JP5558190B2 - Method for producing long CNT isolated dispersion and carbon nanotube coating film - Google Patents
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本発明は、長尺ＣＮＴの単離分散液の製造方法、およびこの製造方法により製造するカーボンナノチューブ塗工膜に関するものである。 The present invention relates to a method for producing an isolated dispersion of long CNTs, and a carbon nanotube coating film produced by this production method.
カーボンナノチューブ（以下、ＣＮＴという）は、その性状、サイズ、等により、各種用途が期待されている物質である。こうしたＣＮＴのうち、長尺ＣＮＴは、アスペクト比が特に高く、他のＣＮＴと比較して、少量でも導電性発現に有利であることが知られており、その産業上の利用分野は広い。例えば導電性ゴムにおいてはＣＮＴが導電フィラーに利用される。この導電性を高めるうえではＣＮＴのアスペクト比が大きいすなわち長尺のＣＮＴがより導電性の発現には有効とされる。また、長尺ＣＮＴが少量でも導電ネットワーク形成効率が高く導電性を発現できるので、樹脂に混合した場合の物性低下を抑制することもできる。このようにして、長尺ＣＮＴの用途がある。このような長尺ＣＮＴが各種形態でＣＮＴが分散している粗ＣＮＴ分散液中に存在している場合では、その粗ＣＮＴ分散液から長尺ＣＮＴのみを得る技術が要求される。なお、長尺ＣＮＴ、短尺ＣＮＴを問わず、高濃度領域では或る程度の導電性の発現を認められるが、比較的少量、低濃度領域ではＣＮＴ長さの効果が顕著となる。また、一般に、ＣＮＴは、合成時に一定長さに制御されていても、その後の分散プロセスにおいて切断による短尺化が進行するものの、その直径は変化しない。 Carbon nanotubes (hereinafter referred to as CNT) are substances that are expected to be used for various purposes depending on their properties, sizes, and the like. Among these CNTs, long CNTs have a particularly high aspect ratio and are known to be advantageous for the development of conductivity even in a small amount as compared with other CNTs, and their industrial application fields are wide. For example, in conductive rubber, CNT is used as a conductive filler. In order to increase the conductivity, a CNT having a large aspect ratio, that is, a long CNT, is effective in developing the conductivity. Moreover, since the conductive network formation efficiency is high and conductivity can be expressed even with a small amount of long CNTs, it is possible to suppress deterioration of physical properties when mixed with resin. Thus, there is a use of long CNT. When such long CNTs are present in a crude CNT dispersion in which CNTs are dispersed in various forms, a technique for obtaining only long CNTs from the coarse CNT dispersion is required. It should be noted that, regardless of whether it is long CNT or short CNT, a certain degree of conductivity is observed in the high concentration region, but the effect of the CNT length becomes significant in a relatively small amount of the low concentration region. In general, even if the CNTs are controlled to have a certain length at the time of synthesis, the diameter of the CNTs does not change, although shortening due to cutting proceeds in the subsequent dispersion process.
なお、特許文献１にはカラムクロマトグラフィを用いてＣＮＴをナノチューブとナノ粒子以外の炭素物質に分離し、さらにナノチューブとナノ粒子の分子量、形状の差による展開速度の差でＣＮＴを分離する技術が開示されているが、粗ＣＮＴ分散液中から長尺ＣＮＴのみを分離して得る具体技術は開示も示唆もされていない。 Patent Document 1 discloses a technique for separating CNTs into carbon materials other than nanotubes and nanoparticles using column chromatography, and further separating CNTs based on differences in the development speed due to differences in the molecular weight and shape of the nanotubes and nanoparticles. However, there is no disclosure or suggestion of a specific technique obtained by separating only long CNTs from the crude CNT dispersion.
