形で、担体上に担持するが、従来カーボンナノチューブ
は疎水性であり、カーボンナノチューブ表面に担持する
ことは困難であった。しかし本発明の親水性のカーボン
ナノチューブを使用すれば、金属塩の水溶液と馴染みが
良く、高分散にカーボンナノチューブ表面に金属触媒を
担持することが出来る。特に、カーボンナノチューブ表
面にカルボニル基やカルボン酸基が存在するため、金属
イオンを、これらの官能基との相互作用により特に良く
分散させることが出来る。本発明で言う触媒成分とは、
触媒能力があれば特に限定されないが、例えば、Pd,Pt,
Ru,Rh,Ag,Au,Re等の貴金属やTi,V,Cr,Mn,Fe,Co,Ni,Cu,Z
n等の金属やその酸化物が挙げられ、還元能や酸化能を
発現することが出来る。カーボンナノチューブはお互い
絡まり合っており、ガスや液の拡散性、濾過性ともに優
れており触媒として非常に適している。さらに、１〜５
層のカーボンナノチューブは直径が細くその外表面積が
大きいので優れている。本発明触媒組成物が優れている
点は、カーボンナノチューブが細いチューブ状であるた
めその曲率が大きく、触媒金属を微粒子化できることで
ある。The hydrophilic carbon nanotubes of the present invention can be preferably used as a catalyst carrier because they are dispersed in water. Metal, which is usually a catalyst component, is supported on a carrier in the form of an aqueous solution of a metal salt, but conventionally, carbon nanotubes are hydrophobic and it has been difficult to support them on the surface of carbon nanotubes. However, when the hydrophilic carbon nanotubes of the present invention are used, they are well compatible with an aqueous solution of a metal salt, and a metal catalyst can be supported on the surface of the carbon nanotubes with high dispersion. In particular, since carbonyl groups and carboxylic acid groups are present on the surface of the carbon nanotubes, the metal ions can be dispersed particularly well by the interaction with these functional groups. The catalyst component referred to in the present invention is
There is no particular limitation as long as it has a catalytic ability, for example, Pd, Pt,
Noble metals such as Ru, Rh, Ag, Au, Re and Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Z
Examples thereof include metals such as n and oxides thereof, and can exhibit reducing ability and oxidizing ability. The carbon nanotubes are entangled with each other, and are excellent in diffusibility of gas or liquid and filterability, and are very suitable as a catalyst. Furthermore, 1-5
The carbon nanotubes of the layer are excellent because of their small diameter and large external surface area. The advantage of the catalyst composition of the present invention is that the carbon nanotube has a thin tubular shape and thus has a large curvature, and the catalyst metal can be made into fine particles.
【００５０】触媒金属が、微粒子化できると金属の表面
積が高くなり、触媒の活性は非常に高くなることは容易
に推定できる。また、金属を微粒子で担持させたカーボ
ンナノチューブは、カーボンナノチューブの製造触媒と
しても使用できる。例えば、コバルトを担持したカーボ
ンナノチューブを管状炉内に設置された石英管に置き、
アルゴン等の不活性ガスを流しながら、管状炉で５００
℃〜１２００℃に加熱し、加熱された時点で炭素含有化
合物を導入する事によりカーボンナノチューブを製造で
きる。It can be easily presumed that if the catalyst metal can be made into fine particles, the surface area of the metal will be high and the activity of the catalyst will be very high. Further, the carbon nanotube supporting the metal in the form of fine particles can also be used as a catalyst for producing the carbon nanotube. For example, placing carbon nanotubes carrying cobalt in a quartz tube installed in a tubular furnace,
While flowing an inert gas such as argon, 500 in a tubular furnace
Carbon nanotubes can be produced by heating to 1800C to 1200C and introducing a carbon-containing compound at the time of heating.
【００５１】また、本発明では次の２つの工程を有する
ことを特徴とする有機化合物含有カーボンナノチューブ
の製造方法によって、優れた有機化合物含有カーボンナ
ノチューブを製造することができる。（１）カーボンナ
ノチューブをプラズマ処理する工程と、（２）プラズマ
処理後のカーボンナノチューブを有機化合物を含有する
液と接触する工程である。ここでいう有機化合物の好ま
しい例として、薬剤を挙げることができる。その理由
と、具体的な製造方法を以下に記す。上記のごとき親水
性のカーボンナノチューブは、薬剤輸送剤としても優れ
た性能を示す。本発明の親水性のカーボンナノチューブ
は、中空部分がオープンになっていれば、中空部分が疎
水性、外表面が親水性である。従って、中空部分に疎水
性の薬剤を吸着させたカーボンナノチューブを水に分散
させたものができる。人間や動物の体は、ほとんどが水
で出来ておりこのような物質は薬剤として使用できる。
中空部分に薬剤を吸着させたカーボンナノチューブを水
に分散させて、カテーテルで患部に挿入しても良く、そ
のまま飲み薬や、塗り薬、点眼薬などとして使用しても
良い。中空部分をオープンにするためには、酸化してや
ればよい。酸化は、気相酸化でも液相酸化でも良い。勿
論酸素プラズマ処理でも良い。薬剤輸送剤として使用す
る場合、重さ当たりの効果を考えた場合、壁が薄い方が
良いので細い方が好ましく、１０層以下、更に好ましく
は５層以下、特に好ましくは２層カーボンナノチューブ
がベストである。体内での移動を考えた場合も、細い方
が好ましく２層カーボンナノチューブが最も好ましい。
単層カーボンナノチューブは、親水性と疎水性の両立が
困難である。このような薬剤の作り方は、特に限定され
ないが、（１）酸化処理によりナノチューブの先端をオ
ープンにする。（ナノチューブ先端は、反応性の高い炭
素５員環を多く含むため選択的に燃えて簡単にオープン
に出来る。オープンになったかどうかは７７Ｋで窒素吸
着実験をすることによって確認できる）（２）本発明の
プラズマ処理を行い、水中で超音波をかけ分散させる。
（３）遠心分離により、浮遊物を取り除く。（４）カー
ボンナノチューブ分散水溶液に、疎水性の薬剤を少量添
加すると、疎水性の薬剤は疎水性のカーボンナノチュー
ブ中空部分に選択的に吸着される。このような工程によ
って作ることが出来る。Further, according to the present invention, an excellent organic compound-containing carbon nanotube can be manufactured by the method for manufacturing an organic compound-containing carbon nanotube, which has the following two steps. (1) a step of plasma-treating the carbon nanotubes; and (2) a step of contacting the carbon nanotubes after the plasma treatment with a liquid containing an organic compound. As a preferable example of the organic compound mentioned here, a drug can be mentioned. The reason and a specific manufacturing method are described below. The hydrophilic carbon nanotubes as described above also show excellent performance as drug transport agents. In the hydrophilic carbon nanotube of the present invention, if the hollow portion is open, the hollow portion is hydrophobic and the outer surface is hydrophilic. Therefore, a carbon nanotube having a hydrophobic drug adsorbed in the hollow portion is dispersed in water. Most human and animal bodies are made of water, and such substances can be used as drugs.
The carbon nanotubes in which the drug is adsorbed in the hollow portion may be dispersed in water and inserted into the affected area with a catheter, or may be used as it is as a swallow, an ointment or an eye drop. In order to open the hollow portion, it may be oxidized. The oxidation may be gas phase oxidation or liquid phase oxidation. Of course, oxygen plasma treatment may also be used. When used as a drug transport agent, considering the effect per weight, it is preferable that the wall is thin so that the wall is thin, so 10 or less, more preferably 5 or less, and particularly preferably double-walled carbon nanotube is the best. Is. Considering the movement in the body, the thinner one is preferable and the double-walled carbon nanotube is most preferable.
It is difficult for the single-walled carbon nanotube to have both hydrophilicity and hydrophobicity. The method for producing such a drug is not particularly limited, but (1) the tip of the nanotube is opened by an oxidation treatment. (The tip of the nanotube contains many highly reactive 5-membered carbon rings and can be selectively burned to open easily. Whether or not it is open can be confirmed by performing a nitrogen adsorption experiment at 77K.) (2) The plasma treatment of the invention is performed, and ultrasonic waves are applied in water to disperse.
(3) Remove the suspended matter by centrifugation. (4) When a small amount of a hydrophobic drug is added to the carbon nanotube-dispersed aqueous solution, the hydrophobic drug is selectively adsorbed by the hollow portion of the hydrophobic carbon nanotube. It can be made by such a process.
【００５２】さらに本発明では、次の２つの工程を有す
ることを特徴とするコーティング用組成物の製造方法に
よって、優れたコーティング用組成物を製造することが
できる。（１）カーボンナノチューブをプラズマ処理す
る工程と、（２）プラズマ処理後のカーボンナノチュー
ブをコーティング用の主剤と混合する工程である。ここ
でいうコーティング用の主剤としては、例えば樹脂を挙
げることができる。樹脂としては、常温で液状態、また
は固体状態のものを挙げることができ、さらに、熱可塑
性、熱硬化性のものを挙げることができる。中でも、常
温で液状態の樹脂を用いることが、プラズマ処理したカ
ーボンナノチューブを樹脂と混合させる工程が常温で行
え工程設備が簡素化できることや、常温でコーティング
したい任意形状の対象物に塗布できることからコーティ
ングの工程設備が簡素化できることから好ましい。さら
に、硬化性の樹脂を用いることが、例えばコーティング
用組成物をコーティングしたい任意形状の対象物表面に
塗布した後、コーティング用組成物を硬化させること
で、コーティング用組成物を任意形状の対象物表面に強
固に固定することができることから好ましい。プラズマ
処理後のカーボンナノチューブをコーティング用の主剤
と混合する方法としては、超音波やホモジナイザー、ア
トライター、ボールミル、バンバリーミキサー、ニーダ
ー、ロール、単軸もしくは二軸の押出機を用いることが
できる。なお、ここでいうコーティング用組成物とは、
ペースト状組成物も含む。本発明のコーティング用組成
物に関する詳細を以下に記す。Further, in the present invention, an excellent coating composition can be produced by the method for producing a coating composition characterized by having the following two steps. (1) a step of plasma-treating the carbon nanotubes, and (2) a step of mixing the carbon nanotubes after the plasma treatment with a main agent for coating. Examples of the main component for coating referred to here include resins. Examples of the resin include those that are in a liquid state or a solid state at room temperature, and further, those that are thermoplastic and thermosetting. Among them, using a resin in a liquid state at room temperature allows the process of mixing the plasma-treated carbon nanotubes with the resin to be performed at room temperature, which simplifies the process equipment and allows coating on an object of any shape desired to be coated at room temperature. This is preferable because the process equipment can be simplified. Further, a curable resin is used, for example, the coating composition is applied to the surface of an object of an arbitrary shape to be coated, and then the coating composition is cured, whereby the coating composition is applied to an object of an arbitrary shape. It is preferable because it can be firmly fixed to the surface. As a method of mixing the carbon nanotubes after the plasma treatment with the main agent for coating, an ultrasonic wave, a homogenizer, an attritor, a ball mill, a Banbury mixer, a kneader, a roll, a single-screw or twin-screw extruder can be used. The coating composition here means
It also includes a pasty composition. Details regarding the coating composition of the present invention are described below.
