JP2006298713A - Method for manufacturing three-layer carbon nanotube and composition containing three-layer carbon nanotube - Google Patents

Method for manufacturing three-layer carbon nanotube and composition containing three-layer carbon nanotube Download PDF

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JP2006298713A
JP2006298713A JP2005124952A JP2005124952A JP2006298713A JP 2006298713 A JP2006298713 A JP 2006298713A JP 2005124952 A JP2005124952 A JP 2005124952A JP 2005124952 A JP2005124952 A JP 2005124952A JP 2006298713 A JP2006298713 A JP 2006298713A
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walled carbon
carbon nanotube
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carbon nanotubes
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JP4849437B2 (en
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Hisanori Shinohara
久典 篠原
Ramesh Palanisamy
パラニサミィ ラメッシュ
Yuji Ozeki
雄治 尾関
Kenichi Sato
謙一 佐藤
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Nagoya University NUC
Toray Industries Inc
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Toray Industries Inc
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<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing three-layer carbon nanotubes excellent in characteristics and durability and having high linearity by a catalytic chemical vapor growth method. <P>SOLUTION: Carbon nanotubes consisting mainly of the three-layer carbon nanotubes are manufactured by bringing a carbon-containing compound into contact with a metal catalyst comprising metal particles whose average diameter is ≤10 nm at a temperature of 600-1,000°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、３層カーボンナノチューブの製造方法及び３層カーボンナノチューブ含有組成物に関し、さらに詳しくは、特性および耐久性に優れた３層カーボンナノチューブの製造方法及び３層カーボンナノチューブ含有組成物に関するものである。   The present invention relates to a method for producing three-walled carbon nanotubes and a composition containing three-walled carbon nanotubes, and more particularly to a method for producing three-walled carbon nanotubes having excellent characteristics and durability and a composition containing three-walled carbon nanotubes. is there.

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、３層に巻いたものを３層カーボンナノチューブ、と言い２層以上のカーボンナノチューブをまとめて多層カーボンナノチューブという。   The carbon nanotube has a shape in which one surface of graphite is wound into a cylindrical shape. A single-walled carbon nanotube is formed by winding one layer, a double-walled carbon nanotube is formed by winding two layers, and a three-layer is formed. The rolled carbon nanotubes are called three-walled carbon nanotubes, and the carbon nanotubes of two or more layers are collectively called multi-walled carbon nanotubes.

カーボンナノチューブは、高い機械的強度、高い導電性等の優れた特性を有することから、燃料電池やリチウム２次電池用負極材として、また、樹脂、金属、セラミックス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、透明導電フィルム、金属電解粉、熱伝導性セラミックス、電磁波シールド材の材料として期待されている。さらに、長さＬと直径Ｄとの比Ｌ／Ｄ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、太陽電池素子、ナノピンセットの材料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、水素などの吸着材料、医療用ナノカプセル、ＭＲＩ造影剤の材料として期待されている。   Since carbon nanotubes have excellent characteristics such as high mechanical strength and high conductivity, they are used as negative electrodes for fuel cells and lithium secondary batteries, and are made of composite materials of resins, metals, ceramics and organic semiconductors. It is expected as a material for high-strength resins, conductive resins, transparent conductive films, metal electrolyte powders, thermally conductive ceramics, and electromagnetic shielding materials. Furthermore, since the ratio L / D between the length L and the diameter D is large and the diameter is several nanometers, it is expected as a material for probes for scanning tunneling microscopes, field electron emission sources, solar cell elements, and nanotweezers. In addition, since it has a nano-sized space, it is expected as a material for adsorption materials such as hydrogen, medical nanocapsules, and MRI contrast agents.

このように期待が大きいカーボンナノチューブは、いずれの用途に使用される場合であっても、高純度のカーボンナノチューブが要求され、また直径の細い単層から５層程度のカーボンナノチューブが有用であり、特に耐久性の点から、２層や３層カーボンナノチューブが有利である。また、グラファイト層の欠陥が少ないものが特性的に優れているとされている。特に、２層〜５層のカーボンナノチューブは、金属やセラミックスとの複合体として、燃料電池やリチウム２次電池用負極材、放熱材料、および電子放出材料として用いることが期待されている。   Carbon nanotubes with high expectations are required for high-purity carbon nanotubes in any application, and carbon nanotubes having a single diameter to about 5 layers with a small diameter are useful. In particular, from the viewpoint of durability, a double-walled or triple-walled carbon nanotube is advantageous. In addition, a graphite layer having few defects is considered to be excellent in characteristics. In particular, the carbon nanotubes having 2 to 5 layers are expected to be used as a negative electrode material for a fuel cell or a lithium secondary battery, a heat dissipation material, and an electron emission material as a composite with metal or ceramics.

従来、カーボンナノチューブの製造方法として、アーク放電法やレーザー蒸発法、化学気相成長法などが知られており（非特許文献１参照）、なかでも、触媒化学気相成長法は、グラファイト層に欠陥の少ない高品質なカーボンナノチューブを安価に製造する方法として知られている（非特許文献２参照）。さらに、触媒化学気相成長法において、原料にアルコールを用いることにより、直線性の高い単層カーボンナノチューブを高純度で合成できることが知られている（非特許文献３参照）。   Conventionally, as a carbon nanotube production method, an arc discharge method, a laser evaporation method, a chemical vapor deposition method, or the like is known (see Non-Patent Document 1). Among them, a catalytic chemical vapor deposition method is applied to a graphite layer. It is known as a method for producing high-quality carbon nanotubes with few defects at low cost (see Non-Patent Document 2). Furthermore, it is known that single-walled carbon nanotubes with high linearity can be synthesized with high purity by using alcohol as a raw material in catalytic chemical vapor deposition (see Non-Patent Document 3).

しかし、高い特性と２層カーボンナノチューブ以上に高い耐久性を併せ持つ直線性の高い３層カーボンナノチューブは合成できなかった。
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、ｐ１７、２３、４７ ケミカル・フィジックス・レターズ（Chemical Physics Letters）303(1999),117-124 ケミカル・フィジックス・レターズ（Chemical Physics Letters）360(2002),229-234 However, highly linear three-walled carbon nanotubes having both high characteristics and higher durability than double-walled carbon nanotubes could not be synthesized.
Yahachi Saito, Shunji Bando, Fundamentals of Carbon Nanotubes, Corona Inc., p17, 23, 47 Chemical Physics Letters 303 (1999), 117-124 Chemical Physics Letters 360 (2002), 229-234

本発明の目的は、触媒化学気相成長法において、特性および耐久性に優れ、直線性が高い３層カーボンナノチューブの製造方法及びその３層カーボンナノチューブを含む組成物の提供することである。   An object of the present invention is to provide a method for producing a three-walled carbon nanotube having excellent characteristics and durability and high linearity in a catalytic chemical vapor deposition method, and a composition containing the three-walled carbon nanotube.

上記目的を達成する本発明の３層カーボンナノチューブの製造方法は、炭素含有化合物を、平均直径が１０ｎｍ以下の金属粒子からなる金属触媒と、温度６００〜１０００℃で接触させることにより、３層カーボンナノチューブを主成分とするカーボンナノチューブを製造する３層カーボンナノチューブの製造方法である。   The method for producing a three-walled carbon nanotube of the present invention that achieves the above object comprises bringing a carbon-containing compound into contact with a metal catalyst comprising metal particles having an average diameter of 10 nm or less at a temperature of 600 to 1000 ° C. This is a method for producing a three-walled carbon nanotube for producing a carbon nanotube mainly composed of a nanotube.

また本発明の３層カーボンナノチューブ含有組成物は、（１）透過型電子顕微鏡で任意に選択した１００本のカーボンナノチューブ中、５０本以上が３層カーボンナノチューブであること、（２）透過型電子顕微鏡で任意に選択した３層カーボンナノチューブ中の屈曲部間距離の平均が１００ｎｍ以上であること、（３）共鳴ラマン散乱測定により、１５６０〜１６００ｃｍ−１の範囲内で最大のピーク強度をＧ、１３１０〜１３５０ｃｍ−１の範囲内で最大のピーク強度をＤとしたとき、Ｇ／Ｄの比が１０以上であること、（４）元素分析による金属含有率が１重量％以下であること、の要件を満たす３層カーボンナノチューブ含有組成物である。 The three-walled carbon nanotube-containing composition of the present invention comprises (1) 50 or more of 100 carbon nanotubes arbitrarily selected by a transmission electron microscope, and (2) transmission-type electrons. The average of the distance between the bent portions in the three-walled carbon nanotube arbitrarily selected with a microscope is 100 nm or more, and (3) the maximum peak intensity in the range of 1560 to 1600 cm −1 is G, by resonance Raman scattering measurement. When the maximum peak intensity within the range of 1310 to 1350 cm −1 is D, the G / D ratio is 10 or more, and (4) the metal content by elemental analysis is 1% by weight or less. A composition containing three-walled carbon nanotubes that satisfies the requirements.

本発明の製造方法によれば、純度が高く、かつ直径が細くて均一な３層カーボンナノチューブを効率よく合成することができる。また、本発明による３層カーボンナノチューブ含有組成物は、個々の３層カーボンナノチューブ中に屈曲構造を含みにくく、直線性に優れた３層カーボンナノチューブとすることができる。   According to the production method of the present invention, it is possible to efficiently synthesize three-walled carbon nanotubes having a high purity and a small diameter and being uniform. In addition, the three-walled carbon nanotube-containing composition according to the present invention can be a three-walled carbon nanotube excellent in linearity because it does not easily include a bent structure in each of the three-walled carbon nanotubes.

本発明の３層カーボンナノチューブの製造方法は、炭素含有化合物を、金属粒子の平均直径が１０ｎｍ以下である金属触媒と温度６００〜１０００℃で接触させることを特徴とする。ここで、金属の種類は、特に限定されないが、好ましくは３〜１２族の金属、より好ましくは５〜１１族の金属が用いられる。中でも、Ｖ，Ｍｏ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｐｄ，Ｐｔ，Ｒｈ、Ｗ、Ｃｕ等が特に好ましく、さらに好ましくは、Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｍｎが用いられる。ここで金属とは、０価の状態とは限らない。反応中では０価の金属状態になっていると推定できるが、広く金属を含む化合物又は金属種という意味で解釈してよい。また金属は微粒子であることが好ましい。微粒子とは粒径が１０ｎｍ以下であり、０．５〜１０ｎｍであることが好ましい。金属が微粒子であると直径が細いカーボンナノチューブが生成しやすい。   The method for producing a three-walled carbon nanotube of the present invention is characterized in that a carbon-containing compound is brought into contact with a metal catalyst having an average diameter of metal particles of 10 nm or less at a temperature of 600 to 1000 ° C. Here, the type of the metal is not particularly limited, but preferably a Group 3-12 metal, more preferably a Group 5-11 metal. Among these, V, Mo, Mn, Fe, Co, Ni, Pd, Pt, Rh, W, Cu, and the like are particularly preferable, and Fe, Co, Ni, Mo, and Mn are more preferable. Here, the metal is not necessarily a zero-valent state. Although it can be presumed that the metal is in a zero-valent state during the reaction, it may be interpreted in the meaning of a compound containing a metal or a metal species. The metal is preferably fine particles. The fine particles have a particle size of 10 nm or less, preferably 0.5 to 10 nm. If the metal is a fine particle, a carbon nanotube with a small diameter is likely to be generated.

