JP2005007861A - Three-layer structure oriented carbon nanotube membrane composite sheet and method for fixing the oriented carbon nanotube membrane - Google Patents

Three-layer structure oriented carbon nanotube membrane composite sheet and method for fixing the oriented carbon nanotube membrane Download PDF

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JP2005007861A
JP2005007861A JP2004123132A JP2004123132A JP2005007861A JP 2005007861 A JP2005007861 A JP 2005007861A JP 2004123132 A JP2004123132 A JP 2004123132A JP 2004123132 A JP2004123132 A JP 2004123132A JP 2005007861 A JP2005007861 A JP 2005007861A
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sheet
carbon nanotube
nanotube film
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oriented carbon
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Takashi Fujii
尊 藤井
Masao Someya
昌男 染谷
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Mitsubishi Gas Chemical Co Inc
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<P>PROBLEM TO BE SOLVED: To provide an oriented CNT (carbon nanotube) membrane composite sheet of three-layer structure where the oriented CNT membrane is sandwiched between functional sheets, and a method for fixing the oriented CNT membrane from a functional sheet onto another functional sheet while retaining its shape. <P>SOLUTION: The functional sheet is a sheet capable of fixing the oriented CNT membrane and provided with adhesivity, thermal bondability, irradiation sensitivity, easy dissolvability or chemical reactivity. The functional sheet is light, deformable and inexpensive. The oriented CNT membrane in the three-layer structure oriented CNT membrane composite sheet is stable in shape and protected from contamination, thereby can be widely disseminated in the industrial fields. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、カーボンナノチューブ（以下、ＣＮＴと略称する）材料およびそれらの取り扱い技術に関する。特に本発明は、配向性ＣＮＴ膜を機能性シート間に挟んだ三層構造の配向性ＣＮＴ膜複合シート、および形状を保たせたまま該配向性ＣＮＴ膜を機能性シートから別の機能性シートへ固定化する方法に関する。   The present invention relates to a carbon nanotube (hereinafter abbreviated as CNT) material and a handling technique thereof. In particular, the present invention relates to an oriented CNT film composite sheet having a three-layer structure in which an oriented CNT film is sandwiched between functional sheets, and the functional sheet from another functional sheet while maintaining the shape. It relates to the method of immobilization.

ＣＮＴは、１９９１年に飯島澄男氏によって発見されたもので（非特許文献１参照）、一般的な形状は、直径０．５〜１００ｎｍ、長さ１〜１００μｍであり、非常に細長い中空のチューブ状の炭素材料である。   CNT was discovered by Sumio Iijima in 1991 (see Non-Patent Document 1). The general shape is 0.5-100 nm in diameter and 1-100 μm in length, and is a very elongated hollow tube. Carbon material.

ＣＮＴの用途としては、電子放出源、アクチュエーター、電池の電極、分離膜、センサー、エネルギー貯蔵、熱伝材料など広い分野で提案、期待されている。但し、これらの用途にＣＮＴを用いる場合では、何万本以上のＣＮＴを集合体として使うことになる。しかしながら、一本のＣＮＴは非常に微細であり、それらの集合体を操作して上記の用途のための装置に組み込むのは容易でなかった。   Applications of CNTs are proposed and expected in a wide range of fields such as electron emission sources, actuators, battery electrodes, separation membranes, sensors, energy storage, and heat transfer materials. However, when CNTs are used for these purposes, tens of thousands or more of CNTs are used as an aggregate. However, a single CNT is very fine, and it has not been easy to manipulate these aggregates and incorporate them into equipment for the above applications.

例えば、ＣＮＴ懸濁液をフィルターに通すことでフィルター表面にＣＮＴ膜を形成させ、該ＣＮＴ膜を電極に転写する方法が知られている（非特許文献２参照）。しかしこの方法ではフィルター表面上に形成されるＣＮＴ膜中のＣＮＴはランダムに堆積しているので、電極表面と接触可能な表面に出ているＣＮＴのみが電極へ移るだけで、無駄が多い。   For example, a method is known in which a CNT film is formed on the filter surface by passing a CNT suspension through a filter, and the CNT film is transferred to an electrode (see Non-Patent Document 2). However, in this method, since the CNTs in the CNT film formed on the filter surface are randomly deposited, only the CNTs appearing on the surface that can come into contact with the electrode surface are transferred to the electrode, which is wasteful.

ここで、個々のＣＮＴの特徴を集約でき、効果的かつ容易に装置に組み込めることができる形状として、ＣＮＴが一方向に配向している形状を成している事が好ましい。その際、配向性のある多数本のＣＮＴは膜状を形成するので、便宜上、配向性ＣＮＴ膜と呼ぶ。通常、配向性ＣＮＴ膜は高温の加熱炉の中、平板の成長基板に垂直に配向して成長させ得られる。従って該成長基板の材質としては、シリコンウエハー、石英、セラミックス等の耐熱性の優れたもののみが使用される（特許文献１参照）。   Here, it is preferable that the shape of the CNTs be oriented in one direction as a shape that allows the characteristics of the individual CNTs to be aggregated and that can be incorporated into the apparatus effectively and easily. At that time, since a large number of oriented CNTs form a film, they are called oriented CNT films for convenience. Usually, the oriented CNT film can be grown in a high-temperature heating furnace by being oriented perpendicularly to a flat growth substrate. Therefore, as the material of the growth substrate, only a material having excellent heat resistance such as silicon wafer, quartz, ceramics or the like is used (see Patent Document 1).

さらに、得られた配向性ＣＮＴ膜を上述の期待されている用途に適合させる工夫が幾通りか成されている。例えば、基体上に垂直配向したＣＮＴを成長させた後、基体を溶解することにより、該基体からＣＮＴを独立させる方法が開示されている（特許文献２参照）。また、基体上に垂直配向しながら成長したＣＮＴ膜を、配向性を保たせながら該基体から剥がす操作が開示されている（特許文献３参照）。基体上に配向性のあるＣＮＴ膜を成長させ、該配向性ＣＮＴ膜を第二の基体に固定する方法が開示されている（特許文献４参照）。
Ｓ．Ｉｉｊｉｍａ，Ｎａｔｕｒｅ，３５４，ｐ．５６−５８（１９９１） Ｗ．Ａ．ｄｅ Ｈｅｅｒら他２名，Ｓｃｉｅｎｃｅ，２７０，ｐ．１１７９−１１８０（１９９５） ＷＯ ００／３０１４１ 特開２００１−１０２３８１ ＷＯ／００６３１１５ ＷＯ ００／７３２０４ Furthermore, several ideas have been made to adapt the obtained oriented CNT film to the above-mentioned expected use. For example, a method is disclosed in which a vertically aligned CNT is grown on a substrate, and then the substrate is dissolved to make the CNT independent from the substrate (see Patent Document 2). Further, an operation is disclosed in which a CNT film grown while being vertically aligned on a substrate is peeled off from the substrate while maintaining the orientation (see Patent Document 3). A method of growing an oriented CNT film on a substrate and fixing the oriented CNT film to a second substrate is disclosed (see Patent Document 4).
S. Iijima, Nature, 354, p. 56-58 (1991) W. A. de Heer et al., 2 others, Science, 270, p. 1179-1180 (1995) WO 00/30141 JP 2001-102381 A WO / 0063115 WO 00/73204

