JP5477702B2 - Boron nitride nanotube derivative, dispersion thereof, and method for producing boron nitride nanotube derivative - Google Patents
Boron nitride nanotube derivative, dispersion thereof, and method for producing boron nitride nanotube derivative Download PDFInfo
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本発明は、各種溶媒への分散性が良好で、樹脂組成物への利用などに好適な窒化ホウ素ナノチューブ誘導体、その分散液、及び該窒化ホウ素ナノチューブ誘導体の製造方法に関する。 The present invention relates to a boron nitride nanotube derivative having good dispersibility in various solvents and suitable for use in a resin composition, a dispersion thereof, and a method for producing the boron nitride nanotube derivative.
カーボンナノチューブをはじめとする多くのナノチューブ材料は、一般的な溶媒に不溶のため、その成形・加工方法が著しく制限されている。この問題が解決されれば、実用上非常に有用であるため、ナノチューブ材料を溶媒に均一分散させる方法が種々検討されている。 Many nanotube materials, including carbon nanotubes, are insoluble in common solvents, and their molding and processing methods are significantly limited. If this problem is solved, it is very useful in practice, and various methods for uniformly dispersing the nanotube material in a solvent have been studied.
例えば非特許文献１においては、カーボンナノチューブの表面を鉱酸により酸化せしめ、水酸基やカルボキシル基を導入し溶媒に対する親和性を高め分散性を向上させることが報告されており、非特許文献２及び３においては、更にカーボンナノチューブの表面に存在するカルボキシル基を塩化チオニルで酸クロライドに変換した後、長鎖アルキル基を有するアルコールやアミンと反応させて、長鎖アルキル基が化学結合したカーボンナノチューブを製造することにより分散性を向上させることが報告されている。 For example, Non-Patent Document 1 reports that the surface of a carbon nanotube is oxidized with a mineral acid and a hydroxyl group or a carboxyl group is introduced to increase the affinity for a solvent and improve dispersibility. In addition, after converting the carboxyl group present on the surface of the carbon nanotube to acid chloride with thionyl chloride, it is reacted with an alcohol or amine having a long chain alkyl group to produce a carbon nanotube in which the long chain alkyl group is chemically bonded. It has been reported that dispersibility is improved by doing so.
ところで、カーボンナノチューブがその直径やキラリティが変化すると、それに伴って特性も変動するのに対して、窒化ホウ素ナノチューブは、その直径やキラリティが変化しても特性は変動せず、応用に当たって制御するパラメーターが少ないという利点がある。更に、窒化ホウ素ナノチューブは、優れた機械的性質、高い熱伝導性、優れた耐酸化性、及び広いバンドギャップエネルギーを有しているので、これらの特性が要求される分野、例えば、半導体材料、エミッタ材料、耐熱性充填材料、高強度材料、触媒等、特に酸化雰囲気や高温雰囲気中で作動するナノメートル（ｎｍ）サイズの半導体において有用であると考えられている。また、窒化ホウ素ナノチューブを複合材料の強化材として利用することで、材料のマトリックス相（連続相とも呼ばれている）の機械的性質や熱伝導率の向上に役立つことができる。よって窒化ホウ素ナノチューブの溶媒への分散性を向上させることができれば、種々の成形・加工方法を適用することができ、優れた機能を有する半導体材料などを得ることができる。 By the way, when the diameter and chirality of carbon nanotubes change, the characteristics change accordingly.On the other hand, the characteristics of boron nitride nanotubes do not change even if the diameter and chirality change. There is an advantage that there is little. Furthermore, boron nitride nanotubes have excellent mechanical properties, high thermal conductivity, excellent oxidation resistance, and wide band gap energy, so that these characteristics are required, for example, semiconductor materials, It is considered to be useful for emitter materials, heat-resistant filling materials, high-strength materials, catalysts, etc., particularly in nanometer (nm) size semiconductors that operate in oxidizing or high-temperature atmospheres. Further, by using boron nitride nanotubes as a reinforcing material for a composite material, it can be useful for improving mechanical properties and thermal conductivity of a matrix phase (also called a continuous phase) of the material. Therefore, if the dispersibility of the boron nitride nanotubes in the solvent can be improved, various molding / processing methods can be applied, and a semiconductor material having an excellent function can be obtained.
窒化ホウ素ナノチューブの分散性を向上する技術に関しては、例えば非特許文献４において、窒化ホウ素ナノチューブとアミン末端ポリエチレングリコールオリゴマーとを、１００℃で３日間加熱を続けることにより、両者の間に非共有結合による付加体を形成させて、溶媒に対する溶解性（分散性）を向上させることが報告されている。しかし、この方法では、窒化ホウ素ナノチューブとアミン末端ポリエチレングリコールオリゴマーとの間に非共有結合による付加体を形成しているため、溶媒、特に有機溶媒への分散性が低く、しかも、製造に要する時間が長く収率が低いという問題がある。 Regarding the technology for improving the dispersibility of boron nitride nanotubes, for example, in Non-Patent Document 4, a boron nitride nanotube and an amine-terminated polyethylene glycol oligomer are heated at 100 ° C. for 3 days to thereby form a non-covalent bond therebetween. It is reported that the adduct formed by the above method is formed to improve the solubility (dispersibility) in a solvent. However, in this method, an adduct formed by non-covalent bonding is formed between the boron nitride nanotube and the amine-terminated polyethylene glycol oligomer, so that the dispersibility in a solvent, particularly an organic solvent, is low, and the time required for production is low. However, there is a problem that the yield is low.
