JP2012218992A - Method for producing water dispersion of carbon nanotube - Google Patents
Method for producing water dispersion of carbon nanotube Download PDFInfo
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本発明は、界面活性剤および尿素を利用したカーボンナノチューブの水分散液の製造方法に関するものである。 The present invention relates to a method for producing an aqueous dispersion of carbon nanotubes using a surfactant and urea.
カーボンナノチューブ（ＣＮＴ）は複合材料や電子機器などへの応用で注目されているが、その電気的特性、生体分子との親和性、比表面積の大きさなどから生体分子を用いた製品においても応用が期待され、検討されている。ＣＮＴの分散溶媒として有機溶媒が多用されるが（例えば、特許文献１参照）、有機溶媒は生体分子に対して悪影響を及ぼすことが多く生物分野での使用に向かない。そこで生体分子に対する影響を低減するため、水系溶媒でのＣＮＴの分散液が求められた（水分散液）。ＣＮＴは疎水性が高く、水のみではＣＮＴを分散させることが困難である。そのため分散剤として界面活性剤が活発に検討された（例えば、特許文献２、特許文献３参照）。 Carbon nanotubes (CNT) are attracting attention for their application to composite materials and electronic devices, but they are also applied to products using biomolecules due to their electrical properties, affinity with biomolecules, and the size of specific surface area. Is expected and studied. An organic solvent is frequently used as a dispersion solvent for CNT (see, for example, Patent Document 1). However, organic solvents often have adverse effects on biomolecules and are not suitable for use in the biological field. Therefore, in order to reduce the influence on biomolecules, a dispersion of CNTs in an aqueous solvent was required (aqueous dispersion). CNT is highly hydrophobic, and it is difficult to disperse CNT only with water. For this reason, surfactants have been actively studied as dispersants (see, for example, Patent Document 2 and Patent Document 3).
しかし、前記界面活性剤により製造されたＣＮＴの分散液は、長期の保存においてＣＮＴが凝集し、沈殿を生じるため、有効なＣＮＴの表面積が時間経過に伴って大きく変動するという課題を有していた。 However, the dispersion of CNTs produced with the surfactant has the problem that the effective surface area of CNTs varies greatly over time because CNTs aggregate and precipitate during long-term storage. It was.
本発明の目的は、カーボンナノチューブの安定な水分散液の製造方法を提供することである。 An object of the present invention is to provide a method for producing a stable aqueous dispersion of carbon nanotubes.
前記従来の課題を解決するために、本発明のカーボンナノチューブの水分散液の製造方法は、非イオン性界面活性剤または陰イオン性界面活性剤と尿素からなる水溶液を用いてカーボンナノチューブを分散する。本構成によって、長期の保存において分散状態を維持したカーボンナノチューブの水分散液を製造することができる。 In order to solve the above-mentioned conventional problems, the method for producing an aqueous dispersion of carbon nanotubes of the present invention disperses carbon nanotubes using an aqueous solution comprising a nonionic surfactant or an anionic surfactant and urea. . With this configuration, it is possible to produce an aqueous dispersion of carbon nanotubes that maintains a dispersed state during long-term storage.
長期の保存において分散状態を維持したカーボンナノチューブの水分散液の製造方法を提供する。 Provided is a method for producing an aqueous dispersion of carbon nanotubes that maintains a dispersed state during long-term storage.
以下、図面を参照しながら、本発明の実施の形態が説明される。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
本発明は非イオン性界面活性剤または陰イオン性界面活性剤と尿素からなる水溶液を用いてカーボンナノチューブ（ＣＮＴ）を分散することを特徴とする、ＣＮＴ水分散液の製造方法である。 The present invention is a method for producing a CNT aqueous dispersion, wherein carbon nanotubes (CNT) are dispersed using an aqueous solution comprising a nonionic surfactant or an anionic surfactant and urea.
界面活性剤は疎水性の物質を水系溶媒に分散させる効果を有する。本発明では界面活性剤として非イオン性界面活性剤や陰イオン性界面活性剤を用いることができる。 The surfactant has an effect of dispersing a hydrophobic substance in an aqueous solvent. In the present invention, a nonionic surfactant or an anionic surfactant can be used as the surfactant.
前記非イオン性界面活性剤はポリオキシエチレンアルキルエーテルまたはポリオキシエチレンアルキルフェニルエーテルが好ましく用いられる。ポリ(オキシエチレン)ソルビタンモノラウレートがより好ましく用いられる。 As the nonionic surfactant, polyoxyethylene alkyl ether or polyoxyethylene alkylphenyl ether is preferably used. Poly (oxyethylene) sorbitan monolaurate is more preferably used.
前記陰イオン性界面活性剤はアルキル硫酸エステル塩、コール酸、デオキシコール酸が好ましく用いられる。 The anionic surfactant is preferably an alkyl sulfate ester salt, cholic acid, or deoxycholic acid.
前記非イオン性界面活性剤および陰イオン性界面活性剤の濃度は臨界ミセル濃度の７０％以上が好ましい。７０％以下ではＣＮＴを分散することが困難となる。 The concentration of the nonionic surfactant and the anionic surfactant is preferably 70% or more of the critical micelle concentration. If it is 70% or less, it becomes difficult to disperse CNTs.