まず、配向性ＣＮＴ膜中の個々のＣＮＴは互いに独立しているため、少なくとも片方の表面を支持基体に固定させておかないと、一個単位として取り扱いができないという難しさがあった。また該支持基体が該配向性ＣＮＴ膜の応用に用いられる基体と同一であるか、該応用に用いられる装置の一部であれば良いが、そうでない場合は、該配向性ＣＮＴ膜の形状を維持しながら移送する必要がある。   First, since the individual CNTs in the oriented CNT film are independent from each other, there is a difficulty that they cannot be handled as a single unit unless at least one surface is fixed to the support substrate. The supporting substrate may be the same as the substrate used for the application of the oriented CNT film or may be a part of an apparatus used for the application. Otherwise, the shape of the oriented CNT film is changed. It is necessary to transport while maintaining.

移送に適した形態としては、配向性ＣＮＴ膜の両面が、軽く変形可能で安価な基体に固定された三層構造の複合シートが好ましい。ここで、配向性ＣＮＴ膜の両面を基体に固定化するのは、形状を保つのにより効果的であることと、同時に該配向性ＣＮＴ膜を移送中の汚染から保護するという目的で好ましいと考えられる。また、該基体が軽く変形可能であれば、該三層構造の複合シートも軽く変形可能となるので移送に便利である。さらに該基体が安価であれば、該三層構造の複合シートを移送後に、該配向性ＣＮＴ膜だけが用途先に必要な場合には該基体は捨ててしまっても構わず、該配向性ＣＮＴ膜を産業上広く流布させる意味で重要である。   As a form suitable for transfer, a composite sheet having a three-layer structure in which both surfaces of the oriented CNT film are fixed to a lightly deformable and inexpensive substrate is preferable. Here, fixing both sides of the oriented CNT film to the substrate is preferable for the purpose of maintaining the shape and at the same time protecting the oriented CNT film from contamination during transportation. It is done. Further, if the substrate can be lightly deformed, the composite sheet having the three-layer structure can be lightly deformed, which is convenient for transportation. Furthermore, if the substrate is inexpensive, the substrate may be discarded if only the oriented CNT film is required after the transfer of the composite sheet having the three-layer structure. This is important in the sense that the membrane is widely distributed in industry.

一方、従来技術において、例えば特許文献２では、配向性ＣＮＴ膜を成長基板から独立させているが、該成長用基板を溶解させた後にはＣＮＴはランダム配向になってしまう。また特許文献３においては、自立した配向性ＣＮＴ膜が得られるが、該配向性ＣＮＴ膜の形状を維持して移送するのは難しくまたその表面を汚染等から保護する手段は記されていない。   On the other hand, in the prior art, for example, in Patent Document 2, the oriented CNT film is made independent of the growth substrate. However, after the growth substrate is dissolved, the CNTs are randomly oriented. In Patent Document 3, a self-supporting oriented CNT film can be obtained. However, it is difficult to maintain and transport the oriented CNT film, and no means for protecting the surface from contamination is described.

特許文献４では配向性ＣＮＴ膜が成長基板と高分子ポリマーとに挟まれた三層構造の複合材が得られている。しかしながら、上述したように成長基板はその素材が強く制限されるため、通常は変形不可能で配向性ＣＮＴ膜と比較するとはるかに重く、また高価であるため、該配向性ＣＮＴ膜を産業上広く流布させる上で該三層構造の複合材は不向きである。   In Patent Document 4, a composite material having a three-layer structure in which an oriented CNT film is sandwiched between a growth substrate and a polymer is obtained. However, as described above, since the material of the growth substrate is strongly limited, it is usually not deformable and much heavier and more expensive than the oriented CNT film. Therefore, the oriented CNT film is widely used in the industry. The three-layer composite is not suitable for distribution.

また、該配向性ＣＮＴ膜には膜の垂直方向に一次元的に繋がったナノメートルスケールの隙間があるため、ガスや液体の分離膜としての応用が期待されている。但し該配向性ＣＮＴ膜を分離膜として使うには透過するガスや液体の影響で該配向性ＣＮＴ膜の形状を損なうことを防ぐことが必要であり、該配向性ＣＮＴ膜の両面を基体で固定化した三層構造を成していることが好ましい。加えて、該配向性ＣＮＴ膜の両面を固定化する基体はガスや液体を透過する材質のものである必要があり、有機系の高分子ポリマーが好ましいが、従来技術には相当する三層構造の複合シートはなかった。   Further, since the oriented CNT film has a nanometer-scale gap connected one-dimensionally in the vertical direction of the film, application as a gas or liquid separation film is expected. However, in order to use the oriented CNT film as a separation membrane, it is necessary to prevent the orientation of the oriented CNT film from being damaged by the effect of a permeating gas or liquid, and both sides of the oriented CNT film are fixed with a substrate. It is preferable to have a three-layer structure. In addition, the substrate for fixing both surfaces of the oriented CNT film needs to be made of a material that allows gas and liquid to permeate, and an organic polymer polymer is preferable. There was no composite sheet.

上記課題を解決するために、本発明では配向性ＣＮＴ膜の両面を二枚の機能性シートに挟んで固定化した三層構造の配向性ＣＮＴ膜複合シートを提供する。機能性シートとしては、配向性ＣＮＴ膜を固定化することができるシートであり、接着性、熱接着性、照射感受性、易溶解性または化学反応性を有する。機能性シートは軽く、変形可能であり、また安価である。本発明における三層構造の配向性ＣＮＴ膜複合シートの中の配向性ＣＮＴ膜は、形状が安定で汚染から保護されているので、産業上広く流布させることができる。   In order to solve the above problems, the present invention provides an oriented CNT film composite sheet having a three-layer structure in which both sides of an oriented CNT film are fixed by sandwiching them between two functional sheets. As a functional sheet, it is a sheet | seat which can fix an orientation CNT film | membrane, and has adhesiveness, thermal adhesiveness, irradiation sensitivity, easy solubility, or chemical reactivity. The functional sheet is light, deformable, and inexpensive. Since the oriented CNT film in the oriented CNT film composite sheet having a three-layer structure in the present invention is stable in shape and protected from contamination, it can be widely distributed industrially.