金属触媒の平均直径の測定法は、カーボンナノチューブ合成後に生成物を電子顕微鏡で観察する方法である。透過型電子顕微鏡を用いることで、ｎｍオーダーの金属粒子の粒子直径を測定することができる。本発明において、金属触媒の平均直径は、透過型電子顕微鏡（倍率２００万倍）において、任意に選んだ１００個以上の金属粒子の粒子直径を測定し、その結果を平均して求めるものとする。   The measurement method of the average diameter of a metal catalyst is a method of observing a product with an electron microscope after carbon nanotube synthesis. By using a transmission electron microscope, it is possible to measure the particle diameter of metal particles of the order of nm. In the present invention, the average diameter of the metal catalyst is obtained by measuring the particle diameters of 100 or more metal particles arbitrarily selected with a transmission electron microscope (magnification of 2 million times) and averaging the results. .

本発明の製造方法において、透過型電子顕微鏡（倍率２００万倍）において、任意に選んだ１００個以上の金属粒子の粒子直径を測定し、金属触媒の粒子直径が２．３から４．５ｎｍである金属触媒の数が８０％以上であることが好ましい。このような粒子直径の金属粒子を触媒に使用することにより、３層カーボンナノチューブの直径を、調整することができる。   In the production method of the present invention, the particle diameter of 100 or more arbitrarily selected metal particles is measured with a transmission electron microscope (magnification 2 million times), and the particle diameter of the metal catalyst is 2.3 to 4.5 nm. The number of certain metal catalysts is preferably 80% or more. By using metal particles having such a particle diameter as a catalyst, the diameter of the three-walled carbon nanotube can be adjusted.

金属は１種類だけを用いても、２種類以上を用いてもよいが、好ましくは、２種類以上を用いた方がよい。２種類の金属を用いる場合は、Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｍｎを含むことが特に好ましい。金属の種類とその役割は特に限定されるものではないが、例えば一つ以上の金属元素からなるグループが、炭化水素を改質しカーボンナノチューブを合成しやすくし、一つ以上の金属元素からなる他のグループが、カーボンナノチューブの合成に用いられる場合もある。   Although only one type of metal may be used or two or more types may be used, it is preferable to use two or more types. When two kinds of metals are used, it is particularly preferable to contain Fe, Co, Ni, Mo, and Mn. The type of metal and its role are not particularly limited, but for example, a group consisting of one or more metal elements makes it easier to synthesize carbon nanotubes by modifying hydrocarbons and consisting of one or more metal elements Other groups may be used for the synthesis of carbon nanotubes.

金属触媒は、担体に担持されていてもよいし、担持されていなくてもよい。すなわち、反応管内で粒子直径１０ｎｍ以下の金属粒子として自立して存在していてもよい。担体に担持しない場合は、ガス化しやすい金属錯体を原料に用いる方法が好んで用いられる。   The metal catalyst may be supported on a carrier or may not be supported. That is, it may exist independently as a metal particle having a particle diameter of 10 nm or less in the reaction tube. When not supported on a carrier, a method using a metal complex that is easily gasified as a raw material is preferably used.

一方、金属触媒を担体に担持する場合、金属触媒の担持方法は、特に限定されない。例えば、担持したい金属の塩を溶解させた非水溶液中（例えばエタノール溶液）又は水溶液中に、担体を含浸し、充分に分散混合した後、乾燥させ、窒素、水素、不活性ガスまたはその混合ガス又は真空中で高温（３００〜６００℃）で加熱することにより、担体に金属を担持させることができる（含浸法）。   On the other hand, when the metal catalyst is supported on the carrier, the method for supporting the metal catalyst is not particularly limited. For example, a carrier is impregnated in a non-aqueous solution (for example, ethanol solution) or an aqueous solution in which a metal salt to be supported is dissolved, thoroughly dispersed and mixed, and then dried, and then nitrogen, hydrogen, an inert gas, or a mixed gas thereof Alternatively, the metal can be supported on the carrier by heating at a high temperature (300 to 600 ° C.) in a vacuum (impregnation method).

金属触媒を担持する量は、多いほどカーボンナノチューブの収量が上がるが、多すぎると金属粒子の粒子直径が大きくなり、生成するカーボンナノチューブが太くなる。金属担持量が少ないと、担持される金属の粒子直径が小さくなり、細いカーボンナノチューブが得られるが、収率が低くなる傾向がある。最適な金属担持量は、担体の細孔容量や外表面積、担持方法によって異なるが、担体に対して０．１〜２０重量％の金属を担持することが好ましい。２種類以上の金属を使用する場合、その比率は限定されない。   The larger the amount of the metal catalyst supported, the higher the yield of carbon nanotubes. However, when the amount is too large, the particle diameter of the metal particles increases and the carbon nanotubes to be produced become thicker. When the amount of supported metal is small, the particle diameter of the supported metal becomes small and thin carbon nanotubes can be obtained, but the yield tends to be low. The optimum metal loading varies depending on the pore volume, outer surface area, and loading method of the carrier, but it is preferable to carry 0.1 to 20% by weight of metal with respect to the carrier. When two or more kinds of metals are used, the ratio is not limited.

このようにして得られた金属触媒を担持した担体に、温度６００〜１０００℃で炭素含有化合物を接触させ、３層カーボンナノチューブを製造する。触媒と炭素含有化合物とを接触させる温度は、６００〜１０００℃であり、好ましくは７００〜９５０℃の範囲がよい。温度が６００℃よりも低いと、カーボンナノチューブの収率が悪くなり、また温度が１０００℃よりも高いと、使用する反応器の材質に制約があると共に、カーボンナノチューブ同士の接合が始まり、カーボンナノチューブの形状のコントロールが困難になる。   A carbon-containing compound is brought into contact with the carrier carrying the metal catalyst thus obtained at a temperature of 600 to 1000 ° C. to produce a three-walled carbon nanotube. The temperature which makes a catalyst and a carbon containing compound contact is 600-1000 degreeC, Preferably the range of 700-950 degreeC is good. When the temperature is lower than 600 ° C., the yield of carbon nanotubes is deteriorated. When the temperature is higher than 1000 ° C., there are restrictions on the material of the reactor to be used, and bonding between the carbon nanotubes starts. It becomes difficult to control the shape.

また、本発明の製造方法は、金属触媒が担体に担持されていることが好ましい。ここで担体の種類は、特に限定されるものではないが、金属、酸化物、カーボンから選ばれる少なくとも一つであることが好ましい。特に、担体は、ゼオライト、アルミナ、シリカ、チタニア、マグネシア等の酸化物が好んで用いられ、各酸化物はメソポアを有するメソポーラス材料を形成していてもよい。   In the production method of the present invention, the metal catalyst is preferably supported on a carrier. Although the kind of support | carrier is not specifically limited here, It is preferable that it is at least one chosen from a metal, an oxide, and carbon. In particular, the support is preferably an oxide such as zeolite, alumina, silica, titania, and magnesia, and each oxide may form a mesoporous material having mesopores.

ここでメソポーラス材料とは、直径２〜５０ｎｍ程度の細孔を持つ材料であり、界面活性剤と無機物質の協奏的な自己組織化により合成される。メソポーラス材料は大きい比表面積と高い安定性など、触媒や吸着剤としての優れた基本物性を有する。この様な材料のメソポーラス細孔は、担体上でカーボンナノチューブを合成する際に金属担持する細孔として有用である。代表的物質としてメソポーラスシリカが挙げられる。メソポーラスシリカの結晶構造は特に限定されないが、例えば、モービル社が開発したヘキサゴナル構造をもつＭＣＭ−４１、キュービック構造をもつＭＣＭ−４８、層状すなわちラメラ構造をもつＭＣＭ−５０があり、特に規則的な六角形の細孔が平行に配列したＭＣＭ−４１構造が好んで用いられる。   Here, the mesoporous material is a material having pores with a diameter of about 2 to 50 nm, and is synthesized by concerted self-assembly of a surfactant and an inorganic substance. Mesoporous materials have excellent basic physical properties as catalysts and adsorbents, such as a large specific surface area and high stability. The mesoporous pores of such a material are useful as pores for supporting a metal when carbon nanotubes are synthesized on a support. A typical material is mesoporous silica. The crystal structure of mesoporous silica is not particularly limited. For example, there are MCM-41 having a hexagonal structure developed by Mobil, MCM-48 having a cubic structure, and MCM-50 having a layered or lamellar structure. The MCM-41 structure in which hexagonal pores are arranged in parallel is preferably used.

また、ゼオライトとは、分子サイズの細孔径を有する結晶性無機酸化物からなるものである。ここに分子サイズとは、世の中に存在する分子のサイズの範囲であり、一般的には、０．２ｎｍから２ｎｍ程度の範囲を意味する。さらに具体的には、結晶性シリケート、結晶性アルミノシリケート、結晶性メタロシリケート、結晶性メタロアルミノシリケート、結晶性アルミノフォスフェート、あるいは結晶性メタロアルミノフォスフェート等で構成された結晶性マイクロポーラス物質のことである。   Zeolite is composed of a crystalline inorganic oxide having a pore size of molecular size. Here, the molecular size is a size range of molecules existing in the world, and generally means a range of about 0.2 nm to 2 nm. More specifically, a crystalline microporous material composed of crystalline silicate, crystalline aluminosilicate, crystalline metallosilicate, crystalline metalloaluminosilicate, crystalline aluminophosphate, crystalline metalloaluminophosphate, or the like. That is.

結晶性シリケート、結晶性アルミノシリケート、結晶性メタロシリケート、結晶性メタロアルミノシリケート、結晶性アルミノフォスフェート、結晶性メタロアルミノフォスフェートとしては、特に種類は制限されないが、例えば、アトラス オブ ゼオライト ストラクチュア タイプス（マイヤー、オルソン、バエロチャー、ゼオライツ、１７（１／２）、１９９６）（Atlas of Zeolite Structure types(W. M. Meier, D. H. Olson, Ch. Baerlocher, Zeolites, 17(1/2),1996)）に掲載されている構造をもつ結晶性無機多孔性物質が挙げられる。また、本発明におけるゼオライトは、前記文献に掲載されているものに限定されるものではなく、近年次々と合成されている新規な構造を有するゼオライトも含む。好ましいゼオライト構造は、入手が容易なＦＡＵ型、ＭＦＩ型、ＭＯＲ型、ＢＥＡ型、ＬＴＬ型、ＬＴＡ型であるが、これに限定されない。   Crystalline silicate, crystalline aluminosilicate, crystalline metallosilicate, crystalline metalloaluminosilicate, crystalline aluminophosphate, crystalline metalloaluminophosphate are not particularly limited, but for example, Atlas of Zeolite Structure Types ( Meyer, Olson, Baerochar, Zeolites, 17 (1/2), 1996) (Atlas of Zeolite Structure types (WM Meier, DH Olson, Ch. Baerlocher, Zeolites, 17 (1/2), 1996)) A crystalline inorganic porous material having a structure of Moreover, the zeolite in this invention is not limited to what is published in the said literature, The zeolite which has the novel structure synthesized one after another is included. Preferred zeolite structures are FAU type, MFI type, MOR type, BEA type, LTL type, and LTA type, which are easily available, but are not limited thereto.