前記界面活性剤溶液に尿素を含めることによりＣＮＴの分散状態が安定化される。前記溶液の尿素は５Ｍ以上の濃度を有することが好ましい。 By containing urea in the surfactant solution, the dispersion state of CNTs is stabilized. The urea in the solution preferably has a concentration of 5M or more.
本発明により分散されるＣＮＴは、単層ＣＮＴおよび多層ＣＮＴである。 The CNTs dispersed according to the present invention are single-walled CNTs and multilayered CNTs.
前記界面活性剤と尿素からなる溶液に乾燥状態の前記ＣＮＴを浸漬し、物理的手段でホモジナイズ処理することで、水溶液中にＣＮＴを分散させることができる。前記ホモジナイズ処理によりＣＮＴの水分散液が調製される。 The CNTs can be dispersed in the aqueous solution by immersing the CNTs in a dry state in a solution comprising the surfactant and urea and performing a homogenization treatment by physical means. An aqueous dispersion of CNTs is prepared by the homogenization treatment.
分散されるＣＮＴの濃度は１ｍｇ／ｍＬ以下が好ましい。 The concentration of the dispersed CNT is preferably 1 mg / mL or less.
ホモジナイズ処理には超音波ホモジナイザー、擂潰機を用いることができる。超音波ホモジナイザーがより好ましい。 An ultrasonic homogenizer and a crusher can be used for the homogenization treatment. An ultrasonic homogenizer is more preferable.
ＣＮＴの水分散液の分散の安定性は吸光度の測定により評価できる。分散されたＣＮＴの濃度と波長５００ｎｍの吸光度は相関しており、ＣＮＴの濃度が高いと吸光度も高い。ＣＮＴの水分散液の分散の安定性が低いと凝集、沈殿を起こし、分散したＣＮＴの濃度が低下するため吸光度も低下する。波長５００ｎｍの吸光度の経時変化を測定することでＣＮＴの水分散液の分散の安定性が評価される。 The dispersion stability of the aqueous dispersion of CNTs can be evaluated by measuring absorbance. The concentration of the dispersed CNT and the absorbance at a wavelength of 500 nm are correlated, and the absorbance is high when the concentration of CNT is high. If the dispersion stability of the aqueous dispersion of CNTs is low, aggregation and precipitation occur, and the concentration of dispersed CNTs decreases, so the absorbance also decreases. The stability of the dispersion of the CNT aqueous dispersion is evaluated by measuring the change with time in absorbance at a wavelength of 500 nm.
以下の実施例１を用いて、本発明はより詳細に説明される。 The following example 1 is used to explain the invention in more detail.
（実施例１）
（界面活性剤溶液の調製）
ポリ(オキシエチレン)ソルビタンモノラウレート（ＡＮＡＰＯＥ‐２０、１０％（ｗ／ｖ）水溶液；Ａｎａｔｒａｃｅ社製）を超純水で希釈し、０．３６％（ｗ／ｖ）の濃度を有するＡＮＡＰＯＥ‐２０溶液を調製した。
Example 1
(Preparation of surfactant solution)
Poly (oxyethylene) sorbitan monolaurate (ANAPOE-20, 10% (w / v) aqueous solution; manufactured by Anatrac) is diluted with ultrapure water and has a concentration of 0.36% (w / v). 20 solutions were prepared.
（尿素溶液の調製）
尿素（特級；和光純薬工業社製）の粉末を超純水で溶解し、８Ｍの濃度を有する尿素溶液を調製した。
(Preparation of urea solution)
Urea (special grade; manufactured by Wako Pure Chemical Industries, Ltd.) powder was dissolved in ultrapure water to prepare a urea solution having a concentration of 8M.
（界面活性剤と尿素からなる溶液の調製）
１０％（ｗ／ｖ）の濃度を有するＡＮＡＰＯＥ‐２０と溶液８Ｍの濃度を有する尿素溶液および超純水を混合し、０．３６％（ｗ／ｖ）の濃度のＡＮＡＰＯＥ‐２０および６Ｍの濃度の尿素を含む溶液を調製した。
(Preparation of solution consisting of surfactant and urea)
ANAPOOE-20 having a concentration of 10% (w / v) is mixed with urea solution having a concentration of 8M and ultrapure water, and the concentrations of ANAPOE-20 and 6M having a concentration of 0.36% (w / v) are mixed. A solution containing urea was prepared.