【００５３】本発明における官能基を付与したカーボン
ナノチューブは、前述したように、親水化処理されたカ
ーボンナノチューブの場合は親水性溶媒に、疎水化され
たカーボンナノチューブは疎水性溶媒に分散、溶解させ
ることが容易である。このため、官能基を付与したカー
ボンナノチューブと、官能基を付与したカーボンナノチ
ューブを分散可能な溶媒を含有する組成物を作成するこ
とで、カーボンナノチューブが高分散した組成物を得る
ことができる。カーボンナノチューブが高分散した組成
物は、カーボンナノチューブの持つ良導電性、高強度特
性、電界電子放出特性を十分に引き出すことができる優
れた組成物となる。As described above, the functionalized carbon nanotubes of the present invention are dispersed and dissolved in a hydrophilic solvent in the case of hydrophilized carbon nanotubes, and the hydrophobic carbon nanotubes in a hydrophobic solvent. It is easy to do. Therefore, by preparing a composition containing a carbon nanotube having a functional group and a solvent in which the carbon nanotube having a functional group can be dispersed, a composition in which carbon nanotubes are highly dispersed can be obtained. The composition in which the carbon nanotubes are highly dispersed becomes an excellent composition that can sufficiently bring out the good conductivity, high strength characteristics, and field electron emission characteristics of the carbon nanotubes.
【００５４】このため、官能基を付与したカーボンナノ
チューブを含有し、好ましくは官能基を付与したカーボ
ンナノチューブが分散可能な溶媒も含有し、さらに好ま
しくは硬化性を有する液状物質をも含有することを特徴
とするコーティング用組成物を作成することで、コーテ
ィング用組成物を固体表面に塗布して固体表面の導電性
を向上することができる。もちろんコーティング用組成
物は固体表面上で硬化させてもよい。また、コーティン
グ用組成物を型に流し込み硬化させることで、導電性や
強度に優れた任意形状の固体物質を得ることができる。
さらに、コーティング用組成物（硬化させた後でも良
い）に電極を取り付けることで、優れた電界電子放出特
性を示す電子デバイスを得ることができる。Therefore, it is preferable to contain a carbon nanotube having a functional group, preferably a solvent in which the carbon nanotube having a functional group can be dispersed, and more preferably a liquid substance having curability. By preparing the characteristic coating composition, the coating composition can be applied to the solid surface to improve the conductivity of the solid surface. Of course the coating composition may be cured on a solid surface. Further, by pouring the coating composition into a mold and curing it, a solid substance having an arbitrary shape excellent in conductivity and strength can be obtained.
Furthermore, by attaching an electrode to the coating composition (which may be after curing), an electronic device exhibiting excellent field electron emission characteristics can be obtained.
【００５５】コーティング用組成物を作成する際に用い
る原料として、透明性を有する原料を選択し、カーボン
ナノチューブの添加量を１ｗｔ％以下にすることで、得
られるコーティング用組成物は透明性を有することがで
きる。コーティング用組成物を作成する際に用いる原料
として、硬化後も透明性を有する原料を選択すること
で、硬化後も透明性を有するコーティング用組成物を得
ることができる。このため、上記特性（良導電性、高強
度特性、電界電子放出特性）に加えて、透明性の特性を
併せ持つことができる。By selecting a raw material having transparency as the raw material used for preparing the coating composition and setting the addition amount of carbon nanotubes to 1 wt% or less, the obtained coating composition has transparency. be able to. By selecting a raw material having transparency even after curing as a raw material used when preparing the coating composition, a coating composition having transparency after curing can be obtained. Therefore, in addition to the above-mentioned characteristics (good conductivity, high strength characteristics, field electron emission characteristics), it is possible to have transparency characteristics.
【００５６】コーティング用組成物を硬化させる方法と
しては、コーティング用組成物に熱硬化や光硬化を起こ
す原料などの、徐々に反応し固体状態へと移行する原料
を含有する方法が挙げられる。例えば、コーティング用
組成物に１分子中に２個以上のエポキシ基を有する化合
物（エポキシ樹脂）と、エポキシ基と反応する水酸基を
有する化合物（硬化剤）、さらに、エポキシ樹脂と硬化
剤の反応を促進する硬化促進剤を含有することで、熱硬
化により硬化させることができる。Examples of the method for curing the coating composition include a method in which the coating composition contains a raw material such as a raw material that causes heat curing or photo-curing, which gradually reacts and shifts to a solid state. For example, in a coating composition, a compound having two or more epoxy groups in one molecule (epoxy resin), a compound having a hydroxyl group that reacts with an epoxy group (curing agent), and a reaction between the epoxy resin and the curing agent are performed. By containing a curing accelerator that accelerates, it can be cured by heat curing.
【００５７】また、常温では固体状態の原料を用いて、
コーティング用組成物を高温で溶融させた状態で保持
し、硬化が必要なときに冷却する方法、などが挙げられ
る。具体的には、常温では比較的固体状態に近い、長鎖
脂肪酸の金属塩、長鎖脂肪酸のエステル、パラフィンワ
ックス、シリコーン化合物などを用いることができる。Further, by using a raw material in a solid state at room temperature,
Examples include a method of holding the coating composition in a molten state at a high temperature and cooling it when curing is required. Specifically, metal salts of long-chain fatty acids, esters of long-chain fatty acids, paraffin wax, silicone compounds, etc., which are relatively solid at room temperature, can be used.
【００５８】上記コーティング用組成物は、非晶性シリ
カ、結晶性シリカ、炭酸カルシウム、炭酸マグネシウ
ム、アルミナ、マグネシア、窒化珪素、酸化マグネシウ
ムアルミニウム、ジルコニア、ジルコン、クレー、タル
ク、マイカ、珪酸カルシウム、酸化チタン、酸化アンチ
モン、アスベスト、ガラス繊維などの無機材料を含んで
いても構わない。The above coating composition comprises amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, silicon nitride, magnesium aluminum oxide, zirconia, zircon, clay, talc, mica, calcium silicate, oxide. It may contain an inorganic material such as titanium, antimony oxide, asbestos, or glass fiber.
【００５９】本発明は、粉末状のカーボンナノチューブ
を効率よくプラズマ処理できる方法を見出したものであ
る。プラズマ処理の結果、表面が特定の官能基化できた
新規なカーボンナノチューブを得ることができ、新規な
カーボンナノチューブの分散液、溶液が得られるように
なった。更には、触媒の担体として、また薬剤輸送材
料、コーティング用組成物として非常に使いやすい状態
となった。プラズマ処理は、マイルドにカーボンナノチ
ューブ表面を親水化できる処理であり、今まで困難であ
った層数の少ない１〜５層のカーボンナノチューブをそ
の構造を大きく壊すことなく処理できる点で有利であ
る。また、プラズマ処理のガスの種類、プラズマ処理条
件を選べば、ＣＶＤ法でカーボンナノチューブを作った
場合に、カーボンナノチューブ表面の熱分解炭素を取り
除いたり、残したまま処理することも可能である。通常
の酸化処理では、熱分解炭素の被覆物は実質的に取り除
かれるケースが多い。The present invention has found a method for efficiently plasma treating powdery carbon nanotubes. As a result of the plasma treatment, a novel carbon nanotube whose surface has a specific functional group can be obtained, and a novel dispersion or solution of the carbon nanotube can be obtained. Furthermore, it has become extremely easy to use as a catalyst carrier, drug delivery material, and coating composition. The plasma treatment is a treatment that can mildly hydrophilize the surface of the carbon nanotubes, and is advantageous in that it is possible to treat carbon nanotubes of 1 to 5 layers having a small number of layers, which has been difficult until now, without significantly destroying the structure. Further, by selecting the type of gas for plasma treatment and the plasma treatment conditions, when carbon nanotubes are produced by the CVD method, it is possible to remove the pyrolytic carbon on the surface of the carbon nanotubes or to treat the carbon nanotubes while leaving them. In the usual oxidation treatment, the pyrolytic carbon coating is often substantially removed.
【００６０】[0060]
【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明はここに掲げる実施例によって限定され
るものではない。The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
【００６１】実施例１（カーボンナノチューブの合成）
Ｋ．Ｈｅｒｎａｄｉ、Ａ．Ｆｏｎｓｅｃａらによる報告
を参照（Ｚｅｏｌｉｔｅｓ １７：４１６−４２３、１
９９６）し、酢酸鉄（２ｇ）、酢酸コバルト（２ｇ）、
Ｙ型ゼオライト（東ソー社製ＨＳＺ−３１０ＮＡＡ Ｌ
ｏｔ．Ｎｏ．ＧＺ−１４３−３〜５）（１０ｇ）を秤量
し、メタノール（１００ｍｌ）を加えて、振とう器にて
１時間攪拌後、メタノール分を乾燥除去し、触媒を得
た。次に、図２に示すＣＶＤ反応装置を用いて、反応管
内の石英ウール上に触媒１ｇをあらかじめセットし、窒
素（３０ｃｃ／分）雰囲気下で６００℃まで昇温後、ア
セチレン（６ｃｃ／分）、窒素（３０ｃｃ／分）雰囲気
下で６００℃×５時間保持しカーボンナノチューブを合
成した。その後、窒素（３０ｃｃ／分）雰囲気下で室温
まで冷却し、反応物を取り出した。Example 1 (Synthesis of carbon nanotube) K. Hernadi, A .; See the report by Fonseca et al. (Zeolites 17: 416-423, 1,
996), iron acetate (2 g), cobalt acetate (2 g),
Y-type zeolite (Tosoh HSZ-310NAA L
ot. No. GZ-143-3 to 5) (10 g) was weighed, methanol (100 ml) was added, and the mixture was stirred for 1 hour on a shaker, and then the methanol content was dried and removed to obtain a catalyst. Next, using the CVD reactor shown in FIG. 2, 1 g of the catalyst was set in advance on the quartz wool in the reaction tube, the temperature was raised to 600 ° C. in a nitrogen (30 cc / min) atmosphere, and then acetylene (6 cc / min) was used. Then, the carbon nanotubes were synthesized by holding at 600 ° C. for 5 hours in a nitrogen (30 cc / min) atmosphere. Then, it was cooled to room temperature under a nitrogen (30 cc / min) atmosphere, and the reaction product was taken out.
【００６２】実施例２（カーボンナノチューブの確認）
実施例１で得られた触媒とカーボンナノチューブの混合
物を、フッ化水素酸１０％水溶液中で３時間攪拌後、ろ
紙（Ｔｏｙｏ Ｒｏｓｈｉ Ｋａｉｓｈａ、Ｆｉｌｔｅ
ｒ Ｐａｐｅｒ ２号 １２５ｍｍ）を用いてろ過し、
ろ紙上の固形物を、イオン交換水、アセトン溶液にて洗
浄後、乾燥し、カーボンナノチューブを得た。図３、４
に、得られたカーボンナノチューブの透過型電子顕微鏡
（ＴＥＭ）観察結果を、図５、６に走査型電子顕微鏡
（ＳＥＭ）の観察結果を示す。図３〜６から、多層カー
ボンナノチューブを多く含むことがわかる。図５、図６
から、繊維状物質がほとんどであり、粒子状物質がない
ことがわかる。つまり、カーボンナノチューブを９０％
以上含むサンプルであることがわかる。また、ＳＥＭの
ＥＤＸを用いて元素分析を行ったところ、Ｙ型ゼオライ
トの存在率はＥＤＸの測定限界以下（ほぼ０％）である
結果を得た。Example 2 (Confirmation of carbon nanotubes) The mixture of the catalyst and carbon nanotubes obtained in Example 1 was stirred in a 10% aqueous solution of hydrofluoric acid for 3 hours, and then filtered (Toyo Roshi Kaisha, Filte).
r Paper No. 125 mm),
The solid matter on the filter paper was washed with ion-exchanged water and an acetone solution and then dried to obtain carbon nanotubes. Figures 3 and 4
The transmission electron microscope (TEM) observation result of the obtained carbon nanotube is shown in FIG. 5, and the scanning electron microscope (SEM) observation result is shown in FIGS. It can be seen from FIGS. 3 to 6 that a large amount of multi-walled carbon nanotubes is contained. 5 and 6
It can be seen from the fact that most of them are fibrous substances and there is no particulate matter. In other words, 90% carbon nanotubes
It can be seen that the sample includes the above. In addition, elemental analysis was performed using EDX of SEM, and the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%).