ゼオライトは、その骨格が４面体の中心にＳｉ又はＡｌやチタン等のヘテロ原子（Ｓｉ以外の原子）、４面体の頂点に酸素を有するシリケート構造を有している。従って、４価の金属がその４面体構造の中心に入るのが最も安定であり、耐熱性が期待できる。したがって、理論的にはＡｌ等の３価の成分を実質的に含まないか、或いは少ないゼオライトが、耐熱性が高い。これらの製造法としては、従来公知の水熱合成法などで直接合成するか、後処理で３価の金属を骨格から抜く方法が好んで用いられる。   Zeolite has a silicate structure in which the skeleton has a heteroatom (atom other than Si) such as Si or Al or titanium at the center of the tetrahedron and oxygen at the apex of the tetrahedron. Therefore, it is most stable that a tetravalent metal enters the center of the tetrahedral structure, and heat resistance can be expected. Therefore, theoretically, a zeolite that does not substantially contain or contains a trivalent component such as Al has high heat resistance. As these production methods, a method of directly synthesizing by a conventionally known hydrothermal synthesis method or a method of removing a trivalent metal from the skeleton by post-treatment is preferably used.

本発明に使用する担体において、ゼオライトに酸またはアルカリ処理を施して、メソポーラス細孔を形成してもよい。酸処理とは、酸化物を酸に接触させる処理であり、使用する酸は特に限定されないが、フッ化水素酸、硫酸、塩酸、硝酸またはこれら混合物が好ましい。   In the carrier used in the present invention, mesoporous pores may be formed by subjecting zeolite to an acid or alkali treatment. The acid treatment is treatment for bringing an oxide into contact with an acid, and the acid to be used is not particularly limited, but hydrofluoric acid, sulfuric acid, hydrochloric acid, nitric acid or a mixture thereof is preferable.

酸処理よる酸化物のメソポーラス細孔形成法は特に限定されない。例えば０．０１〜１．００Ｍの酸の水溶液中に、１〜１００ｇの前記酸化物を含浸し、０〜１００℃で充分に攪拌して分散混合した後、水洗し、５０〜２００℃で乾燥することによりメソポーラス細孔を形成することができる。   The method for forming mesoporous pores of oxide by acid treatment is not particularly limited. For example, 1 to 100 g of the above oxide is impregnated in an aqueous solution of 0.01 to 1.00 M acid, and thoroughly stirred and dispersed and mixed at 0 to 100 ° C., then washed with water and dried at 50 to 200 ° C. By doing so, mesoporous pores can be formed.

またアルカリ処理とは、酸化物にアルカリを接触させて、メソポーラス細孔を形成する方法であり、いくつかのアルカリによる処理を挙げることができる。使用するアルカリは特に限定されないが、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化バリウム、炭酸ナトリウム、炭酸水素ナトリウムまたはこれら混合物が好ましい。特に、水酸化ナトリウム、水酸化カリウムが好ましい。   Alkali treatment is a method of forming mesoporous pores by bringing an oxide into contact with an alkali, and several treatments with alkali can be mentioned. The alkali to be used is not particularly limited, but sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate or a mixture thereof is preferable. In particular, sodium hydroxide and potassium hydroxide are preferable.

アルカリ処理による酸化物のメソポーラス細孔形成法は特に限定されない。例えば０．０１〜１．００Ｍのアルカリの水溶液中に、１〜１００ｇの前記酸化物を含浸し、０〜１００℃で充分に攪拌して分散混合した後、水洗し、５０〜２００℃で乾燥することによりメソポーラス細孔を形成することができる。   The method for forming mesoporous pores of oxide by alkali treatment is not particularly limited. For example, 1 to 100 g of the oxide is impregnated in an aqueous solution of 0.01 to 1.00 M alkali, dispersed and mixed with sufficient stirring at 0 to 100 ° C., washed with water, and dried at 50 to 200 ° C. By doing so, mesoporous pores can be formed.

また、担体材料がチタン、ホウ素、ジルコニウムから選ばれる少なくとも一つをケイ素との原子比で０．０１以上含むことが好ましい。担体にチタン、ホウ素、ジルコニウムから選ばれる少なくとも一つを含むことで、担体上に担持された金属触媒と担体との相互作用で触媒活性を制御することができ、生成する３層カーボンナノチューブの物性を制御しやすい。ホウ素、ジルコニウムから選ばれる少なくとも一つとケイ素との原子比は０．０１以上が好ましい。この比率が０．０１未満では担体の触媒活性に及ぼす影響が小さい。一方、この比率が０．１を超えると、逆に触媒活性を抑制する効果が働き、３層カーボンナノチューブの合成量が低減する。このため、ホウ素、ジルコニウムから選ばれる少なくとも一つとケイ素との原子比は０．０１以上、０．１以下が好ましく用いられる。   The carrier material preferably contains at least one selected from titanium, boron, and zirconium in an atomic ratio with silicon of 0.01 or more. By including at least one selected from titanium, boron and zirconium in the support, the catalytic activity can be controlled by the interaction between the metal catalyst supported on the support and the support, and the physical properties of the generated three-walled carbon nanotubes Easy to control. The atomic ratio of at least one selected from boron and zirconium to silicon is preferably 0.01 or more. If this ratio is less than 0.01, the influence on the catalyst activity of the carrier is small. On the other hand, when the ratio exceeds 0.1, the effect of suppressing the catalytic activity is exerted, and the synthesis amount of the three-walled carbon nanotube is reduced. For this reason, the atomic ratio of at least one selected from boron and zirconium to silicon is preferably 0.01 or more and 0.1 or less.

また、本発明の製造方法は、担体が、窒素吸着法による細孔分布測定で２〜１０ｎｍの領域に少なくとも一つのピークを有することが、好ましい。本発明で用いる担体の比表面積および細孔分布は、窒素吸着法により、液体窒素温度での窒素の物理吸着から求めることができる。すなわち、ＢＥＴ法として知られる手法を用い、減圧下に置いた担体に窒素を徐々に投入し、高真空から大気圧の窒素の吸着等温線をとり、大気圧まで到達したら徐々に窒素を減らしていき、窒素の脱着等温線をとるようにすればよい。   In the production method of the present invention, it is preferable that the carrier has at least one peak in a region of 2 to 10 nm by pore distribution measurement by a nitrogen adsorption method. The specific surface area and pore distribution of the carrier used in the present invention can be determined from the physical adsorption of nitrogen at a liquid nitrogen temperature by a nitrogen adsorption method. That is, using a technique known as the BET method, gradually put nitrogen into a carrier placed under reduced pressure, take an adsorption isotherm of nitrogen from high vacuum to atmospheric pressure, and gradually reduce nitrogen when it reaches atmospheric pressure. The nitrogen desorption isotherm should be taken.

細孔径が２から１０ｎｍの領域にある担体の細孔径分布を求めるためには、通常脱着等温線を使用して計算する。細孔径分布を求める理論式としては、Dollimore-Heal法（以下、Ｄ−Ｈ法と略称）が知られている。本発明で定義する細孔径分布は窒素の脱着等温線からＤ−Ｈ法で求めたものであり、この２〜１０ｎｍの領域にピークを一つ以上有する。担体が、細孔分布測定で２〜１０ｎｍの領域に少なくとも一つのピークを有することで、その担体がメソポアを有することを意味し、メソポア径に近い大きさの金属粒子を担持しやすいことを意味する。   In order to obtain the pore size distribution of a carrier having a pore size in the region of 2 to 10 nm, calculation is usually performed using a desorption isotherm. As a theoretical formula for obtaining the pore size distribution, the Dollimore-Heal method (hereinafter abbreviated as DH method) is known. The pore size distribution defined in the present invention is obtained from the desorption isotherm of nitrogen by the DH method, and has one or more peaks in this 2 to 10 nm region. When the carrier has at least one peak in the region of 2 to 10 nm in the pore distribution measurement, it means that the carrier has mesopores, which means that it is easy to carry metal particles having a size close to the mesopore diameter. To do.

また、一般に細孔径分布は、細孔容積（Ｖｐ）を細孔直径（Ｄｐ）で微分した値（△Ｖｐ／△Ｄｐ）を縦軸にとり、横軸に細孔直径（Ｄｐ）をとることで求められ、細孔容量はこのグラフの面積から求めることができる。また、細孔の深さの指標であるΔＶｐ／ΔDｐは特に限定されないが、好ましくは１０００以上である。   In general, the pore size distribution is obtained by taking the value (ΔVp / ΔDp) obtained by differentiating the pore volume (Vp) by the pore diameter (Dp) on the vertical axis and the pore diameter (Dp) on the horizontal axis. The pore volume can be determined from the area of this graph. Further, ΔVp / ΔDp, which is an index of the depth of the pore, is not particularly limited, but is preferably 1000 or more.

また、本発明の製造方法は、担体が、空気中８００℃焼成前後のＸ線回折においてピーク強度の変化率が５％以下であることが、好ましい。本発明で使用する担体が、空気中８００℃焼成前後のＸ線回折においてピーク強度の変化率が５％以下であるとは、担体を、乾燥空気の雰囲気中において、温度８００℃で３０分間焼成するときに、その焼成前後において室温で粉末Ｘ線回折（ＸＲＤ）を測定して、それらの担体における任意の２本のピークを取り出して、そのピーク強度比の変化率が５％以下であることを言う。ピーク強度比は、測定サンプルの調製により変化するので測定に用いる量が一定となるように注意する必要がある。   In the production method of the present invention, the carrier preferably has a peak intensity change rate of 5% or less in X-ray diffraction before and after baking at 800 ° C. in air. The carrier used in the present invention has a rate of change of peak intensity of 5% or less in X-ray diffraction before and after firing at 800 ° C. in air. The carrier is fired at 800 ° C. for 30 minutes in an atmosphere of dry air The powder X-ray diffraction (XRD) is measured at room temperature before and after the firing, and two arbitrary peaks in those carriers are taken out, and the rate of change in the peak intensity ratio is 5% or less. Say. Since the peak intensity ratio varies depending on the preparation of the measurement sample, care must be taken so that the amount used for measurement is constant.

担体が、空気中８００℃焼成前後のＸ線回折においてピーク強度の変化率が５％以下であることは、焼成による構造変化が実質的にないことを示しており、カーボンナノチューブ合成中に担体が変化しないため、好ましい。   The rate of change of the peak intensity in the X-ray diffraction before and after firing at 800 ° C. in air is 5% or less, indicating that there is substantially no structural change due to firing. Since it does not change, it is preferable.

担体の焼成による実質的構造変化の有無は、窒素雰囲気中で５℃／分で昇温して８００℃まで示差熱分析（ＤＴＡ）を行ったとき、６００〜８００℃までに発熱ピークが現れるかどうかでも判断することができる。すなわち、６００〜８００℃の範囲に発熱ピークがないものは８００℃まで実質上構造変化はないと判断できる。   Whether or not there is a substantial structural change due to the firing of the carrier, is an exothermic peak appearing at 600 to 800 ° C. when differential thermal analysis (DTA) is performed up to 800 ° C. by raising the temperature at 5 ° C./min in a nitrogen atmosphere? I can judge it. In other words, it can be determined that those having no exothermic peak in the range of 600 to 800 ° C. have substantially no structural change up to 800 ° C.