また、特許文献１では、窒化ホウ素ナノチューブ、ポリ［ｍ−フェニレンビニレン−ｃｏ−（２，５−ジオクトキシ−ｐ−フェニレンビニレン）］（以下、ラッピングポリマーと称する）、及び有機溶媒からなる窒化ホウ素ナノチューブ分散液が均一かつ透明であることが示されている。しかし、この技術は、液中にラッピングポリマーの存在を必須としている上、このラッピングポリマーを除去するには、有機溶媒除去後に数百℃の温度でラッピングポリマーを熱分解することを必要としている。このため、例えば、ラッピングポリマーとは別の種類のポリマーと窒化ホウ素ナノチューブとの組成物のキャストフィルムを得たい場合に当該技術の分散液を用いることができるのは、ラッピングポリマーの残存が許容される場合に限られる。このように、特許文献１の分散液は、様々な分野で利用しようとしても、適用できる場合が極めて限定されるという問題がある。 Patent Document 1 discloses a boron nitride nanotube comprising a boron nitride nanotube, poly [m-phenylene vinylene-co- (2,5-dioctoxy-p-phenylene vinylene)] (hereinafter referred to as a wrapping polymer), and an organic solvent. The dispersion is shown to be uniform and transparent. However, this technique requires the presence of the wrapping polymer in the liquid, and in order to remove the wrapping polymer, it is necessary to thermally decompose the wrapping polymer at a temperature of several hundred degrees Celsius after removing the organic solvent. For this reason, for example, when it is desired to obtain a cast film of a composition of a different type of polymer from the wrapping polymer and boron nitride nanotubes, the dispersion of the technology can be used because the remaining wrapping polymer is allowed. Limited to Thus, even if it is going to utilize the dispersion liquid of patent document 1 in various fields, there exists a problem that the case where it can apply is very limited.
本発明は、溶媒への分散性が良好な窒化ホウ素ナノチューブ誘導体、その分散液、及びその簡便な製造方法を提供することを目的とする。 An object of the present invention is to provide a boron nitride nanotube derivative having good dispersibility in a solvent, a dispersion thereof, and a simple production method thereof.
本発明者らは、前記課題に鑑み、窒化ホウ素ナノチューブの分散性改良について鋭意検討した結果、窒化ホウ素ナノチューブを酸化処理し、表面元素組成の３原子％以上が酸素である窒化ホウ素ナノチューブ誘導体が際立って良好な分散性を示すことを見出し、本発明を完成するに至った。本発明の要旨を以下に示す。 In view of the above-mentioned problems, the present inventors have made extensive studies on improving the dispersibility of boron nitride nanotubes. As a result, the boron nitride nanotube derivatives in which the boron nitride nanotubes are oxidized and oxygen is 3 atomic% or more of the surface elemental composition stand out. As a result, the present invention was completed. The gist of the present invention is shown below.
１． 表面元素組成の３原子％以上が酸素であることを特徴とする窒化ホウ素ナノチューブ誘導体。
２． 平均直径が０．４ｎｍ〜１μｍであり、平均長さが１〜１０μｍである、前記１項に記載の窒化ホウ素ナノチューブ誘導体。
３． 前記１又は２に記載の窒化ホウ素ナノチューブ誘導体が溶媒中に分散している、窒化ホウ素ナノチューブ誘導体分散液。
４． 溶媒が、水、クロロホルム、Ｎ，Ｎ−ジメチルアセトアミド、テトラヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミド、アセトン、トルエン及びエタノールよりなる群から選ばれる少なくとも１種である、前記３項に記載の窒化ホウ素ナノチューブ誘導体分散液。
５． 窒化ホウ素ナノチューブを３〜７０質量％の過酸化水素溶液、または過酸化水素を３〜７０質量％、鉄（ＩＩ）イオンを１０〜１０００質量ｐｐｍ含む混合組成物溶液にて処理することを特徴とする、前記１項又は２項に記載の窒化ホウ素ナノチューブ誘導体の製造方法。
６． 窒化ホウ素ナノチューブに対して、質量比で２倍を超える量の前記過酸化水素溶液、または質量比で２倍を超える量の前記混合組成物溶液を添加して該窒化ホウ素ナノチューブを処理する、前記５項に記載の窒化ホウ素ナノチューブ誘導体の製造方法。
1. A boron nitride nanotube derivative characterized in that 3 atomic% or more of the surface elemental composition is oxygen.
2. 2. The boron nitride nanotube derivative according to 1 above, having an average diameter of 0.4 nm to 1 μm and an average length of 1 to 10 μm.
3. 3. A boron nitride nanotube derivative dispersion in which the boron nitride nanotube derivative according to 1 or 2 is dispersed in a solvent.
4). 4. The boron nitride nanotube derivative according to 3 above, wherein the solvent is at least one selected from the group consisting of water, chloroform, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, acetone, toluene and ethanol. Dispersion.
5. The boron nitride nanotube is treated with a hydrogen peroxide solution of 3 to 70% by mass or a mixed composition solution containing 3 to 70% by mass of hydrogen peroxide and 10 to 1000 ppm by mass of iron (II) ions. The method for producing a boron nitride nanotube derivative according to Item 1 or 2.
6). The boron nitride nanotubes are treated by adding the hydrogen peroxide solution in an amount exceeding twice the mass ratio or the mixed composition solution in an amount exceeding twice the mass ratio to the boron nitride nanotubes, 6. A method for producing a boron nitride nanotube derivative according to item 5.
