JP2013100206A - Carbon nanotube dispersion liquid and method for producing carbon nanotube dispersion liquid - Google Patents
Carbon nanotube dispersion liquid and method for producing carbon nanotube dispersion liquid Download PDFInfo
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Abstract
Description
本発明は、カーボンナノチューブの分散液、及びカーボンナノチューブの分散液の製造方法に関する。 The present invention relates to a carbon nanotube dispersion and a method for producing a carbon nanotube dispersion.
カーボンナノチューブ（以下、場合により「ＣＮＴ」と称す。）は、平面状のグラファト（グラフェンシート）を丸めた円筒状の構造を有している。そのナノ構造の特異性に起因して、ＣＮＴは様々な特性を示す。特に、銅の１０００倍以上の高い電流密度耐性、銅の約１０倍の高い熱伝導性、及び鋼鉄の約２０倍の引っ張り強度といった特性において、ＣＮＴは優れている。これらの特性は、電子材料、熱伝導材料及びコンポジット材料等の特性向上に大きく寄与すると考えられており、近年ＣＮＴの様々な分野への応用が試みられている。 A carbon nanotube (hereinafter, referred to as “CNT” in some cases) has a cylindrical structure obtained by rounding a planar graphato (graphene sheet). Due to their nanostructure specificity, CNTs exhibit various properties. In particular, CNTs are excellent in properties such as high current density resistance 1000 times or more that of copper, high thermal conductivity about 10 times that of copper, and tensile strength about 20 times that of steel. These characteristics are considered to greatly contribute to the improvement of characteristics of electronic materials, heat conductive materials, composite materials, etc., and in recent years, application of CNTs to various fields has been attempted.
ＣＮＴの優れた機械的強度や熱伝導度を、電子材料、電線、建材等のＣＮＴ単体よりもスケールの大きな材料に活かすには、より長いカーボンナノチューブを大量に合成する必要がある。近年、ＣＶＤ法を用いてＣＮＴをｍｍ以上に長尺化する技術が実現してきている（上記非特許文献１及び２参照。）。 In order to make use of the excellent mechanical strength and thermal conductivity of CNTs for materials having a scale larger than that of CNTs alone such as electronic materials, electric wires, and building materials, it is necessary to synthesize longer carbon nanotubes in large quantities. In recent years, a technique for elongating CNTs to mm or longer using a CVD method has been realized (see Non-Patent Documents 1 and 2 above).
しかしながら、ＣＮＴは、その表面の原子が配位的に不飽和であるため、ファンデルワールス力で凝集し易い。そのためＣＮＴの合成プロセスにおいて、バンドル状、毛玉状又はブラシ状等のＣＮＴの凝集体が形成され易い。特にＣＮＴが長尺化するほど、ＣＮＴ間のファンデルワールス力が大きくなり、ＣＮＴが凝集して複数本のＣＮＴから成るバンドル構造が形成され易くなる。このようなＣＮＴの凝集体では、ＣＮＴのナノ構造に起因する上記の特異な物性を十分に得ることができない。例えばＣＮＴ−ＣＮＴ間の接合部位は電気伝導性や熱伝導性の損失を招いてしまう。 However, CNT is easily aggregated by van der Waals force because atoms on its surface are coordinately unsaturated. Therefore, in the CNT synthesis process, CNT aggregates such as bundles, pills, or brushes are easily formed. In particular, the longer the CNT, the greater the van der Waals force between the CNTs, and the CNTs aggregate to form a bundle structure composed of a plurality of CNTs. Such an agglomerate of CNTs cannot sufficiently obtain the above specific physical properties due to the nanostructure of CNTs. For example, the junction part between CNT and CNT invites loss of electrical conductivity and thermal conductivity.
したがって、ＣＮＴの高い凝集性は、ＣＮＴの化学的・物理的操作や、ＣＮＴの産業への利用において最大の障害となっている。ＣＮＴの特異な物性を発現させるためには、ＣＮＴの凝集体をほぐして、ＣＮＴ間の接合部位数を減少させ、単分散したＣＮＴを得ることが必要である。 Therefore, the high cohesiveness of CNTs is the biggest obstacle in the chemical and physical operation of CNTs and the utilization of CNTs in the industry. In order to develop the unique physical properties of CNTs, it is necessary to loosen the aggregates of CNTs, reduce the number of bonding sites between CNTs, and obtain monodispersed CNTs.
しかし、従来のＣＮＴの分散技術では、分散処理の過程でＣＮＴの凝集体に加えられる剪断力によって、分散処理後のＣＮＴの長さが分散処理前の長さ（生成時のＣＮＴの長さ）よりも大幅に短くなってしまう問題が顕在化している。従来のＣＮＴの分散技術としては、例えば上記非特許文献３、特許文献１及び２に記載の技術が知られている。 However, in the conventional CNT dispersion technology, the length of the CNT after the dispersion treatment is the length before the dispersion treatment (the length of the CNT at the time of generation) due to the shearing force applied to the CNT aggregate during the dispersion treatment. The problem of becoming much shorter than that has become apparent. As conventional CNT dispersion techniques, for example, the techniques described in Non-Patent Document 3 and Patent Documents 1 and 2 are known.
上記非特許文献３に記載されたＣＮＴの分散液の製造方法では、ＣＮＴを孤立分散させることに主眼が置かれている。この方法では、超音波法によりＣＮＴを一部分散させた分散液からＣＮＴの凝集体を遠心分離法で分離し、このＣＮＴの凝集体（全ＣＮＴの約９０％）を廃棄し、上澄みのみを分散液として得ている。つまり、この方法を用いた場合、ＣＮＴのロス（損失）が多く、分散液の生産性が低い。またこの製造方法では、分散液の原料として用いるＣＮＴの元々の長さが短い。したがって、得られる分散液中のＣＮＴの長さも短く、４μｍ以下に限定されている。そもそも上記非特許文献３の製造方法では、分散処理の過程においてＣＮＴの切断を抑制するという課題自体が存在していない。 In the method for producing a CNT dispersion described in Non-Patent Document 3, the main focus is on isolating and dispersing CNTs. In this method, an aggregate of CNTs is separated from a dispersion liquid in which CNTs are partially dispersed by an ultrasonic method, and the aggregates of CNTs (about 90% of all CNTs) are discarded, and only the supernatant is dispersed. It is obtained as a liquid. That is, when this method is used, the loss (loss) of CNT is large and the productivity of the dispersion is low. In this manufacturing method, the original length of CNT used as a raw material for the dispersion is short. Therefore, the length of the CNT in the obtained dispersion is short and limited to 4 μm or less. In the first place, in the manufacturing method of Non-Patent Document 3, there is no problem itself of suppressing the cutting of CNTs during the dispersion process.
また上記特許文献１及び２に開示されたＣＮＴの分散技術は、分散液中のＣＮＴの高濃度化や分散安定性を目的としたものであり、分散処理後のＣＮＴの長さに着目していない。 The CNT dispersion techniques disclosed in Patent Documents 1 and 2 are aimed at increasing the concentration and stability of CNT in the dispersion, and pay attention to the length of the CNT after the dispersion treatment. Absent.
以上のように、近年ＣＶＤ法等により合成可能になった長尺のＣＮＴを実用化するために、ＣＮＴの切断を抑制しながらＣＮＴを分散させる技術が求められている。つまり、分散処理後においてもＣＮＴができるだけ生成時の長さを保持していることが望まれている。 As described above, in order to put into practical use long CNTs that can be synthesized by the CVD method or the like in recent years, a technique for dispersing CNTs while suppressing cutting of CNTs is required. That is, it is desired that the length of CNTs is kept as long as possible even after the dispersion treatment.