温度６００℃以降の測定に、ＤＴＡ曲線が一度上に上がってから下に下がり、そのピークが８００℃以前にある場合は、発熱ピークが現れるという。ピークかどうか判断が付かない場合は、曲線の登りはじめと、下がりきったところを結んでベースラインとし、そのベースラインからの垂線とＤＴＡ曲線が交わったところで一番長いところを選び、その長さが、ノイズの高さの５倍以上の長さがある場合をピークという。また、その交点の温度を読みとり、発熱曲線のピークとする。   In the measurement after a temperature of 600 ° C., when the DTA curve goes up once and then goes down and the peak is before 800 ° C., an exothermic peak appears. If it is not possible to determine whether it is a peak or not, the base line is formed by linking the beginning and end of the curve, and the longest point at the intersection of the perpendicular line from the base line and the DTA curve is selected. However, the case where there is a length of 5 times or more the noise height is called a peak. Also, the temperature at the intersection is read and used as the peak of the exothermic curve.

また、本発明の製造方法は、炭素含有化合物が、炭素数１から５の脂肪族炭化水素、および炭素数１から５のアルコールから選ばれる少なくとも一つを含むことが好ましい。   In the production method of the present invention, the carbon-containing compound preferably contains at least one selected from aliphatic hydrocarbons having 1 to 5 carbon atoms and alcohols having 1 to 5 carbon atoms.

炭素数が１から５の脂肪族炭化水素としては、例えば、メタン若しくはエタン、エチレン、アセチレン、プロパン、プロピレン、プロピン、ノルマルブタン、イソブタン、１−ブテン、２−ブテン、１−ブチン、２−ブチン、ブタジエン、ノルマルペンタン、イソペンタン、ネオペンタン、シクロペンタン、１−ペンテン、２−ペンテン、２−メチル−１−ブテン、３−メチル−１−ブテン、３−メチル−２−ブテン、シクロペンテンが好んで用いられる。炭素数１から５のアルコールとして、例えばメタノール若しくはエタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノールなどが好んで用いられる。   Examples of the aliphatic hydrocarbon having 1 to 5 carbon atoms include methane or ethane, ethylene, acetylene, propane, propylene, propyne, normal butane, isobutane, 1-butene, 2-butene, 1-butyne and 2-butyne. , Butadiene, normal pentane, isopentane, neopentane, cyclopentane, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-2-butene and cyclopentene are preferred. It is done. As the alcohol having 1 to 5 carbon atoms, for example, methanol or ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol and the like are preferably used. .

これらの中でも、特にメタン、エタノール、プロパノールが３層カーボンナノチューブ合成には好ましい炭素含有化合物である。   Among these, methane, ethanol, and propanol are particularly preferable carbon-containing compounds for the synthesis of three-walled carbon nanotubes.

また、本発明の製造方法は、金属触媒に炭素含有化合物を接触させる工程の全圧力が５０００Ｐａ以下であることが好ましい。また、炭素含有化合物の分圧は、１５０Ｐａ以上３０００Ｐａ以下であることが好ましい。とりわけ、金属触媒に炭素含有化合物を接触させる工程の全圧力が５０００Ｐａ以下であり、かつ炭素含有化合物の分圧が１５０Ｐａ以上３０００Ｐａ以下であることがより好ましい。   In the production method of the present invention, the total pressure in the step of bringing the carbon-containing compound into contact with the metal catalyst is preferably 5000 Pa or less. Moreover, it is preferable that the partial pressure of a carbon containing compound is 150 Pa or more and 3000 Pa or less. In particular, it is more preferable that the total pressure in the step of bringing the carbon-containing compound into contact with the metal catalyst is 5000 Pa or less, and the partial pressure of the carbon-containing compound is 150 Pa or more and 3000 Pa or less.

金属触媒に炭素含有化合物を接触させる工程の全圧力が５０００Ｐａを超えると、３層カーボンナノチューブの収率が低下する傾向があり、好ましくない。また、炭素含有化合物の分圧が１５０Ｐａ未満では３層カーボンナノチューブの収率が低下する傾向があり、３０００Ｐａを超えると４層以上の多層カーボンナノチューブの生成が促進される傾向があり、好ましくない。この炭素含有化合物の分圧、炭素含有化合物の触媒への吸着のしやすさ、炭素含有化合物の炭素数を変えることで、生成するカーボンナノチューブの層数を制御することができる。特に、炭素源となる炭素含有化合物にプロパノールを分圧１５０Ｐａ以上３０００Ｐａ以下で用いると、３層カーボンナノチューブの生成しやすいため、さらに好ましい。   If the total pressure in the step of bringing the carbon-containing compound into contact with the metal catalyst exceeds 5000 Pa, the yield of the three-walled carbon nanotube tends to decrease, such being undesirable. Further, when the partial pressure of the carbon-containing compound is less than 150 Pa, the yield of the three-walled carbon nanotube tends to decrease, and when it exceeds 3000 Pa, the generation of the multi-walled carbon nanotube having four or more layers tends to be promoted. By changing the partial pressure of the carbon-containing compound, the ease of adsorption of the carbon-containing compound to the catalyst, and the number of carbon atoms of the carbon-containing compound, the number of carbon nanotube layers to be generated can be controlled. In particular, it is more preferable to use propanol at a partial pressure of 150 Pa or more and 3000 Pa or less as the carbon-containing compound serving as the carbon source because three-walled carbon nanotubes are easily generated.

金属触媒と炭素含有化合物との接触のさせ方は、特に限定されない。例えば、管状炉に設置された石英製、アルミナ製等の耐熱性の反応管内に、上述した金属触媒を置き、減圧、加熱下に炭素含有化合物のガスを流すことにより接触させることができる。金属触媒と炭素含有化合物の接触方法は、上記のような方法のほかに、触媒を噴霧する方法、触媒を攪拌しながら接触させる方法であってもよい。   The method for contacting the metal catalyst with the carbon-containing compound is not particularly limited. For example, the above-described metal catalyst can be placed in a heat-resistant reaction tube made of quartz, alumina, or the like installed in a tubular furnace, and contacted by flowing a carbon-containing compound gas under reduced pressure and heating. The contact method of the metal catalyst and the carbon-containing compound may be a method of spraying the catalyst or a method of bringing the catalyst into contact with stirring, in addition to the above method.

本発明の製造方法により得られる３層カーボンナノチューブは、好ましくは、以下の要件を満たしているものである。   The three-walled carbon nanotube obtained by the production method of the present invention preferably satisfies the following requirements.

すなわち、本発明において、３層カーボンナノチューブは、透過型電子顕微鏡で任意に選択した１００本のカーボンナノチューブ中、５０本以上が３層カーボンナノチューブであることが、好ましい。その測定方法は、透過型電子顕微鏡で１００万倍の倍率で観察し、１５０ｎｍ四方の視野の中で視野面積の１０％以上がカーボンナノチューブで、かつ複数の視野中から任意に抽出した１００本のカーボンナノチューブにおける層数を観察測定し、上記測定を１０箇所について行った平均値で評価するものとする。３層カーボンナノチューブの割合が、１００本中５０本未満であると、機械的強度および耐久性が十分に発揮されず、好ましくない。   That is, in the present invention, it is preferable that 50 or more of the 100 carbon nanotubes arbitrarily selected by the transmission electron microscope are the 3 wall carbon nanotubes. The measurement method was observed with a transmission electron microscope at a magnification of 1,000,000 times, 10% or more of the visual field area was a carbon nanotube in a 150 nm square field of view, and 100 pieces arbitrarily extracted from a plurality of fields of view. The number of layers in the carbon nanotube is observed and measured, and the above measurement is evaluated with an average value obtained for 10 locations. When the ratio of the three-walled carbon nanotube is less than 50 out of 100, the mechanical strength and durability are not sufficiently exhibited, which is not preferable.

また、本発明において、透過型電子顕微鏡で任意に選択した１００本の３層カーボンナノチューブ中、８０本以上がその外径が１．８から５．０ｎｍの範囲内にあることが、好ましい。その測定方法は、透過型電子顕微鏡で１００万倍の倍率で観察し、複数の視野中から任意に抽出した１００本の３層カーボンナノチューブの外径を測定し、その外径が１．８から５．０ｎｍの範囲内にある３層カーボンナノチューブの数を数えて、上記測定を１０箇所について行った平均値で評価するものとする。   In the present invention, it is preferable that 80 or more of 100 three-walled carbon nanotubes arbitrarily selected by a transmission electron microscope have an outer diameter in the range of 1.8 to 5.0 nm. The measurement method was observed with a transmission electron microscope at a magnification of 1,000,000, and the outer diameter of 100 three-walled carbon nanotubes arbitrarily extracted from a plurality of fields of view was measured. The number of the three-walled carbon nanotubes in the range of 5.0 nm is counted, and the above measurement is evaluated with an average value obtained for 10 places.

さらに、本発明において、３層カーボンナノチューブを合成するための反応場に供給するガス中の水素濃度が１００ｐｐｍ以下であることが、好ましい。水素は触媒表面を清浄化する作用があるものの、同時に高温で触媒のシンタリングを促進する。本発明のように炭素原料にアルコールを用いた場合、アルコール自体に触媒を清浄化する作用があることから、水素の添加効果は、シンタリング効果のみが優先するため、好ましくない。   Furthermore, in the present invention, the hydrogen concentration in the gas supplied to the reaction field for synthesizing the three-walled carbon nanotube is preferably 100 ppm or less. Although hydrogen acts to clean the catalyst surface, it simultaneously promotes sintering of the catalyst at high temperatures. When alcohol is used as the carbon raw material as in the present invention, since the alcohol itself has an action of cleaning the catalyst, the effect of adding hydrogen is not preferable because only the sintering effect takes precedence.

本発明の製造方法は、担体が基板の上に製膜されていることも、好ましい。ここで、基板の種類は特に限定されるものではないが、担体材料を塗布する面は１ｍｍ２以上あることが好ましく、１ｃｍ２以上あることがさらに好ましい。基板の材質はガラス、石英ガラス、シリコン、金属、酸化物があげられる。基板上へのメソポーラス材料の製膜方法は特に限定されないが、例えば、粉末状に合成したメソポーラス材料を後からコーティングしてもよいし、基板上にその場合成してもよい。この製膜されたメソポーラス材料上に、金属触媒を担持して、３層カーボンナノチューブを合成することで、３層カーボンナノチューブ基板を得ることができる。 In the production method of the present invention, it is also preferable that the carrier is formed on a substrate. Here, the type of the substrate is not particularly limited, but the surface on which the carrier material is applied is preferably 1 mm 2 or more, and more preferably 1 cm 2 or more. Examples of the material of the substrate include glass, quartz glass, silicon, metal, and oxide. The method for forming the mesoporous material on the substrate is not particularly limited. For example, a mesoporous material synthesized in a powder form may be coated later, or may be formed on the substrate in that case. A three-layer carbon nanotube substrate can be obtained by supporting a metal catalyst on the film-formed mesoporous material and synthesizing the three-layer carbon nanotube.