ここで、本発明における三層構造の配向性ＣＮＴ膜複合シートを有効活用させる目的で、第一の機能性シートに配向性ＣＮＴ膜を固定化した二層構造の配向性ＣＮＴ膜複合シートを出発として、上記の三層構造の配向性ＣＮＴ膜複合シートを経て、第二の機能性シートに配向性ＣＮＴ膜を固定化した二層構造の配向性ＣＮＴ膜複合シートに至る、配向性ＣＮＴ膜の固定化技術も併せて提供する。   Here, for the purpose of effectively utilizing the three-layer oriented CNT film composite sheet in the present invention, a two-layer oriented CNT film composite sheet in which the oriented CNT film is fixed to the first functional sheet is started. As described above, through the above-described three-layer oriented CNT film composite sheet, to the two-layer oriented CNT film composite sheet in which the oriented CNT film is fixed to the second functional sheet, It also provides immobilization technology.

本発明では配向性ＣＮＴ膜の両面を二枚の機能性シートに挟んで固定化した三層構造の配向性ＣＮＴ膜複合シートを提供する。該配向性ＣＮＴ膜複合シートはガスや液体の分離膜などの用途に好適である。また、該配向性ＣＮＴ膜を他の用途に使用する場合でも、該配向性ＣＮＴ膜複合シートの状態で移送することにより、該配向性ＣＮＴ膜の形状を損なわず不純物を付着させることなく、産業上広く流布させることができる。併せて、本発明の配向性ＣＮＴ膜の固定化方法を用いれば、該配向性ＣＮＴ膜を任意の基体から任意の基体へ固定化する技術に応用できる。   In the present invention, an oriented CNT film composite sheet having a three-layer structure in which both sides of an oriented CNT film are fixed by being sandwiched between two functional sheets is provided. The oriented CNT membrane composite sheet is suitable for applications such as gas or liquid separation membranes. In addition, even when the oriented CNT film is used for other applications, by transferring it in the state of the oriented CNT film composite sheet, the shape of the oriented CNT film is not impaired and impurities are not attached. Can be widely distributed. In addition, if the method for immobilizing an oriented CNT film of the present invention is used, it can be applied to a technique for immobilizing the oriented CNT film from an arbitrary substrate to an arbitrary substrate.

以下に本発明を詳しく説明する。本発明では配向性ＣＮＴ膜の両面を二枚の機能性シートに挟んで固定化した三層構造の配向性ＣＮＴ膜複合シート（図１参照）を提供する。固定化というのは、配向性ＣＮＴ膜の膜面部分と機能性シートの表面部分とが接着することで、配向性ＣＮＴ膜の表面を覆い、さらにその形状を保持することを意味する。   The present invention is described in detail below. In the present invention, an oriented CNT film composite sheet (see FIG. 1) having a three-layer structure in which both sides of an oriented CNT film are fixed by being sandwiched between two functional sheets is provided. Immobilization means that the film surface portion of the oriented CNT film and the surface portion of the functional sheet adhere to each other, thereby covering the surface of the oriented CNT film and further maintaining its shape.

次に用いられる機能性シートについて説明する。機能性シートは、高分子有機系ポリマーや低融点金属薄膜など、容易に変形が可能で軽く安価なシート状材料であり、様々な化学的、または物理的機能を備えたシートである。本発明で用いられる機能性シートは配向性ＣＮＴ膜を固定化することができる機能性シートであれば何でも良いが、固定化の方法としては下記の二通りの方法が好ましい。すなわち該機能性シートを、該配向性ＣＮＴ膜の表面と接触させ固定化する方法と、機能性シートの前駆体と該配向性ＣＮＴ膜の表面とを接触させ該機能性シートを硬化形成することにより固定化する方法とがある。本発明で用いられる二枚の機能性シートのうち、片方、または両方がこれらどちらかの方法で該配向性ＣＮＴ膜を固定化できる機能性シートであることが好ましい。   Next, the functional sheet used will be described. The functional sheet is a sheet-like material that can be easily deformed and is light and inexpensive, such as a polymer organic polymer and a low-melting-point metal thin film, and is a sheet having various chemical or physical functions. The functional sheet used in the present invention may be any functional sheet that can fix the oriented CNT film, but the following two methods are preferable as the fixing method. That is, the functional sheet is brought into contact with the surface of the oriented CNT film and fixed, and the precursor of the functional sheet and the surface of the oriented CNT film are brought into contact with each other to cure the functional sheet. There is a method of immobilization. Of the two functional sheets used in the present invention, one or both are preferably functional sheets capable of fixing the oriented CNT film by either one of these methods.

また、本発明で用いられる二枚の機能性シートのうち、片方、または両方が配向性ＣＮＴ膜の形状を崩さずに、該配向性ＣＮＴ膜と該機能性シートとを剥離可能な機能性シートであることが好ましい。剥離する方法としては、特に処理しないで剥離できる機能性シートでも良いし、軟化させて剥離する機能性シートでも良いし、該配向性ＣＮＴ膜との接着層を溶媒等で溶出することによって剥離する機能性シートでも良い。すなわち、本発明で用いられる二枚の機能性シートのうち、片方または両方が軟化、または硬化が可能な機能性シートである方が、該機能性シートを用いて配向性ＣＮＴ膜を固定化する操作、または該配向性ＣＮＴ膜と該機能性シートとを剥離する操作が容易となる。   Moreover, the functional sheet which can peel this orientation CNT film | membrane and this functional sheet, without destroying the shape of an orientation CNT film | membrane among the two functional sheets used by this invention, or both It is preferable that As a method of peeling, a functional sheet that can be peeled off without any treatment may be used, or a functional sheet that is softened and peeled off may be used, or the adhesive layer with the oriented CNT film may be peeled off by elution with a solvent or the like. A functional sheet may be used. That is, of the two functional sheets used in the present invention, one or both of them is a functional sheet that can be softened or cured, and the orientation CNT film is fixed using the functional sheet. The operation or the operation of peeling the oriented CNT film and the functional sheet becomes easy.

これら機能性シートの機能としては、接着性、熱接着性、照射感受性、易溶解性、および化学反応性から選ばれた単独または複数の機能を有することが好ましい。複数の機能を有する機能性シートの場合は、配向性ＣＮＴ膜表面を固定化する側の表面の機能が最も重要となる。   As the function of these functional sheets, it is preferable to have a single function or a plurality of functions selected from adhesiveness, thermal adhesiveness, irradiation sensitivity, easy solubility, and chemical reactivity. In the case of a functional sheet having a plurality of functions, the function of the surface on the side where the oriented CNT film surface is fixed is most important.