本発明は、上記事情に鑑みてなされたものであり、長尺のカーボンナノチューブの分散性に優れたカーボンナノチューブの分散液、及び当該カーボンナノチューブの分散液の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a carbon nanotube dispersion excellent in dispersibility of long carbon nanotubes, and a method for producing the carbon nanotube dispersion. .
本発明に係るカーボンナノチューブの分散液の一態様は、分散媒と、平均長さが８μｍ以上１０ｍｍ以下であるカーボンナノチューブと、分子内に親水構造部と疎水構造部とを有する二種以上の界面活性剤と、を備える。 One aspect of the carbon nanotube dispersion liquid according to the present invention is a dispersion medium, carbon nanotubes having an average length of 8 μm or more and 10 mm or less, and two or more kinds of interfaces having a hydrophilic structure portion and a hydrophobic structure portion in the molecule. An activator.
上記態様によれば、長尺のカーボンナノチューブを分散媒中に分散させることができる。 According to the above aspect, long carbon nanotubes can be dispersed in the dispersion medium.
上記本発明の一態様では、界面活性剤のうち一部のみが親水構造部として両性イオン基を有することが好ましい。 In one embodiment of the present invention, it is preferable that only a part of the surfactant has a zwitterionic group as the hydrophilic structure.
上記本発明の一態様では、前記界面活性剤の分子量が１０００以下であることが好ましい。 In one aspect of the present invention, the surfactant preferably has a molecular weight of 1000 or less.
上記本発明の一態様では、二種以上の界面活性剤が、同一の又は類似の前記疎水構造部として、脂肪族炭化水素、芳香族炭化水素及び環状ヘミアセタールからなる群より選ばれる少なくとも一種を有することが好ましい。 In one aspect of the present invention, two or more surfactants are at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and cyclic hemiacetals as the same or similar hydrophobic structure. It is preferable to have.
上記本発明の一態様では、分散液中のカーボンナノチューブの含有率が０．０００１〜１０重量％であることが好ましい。 In one embodiment of the present invention, the carbon nanotube content in the dispersion is preferably 0.0001 to 10% by weight.
上記本発明の一態様では、長さが８μｍ以上１０ｍｍ以下であるカーボンナノチューブの数が占める割合が、カーボンナノチューブの全数に対して５０％以上であることが好ましい。 In one embodiment of the present invention, the ratio of the number of carbon nanotubes having a length of 8 μm to 10 mm is preferably 50% or more based on the total number of carbon nanotubes.
上記本発明の一態様では、カーボンナノチューブの層数は１〜５であることが好ましい。 In one embodiment of the present invention, the number of carbon nanotube layers is preferably 1 to 5.
上記本発明の一態様では、複数のカーボンナノチューブから構成されるバンドル、及び単独で存在するカーボンナノチューブの平均太さが、１００ｎｍ以下であることが好ましい。 In the above-described embodiment of the present invention, it is preferable that the average thickness of a bundle composed of a plurality of carbon nanotubes and a carbon nanotube present alone is 100 nm or less.
上記本発明の一態様では、分散媒が水であることが好ましい。 In one embodiment of the present invention, the dispersion medium is preferably water.
上記本発明の一態様では、２５℃における分散液の粘度が１０ｍＰａ・ｓ以下であることが好ましい。 In one embodiment of the present invention, the viscosity of the dispersion at 25 ° C. is preferably 10 mPa · s or less.
本発明に係るカーボンナノチューブの分散液の製造方法の一態様は、分散媒、カーボンナノチューブ及び界面活性剤を含む混合液を、攪拌式ボールミルにより攪拌する工程を備える。これにより、上記本発明に係るカーボンナノチューブの分散液を製造することができる。 One aspect of the method for producing a dispersion of carbon nanotubes according to the present invention includes a step of stirring a mixed solution containing a dispersion medium, carbon nanotubes, and a surfactant with a stirring ball mill. Thereby, the dispersion liquid of the carbon nanotube which concerns on the said this invention can be manufactured.
本発明に係るカーボンナノチューブの分散液の製造方法の一態様は、混合液に超音波を伝播させる工程をさらに備えることが好ましい。 It is preferable that the one aspect | mode of the manufacturing method of the dispersion liquid of the carbon nanotube which concerns on this invention further comprises the process of propagating an ultrasonic wave to a liquid mixture.
本発明によれば、長尺のカーボンナノチューブの分散性に優れたカーボンナノチューブの分散液、及び当該カーボンナノチューブの分散液の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the dispersion liquid of the carbon nanotube excellent in the dispersibility of a long carbon nanotube, and the dispersion liquid of the said carbon nanotube can be provided.
以下、本発明の好適な実施形態について説明する。ただし、本発明は下記記実施形態に何ら限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiment.
（ＣＮＴの分散液）
本実施形態に係るカーボンナノチューブの分散液は、分散媒（溶媒）と、平均長さが８μｍ以上１０ｍｍ以下であるカーボンナノチューブカーボンナノチューブと、分子内に親水構造部と疎水構造部とを有する二種以上の界面活性剤と、を含有する。
(CNT dispersion)
The carbon nanotube dispersion liquid according to this embodiment includes a dispersion medium (solvent), carbon nanotube carbon nanotubes having an average length of 8 μm or more and 10 mm or less, and two types having a hydrophilic structure portion and a hydrophobic structure portion in the molecule. And the above surfactant.
本実施形態では、二種以上の界面活性剤の疎水構造部がＣＮＴの表面に化学吸着し、ＣＮＴがこれらの界面活性剤で覆われる。これにより、ＣＮＴの親溶媒性（特に親水性）が高まり、一種の界面活性剤のみを用いた場合比べて、ＣＮＴの分散性が向上する。つまり、二種以上の界面活性剤は分散剤として機能する。ＣＮＴの分散に必要な分散剤の特性としては、ＣＮＴ間への浸透性やＣＮＴ表面への吸着性、溶媒への溶解性等が挙げられる。しかし、一種類の界面活性剤の化学構造はこれら全ての特性を併せ持つことが困難である。そのため、本実施形態では、それぞれの特性に応じた二種以上の界面活性剤を併用することで、界面活性剤同士が互いの特性を補い合い、一種の界面活性剤のみを用いた場合比べて、高いＣＮＴの分散性が実現する。また二種以上の界面活性剤が同じ極性の電荷を有する親水構造部を有する場合、界面活性剤は親溶媒性を高めるだけではなく、同じ極性の電荷を有する親水構造部どうしの斥力を利用して、分散したＣＮＴ同士の再凝集を抑制し、分散状態を安定化することも可能である。一種の界面活性剤のみを用いた場合比べて、ＣＮＴの分散性が向上する理由においては、ＣＮＴの分散に必要な分散剤の特性にＣＮＴ間への浸透性やＣＮＴ表面への吸着性および分散状態安定化が挙げられるが、一種類の化学構造ではすべてを併せ持つことが困難であるため、それぞれの特性に応じた
分散剤を併用することで、これを補おうというものである。
In this embodiment, the hydrophobic structure part of 2 or more types of surfactants chemisorbs on the surface of CNT, and CNT is covered with these surfactants. As a result, the solvophilicity (particularly hydrophilicity) of the CNT is increased, and the dispersibility of the CNT is improved as compared with the case where only one kind of surfactant is used. That is, two or more surfactants function as a dispersant. Examples of the characteristics of the dispersant necessary for the dispersion of CNT include permeability between CNTs, adsorption to the CNT surface, and solubility in a solvent. However, it is difficult for the chemical structure of one type of surfactant to have all these characteristics. Therefore, in this embodiment, by using two or more types of surfactants according to the respective properties, the surfactants complement each other's properties, compared with the case where only one type of surfactant is used, High CNT dispersibility is achieved. When two or more kinds of surfactants have a hydrophilic structure part having the same polarity charge, the surfactant not only enhances the solvophilicity but also utilizes the repulsive force between hydrophilic structure parts having the same polarity charge. Thus, it is possible to suppress reaggregation of dispersed CNTs and stabilize the dispersion state. The reason why the dispersibility of CNT is improved as compared with the case of using only one type of surfactant is that the properties of the dispersant necessary for the dispersion of CNT include the permeability between CNTs and the adsorptivity and dispersion on the CNT surface. State stabilization can be mentioned, but it is difficult to have all of them in one type of chemical structure, so this is to be compensated by using a dispersant according to each property.