また、本発明の製造方法は、３層カーボンナノチューブが、実質的に基板から垂直方向に配向成長していることが、好ましい。３層カーボンナノチューブが、実質的に基板から垂直方向に配向成長しているとは、基板断面の電子顕微鏡写真から、任意に選んだ３層カーボンナノチューブの上端と下端を結んだ直線と基板表面とが形成する角度を１０本以上について平均し、その結果が９０°±１０°であることを言う。基板から垂直方向に配向成長することで、フィールドエミッションディスプレイや太陽電池として良好な電子放出特性を示す。   In the production method of the present invention, it is preferable that the three-walled carbon nanotubes are oriented and grown substantially vertically from the substrate. The three-walled carbon nanotubes are substantially aligned and grown in the vertical direction from the substrate. From the electron micrograph of the cross section of the substrate, the straight line connecting the upper and lower ends of the arbitrarily selected three-walled carbon nanotube and the substrate surface The angle formed by is averaged over 10 or more, and the result is 90 ° ± 10 °. Alignment growth in the vertical direction from the substrate shows good electron emission characteristics for field emission displays and solar cells.

また、本発明の製造方法は、炭素含有化合物と金属触媒が接触する反応管において、反応管の上流側に設置した金属触媒で炭素含有化合物を改質し、反応管の下流側に設置した金属触媒で３層カーボンナノチューブを合成することが、好ましい。上流側に設置する金属触媒の金属の種類は、特に限定されないが、好ましくは３〜１２族の金属、より好ましくは、５〜１１族の金属が用いられる。中でも、Ｖ，Ｍｏ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｐｄ，Ｐｔ，Ｒｈ、Ｗ、Ｃｕ等が好ましく、さらに好ましくは、Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｍｎが用いられる。   Further, the production method of the present invention is a method in which, in a reaction tube in which a carbon-containing compound and a metal catalyst are in contact with each other, a carbon-containing compound is reformed with a metal catalyst installed on the upstream side of the reaction tube, It is preferable to synthesize three-walled carbon nanotubes with a catalyst. Although the kind of metal of the metal catalyst installed in an upstream is not specifically limited, Preferably a 3-12 group metal, More preferably, a 5-11 group metal is used. Among these, V, Mo, Mn, Fe, Co, Ni, Pd, Pt, Rh, W, Cu, and the like are preferable, and Fe, Co, Ni, Mo, and Mn are more preferable.

本発明の３層カーボンナノチューブ含有組成物は、下記の要件（１）〜（４）を満たすものである。
（１）透過型電子顕微鏡で任意に選択した１００本のカーボンナノチューブ中、５０本以上が３層カーボンナノチューブであること。
（２）透過型電子顕微鏡で任意に選択した３層カーボンナノチューブ中の屈曲部間距離の平均が１００ｎｍ以上であること。
（３）共鳴ラマン散乱測定により、１５６０〜１６００ｃｍ−１の範囲内で最大のピーク強度をＧ、１３１０〜１３５０ｃｍ−１の範囲内で最大のピーク強度をＤとしたとき、Ｇ／Ｄの比が１０以上であること。
（４）元素分析による金属含有率が１重量％以下であること。 The three-walled carbon nanotube-containing composition of the present invention satisfies the following requirements (1) to (4).
(1) Of 100 carbon nanotubes arbitrarily selected by a transmission electron microscope, 50 or more are three-layer carbon nanotubes.
(2) The average distance between the bent portions in the three-walled carbon nanotube arbitrarily selected by the transmission electron microscope is 100 nm or more.
(3) By resonance Raman scattering measurement, the maximum peak intensity in the range of 1560~1600cm -1 G, when the maximum peak intensity is D within the 1310～1350Cm -1, the ratio of G / D 10 or more.
(4) The metal content by elemental analysis is 1% by weight or less.

このような３層カーボンナノチューブ含有組成物は、本発明の３層カーボンナノチューブの製造方法により、得ることができる。   Such a three-walled carbon nanotube-containing composition can be obtained by the method for producing a three-walled carbon nanotube of the present invention.

ここで、３層カーボンナノチューブ中の屈曲部とは、カーボンナノチューブのグラファイト構造中に炭素５員環と７員環が存在することによる屈曲を言い、高分解能透過型電子顕微鏡写真で図１の通りカーボンナノチューブが折れ曲がって観察される部分のことを言う。   Here, the bent portion in the three-walled carbon nanotube refers to a bent due to the presence of a 5-membered ring and a 7-membered carbon in the graphite structure of the carbon nanotube, and is a high-resolution transmission electron micrograph as shown in FIG. This refers to the portion where carbon nanotubes are bent and observed.

本発明の３層カーボンナノチューブ含有組成物において、高分解能透過型電子顕微鏡で選んだ任意の３層カーボンナノチューブについて屈曲部から屈曲部までの距離の平均を求め、それを１０本以上の３層カーボンナノチューブについて平均した結果が、１００ｎｍ以上であることが好ましい。屈曲部から屈曲部までの距離が長ければ長いほど、３層カーボンナノチューブの直線性は向上し、導電性、熱伝導性が高い３層カーボンナノチューブとなる。屈曲部間距離は長いほど好ましいため、３００ｎｍ以上がより好ましく、５００ｎｍ以上がさらに好ましく、１μｍ以上が最も好ましい。   In the three-walled carbon nanotube-containing composition of the present invention, the average distance from the bent portion to the bent portion is determined for any three-walled carbon nanotube selected with a high-resolution transmission electron microscope, and this is calculated as 10 or more three-layer carbon nanotubes. The averaged result for the nanotubes is preferably 100 nm or more. As the distance from the bent portion to the bent portion is longer, the linearity of the three-walled carbon nanotube is improved, and a three-walled carbon nanotube having higher conductivity and thermal conductivity is obtained. Since the distance between the bent portions is preferably as long as possible, 300 nm or more is more preferable, 500 nm or more is more preferable, and 1 μm or more is most preferable.

また、本発明の３層カーボンナノチューブ含有組成物は、ラマン分光法により品質の評価が可能である。ラマンスペクトルにおいて１５６０〜１６００ｃｍ−１の範囲に見られるラマンシフトはグラファイト由来のＧバンドと呼ばれ、１３１０〜１３５０ｃｍ−１の範囲に見られるラマンシフトはアモルファスカーボンやグラファイトの欠陥に由来のＤバンドと呼ばれる。このＧ／Ｄ比が高いほどグラファイト化度が高く、高品質なカーボンナノチューブを意味する。本発明にある３層カーボンナノチューブは、そのＧ／Ｄ比が１０以上であることが好ましい。より好ましくは１５以上、最も好ましくは２０以上である。 In addition, the quality of the three-walled carbon nanotube-containing composition of the present invention can be evaluated by Raman spectroscopy. In the Raman spectrum, the Raman shift found in the range of 1560 to 1600 cm −1 is called the G band derived from graphite, and the Raman shift found in the range of 1310 to 1350 cm −1 is the D band derived from defects in amorphous carbon and graphite. be called. The higher the G / D ratio, the higher the degree of graphitization, which means a higher quality carbon nanotube. The G / D ratio of the three-walled carbon nanotube in the present invention is preferably 10 or more. More preferably, it is 15 or more, and most preferably 20 or more.

また、本発明の３層カーボンナノチューブ含有組成物は、元素分析による金属含有率が１重量％以下であることが好ましい。金属含有率が高いと、ポリマーへ添加する用途、および医療医薬用途において異物となり、人体へ悪影響を及ぼすことが懸念される。本発明の３層カーボンナノチューブの製造方法では、触媒金属は担体と３層カーボンナノチューブの界面に存在することから、後述の通りその界面で３層カーボンナノチューブを切断することで、容易に３層カーボンナノチューブと金属触媒を分離することができる。金属含有率は低いほど好ましく、より好ましくは０．５重量％以下、最も好ましくは０．１重量％以下である。   In addition, the three-walled carbon nanotube-containing composition of the present invention preferably has a metal content by elemental analysis of 1% by weight or less. When the metal content is high, there is a concern that it may become a foreign substance in a use added to a polymer and a medical and pharmaceutical use, and adversely affect the human body. In the method for producing a three-walled carbon nanotube of the present invention, since the catalytic metal is present at the interface between the support and the three-walled carbon nanotube, the three-walled carbon nanotube can be easily cut by cutting the three-walled carbon nanotube at the interface as described later. Nanotubes and metal catalysts can be separated. The metal content is preferably as low as possible, more preferably 0.5% by weight or less, and most preferably 0.1% by weight or less.

また本発明のカーボンナノチューブ含有組成物は、合成したままの状態で利用してもよく、好ましくは担体材料や触媒金属を除いて使用した方がよい。担体材料や触媒金属は、酸などで取り除くことができる。例えば、担体としてゼオライト、触媒金属としてコバルトを使った場合には、特願２００３−１２６２１１に記述されたように、フッ化水素酸でゼオライトを、塩酸でコバルトを取り除くことができる。また、特願２００４−０４７１８２に記述されたように、水酸化ナトリウム水溶液でもゼオライトを取り除くことができる。さらに、特願２００３−３３１２４０に記述されたように、有機溶媒と水との２液を用いた分離方法で、ゼオライトおよびコバルトとカーボンナノチューブを分離して個別に回収することもできる。また、特願２００３−１２６２１１に記述されたように、触媒金属の量を高度に取り除きたい場合には、焼成処理を行ってから酸で処理するとよい。それは、金属がグラファイトなどの炭素化合物で覆われているため、一度触媒周りの炭素を焼きとばしてから酸処理すれば、金属を効率よく除去することができるからである。   In addition, the carbon nanotube-containing composition of the present invention may be used as it is synthesized, and is preferably used without the support material and the catalyst metal. The support material and the catalyst metal can be removed with an acid or the like. For example, when zeolite is used as the carrier and cobalt is used as the catalyst metal, zeolite can be removed with hydrofluoric acid and cobalt can be removed with hydrochloric acid, as described in Japanese Patent Application No. 2003-126211. Further, as described in Japanese Patent Application No. 2004-047182, zeolite can be removed even with an aqueous sodium hydroxide solution. Further, as described in Japanese Patent Application No. 2003-331240, zeolite, cobalt and carbon nanotubes can be separated and recovered individually by a separation method using two liquids of an organic solvent and water. In addition, as described in Japanese Patent Application No. 2003-126211, when it is desired to remove the amount of the catalytic metal to a high degree, it is preferable to perform a calcination treatment and then treat with an acid. This is because the metal is covered with a carbon compound such as graphite, and therefore, once the carbon around the catalyst is burned out, the metal can be efficiently removed by acid treatment.

本発明の３層カーボンナノチューブ含有組成物は、電子放出材料として有用である。例えば、本発明のカーボンナノチューブ含有組成物をフィールドエミッションの電子源に用いた場合、直径が細く、電荷の集中が起こりやすいので、印加電圧を低く抑えることができる。また、長時間電圧を印加しても単層カーボンナノチューブや２層カーボンナノチューブに比べ大幅に寿命が長いことが特徴である。   The three-walled carbon nanotube-containing composition of the present invention is useful as an electron emission material. For example, when the carbon nanotube-containing composition of the present invention is used as a field emission electron source, the applied voltage can be kept low because the diameter is small and charge concentration tends to occur. In addition, even when a voltage is applied for a long time, the lifetime is significantly longer than single-walled carbon nanotubes and double-walled carbon nanotubes.