【００６３】実施例３（プラズマ処理）
実施例２で得られたカーボンナノチューブ０．５ｇを、
ガラス製シャーレー上にうすく広げて、ＹＡＭＡＴＯ化
学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ ＭＯＤＥＬ ＰＣ
−１０１Ａを用いて、酸素ガス、圧力２０Ｐａ、ＰＯＷ
ＥＲ３００Ｗの条件で、５分間プラズマ処理を行った。
図７、８に、得られたプラズマ処理カーボンナノチュー
ブの透過型電子顕微鏡（ＴＥＭ）観察結果を、図９，１
０に走査型電子顕微鏡（ＳＥＭ）の観察結果を示す。図
７〜１０から、多層カーボンナノチューブを多く含み、
その大きさは、実施例２で得られたものと同様であるこ
とがわかる。そして、カーボンナノチューブ外表面の付
着物が減少していることも確認できる。Example 3 (plasma treatment) 0.5 g of the carbon nanotube obtained in Example 2 was
Spread it lightly on a glass Petri dish and make a YAMATO Chemical PLASMA CHAMBER MODEL PC.
-101A, oxygen gas, pressure 20Pa, POW
Plasma treatment was performed for 5 minutes under the condition of ER300W.
7 and 8 show transmission electron microscope (TEM) observation results of the obtained plasma-treated carbon nanotubes.
0 shows the observation result of the scanning electron microscope (SEM). From FIGS. 7 to 10, containing many multi-walled carbon nanotubes,
It can be seen that its size is similar to that obtained in Example 2. It can also be confirmed that the adhered substances on the outer surface of the carbon nanotube are reduced.
【００６４】実施例４（分散液の製造）
実施例３で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、イオン交換水５０ｍｌを加えて、振と
う器にて１時間攪拌後、４８時間静置した結果、カーボ
ンナノチューブ分散液と黒い沈殿物が確認できた。スポ
イトで分散液部分を回収し、乾燥させた試料を走査型電
子顕微鏡（ＳＥＭ）を用いて観察したところ、分散液に
図９、１０と同様のカーボンナノチューブが確認でき
た。Example 4 (Production of Dispersion Liquid) To 10 mg of the carbon nanotubes after plasma treatment obtained in Example 3, 50 ml of ion-exchanged water was added, and the mixture was stirred for 1 hour on a shaker and allowed to stand for 48 hours. As a result, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion sample was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 9 and 10 were confirmed in the dispersion sample.
【００６５】実施例５（プラズマ処理）
実施例２で得られたカーボンナノチューブ０．５ｇを、
ガラス製シャーレー上にうすく広げて、ＹＡＭＡＴＯ化
学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ ＭＯＤＥＬ ＰＣ
−１０１Ａを用いて、酸素ガス、圧力２０Ｐａ、ＰＯＷ
ＥＲ３００Ｗの条件で、５分間プラズマ処理を行い、一
度取り出して、シャーレー上のプラズマ処理カーボンナ
ノチューブを、かき混ぜ（ひっくり返す、転がす等の動
作）、シャーレー上にうすく広げ、再び同様のプラズマ
処理を行う作業を繰り返し、合計１５分（計３回）のプ
ラズマ処理を行った。図１１、１２に、得られたプラズ
マ処理カーボンナノチューブの透過型電子顕微鏡（ＴＥ
Ｍ）観察結果を、図１３、１４に走査型電子顕微鏡（Ｓ
ＥＭ）の観察結果を示す。図７〜１０とよく似た結果で
あり、多層カーボンナノチューブを多く含み、その大き
さは、実施例２と同様であることが確認できた。そし
て、カーボンナノチューブ外表面の付着物が減少してい
た。Example 5 (plasma treatment) 0.5 g of the carbon nanotubes obtained in Example 2 was
Spread it lightly on a glass Petri dish and make a YAMATO Chemical PLASMA CHAMBER MODEL PC.
-101A, oxygen gas, pressure 20Pa, POW
Perform plasma treatment for 5 minutes under the condition of ER300W, take out once, stir the plasma-treated carbon nanotubes on the Petri dish (turn over, roll, etc.), spread them thinly on the Petri dish, and perform the same plasma treatment again. Repeatedly, plasma treatment was performed for a total of 15 minutes (total 3 times). 11 and 12 show transmission electron microscope (TE) of the obtained plasma-treated carbon nanotubes.
M) The observation results are shown in FIGS.
The observation result of (EM) is shown. It was confirmed that the results are very similar to those in FIGS. And, the deposits on the outer surface of the carbon nanotube were reduced.
【００６６】実施例６（分散液の製造）
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、イオン交換水５０ｍｌを加えて、振と
う器にて１時間攪拌後、４８時間静置した結果、カーボ
ンナノチューブ分散液と黒い沈殿物が確認できた。スポ
イトで分散液部分を回収し、乾燥させた試料を走査型電
子顕微鏡（ＳＥＭ）を用いて観察したところ、分散液に
図１３、１４と同様のカーボンナノチューブが確認でき
た。Example 6 (Production of Dispersion Liquid) To 10 mg of the carbon nanotubes after plasma treatment obtained in Example 5, 50 ml of ion-exchanged water was added, and the mixture was stirred for 1 hour on a shaker and allowed to stand for 48 hours. As a result, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion liquid portion was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 13 and 14 were confirmed in the dispersion liquid.
【００６７】実施例７ （分散液の製造）
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、イオン交換水５０ｍｌを加えて、超音
波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１
０、発信周波数４７ＫＨｚ、出力１３０Ｗ）にて１時間
処理後、４８時間静置して得られた試料を観察したとこ
ろ、カーボンナノチューブ分散液と黒い沈殿物が確認で
きた。スポイトで分散液部分を回収し、乾燥させた試料
を走査型電子顕微鏡（ＳＥＭ）を用いて観察したとこ
ろ、分散液に図１３、１４と同様のカーボンナノチュー
ブが確認できた。Example 7 (Production of Dispersion) To 10 mg of the carbon nanotubes after the plasma treatment obtained in Example 5, 50 ml of ion-exchanged water was added, and an ultrasonic cleaner (manufactured by YAMATO Chemical Co., BRANSON321) was used.
After observing the sample obtained after treating for 1 hour at 0, oscillation frequency 47 KHz, output 130 W) and standing for 48 hours, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion liquid portion was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 13 and 14 were confirmed in the dispersion liquid.
【００６８】実施例８
実施例４、実施例６、実施例７で得られたカーボンナノ
チューブ分散液２０ｍｌを透明ガラス製サンプル瓶に移
して比較した結果、実施例７＞実施例６＞実施例４の順
で分散液が濃い結果を得た。プラズマ処理の際にカーボ
ンナノチューブをかき混ぜる、さらに超音波処理を用い
ることで、より高濃度なカーボンナノチューブ分散液が
得られることがわかる。Example 8 20 ml of the carbon nanotube dispersions obtained in Examples 4, 6 and 7 were transferred to a transparent glass sample bottle and compared with each other. As a result, Example 7> Example 6> Example 4 In this order, the dispersion was thick. It can be seen that the carbon nanotube dispersion liquid having a higher concentration can be obtained by stirring the carbon nanotubes during the plasma treatment and further using the ultrasonic treatment.
【００６９】実施例９
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、エタノール５０ｍｌを加えて、超音波
洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１
０、発信周波数４７ＫＨｚ、出力１３０Ｗ）にて１時間
処理後、４８時間静置して得られた試料を観察したとこ
ろ、カーボンナノチューブ分散液と黒い沈殿物が確認で
きた。スポイトで分散液部分を回収し、乾燥させた試料
を走査型電子顕微鏡（ＳＥＭ）を用いて観察したとこ
ろ、分散液に図１３、１４と同様のカーボンナノチュー
ブが確認できた。Example 9 To 50 mg of the carbon nanotubes obtained in Example 5 after the plasma treatment, 50 ml of ethanol was added, and an ultrasonic cleaner (manufactured by YAMATO Chemical Co., BRANSON321) was used.
After observing the sample obtained after treating for 1 hour at 0, oscillation frequency 47 KHz, output 130 W) and standing for 48 hours, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion liquid portion was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 13 and 14 were confirmed in the dispersion liquid.
【００７０】実施例１０
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、エチレングリコール５０ｍｌを加え
て、超音波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯ
Ｎ３２１０、発信周波数４７ＫＨｚ、出力１３０Ｗ）に
て１時間処理後、４８時間静置して得られた試料を観察
したところ、カーボンナノチューブ分散液と黒い沈殿物
が確認できた。スポイトで分散液部分を回収し、乾燥さ
せた試料を走査型電子顕微鏡（ＳＥＭ）を用いて観察し
たところ、分散液に図１３、１４と同様のカーボンナノ
チューブが確認できた。Example 10 To 10 mg of the carbon nanotubes after the plasma treatment obtained in Example 5, 50 ml of ethylene glycol was added, and an ultrasonic cleaner (manufactured by YAMATO Chemical Co., BRANSO) was used.
After observing the sample obtained by treating with N3210, an oscillation frequency of 47 KHz, an output of 130 W) for 1 hour and then allowing it to stand for 48 hours, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion liquid portion was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 13 and 14 were confirmed in the dispersion liquid.
【００７１】実施例１１
実施例７で得られた、カーボンナノチューブ分散液を、
ろ紙（Ｔｏｙｏ Ｒｏｓｈｉ Ｋａｉｓｈａ、Ｆｉｌｔ
ｅｒ Ｐａｐｅｒ ２号 １２５ｍｍ）を用いてろ過し
たところ、ろ紙を通過したろ液として、透明感のある黒
色の溶液を得た。図１５、１６に、得られた溶液を乾燥
させた試料の、透過型電子顕微鏡（ＴＥＭ）観察結果
を、図１７、１８に得られた溶液を乾燥させた試料の、
走査型電子顕微鏡（ＳＥＭ）の観察結果を示す。図１５
〜１８から、多層カーボンナノチューブを多く含み、そ
の大きさは図１１〜１４と比較して長軸方向に短く、互
いに絡まり合っていないことがわかる。Example 11 The carbon nanotube dispersion liquid obtained in Example 7 was
Filter paper (Toyo Roshi Kaisha, Filt)
er Paper No. 125 mm), a transparent black solution was obtained as the filtrate that passed through the filter paper. 15 and 16 show transmission electron microscope (TEM) observation results of the sample obtained by drying the obtained solution, and FIGS. 17 and 18 show results of the sample obtained by drying the obtained solution.
The observation result of a scanning electron microscope (SEM) is shown. Figure 15
From 18 to 18, it can be seen that a large amount of multi-walled carbon nanotubes is included, the size thereof is shorter in the major axis direction than in FIGS. 11 to 14, and they are not entangled with each other.
【００７２】実施例１２
実施例７で得られた、カーボンナノチューブ分散液を、
遠心分離器（装置：ＫＵＢＯＴＡ ＫＲ−２００００
Ｔ、ローター：ＲＡ−３ ５０ｍｌ×８本）を用いて、
回転数１２０００ｒｐｍ（約１７０００（×ｇ））×１
時間、遠心分離したところ、上澄み液として、透明感の
ある黒色の溶液を得た。スポイトで溶液部分を回収し、
乾燥させた試料を走査型電子顕微鏡（ＳＥＭ）を用いて
観察したところ、溶液に図１７、１８と同様のカーボン
ナノチューブが確認できた。Example 12 The carbon nanotube dispersion liquid obtained in Example 7 was
Centrifuge (device: KUBOTA KR-20000)
T, rotor: RA-3 50 ml x 8)
Rotation speed 12000 rpm (about 17,000 (xg)) x 1
After centrifugation for a period of time, a transparent black solution was obtained as a supernatant. Collect the solution part with a dropper,
When the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 17 and 18 were confirmed in the solution.