ＣＮＴの平均長さは８μｍ以上１０ｍｍ以下である。好ましくは、ＣＮＴの平均長さは１０μｍ以上１０ｍｍ以下であり、より好ましくは、１０μｍ以上１２μｍ以下である。ＣＮＴの平均長さが上記数値範囲内であることで、導電性、機械的強度又は熱伝導性等のＣＮＴのナノ構造に特有の優れた物性を有効に活用することができる。ＣＮＴが短すぎるとこれらの物性が十分に発現されない。またＣＮＴが長すぎると、分散液の塗工性が悪くなる場合がある。 The average length of CNT is 8 μm or more and 10 mm or less. Preferably, the average length of CNT is 10 μm or more and 10 mm or less, and more preferably 10 μm or more and 12 μm or less. When the average length of the CNT is within the above numerical range, excellent physical properties unique to the nanostructure of the CNT, such as conductivity, mechanical strength, or thermal conductivity, can be effectively utilized. If the CNTs are too short, these physical properties are not sufficiently expressed. Moreover, when CNT is too long, the applicability | paintability of a dispersion liquid may worsen.
ＣＮＴはそれを構成する層（グラフェンシート）の数を基準として、一層構造のシングルウォールカーボンナノチューブ（ＳＷＣＮＴ）、二層構造のダブルウォールカーボンナノチューブ（ＤＷＣＮＴ）、三層以上から構成される構造のマルチウォールカーボンナノチューブ（ＭＷＣＮＴ）などに分類される。ＭＷＣＮＴとは、換言すれば、円筒状に閉じた複数のグラフェンシートが入れ子状に積層された構造を有する。ＳＷＣＮＴ、ＤＷＣＮＴ及びＭＷＣＮＴのいずれも本実施形態の分散液に使用可能である。本実施形態では、カーボンナノチューブの平均層数は１〜５程度であればよい。分散液がＳＷＣＮＴ、ＤＷＣＮＴ及びＭＷＣＮＴからなる群より選ばれる二種以上のＣＮＴを含有してもよい。 CNT is based on the number of layers (graphene sheet) that composes it. Single-walled carbon nanotubes (SWCNT) with a single-layer structure, double-walled carbon nanotubes (DWCNT) with a double-layer structure, and multi-layers with three or more layers. It is classified into wall carbon nanotube (MWCNT). In other words, the MWCNT has a structure in which a plurality of graphene sheets closed in a cylindrical shape are stacked in a nested manner. Any of SWCNT, DWCNT, and MWCNT can be used for the dispersion of this embodiment. In the present embodiment, the average number of carbon nanotube layers may be about 1 to 5. The dispersion may contain two or more CNTs selected from the group consisting of SWCNT, DWCNT and MWCNT.
分散液中のＣＮＴの寸法や形状は、分散液の希薄溶液を平滑基板上にスピンコートしたサンプル（スピンコート膜）を各種手法によって分析することによって調べればよい。ここで分散液を希釈するのは、分析の過程においてスピンコート膜中のＣＮＴ同士が再凝集することを抑制し、ＣＮＴを孤立した状態を維持するためである。分散液中ＣＮＴの平均長さは、上記スピンコート膜中のＣＮＴをＳＥＭ等で観察することによって測定すればよい。分散液中のＣＮＴの平均長さは、スピンコート膜中の任意のＣＮＴの長さの平均値である。ＣＮＴの長さの平均値は、分散液の製造において原料として用いるＣＮＴの長さ、分散処理方法の選択、分散処理時間等によって適宜調整可能である。 The size and shape of the CNT in the dispersion may be examined by analyzing a sample (spin coat film) obtained by spin-coating a diluted solution of the dispersion on a smooth substrate by various methods. The reason why the dispersion is diluted here is to prevent the CNTs in the spin coat film from reaggregating in the course of analysis, and to maintain the isolated state of the CNTs. The average length of the CNTs in the dispersion may be measured by observing the CNTs in the spin coat film with an SEM or the like. The average length of CNTs in the dispersion is an average value of the lengths of arbitrary CNTs in the spin coat film. The average value of the CNT length can be appropriately adjusted depending on the length of the CNT used as a raw material in the production of the dispersion, the selection of the dispersion treatment method, the dispersion treatment time, and the like.
分散液中で孤立して存在するカーボンナノチューブ、及び分散液中で複数のカーボンナノチューブから構成されるバンドルの太さの平均値（ＣＮＴ平均太さ）は０．５ｎｍ以上１００ｎｍ以下であることが好ましく、８０ｎｍ以下であることがより好ましい。ＣＮＴ平均太さが１００ｎｍ以下であれば、本実施形態のＣＮＴ分散液から作製したＣＮＴ薄膜において、その可視光透過率が８０％である時のヘイズ値を１０％以下とすることができる。ＣＮＴ平均太さは、スピンコート膜中の任意の孤立したＣＮＴ及び孤立したバンドルの太さの平均値である。ＣＮＴ平均太さの測定方法は、ＳＥＭの変わりに、透過型電子顕微鏡（ＴＥＭ：Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）を用いること以外は、ＣＮＴの平均長さの測定方法とほぼ同様であるを。 It is preferable that the average value of the thickness (CNT average thickness) of the carbon nanotubes that are present in isolation in the dispersion and a plurality of carbon nanotubes in the dispersion is 0.5 nm or more and 100 nm or less. 80 nm or less is more preferable. If the CNT average thickness is 100 nm or less, the haze value when the visible light transmittance is 80% in the CNT thin film produced from the CNT dispersion of this embodiment can be 10% or less. The average CNT thickness is an average value of the thickness of any isolated CNT and isolated bundle in the spin coat film. The method for measuring the average thickness of CNTs is substantially the same as the method for measuring the average length of CNTs, except that a transmission electron microscope (TEM) is used instead of SEM.
分散液中のカーボンナノチューブの含有率は、０．０００１〜１０重量％であることが好ましい。この場合、分散液を塗料として用い易く、また分散液と他の基材とからコンポジット材料を構成し易い。 The content of carbon nanotubes in the dispersion is preferably 0.0001 to 10% by weight. In this case, it is easy to use the dispersion as a coating material, and it is easy to form a composite material from the dispersion and another substrate.
長さの絶対値が８μｍ以上１０ｍｍ以下であるカーボンナノチューブの数が占める割合は、分散液中のカーボンナノチューブの全数に対して５０％以上であることが好ましく、６０％以上であることがより好ましく、７０％以上であることがさらに好ましい。つまり、本実施形態に係る分散液は、従来の分散液に比べて、長尺のＣＮＴを高い割合で含有しているため、電子材料、電線、建材等に適用し易い。 The ratio of the number of carbon nanotubes having an absolute length of 8 μm or more and 10 mm or less is preferably 50% or more, more preferably 60% or more, based on the total number of carbon nanotubes in the dispersion. 70% or more is more preferable. That is, since the dispersion liquid according to the present embodiment contains a long proportion of CNTs as compared with the conventional dispersion liquid, it is easy to apply to electronic materials, electric wires, building materials, and the like.