また、本発明は、３層カーボンナノチューブ含有組成物を含み、光透過率が８５％以上、かつ表面抵抗が１０００Ω／□以下である透明導電フィルムとして有用である。３層カーボンナノチューブは、直径が適度に細いために光透過の阻害が少なく、かつ単層カーボンナノチューブや２層カーボンナノチューブに比べて直径が太いため、金属的な電気伝導性を示すカーボンナノチューブの含有率が高く、導電性を求められる用途に有利である。   In addition, the present invention is useful as a transparent conductive film containing a three-walled carbon nanotube-containing composition, having a light transmittance of 85% or more and a surface resistance of 1000Ω / □ or less. Three-walled carbon nanotubes contain carbon nanotubes that exhibit metallic electrical conductivity because they are moderately thin and have little light transmission hindrance and are thicker than single-walled or double-walled carbon nanotubes. The rate is high, which is advantageous for applications that require electrical conductivity.

以下、実施例により本発明を具体的に説明するが、下記の実施例は例示のために示すものであって、いかなる意味においても、本発明を限定的に解釈するものとして使用してはならない。   EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are given for illustrative purposes and should not be used in any way as a limited interpretation of the present invention. .

＜実施例１＞
内径３２ｍｍの石英管内を真空引きし、温度８５０℃で１０Ｐａ以下になったことを確認後に、フェロセンを５０Ｐａ、メタンを３００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が１０００Ｐａになるようにガスを調製し、２０分間導入した。メタンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。 <Example 1>
After evacuating the inside of a quartz tube with an inner diameter of 32 mm and confirming that the temperature became 10 Pa or less at a temperature of 850 ° C., the total pressure with ferrocene 50 Pa, methane 300 Pa, and high-purity argon gas (manufactured by High Pressure Gas Industry) becomes 1000 Pa. The gas was prepared and introduced for 20 minutes. After stopping the introduction of methane, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが６０％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．５ｎｍであった。また、屈曲間距離の平均は、約６００ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１７であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０７％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-layered carbon nanotubes was 60%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.5 nm. The average distance between the bends was about 600 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 17. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.07%.

＜実施例２＞
（ＭＣＭ−４１の合成）
セチルトリメチルアンモニウムブロマイド（ＣＴＡＢ：アルドリッチ製）３．６４ｇと、テトラメチルアンモニウムヒドロキシド（ＴＭＡＯＨ：アルドリッチ製）１．４５ｇを３５℃のイオン交換水２８．８ｍｌに加えた後に、ヒュームドシリカ（アルドリッチ製）２．４ｇを加え１時間撹拌した。２０時間エージング後に、オートクレーブに移し、１５０℃で９６時間、水熱合成した。水熱合成後に生成物をろ取、洗浄後に５５０℃で８時間焼成後に、８００℃で１時間焼成した <Example 2>
(Synthesis of MCM-41)
After adding 3.64 g of cetyltrimethylammonium bromide (CTAB: manufactured by Aldrich) and 1.45 g of tetramethylammonium hydroxide (TMAOH: manufactured by Aldrich) to 28.8 ml of ion-exchanged water at 35 ° C., fumed silica (manufactured by Aldrich) ) 2.4g was added and stirred for 1 hour. After aging for 20 hours, it was transferred to an autoclave and hydrothermally synthesized at 150 ° C. for 96 hours. After hydrothermal synthesis, the product was collected by filtration, washed, calcined at 550 ° C. for 8 hours, and then calcined at 800 ° C. for 1 hour.

（ＭＣＭ−４１への金属塩の担持）
硝酸鉄・９水和物（関東化学社製）０．０３ｇと硝酸コバルト・６水和物（関東化学社製）０．１７ｇとをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、ＭＣＭ−４１を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、ＭＣＭ−４１粉末に金属塩が担持された固体触媒を得た。 (Support of metal salt on MCM-41)
0.03 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co., Ltd.) and 0.17 g of cobalt nitrate hexahydrate (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 1.4 g of MCM-41 was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated at 400 degreeC in the air for 1 hour, and obtained the solid catalyst with which the metal salt was carry | supported by MCM-41 powder.

（３層カーボンナノチューブを含有する組成物の合成）
内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を９３０℃に加熱した（昇温時間６０分）。９３０℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、エタノール蒸気を１５００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が４０００Ｐａになるようにガスを調製し、２０分間導入した。エタノール蒸気の導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。 (Synthesis of a composition containing three-walled carbon nanotubes)
On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 930 ° C. (temperature raising time 60 minutes). After reaching 930 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, gas is used so that ethanol vapor is 1500 Pa and the total pressure with high-purity argon gas (manufactured by High Pressure Gas Industry) is 4000 Pa. Was prepared and introduced for 20 minutes. After stopping the introduction of ethanol vapor, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

（３層カーボンナノチューブを含有する組成物の高分解能透過型電子顕微鏡分析）
上記のようにして得たカーボンナノチューブを含有する組成物を高分解能透過型電子顕微鏡で観察したところ、図２のようにカーボンナノチューブはきれいなグラファイト層で構成されており、層数が３層のカーボンナノチューブが７０％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．６ｎｍであった。また、屈曲間距離の平均は、約８００ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。 (High-resolution transmission electron microscope analysis of a composition containing three-walled carbon nanotubes)
When the composition containing the carbon nanotubes obtained as described above was observed with a high-resolution transmission electron microscope, the carbon nanotubes were composed of a clean graphite layer as shown in FIG. Nanotubes were 70%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.6 nm. The average distance between the bends was about 800 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm.

（３層カーボンナノチューブを含有する組成物の共鳴ラマン分光分析）
上記のようにして得たカーボンナノチューブを含有する組成物を共鳴ラマン分光計（ホリバ ジョバンイボン製 ＩＮＦ−３００）でレーザー波数６３０〜６５０ｃｍ−１で測定してＧ／Ｄ比を求めた結果、約１８であり、Ｇバンドは***して観測された。 (Resonance Raman spectroscopic analysis of a composition containing three-walled carbon nanotubes)
The composition containing the carbon nanotubes obtained as described above was measured with a resonance Raman spectrometer (INF-300 manufactured by Horiba Joban Yvon) at a laser wave number of 630 to 650 cm −1 to obtain a G / D ratio. 18 and the G band was split and observed.

（精製・元素分析）
上記のようにして得たカーボンナノチューブを含有する組成物を、空気中４００℃で３０分間焼成した後に、トルエン５０ｃｃ（和光純薬製）に加え、４０分間超音波振動を加えた。次に、イオン交換水５０ｃｃを加え、１０分間、激しく攪拌した。黒色のトルエン相と灰色の水相を分液漏斗で分け、トルエン相をろ過した。トルエン相はカーボンナノチューブを主成分とし、水相はＭＣＭ−４１，触媒金属を主成分とすることを、ＳＥＭおよびＥＤＸ（オックスフォード社製ＩＳＩＳ）で確認した。トルエン相から回収されたカーボンナノチューブ組成物のＥＤＸ元素分析の結果、鉄の含有量は０．０３％、コバルトの含有量は０．２％であった。 (Purification / elemental analysis)
The composition containing carbon nanotubes obtained as described above was baked at 400 ° C. for 30 minutes in air, and then added to 50 cc of toluene (manufactured by Wako Pure Chemical Industries), and subjected to ultrasonic vibration for 40 minutes. Next, 50 cc of ion-exchanged water was added and vigorously stirred for 10 minutes. The black toluene phase and the gray aqueous phase were separated with a separatory funnel, and the toluene phase was filtered. It was confirmed by SEM and EDX (ISIS manufactured by Oxford) that the toluene phase was mainly composed of carbon nanotubes and the aqueous phase was mainly composed of MCM-41 and catalytic metal. As a result of EDX elemental analysis of the carbon nanotube composition recovered from the toluene phase, the iron content was 0.03% and the cobalt content was 0.2%.

＜実施例３＞
硝酸コバルト・６水和物（関東化学社製）０．１７ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、ゼオライト（東レ株式会社製、ボロシリケート）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、ゼオライト粉末に金属塩が担持された固体触媒を得た。 <Example 3>
Cobalt nitrate hexahydrate (manufactured by Kanto Chemical Co.) 0.17 g was dissolved in ethanol (manufactured by Kanto Chemical Co., Ltd.) 15 ml. To this solution, 1.4 g of zeolite (manufactured by Toray Industries, Inc., borosilicate) was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Thereafter, it was heated in air at 400 ° C. for 1 hour to obtain a solid catalyst in which a metal salt was supported on zeolite powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を９００℃に加熱した（昇温時間６０分）。９００℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、プロパノール蒸気を２０００Ｐａ、２０分間導入した。プロパノール蒸気の導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 900 ° C. (temperature rising time 60 minutes). After reaching 900 ° C., the inside of the reaction tube was evacuated, and after confirming that the pressure became 10 Pa or less, propanol vapor was introduced at 2000 Pa for 20 minutes. After the introduction of propanol vapor was stopped, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが７５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．６ｎｍであった。また、屈曲間距離の平均は、約６５０ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１８であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０４％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-layered carbon nanotubes was 75%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.6 nm. The average distance between the bends was about 650 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 18. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.04%.

＜実施例４＞
硝酸ニッケル・６水和物（和光純薬社製）０．１７ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、α−アルミナ（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、α−アルミナ粉末に金属塩が担持された固体触媒を得た。 <Example 4>
0.17 g of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Inc.). To this solution, 1.4 g of α-alumina (manufactured by Wako Pure Chemical Industries, Ltd.) was added, treated with an ultrasonic cleaner for 30 minutes, and ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated in air at 400 degreeC for 1 hour, and obtained the solid catalyst by which the metal salt was carry | supported by the alpha alumina powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を７５０℃に加熱した（昇温時間６０分）。７５０℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、エタンを１５００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が２０００Ｐａになるようにガスを調製し２０分間導入した。エタンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 750 ° C. (temperature raising time 60 minutes). After reaching 750 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure of ethane is 1500 Pa and the total pressure with high purity argon gas (manufactured by High Pressure Gas Industry) is 2000 Pa. Prepared and introduced for 20 minutes. After stopping the introduction of ethane, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが５５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．４ｎｍであった。また、屈曲間距離の平均は、約５５０ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１２であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０２％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-walled carbon nanotube was 55%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.4 nm. The average distance between the bends was about 550 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 12. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.02%.

＜実施例５＞
硝酸鉄・９水和物（関東化学社製）０．３ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、マグネシア（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、マグネシア粉末に金属塩が担持された固体触媒を得た。 <Example 5>
0.3 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co.) was dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 1.4 g of magnesia (manufactured by Wako Pure Chemical Industries, Ltd.) was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated at 400 degreeC in the air for 1 hour, and obtained the solid catalyst by which the metal salt was carry | supported by the magnesia powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を９５０℃に加熱した（昇温時間６０分）。９５０℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、メタンを９００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が３０００Ｐａになるようにガスを調製し２０分間導入した。メタンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 950 ° C. (temperature raising time 60 minutes). After reaching 950 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure with 900 Pa of methane and high-purity argon gas (manufactured by High Pressure Gas Industry) is 3000 Pa. Prepared and introduced for 20 minutes. After stopping the introduction of methane, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが６５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．７ｎｍであった。また、屈曲間距離の平均は、約７５０ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１８であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０９％であった。   When the composition containing the obtained three-layer carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-layer carbon nanotube was 65%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.7 nm. The average distance between the bends was about 750 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 18. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.09%.