【００７３】実施例１３
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブについて、Ｘ線光電子分光法を用いたカーボンナノ
チューブの表面組成分析を行った結果、酸素原子が１０
％の割合であり、Ｃ１ｓピーク分割から、芳香環又はＣ
Ｈｘ（８８％）に対して、カルボキシル基又はエステル
（ＣＯＯ、２％）、カルボニル基（Ｃ＝Ｏ、４％）、エ
ーテル基又は水酸基（Ｃ−Ｏ、５％）の官能基を持つ結
果を得た。カルボキシル基又はフェノール性水酸基の影
響で、分散液や溶液は、酸性を呈すると考えられる。Example 13 With respect to the carbon nanotubes after the plasma treatment obtained in Example 5, the surface composition of the carbon nanotubes was analyzed by X-ray photoelectron spectroscopy.
% Of the aromatic ring or C
Hx (88%) has a functional group of a carboxyl group or ester (COO, 2%), a carbonyl group (C = O, 4%), an ether group or a hydroxyl group (C-O, 5%). Obtained. It is considered that the dispersion or solution exhibits acidity due to the influence of the carboxyl group or the phenolic hydroxyl group.
【００７４】実施例１４
実施例５で得られたプラズマ処理後のカーボンナノチュ
ーブ１０ｍｇに、イオン交換水５０ｍｌを加えて、超音
波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１
０、発信周波数４７ＫＨｚ、出力１３０Ｗ）にて１時間
処理後、４８時間静置して得られた分散液のｐＨを、ガ
ラス電極式水素イオン濃度計（東亜電波工業、ＨＭ−３
０Ｖ）を用いて測定したところ、ｐＨ＝５．５であっ
た。一般によく知られた中和滴定を、４２．５×１０-6
（ｍｏｌ／ｌ）の水酸化ナトリウム水溶液を用いて、ｐ
Ｈ＝７．０を終点として行った結果、水酸化ナトリウム
水溶液１４５ｍｌを要した。つまり、０．２５ｍｇの水
酸化ナトリウム（ＮａＯＨ、４０ｇ／ｍｏｌ）を要し
た。この結果から、プラズマ処理後のカーボンナノチュ
ーブ１０ｍｇ中の酸性官能基のモル数は６．３×１０-6
（ｍｏｌ）と計算できる。Example 14 To 10 mg of carbon nanotubes after plasma treatment obtained in Example 5, 50 ml of ion-exchanged water was added, and an ultrasonic cleaner (BRANSON321 manufactured by YAMATO Chemical Co., Ltd.) was added.
The pH of the dispersion liquid obtained by standing at 0, an oscillation frequency of 47 KHz, an output of 130 W) for 1 hour and then allowing it to stand for 48 hours was measured by a glass electrode type hydrogen ion concentration meter (Toa Denpa Kogyo, HM-3).
It was pH = 5.5 when it measured using 0V). The well-known neutralization titration is 42.5 × 10 -6
(Mol / l) aqueous sodium hydroxide solution
As a result of performing H = 7.0 as the end point, 145 ml of an aqueous sodium hydroxide solution was required. That is, 0.25 mg of sodium hydroxide (NaOH, 40 g / mol) was required. From this result, the number of moles of acidic functional groups in 10 mg of carbon nanotubes after plasma treatment was 6.3 × 10 −6.
(Mol) can be calculated.
【００７５】実施例１５
図３、４に示す透過型電子顕微鏡（ＴＥＭ）を用いて、
ひとつのカーボンナノチューブを重複して用いないルー
ルを適用して、任意に２０点のカーボンナノチューブの
外半径、内半径を計測し、それぞれ平均値を計算した結
果、Ｒａ：カーボンナノチューブ平均外半径１１．５ｎ
ｍ、Ｒｂ：カーボンナノチューブ平均内半径３．３ｎｍ
の結果を得た。また、Ｒｋ：カーボンナノチューブ層間
距離０．３４ｎｍを用いた。Example 15 Using a transmission electron microscope (TEM) shown in FIGS.
Applying the rule that one carbon nanotube is not used redundantly, the outer and inner radii of 20 carbon nanotubes are arbitrarily measured, and the average values are calculated. As a result, Ra: carbon nanotube average outer radius 11. 5n
m, Rb: carbon nanotube average inner radius 3.3 nm
Got the result. Further, Rk: carbon nanotube interlayer distance of 0.34 nm was used.
【００７６】実施例１６
実施例１４、１５の結果から、前記式を用いてカーボン
ナノチューブ外表面の炭素に対する酸性官能基の含有率
（％）を計算した結果、１２％の結果を得た。Example 16 From the results of Examples 14 and 15, as a result of calculating the content (%) of the acidic functional group with respect to the carbon on the outer surface of the carbon nanotube using the above formula, a result of 12% was obtained.
【００７７】実施例１７
実施例１で得られた触媒とカーボンナノチューブの混合
物０．５ｇを、ガラス製シャーレー上にうすく広げて、
ＹＡＭＡＴＯ化学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ Ｍ
ＯＤＥＬ ＰＣ−１０１Ａを用いて、酸素ガス、圧力２
０Ｐａ、ＰＯＷＥＲ３００Ｗの条件で、５分間プラズマ
処理を行った。Example 17 0.5 g of the mixture of the catalyst obtained in Example 1 and carbon nanotubes was thinly spread on a glass Petri dish,
YAMATO CHEMICAL PLASMA CHAMBER M
Using ODEL PC-101A, oxygen gas, pressure 2
Plasma treatment was performed for 5 minutes under the conditions of 0 Pa and POWER 300W.
【００７８】実施例１８
実施例１７で得られたプラズマ処理後の触媒とカーボン
ナノチューブの混合物１０ｍｇに、イオン交換水５０ｍ
ｌを加えて、超音波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲ
ＡＮＳＯＮ３２１０、発信周波数４７ＫＨｚ、出力１３
０Ｗ）にて１時間処理後、４８時間静置して得られた試
料を観察したところ、カーボンナノチューブ分散液と黒
い沈殿物が確認できた。スポイトで分散液部分を回収
し、乾燥させた試料を走査型電子顕微鏡（ＳＥＭ）で観
察した結果、分散液に図９、１０と同様のカーボンナノ
チューブが確認できた。さらに、ＳＥＭのＥＤＸを用い
て元素分析を行ったところ、Ｙ型ゼオライトの存在率は
ＥＤＸの測定限界以下（ほぼ０％）である結果を得た。
一方、沈殿物のＥＤＸ測定結果では、Ｙ型ゼオライトの
存在が確認された。これにより、分散液を回収する、す
なわち分級することによって、実施例２のような強酸を
用いなくても、触媒部分を除去でき、カーボンナノチュ
ーブの精製が可能であることがわかる。Example 18 10 mg of the mixture of the catalyst and the carbon nanotube after the plasma treatment obtained in Example 17 was added to 50 m of ion-exchanged water.
ultrasonic cleaner (YAMATO Chemical, BR
ANSON3210, oscillation frequency 47KHz, output 13
When the sample obtained by treating for 1 hour at 0 W) and then standing for 48 hours was observed, a carbon nanotube dispersion liquid and a black precipitate were confirmed. As a result of observing the dried sample by collecting the dispersion liquid portion with a dropper and using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 9 and 10 were confirmed in the dispersion liquid. Further, when elemental analysis was performed using EDX of SEM, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%).
On the other hand, the EDX measurement result of the precipitate confirmed the presence of Y-type zeolite. From this, it is understood that the catalyst portion can be removed and the carbon nanotubes can be purified by recovering, that is, classifying the dispersion liquid without using a strong acid as in Example 2.
【００７９】実施例１９
実施例１で得られた触媒とカーボンナノチューブの混合
物０．５ｇを、ガラス製シャーレー上にうすく広げて、
ＹＡＭＡＴＯ化学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ Ｍ
ＯＤＥＬ ＰＣ−１０１Ａを用いて、酸素ガス、圧力２
０Ｐａ、ＰＯＷＥＲ３００Ｗの条件で、５分間プラズマ
処理を行い、シャーレー上のプラズマ処理カーボンナノ
チューブを、かき混ぜ（ひっくり返す、転がす等の動
作）、シャーレー上にうすく広げ、再び同様のプラズマ
処理を行う作業を繰り返し、合計１５分（計３回）のプ
ラズマ処理を行った。Example 19 0.5 g of the mixture of the catalyst and carbon nanotubes obtained in Example 1 was thinly spread on a glass Petri dish,
YAMATO CHEMICAL PLASMA CHAMBER M
Using ODEL PC-101A, oxygen gas, pressure 2
Plasma treatment is performed for 5 minutes under the conditions of 0 Pa and POWER 300 W, the plasma-treated carbon nanotubes on the Petri dish are stirred (turned over, rolled, etc.), thinly spread on the Petri dish, and the same plasma treatment is repeated again. Plasma treatment was performed for a total of 15 minutes (total 3 times).
【００８０】実施例２０
実施例１９で得られたプラズマ処理後の触媒とカーボン
ナノチューブの混合物１０ｍｇに、イオン交換水５０ｍ
ｌを加えて、超音波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲ
ＡＮＳＯＮ３２１０、発信周波数４７ＫＨｚ、出力１３
０Ｗ）にて１時間処理後、４８時間静置して得られた試
料を観察したところ、カーボンナノチューブ分散液と黒
い沈殿物が確認できた。スポイトで分散液部分を回収
し、乾燥させた試料を走査型電子顕微鏡（ＳＥＭ）を用
いて観察したところ、分散液に図１３、１４と同様のカ
ーボンナノチューブが確認できた。さらに、ＳＥＭのＥ
ＤＸを用いて元素分析を行ったところ、Ｙ型ゼオライト
の存在率はＥＤＸの測定限界以下（ほぼ０％）である結
果を得た。一方、沈殿物のＥＤＸ測定結果では、Ｙ型ゼ
オライトの存在が確認された。これにより、実施例１８
同様、分散液を回収する、すなわち分級することによっ
て、実施例２のような強酸を用いなくても、触媒部分を
除去でき、カーボンナノチューブの精製が可能であるこ
とがわかる。Example 20 10 mg of the mixture of the catalyst and the carbon nanotube after the plasma treatment obtained in Example 19 was added to 50 m of ion-exchanged water.
ultrasonic cleaner (YAMATO Chemical, BR
ANSON3210, oscillation frequency 47KHz, output 13
When the sample obtained by treating for 1 hour at 0 W) and then standing for 48 hours was observed, a carbon nanotube dispersion liquid and a black precipitate were confirmed. When the dispersion liquid portion was collected with a dropper and the dried sample was observed using a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 13 and 14 were confirmed in the dispersion liquid. Furthermore, E of SEM
When elemental analysis was performed using DX, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%). On the other hand, the EDX measurement result of the precipitate confirmed the presence of Y-type zeolite. This gives Example 18
Similarly, it is understood that the catalyst portion can be removed and the carbon nanotubes can be purified by recovering the dispersion, that is, classifying it, without using a strong acid as in Example 2.