粗ＣＮＴ分散液中では、ＣＮＴは長尺や短尺の形態で分散していたり、あるいはファンデルワールス力で長尺や短尺を問わず塊状、束状の凝集物になって分散している。そうした粗ＣＮＴ分散液中から長尺ＣＮＴのみを得ることは容易ではない。 In the crude CNT dispersion, the CNTs are dispersed in a long or short form, or are dispersed in the form of agglomerates or bundles regardless of the long or short form by van der Waals force. It is not easy to obtain only long CNTs from such a crude CNT dispersion.
本発明においては、粗ＣＮＴ分散液から長尺ＣＮＴが単離分散した単離分散液の製造方法を提供し、また、その方法により製造した長尺ＣＮＴの単離分散液を用いたＣＮＴ塗工膜を提供することを解決すべき課題としている。 In the present invention, a method for producing an isolated dispersion in which long CNTs are isolated and dispersed from a crude CNT dispersion is provided, and a CNT coating using the long CNT isolated dispersion produced by the method is provided. Providing a film is a problem to be solved.
本発明第１による長尺ＣＮＴの単離分散液の製造方法は、長尺ＣＮＴに対応した所定粒径範囲のビーズをカラム中に固定相として充填する第１ステップと、各種形状のＣＮＴを含む粗ＣＮＴ分散液を移動相として前記カラム入口から該カラム内に展開する第２ステップと、上記カラム出口から順次に形状ごとに揃って流れ出てくる各種単離分散液から長尺ＣＮＴの単離分散液を選択する第３ステップと、を含むことを特徴とする。 The method for producing an isolated dispersion of long CNTs according to the first aspect of the present invention includes a first step of filling beads having a predetermined particle size range corresponding to the long CNTs as a stationary phase in the column, and CNTs having various shapes. A second step of developing the crude CNT dispersion liquid from the column inlet into the column as a mobile phase, and isolating and dispersing long CNTs from various isolated dispersion liquids flowing out from the column outlet in order for each shape. And a third step of selecting a liquid.
本発明第２によるＣＮＴ分散液の製造方法は、長尺ＣＮＴに対応した所定粒径範囲のビーズを固定相としてカラム中に充填する第１ステップと、各種形状のＣＮＴを含む粗ＣＮＴ分散液を上記カラム内の固定相上に展開する第２ステップと、上記カラム内に所定の溶媒を移動相として流す第３ステップと、上記カラム出口から順次に形状ごとに揃って流れ出てくる各種単離分散液から長尺ＣＮＴの単離分散液を選択する第４ステップと、を含むことを特徴とする。 The method for producing a CNT dispersion according to the second aspect of the present invention includes a first step of filling a column with beads having a predetermined particle size range corresponding to long CNTs as a stationary phase, and a crude CNT dispersion containing CNTs of various shapes. A second step of developing on the stationary phase in the column; a third step of flowing a predetermined solvent as a mobile phase in the column; and various isolation dispersions flowing out from the column outlet in order for each shape. And a fourth step of selecting an isolated dispersion of long CNTs from the liquid.
好ましくは、上記選択は、カラム出口から長尺ＣＮＴの展開速度に応じたタイミングで出てくる長尺ＣＮＴの単離分散液を選択することである。 Preferably, the selection is to select an isolated dispersion of long CNT that comes out from the column outlet at a timing corresponding to the development speed of the long CNT.
好ましくは、上記カラムに充填するビーズの粒径範囲は０．０５ｍｍ〜５ｍｍであり、より好ましくは、０．１ｍｍ〜１ｍｍ、最適には０．３５ｍｍ〜０．５ｍｍである。なお、ビーズ径が０．０５ｍｍ未満であるとＣＮＴがカラム中に展開せず、また、５ｍｍ超であると形状ごとの分離が困難である。 Preferably, the particle size range of the beads packed into the column is 0.05 mm to 5 mm, more preferably 0.1 mm to 1 mm, and most preferably 0.35 mm to 0.5 mm. When the bead diameter is less than 0.05 mm, the CNTs do not expand in the column, and when the bead diameter exceeds 5 mm, separation by shape is difficult.