本発明によれば、溶媒への分散性に優れた窒化ホウ素ナノチューブ誘導体を提供することができる。また、本発明の製造方法によれば、窒化ホウ素ナノチューブ誘導体を高収率で得ることができる。本発明の窒化ホウ素ナノチューブ誘導体の分散液を用いて種々の成形加工を行うことが可能になる。 ADVANTAGE OF THE INVENTION According to this invention, the boron nitride nanotube derivative excellent in the dispersibility to a solvent can be provided. Moreover, according to the production method of the present invention, a boron nitride nanotube derivative can be obtained in high yield. Various molding processes can be performed using the dispersion liquid of the boron nitride nanotube derivative of the present invention.
本発明の窒化ホウ素ナノチューブ誘導体とは、窒化ホウ素ナノチューブを過酸化水素水によって処理すること等により得られる、表面元素組成の３原子％以上が酸素であることを特徴とする窒化ホウ素ナノチューブ誘導体である。窒化ホウ素ナノチューブ誘導体の表面元素組成は窒化ホウ素ナノチューブ誘導体をＸ線光電子分光分析（ＸＰＳ）、オージェ電子分光分析（ＡＥＳ）などにより求めることができる。また、本発明の窒化ホウ素ナノチューブ誘導体の表面元素組成における酸素の割合の上限としては、５０原子％以下が好ましく、３０原子％以下であるとより好ましく、１０原子％以下であるとより一層好ましい。 The boron nitride nanotube derivative of the present invention is a boron nitride nanotube derivative obtained by treating boron nitride nanotubes with aqueous hydrogen peroxide or the like, wherein 3 atomic% or more of the surface element composition is oxygen. . The surface elemental composition of the boron nitride nanotube derivative can be determined by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) or the like of the boron nitride nanotube derivative. Further, the upper limit of the proportion of oxygen in the surface element composition of the boron nitride nanotube derivative of the present invention is preferably 50 atomic percent or less, more preferably 30 atomic percent or less, and even more preferably 10 atomic percent or less.
本発明の窒化ホウ素ナノチューブ誘導体は、平均直径が０．４ｎｍ〜１μｍ（１０００ｎｍ）であると好ましく、０．６〜５００ｎｍであるとより好ましく、０．８〜２００ｎｍのものであると更に好ましい。 The boron nitride nanotube derivative of the present invention preferably has an average diameter of 0.4 nm to 1 μm (1000 nm), more preferably 0.6 to 500 nm, and still more preferably 0.8 to 200 nm.
本発明の窒化ホウ素ナノチューブ誘導体は、平均長さが、１０μｍ以下であると好ましく、５μｍ以下であるとより好ましく、アスペクト比が５以上であると好ましく、１０以上であるとさらに好ましい。なお、本発明の窒化ホウ素ナノチューブ誘導体の平均長さの下限については、２ｎｍ以上が好ましく、４ｎｍ以上がより好ましく、１００ｎｍ以上であるとより好ましく、１０００ｎｍ（１μｍ）以上であると極めて好ましい。前記の平均直径、平均長さなど、窒化ホウ素ナノチューブ誘導体の寸法は、原料である窒化ホウ素ナノチューブと同程度である。 The boron nitride nanotube derivative of the present invention has an average length of preferably 10 μm or less, more preferably 5 μm or less, an aspect ratio of 5 or more, and even more preferably 10 or more. The lower limit of the average length of the boron nitride nanotube derivative of the present invention is preferably 2 nm or more, more preferably 4 nm or more, more preferably 100 nm or more, and extremely preferably 1000 nm (1 μm) or more. The dimensions of the boron nitride nanotube derivative, such as the average diameter and the average length, are the same as those of the boron nitride nanotube as a raw material.
本発明の窒化ホウ素ナノチューブ誘導体の原料である窒化ホウ素ナノチューブとは、窒化ホウ素からなるチューブ状材料であり、理想的な構造としては６角網目の面がチューブ軸に平行に管を形成し、一重管もしくは多重管になっているものである。 The boron nitride nanotube, which is a raw material of the boron nitride nanotube derivative of the present invention, is a tube-shaped material made of boron nitride. As an ideal structure, a hexagonal mesh surface forms a tube parallel to the tube axis, It is a tube or multiple tubes.
前記の窒化ホウ素ナノチューブは、一般的にはアーク放電法、レーザー加熱法、化学的気相成長法を用いて合成できる。また、ホウ化ニッケルを触媒として使用し、ボラジンを原料として合成する方法も知られている。また、カーボンナノチューブを鋳型として利用して、酸化ホウ素と窒素を反応させて合成する方法も提案されている。本発明に用いられる窒化ホウ素ナノチューブは、特定の方法により製造されるものに限定されず、各種製法により作製されたものを用いることができる。特にホウ素、酸化鉄（ＩＩ）（ＦｅＯ）及び酸化マグネシウム（ＭｇＯ）の混合物を１１００〜１７００℃に加熱して、酸化ホウ素の蒸気を発生させ、この発生した蒸気にアンモニアガスを作用させて合成したものを用いるのが、収量及び高純度の点から好ましい。これらの方法においては、条件によりナノチューブの表面組成の０〜１％程度が酸化またはヒドロキシル化される場合があるが、反応の特性上、大部分は窒化ホウ素結合が優先して生成することにより、それ以上のヒドロキシル基の導入は起こらない。 The boron nitride nanotubes can be synthesized generally using an arc discharge method, a laser heating method, or a chemical vapor deposition method. A method of synthesizing borazine as a raw material using nickel boride as a catalyst is also known. A method of synthesizing boron oxide and nitrogen by using carbon nanotubes as a template has also been proposed. The boron nitride nanotubes used in the present invention are not limited to those produced by a specific method, and those produced by various production methods can be used. In particular, a mixture of boron, iron (II) oxide (FeO) and magnesium oxide (MgO) was heated to 1100 to 1700 ° C. to generate boron oxide vapor, which was synthesized by causing ammonia gas to act on the generated vapor. It is preferable to use one from the viewpoint of yield and high purity. In these methods, about 0 to 1% of the surface composition of the nanotubes may be oxidized or hydroxylated depending on conditions, but due to the characteristics of the reaction, most of them are formed by boron nitride bonds preferentially. No further introduction of hydroxyl groups occurs.