【００８１】実施例２１
実施例２０で得られた、カーボンナノチューブ分散液
を、ろ紙（Ｔｏｙｏ Ｒｏｓｈｉ Ｋａｉｓｈａ、Ｆｉ
ｌｔｅｒ Ｐａｐｅｒ ２号 １２５ｍｍ）を用いてろ
過したところ、ろ紙を通過したろ液として、透明感のあ
る黒色の溶液を得た。スポイトで溶液部分を回収し、乾
燥させた試料を透過型電子顕微鏡（ＴＥＭ）、走査型電
子顕微鏡（ＳＥＭ）を用いて観察したところ、溶液に図
１５〜１８と様のカーボンナノチューブが確認できた。
さらに、ＳＥＭのＥＤＸを用いて元素分析を行ったとこ
ろ、Ｙ型ゼオライトの存在率はＥＤＸの測定限界以下
（ほぼ０％）である結果を得た。Example 21 The carbon nanotube dispersion obtained in Example 20 was filtered with a filter paper (Toyo Roshi Kaisha, Fi).
lter Paper No. 125 mm), a transparent black solution was obtained as the filtrate that passed through the filter paper. The solution portion was collected with a dropper, and the dried sample was observed using a transmission electron microscope (TEM) and a scanning electron microscope (SEM). As a result, carbon nanotubes as shown in FIGS. 15 to 18 were confirmed. .
Further, when elemental analysis was performed using EDX of SEM, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%).
【００８２】実施例２２
実施例２０で得られた、カーボンナノチューブ分散液
を、遠心分離器（装置：ＫＵＢＯＴＡ ＫＲ−２０００
０Ｔ、ローター：ＲＡ−３ ５０ｍｌ×８本）を用い
て、回転数１２０００ｒｐｍ（約１７０００（×ｇ））
×１時間、遠心分離したところ、上澄み液として、透明
感のある黒色の溶液を得た。スポイトで溶液部分を回収
し、乾燥させた試料を透過型電子顕微鏡（ＴＥＭ）、走
査型電子顕微鏡（ＳＥＭ）を用いて観察したところ、溶
液に図１５〜１８と同様のカーボンナノチューブが確認
できた。さらに、ＳＥＭのＥＤＸを用いて元素分析を行
ったところ、Ｙ型ゼオライトの存在率はＥＤＸの測定限
界以下（ほぼ０％）である結果を得た。Example 22 The carbon nanotube dispersion obtained in Example 20 was centrifuged (apparatus: KUBOTA KR-2000).
0T, rotor: RA-3 50 ml × 8), rotation speed 12000 rpm (about 17,000 (× g))
After centrifugation for 1 hour, a transparent black solution was obtained as a supernatant. When the solution sample was collected with a dropper and the dried sample was observed using a transmission electron microscope (TEM) and a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 15 to 18 were confirmed in the solution. . Further, when elemental analysis was performed using EDX of SEM, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%).
【００８３】実施例２３
実施例２１で得られた、ろ紙を通過しなかったろ紙上の
固形物を回収し、イオン交換水５０ｍｌを加えて、超音
波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１
０、発信周波数４７ＫＨｚ、出力１３０Ｗ）にて１時間
処理後、４８時間静置して得られた試料を観察したとこ
ろ、カーボンナノチューブ分散液、黒い沈殿物が得ら
れ、ろ紙（Ｔｏｙｏ Ｒｏｓｈｉ Ｋａｉｓｈａ、Ｆｉ
ｌｔｅｒＰａｐｅｒ ２号 １２５ｍｍ）を用いてろ過
したところ、ろ紙を通過したろ液として、透明感のある
黒色の溶液を得た。スポイトで溶液部分を回収し、乾燥
させた試料を透過型電子顕微鏡（ＴＥＭ）、走査型電子
顕微鏡（ＳＥＭ）を用いて観察したところ、溶液に図１
５〜１８と同様のカーボンナノチューブの存在が確認で
きた。さらに、ＳＥＭのＥＤＸを用いて元素分析を行っ
たところ、Ｙ型ゼオライトの存在率はＥＤＸの測定限界
以下（ほぼ０％）である結果を得た。Example 23 The solid matter on the filter paper that did not pass through the filter paper obtained in Example 21 was recovered, 50 ml of ion-exchanged water was added, and an ultrasonic cleaner (YAMATO CHEMICAL, BRANSON321) was added.
After observing the sample obtained after treating for 1 hour at 0, oscillation frequency 47 KHz, output 130 W) and standing for 48 hours, a carbon nanotube dispersion liquid and a black precipitate were obtained, and a filter paper (Toyo Roshi Kaisha, Fi
lterPaper 2 125 mm), a transparent black solution was obtained as the filtrate that passed through the filter paper. The solution was collected with a dropper, and the dried sample was observed using a transmission electron microscope (TEM) and a scanning electron microscope (SEM).
The presence of carbon nanotubes similar to 5 to 18 was confirmed. Further, when elemental analysis was performed using EDX of SEM, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (approximately 0%).
【００８４】実施例２４
実施例２２で得られた、沈殿物を回収し、イオン交換水
５０ｍｌを加えて、超音波洗浄機（ＹＡＭＡＴＯ化学
製、ＢＲＡＮＳＯＮ３２１０、発信周波数４７ＫＨｚ、
出力１３０Ｗ）にて１時間処理後、４８時間静置して得
られた試料を観察したところ、カーボンナノチューブ分
散液、黒い沈殿物が得られ、遠心分離器（装置：ＫＵＢ
ＯＴＡ ＫＲ−２００００Ｔ、ローター：ＲＡ−３ ５
０ｍｌ×８本）を用いて、回転数１２０００ｒｐｍ（約
１７０００（×ｇ））×１時間、遠心分離したところ、
上澄み液として、透明感のある黒色の溶液を得た。スポ
イトで溶液部分を回収し、乾燥させた試料を透過型電子
顕微鏡（ＴＥＭ）、走査型電子顕微鏡（ＳＥＭ）を用い
て観察したところ、溶液に図１５〜１８と同様のカーボ
ンナノチューブが確認できた。さらに、ＳＥＭのＥＤＸ
を用いて元素分析を行ったところ、Ｙ型ゼオライトの存
在率はＥＤＸの測定限界以下（ほぼ０％）である結果を
得た。Example 24 The precipitate obtained in Example 22 was recovered, 50 ml of ion-exchanged water was added, and an ultrasonic cleaner (YAMATO Chemical Co., BRANSON 3210, oscillation frequency 47 KHz,
After processing for 1 hour at 130 W) and standing for 48 hours, a sample obtained was observed, and a carbon nanotube dispersion liquid and a black precipitate were obtained, and a centrifuge (device: KUB
OTA KR-20000T, rotor: RA-35
0 ml × 8 bottles) were used and centrifuged at 12,000 rpm (about 17,000 (× g)) × 1 hour,
As a supernatant, a transparent black solution was obtained. When the solution sample was collected with a dropper and the dried sample was observed using a transmission electron microscope (TEM) and a scanning electron microscope (SEM), carbon nanotubes similar to those in FIGS. 15 to 18 were confirmed in the solution. . In addition, SEM EDX
As a result of elemental analysis using, the result was that the abundance of Y-type zeolite was below the measurement limit of EDX (nearly 0%).
【００８５】実施例２５
実施例２２で得られた溶液を、６０℃に保った恒温槽に
静置したところ、溶液が濃縮され、さらに、６０℃に保
った恒温槽に静置したところ、カーボンナノチューブ粉
末が得られた。Example 25 The solution obtained in Example 22 was allowed to stand in a constant temperature bath kept at 60 ° C. to concentrate the solution, and further left to stand in a constant temperature bath kept at 60 ° C. A nanotube powder was obtained.
【００８６】比較例１
実施例２で得られたカーボンナノチューブ１０ｍｇに、
イオン交換水５０ｍｌを加えて、超音波洗浄機（ＹＡＭ
ＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１０、発信周波数４
７ＫＨｚ、出力１３０Ｗ）にて１時間処理後、４８時間
静置して得られた試料を観察したところ、液状の上層部
は無色透明で、黒い沈殿物のみが確認できた。Comparative Example 1 10 mg of the carbon nanotubes obtained in Example 2 were
Ion-exchanged water (50 ml) is added to the ultrasonic cleaner (YAM
ATO Chemical, BRANSON3210, transmission frequency 4
After observing the sample obtained by treating for 1 hour at 7 KHz and an output of 130 W) and then allowing it to stand for 48 hours, the upper layer of the liquid was colorless and transparent, and only a black precipitate was confirmed.
【００８７】比較例２
実施例２で得られたカーボンナノチューブについて、Ｘ
線光電子分光法を用いたカーボンナノチューブの表面組
成分析を行った結果、酸素原子が１％の割合であり、Ｃ
１ｓピーク分割から、芳香環又はＣＨｘ（９８％）に対
して、カルボキシル基又はエステル（ＣＯＯ、０％）、
カルボニル基（Ｃ＝Ｏ、１％）、エーテル基又は水酸基
（Ｃ−Ｏ、１％）の官能基を持つ結果を得た。Comparative Example 2 For the carbon nanotubes obtained in Example 2, X
As a result of analyzing the surface composition of the carbon nanotubes using the line photoelectron spectroscopy, it was found that the oxygen atom content was 1%, and C
From 1s peak splitting, for aromatic ring or CHx (98%), carboxyl group or ester (COO, 0%),
Results were obtained with functional groups such as carbonyl groups (C = O, 1%), ether groups or hydroxyl groups (C-O, 1%).
【００８８】比較例３
実施例２で得られたカーボンナノチューブ１０ｍｇに、
イオン交換水５０ｍｌを加えて、超音波洗浄機（ＹＡＭ
ＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１０、発信周波数４
７ＫＨｚ、出力１３０Ｗ）にて１時間処理後、４８時間
静置して得られた試料のｐＨをガラス電極式水素イオン
濃度計（東亜電波工業、ＨＭ−３０Ｖ）を用いて測定し
たところ、ｐＨ＝７．０であった（酸性官能基の含有率
０％）。Comparative Example 3 10 mg of the carbon nanotubes obtained in Example 2 were
Ion-exchanged water (50 ml) is added to the ultrasonic cleaner (YAM
ATO Chemical, BRANSON3210, transmission frequency 4
After treatment for 1 hour at 7 KHz and an output of 130 W), the sample was allowed to stand for 48 hours, and the pH of the sample was measured using a glass electrode type hydrogen ion concentration meter (Toa Denpa Kogyo HM-30V). The value was 7.0 (content of acidic functional group: 0%).
【００８９】実施例２６
酢酸第一鉄（アルドリッチ社製）０．０８ｇと酢酸コバ
ルト４水和物（ナカライテスク）社製）０．１１ｇとを
水７ｍｌに加え、超音波洗浄機で１０分間懸濁した。実
施例５で得られたプラズマ処理したカーボンナノチュー
ブを１．０ｇ加え、超音波洗浄機で１０分間処理し、６
０℃の恒温下で水を除去して金属塩が担持した触媒を得
た。内径３０ｍｍの石英管の中央部の石英プレート上
に、上記で得た金属塩を担持したカーボンナノチューブ
を０．０５０ｇ取り、窒素を３０ｍｌ／分で供給した。
石英管を電気炉中に設置して中心温度を６００℃に加熱
した。超高純度アセチレンガス（高圧ガス工業製）を６
ｍｌ／分で３０分間供給した後、アセチレンガスの供給
をやめ、温度を室温まで冷却した。石英プレート上に堆
積した反応物を日本電子データム（株）走査電子顕微鏡
ＪＳＭ６３０１ＮＦで観察したところ、ほとんど非晶質
のカーボン質の堆積は無かった。ファイバー状物質の形
状を透過型電子顕微鏡で測定したところ、外径が２０ｎ
ｍ以下で内径が５ｎｍ程度の細い中空状ナノファイバー
が主成分であることがわかった。高分解能透過型電子顕
微鏡で中空状ナノファイバーを観察したところナノファ
イバーの壁はグラファイト層で構成されていた。Example 26 0.08 g of ferrous acetate (manufactured by Aldrich) and 0.11 g of cobalt acetate tetrahydrate (manufactured by Nacalai Tesque) were added to 7 ml of water, and the mixture was suspended in an ultrasonic cleaner for 10 minutes. It became cloudy. 1.0 g of the plasma treated carbon nanotubes obtained in Example 5 was added and treated with an ultrasonic cleaner for 10 minutes,
Water was removed under a constant temperature of 0 ° C. to obtain a metal salt-supported catalyst. On a quartz plate at the center of a quartz tube having an inner diameter of 30 mm, 0.050 g of the carbon salt carrying the metal salt obtained above was taken and nitrogen was supplied at 30 ml / min.