（カーボンナノチューブ（ＣＮＴ）の水分散の調製）
４ｍＬの前記界面活性剤と尿素からなる溶液に２ｍｇのＣＮＴ（単層ＣＮＴ；Ｎａｎｏｉｎｔｅｇｒｉｓ社製）が添加された。その後、超音波ホモジナイザー（ｓｏｎｉｆｉｅｒ １５０；Ｂｒａｎｓｏｎ社製）を用いて、出力１０ Ｗａｔｔｓ （ＲＭＳ）で５分間処理した。０．５ｍＬの前記溶液に４．５ｍＬの前記界面活性剤と尿素からなる溶液を添加した。その後、超音波ホモジナイザーを用いて、出力１０ Ｗａｔｔｓ （ＲＭＳ）で５分間処理し、前記界面活性剤と尿素からなる溶液で処理したＣＮＴの水分散液を得た。
(Preparation of water dispersion of carbon nanotube (CNT))
2 mg of CNT (single-walled CNT; manufactured by Nanointegris) was added to 4 mL of the surfactant and urea solution. Then, it processed for 5 minutes by
同様に、前記０．３６％（ｗ／ｖ）の濃度を有するＡＮＡＰＯＥ‐２０溶液（界面活性剤溶液）を用いてＣＮＴを処理することでＣＮＴの水分散液を得た。 Similarly, an aqueous dispersion of CNTs was obtained by treating CNTs with the ANAPOE-20 solution (surfactant solution) having a concentration of 0.36% (w / v).
同様に、前記６Ｍの濃度を有する尿素溶液を用いてＣＮＴを処理することでＣＮＴの水分散液を得た。
（吸光度測定によるＣＮＴ水分散液の安定性評価）
（測定装置）
ＣＮＴ水分散液の安定性は吸光度により測定された。吸光度測定には、紫外可視分光光度計（ＵＶ-１６００ＰＣ；島津製作所社製）を使用した。測定容器は光路長１ｃｍのセル（セミマイクロブラックセル、石英；ＧＥヘルスケア社製）が用いられた。
Similarly, an aqueous dispersion of CNTs was obtained by treating CNTs with a urea solution having a concentration of 6M.
(Stability evaluation of CNT aqueous dispersion by measuring absorbance)
(measuring device)
The stability of the CNT aqueous dispersion was measured by absorbance. An ultraviolet-visible spectrophotometer (UV-1600PC; manufactured by Shimadzu Corporation) was used for the absorbance measurement. As the measurement container, a cell having a light path length of 1 cm (semi-micro black cell, quartz; manufactured by GE Healthcare) was used.
（吸光度の測定）
前記界面活性剤と尿素からなる溶液で処理したＣＮＴの水分散液及び前記界面活性剤溶液で処理したＣＮＴの水分散液について、波長５００ｎｍの吸光度を前記水分散液の調製後、２時間後、３日後および６０日後の時点について測定した。目視により確認できる沈殿を生じた場合は沈殿を残し、上清だけを測定に用いた。
(Measurement of absorbance)
For an aqueous dispersion of CNT treated with a solution comprising the surfactant and urea and an aqueous dispersion of CNT treated with the surfactant solution, the absorbance at a wavelength of 500 nm was measured for 2 hours after the preparation of the aqueous dispersion, Measurements were made at 3 and 60 days. When a precipitate that could be visually confirmed was generated, the precipitate was left and only the supernatant was used for the measurement.
図１はＣＮＴ水分散液の経時測定の結果を示す。界面活性剤で分散したＣＮＴは時間の経過に従い吸光度が低下し、60日が経過した後では調製直後（２時間）の吸光度の値に対して値が５７％に低下した。一方、界面活性剤と尿素からなる溶液で分散したＣＮＴは調製直後の値に対して９０％を維持した。 FIG. 1 shows the results of measurement over time of a CNT aqueous dispersion. The CNT dispersed with the surfactant decreased in absorbance as time passed, and after 60 days, the value decreased to 57% with respect to the absorbance value immediately after preparation (2 hours). On the other hand, CNT dispersed in a solution comprising a surfactant and urea maintained 90% of the value immediately after preparation.
従って、界面活性剤と尿素からなる溶液で分散したＣＮＴは、長期の保存において分散状態を維持したＣＮＴの水分散液であることを当業者は図１に基づいて理解するであろう。 Therefore, those skilled in the art will understand based on FIG. 1 that a CNT dispersed in a solution composed of a surfactant and urea is an aqueous dispersion of CNT that maintains a dispersed state during long-term storage.
本発明は、バイオセンサやバイオリアクターに用いられ得る。本発明は、バイオセンサやバイオリアクターにおける生体分子の担体や電極として特に有用である。 The present invention can be used for biosensors and bioreactors. The present invention is particularly useful as a biomolecule carrier or electrode in a biosensor or bioreactor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112675317A (en) * | 2020-12-24 | 2021-04-20 | 广东药科大学 | CO2/N2Switch type fluorescent liquid-liquid phase separation nano liquid drop and preparation method thereof |
| US11479469B2 (en) | 2018-03-23 | 2022-10-25 | Nec Corporation | Method for storing a nanocarbon dispersion liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11479469B2 (en) | 2018-03-23 | 2022-10-25 | Nec Corporation | Method for storing a nanocarbon dispersion liquid |
| CN112675317A (en) * | 2020-12-24 | 2021-04-20 | 广东药科大学 | CO2/N2Switch type fluorescent liquid-liquid phase separation nano liquid drop and preparation method thereof |
| CN112675317B (en) * | 2020-12-24 | 2023-03-14 | 广东药科大学 | CO2/N2 switch type fluorescent liquid-liquid phase separation nano liquid drop and preparation method thereof |
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