接着性を有する機能性シートに関しては、シートの表面に粘着層が有るものならば何でも良く、配向性ＣＮＴ膜の表面と粘着層が接触するだけ、または接触させて加圧するなどの方法で、該配向性ＣＮＴ膜と接着させ固定化することができる。また、配向性ＣＮＴ膜が接着性シートに固定化されている場合、該配向性ＣＮＴ膜の他の面が他の基体に固定されていれば、該配向性ＣＮＴ膜の形状を保たせながら該接着性シートを剥離することができる。この際、材質によっては該接着性シートの一部が該配向性ＣＮＴ膜の表面に残る場合もあるが、溶出等で簡単に除ける。   As for the functional sheet having adhesiveness, any sheet having an adhesive layer on the surface of the sheet may be used, and the surface of the oriented CNT film and the adhesive layer may be in contact with each other, or may be pressed by contact. It can be bonded and fixed to the oriented CNT film. Further, when the oriented CNT film is fixed to the adhesive sheet, if the other surface of the oriented CNT film is fixed to another substrate, the shape of the oriented CNT film is maintained while maintaining the shape. The adhesive sheet can be peeled off. At this time, a part of the adhesive sheet may remain on the surface of the oriented CNT film depending on the material, but it can be easily removed by elution or the like.

具体的な接着性シートの構成としては、支持基体としてポリオレフィンまたはポリエチレンテレフタレート、接着層としてアクリル樹脂またはＥＶＡ樹脂（エチレン・酢酸ビニル共重合体）に例示される樹脂からなる機能性シートが挙げられる。これら支持基体と接着層の組み合わせには特例はない。   Specific examples of the configuration of the adhesive sheet include a functional sheet made of a resin such as polyolefin or polyethylene terephthalate as a supporting substrate and an acrylic resin or EVA resin (ethylene / vinyl acetate copolymer) as an adhesive layer. There is no special case for the combination of the supporting substrate and the adhesive layer.

熱接着性を有する機能性シートに関しては、熱で軟化または硬化する機能を利用して、配向性ＣＮＴ膜と接着させ固定化することができる。また、配向性ＣＮＴ膜が熱接着性シートに固定化されている場合、該配向性ＣＮＴ膜の他の面が他の基体に固定されていれば、上記の機能を利用して、該配向性ＣＮＴ膜の形状を保たせながら該熱接着性シートを剥離することができる。剥離の際、材質によっては該熱接着性シートの一部が該配向性ＣＮＴ膜の表面に残る場合もあるが、溶出等で簡単に除ける。   With respect to the functional sheet having thermal adhesiveness, it can be bonded and fixed to the oriented CNT film by utilizing the function of being softened or cured by heat. In addition, when the oriented CNT film is fixed to the heat-adhesive sheet, if the other surface of the oriented CNT film is fixed to another substrate, the above-described function can be used for the orientation. The thermal adhesive sheet can be peeled off while maintaining the shape of the CNT film. At the time of peeling, a part of the thermal adhesive sheet may remain on the surface of the oriented CNT film depending on the material, but it can be easily removed by elution.

具体的な熱接着性シートとしては、エポキシ樹脂、フッ素樹脂、ポリアミド、フェノール樹脂またはポリ塩化ビニルが挙げられる。   Specific examples of the heat-adhesive sheet include epoxy resin, fluororesin, polyamide, phenol resin, and polyvinyl chloride.

照射感受性シートに関しては、光照射、電子線照射、イオン照射または放射線照射によって軟化あるいは硬化する機能性を利用して、配向性ＣＮＴ膜と接着させ固定化することができる。また、配向性ＣＮＴ膜が照射感受性シートに固定化されている場合、該配向性ＣＮＴ膜の他の面が他の基体に固定されていれば、上記の機能を利用して、該配向性ＣＮＴ膜の形状を保たせながら該照射感受性シートを剥離することができる。剥離の際、材質によっては該照射感受性シートの一部が該配向性ＣＮＴ膜の表面に残る場合もあるが、溶出等で簡単に除ける。   The irradiation sensitive sheet can be fixed by adhering to the oriented CNT film by utilizing the functionality of being softened or cured by light irradiation, electron beam irradiation, ion irradiation or radiation irradiation. In addition, when the oriented CNT film is fixed to the radiation sensitive sheet, if the other surface of the oriented CNT film is fixed to another substrate, the oriented CNT film is utilized using the above function. The radiation sensitive sheet can be peeled while maintaining the shape of the film. At the time of peeling, a part of the radiation sensitive sheet may remain on the surface of the oriented CNT film depending on the material, but it can be easily removed by elution or the like.

具体的な照射感受性シートとしては、ポリエポキシアクリレート、ポリウレタンアクリレート、ポリエステルアクリレートまたはポリエーテルアクリレートが挙げられる。   Specific examples of the radiation sensitive sheet include polyepoxy acrylate, polyurethane acrylate, polyester acrylate, and polyether acrylate.

易溶解性を有する機能性シートに関しては、溶媒または溶媒の蒸気にさらす等の操作により軟化する機能を利用して、配向性ＣＮＴ膜を固定化することができる。また、配向性ＣＮＴ膜が易溶解性シートに固定化されている場合、該配向性ＣＮＴ膜の他の面が他の基体に固定されていれば、溶媒または溶媒の蒸気にさらす等の操作により軟化させるか溶解させるなどの方法で、該配向性ＣＮＴ膜の形状を保たせながら該易溶解性シートを剥離することができる。剥離の際、材質によっては該易溶解性シートの一部が該配向性ＣＮＴ膜の表面に残る場合もあるが、溶出等で簡単に除ける。   With respect to the functional sheet having easy solubility, the oriented CNT film can be fixed by utilizing a function of softening by an operation such as exposure to a solvent or vapor of the solvent. Further, when the oriented CNT film is fixed to an easily soluble sheet, if the other surface of the oriented CNT film is fixed to another substrate, it may be exposed to a solvent or a vapor of the solvent. The easily soluble sheet can be peeled off while maintaining the shape of the oriented CNT film by a method such as softening or dissolving. At the time of peeling, depending on the material, a part of the easily soluble sheet may remain on the surface of the oriented CNT film, but it can be easily removed by elution or the like.

具体的な易溶解性シートとしては、ポリビニルアルコールまたはポリエチレンオキサイドが挙げられる。   Specific examples of the easily soluble sheet include polyvinyl alcohol and polyethylene oxide.

化学反応性を有する機能性シートに関しては、液状またはガス状の化学反応物質にさらす等の操作により軟化または硬化する機能を利用して、配向性ＣＮＴ膜を固定化することができる。また、配向性ＣＮＴ膜が化学反応性シートに固定化されている場合、該配向性ＣＮＴ膜の他の面が他の基体に固定されていれば、液状またはガス状の化学反応物質にさらす等の操作により溶解、軟化または硬化する機能を利用して、該配向性ＣＮＴ膜の形状を保たせながら該化学反応性シートを剥離することができる。剥離の際、材質によっては該化学反応性シートの一部が該配向性ＣＮＴ膜の表面に残る場合もあるが、溶出等で簡単に除ける。   With regard to the functional sheet having chemical reactivity, the oriented CNT film can be fixed by utilizing a function of softening or curing by an operation such as exposure to a liquid or gaseous chemical reaction material. Further, when the oriented CNT film is fixed to a chemically reactive sheet, if the other surface of the oriented CNT film is fixed to another substrate, it is exposed to a liquid or gaseous chemically reactive substance, etc. The chemically reactive sheet can be peeled while maintaining the shape of the oriented CNT film by utilizing the function of dissolving, softening or curing by the above operation. At the time of peeling, a part of the chemically reactive sheet may remain on the surface of the oriented CNT film depending on the material, but it can be easily removed by elution or the like.