分散液から作製したＣＮＴ薄膜の可視光透過率８０％時のヘイズ値は、１０%以下であることが好ましい。ヘイズ値とは、分散液中のＣＮＴの分散性を評価する尺度であり、ヘイズ値が大きいほど、分散液中のＣＮＴの凝集体が粗大であり、その数が多いことを意味する。本実施形態の低いヘイズ値は、分散液が従来よりも長尺で凝集し易いＣＮＴを含有するにも係らず、分散液中のＣＮＴの分散性が高く、ＣＮＴが凝集し難いことを意味する。 The haze value of the CNT thin film prepared from the dispersion when the visible light transmittance is 80% is preferably 10% or less. The haze value is a scale for evaluating the dispersibility of CNTs in the dispersion, and the larger the haze value, the coarser the aggregates of CNTs in the dispersion and the greater the number. The low haze value of the present embodiment means that the CNTs in the dispersion are highly dispersible and the CNTs are less likely to aggregate despite the fact that the dispersion contains longer and more easily aggregated CNTs. .
界面活性剤は、分子内に疎水構造部と親水構造部とを有するものであり、分散媒とＣＮＴの双方に親和性を持ち、ＣＮＴを分散媒中に分散させる作用を持つ。このような特徴を有するものであれば、界面活性剤は特に制限されるものではない。界面活性剤は、純水に溶解した際の親水構造の電荷の種類に基づいて、アニオン系界面活性剤、カチオン系界面活性剤、両性イオン系界面活性剤及び非イオン系界面活性剤に大別される。分散液は、これらからなる群より選ばれる二種以上を含有する。 The surfactant has a hydrophobic structure portion and a hydrophilic structure portion in the molecule, has an affinity for both the dispersion medium and the CNT, and has an action of dispersing the CNT in the dispersion medium. The surfactant is not particularly limited as long as it has such characteristics. Surfactants are roughly classified into anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants based on the type of hydrophilic structure charge when dissolved in pure water. Is done. The dispersion contains two or more selected from the group consisting of these.
アニオン系界面活性剤としては、以下のスルホン酸誘導体、カルボン酸誘導体等が例に挙げられるが、これに制限されるものではない。スルホン酸誘導体では、ラウリルスルホン酸ナトリウム等のアルキルスルホン酸塩、ドデシルベンゼンスルホン酸ナトリウム塩（以下「ＳＤＢＳ」と称す。）等のアルキルベンゼンスルホン酸塩、ドデシルフェニルエーテルスルホン酸塩等の芳香族スルホン酸系界面活性剤などが例示できる。またカルボン酸誘導体としては、ミリスチン酸ナトリウムやステアリン酸ナトリウム等の直鎖脂肪酸や生体物質である胆汁酸の成分であるコール酸ナトリウムなどが例示できる。 Examples of the anionic surfactant include the following sulfonic acid derivatives and carboxylic acid derivatives, but are not limited thereto. Examples of the sulfonic acid derivatives include alkyl sulfonates such as sodium lauryl sulfonate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate (hereinafter referred to as “SDBS”), and aromatic sulfonic acids such as dodecyl phenyl ether sulfonate. Examples thereof include system surfactants. Examples of the carboxylic acid derivative include linear fatty acids such as sodium myristate and sodium stearate and sodium cholate which is a component of bile acid which is a biological substance.
カチオン系界面活性剤としては、四級アンモニウム塩が使用できる。例えば、トリメチルセチルアンモニウムクロライド、ドデシルトリメチルアンモニウムハライド、ヤシ油アルキルトリメチルアンモニウムハライド、ヘキサデシルトリメチルアンモニウムハライド、牛脂アルキルトリメチルアンモニウムハライド、オクタデシルアンモニウムハライド、アルキルイミダゾリウムハライド等が挙げられる。ただし、カチオン系界面活性剤はこれらに制限されるものではない。 A quaternary ammonium salt can be used as the cationic surfactant. Examples include trimethylcetylammonium chloride, dodecyltrimethylammonium halide, coconut oil alkyltrimethylammonium halide, hexadecyltrimethylammonium halide, beef tallow alkyltrimethylammonium halide, octadecylammonium halide, alkylimidazolium halide and the like. However, the cationic surfactant is not limited to these.
両性イオン系界面活性剤としては、以下のものが例に挙げられるが、これに制限されるものではない。例えば、２−メタクリロイルオキシエチルホスホリルコリンのポリマーやポリペプチド等の両性高分子、３−（Ｎ，Ｎ−ジメチルステアリルアンモニオ）プロパンスルホネート、３−（Ｎ，Ｎ−ジメチルミリスチルアンモニオ）プロパンスルホネート、３−［（３−コールアミドプロピル）ジメチルアンモニオ］−１−プロパンスルホネート（ＣＨＡＰＳ）、３−［（３−コールアミドプロピル）ジメチルアンモニオ］−２−ヒドロキシプロパンスルホネート（ＣＨＡＰＳＯ）、ｎ−ドデシル−Ｎ,Ｎ'−ジメチル−３−アンモニオ−１−プロパンスルホネート、ｎ−ヘキサデシル−Ｎ,Ｎ'−ジメチル−３−アンモニオ−１−プロパンスルホネート、３−（テトラデシルジメチルアミニオ）プロパン−１−スルホナート、ｎ−オクチルホスホコリン、ｎ−ドデシルホスホコリン、ｎ−テトラデシルホスホコリン、ｎ−ヘキサデシルホスホコリン、ジメチルアルキルベタイン、パーフルオロアルキルベタイン、レシチン等の両性低分子（両性界面活性剤を含む）などが挙げられる。 Examples of zwitterionic surfactants include the following, but are not limited thereto. For example, amphoteric polymers such as 2-methacryloyloxyethyl phosphorylcholine polymer and polypeptide, 3- (N, N-dimethylstearylammonio) propanesulfonate, 3- (N, N-dimethylmyristylammonio) propanesulfonate, 3 -[(3-Choleamidopropyl) dimethylammonio] -1-propanesulfonate (CHAPS), 3-[(3-Cholamidopropyl) dimethylammonio] -2-hydroxypropanesulfonate (CHAPSO), n-dodecyl- N, N′-dimethyl-3-ammonio-1-propanesulfonate, n-hexadecyl-N, N′-dimethyl-3-ammonio-1-propanesulfonate, 3- (tetradecyldimethylaminio) propane-1-sulfonate , N-octylphosphocholine And amphoteric small molecules (including amphoteric surfactants) such as n-dodecylphosphocholine, n-tetradecylphosphocholine, n-hexadecylphosphocholine, dimethylalkylbetaine, perfluoroalkylbetaine, and lecithin.
ノニオン系界面活性剤としては、以下のものが例に挙げられるが、これに制限されるものではない。ノニオン系界面活性剤としては、例えば、ポリアクリル酸、ポリエチレングリコール、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンドデシルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンアルキルアミン、アルキルポリグルコシド、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、プロピレングリコール脂肪酸エステルなどを好適に用いることができる。 Examples of nonionic surfactants include, but are not limited to, the following. Nonionic surfactants include, for example, polyacrylic acid, polyethylene glycol, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene fatty acid ester, polyoxyethylene Oxyethylene polyoxypropylene block polymers, polyoxyethylene alkylamines, alkyl polyglucosides, glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters and the like can be suitably used.