前記の窒化ホウ素ナノチューブの寸法は前記のとおり、窒化ホウ素ナノチューブ誘導体と同程度であり、窒化ホウ素ナノチューブの平均直径は、好ましくは０．４ｎｍ〜１μｍ（１０００ｎｍ）、より好ましくは０．６〜５００ｎｍ、さらにより好ましくは０．８〜２００ｎｍである。ここでいう平均直径とは、一重管の場合、その平均外径を、多重管の場合はその最外側の管の平均外径を意味する。窒化ホウ素ナノチューブの平均長さは、好ましくは１０μｍ以下、より好ましくは５μｍ以下である。アスペクト比は、好ましくは５以上、さらに好ましくは１０以上である。アスペクト比の上限は、平均長さが１０μｍ以下であれば限定されるものではないが、上限は実質２５０００である。よって、窒化ホウ素ナノチューブは、平均直径が０．４ｎｍ〜１μｍ、アスペクト比が５以上であることが好ましい。 As described above, the boron nitride nanotube has the same size as the boron nitride nanotube derivative, and the average diameter of the boron nitride nanotube is preferably 0.4 nm to 1 μm (1000 nm), more preferably 0.6 to 500 nm, Even more preferably, it is 0.8 to 200 nm. The average diameter here means the average outer diameter in the case of a single pipe, and the average outer diameter of the outermost pipe in the case of a multiple pipe. The average length of the boron nitride nanotubes is preferably 10 μm or less, more preferably 5 μm or less. The aspect ratio is preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is not limited as long as the average length is 10 μm or less, but the upper limit is substantially 25000. Therefore, the boron nitride nanotubes preferably have an average diameter of 0.4 nm to 1 μm and an aspect ratio of 5 or more.
本発明の窒化ホウ素ナノチューブ誘導体、及びその原料である窒化ホウ素ナノチューブの平均直径、平均長さ、およびアスペクト比は、電子顕微鏡による観察から求めることが出来る。例えばＴＥＭ（透過型電子顕微鏡）測定を行い、その画像から直接窒化ホウ素ナノチューブの直径および長手方向の長さを測定することが可能である。また組成物中の窒化ホウ素ナノチューブの形態は例えば繊維軸と平行に切断した繊維断面のＴＥＭ（透過型電子顕微鏡）測定により把握することが出来る。 The average diameter, average length, and aspect ratio of the boron nitride nanotube derivative of the present invention and the boron nitride nanotube that is a raw material thereof can be determined from observation with an electron microscope. For example, a TEM (transmission electron microscope) measurement is performed, and the diameter and the length in the longitudinal direction of the boron nitride nanotube can be directly measured from the image. The form of the boron nitride nanotubes in the composition can be grasped by, for example, TEM (transmission electron microscope) measurement of a fiber cross section cut parallel to the fiber axis.
本発明の窒化ホウ素ナノチューブ誘導体は、種々の溶媒への分散性が良好である。該窒化ホウ素ナノチューブ誘導体を溶媒に分散させたものである本発明の窒化ホウ素ナノチューブ誘導体分散液は極めて安定で長期間、例えば１週間保存しても窒化ホウ素ナノチューブ誘導体の凝集や相分離による沈殿を生じない。また、本発明の窒化ホウ素ナノチューブ誘導体は有機溶媒だけでなく水への分散性も良好であり、例えば窒化ホウ素ナノチューブ誘導体の分散液から抄紙法により不織布状物を得る際に安価で不燃性の水を用いることができ有利である。この水溶媒使用時も含めた極めて良好な分散性、および分散液の安定性から考えると、窒化ホウ素ナノチューブを過酸化水素水等で処理し本発明の窒化ホウ素ナノチューブ誘導体とした場合の表面元素組成における酸素原子の増分は、当該処理時に、該誘導体の表面へのヒドロキシ基の導入に起因するものである。 The boron nitride nanotube derivative of the present invention has good dispersibility in various solvents. The boron nitride nanotube derivative dispersion of the present invention, which is obtained by dispersing the boron nitride nanotube derivative in a solvent, is extremely stable and causes precipitation of the boron nitride nanotube derivative or phase separation even when stored for a long period of time, for example, one week. Absent. Further, the boron nitride nanotube derivative of the present invention has good dispersibility in water as well as an organic solvent. For example, when a nonwoven fabric is obtained from a dispersion of boron nitride nanotube derivative by a papermaking method, it is inexpensive and nonflammable water. Can be used advantageously. Considering the extremely good dispersibility, including the use of this aqueous solvent, and the stability of the dispersion, the surface element composition when the boron nitride nanotubes were treated with hydrogen peroxide water to obtain the boron nitride nanotube derivatives of the present invention. The increment of oxygen atoms in is due to the introduction of hydroxy groups on the surface of the derivative during the treatment.