上記長尺ＣＮＴの長さは、好ましくは５μｍ以上である。 The length of the long CNT is preferably 5 μm or more.
上記長尺ＣＮＴは、単層ＣＮＴでも多層ＣＮＴでもよい。 The long CNT may be a single-wall CNT or a multi-wall CNT.
また、上記長尺ＣＮＴは、その直径に限定されない。 The long CNT is not limited to its diameter.
上記ビーズは、無機質ビーズ、プラスチックビーズ、金属ビーズ、等を含むことができる。無機質ビーズには、ガラス、セラミック（アルミナ、ジルコニア等）、を含む。プラスチックビーズには、ポリエチレン、ポリプロピレン、テフロン（登録商標）、アクリル樹脂、ポリカーボネイト、等を含む。 The beads can include inorganic beads, plastic beads, metal beads, and the like. The inorganic beads include glass and ceramic (alumina, zirconia, etc.). Plastic beads include polyethylene, polypropylene, Teflon (registered trademark), acrylic resin, polycarbonate, and the like.
カラム内にはそのカラム入口側からカラム出口側まで粒径一定のビーズを充填するが、粒径が上記範囲内であれば、粒径が多少相違してもよい。カラム出口側には上記粒径の上限を超過した粒径のビーズを配置してもよい。 The column is filled with beads having a constant particle size from the column inlet side to the column outlet side, but the particle size may be slightly different as long as the particle size is within the above range. You may arrange | position the bead of the particle size which exceeded the upper limit of the said particle size on the column exit side.
粗ＣＮＴ分散液は、少なくとも長尺ＣＮＴが他の形態のＣＮＴ、例えば短尺ＣＮＴおよび／または塊状ないし束状に凝集しているＣＮＴと共に複数分散している分散液である。したがって、粗ＣＮＴ分散液には複数の長尺ＣＮＴに対して他のＣＮＴが各種組合せで分散している。 The crude CNT dispersion is a dispersion in which a plurality of long CNTs are dispersed together with CNTs in other forms, for example, short CNTs and / or CNTs aggregated in a lump or bundle. Therefore, in the coarse CNT dispersion, other CNTs are dispersed in various combinations with respect to the plurality of long CNTs.
本発明第１、第２の製造方法により製造した長尺ＣＮＴの単離分散液は、溶媒中に長尺ＣＮＴが単離状態で分散している溶液である。 The long CNT isolated dispersion produced by the first and second production methods of the present invention is a solution in which long CNTs are dispersed in a solvent in an isolated state.
本発明第１、第２の長尺ＣＮＴの単離分散液中には、長尺ＣＮＴ以外の他の形態のＣＮＴも含むことがある。したがって、本発明第１の第３ステップ、本発明第２の第４ステップを一部に実施する限りにおいては、長尺ＣＮＴと共にこの長尺ＣＮＴ以外のＣＮＴを一部に含む単離分散液も本発明の範囲に含む単離分散液である。 The isolated dispersion liquid of the first and second long CNTs of the present invention may contain other forms of CNTs other than the long CNTs. Therefore, as long as the first third step of the present invention and the fourth step of the second embodiment of the present invention are performed in part, an isolated dispersion liquid that includes CNTs other than the long CNT together with the long CNT is also included. It is an isolated dispersion within the scope of the present invention.
本発明によれば、粗ＣＮＴ分散液から長尺ＣＮＴが分散した単離分散液を得ることができる。 According to the present invention, an isolated dispersion in which long CNTs are dispersed from a crude CNT dispersion can be obtained.