具体的な化学反応性シートとしては、エポキシ樹脂またはキシレン樹脂が挙げられる。   Specific examples of the chemically reactive sheet include an epoxy resin and a xylene resin.

次に本発明で示された三層構造の配向性ＣＮＴ膜複合シートの製造方法について述べる。まず始めの工程としては、配向性ＣＮＴ膜を合成する。配向性ＣＮＴ膜の合成方法としては、発明者らが特開２００２−３３８２２１号公報で開示した方法に例示されるように、触媒粒子が平面的に付着した成長用基礎基板を、炭素化合物ガス雰囲気下で高温処理することにより得る方法が一般的である。次の工程では、一枚目の機能性シートを前の工程で得られた配向性ＣＮＴ膜表面に上述した方法で固定化する。さらに該配向性ＣＮＴ膜を該一枚目の機能性シートに固定化したまま成長用基礎基板から剥離することにより、二層構造の配向性ＣＮＴ膜複合シートが得られる。最後の工程では、配向性ＣＮＴ膜の表面のうち機能性シートに固定化されていない側に、二枚目の機能性シートを上述した方法で固定化することにより目的とする三層構造の配向性ＣＮＴ膜複合シートを得る。   Next, a method for producing an oriented CNT film composite sheet having a three-layer structure according to the present invention will be described. As a first step, an oriented CNT film is synthesized. As a method for synthesizing an oriented CNT film, as exemplified by the method disclosed by the inventors in Japanese Patent Application Laid-Open No. 2002-338221, a basic substrate for growth on which catalyst particles are adhered in a plane is formed in a carbon compound gas atmosphere. A method obtained by high-temperature treatment under is generally used. In the next step, the first functional sheet is fixed to the surface of the oriented CNT film obtained in the previous step by the method described above. Furthermore, the oriented CNT film composite sheet having a two-layer structure is obtained by peeling the oriented CNT film from the growth base substrate while being fixed to the first functional sheet. In the last step, the orientation of the target three-layer structure is achieved by immobilizing the second functional sheet by the above-described method on the surface of the oriented CNT film that is not immobilized on the functional sheet. A conductive CNT film composite sheet is obtained.

本発明によって得られた三層構造の配向性ＣＮＴ膜複合シートは、長さの揃った何万本ものＣＮＴが垂直に配向して上下の先端が機能性シートに接しているという特異な材料であり、該複合シートそのものが様々な応用に期待できる。例えば、機能性シートが透過性の高分子膜である場合、ＣＮＴの外壁が成す微細な空間、またはＣＮＴの内壁が成す円筒型の極微細な空間を利用して液体やガスの分離膜として応用できる。   The three-layer oriented CNT film composite sheet obtained by the present invention is a unique material in which tens of thousands of CNTs with uniform length are vertically oriented and the top and bottom tips are in contact with the functional sheet. Yes, the composite sheet itself can be expected for various applications. For example, when the functional sheet is a permeable polymer membrane, it can be used as a liquid or gas separation membrane by utilizing the minute space formed by the outer wall of CNT or the cylindrical minute space formed by the inner wall of CNT. it can.

また、本発明によって得られた三層構造の配向性ＣＮＴ膜複合シートに含まれる配向性ＣＮＴ膜は、二枚の機能性シートによって形状が保たれ、両方の膜面が汚染から保護されているので、産業上広く流布することができる。さらに該三層構造の配向性ＣＮＴ膜複合シートはすべて変形可能な素材で成っているので、ロール状にするなど、移送にも適している。   Moreover, the orientation CNT film contained in the orientation CNT film composite sheet having a three-layer structure obtained by the present invention is maintained in shape by two functional sheets, and both film surfaces are protected from contamination. Therefore, it can be widely distributed in industry. Further, since the three-layer oriented CNT film composite sheet is made of a deformable material, it is suitable for transfer, for example, in the form of a roll.

ここで、三層構造の配向性ＣＮＴ膜複合シートを産業上広く流布したとして、該複合シートに含まれる配向性ＣＮＴ膜が素材として必要とされる場合、形状を損なうことなく他の基体に該配向性ＣＮＴ膜を固定化する技術も必要である。その固定化技術の基礎技術として、以下に、ある機能性シートに固定化された配向性ＣＮＴ膜を、他の機能性シートへ固定化する方法を示す。   Here, assuming that the oriented CNT film composite sheet having a three-layer structure is widely distributed in the industry, when the oriented CNT film contained in the composite sheet is required as a material, it is applied to another substrate without impairing the shape. A technique for fixing the oriented CNT film is also necessary. As a basic technique of the immobilization technique, a method for immobilizing an oriented CNT film immobilized on a certain functional sheet to another functional sheet will be described below.

この固定化方法としては、まず、配向性ＣＮＴ膜の片側の表面を第一の機能性シートで固定化した、二層構造の配向性ＣＮＴ膜複合シートを準備する。次に、第二の機能性シートを用いて、もう片側の配向性ＣＮＴ膜の表面を固定化する。この固定化の方法は、上述した二通りの方法、すなわち、該第二の機能性シートを、該配向性ＣＮＴ膜の表面と接触させ固定化する方法と、該第二の機能性シートの前駆体と該配向性ＣＮＴ膜の表面とを接触させ該第二の機能性シートを硬化形成することにより固定化する方法が好ましい。この操作の結果として、配向性ＣＮＴ膜の両面が第一と第二の二枚の機能性シートに固定化された、三層構造の配向性ＣＮＴ膜複合シートが得られる。さらに、配向性ＣＮＴ膜の形状を崩さずに、該配向性ＣＮＴ膜と第一の機能性シートとを剥離すると、該配向性ＣＮＴ膜が第二の機能性シートにのみ固定化された二層構造体が得られる。結果として、第一の機能性シートから第二の機能性シートへの配向性ＣＮＴ膜の固定化ができた。   As this immobilization method, first, an oriented CNT film composite sheet having a two-layer structure in which the surface of one side of the oriented CNT film is immobilized with a first functional sheet is prepared. Next, the surface of the oriented CNT film on the other side is fixed using the second functional sheet. This immobilization method includes the two methods described above, that is, a method in which the second functional sheet is brought into contact with the surface of the oriented CNT film to immobilize, and a precursor of the second functional sheet. A method of fixing the second functional sheet by bringing the body into contact with the surface of the oriented CNT film and curing the second functional sheet is preferable. As a result of this operation, an oriented CNT film composite sheet having a three-layer structure in which both sides of the oriented CNT film are fixed to the first and second functional sheets is obtained. Further, when the oriented CNT film and the first functional sheet are peeled off without breaking the shape of the oriented CNT film, the oriented CNT film is fixed only on the second functional sheet. A structure is obtained. As a result, the orientation CNT film was immobilized from the first functional sheet to the second functional sheet.