次に本発明の窒化ホウ素ナノチューブ誘導体分散液について説明する。
本発明の窒化ホウ素ナノチューブ誘導体分散液は、前記の本発明の窒化ホウ素ナノチューブ誘導体を溶媒に分散させたものであり、分散濃度としては、溶媒１００質量部にていして窒化ホウ素ナノチューブ誘導体が０．１〜４０質量部であると好ましく、０．３〜２０質量部であるとより好ましく、０．５〜１０質量部であると更に好ましく、０．８〜５質量部であると極めて好ましい。
Next, the boron nitride nanotube derivative dispersion of the present invention will be described.
The boron nitride nanotube derivative dispersion of the present invention is obtained by dispersing the boron nitride nanotube derivative of the present invention in a solvent, and the dispersion concentration is 100 parts by mass of the solvent. It is preferably 1 to 40 parts by mass, more preferably 0.3 to 20 parts by mass, still more preferably 0.5 to 10 parts by mass, and extremely preferably 0.8 to 5 parts by mass.
本発明の窒化ホウ素ナノチューブ誘導体分散液の溶媒としては、水または有機溶媒が好ましく、有機溶媒としては、アルコール、アミド系溶媒、ハロゲン化炭化水素、エステル、ケトン、エーテル、芳香族炭化水素、脂肪族炭化水素など、一般的に使用されるものであれば特に制限は無い。該有機溶媒として具体的には、メタノール、エタノール、プロパノールおよびブタノール、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、塩化メチレン、クロロホルム、四塩化炭素、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、γ―ブチロラクトン、アセトン、２−ブタノン、テトラヒドロフラン、ジオキソラン、ジオキサン、アニソール、トルエン、キシレン及びベンゼンよりなる群から選ばれる１種類以上が挙げられる。前記の溶媒のうち、特に、水、クロロホルム、Ｎ，Ｎ−ジメチルアセトアミド、テトラヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミド、アセトン、トルエン及びエタノールよりなる群から選ばれる１種類以上が好適である。 As a solvent of the boron nitride nanotube derivative dispersion liquid of the present invention, water or an organic solvent is preferable. As the organic solvent, alcohol, amide solvent, halogenated hydrocarbon, ester, ketone, ether, aromatic hydrocarbon, aliphatic There is no particular limitation as long as it is generally used such as hydrocarbon. Specific examples of the organic solvent include methanol, ethanol, propanol and butanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, methylene chloride, chloroform, carbon tetrachloride. And at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, acetone, 2-butanone, tetrahydrofuran, dioxolane, dioxane, anisole, toluene, xylene and benzene. Among these solvents, one or more selected from the group consisting of water, chloroform, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, acetone, toluene and ethanol are particularly preferable.
本発明の窒化ホウ素ナノチューブ誘導体分散液を調製するにおいては、窒化ホウ素ナノチューブ誘導体と溶媒との混合液を機械的に撹拌して分散させる方法や、該混合液を超音波処理して分散させる方法、該混合液を湿式ジェットミルやビーズミルなどの粉砕機により分散させる方法などが挙げられる。なかでも超音波処理により分散させる方法は、簡便であり好ましい。 In preparing the boron nitride nanotube derivative dispersion of the present invention, a method of mechanically stirring and dispersing the mixture of the boron nitride nanotube derivative and the solvent, a method of dispersing the mixture by ultrasonic treatment, Examples thereof include a method of dispersing the mixed solution by a pulverizer such as a wet jet mill or a bead mill. Among them, the method of dispersing by ultrasonic treatment is simple and preferable.
本発明の窒化ホウ素ナノチューブ誘導体分散液を用いれば、窒化ホウ素ナノチューブ誘導体を材料とした成形・加工物を容易に得ることができる。例えば、基板やベルト状物の上に、窒化ホウ素ナノチューブ誘導体の分散液を流延し、加熱して溶媒を蒸発することにより、窒化ホウ素ナノチューブ誘導体からなるフィルム状物を容易に且つ効率よく製造することができる。 If the boron nitride nanotube derivative dispersion liquid of the present invention is used, a molded / processed product using the boron nitride nanotube derivative as a material can be easily obtained. For example, a boron nitride nanotube derivative dispersion is cast on a substrate or belt-like material, and heated to evaporate the solvent, thereby easily and efficiently producing a film-like material made of the boron nitride nanotube derivative. be able to.
次に本発明の窒化ホウ素ナノチューブ誘導体の製造方法について説明する。
本発明の窒化ホウ素ナノチューブ誘導体は、前記の窒化ホウ素ナノチューブを３〜７０質量％の過酸化水素溶液、または過酸化水素を３〜７０質量％、鉄（ＩＩ）イオンを１０〜１０００質量ｐｐｍ含む混合組成物溶液にて処理することにより得られる。
前記の過酸化水素の濃度としては５〜６０質量％であると好ましく、３０〜５５質量％であるとより好ましい。
Next, a method for producing the boron nitride nanotube derivative of the present invention will be described.
The boron nitride nanotube derivative of the present invention is a 3-70 mass% hydrogen peroxide solution containing the boron nitride nanotube, or a mixture containing 3-70 mass% hydrogen peroxide and 10-1000 mass ppm iron (II) ions. It is obtained by treating with a composition solution.
The concentration of the hydrogen peroxide is preferably 5 to 60% by mass, and more preferably 30 to 55% by mass.
過酸化水素と鉄（ＩＩ）イオンを含む前記混合組成物溶液中の鉄（ＩＩ）イオン濃度としては５０〜５００質量ｐｐｍであるとより好ましく、１００〜３００質量ｐｐｍであると特に好ましい。 The iron (II) ion concentration in the mixed composition solution containing hydrogen peroxide and iron (II) ions is more preferably 50 to 500 ppm by mass, and particularly preferably 100 to 300 ppm by mass.