以下、添付した図面を参照して、本発明の実施の形態に係るＣＮＴ分散液の製造方法を説明する。図１に粗ＣＮＴ分散液を示す。粗ＣＮＴ分散液１は、その一部拡大を円Ａ内で示すように、複数のＣＮＴがファンデルワールス力により塊状に凝集集合してなる複数の集合物２ａ、複数のＣＮＴが束状に凝集集合してなる複数の集合物２ｂ、長さが一定以下で上記凝集集合形態をとらずに単離している複数の短尺ＣＮＴ２ｃ、長さが一定以上で上記凝集集合形態をとらずに単離している複数の長尺ＣＮＴ２ｄを示す。また、これ以外の形態で分散するＣＮＴも含む。ここで、実施形態における長尺ＣＮＴ２ｄの長さは、短尺ＣＮＴと比較して相対的であり、上記背景技術で説明したように産業用途に応じて決めることができ、実施形態では、例えば５μｍ以上のＣＮＴを長尺ＣＮＴとし、５μｍ未満のＣＮＴを短尺ＣＮＴと言うこととする。このような図１で示すような粗ＣＮＴ分散液１は本発明を限定するものではなく、長尺ＣＮＴ２ｄに対して、集合物２ａ，２ｂ，短尺ＣＮＴ２ｃの少なくともいずれか１つ、あるいは実施形態では記載していない他の形態のＣＮＴをも含む分散液であれば粗ＣＮＴ分散液１に含むことができる。 Hereinafter, a method for producing a CNT dispersion according to an embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 1 shows a crude CNT dispersion. As shown in the circle A, the coarse CNT dispersion 1 shows a plurality of aggregates 2a formed by agglomerating and aggregating a plurality of CNTs in a lump by van der Waals force, and a plurality of CNTs agglomerating in a bundle. A plurality of aggregates 2b formed by aggregation, a plurality of short CNTs 2c having a length that is less than a certain length and not taking the aggregated aggregate form, and a length that is greater than a certain value and not taking the aggregated aggregate form A plurality of long CNTs 2d are shown. In addition, CNTs dispersed in other forms are also included. Here, the length of the long CNT 2d in the embodiment is relative to that of the short CNT, and can be determined according to the industrial application as described in the background art, and in the embodiment, for example, 5 μm or more. These CNTs are referred to as long CNTs, and CNTs less than 5 μm are referred to as short CNTs. Such a coarse CNT dispersion 1 as shown in FIG. 1 does not limit the present invention, and is not limited to the long CNT 2d, but at least one of the aggregates 2a, 2b and the short CNT 2c, or in the embodiment. Any dispersion containing other forms of CNTs not described can be included in the crude CNT dispersion 1.
粗ＣＮＴ分散液１における溶媒は、ＣＮＴを分散できる溶媒であれば特に限定しないが、実施形態ではこの溶媒は例えばエチルセルロース系樹脂と、ブチルカルビトールアセテートと、エタノールとを含んでいる。 The solvent in the crude CNT dispersion 1 is not particularly limited as long as it is a solvent that can disperse CNTs. However, in the embodiment, this solvent includes, for example, an ethyl cellulose resin, butyl carbitol acetate, and ethanol.