これら第一および第二の機能性シートの種類としては、前述した機能を有しているものなら何でも良いが、好ましくは、接着性、熱接着性、照射感受性、易溶解性、および化学反応性から選ばれた単独または複数の機能を有している機能性シートが良い。これら各機能に関しては上記を参照されたい。   Any kind of these first and second functional sheets may be used as long as they have the functions described above, but preferably adhesiveness, thermal adhesiveness, irradiation sensitivity, easy solubility, and chemical reactivity. A functional sheet having a single function or a plurality of functions selected from the above is preferable. See above for each of these functions.

この配向性ＣＮＴ膜の固定化方法の簡単な例としては、二種類の接着性シートの接着力の差を利用する方法がある。つまり、第一の接着シートの接着力が第二の接着性シートの接着力よりも弱い組み合わせの接着性シートを用いれば、配向性ＣＮＴ膜表面への接触と剥離という簡便な方法で該第一の接着性シートから該第二の接着性シートへの固定化が可能である。   As a simple example of the method for immobilizing the oriented CNT film, there is a method using a difference in adhesive force between two types of adhesive sheets. That is, if an adhesive sheet having a combination in which the adhesive strength of the first adhesive sheet is weaker than the adhesive strength of the second adhesive sheet is used, the first method can be performed by a simple method of contacting and peeling the surface of the oriented CNT film. It is possible to fix the second adhesive sheet to the second adhesive sheet.

例えば、ポリオレフィン／アクリル樹脂から成る接着性シートの場合、第二の接着性シートの粘着性が第一の接着性シートの粘着性よりも単位ｇ／ｍｍにして三倍以上の開きがある場合は上述の固定化を問題なく行なうことができる。   For example, in the case of an adhesive sheet made of polyolefin / acrylic resin, when the adhesiveness of the second adhesive sheet is more than three times the unit g / mm than the adhesiveness of the first adhesive sheet The above-described immobilization can be performed without problems.

以下に実施例をあげて本発明を更に詳しく説明するが、本発明はこれらの実施例によって何ら限定されるものではない。
実施例１
［水溶性シートから接着性シートへの配向性ＣＮＴ膜の固定化方法］
図１（ａ）〜（ｉ）は本実施例に係る易溶解性シート（ポリビニルアルコール）から接着性シート（ポリエチレン／アクリル樹脂）への配向性ＣＮＴ膜の固定化方法を示す具体例として、各工程を段階的に示す断面図である。
まず配向性ＣＮＴ膜１を成長用基礎基板２の表面に合成する（ａ）。次に易溶解性シート３に加湿器４を用いて水蒸気を１０分間あて、膨潤させた（ｂ）。膨潤させた易溶解性シート３と配向性ＣＮＴ膜１の表面とを接触させ、プレス機５にて１０ｋｇ／ｃｍ２で圧着した（ｃ）。脱圧後、成長用基礎基板２から配向性ＣＮＴ膜１を剥離することで配向性ＣＮＴ膜１が易溶解性シート３に固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた（ｄ）。
次に配向性ＣＮＴ膜１の易溶解性シート３に固定化されていない側の表面と接着性シート６を接触させ、プレス機５にて１０ｋｇ／ｃｍ２で圧着した（ｅ）。脱圧後、配向性ＣＮＴ膜１が易溶解性シート３と接着性シート６とに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた（ｆ）。さらに該配向性ＣＮＴ膜複合シートの易溶解性シート３側に加湿器４を用いて水蒸気を１０分間あてた（ｇ）。水蒸気で膨潤した易溶解性シート３を該配向性ＣＮＴ膜複合シートから剥離させた（ｈ）。水洗浄を行い、配向性ＣＮＴ膜１表面に残った易溶解性シート３の残留物を除くことで、配向性を保たせたまま不純物を付着させることなく、該配向性ＣＮＴ膜１が接着性シート６に固定化された（ｉ）。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1
[Method for Immobilizing Oriented CNT Film from Water-soluble Sheet to Adhesive Sheet]
1 (a) to 1 (i) are specific examples showing a method for fixing an oriented CNT film from an easily soluble sheet (polyvinyl alcohol) to an adhesive sheet (polyethylene / acrylic resin) according to the present embodiment. It is sectional drawing which shows a process in steps.
First, the oriented CNT film 1 is synthesized on the surface of the growth base substrate 2 (a). Next, water vapor was applied to the easily soluble sheet 3 using a humidifier 4 for 10 minutes to swell (b). The swollen easily soluble sheet 3 and the surface of the oriented CNT film 1 were brought into contact with each other and pressed by a press 5 at 10 kg / cm 2 (c). After depressurization, the oriented CNT film 1 was peeled from the growth base substrate 2 to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film 1 was fixed to the easily soluble sheet 3. (D).
Next, the adhesive sheet 6 was brought into contact with the surface of the orientation CNT film 1 on the side not fixed to the easily soluble sheet 3 and pressed by a press 5 at 10 kg / cm 2 (e). After depressurization, an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film 1 was fixed to the easily soluble sheet 3 and the adhesive sheet 6 was obtained (f). Further, water vapor was applied for 10 minutes using the humidifier 4 to the easily soluble sheet 3 side of the oriented CNT film composite sheet (g). The easily soluble sheet 3 swollen with water vapor was peeled from the oriented CNT film composite sheet (h). The oriented CNT film 1 is adhered without removing impurities while maintaining the orientation by removing the residue of the easily soluble sheet 3 remaining on the surface of the oriented CNT film 1 by washing with water. It was fixed to the sheet 6 (i).

実施例２
実施例１と同様な方法で成長用基礎基板上に配向性ＣＮＴ膜を準備した。フッ素樹脂シートと該配向性ＣＮＴ膜の表面とを接触させ、プレス機にて１０ｋｇ／ｃｍ２で圧着しながら１５０℃で３０分間加熱した。脱圧、冷却後、成長用基礎基板から配向性ＣＮＴ膜を剥離することで配向性ＣＮＴ膜がフッ素樹脂シートに固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた。
次に配向性ＣＮＴ膜のフッ素樹脂シートに固定化されていない側の表面とポリエポキシアクリレートシートを接触させ、全体を二枚のアクリル板に挟み、ポリエポキシアクリレートシート側の面を光源に向け３０分間ＵＶ照射を行なった。照射後、アクリル板を外すことで、配向性ＣＮＴ膜がフッ素樹脂シートとポリエポキシアクリレートシートとに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた。 Example 2
An oriented CNT film was prepared on the growth base substrate in the same manner as in Example 1. The fluororesin sheet was brought into contact with the surface of the oriented CNT film, and heated at 150 ° C. for 30 minutes while being pressure-bonded at 10 kg / cm 2 with a press machine. After depressurization and cooling, the oriented CNT film was peeled from the growth base substrate to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film was fixed to a fluororesin sheet.
Next, the surface of the oriented CNT film not fixed to the fluororesin sheet is brought into contact with the polyepoxy acrylate sheet, the whole is sandwiched between two acrylic plates, and the surface on the polyepoxy acrylate sheet side is directed to the light source. UV irradiation was performed for a minute. After the irradiation, the acrylic plate was removed to obtain an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film was fixed to a fluororesin sheet and a polyepoxyacrylate sheet.