本発明の窒化ホウ素ナノチューブ誘導体の製造方法においては、市販の過酸化水素水溶液を用いる他、これを水などで適当に希釈して用いることもできる。鉄（ＩＩ）イオンは硫酸鉄、塩化鉄、酢酸鉄、及び硝酸鉄、など、通常の鉄（ＩＩ）塩を過酸化水素溶液に添加することで好適に使用することができる。 In the method for producing a boron nitride nanotube derivative of the present invention, a commercially available aqueous hydrogen peroxide solution can be used, or it can be appropriately diluted with water or the like. Iron (II) ions can be suitably used by adding ordinary iron (II) salts such as iron sulfate, iron chloride, iron acetate, and iron nitrate to the hydrogen peroxide solution.
本発明の製造方法において、前記の過酸化水素溶液、または過酸化水素と鉄（II）イオンとの前記の混合組成物溶液にて反応処理する際は、室温あるいは反応を加速するために適温（３０〜１００℃以下）に加熱するほか、超音波を印加しながら処理することも好ましい。また、加圧下に高温（１００℃以上）反応にて処理するなど、窒化ホウ素ナノチューブ誘導体表面の酸素原子量の程度や処理時間を制御するための各種処理条件を好適に適用することができる。 In the production method of the present invention, when the reaction treatment is performed in the hydrogen peroxide solution or the mixed composition solution of hydrogen peroxide and iron (II) ions, the room temperature or a suitable temperature (accelerated for accelerating the reaction) In addition to heating to 30 to 100 ° C. or lower, it is also preferable to perform treatment while applying ultrasonic waves. In addition, various treatment conditions for controlling the amount of oxygen atoms on the surface of the boron nitride nanotube derivative and the treatment time, such as treatment with a high temperature (100 ° C. or higher) reaction under pressure, can be suitably applied.
本発明の製造方法においては、原料である前記窒化ホウ素ナノチューブに対して、質量比で２倍を超える量の前記過酸化水素溶液、または質量比で２倍を超える量の前記混合組成物溶液を添加して該窒化ホウ素ナノチューブを処理することが好ましい。この量よりも前記過酸化水素溶液、または前記混合組成物溶液の量が少ない場合は、窒化ホウ素ナノチューブへの酸素原子（ヒドロキシ基）の導入が進まず、得られた窒化ホウ素ナノチューブ誘導体の溶媒への分散性が不十分となることがあり好ましくない。 In the production method of the present invention, the hydrogen peroxide solution in an amount exceeding twice the mass ratio or the mixed composition solution in an amount exceeding twice the mass ratio with respect to the boron nitride nanotube as a raw material. It is preferable to add and treat the boron nitride nanotubes. When the amount of the hydrogen peroxide solution or the mixed composition solution is less than this amount, introduction of oxygen atoms (hydroxy groups) into the boron nitride nanotube does not proceed, and the resulting boron nitride nanotube derivative is added to the solvent. This is not preferable because the dispersibility of the resin may become insufficient.
以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例の記載に何ら限定されるものではない。
＜窒化ホウ素ナノチューブ及びその誘導体の平均直径、平均長さ、及び外観＞
透過型電子顕微鏡（ＴＥＭ）により５０点以上窒化ホウ素ナノチューブを観察し、その直径と長さの平均をとることで窒化ホウ素ナノチューブの平均直径および平均長さとした。また、窒化ホウ素ナノチューブ誘導体についても同様に観察及び測定を行い、写真撮影も行った。
＜窒化ホウ素ナノチューブ及びその誘導体の表面元素組成＞
窒化ホウ素ナノチューブ及びその誘導体の試料を用いて、硬Ｘ線光電子分光スペクトル測定を行い、表面元素組成の分析を行った。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.
<Average diameter, average length, and appearance of boron nitride nanotube and its derivatives>
More than 50 boron nitride nanotubes were observed with a transmission electron microscope (TEM), and the average diameter and length thereof were taken to obtain the average diameter and average length of the boron nitride nanotubes. The boron nitride nanotube derivative was also observed and measured in the same manner and photographed.
<Surface elemental composition of boron nitride nanotubes and their derivatives>
Using samples of boron nitride nanotubes and derivatives thereof, hard X-ray photoelectron spectroscopy was performed to analyze the surface elemental composition.