The quartz tube was placed in an electric furnace and heated to a central temperature of 600 ° C. Ultra high purity acetylene gas (manufactured by High Pressure Gas Industry) 6
After supplying at 30 ml / min for 30 minutes, the supply of acetylene gas was stopped and the temperature was cooled to room temperature. When the reaction product deposited on the quartz plate was observed with a scanning electron microscope JSM6301NF of JEOL Datum Co., Ltd., almost no amorphous carbonaceous material was deposited. When the shape of the fibrous material was measured with a transmission electron microscope, the outer diameter was 20n.
It was found that the main component is a thin hollow nanofiber having an inner diameter of about 5 nm and a diameter of m or less. Observation of the hollow nanofibers with a high-resolution transmission electron microscope revealed that the walls of the nanofibers were composed of graphite layers.
【００９０】実施例２７
実施例２で得られた多層カーボンナノチューブを空気中
４００℃で３０分焼成した。焼成後、実施例５の方法で
プラズマ処理し実施例７の方法で水に分散させた。イブ
プロフェンを少量この系に加えた。５時間後１２０００
回転の遠心分離で固形分を回収し、液部分のイブプロフ
ェンを定量したところ、イブプロフェンは加えた量の半
分以下になっていた。回収した固形分であるカーボンナ
ノチューブは再び水を加え、超音波をかけると分散し
た。中空部分に薬剤を吸着した多層カーボンナノチュー
ブの分散水がえられた。Example 27 The multi-walled carbon nanotube obtained in Example 2 was fired in air at 400 ° C. for 30 minutes. After firing, plasma treatment was performed by the method of Example 5 and dispersed in water by the method of Example 7. A small amount of ibuprofen was added to this system. 5 hours later 12000
The solid content was recovered by rotary centrifugation and the amount of ibuprofen in the liquid portion was quantified. As a result, the amount of ibuprofen was less than half of the added amount. The recovered solid carbon nanotubes were dispersed again by adding water and applying ultrasonic waves. Dispersed water of the multi-walled carbon nanotubes having the drug adsorbed in the hollow portion was obtained.
【００９１】実施例２８（窒素プラズマ処理）
実施例２で得られたカーボンナノチューブ０．５ｇを、
ガラス製シャーレー上にうすく広げて、ＹＡＭＡＴＯ化
学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ ＭＯＤＥＬ ＰＣ
−１０１Ａを用いて、窒素ガス、圧力２０Ｐａ、ＰＯＷ
ＥＲ３００Ｗの条件で、５分間プラズマ処理を行い、一
度取り出して、シャーレー上のプラズマ処理カーボンナ
ノチューブを、かき混ぜ（ひっくり返す、転がす等の動
作）、シャーレー上にうすく広げ、再び同様のプラズマ
処理を行う作業を繰り返し、合計１５分（計３回）のプ
ラズマ処理を行った。透過型電子顕微鏡（ＴＥＭ）観察
と走査型電子顕微鏡（ＳＥＭ）の観察の結果、実施例２
と同様のカーボンナノチューブであることが確認でき
た。高分解能透過型電子顕微鏡で観察したところプラズ
マ処理前後とも熱分解炭素の被覆が確認できた。Example 28 (Nitrogen Plasma Treatment) 0.5 g of the carbon nanotubes obtained in Example 2 was
Spread it lightly on a glass Petri dish and make a YAMATO Chemical PLASMA CHAMBER MODEL PC.
-101A, nitrogen gas, pressure 20Pa, POW
Perform plasma treatment for 5 minutes under the condition of ER300W, take out once, stir the plasma-treated carbon nanotubes on the Petri dish (turn over, roll, etc.), spread them thinly on the Petri dish, and perform the same plasma treatment again. Repeatedly, plasma treatment was performed for a total of 15 minutes (total 3 times). As a result of observation with a transmission electron microscope (TEM) and observation with a scanning electron microscope (SEM), Example 2
It was confirmed that the carbon nanotubes were similar to. Observation with a high-resolution transmission electron microscope confirmed the coating of pyrolytic carbon before and after plasma treatment.
【００９２】実施例２９
実施例２８で得られたプラズマ処理後のカーボンナノチ
ューブについて、Ｘ線光電子分光法を用いたカーボンナ
ノチューブの表面組成分析を行った結果、酸素原子が１
０％の割合であり、Ｃ１ｓピーク分割から、芳香環又は
ＣＨｘ（８８％）に対して、カルボキシル基又はエステ
ル（ＣＯＯ、２％）、カルボニル基（Ｃ＝Ｏ、３％）、
エーテル基又は水酸基（Ｃ−Ｏ、６％）の官能基を持つ
結果を得た。カルボキシル基やフェノール性水酸基の影
響で、分散液や溶液は、酸性を呈すると考えられる。Example 29 With respect to the carbon nanotube after the plasma treatment obtained in Example 28, the surface composition of the carbon nanotube was analyzed by X-ray photoelectron spectroscopy.
The ratio is 0%, and from the C1s peak division, with respect to the aromatic ring or CHx (88%), a carboxyl group or ester (COO, 2%), a carbonyl group (C═O, 3%),
Results were obtained with ether or hydroxyl (CO, 6%) functional groups. It is considered that the dispersion or solution exhibits acidity due to the influence of the carboxyl group and the phenolic hydroxyl group.
【００９３】実施例３０
実施例２８で得られたプラズマ処理後のカーボンナノチ
ューブ１０ｍｇに、イオン交換水５０ｍｌを加えて、超
音波洗浄機（ＹＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２
１０、発信周波数４７ＫＨｚ、出力１３０Ｗ）にて１時
間処理後、４８時間静置して得られた分散液のｐＨを、
ガラス電極式水素イオン濃度計（東亜電波工業、ＨＭ−
３０Ｖ）を用いて測定したところ、ｐＨ＝５．５であっ
た。一般によく知られた中和滴定を、４２．５×１０-6
（ｍｏｌ／ｌ）の水酸化ナトリウム水溶液を用いて、ｐ
Ｈ＝７．０を終点として行った結果、水酸化ナトリウム
水溶液１１８ｍｌを要した。つまり、０．２０ｍｇの水
酸化ナトリウム（ＮａＯＨ、４０ｇ／ｍｏｌ）を要し
た。この結果から、プラズマ処理後のカーボンナノチュ
ーブ１０ｍｇ中の酸性官能基のモル数は５．０×１０-6
（ｍｏｌ）と計算できる。Example 30 To 10 mg of the carbon nanotubes after the plasma treatment obtained in Example 28, 50 ml of ion-exchanged water was added, and an ultrasonic cleaner (manufactured by YAMATO Chemical Co., BRANSON32) was used.
10, the oscillation frequency of 47 KHz, the output of 130W) for 1 hour, then allowed to stand for 48 hours, the pH of the obtained dispersion liquid,
Glass electrode type hydrogen ion concentration meter (Toa Denpa Kogyo, HM-
It was pH = 5.5 when measured using 30 V). The well-known neutralization titration is 42.5 × 10 -6
(Mol / l) aqueous sodium hydroxide solution
As a result of carrying out H = 7.0 as the end point, 118 ml of an aqueous sodium hydroxide solution was required. That is, 0.20 mg of sodium hydroxide (NaOH, 40 g / mol) was required. From these results, the number of moles of acidic functional groups in 10 mg of carbon nanotubes after plasma treatment was 5.0 × 10 −6.
(Mol) can be calculated.
【００９４】実施例３１
図３、４に示す透過型電子顕微鏡（ＴＥＭ）を用いて、
ひとつのカーボンナノチューブを重複して用いないルー
ルを適用して、任意に２０点のカーボンナノチューブの
外半径、内半径を計測し、それぞれ平均値を計算した結
果、Ｒａ：カーボンナノチューブ平均外半径１１．５ｎ
ｍ、Ｒｂ：カーボンナノチューブ平均内半径３．３ｎｍ
の結果を得た。また、Ｒｋ：カーボンナノチューブ層間
距離０．３４ｎｍを用いた。Example 31 Using a transmission electron microscope (TEM) shown in FIGS.
Applying the rule that one carbon nanotube is not used redundantly, the outer and inner radii of 20 carbon nanotubes are arbitrarily measured, and the average values are calculated. As a result, Ra: carbon nanotube average outer radius 11. 5n
m, Rb: carbon nanotube average inner radius 3.3 nm
Got the result. Further, Rk: carbon nanotube interlayer distance of 0.34 nm was used.
【００９５】実施例３２
実施例３０、３１の結果から、前記式を用いてカーボン
ナノチューブ外表面の炭素に対する酸性官能基の含有率
（％）を計算した結果、９．６％の結果を得た。Example 32 From the results of Examples 30 and 31, the content (%) of the acidic functional group with respect to the carbon on the outer surface of the carbon nanotube was calculated using the above formula, and a result of 9.6% was obtained. .
【００９６】実施例３３
J.L.Hutchisonらの方法（Carbon 39 (2001) 761-770)に
従って、アーク放電法でカーボンナノチューブを生成し
た。アノードは直径3.2mm長さ140mmの穴に触媒が埋め込
まれた直径8.2mmのグラファイトロッド、カソードは直
径10mm,長さ25mmのグラファイトロッドとした。触媒
は、次のように調製した。粒子径2-5μmのNi,Co,Fe粉末
の混合物と硫黄原子を良く粉砕した後、アルゴンガス下
で５００℃１時間焼成した。ボールミルでμサイズまで
粉砕した後すぐにカーボン粉末と混ぜた。3.2mmの穴を
ドリルであけたグラファイトロッドにぎっしりつめた。
アノードの組成は、カーボンに対して、Ni 2.6at%,Co
0.7at%,Fe 1.45at%,S 0.75at%であった。アルゴン：水
素体積比１：１で３５０torrで７５−８０Aのアーク電
流でＣＮＴ合成を行った。両電極は2mmの距離で電圧差
は２６〜２８Ｖとした。Example 33 Carbon nanotubes were produced by an arc discharge method according to the method of JL Hutchison et al. (Carbon 39 (2001) 761-770). The anode was a graphite rod with a diameter of 8.2 mm, in which a catalyst was embedded in a hole with a diameter of 3.2 mm and a length of 140 mm, and the cathode was a graphite rod with a diameter of 10 mm and a length of 25 mm. The catalyst was prepared as follows. A mixture of Ni, Co and Fe powders having a particle size of 2-5 μm and sulfur atoms were well pulverized and then calcined at 500 ° C. for 1 hour under argon gas. It was pulverized to a μ size with a ball mill and immediately mixed with carbon powder. A 3.2 mm hole was tightly packed into a drilled graphite rod.
The composition of the anode was Ni 2.6at%, Co
The values were 0.7 at%, Fe 1.45 at% and S 0.75 at%. CNT synthesis was performed with an argon: hydrogen volume ratio of 1: 1 and an arc current of 75-80 A at 350 torr. Both electrodes had a distance of 2 mm and a voltage difference of 26 to 28V.