界面活性剤のうち一部は、親水構造部として、カチオン（正電荷）とアニオン（負電荷）の両方を備える両性イオン基を有し、他の界面活性剤は、両性イオン基以外の親水構造部を有することが好ましい。つまり、両性イオン系界面活性剤とそれ以外の界面活性剤とを併用することが好ましい。これにより、ＣＮＴの分散性が著しく向上し、分散したＣＮＴの再凝集が顕著に抑制される。二種以上の界面活性剤の全てが両性イオン系界面活性剤であった場合、高濃度分散液において、ＣＮＴ表面に吸着している界面活性剤のカチオン（正電荷）部分とアニオン（負電荷）部分がＣＮＴ間で互いに会合し、ＣＮＴが自己組織化して凝集体を形成し、ＣＮＴの分散性が低下する傾向がある。 Some of the surfactants have a zwitterionic group having both a cation (positive charge) and an anion (negative charge) as a hydrophilic structure, and other surfactants have a hydrophilic structure other than the zwitterionic group. It is preferable to have a part. That is, it is preferable to use a zwitterionic surfactant in combination with another surfactant. Thereby, the dispersibility of CNT improves remarkably and reaggregation of the dispersed CNT is remarkably suppressed. When all of the two or more surfactants are zwitterionic surfactants, the cation (positive charge) portion and anion (negative charge) of the surfactant adsorbed on the CNT surface in the high concentration dispersion The portions are associated with each other between the CNTs, and the CNTs self-assemble to form aggregates, which tends to reduce the dispersibility of the CNTs.
両性イオン基によるＣＮＴの分散機構は以下の通りである、と本発明者らは考える。両性イオン基を有する界面活性剤の疎水構造部はＣＮＴ又はその凝集体の表面に結合する。そして、正電荷及び負電荷を有する両性イオン基は、ＣＮＴ凝集体の表面上で自己組織化し、両性イオン分子膜（ＳＡＺＭ： Ｓｅｌｆ−Ａｓｓｅｍｂｌｅｄ Ｚｗｉｔｔｅｒｉｏｎｉｃ Ｍｏｎｏｌａｙｅｒ）を形成する。ＣＮＴ凝集体を覆うＳＡＺＭは、双極子間の強い静電的相互作用によって、他のＣＮＴ凝集体を覆うＳＡＺＭと静電的に結合する傾向がある。この静電的な力によって混合物中の各ＣＮＴ凝集体が互いに引っ張りあうことにより、ＣＮＴ凝集体を構成する各ＣＮＴの引き剥がれが起き、新たなＣＮＴ凝集体の表面が露出する。新しく露出した表面は、新たにＳＡＺＭによって覆われる。以上の反応が、ＣＮＴ凝集体を構成するＣＮＴが完全に孤立分散するまで繰り返されるので、最終的にはＣＮＴが完全に単分散される。 The present inventors consider that the dispersion mechanism of CNTs by zwitterionic groups is as follows. The hydrophobic structure portion of the surfactant having the zwitterionic group is bonded to the surface of the CNT or its aggregate. And the zwitterionic group which has a positive charge and a negative charge self-assembles on the surface of a CNT aggregate, and forms a zwitterionic molecular film (SAZM: Self-Assembled Zwitterionic Monolayer). SAZM covering CNT aggregates tends to electrostatically bond with SAZM covering other CNT aggregates due to strong electrostatic interactions between dipoles. The electrostatic force causes the CNT aggregates in the mixture to pull each other, causing the CNTs constituting the CNT aggregates to peel off, and the surface of the new CNT aggregates is exposed. The newly exposed surface is newly covered with SAZM. The above reaction is repeated until the CNTs constituting the CNT aggregate are completely isolated and dispersed, so that the CNTs are finally completely monodispersed.
上記二種以上の界面活性剤は、同一の又は類似の前記疎水構造部として、鎖状脂肪族炭化水素、鎖状脂肪族炭化水素、芳香族炭化水素、及び環状ヘミアセタール（ピラノース、フラノース等）からなる群より選ばれる少なくとも一種を有することが好ましい。同一の又は類似の疎水構造部を有する界面活性剤の組合せとしては、例えば、コール酸基を具備するＣＨＡＰＳとコール酸ナトリウム、飽和脂肪酸基を有する３−（テトラデシルジメチルアミニオ）プロパン−１−スルホナートとミリスチン酸ナトリウムが挙げられる。界面活性剤の疎水構造部が同一の又は類似のものである場合、同一の又は類似の疎水構造部は、ＣＮＴに対する吸着力の差が小さく、他方の界面活性剤を排斥することが無いため、お互いの分散能発現に阻害をおこしにくい。 The two or more kinds of surfactants are the same or similar hydrophobic structures, such as chain aliphatic hydrocarbons, chain aliphatic hydrocarbons, aromatic hydrocarbons, and cyclic hemiacetals (pyranose, furanose, etc.) It is preferable to have at least one selected from the group consisting of Examples of the combination of surfactants having the same or similar hydrophobic structure include, for example, CHAPS having a cholic acid group and sodium cholate, and 3- (tetradecyldimethylaminio) propane-1- having a saturated fatty acid group. Examples include sulfonate and sodium myristate. When the hydrophobic structure part of the surfactant is the same or similar, the same or similar hydrophobic structure part has a small difference in adsorption force to CNT and does not eliminate the other surfactant. It is difficult to inhibit each other's expression of dispersibility.
上記界面活性剤の分子量（特にノニオン系界面活性剤の分量）が１０００以下であることが好ましく、４００〜６００程度であることがより好ましい。ここでいう分子量とは、重量平均分子量である。界面活性剤の分子量が小さいほど、界面活性剤がバンドル（凝集体）を構成するＣＮＴ間の隙間に侵入して、ＣＮＴを分散させ易くなる。また、界面活性剤の分子量が小さいほど、分散液からなる塗膜から界面活性剤を除去し易い。 The molecular weight of the surfactant (particularly the amount of nonionic surfactant) is preferably 1000 or less, and more preferably about 400 to 600. The molecular weight here is a weight average molecular weight. The smaller the molecular weight of the surfactant, the easier it is for the surfactant to enter the gaps between the CNTs constituting the bundle (aggregate) and to disperse the CNTs. Further, the smaller the molecular weight of the surfactant, the easier it is to remove the surfactant from the coating film made of the dispersion.
２５℃における分散液の粘度は１０ｍＰａ・ｓ以下であることが好ましい。分散液の粘度の粘度が低いことは界面活性剤の分子量の小さいことに起因する。分散液の粘度の粘度が低いほど、溶媒によるＣＮＴの界面活性剤の溶解、洗浄、除去が容易であり、ＣＮＴを単離し易い。 The viscosity of the dispersion at 25 ° C. is preferably 10 mPa · s or less. The low viscosity of the dispersion is due to the low molecular weight of the surfactant. The lower the viscosity of the dispersion, the easier it is to dissolve, wash, and remove the CNT surfactant with the solvent, and it is easier to isolate the CNTs.
界面活性剤は溶媒に可溶であることが好ましい。界面活性剤はＣＮＴに結合することによってＣＮＴの熱抵抗や電気抵抗を増加させる傾向がある。界面活性剤が溶剤に可溶であれば、洗浄によってＣＮＴ表面から界面活性剤を容易に除去できるため、分散液から単利したＣＮＴの熱抵抗や電気抵抗等の特性を向上させ易い。 The surfactant is preferably soluble in the solvent. Surfactants tend to increase the thermal resistance and electrical resistance of CNTs by binding to CNTs. If the surfactant is soluble in the solvent, the surfactant can be easily removed from the CNT surface by washing, so that it is easy to improve characteristics such as thermal resistance and electrical resistance of the CNT obtained simply from the dispersion.
分散媒は極性溶媒であることが好ましく、水であることがさらに好ましい。水以外の分散媒としては例えば、メタノール、エタノール、プロパンノール、ブタノール、イソプロピルアルコール等のアルコール系溶剤、アセトン、２−ブタノン、メチルイソブチルケトン、Ｎ―メチルピロリドン等のケトン系溶剤、テトラヒドロフラン、ガンマブチロラクトン、ジメチルホルムアミド等が挙げられる。これら複数の分散媒の混合液を用いても良い。 The dispersion medium is preferably a polar solvent, and more preferably water. Examples of the dispersion medium other than water include alcohol solvents such as methanol, ethanol, propanol, butanol and isopropyl alcohol, ketone solvents such as acetone, 2-butanone, methyl isobutyl ketone and N-methylpyrrolidone, tetrahydrofuran, and gamma butyrolactone. And dimethylformamide. A mixed liquid of these plural dispersion media may be used.