[参考例１ 窒化ホウ素ナノチューブの製造]
窒化ホウ素製のるつぼに、１：１のモル比でホウ素と酸化マグネシウムを入れ、坩堝を高周波誘導加熱炉で１３００℃に加熱した。ホウ素と酸化マグネシウムは反応し、気体状の酸化ホウ素（Ｂ２Ｏ２）とマグネシウムの蒸気が生成した。この生成物をアルゴンガスにより反応室へ移送し、温度を１１００℃に維持してアンモニアガスを導入した。酸化ホウ素とアンモニアが反応し、窒化ホウ素が生成した。１．５５ｇの混合物を十分に加熱し、副生成物を蒸発させると、反応室の壁から３１０ｍｇの白色の固体が得られた。続いて得られた白色固体を濃塩酸で洗浄、イオン交換水で中性になるまで洗浄後、６０℃で減圧乾燥を行い窒化ホウ素ナノチューブ（以下、ＢＮＮＴと略すことがある）を得た。得られたＢＮＮＴは、平均直径が２７．６ｎｍ、平均長さが２４６０ｎｍ（２．４６μｍ）のチューブ状であった。表１に前記の窒化ホウ素ナノチューブの表面元素組成解析結果を示した。
[Reference Example 1 Production of Boron Nitride Nanotubes]
Boron and a magnesium oxide were put into the crucible made from boron nitride by the molar ratio of 1: 1, and the crucible was heated at 1300 degreeC with the high frequency induction heating furnace. Boron and magnesium oxide reacted to form gaseous boron oxide (B 2 O 2 ) and magnesium vapor. This product was transferred to the reaction chamber with argon gas, and ammonia gas was introduced while maintaining the temperature at 1100 ° C. Boron oxide and ammonia reacted to form boron nitride. When 1.55 g of the mixture was fully heated and the by-product was evaporated, 310 mg of a white solid was obtained from the walls of the reaction chamber. Subsequently, the obtained white solid was washed with concentrated hydrochloric acid and washed with ion-exchanged water until neutral, and then dried at 60 ° C. under reduced pressure to obtain boron nitride nanotubes (hereinafter sometimes abbreviated as BNNT). The obtained BNNT was in the form of a tube having an average diameter of 27.6 nm and an average length of 2460 nm (2.46 μm). Table 1 shows the results of surface element composition analysis of the boron nitride nanotubes.
［実施例１］
参考例１と同様の方法にて調製した窒化ホウ素ナノチューブ１ｇ及び５０％過酸化水素水溶液（アルドリッチ（株）製）５０ｍＬをフラスコに入れ、超音波照射下に５０℃で２４時間撹拌した。その後、この分散液を２０００ｒｐｍの条件で遠心分離し、得られた固体分をロ別、イオン交換水５００ｍＬおよびメタノール洗浄することで、白色粉末の窒化ホウ素ナノチューブ誘導体１ｇを得た。図１に、該窒化ホウ素ナノチューブ誘導体試料の透過型電子顕微鏡写真図を示す。該窒化ホウ素ナノチューブ誘導体は、平均直径が２７．１ｎｍであり、平均長さが２４１０ｎｍ（２．４１μｍ）であった。これにより、窒化ホウ素ナノチューブ誘導体の一次元性、寸法およびアスペクト比は処理前の窒化ホウ素ナノチューブの構造が維持されていることが確認できた。また、表１に窒化ホウ素ナノチューブ誘導体の表面元素組成解析結果を示した。表１から明らかなように、処理前後の窒化ホウ素ナノチューブ組成と比較して、窒化ホウ素ナノチューブ誘導体では酸素原子由来の吸収ピークが増大しており、表面組成の約５原子％が酸素となったことが確認された。
[Example 1]
1 g of boron nitride nanotubes prepared in the same manner as in Reference Example 1 and 50 mL of a 50% aqueous hydrogen peroxide solution (manufactured by Aldrich) were placed in a flask and stirred at 50 ° C. for 24 hours under ultrasonic irradiation. Thereafter, the dispersion was centrifuged under the condition of 2000 rpm, and the obtained solid was separated and washed with 500 mL of ion-exchanged water and methanol to obtain 1 g of boron nitride nanotube derivative of white powder. FIG. 1 shows a transmission electron micrograph of the boron nitride nanotube derivative sample. The boron nitride nanotube derivative had an average diameter of 27.1 nm and an average length of 2410 nm (2.41 μm). Accordingly, it was confirmed that the one-dimensionality, size, and aspect ratio of the boron nitride nanotube derivative maintained the structure of the boron nitride nanotube before treatment. Table 1 shows the results of surface elemental composition analysis of boron nitride nanotube derivatives. As is apparent from Table 1, the boron nitride nanotube derivative has an increased absorption peak due to oxygen atoms compared to the boron nitride nanotube composition before and after the treatment, and about 5 atomic% of the surface composition is oxygen. Was confirmed.
イオン交換水、エタノール、Ｎ，Ｎ−ジメチルアセトアミド、テトラヒドロフラン、クロロホルムの各溶媒（１０質量部ずつ）に対して、前記の窒化ホウ素ナノチューブ誘導体０．１質量部を加え、バス型超音波分散機にて２０秒分散処理を行って、窒化ホウ素ナノチューブ誘導体分散液を調製した後、これを室温に静置して分散状態を観察評価した。得られた分散液は、何れの溶媒系でも安定に分散状態を保ち、一週間そのまま保存しても窒化ホウ素ナノチューブ誘導体の凝集や相分離による沈殿を生じることはなかった。 Add 0.1 part by mass of the boron nitride nanotube derivative to each solvent (10 parts by mass) of ion-exchanged water, ethanol, N, N-dimethylacetamide, tetrahydrofuran, and chloroform, and add to the bath-type ultrasonic disperser. Then, after carrying out a dispersion treatment for 20 seconds to prepare a boron nitride nanotube derivative dispersion liquid, this was left at room temperature to observe and evaluate the dispersion state. The obtained dispersion maintained a stable dispersion state in any solvent system, and even when stored as it was for one week, the boron nitride nanotube derivative did not aggregate or precipitate due to phase separation.