＜実施例６＞
硝酸鉄・９水和物（関東化学社製）０．３ｇと塩化モリブデン（和光純薬社製）０．１６ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、チタニア（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、チタニア粉末に金属塩が担持された固体触媒を得た。 <Example 6>
0.3 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co., Ltd.) and 0.16 g of molybdenum chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 1.4 g of titania (manufactured by Wako Pure Chemical Industries, Ltd.) was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Thereafter, the mixture was heated in air at 400 ° C. for 1 hour to obtain a solid catalyst in which a metal salt was supported on titania powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を８００℃に加熱した（昇温時間６０分）。８００℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、プロパンを１５００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が４０００Ｐａになるようにガスを調製し２０分間導入した。プロパンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was placed in an electric furnace, and the center temperature was heated to 800 ° C. (temperature rising time 60 minutes). After reaching 800 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure with propane is 1500 Pa and high-purity argon gas (manufactured by High Pressure Gas Industry) is 4000 Pa. Prepared and introduced for 20 minutes. After the introduction of propane was stopped, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが５５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．５ｎｍであった。また、屈曲間距離の平均は、約７００ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１４であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０８％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-walled carbon nanotube was 55%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.5 nm. The average distance between the bends was about 700 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 14. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.08%.

＜実施例７＞
硝酸マンガン・６水和物（和光純薬社製）０．１７ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、活性炭（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、活性炭粉末に金属塩が担持された固体触媒を得た。 <Example 7>
Manganese nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.17 g was dissolved in ethanol (manufactured by Kanto Chemical Co.) 15 ml. To this solution, 1.4 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated at 400 degreeC in the air for 1 hour, and obtained the solid catalyst with which the activated carbon powder carry | supported the metal salt.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を６５０℃に加熱した（昇温時間６０分）。６５０℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、アセチレンを１５００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が５０００Ｐａになるようにガスを調製し２０分間導入した。アセチレンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was placed in an electric furnace, and the center temperature was heated to 650 ° C. (temperature rising time 60 minutes). After reaching 650 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure with acetylene is 1500 Pa and high-purity argon gas (manufactured by High Pressure Gas Industry) is 5000 Pa. Prepared and introduced for 20 minutes. After stopping the introduction of acetylene, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが５５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．３ｎｍであった。また、屈曲間距離の平均は、約５５０ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１２であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０３％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-walled carbon nanotube was 55%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.3 nm. The average distance between the bends was about 550 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 12. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.03%.

＜実施例８＞
硝酸ニッケル・６水和物（和光純薬社製）０．１７ｇと硝酸コバルト・６水和物（和光純薬社製）０．１７ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、多孔質ステンレス鋼を３．０ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、ステンレス鋼粉末に金属塩が担持された固体触媒を得た。 <Example 8>
Nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.17 g and cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.17 g were dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Inc.). To this solution, 3.0 g of porous stainless steel was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated at 400 degreeC in the air for 1 hour, and obtained the solid catalyst by which the metal salt was carry | supported by the stainless steel powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を７００℃に加熱した（昇温時間６０分）。７００℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、１−ブタノールを１５００Ｐａ、２０分間導入した。１−ブタノールの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 700 ° C. (temperature rising time 60 minutes). After reaching 700 ° C., the inside of the reaction tube was evacuated, and after confirming that the pressure was 10 Pa or less, 1-butanol was introduced at 1500 Pa for 20 minutes. After stopping the introduction of 1-butanol, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが５５％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．４ｎｍであった。また、屈曲間距離の平均は、約６００ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１４であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０９％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-walled carbon nanotube was 55%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.4 nm. The average distance between the bends was about 600 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 14. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.09%.

＜実施例９＞
硝酸鉄・９水和物（関東化学社製）０．３ｇをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、マグネシア（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、マグネシア粉末に金属塩が担持された固体触媒を得た。 <Example 9>
0.3 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co.) was dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 1.4 g of magnesia (manufactured by Wako Pure Chemical Industries, Ltd.) was added, treated with an ultrasonic cleaner for 30 minutes, ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Then, it heated at 400 degreeC in the air for 1 hour, and obtained the solid catalyst by which the metal salt was carry | supported by the magnesia powder.

これとは別に、塩化モリブデン（和光純薬社製）０．１６ｇをエタノール（関東化学社製）１５ｍｌに溶解し、この溶液に、α−アルミナ（和光純薬社製）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、α−アルミナ粉末に金属塩が担持された固体触媒を得た。   Separately, 0.16 g of molybdenum chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.), and 1.4 g of α-alumina (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution. It processed for 30 minutes with the ultrasonic cleaner, ethanol was removed and dried under the constant temperature of 60 degreeC and 120 degreeC. Then, it heated in air at 400 degreeC for 1 hour, and obtained the solid catalyst by which the metal salt was carry | supported by the alpha alumina powder.

内径３２ｍｍの石英管の反応ガス上流側の石英ウール上にモリブデン／α−アルミナ触媒を１．０ｇとり、中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を９００℃に加熱した（昇温時間６０分）。９００℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、メタンを３００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が３０００Ｐａになるようにガスを調製し２０分間導入した。メタンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、３層カーボンナノチューブを含有する組成物を取り出した。   Take 1.0 g of the molybdenum / α-alumina catalyst on the quartz wool on the upstream side of the reaction gas of the quartz tube with an inner diameter of 32 mm, and take 1.0 g of the solid catalyst prepared above on the quartz wool in the center, and add argon gas. It was supplied at 600 cc / min. The quartz tube was installed in an electric furnace, and the center temperature was heated to 900 ° C. (temperature rising time 60 minutes). After reaching 900 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure with methane is 300 Pa and high-purity argon gas (manufactured by High Pressure Gas Industry) is 3000 Pa. Prepared and introduced for 20 minutes. After stopping the introduction of methane, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing three-walled carbon nanotubes was taken out.

得られた３層カーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が３層のカーボンナノチューブが７０％であった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。３層カーボンナノチューブの外径は、平均は２．６ｎｍであった。また、屈曲間距離の平均は、約７５０ｎｍであった。末端部分の構造は、観察された３層カーボンナノチューブの９０％以上が開放端であった。また、金属触媒の粒子直径の８０％以上が２．３から４．５ｎｍであった。ラマンＧ／Ｄ比は約１６であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０９％であった。   When the composition containing the obtained three-walled carbon nanotube was observed with a high-resolution transmission electron microscope, the number of the three-layered carbon nanotubes was 70%. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the three-walled carbon nanotube was 2.6 nm. The average distance between the bends was about 750 nm. As for the structure of the terminal portion, 90% or more of the observed three-walled carbon nanotubes were open ends. Further, 80% or more of the particle diameter of the metal catalyst was 2.3 to 4.5 nm. The Raman G / D ratio was about 16. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.09%.

＜比較例１＞
硝酸鉄・９水和物（関東化学社製）０．０３ｇと硝酸コバルト・６水和物（関東化学社製）０．１７ｇとをエタノール（関東化学社製）１５ｍｌに溶解した。この溶液に、ゼオライト（東レ株式会社製チタノシリケート）を１．４ｇ加え、超音波洗浄機で３０分間処理し、６０℃及び１２０℃の恒温下でエタノールを除去して乾燥した。その後空気中、４００℃で１時間加熱し、ゼオライト粉末に金属塩が担持された固体触媒を得た。 <Comparative Example 1>
0.03 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co., Ltd.) and 0.17 g of cobalt nitrate hexahydrate (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 15 ml of ethanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 1.4 g of zeolite (Titanosilicate manufactured by Toray Industries, Inc.) was added, treated with an ultrasonic cleaner for 30 minutes, and ethanol was removed at a constant temperature of 60 ° C. and 120 ° C. and dried. Thereafter, it was heated in air at 400 ° C. for 1 hour to obtain a solid catalyst in which a metal salt was supported on zeolite powder.

内径３２ｍｍの石英管の中央部の石英ウール上に、上記で調製した固体触媒１．０ｇをとり、アルゴンガスを６００ｃｃ／分で供給した。石英管を電気炉中に設置して、中心温度を８００℃に加熱した（昇温時間６０分）。８００℃に到達した後、反応管内を真空引きし、１０Ｐａ以下になったことを確認後に、アセチレンを６０００Ｐａ、高純度アルゴンガス（高圧ガス工業製）との全圧が３００００Ｐａになるようにガスを調製し、２０分間導入した。アセチレンの導入を止めた後に、アルゴンガスのみを５ｃｃ／分で３０分供給し、温度を室温まで冷却し、カーボンナノチューブを含有する組成物を取り出した。   On the quartz wool at the center of a quartz tube having an inner diameter of 32 mm, 1.0 g of the solid catalyst prepared above was taken, and argon gas was supplied at 600 cc / min. The quartz tube was placed in an electric furnace, and the center temperature was heated to 800 ° C. (temperature rising time 60 minutes). After reaching 800 ° C., the inside of the reaction tube is evacuated, and after confirming that the pressure is 10 Pa or less, the gas is adjusted so that the total pressure of acetylene is 6000 Pa and high-purity argon gas (manufactured by High Pressure Gas Industry) is 30000 Pa. Prepared and introduced for 20 minutes. After the introduction of acetylene was stopped, only argon gas was supplied at 5 cc / min for 30 minutes, the temperature was cooled to room temperature, and a composition containing carbon nanotubes was taken out.

得られたカーボンナノチューブを含有する組成物を、高分解能透過型電子顕微鏡で観察したところ、層数が２層のカーボンナノチューブが６０％で、３層カーボンナノチューブは見られなかった。カーボンナノチューブ以外の炭素不純物（フラーレン、ナノパーティクル、アモルファスカーボン等）はほとんど観察されなかった。２層カーボンナノチューブの外径は、平均は１．５ｎｍであった。また、屈曲間距離の平均は、約１００ｎｍであった。末端部分の構造は、観察された２層カーボンナノチューブの９０％以上が開放端であった。ラマンＧ／Ｄ比は約６であった。精製後のＥＤＸ元素分析の結果、金属触媒含有量は０．０６％であった。   When the composition containing the obtained carbon nanotube was observed with a high-resolution transmission electron microscope, the number of carbon nanotubes with two layers was 60%, and no three-walled carbon nanotubes were observed. Carbon impurities other than carbon nanotubes (fullerene, nanoparticles, amorphous carbon, etc.) were hardly observed. The average outer diameter of the double-walled carbon nanotubes was 1.5 nm. The average distance between the bends was about 100 nm. As for the structure of the terminal portion, 90% or more of the observed double-walled carbon nanotubes were open ends. The Raman G / D ratio was about 6. As a result of EDX elemental analysis after purification, the metal catalyst content was 0.06%.

実施例１〜９および比較例１の製造条件および評価結果を表１に示す。   Table 1 shows the production conditions and evaluation results of Examples 1 to 9 and Comparative Example 1.