【００９７】実施例３４
実施例３３で得られたカーボンナノチューブを含むカー
ボン０．５ｇを、ガラス製シャーレー上にうすく広げ
て、ＹＡＭＡＴＯ化学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ
ＭＯＤＥＬ ＰＣ−１０１Ａを用いて、窒素ガス、圧
力２０Ｐａ、ＰＯＷＥＲ３００Ｗの条件で、５分間プラ
ズマ処理を行い、一度取り出して、シャーレー上のプラ
ズマ処理カーボンナノチューブを、かき混ぜ（ひっくり
返す、転がす等の動作）、シャーレー上にうすく広げ、
再び同様のプラズマ処理を行う作業を繰り返し、合計１
０分（計２回）のプラズマ処理を行った。Example 34 0.5 g of carbon containing the carbon nanotubes obtained in Example 33 was thinly spread on a glass Petri dish, and PLASMA CHAMBER manufactured by YAMATO CHEMICAL CO., LTD.
Using MODEL PC-101A, perform a plasma treatment for 5 minutes under the conditions of nitrogen gas, pressure 20 Pa, and POWER 300 W, take it out once, and stir the plasma-treated carbon nanotubes on the Petri dish (turn over, roll, etc.), petri dish. Spread thinly on top,
Repeating the same plasma treatment again, a total of 1
Plasma treatment was performed for 0 minutes (twice in total).
【００９８】プラズマ処理後のカーボン材料１０ｍｇ
に、イオン交換水５０ｍｌを加えて、超音波洗浄機（Ｙ
ＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１０、発信周波
数４７ＫＨｚ、出力１３０Ｗ）にて１時間処理後、４８
時間静置して得られた試料を観察したところ、カーボン
ナノチューブ分散液と黒い沈殿物が確認できた。分散液
を、遠心分離器（装置：ＫＵＢＯＴＡ ＫＲ−２０００
０Ｔ、ローター：ＲＡ−３ ５０ｍｌ×８本）を用い
て、回転数１２０００ｒｐｍ（約１７０００（×ｇ））
×１時間、遠心分離したところ、上澄み液として、透明
感のある黒色の溶液を得た。スポイトで溶液部分を回収
し、高分解能透過型電子顕微鏡で観察した結果、炭素不
純物の付着した２〜５層のカーボンナノチューブが多く
見られた。５万倍の走査型電子顕微鏡で見たところ、８
０％は、繊維状物質で、２０％は粒子状物質であった。10 mg of carbon material after plasma treatment
50 ml of deionized water is added to the ultrasonic cleaner (Y
48 hours after processing for 1 hour with BRANSON 3210 manufactured by AMATO Chemical, transmission frequency 47 KHz, output 130 W)
When the sample obtained after standing for a while was observed, a carbon nanotube dispersion liquid and a black precipitate were confirmed. The dispersion liquid was centrifuged (device: KUBOTA KR-2000).
0T, rotor: RA-3 50 ml × 8), rotation speed 12000 rpm (about 17,000 (× g))
After centrifugation for 1 hour, a transparent black solution was obtained as a supernatant. As a result of collecting the solution portion with a dropper and observing with a high-resolution transmission electron microscope, many carbon nanotubes of 2 to 5 layers having carbon impurities attached were found. When viewed with a scanning electron microscope with a magnification of 50,000, 8
0% was fibrous material and 20% was particulate material.
【００９９】乾燥させて重量を図り、再度水に分散させ
て、先の実施例と同様に酸量を量り、酸性官能基の含有
率を求めたところ、８．５％であった。
実施例３５
実施例３３で得られたカーボンナノチューブを含むカー
ボン０．５ｇを、ガラス製シャーレー上にうすく広げ
て、ＹＡＭＡＴＯ化学製ＰＬＡＳＭＡ ＣＨＡＭＢＥＲ
ＭＯＤＥＬ ＰＣ−１０１Ａを用いて、窒素ガス、圧
力２０Ｐａ、ＰＯＷＥＲ３００Ｗの条件で、５分間プラ
ズマ処理を行い、一度取り出して、シャーレー上のプラ
ズマ処理カーボンナノチューブを、かき混ぜ（ひっくり
返す、転がす等の動作）、シャーレー上にうすく広げ、
再び同様のプラズマ処理を行う作業を繰り返し、合計２
０分（計４回）のプラズマ処理を行った。The dried product was weighed, redispersed in water, the amount of acid was measured in the same manner as in the previous example, and the content of acidic functional groups was determined to be 8.5%. Example 35 0.5 g of carbon containing the carbon nanotubes obtained in Example 33 was thinly spread on a glass Petri dish, and PLASMA CHAMBER manufactured by YAMATO CHEMICAL CO., LTD.
Using MODEL PC-101A, perform a plasma treatment for 5 minutes under the conditions of nitrogen gas, pressure 20 Pa, and POWER 300 W, take it out once, and stir the plasma-treated carbon nanotubes on the Petri dish (turn over, roll, etc.), petri dish. Spread thinly on top,
Repeat the same plasma treatment again, totaling 2
Plasma treatment was performed for 0 minutes (four times in total).
【０１００】プラズマ処理後のカーボン材料１０ｍｇ
に、イオン交換水５０ｍｌを加えて、超音波洗浄機（Ｙ
ＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１０、発信周波
数４７ＫＨｚ、出力１３０Ｗ）にて１時間処理後、４８
時間静置して得られた試料を観察したところ、カーボン
ナノチューブ分散液と黒い沈殿物が確認できた。分散液
を、遠心分離器（装置：ＫＵＢＯＴＡ ＫＲ−２０００
０Ｔ、ローター：ＲＡ−３ ５０ｍｌ×８本）を用い
て、回転数１２０００ｒｐｍ（約１７０００（×ｇ））
×１時間、遠心分離したところ、上澄み液として、透明
感のある黒色の溶液を得た。スポイトで溶液部分を回収
し、高分解能透過型電子顕微鏡で観察した結果、炭素不
純物の付着した２〜５層のカーボンナノチューブが多く
見られた。
実施例３６
フロンティアカーボン社より購入した単層カーボンナノ
チューブ（純度２０％）０．５ｇを、ガラス製シャーレ
ー上にうすく広げて、ＹＡＭＡＴＯ化学製ＰＬＡＳＭＡ
ＣＨＡＭＢＥＲ ＭＯＤＥＬ ＰＣ−１０１Ａを用い
て、窒素ガス、圧力２０Ｐａ、ＰＯＷＥＲ３００Ｗの条
件で、５分間プラズマ処理を行い、一度取り出して、シ
ャーレー上のプラズマ処理カーボンナノチューブを、か
き混ぜ（ひっくり返す、転がす等の動作）、シャーレー
上にうすく広げ、再び同様のプラズマ処理を行う作業を
繰り返し、合計１５分（計３回）のプラズマ処理を行っ
た。10 mg of carbon material after plasma treatment
50 ml of deionized water is added to the ultrasonic cleaner (Y
48 hours after processing for 1 hour with BRANSON 3210 manufactured by AMATO Chemical, transmission frequency 47 KHz, output 130 W)
When the sample obtained after standing for a while was observed, a carbon nanotube dispersion liquid and a black precipitate were confirmed. The dispersion liquid was centrifuged (device: KUBOTA KR-2000).
0T, rotor: RA-3 50 ml × 8), rotation speed 12000 rpm (about 17,000 (× g))
After centrifugation for 1 hour, a transparent black solution was obtained as a supernatant. As a result of collecting the solution portion with a dropper and observing with a high-resolution transmission electron microscope, many carbon nanotubes of 2 to 5 layers having carbon impurities attached were found. Example 36 0.5 g of single-walled carbon nanotubes (purity 20%) purchased from Frontier Carbon Co., Ltd. were thinly spread on a glass Petri dish, and YAMATO Chemical's PLASMA was used.
Using CHAMBER MODEL PC-101A, plasma treatment was performed for 5 minutes under the conditions of nitrogen gas, pressure 20 Pa, and POWER 300 W, and was taken out once, and the plasma-treated carbon nanotubes on the Petri dish were stirred (turned over, rolled, etc.), The work of thinly spreading on a Petri dish and performing the same plasma treatment again was repeated, and the plasma treatment was performed for a total of 15 minutes (total 3 times).
【０１０１】プラズマ処理後のカーボン材料１０ｍｇ
に、イオン交換水５０ｍｌを加えて、超音波洗浄機（Ｙ
ＡＭＡＴＯ化学製、ＢＲＡＮＳＯＮ３２１０、発信周波
数４７ＫＨｚ、出力１３０Ｗ）にて１時間処理後、４８
時間静置して得られた試料を観察したところ、カーボン
ナノチューブ分散液と黒っぽい沈殿物が確認できた。分
散液を、遠心分離器（装置：ＫＵＢＯＴＡ ＫＲ−２０
０００Ｔ、ローター：ＲＡ−３ ５０ｍｌ×８本）を用
いて、回転数１２０００ｒｐｍ（約１７０００（×
ｇ））×１時間、遠心分離したところ、上澄み液とし
て、透明感のある黒っぽい色の溶液を得た。スポイトで
溶液部分を回収し、高分解能透過型電子顕微鏡で観察し
た結果、単層のカーボンナノチューブが多く見られた。
実施例３７
ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９
０）１６０重量部、ジグリシジルエーテル型希釈剤（エ
ポキシ当量１５０）４０重量部、無機充填材であるアエ
ロジル（平均粒子径３０ｎｍ）１０重量部と、カルボン
酸無水物であるメチルテトラヒドロ無水フタル酸１６０
重量部とトリフェニルホスフィン４重量部を溶解して得
た硬化剤液と、実施例３６で得られたプラズマ処理した
カーボンナノチューブ１重量部と、エタノール１００重
量部を配合して、カーボンナノチューブの高分散したペ
ースト状組成物を得た。ペースト状組成物を直径３ｃ
ｍ、厚さ５ｍｍの型に流し込み、７０℃で１時間、さら
に１８０℃で２時間加熱したところ、ペースト状組成物
は硬化し、カーボンナノチューブが高分散した固体の円
盤が得られた。10 mg of carbon material after plasma treatment
50 ml of deionized water is added to the ultrasonic cleaner (Y
48 hours after processing for 1 hour with BRANSON 3210 manufactured by AMATO Chemical, transmission frequency 47 KHz, output 130 W)
When the sample obtained after standing for a while was observed, a carbon nanotube dispersion liquid and a dark precipitate were confirmed. The dispersion liquid was centrifuged (device: KUBOTA KR-20
000T, rotor: RA-3 50 ml × 8, using a rotation speed of 12000 rpm (about 17,000 (×
g)) × 1 hour, and as a supernatant liquid, a transparent, dark-colored solution was obtained. As a result of collecting the solution portion with a dropper and observing with a high resolution transmission electron microscope, many single-walled carbon nanotubes were seen. Example 37 Bisphenol A type epoxy resin (epoxy equivalent 19
0) 160 parts by weight, diglycidyl ether type diluent (epoxy equivalent 150) 40 parts by weight, inorganic filler Aerosil (average particle diameter 30 nm) 10 parts by weight, and carboxylic acid anhydride methyltetrahydrophthalic anhydride 160
1 part by weight of the plasma-treated carbon nanotubes obtained in Example 36 and 100 parts by weight of ethanol were mixed to obtain a high carbon nanotube content. A dispersed paste composition was obtained. 3c diameter paste composition
It was poured into a mold having a thickness of m and a thickness of 5 mm, and heated at 70 ° C. for 1 hour and further at 180 ° C. for 2 hours.
【０１０２】[0102]
【発明の効果】本発明によれば、プラズマ処理したカー
ボンナノチューブ、分散液、溶液および組成物を得るこ
とができる。According to the present invention, it is possible to obtain plasma-treated carbon nanotubes, dispersions, solutions and compositions.