界面活性剤の濃度は、ＣＮＴの量に応じて適宜設定することができる。例えば、分散液が含むＣＮＴの全重量を１重量部とするとき、分散液が含む界面活性剤の重量は１〜１０００重量部であることが好ましく、５〜１００重量部であることがより好ましい。これにより本発明の効果がより顕著になる。 The concentration of the surfactant can be appropriately set according to the amount of CNT. For example, when the total weight of CNTs contained in the dispersion is 1 part by weight, the weight of the surfactant contained in the dispersion is preferably 1-1000 parts by weight, and more preferably 5-100 parts by weight. . Thereby, the effect of the present invention becomes more remarkable.
分散液は、上記界面活性剤に加えて安定剤を含有してもよい。これらの併用により、ＣＮＴの分散状態がより安定する。安定剤としては、例えば、グリセロール、多級アルコール、ポリビニルアルコール、アルキルアミン、酸性高分子、塩基性高分子などの水素結合を形成する物質が挙げられる。上記酸性高分子としては、例えば、κ−カラギーナン（κ-ｃａｒｒａｇｅｅｎａｎ）、ＤＮＡ、ナフィオン（登録商標）、酢酸セルロース、リン酸セルロース、スルホン酸セルロース、ゲラン、アラビアンガム、ポリリン酸などが挙げられる。 The dispersion may contain a stabilizer in addition to the surfactant. By using these in combination, the dispersion state of CNT is more stable. Examples of the stabilizer include substances that form hydrogen bonds, such as glycerol, polyhydric alcohol, polyvinyl alcohol, alkylamine, acidic polymer, and basic polymer. Examples of the acidic polymer include κ-carrageenan, DNA, Nafion (registered trademark), cellulose acetate, cellulose phosphate, cellulose sulfonate, gellan, arabian gum, and polyphosphoric acid.
本実施形態に係るＣＮＴの分散液は、電子材料、電線、建材等の原料として好適である。分散液中にＣＮＴの特性の劣化の原因となる不純物が多く含まれると、ＣＮＴの品質が劣化する。また、分散液中の不純物が多い場合、分散液中のＣＮＴをさらに精製する必要が生じて、電子材料、電線、建材等の生産コストが上昇する。よって、分散液中の不純物の量は少ないほど好ましい。 The CNT dispersion according to this embodiment is suitable as a raw material for electronic materials, electric wires, building materials, and the like. If the dispersion contains many impurities that cause deterioration of the CNT characteristics, the quality of the CNT deteriorates. Moreover, when there are many impurities in a dispersion liquid, it will be necessary to refine | purify further CNT in a dispersion liquid, and production costs, such as an electronic material, an electric wire, and a building material, will rise. Therefore, the smaller the amount of impurities in the dispersion, the better.
（ＣＮＴの分散液の製造方法）
本実施形態に係るＣＮＴの分散液の製造方法は、カーボンナノチューブ、上記分散媒、及び上記界面活性剤を含む混合液を、攪拌式ボールミルにより攪拌する工程（攪拌工程）を備える。これにより、上記本実施形態に係るＣＮＴの分散液を製造することができる。
(Method for producing CNT dispersion)
The method for producing a dispersion of CNTs according to this embodiment includes a step (stirring step) of stirring a mixed solution containing carbon nanotubes, the dispersion medium, and the surfactant using a stirring ball mill. Thereby, the dispersion liquid of CNT which concerns on the said this embodiment can be manufactured.
分散液の原料として、長さが８μｍ以上１０ｍｍ以下であるＣＮＴを用いる。原料として用いるＣＮＴは、アーク放電法、ＣＶＤ法、レーザーアブレーション法等の方法で製造すればよい。中でもＣＶＤ法が好ましい。ＣＶＤ法によれば、アーク放電法やレーザーアブレーション法によって合成されるＣＮＴに比べて、長尺のＣＮＴを容易に合成できる。ＣＶＤ法によれば、他の方法に比べて、ＣＮＴの安定した量産化と生産コストの低減が可能である。 As the raw material of the dispersion, CNT having a length of 8 μm or more and 10 mm or less is used. The CNT used as a raw material may be manufactured by an arc discharge method, a CVD method, a laser ablation method, or the like. Of these, the CVD method is preferable. According to the CVD method, it is possible to easily synthesize long CNTs as compared with CNTs synthesized by an arc discharge method or a laser ablation method. According to the CVD method, stable mass production of CNTs and reduction of production costs are possible compared to other methods.
攪拌工程では、攪拌式ボールミルによりＣＮＴに剪断力を作用させ、その凝集を解消する。なお、攪拌式ボールミルとは、容器内部に差し入れた攪拌羽を外部動力で回転させて容器内に充填したメディアを攪拌したり、内部のメディアを攪拌できるような構造を備えた容器を外部動力で回転させたりすることによって、容器内部のメディアを流動させる機構を有するものである。メディアの粒径は、分散効率を考えて１０ｍｍ以下であることが好ましい。加えてメディアの材質は磨耗によるコンタミ（ｃｏｎｔａｍｉｎａｔｉｏｎ）抑制のため、硬質のセラミックであることが好ましく、ジルコニアであることがさらに好ましい。 In the stirring step, a shearing force is applied to the CNTs by a stirring ball mill to eliminate the aggregation. Note that the agitating ball mill is a container equipped with a structure capable of stirring the media filled in the container by rotating the stirring blade inserted in the container with external power or stirring the media inside. It has a mechanism for flowing the media inside the container by rotating it. The particle size of the media is preferably 10 mm or less in consideration of dispersion efficiency. In addition, the material of the medium is preferably a hard ceramic, and more preferably zirconia, in order to suppress contamination due to wear.
本実施形態に係る製造方法は、混合液を超音波で処理する工程（超音波処理工程）をさらに備えてもよい。超音波処理工程によりＣＮＴの分散性がより向上する。攪拌工程と超音波処理工程とを同時に実施しても良く、個別に実施してもよい。 The manufacturing method according to the present embodiment may further include a step of treating the mixed solution with ultrasonic waves (ultrasonic treatment step). The dispersibility of CNT is further improved by the ultrasonic treatment process. The stirring step and the ultrasonic treatment step may be performed simultaneously or individually.
本実施形態では、攪拌式ボールミルの他に、ビーズやロール等のメディア式の分散工程をさらに実施してもよい。また、分散工程後のＣＮＴ中から凝集体や短尺のＣＮＴ（例えば分散工程において剪断力を受けて短小化したＣＮＴ）を取り除くために、遠心分離工程を行ってもよい。これにより、最終的に分散液に含有されるＣＮＴの長尺化及び単分散が容易となる。 In this embodiment, in addition to the stirring ball mill, a media-type dispersion step such as beads and rolls may be further performed. Further, a centrifugal separation step may be performed in order to remove aggregates and short CNTs (for example, CNTs shortened by receiving a shearing force in the dispersion step) from the CNTs after the dispersion step. Thereby, lengthening and monodispersion of CNT finally contained in a dispersion liquid become easy.