Figure 2006298713
Figure 2006298713

＜実施例１０＞
（３層カーボンナノチューブを含む組成物の電子放出特性）
実施例２で得られた３層カーボンナノチューブ組成物を１−プロパノールに分散し、直径１０ｍｍφのステンレス基板上にスプレー塗布した。該基板を、エミッションプロファイラ（東京カソード製）のチャンバー内に設置し、チャンバー内を１０−７Ｐａまで真空引きした。カーボンナノチューブを塗布した基板をカソードとし、アノードを対向して設置し、カソード／アノード間距離を１００μｍに設定した。両電極間に電圧を印加した結果、１３５Ｖ印加時にエミッションに起因する電流値が観察されはじめ、２８０Ｖ印加時に電流値が１０００μＡ／ｃｍ２に達した。 <Example 10>
(Electron emission characteristics of a composition containing three-walled carbon nanotubes)
The three-walled carbon nanotube composition obtained in Example 2 was dispersed in 1-propanol and spray-coated on a stainless steel substrate having a diameter of 10 mmφ. The substrate was placed in a chamber of an emission profiler (manufactured by Tokyo Cathode), and the inside of the chamber was evacuated to 10 −7 Pa. The substrate coated with carbon nanotubes was used as the cathode, the anode was placed facing the substrate, and the cathode / anode distance was set to 100 μm. As a result of applying a voltage between both electrodes, a current value due to emission was observed when 135 V was applied, and the current value reached 1000 μA / cm 2 when 280 V was applied.

＜実施例１１＞
（３層カーボンナノチューブを含む透明導電フィルム）
実施例２で得られた３層カーボンナノチューブ組成物１０ｍｇをイオン交換水に加え、次いでドデシルベンゼンスルホン酸ナトリウム３０ｍｇを添加し、超音波振動を３０分間加えたところ、黒色の懸濁液が得られた。これをＰＥＴフィルム（１０ｃｍ２）に数滴滴下し、バーコーター（Ｎｏ．８）で塗布した。水を乾燥させた後、光透過率と表面抵抗を測定した。上記塗布操作を数回繰り返し、光透過率が８５％以上を維持したときの表面抵抗を測定した結果、５５０Ω／□であった。 <Example 11>
(Transparent conductive film containing three-walled carbon nanotubes)
When 10 mg of the three-walled carbon nanotube composition obtained in Example 2 was added to ion-exchanged water, then 30 mg of sodium dodecylbenzenesulfonate was added, and ultrasonic vibration was added for 30 minutes to obtain a black suspension. It was. A few drops of this were dropped onto a PET film (10 cm 2 ) and applied with a bar coater (No. 8). After drying the water, the light transmittance and the surface resistance were measured. The coating operation was repeated several times, and as a result of measuring the surface resistance when the light transmittance was maintained at 85% or more, it was 550Ω / □.

本発明によれば、直線性の高い３層カーボンナノチューブを高収率で合成することができる。   According to the present invention, a highly linear three-walled carbon nanotube can be synthesized with a high yield.

カーボンナノチューブの屈曲部の高分解能透過型電子顕微鏡写真図である。It is a high-resolution transmission electron microscope photograph figure of the bending part of a carbon nanotube. 実施例２で得られた３層カーボンナノチューブ含有組成物の高分解能透過型電子顕微鏡写真図である。3 is a high-resolution transmission electron microscope photograph of the three-walled carbon nanotube-containing composition obtained in Example 2. FIG.

Claims (21)

炭素含有化合物を、平均直径が１０ｎｍ以下の金属粒子からなる金属触媒と、温度６００〜１０００℃で接触させることにより、３層カーボンナノチューブを主成分とするカーボンナノチューブを製造する３層カーボンナノチューブの製造方法。   Manufacture of a three-layer carbon nanotube for manufacturing a carbon nanotube mainly composed of a three-layer carbon nanotube by bringing a carbon-containing compound into contact with a metal catalyst composed of metal particles having an average diameter of 10 nm or less at a temperature of 600 to 1000 ° C. Method. 前記金属触媒が、担体に担持されている請求項１に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to claim 1, wherein the metal catalyst is supported on a carrier. 前記担体が、金属、酸化物、カーボンから選ばれる少なくとも一つである請求項２に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to claim 2, wherein the carrier is at least one selected from a metal, an oxide, and carbon. 前記酸化物が、ゼオライト、アルミナ、シリカ、チタニア、マグネシアから選ばれる少なくとも一つである請求項３に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to claim 3, wherein the oxide is at least one selected from zeolite, alumina, silica, titania, and magnesia. 前記担体が、窒素吸着法による細孔分布測定で２〜１０ｎｍの領域に少なくとも一つのピークを有する請求項２から４のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 2 to 4, wherein the carrier has at least one peak in a region of 2 to 10 nm by pore distribution measurement by a nitrogen adsorption method. 前記担体が、空気中８００℃焼成前後のＸ線回折においてピーク強度の変化率が５％以下である請求項２から５のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 2 to 5, wherein the carrier has a peak intensity change rate of 5% or less in X-ray diffraction before and after baking at 800 ° C in air. 前記金属触媒が、鉄、コバルト、ニッケル、モリブデン、マンガンから選ばれる少なくとも一つを含む請求項１から６のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 1 to 6, wherein the metal catalyst contains at least one selected from iron, cobalt, nickel, molybdenum, and manganese. 前記炭素含有化合物が、炭素数１から５の脂肪族炭化水素、および炭素数１から５のアルコールからなる群から選ばれる少なくとも一つを含む請求項１から７のいずれか１項に記載の３層カーボンナノチューブの製造方法。   8. The 3 according to claim 1, wherein the carbon-containing compound includes at least one selected from the group consisting of an aliphatic hydrocarbon having 1 to 5 carbon atoms and an alcohol having 1 to 5 carbon atoms. For producing single-walled carbon nanotubes. 前記金属触媒に炭素含有化合物を接触させる工程における前記炭素含有化合物の分圧が、１５０Ｐａ以上３０００Ｐａ以下である請求項１から８のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 1 to 8, wherein a partial pressure of the carbon-containing compound in the step of bringing the carbon-containing compound into contact with the metal catalyst is 150 Pa or more and 3000 Pa or less. 前記炭素含有化合物が、プロパノールである請求項９に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to claim 9, wherein the carbon-containing compound is propanol. 前記金属触媒に炭素含有化合物を接触させる工程の全圧力が、５０００Ｐａ以下である請求項１から１０のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 1 to 10, wherein the total pressure in the step of bringing the carbon-containing compound into contact with the metal catalyst is 5000 Pa or less. 前記３層カーボンナノチューブが、透過型電子顕微鏡で任意に選択した１００本のカーボンナノチューブ中、５０本以上が３層カーボンナノチューブである請求項１から１１のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The three-walled carbon nanotube according to any one of claims 1 to 11, wherein 50 or more of the three-walled carbon nanotubes are three-walled carbon nanotubes among 100 carbon nanotubes arbitrarily selected by a transmission electron microscope. Manufacturing method. 前記３層カーボンナノチューブが、透過型電子顕微鏡で任意に選択した１００本の３層カーボンナノチューブ中、８０本以上がその外径が１．８から５．０ｎｍの範囲内である請求項１から１２のいずれか１項に記載の３層カーボンナノチューブの製造方法。   13. The 100 or more of the three-walled carbon nanotubes arbitrarily selected by a transmission electron microscope, 80 or more of the three-walled carbon nanotubes have an outer diameter in the range of 1.8 to 5.0 nm. The method for producing a three-walled carbon nanotube according to any one of the above. 前記３層カーボンナノチューブを合成する反応場に供給するガス中の水素濃度が、１００ｐｐｍ以下である請求項１から１３のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 1 to 13, wherein a hydrogen concentration in a gas supplied to a reaction field for synthesizing the three-walled carbon nanotube is 100 ppm or less. 前記担体が、基板の上に製膜されている請求項２から１４のいずれか１項に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to any one of claims 2 to 14, wherein the carrier is formed on a substrate. 前記３層カーボンナノチューブが、実質的に基板から垂直方向に配向成長している請求項１５に記載の３層カーボンナノチューブの製造方法。   The method for producing a three-walled carbon nanotube according to claim 15, wherein the three-walled carbon nanotube is oriented and grown substantially vertically from the substrate. 前記炭素含有化合物と金属触媒が接触する反応管において、前記反応管の上流側に設置した金属触媒で炭素含有化合物を改質し、前記反応管の下流側に設置した金属触媒で３層カーボンナノチューブを合成する請求項１から１６のいずれか１項に記載の３層カーボンナノチューブの製造方法。   In the reaction tube in which the carbon-containing compound and the metal catalyst are in contact, the carbon-containing compound is modified with a metal catalyst installed on the upstream side of the reaction tube, and the three-walled carbon nanotube is formed with the metal catalyst installed on the downstream side of the reaction tube The method for producing a three-walled carbon nanotube according to any one of claims 1 to 16, wherein: 前記金属触媒の粒子直径が２．３から４．５ｎｍである金属触媒の数が８０％以上である請求項１から１７のいずれか１項に記載の３層カーボンナノチューブの製造方法。   18. The method for producing a three-walled carbon nanotube according to claim 1, wherein the number of metal catalysts having a particle diameter of 2.3 to 4.5 nm of the metal catalyst is 80% or more. 下記の要件（１）〜（４）を満たす３層カーボンナノチューブ含有組成物。
（１）透過型電子顕微鏡で任意に選択した１００本のカーボンナノチューブ中、５０本以上が３層カーボンナノチューブであること。
（２）透過型電子顕微鏡で任意に選択した３層カーボンナノチューブ中の屈曲部間距離の平均が１００ｎｍ以上であること。
（３）共鳴ラマン散乱測定により、１５６０〜１６００ｃｍ−１の範囲内で最大のピーク強度をＧ、１３１０〜１３５０ｃｍ−１の範囲内で最大のピーク強度をＤとしたとき、Ｇ／Ｄの比が１０以上であること。
（４）元素分析による金属含有率が１重量％以下であること。 A three-walled carbon nanotube-containing composition that satisfies the following requirements (1) to (4).
(1) Of 100 carbon nanotubes arbitrarily selected with a transmission electron microscope, 50 or more are three-layer carbon nanotubes.
(2) The average distance between the bent portions in the three-walled carbon nanotube arbitrarily selected by the transmission electron microscope is 100 nm or more.
(3) By resonance Raman scattering measurement, the maximum peak intensity in the range of 1560~1600cm -1 G, when the maximum peak intensity is D within the 1310～1350Cm -1, the ratio of G / D 10 or more.
(4) The metal content by elemental analysis is 1% by weight or less. 請求項１９に記載の３層カーボンナノチューブ含有組成物を含むことを特徴とする電子放出材料。   An electron emission material comprising the three-walled carbon nanotube-containing composition according to claim 19. 請求項１９に記載の３層カーボンナノチューブ含有組成物を含み、光透過率が８５％以上、かつ表面抵抗が１０００Ω／□以下であることを特徴とする透明導電フィルム。
A transparent conductive film comprising the three-walled carbon nanotube-containing composition according to claim 19, having a light transmittance of 85% or more and a surface resistance of 1000Ω / □ or less.
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