図２を参照してカラムクロマトグラフィを説明すると、実施形態のカラムクロマトグラフィに用いるカラム（管柱）３は、例えばガラス、ステンレス、アクリル樹脂等からなり、図２（ａ）で示すようにカラム出口３ａが小径となっている以外は一定内径のカラムである。このカラムクロマトグラフィでは、図２（ｂ）で示すようにカラム３内にはカラム充填剤（固定相）としてガラスビーズが充填される。ガラスビーズはカラム出口側３ａには大径のガラスビーズ４ａが充填され、その大径ガラスビーズ４ａの充填位置からカラム入口側３ｂへかけて一定小径のガラスビーズ４ｂが充填される。大径のガラスビーズ４ａがカラム出口側３ａに充填されるのは、カラム出口３ａからガラスビーズ４ｂが流出するのを防止するためである。この小径ガラスビーズ４ｂの粒径は、０．０５ｍｍ〜５ｍｍの範囲において、粒径一定のガラスビーズ４ｂが選択されて配置される。このガラスビーズ４ｂの粒径は、粗ＣＮＴ分散液１内の集合物２ａ，２ｂ、短尺ＣＮＴ２ｃ、長尺ＣＮＴ２ｄとの接触に関わる表面積、接触経路等に関わり、粗ＣＮＴ分散液１からの長尺ＣＮＴ２ｄの分離効率を決めることに関与する。なお、ガラスビーズ４ｂの形状は球状（真円球、楕円球、等）であることが好ましい。 The column chromatography will be described with reference to FIG. 2. The column (tube column) 3 used in the column chromatography of the embodiment is made of, for example, glass, stainless steel, acrylic resin, and the like, and as shown in FIG. Is a column with a constant inner diameter except that has a small diameter. In this column chromatography, as shown in FIG. 2B, the column 3 is filled with glass beads as a column filler (stationary phase). The glass beads are filled with a large-diameter glass bead 4a on the column outlet side 3a, and are filled with a constant small-diameter glass bead 4b from the filling position of the large-diameter glass bead 4a to the column inlet side 3b. The reason why the large diameter glass beads 4a are filled in the column outlet side 3a is to prevent the glass beads 4b from flowing out from the column outlet 3a. The small diameter glass beads 4b have a particle diameter of 0.05 mm to 5 mm, and the glass beads 4b having a constant particle diameter are selected and arranged. The particle size of the glass beads 4b is related to the surface area, contact path, etc. associated with the aggregates 2a, 2b, short CNTs 2c, and long CNTs 2d in the coarse CNT dispersion 1, and the long beads from the coarse CNT dispersion 1 It is involved in determining the separation efficiency of CNT2d. In addition, it is preferable that the shape of the glass bead 4b is spherical (a perfect sphere, an ellipsoid, etc.).
次に、このように粒径０．０５ｍｍ〜５ｍｍの範囲で選択されたガラスビーズ４ｂが充填されたカラム３に対して、図２（ｃ）で示すようにカラム入口側３ｂから粗ＣＮＴ分散液（移動相）１を展開溶媒として投入する。この粗ＣＮＴ分散液１内の溶媒は重力あるいはカラム入口側３ｂから図示略の加圧装置で加圧、あるいはカラム出口側３ａから図示略の吸引装置での吸引により、カラム出口側３ａ側から粗ＣＮＴ分散液１内のＣＮＴの形状差に基づいた展開速度差によりＣＮＴを分離する。この分離の様子を図２（ｄ）に示す。図２（ｄ）はカラム３内のカラム充填剤であるガラスビーズ４ａ，４ｂの図示を略した状態で粗ＣＮＴ分散液１内のＣＮＴのモデル的分離形態を示す。このＣＮＴ形態のうち、塊状の集合形態である集合物２ａが最も分離されずに展開速度が最も遅いのでカラム入口側３ｂにあり、束状の集合形態である集合物２ｂは塊状集合物２ａよりも展開速度が速いので塊状集合物２ａよりもカラム出口３ａ側に近く位置し、長尺ＣＮＴ２ｄは束状集合物２ｂよりも展開速度が速いのでさらにカラム出口３ａ側に束状集合物２ｂよりは近く位置し、短尺ＣＮＴ２ｃは最も展開速度が速いのでカラム出口３ａ側に最も近い。そして、このカラム３からはこの展開速度の順序でＣＮＴが出てくるので、長尺ＣＮＴ２ｄの展開速度に応じたタイミングに合わせてＣＮＴ分散液を選択すると、長尺ＣＮＴ２ｄが単離状態で分散しているＣＮＴ分散液（長尺ＣＮＴ単離分散液）を得ることができる。 Next, as shown in FIG. 2 (c), the crude CNT dispersion liquid is supplied from the column inlet side 3b to the column 3 packed with the glass beads 4b selected in the particle diameter range of 0.05 mm to 5 mm. (Mobile phase) 1 is charged as a developing solvent. The solvent in the crude CNT dispersion 1 is coarsely applied from the column outlet side 3a side by gravity or pressurized from the column inlet side 3b by a pressurizing device (not shown) or sucked from the column outlet side 3a by a suction device (not shown). The CNTs are separated by the