本実施形態では、原料として従来よりも長尺のＣＮＴを用いる。また本実施形態では、二種以上の界面活性剤の化学的作用によってＣＮＴの凝集を容易に解消することができるため、攪拌工程においてＣＮＴに作用させる剪断力を従来よりも低減してＣＮＴの短小化を抑制しつつ、ＣＮＴの凝集を十分に解消することが可能である。したがって、本実施形態では短尺のＣＮＴがそもそも形成され難く、遠心分離工程によって短尺のＣＮＴを除去する必要性が小さい。また本実施形態では、上記界面活性剤の作用によってＣＮＴの凝集体が容易に解消されるため、遠心分離工程によってＣＮＴの凝集体を除去する必要性も小さい。以上の理由から、本実施形態では、必ずしも遠心分離工程を必要とせず、凝集体や短尺のＣＮＴの除去によるＣＮＴ原料の損失を低減することが可能である。よって本実施形態によれば、ＣＮＴの分散液の生産コストが低減される。 In the present embodiment, CNTs that are longer than conventional CNTs are used as raw materials. In this embodiment, since the aggregation of CNTs can be easily eliminated by the chemical action of two or more surfactants, the shearing force acting on the CNTs in the stirring step is reduced compared to the conventional case, and the CNTs are shortened. It is possible to sufficiently eliminate the aggregation of CNTs while suppressing the formation. Therefore, in this embodiment, short CNTs are hardly formed in the first place, and there is little need to remove short CNTs by a centrifugation process. Further, in this embodiment, since the aggregate of CNTs is easily eliminated by the action of the surfactant, it is not necessary to remove the aggregates of CNTs by a centrifugation step. For the reasons described above, in this embodiment, the centrifugation step is not necessarily required, and it is possible to reduce the loss of the CNT raw material due to the removal of aggregates and short CNTs. Therefore, according to this embodiment, the production cost of the dispersion liquid of CNT is reduced.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
（カーボンナノチューブの合成）
下記実施例１、３及び比較例１〜３の各分散液の原料として用いるＳＷＣＮＴを以下の手順で合成した。まず、熱酸化膜付シリコン基板上にスパッタ法でＡｌ膜（１５ｎｍ厚）とＦｅ膜（０．６ｎｍ）を形成した。この基板を反応炉内に設置して、８００℃のＡｒ，Ｈ２及びＣ２Ｈ２を主成分とする混合ガスを炉内で反応させ、約１ｍｍの平均長さを有するＳＷＣＮＴを基板上に成長させた。
(Synthesis of carbon nanotubes)
SWCNTs used as raw materials for the dispersions of Examples 1 and 3 and Comparative Examples 1 to 3 below were synthesized by the following procedure. First, an Al film (15 nm thick) and an Fe film (0.6 nm) were formed on a silicon substrate with a thermal oxide film by sputtering. This substrate was placed in a reaction furnace, and a mixed gas mainly composed of 800 ° C. Ar, H 2 and C 2 H 2 was reacted in the furnace, and SWCNT having an average length of about 1 mm was placed on the substrate. Grown up.
下記実施例２，４の各分散液の原料として用いるＭＷＣＮＴを以下の手順で合成した。まず、熱酸化膜付シリコン基板上にスパッタ法でＡｌ膜（１５ｎｍ厚）とＦｅ膜（２ｎｍ）を形成した。この基板を反応炉内に設置して、８００℃のＡｒ、Ｈ２及びＣ２Ｈ２を主成分とする混合ガスを炉内で反応させ、約０．４ｍｍの平均長さを有するＭＷＣＮＴを基板上に成長させた。ＭＷＣＮＴの平均層数は３であった。 MWCNT used as a raw material for each dispersion in Examples 2 and 4 below were synthesized by the following procedure. First, an Al film (15 nm thickness) and an Fe film (2 nm) were formed on a silicon substrate with a thermal oxide film by sputtering. This substrate is placed in a reaction furnace, and a mixed gas mainly composed of 800 ° C. Ar, H 2 and C 2 H 2 is reacted in the furnace, and MWCNT having an average length of about 0.4 mm is obtained as the substrate. Grow up. The average number of layers of MWCNT was 3.
（実施例１）
上記のＳＷＣＮＴ０．１ｇ、界面活性剤であるＣＨＡＰＳ０．４ｇ及びコール酸ナトリウム１．６ｇをそれぞれ量り取り、これらを１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。これらの手順で、実施例１のＣＮＴの分散液を得た。
Example 1
0.1 g of the above SWCNT, 0.4 g of CHAPS as a surfactant and 1.6 g of sodium cholate were weighed out and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). Through these procedures, a CNT dispersion of Example 1 was obtained.
（実施例２）
上記のＭＷＣＮＴ０．１ｇ、界面活性剤であるＣＨＡＰＳ０．４ｇ及びコール酸ナトリウム１．６ｇをそれぞれ量り取り、１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。これらの手順で、実施例２のＣＮＴの分散液を得た。
(Example 2)
0.1 g of the above MWCNT, 0.4 g of CHAPS as a surfactant, and 1.6 g of sodium cholate were weighed and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). Through these procedures, a CNT dispersion of Example 2 was obtained.
（実施例３）
上記のＳＷＣＮＴ０．０１ｇ、界面活性剤である３−（テトラデシルジメチルアミニオ）プロパン−１−スルホナート０．０４ｇ及びミリスチン酸ナトリウム０．１６ｇをそれぞれ量り取り、１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。５０００Ｇの遠心分離によって、攪拌後の混合液から短尺のＣＮＴを分離、除去した。この遠心分離による精製を経て、実施例３の分散液を得た。なお、３−（テトラデシルジメチルアミニオ）プロパン−１−スルホナートは下記化学式（１）で表される。
Weigh out 0.01 g of SWCNT, 0.04 g of surfactant 3- (tetradecyldimethylaminio) propane-1-sulfonate and 0.16 g of sodium myristate, and dilute and mix with 1 L of ultrapure water. A liquid was prepared. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). Short CNTs were separated and removed from the mixed liquid after stirring by centrifugation at 5000G. A dispersion of Example 3 was obtained through purification by centrifugation. Note that 3- (tetradecyldimethylaminio) propane-1-sulfonate is represented by the following chemical formula (1).
（実施例４）
上記のＭＷＣＮＴ０．０１ｇ、界面活性剤であるＣＨＡＰＳ０．０４ｇ及びコール酸ナトリウム０．１６ｇをそれぞれ量り取り、１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、ジルコニアビーズ(φ＝５ｍｍ)と共にバスソニケータに充填し、スリーワンモータを使用してバスソニケータ中の混合液を回転数２００ｒｐｍで５日間攪拌した。５０００Ｇの遠心分離によって、攪拌後の混合液から短尺のＣＮＴを分離、除去した。この遠心分離による精製を経て、実施例４の分散液を得た。
Example 4
0.01 g of the above MWCNT, 0.04 g of CHAPS as a surfactant, and 0.16 g of sodium cholate were weighed and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed liquid after cooling was filled into a bath sonicator together with zirconia beads (φ = 5 mm), and the mixed liquid in the bus sonicator was stirred at a rotational speed of 200 rpm for 5 days using a three-one motor. Short CNTs were separated and removed from the mixed liquid after stirring by centrifugation at 5000G. A dispersion of Example 4 was obtained through purification by centrifugation.
（比較例１）
上記のＳＷＣＮＴ０．１ｇと、界面活性剤であるＣＨＡＰＳ２．０ｇと量り取り、これらを１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。これらの手順で、比較例１のＣＮＴの分散液を得た。
(Comparative Example 1)
The above SWCNT 0.1 g and the surfactant CHAPS 2.0 g were weighed out and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). With these procedures, a CNT dispersion of Comparative Example 1 was obtained.
（比較例２）
上記のＳＷＣＮＴ０．１ｇと、界面活性剤であるコール酸ナトリウム２．０ｇと量り取り、これらを１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。これらの手順で、比較例２のＣＮＴの分散液を得た。
(Comparative Example 2)
The above SWCNT 0.1 g and surfactant sodium cholate 2.0 g were weighed and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). With these procedures, a CNT dispersion of Comparative Example 2 was obtained.