実施例３
実施例１と同様な方法で成長用基礎基板上に配向性ＣＮＴ膜を準備した。次にエポキシ樹脂シートにメタノール蒸気を１０分間あて、配向性ＣＮＴ膜の表面と接触させ、プレス機にて５ｋｇ／ｃｍ２で圧着した。脱圧、乾燥後、成長用基礎基板から配向性ＣＮＴ膜を剥離することで配向性ＣＮＴ膜がエポキシ樹脂シートに固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた。
次に配向性ＣＮＴ膜のエポキシ樹脂シートに固定化されていない側の表面とポリアミドシートを接触させ、プレス機にて１０ｋｇ／ｃｍ２で圧着しながら１２０℃で３０分間加熱した。脱圧、冷却後、配向性ＣＮＴ膜がエポキシ樹脂シートとポリアミドシートとに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた。 Example 3
An oriented CNT film was prepared on the growth base substrate in the same manner as in Example 1. Next, methanol vapor was applied to the epoxy resin sheet for 10 minutes to bring it into contact with the surface of the oriented CNT film, followed by pressure bonding at 5 kg / cm 2 with a press machine. After depressurization and drying, the oriented CNT film was peeled from the growth base substrate to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film was fixed to the epoxy resin sheet.
Next, the surface of the oriented CNT film not fixed to the epoxy resin sheet was brought into contact with the polyamide sheet, and heated at 120 ° C. for 30 minutes while being pressure-bonded at 10 kg / cm 2 with a press. After depressurization and cooling, an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film was fixed to an epoxy resin sheet and a polyamide sheet was obtained.

実施例４
実施例１と同様な方法で成長用基礎基板上に配向性ＣＮＴ膜を準備した。次にポリウレタンアクリレートシートと配向性ＣＮＴ膜の表面と接触させ、全体を二枚のアクリル板に挟み、ポリウレタンアクリレートシート側の面を光源に向け３０分間ＵＶ照射を行なった。照射後、成長用基礎基板から配向性ＣＮＴ膜を剥離することで配向性ＣＮＴ膜がポリウレタンアクリレートシートに固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた。
次にポリエチレンオキサイドシートに水蒸気を１０分間あて、配向性ＣＮＴ膜のポリウレタンアクリレートシートに固定化されていない側の表面とポリエチレンオキサイドシートを接触させ、プレス機にて１０ｋｇ／ｃｍ２で圧着しながら１００℃で３０分間加熱した。脱圧、冷却後、配向性ＣＮＴ膜がポリウレタンアクリレートシートとポリエチレンオキサイドシートとに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた。 Example 4
An oriented CNT film was prepared on the growth base substrate in the same manner as in Example 1. Next, the polyurethane acrylate sheet and the surface of the oriented CNT film were brought into contact with each other, and the whole was sandwiched between two acrylic plates. After the irradiation, the oriented CNT film was peeled from the growth base substrate to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film was fixed to the polyurethane acrylate sheet.
Next, water vapor is applied to the polyethylene oxide sheet for 10 minutes, the surface of the oriented CNT film not fixed to the polyurethane acrylate sheet is brought into contact with the polyethylene oxide sheet, and the pressure is 100 kg while pressing with a press machine at 10 kg / cm 2. Heat at 30 ° C. for 30 minutes. After depressurization and cooling, an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film was fixed to a polyurethane acrylate sheet and a polyethylene oxide sheet was obtained.

実施例５
実施例１と同様な方法で成長用基礎基板上に配向性ＣＮＴ膜を準備した。次にキシレン樹脂シートにヘキサン蒸気を１０分間あて、配向性ＣＮＴ膜の表面と接触させ、プレス機にて５ｋｇ／ｃｍ２で圧着した。脱圧、乾燥後、成長用基礎基板から配向性ＣＮＴ膜を剥離することで配向性ＣＮＴ膜がキシレン樹脂シートに固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた。
次に配向性ＣＮＴ膜のキシレン樹脂シートに固定化されていない側の表面とフェノール樹脂シートを接触させ、プレス機にて１０ｋｇ／ｃｍ２で圧着しながら１２０℃で３０分間加熱した。脱圧、冷却後、配向性ＣＮＴ膜がキシレン樹脂シートとフェノール樹脂シートとに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた。 Example 5
An oriented CNT film was prepared on the growth base substrate in the same manner as in Example 1. Next, hexane vapor was applied to the xylene resin sheet for 10 minutes to bring it into contact with the surface of the oriented CNT film, followed by pressure bonding at 5 kg / cm 2 with a press machine. After depressurization and drying, the oriented CNT film was peeled from the growth base substrate to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film was fixed to a xylene resin sheet.
Next, the surface of the oriented CNT film not fixed to the xylene resin sheet was brought into contact with the phenol resin sheet, and heated at 120 ° C. for 30 minutes while being pressure-bonded at 10 kg / cm 2 with a press. After depressurization and cooling, an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film was fixed to a xylene resin sheet and a phenol resin sheet was obtained.

実施例６
実施例１と同様な方法で成長用基礎基板上に配向性ＣＮＴ膜を準備した。次にポリプロピレン／ＥＶＡ樹脂シートと配向性ＣＮＴ膜の表面と接触させ、プレス機にて５ｋｇ／ｃｍ２で圧着した。脱圧後、成長用基礎基板から配向性ＣＮＴ膜を剥離することで配向性ＣＮＴ膜がポリプロピレン／ＥＶＡ樹脂シートに固定化された二層構造の配向性ＣＮＴ膜複合シートが得られた。
次に配向性ＣＮＴ膜のポリプロピレン／ＥＶＡ樹脂シートに固定化されていない側の表面とポリ塩化ビニルシートを接触させ、プレス機にて１０ｋｇ／ｃｍ２で圧着しながら１００℃で３０分間加熱した。脱圧、冷却後、配向性ＣＮＴ膜がポリプロピレン／ＥＶＡ樹脂シートと塩化ビニルシートとに固定化された三層構造の配向性ＣＮＴ膜複合シートが得られた。 Example 6
An oriented CNT film was prepared on the growth base substrate in the same manner as in Example 1. Next, it was brought into contact with the surface of the polypropylene / EVA resin sheet and the oriented CNT film, and pressure-bonded with a press at 5 kg / cm 2 . After depressurization, the oriented CNT film was peeled from the growth base substrate to obtain an oriented CNT film composite sheet having a two-layer structure in which the oriented CNT film was fixed to a polypropylene / EVA resin sheet.
Next, the surface of the oriented CNT film not fixed to the polypropylene / EVA resin sheet was brought into contact with the polyvinyl chloride sheet, and heated at 100 ° C. for 30 minutes while being pressure-bonded at 10 kg / cm 2 with a press. After depressurization and cooling, an oriented CNT film composite sheet having a three-layer structure in which the oriented CNT film was fixed to a polypropylene / EVA resin sheet and a vinyl chloride sheet was obtained.