difference in the development speed based on the shape difference of the CNTs in the CNT dispersion liquid 1. The state of this separation is shown in FIG. FIG. 2 (d) shows a model separation form of CNTs in the crude CNT dispersion 1 with the glass beads 4 a and 4 b being column fillers in the column 3 omitted. Among the CNT forms, the aggregate 2a which is a massive aggregate form is not separated most and the development speed is the slowest, so it is on the column inlet side 3b, and the aggregate 2b which is a bundle-like aggregate form is more than the massive aggregate 2a. Since the development speed is fast, it is positioned closer to the column outlet 3a side than the massive aggregate 2a, and the long CNT 2d is faster than the bundle aggregate 2b, so that it is further closer to the column outlet 3a than the bundle aggregate 2b. The short CNT 2c is located closest to the column outlet 3a side because it has the fastest deployment speed. Since the CNTs come out from the column 3 in the order of the developing speed, when the CNT dispersion liquid is selected in accordance with the timing corresponding to the developing speed of the long CNT 2d, the long CNT 2d is dispersed in an isolated state. CNT dispersion liquid (long CNT isolation dispersion liquid) can be obtained.
なお、図３（ａ）では、ガラスビーズが粒径５ｍｍ超の大径のガラスビーズ４ｂ１である場合、塊状集合物２ａ、束状集合物２ｂ、短尺ＣＮＴ２ｃ、長尺ＣＮＴ２ｄのいずれもがカラム３内では分離されない様子を示す。図３（ｂ）ではガラスビーズが粒径０．０５ｍｍ〜５ｍｍのガラスビーズ４ｂ２である場合、塊状集合物２ａ、束状集合物２ｂ、短尺ＣＮＴ２ｃ、長尺ＣＮＴ２ｄいずれもカラム３内で分離されている様子を示す。図３（ｃ）ではガラスビーズが粒径０．０５ｍｍ未満のガラスビーズ４ｂ３である場合、塊状集合物２ａ、束状集合物２ｂ、短尺ＣＮＴ２ｃ、長尺ＣＮＴ２ｄいずれもカラム３内で分離されない様子を示す。以上からガラスビーズは粒径０．０５ｍｍ〜５ｍｍの範囲内であることが好ましい。
In FIG. 3A, when the glass beads are large-diameter glass beads 4b1 having a particle diameter of more than 5 mm, all of the aggregated aggregate 2a, bundled aggregate 2b, short CNT2c, and long CNT2d are in column 3. It shows how it is not separated. In FIG. 3B, when the glass beads are glass beads 4b2 having a particle diameter of 0.05 mm to 5 mm, all of the aggregate 2a, the bundle 2b, the short CNT 2c, and the long CNT 2d are separated in the column 3. It shows how it is. In FIG. 3C, when the glass beads are glass beads 4b3 having a particle size of less than 0.05 mm, the bulk aggregate 2a, the bundle aggregate 2b, the short CNT 2c, and the long CNT 2d are not separated in the column 3. Show. From the above, it is preferable that the glass beads have a particle diameter of 0.05 mm to 5 mm.
次にビーズ４ｂは表面処理することでＣＮＴ長さの分布をより細やかに高精度にして分離することができる。すなわち、カラムクロマトグラフィでは移動相である粗ＣＮＴ分散液と、粗ＣＮＴ分散液内の成分と、カラム充填剤との相互関係（親和性）の違いを利用することで成分ごとに分離するものである。そしてビーズ４ｂに表面処理を施すことで上記相互関係を調整し、上記成分の分離度とか処理効率（展開速度）等を向上させることができる。 Next, the beads 4b can be separated with a finer and more precise distribution of CNT lengths by surface treatment. That is, in column chromatography, the components are separated by utilizing the difference (affinity) between the crude CNT dispersion that is the mobile phase, the components in the crude CNT dispersion, and the column filler. . Then, by applying a surface treatment to the beads 4b, the mutual relationship can be adjusted, and the degree of separation of the components, processing efficiency (development speed), and the like can be improved.