（比較例３）
上記のＳＷＣＮＴ０．１ｇ、界面活性剤であるＣＨＡＰＳ０．４ｇ及びミリスチン酸ナトリウム１．６ｇをそれぞれ量り取り、これらを１Ｌの超純水で希釈して混合液を調製した。混合液を高温高圧下でなじませた後、冷却した。冷却後の混合液を、攪拌式ボールミル（日本コークス社製、ジルコニアビーズφ＝５ｍｍ）を使用して回転数２００ｒｐｍで２週間攪拌した。これらの手順で、比較例３のＣＮＴの分散液を得た。
(Comparative Example 3)
0.1 g of the above SWCNT, 0.4 g of surfactant CHAPS and 1.6 g of sodium myristate were weighed out and diluted with 1 L of ultrapure water to prepare a mixed solution. The mixture was allowed to cool under high temperature and pressure and then cooled. The mixed solution after cooling was stirred for 2 weeks at a rotation speed of 200 rpm using a stirring ball mill (manufactured by Nippon Coke Co., Ltd., zirconia beads φ = 5 mm). With these procedures, a CNT dispersion of Comparative Example 3 was obtained.
＜ＣＮＴの平均太さの測定＞
各分散液に含まれるＣＮＴ単体及びＣＮＴのバンドルの直径の平均値（平均太さ）については、以下の方法で測定した。各分散液の希薄溶液を基板上にスピンコートし、各ＣＮＴ単体及びＣＮＴのバンドルがそれぞれ孤立した状態にあるサンプルを作製した。サンプルをＴＥＭで観察し、得られた画像中から任意に１０個のＣＮＴ単体及びＣＮＴのバンドルを選択し、それらの直径をピクセル数から算出した。１０個の算出値の平均値を、ＣＮＴ全体の平均太さと規定した。同様に、１０個のＣＮＴの層数を観察し、それらの平均値をＣＮＴの平均層数と規定した。
<Measurement of average thickness of CNT>
About the average value (average thickness) of the CNT single-piece | unit and the bundle of CNT contained in each dispersion liquid, it measured with the following method. A dilute solution of each dispersion was spin-coated on a substrate to prepare a sample in which each single CNT and each CNT bundle were isolated. Samples were observed with a TEM, and 10 CNTs and CNT bundles were arbitrarily selected from the obtained images, and their diameters were calculated from the number of pixels. The average value of 10 calculated values was defined as the average thickness of the entire CNT. Similarly, the number of 10 CNT layers was observed, and the average value thereof was defined as the average number of CNT layers.
＜ＣＮＴの平均長さの測定＞
各分散液中のＣＮＴの平均長さについては、以下の方法で測定した。分散液の希薄溶液を基板上にスピンコートし、各ＣＮＴ単体が孤立状態にあるサンプルを作製した。サンプルをＳＥＭまたはＡＦＭで観察し、得られた画像中から任意の１０個のＣＮＴ単体を選択し、その長さをピクセル数から算出した。１０個の算出値の平均値を、ＣＮＴ全体の平均長さと規定した。
<Measurement of average length of CNT>
About the average length of CNT in each dispersion liquid, it measured with the following method. A diluted solution of the dispersion was spin-coated on the substrate to prepare a sample in which each CNT alone was in an isolated state. The sample was observed with SEM or AFM, and arbitrary 10 CNTs were selected from the obtained images, and the length was calculated from the number of pixels. The average value of 10 calculated values was defined as the average length of the entire CNT.
＜分散液の粘度の測定＞
振動式粘度計（ＳＶ−１０）を使用して、測定温度２５℃における各分散液の粘度を測定した。
<Measurement of viscosity of dispersion>
Using a vibration viscometer (SV-10), the viscosity of each dispersion at a measurement temperature of 25 ° C. was measured.
＜ヘイズ値の測定＞
各分散液をＰＥＴフィルム（東洋紡株式会社製、コスモシャインＡ４１００）上にスプレーコータを使用して塗布し、可視光透過率が約８０％である透明電極を作製した。この透明電極のヘイズ値をヘイズメータ（日本電色株式会社製ＮＤＨ−５０００）で測定した。
<Measurement of haze value>
Each dispersion was coated on a PET film (Toyobo Co., Ltd., Cosmo Shine A4100) using a spray coater to produce a transparent electrode having a visible light transmittance of about 80%. The haze value of this transparent electrode was measured with a haze meter (NDH-5000 manufactured by Nippon Denshoku Co., Ltd.).
いかに、各実施例及び比較例のＣＮＴの平均長さ、平均太さ、分散液の粘度、及びヘイズ値を示す。なお、実施例１〜４のいずれにおいても、長さの絶対値が８μｍ〜１０ｍｍの範囲であるＣＮＴの数の割合は、ＣＮＴの全数に対して７０％以上であった。 How the average length, average thickness, viscosity of the dispersion, and haze value of each example and comparative example are shown. In any of Examples 1 to 4, the ratio of the number of CNTs whose absolute length was in the range of 8 μm to 10 mm was 70% or more with respect to the total number of CNTs.
Claims (12)
平均長さが８μｍ以上１０ｍｍ以下であるカーボンナノチューブと、
分子内に親水構造部と疎水構造部とを有する二種以上の界面活性剤と、を備える、
カーボンナノチューブの分散液。 A dispersion medium;
Carbon nanotubes having an average length of 8 μm or more and 10 mm or less;
Two or more surfactants having a hydrophilic structure part and a hydrophobic structure part in the molecule,
Carbon nanotube dispersion.
請求項１に記載のカーボンナノチューブの分散液。 Only a part of the surfactant has a zwitterionic group as a hydrophilic structure,
The dispersion of carbon nanotubes according to claim 1.
請求項１又は２に記載のカーボンナノチューブの分散液。 The molecular weight of the surfactant is 1000 or less,
A dispersion of carbon nanotubes according to claim 1 or 2.
請求項１〜３のいずれか一項に記載のカーボンナノチューブの分散液。 The two or more surfactants have at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and cyclic hemiacetals as the same or similar hydrophobic structure portion,
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-3.
請求項１〜４のいずれか一項に記載のカーボンナノチューブの分散液。 The content of the carbon nanotube is 0.0001 to 10% by weight,
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-4.
請求項１〜５のいずれか一項に記載のカーボンナノチューブの分散液。 The ratio of the number of carbon nanotubes having a length of 8 μm or more and 10 mm or less is 50% or more based on the total number of the carbon nanotubes.
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-5.
請求項１〜６のいずれか一項に記載のカーボンナノチューブの分散液。 The number of layers of the carbon nanotube is 1 to 5,
The dispersion of carbon nanotubes according to any one of claims 1 to 6.
請求項１〜７のいずれか一項に記載のカーボンナノチューブの分散液。 A bundle composed of a plurality of the carbon nanotubes, and the average thickness of the carbon nanotubes present alone is 100 nm or less,
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-7.
請求項１〜８のいずれか一項に記載のカーボンナノチューブの分散液。 The dispersion medium is water;
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-8.
請求項１〜９のいずれか一項に記載のカーボンナノチューブの分散液。 The viscosity at 25 ° C. is 10 mPa · s or less,
The dispersion liquid of the carbon nanotube as described in any one of Claims 1-9.
前記分散媒、前記カーボンナノチューブ及び前記二種以上の界面活性剤を含む混合液を、攪拌式ボールミルにより攪拌する工程を備える、
カーボンナノチューブの分散液の製造方法。 A method for producing a dispersion of carbon nanotubes according to any one of claims 1 to 10,
A step of stirring a mixed liquid containing the dispersion medium, the carbon nanotubes, and the two or more surfactants by a stirring ball mill;
A method for producing a dispersion of carbon nanotubes.
請求項１１に記載のカーボンナノチューブの分散液の製造方法。
Further comprising the step of propagating ultrasonic waves to the mixture.
A method for producing a dispersion of carbon nanotubes according to claim 11.
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