［実施例２］
硫酸鉄（ＩＩ）七水和物４０ｍｇを３０ｍＬサンプル菅瓶に取り、これにイオン交換水を加え、全量が１０ｇになるよう調製した。これを、フラスコ中にて５０％過酸化水素水（アルドリッチ（株）製、密度１．２０ｇ／ｍＬ）５０ｍＬに氷浴上で滴下、混合してフェントン試薬を調製した（混合液中の鉄イオン濃度は１１５質量ｐｐｍ）。これに参考例１と同様の方法にて調製した窒化ホウ素ナノチューブ１ｇを加え、超音波照射下に５０℃で３時間撹拌した。その後、この分散液を２０００ｒｐｍの条件で遠心分離し、得られた固体分をロ別、イオン交換水５００ｍＬおよびメタノール洗浄することで、白色粉末の窒化ホウ素ナノチューブ誘導体１ｇを得た。図２に、該窒化ホウ素ナノチューブ誘導体試料の透過型電子顕微鏡写真図を示す。該窒化ホウ素ナノチューブ誘導体は、平均直径が２６．５ｎｍであり、その平均長さが２３８０ｎｍ（２．３８μｍ）であることが分かった。これにより、窒化ホウ素ナノチューブ誘導体の一次元性、寸法およびアスペクト比は処理前の窒化ホウ素ナノチューブの構造が維持されていることが確認できた。また、表１に該窒化ホウ素ナノチューブ誘導体の表面元素組成を示した。
[Example 2]
40 mg of iron (II) sulfate heptahydrate was placed in a 30 mL sample bottle, and ion-exchanged water was added thereto to prepare a total amount of 10 g. This was added dropwise to 50 mL of 50% hydrogen peroxide (Aldrich Corp., density 1.20 g / mL) in an flask on an ice bath to prepare a Fenton reagent (iron ions in the mixture). The concentration is 115 ppm by mass). To this was added 1 g of boron nitride nanotubes prepared by the same method as in Reference Example 1, and the mixture was stirred at 50 ° C. for 3 hours under ultrasonic irradiation. Thereafter, the dispersion was centrifuged under the condition of 2000 rpm, and the obtained solid was separated and washed with 500 mL of ion-exchanged water and methanol to obtain 1 g of boron nitride nanotube derivative of white powder. FIG. 2 shows a transmission electron micrograph of the boron nitride nanotube derivative sample. The boron nitride nanotube derivative was found to have an average diameter of 26.5 nm and an average length of 2380 nm (2.38 μm). Accordingly, it was confirmed that the one-dimensionality, size, and aspect ratio of the boron nitride nanotube derivative maintained the structure of the boron nitride nanotube before treatment. Table 1 shows the surface elemental composition of the boron nitride nanotube derivative.
イオン交換水、エタノール、Ｎ，Ｎ−ジメチルアセトアミド、テトラヒドロフラン、クロロホルムの各溶媒（１０質量部ずつ）に対して、前記の窒化ホウ素ナノチューブ誘導体０．１質量部を加え、バス型超音波分散機にて２０秒分散処理を行って、窒化ホウ素ナノチューブ誘導体分散液を調製した後、これを室温に静置して分散状態を観察評価した。得られた分散液は、何れの溶媒系でも安定に分散状態を保ち、一週間そのまま保存しても窒化ホウ素ナノチューブ誘導体の凝集や相分離による沈殿を生じることはなかった。 Add 0.1 part by mass of the boron nitride nanotube derivative to each solvent (10 parts by mass) of ion-exchanged water, ethanol, N, N-dimethylacetamide, tetrahydrofuran, and chloroform, and add to the bath-type ultrasonic disperser. Then, after carrying out a dispersion treatment for 20 seconds to prepare a boron nitride nanotube derivative dispersion liquid, this was left at room temperature to observe and evaluate the dispersion state. The obtained dispersion maintained a stable dispersion state in any solvent system, and even when stored as it was for one week, the boron nitride nanotube derivative did not aggregate or precipitate due to phase separation.
［比較例１］
イオン交換水、エタノール、Ｎ，Ｎ−ジメチルアセトアミド、テトラヒドロフラン、クロロホルムの各溶媒（１０質量部ずつ）に対して、参考例１と同様の方法にて調製した窒化ホウ素ナノチューブ０．１質量部を加え、バス型超音波分散機にて２０秒分散処理を行った処理液を室温に静置して分散状態を観察評価したが、いずれの溶媒においても１週間安定な分散状態を維持することはできず、窒化ホウ素ナノチューブの凝集や相分離による沈殿が起こり、安定な分散液にはならなかった。
[Comparative Example 1]
0.1 parts by mass of boron nitride nanotubes prepared in the same manner as in Reference Example 1 was added to each solvent (10 parts by mass) of ion-exchanged water, ethanol, N, N-dimethylacetamide, tetrahydrofuran, and chloroform. In addition, the treatment liquid that was subjected to the dispersion treatment for 20 seconds with a bath-type ultrasonic disperser was allowed to stand at room temperature, and the dispersion state was observed and evaluated. In any solvent, a stable dispersion state can be maintained for one week. First, the boron nitride nanotubes aggregated and precipitated due to phase separation, and the dispersion was not stable.
本発明により、種々の溶媒への分散性が極めて良好な窒化ホウ素ナノチューブ誘導体を得ることができる。この窒化ホウ素ナノチューブ誘導体を用いて分散液を作製することができる。この分散液を用いれば、窒化ホウ素ナノチューブ誘導体を成形加工し、半導体材料など多くの分野で活用することが可能となる。 According to the present invention, boron nitride nanotube derivatives having extremely good dispersibility in various solvents can be obtained. A dispersion can be produced using this boron nitride nanotube derivative. If this dispersion is used, the boron nitride nanotube derivative can be molded and used in many fields such as semiconductor materials.
Claims (6)
The boron nitride nanotubes are treated by adding the hydrogen peroxide solution in an amount exceeding twice the mass ratio or the mixed composition solution in an amount exceeding twice the mass ratio to the boron nitride nanotubes. Item 6. A method for producing a boron nitride nanotube derivative according to Item 5.
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