実施形態のカラム充填剤としてはガラスビーズに限定されないが、ガラスビーズ以外でも、その粒径範囲は同様またはほぼ同様である。 The column filler of the embodiment is not limited to glass beads, but the particle size range is the same or substantially the same except for glass beads.
図４（ａ）に長さが一定以上の長尺ＣＮＴ２ｄのみが単離して分散している長尺ＣＮＴ単離分散液５を示し、図４（ｂ）に長さが一定以下の短尺ＣＮＴ２ｃのみが単離した短尺ＣＮＴ単離分散液６を示す。 FIG. 4 (a) shows a long CNT isolation dispersion 5 in which only long CNTs 2d having a certain length or more are isolated and dispersed, and FIG. 4 (b) shows only short CNTs 2c having a certain length or less. Shows the isolated short CNT dispersion 6.
（ａ）ＥＣビヒクル（日新化成社製ＥＣ−１００ＦＴＰ、エチルセルロースとブチルカルビトールアセテートの混合物）１００ｇに、熱ＣＶＤ法により合成したＣＮＴ（基板上に合成されて非晶質炭素を含む長短各種形態のＣＮＴ）１０ｍｇを投入し、分散装置である回転式ホモジナイザ−で１時間攪拌する。これにより粗ＣＮＴ分散液を得る。 (A) CNTs synthesized by a thermal CVD method on 100 g of an EC vehicle (EC-100 FTP manufactured by Nisshin Kasei Co., Ltd., a mixture of ethyl cellulose and butyl carbitol acetate) (a variety of long and short forms containing amorphous carbon and synthesized on a substrate) Of CNT), and stirred for 1 hour with a rotary homogenizer serving as a dispersion apparatus. Thereby, a crude CNT dispersion is obtained.
（ｂ）上記（ａ）で得た粗ＣＮＴ分散液を攪拌しつつエタノールで１０倍の粗ＣＮＴ分散液に希釈する。 (B) The crude CNT dispersion obtained in (a) above is diluted to 10 times the crude CNT dispersion with ethanol while stirring.
（ｃ）クロマトグラフィ用のカラム管（硼珪酸ガラス、カラム長３００ｍｍ、内径２０ｍｍ）にガラスビーズ（ソーダガラス、直径０．１０５ｍｍ〜０．１２５ｍｍ）とエタノールとを高さ５０ｍｍとなるように充填し、（ｂ）で得た粗ＣＮＴ分散液４ｍｌをカラムに展開させる。 (C) A column tube for chromatography (borosilicate glass, column length 300 mm, inner diameter 20 mm) is filled with glass beads (soda glass, diameter 0.105 mm to 0.125 mm) and ethanol so that the height is 50 mm, 4 ml of the crude CNT dispersion obtained in (b) is developed on a column.
（ｄ）カラム中を透過したＣＮＴ分散液を１ｍｌずつ分取し３番目および４番目の液をロータリーエバポレータ−を用いて減圧除去してエタノールを除去する。 (D) 1 ml of CNT dispersion liquid permeated through the column is fractionated, and the third and fourth liquids are removed under reduced pressure using a rotary evaporator to remove ethanol.
（ｅ）上記で得たＣＮＴ分散液をバーコーターを用いて基板上に塗布する。 (E) The CNT dispersion obtained above is applied onto a substrate using a bar coater.
（ｆ）上記塗布したＣＮＴ分散液を１５０℃雰囲気で乾燥し、ＣＮＴ塗工膜を得る。 (F) The coated CNT dispersion is dried in an atmosphere of 150 ° C. to obtain a CNT coated film.
なお、上記分散装置としては回転式ホモジナイザ−以外に超音波ホモジナイザ−、圧力式ホモジナイザ−、ボールミル、ビーズミル等がある。 Examples of the dispersing device include an ultrasonic homogenizer, a pressure homogenizer, a ball mill, a bead mill and the like in addition to the rotary homogenizer.