【０１０３】カーボンナノチューブをプラズマ処理（特
に酸素ガスプラズマが好ましい）する方法は、カーボン
ナノチューブの分散性の向上、精製度の改良、外表面へ
の官能基付与が同時に、簡易的に短時間で行うことがで
きる優れた処理方法である。In the method of plasma-treating carbon nanotubes (preferably oxygen gas plasma), the dispersibility of carbon nanotubes, the degree of purification, and the addition of a functional group to the outer surface are simultaneously and simply carried out in a short time. It is an excellent processing method that can be performed.
【０１０４】層数の少ない、単層や２〜５層のカーボン
ナノチューブにおいても、プラズマ処理（特に窒素ガス
プラズマが好ましい）であれば、その構造を大きく破壊
することなく、分散性の向上、精製度の改良、外表面へ
の官能基付与が可能である。Even in the case of single-walled or 2- to 5-walled carbon nanotubes having a small number of layers, the plasma treatment (particularly nitrogen gas plasma is preferable) can improve the dispersibility and the purification without significantly destroying the structure. It is possible to improve the degree and add a functional group to the outer surface.
【０１０５】プラズマ処理の際にカーボンナノチューブ
をかき混ぜることで、より大きな効果が得られる。A larger effect can be obtained by stirring the carbon nanotubes during the plasma treatment.
【０１０６】カーボンナノチューブ分散液、溶液は、プ
ラズマ処理したカーボンナノチューブ（カーボンナノチ
ューブ外表面の炭素に対する酸性官能基の含有率が２％
以上のカーボンナノチューブ）を用いることで得られ
る。The carbon nanotube dispersion liquid and the solution were plasma treated carbon nanotubes (the content of the acidic functional group with respect to the carbon on the outer surface of the carbon nanotube was 2%.
It is obtained by using the above carbon nanotubes).
【０１０７】また、カーボンナノチューブ分散液、溶液
を分級することでカーボンナノチューブを精製すること
ができる。さらに、カーボンナノチューブの製造に触媒
を用いた場合、カーボンナノチューブ分散液、溶液を分
級することで触媒を除去する精製も行うことができる。Further, the carbon nanotubes can be purified by classifying the carbon nanotube dispersion liquid and the solution. Furthermore, when a catalyst is used for the production of carbon nanotubes, purification can be performed by removing the catalyst by classifying the carbon nanotube dispersion liquid and the solution.
【０１０８】カーボンナノチューブ分散液、溶液、およ
びこれらから得られるカーボンナノチューブは、塗料や
樹脂への添加剤用途、電子部品用途、医療用途など、そ
の用途は広く期待できる。さらに、カーボンナノチュー
ブ分散液、溶液の分級によるカーボンナノチューブの精
製方法は、強酸等を用いないことや触媒のリサイクルが
可能となり、人体への影響や環境問題の観点から有効で
ある。これらのことにより、本発明による産業上の利用
価値は大きい。The carbon nanotube dispersions, solutions, and carbon nanotubes obtained from them can be widely expected to be used as additives to paints and resins, electronic parts, medical applications and the like. Further, the method for purifying carbon nanotubes by classifying the carbon nanotube dispersion liquid and the solution makes it possible to recycle the catalyst without using strong acid or the like, and is effective from the viewpoints of influence on the human body and environmental problems. Because of these, the industrial utility value of the present invention is great.
【図１】多層カーボンナノチューブの模式図である。FIG. 1 is a schematic view of a multi-walled carbon nanotube.
【図２】ＣＶＤ装置の断面図である。FIG. 2 is a sectional view of a CVD apparatus.
【図３】実施例２で得たカーボンナノチューブのＴＥＭ
写真（×４０００００）。FIG. 3 is a TEM of the carbon nanotube obtained in Example 2.
Photo (× 400000).
【図４】実施例２で得たカーボンナノチューブのＴＥＭ
写真（×１６００００）。FIG. 4 is a TEM of carbon nanotubes obtained in Example 2.
Photo (× 160000).
【図５】実施例２で得たカーボンナノチューブのＳＥＭ
写真（×５００００）。FIG. 5 SEM of carbon nanotubes obtained in Example 2
Photo (x50000).
【図６】実施例２で得たカーボンナノチューブのＳＥＭ
写真（×５００００）。FIG. 6 is an SEM of carbon nanotubes obtained in Example 2.
Photo (x50000).
【図７】実施例３で得たカーボンナノチューブのＴＥＭ
写真（×４０００００）。FIG. 7: TEM of carbon nanotube obtained in Example 3
Photo (× 400000).
【図８】実施例３で得たカーボンナノチューブのＴＥＭ
写真（×１６００００）。FIG. 8: TEM of carbon nanotube obtained in Example 3
Photo (× 160000).
【図９】実施例３で得たカーボンナノチューブのＳＥＭ
写真（×５００００）。FIG. 9 SEM of carbon nanotubes obtained in Example 3
Photo (x50000).
【図１０】実施例３で得たカーボンナノチューブのＳＥ
Ｍ写真（×５００００）。FIG. 10 SE of the carbon nanotube obtained in Example 3
M photograph (× 50000).
【図１１】実施例５で得たカーボンナノチューブのＴＥ
Ｍ写真（×４０００００）。FIG. 11: TE of the carbon nanotube obtained in Example 5
M photograph (× 400000).
【図１２】実施例５で得たカーボンナノチューブのＴＥ
Ｍ写真（×１６００００）。FIG. 12: TE of the carbon nanotube obtained in Example 5
M photograph (× 160000).
【図１３】実施例５で得たカーボンナノチューブのＳＥ
Ｍ写真（×５００００）。FIG. 13 SE of the carbon nanotube obtained in Example 5
M photograph (× 50000).
【図１４】実施例５で得たカーボンナノチューブのＳＥ
Ｍ写真（×５００００）。FIG. 14 SE of carbon nanotube obtained in Example 5
M photograph (× 50000).
【図１５】実施例１１で得たカーボンナノチューブのＴ
ＥＭ写真（×４０００００）。FIG. 15: T of the carbon nanotube obtained in Example 11
EM photograph (× 400000).
【図１６】実施例１１で得たカーボンナノチューブのＴ
ＥＭ写真（×１６００００）。16 is a graph of T of the carbon nanotube obtained in Example 11. FIG.
EM photograph (× 160000).
【図１７】実施例１１で得たカーボンナノチューブのＳ
ＥＭ写真（×５００００）。FIG. 17: S of carbon nanotubes obtained in Example 11
EM photograph (× 50000).
【図１８】実施例１１で得たカーボンナノチューブのＳ
ＥＭ写真（×５００００）。FIG. 18 S of the carbon nanotube obtained in Example 11
EM photograph (× 50000).
フロントページの続き Ｆターム(参考） 4G069 AA01 AA03 AA08 BA08A BA08B BB02B BB04A BC31A BC32A BC33A BC57A BC61A BC65A BC66B BC67B BC69A EA03X EA03Y EB08 ED02 FA02 FB17 FB58 4G146 AA11 AB01 AB10 AD17 AD35 AD37 BA04 CB10 CB16 CB35Continued front page F-term (reference) 4G069 AA01 AA03 AA08 BA08A BA08B BB02B BB04A BC31A BC32A BC33A BC57A BC61A BC65A BC66B BC67B BC69A EA03X EA03Y EB08 ED02 FA02 FB17 FB58 4G146 AA11 AB01 AB10 AD17 AD35 AD37 BA04 CB10 CB16 CB35
Claims (13)
徴とする、炭素質材料の処理方法。1. A method for treating a carbonaceous material, which comprises treating the carbonaceous material with plasma.
素質材料をかき混ぜることを特徴とする、請求項１記載
の炭素質材料の処理方法。2. The method for treating a carbonaceous material according to claim 1, wherein the carbonaceous material is agitated when the carbonaceous material is treated with plasma.
することを特徴とする請求項１または２記載の炭素質材
料の処理方法。3. The method for treating a carbonaceous material according to claim 1 or 2, wherein the carbonaceous material contains carbon nanotubes.
とを特徴とする、請求項３記載の炭素質材料の処理方
法。4. The method for treating a carbonaceous material according to claim 3, wherein the carbon nanotube has 1 to 5 layers.
カーボンナノチューブを、液に分散させることを特徴と
する、カーボンナノチューブ分散液を得る方法。5. A method for obtaining a carbon nanotube dispersion liquid, which comprises dispersing the plasma-treated carbon nanotubes according to claim 3 or 4 in a liquid.
カーボンナノチューブを、液に分散させた後、固液分離
することを特徴とする、カーボンナノチューブ溶液を得
る方法。6. A method of obtaining a carbon nanotube solution, which comprises dispersing the plasma-treated carbon nanotubes according to claim 3 or 4 in a liquid and then performing solid-liquid separation.
カーボンナノチューブを、液に分散させた後、分級する
ことを特徴とする精製カーボンナノチューブ溶液を得る
方法。7. A method for obtaining a purified carbon nanotube solution, which comprises dispersing the plasma-treated carbon nanotubes according to claim 3 or 4 in a liquid and then classifying.
ノチューブ分散液、請求項６記載の方法により得たカー
ボンナノチューブ溶液または請求項７記載の方法により
得た精製カーボンナノチューブ溶液を、濃縮することを
特徴とする高濃度カーボンナノチューブ分散液、高濃度
カーボンナノチューブ溶液または高濃度精製カーボンナ
ノチューブ溶液の製造方法。8. Concentrating the carbon nanotube dispersion obtained by the method of claim 5, the carbon nanotube solution obtained by the method of claim 6, or the purified carbon nanotube solution obtained by the method of claim 7. A method for producing a high-concentration carbon nanotube dispersion liquid, a high-concentration carbon nanotube solution, or a high-concentration purified carbon nanotube solution.
ノチューブ分散液、請求項６記載の方法により得たカー
ボンナノチューブ溶液または請求項７記載の方法により
得た精製カーボンナノチューブ溶液を、乾燥することを
特徴とする粉末状カーボンナノチューブの製造方法。9. Drying the carbon nanotube dispersion obtained by the method of claim 5, the carbon nanotube solution obtained by the method of claim 6, or the purified carbon nanotube solution obtained by the method of claim 7. A method for producing a powdery carbon nanotube, comprising:
（２）カーボンナノチューブプラズマ処理工程、（３）
カーボンナノチューブを液に分散する工程、（４）カー
ボンナノチューブを分級又は固液分離する工程の４つの
工程を含有することを特徴とするカーボンナノチューブ
の製造方法。10. (1) Carbon nanotube synthesis step,
(2) Carbon nanotube plasma treatment step, (3)
A method for producing a carbon nanotube, which comprises four steps of a step of dispersing the carbon nanotube in a liquid and a step (4) of classifying or solid-liquid separating the carbon nanotube.
特徴とする触媒組成物の製造方法。 （１）カーボンナノチューブをプラズマ処理する工程 （２）プラズマ処理後のカーボンナノチューブを金属を
含有する液と接触する工程11. A method for producing a catalyst composition, which comprises the following two steps. (1) A step of plasma-treating the carbon nanotubes (2) A step of contacting the carbon nanotubes after the plasma treatment with a liquid containing a metal
る有機化合物含有カーボンナノチューブの製造方法。 （１）カーボンナノチューブをプラズマ処理する工程 （２）プラズマ処理後のカーボンナノチューブを有機化
合物を含有する液と接触する工程12. A method for producing an organic compound-containing carbon nanotube, comprising the following two steps. (1) Process of plasma-treating carbon nanotubes (2) Process of contacting carbon nanotubes after plasma treatment with a liquid containing an organic compound
るコーティング用組成物の製造方法。 （１）カーボンナノチューブをプラズマ処理する工程 （２）プラズマ処理後のカーボンナノチューブをコーテ
ィング用の主剤と混合する工程13. A method for producing a coating composition, which comprises the following two steps. (1) A step of plasma-treating the carbon nanotubes (2) A step of mixing the carbon nanotubes after the plasma treatment with a main agent for coating
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