図５（ａ）に粗ＣＮＴ分散液１（カラムクロマトグラフィ未処理分散液）を基板上に塗工した場合のＣＮＴ塗工膜表面の状態のＳＥＭ写真（×５０ｋ）と表面抵抗率（Ω／□）と波長５５０ｎｍの光の透過率（％）とを示し、図５（ｂ）に実施形態の長尺ＣＮＴ単離分散液５（カラムクロマトグラフィ処理分散液）を基板上に塗工した場合のＣＮＴ塗工膜表面の状態をＳＥＭ写真（×５０ｋ）と表面抵抗率（Ω／□）と上記光透過率（％）とを示す。 FIG. 5 (a) shows an SEM photograph (× 50k) and surface resistivity (Ω / □) of the surface of the CNT-coated film when the crude CNT dispersion 1 (column chromatography untreated dispersion) was applied on the substrate. ) And the transmittance (%) of light having a wavelength of 550 nm, and FIG. 5B shows the CNT when the long CNT isolation dispersion 5 (column chromatography treatment dispersion) of the embodiment is applied on the substrate. The state of the coating film surface is shown by an SEM photograph (× 50k), surface resistivity (Ω / □), and the light transmittance (%).
これらをＳＥＭ写真で比較して示すように、図５の左側ＳＥＭ写真で示す未処理ＣＮＴ塗工膜では表面抵抗率１．３×１０4、図５（ｂ）の右側ＳＥＭ写真で示す処理ＣＮＴ塗工膜では表面抵抗率３．８×１０3、であり、光透過率は未処理ＣＮＴ塗工膜で８９．０％、処理ＣＮＴ塗工膜で９２．８％であった。これらＳＥＭ写真の比較で明らかであるように、未処理ＣＮＴ塗工膜には塊状や束状の凝集物が存在していることにより表面全体に互いに入り組んだ線状の凹凸が存在している。これに対して本実施形態のＣＮＴ塗工膜では、塊状や束状の凝集物が存在しないため、表面全体の平坦性が高く、透明性も高いので、例えば透明電極の用途に適する。 As shown in comparison with SEM photographs, the untreated CNT-coated film shown in the left SEM photograph of FIG. 5 has a surface resistivity of 1.3 × 10 4 , and the treated CNT shown in the right SEM photograph of FIG. The coated film had a surface resistivity of 3.8 × 10 3 , and the light transmittance was 89.0% for the untreated CNT-coated film and 92.8% for the treated CNT-coated film. As is clear from the comparison of these SEM photographs, the untreated CNT coated film has lumps and bundles of linear aggregates due to the presence of massive aggregates and bundles. On the other hand, in the CNT coating film of this embodiment, since no aggregates or bundles are present, the flatness of the entire surface is high and the transparency is also high.
以上説明したように本実施形態では、カラムクロマトグラフィに用いるカラム中に長尺ＣＮＴに対応したビーズ径０．０５ｍｍ〜５ｍｍの範囲内のビーズを充填剤として充填するようにしたので、長尺ＣＮＴを含む単離分散液を効果的に得ることができる。 As described above, in the present embodiment, beads in a range of beads having a diameter of 0.05 mm to 5 mm corresponding to the long CNT are packed as fillers in the column used for column chromatography. An isolated dispersion containing it can be obtained effectively.
１ 粗ＣＮＴ分散液
２ａ 塊状集合物
２ｂ 束状集合物
２ｃ 短尺ＣＮＴ
２ｄ 長尺ＣＮＴ
３ カラム
３ａ カラム出口
３ｂ カラム入口
４ａ，４ｂ ガラスビーズ
1 Coarse CNT dispersion 2a Bulk aggregate 2b Bundle aggregate 2c Short CNT
2d long CNT
3 Column 3a Column outlet 3b Column inlet 4a, 4b Glass beads
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