本実施例１〜６に係る三層構造の配向性ＣＮＴ膜複合シートについて、用いたフィルムの材質および機能を表１にまとめた。   Table 1 summarizes the materials and functions of the films used in the three-layer oriented CNT film composite sheets according to Examples 1 to 6.

Figure 2005007861
Figure 2005007861

実施例１における水溶性シートから接着性シートへの配向性ＣＮＴ膜の固定化方法を示す断面図で、（ａ）〜（ｉ）は各工程を段階的に示している。It is sectional drawing which shows the fixing method of the orientation CNT film | membrane from the water-soluble sheet | seat to an adhesive sheet in Example 1, (a)-(i) has shown each process stepwise.

符号の説明Explanation of symbols

１：配向性ＣＮＴ膜
２：成長用基礎基板
３：易溶解性シート
４：加湿器
５：プレス機
６：接着性シート 1: Oriented CNT film 2: Growth base substrate 3: Easily soluble sheet 4: Humidifier 5: Press machine 6: Adhesive sheet

Claims (21)

配向性カーボンナノチューブ膜の両面が二枚の機能性シートに固定化された、三層構造の配向性カーボンナノチューブ膜複合シート。   An oriented carbon nanotube film composite sheet having a three-layer structure in which both surfaces of an oriented carbon nanotube film are fixed to two functional sheets. 片方または両方の機能性シートが、配向性カーボンナノチューブ膜の表面と該機能性シートとを接触させることにより、該配向性カーボンナノチューブ膜を固定化することができる機能性シートであることを特徴とする、請求項１記載の三層構造の配向性カーボンナノチューブ膜複合シート。   One or both of the functional sheets are functional sheets that can fix the oriented carbon nanotube film by bringing the surface of the oriented carbon nanotube film into contact with the functional sheet. The oriented carbon nanotube film composite sheet having a three-layer structure according to claim 1. 片方または両方の機能性シートが、配向性カーボンナノチューブ膜の表面と該機能性シート前駆体とを接触させ、該機能性シートを硬化形成することにより、該配向性カーボンナノチューブ膜を固定化することができる機能性シートであることを特徴とする、請求項１または２記載の三層構造の配向性カーボンナノチューブ膜複合シート。   One or both of the functional sheets contact the surface of the oriented carbon nanotube film with the functional sheet precursor and cure the functional sheet to fix the oriented carbon nanotube film. The oriented carbon nanotube film composite sheet having a three-layer structure according to claim 1, wherein the sheet is a functional sheet capable of forming a three-layer structure. 片方または両方の機能性シートが、配向性カーボンナノチューブ膜の形状を崩さずに、該配向性カーボンナノチューブ膜と該機能性シートとを剥離することができる機能性シートであることを特徴とする、請求項１〜３のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   One or both of the functional sheets is a functional sheet that can peel the oriented carbon nanotube film and the functional sheet without breaking the shape of the oriented carbon nanotube film, The oriented carbon nanotube film composite sheet having a three-layer structure according to any one of claims 1 to 3. 片方または両方の機能性シートが、軟化または硬化することが可能な機能性シートであることを特徴とする、請求項１〜４のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The one- or both-functional sheet is a functional sheet that can be softened or cured, and the three-layer oriented carbon nanotube film composite sheet according to any one of claims 1 to 4 . 片方または両方の機能性シートが、接着性、熱接着性、照射感受性、易溶解性、および化学反応性から選ばれた単独または複数の機能を有するシートであることを特徴とする、請求項１〜５のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The one or both functional sheets are sheets having one or a plurality of functions selected from adhesiveness, thermal adhesiveness, irradiation sensitivity, easy solubility, and chemical reactivity. The oriented carbon nanotube film composite sheet having a three-layer structure according to any one of? 接着性を有する機能性シートが、支持基体の表面に粘着層を有する機能性シートであることを特徴とする請求項１〜６のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The oriented carbon nanotube film composite sheet having a three-layer structure according to any one of claims 1 to 6, wherein the functional sheet having adhesiveness is a functional sheet having an adhesive layer on the surface of a support substrate. . 支持基体が、ポリオレフィンおよびポリエチレンテレフタレートから選ばれた単独または複数の樹脂からなる支持基体であることを特徴とする請求項７記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The oriented carbon nanotube film composite sheet having a three-layer structure according to claim 7, wherein the supporting base is a supporting base made of a single resin or a plurality of resins selected from polyolefin and polyethylene terephthalate. 粘着層が、アクリル樹脂およびＥＶＡ樹脂から選ばれた単独または複数の樹脂からなる支持基体であることを特徴とする請求項７記載の三層構造の配向性カーボンナノチューブ膜複合シート。   8. The aligned carbon nanotube film composite sheet having a three-layer structure according to claim 7, wherein the adhesive layer is a support base composed of one or a plurality of resins selected from an acrylic resin and an EVA resin. 熱接着性を有する機能性シートが、加熱によって軟化または硬化する機能性シートであることを特徴とする請求項１〜６のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The three-layer oriented carbon nanotube film composite sheet according to any one of claims 1 to 6, wherein the functional sheet having thermal adhesiveness is a functional sheet that is softened or cured by heating. 熱接着性を有する機能性シートが、エポキシ樹脂、フッ素樹脂、ポリアミド、フェノール樹脂およびポリ塩化ビニルから選ばれた単独または複数の樹脂からなる機能性シートであることを特徴とする請求項１０記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The functional sheet having thermal adhesiveness is a functional sheet made of one or a plurality of resins selected from an epoxy resin, a fluororesin, a polyamide, a phenol resin, and polyvinyl chloride. Three-layer oriented carbon nanotube film composite sheet. 照射感受性を有する機能性シートが、光照射、電子線照射、イオン照射または放射線照射によって軟化または硬化する機能性シートであることを特徴とする請求項１〜６のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The three-layer structure according to any one of claims 1 to 6, wherein the functional sheet having irradiation sensitivity is a functional sheet that is softened or cured by light irradiation, electron beam irradiation, ion irradiation, or radiation irradiation. Oriented carbon nanotube film composite sheet. 照射感受性を有する機能性シートが、ポリエポキシアクリレート、ポリウレタンアクリレート、ポリエステルアクリレートおよびポリエーテルアクリレートから選ばれた単独または複数の樹脂からなる機能性シートであることを特徴とする請求項１２記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The three-layered product according to claim 12, wherein the functional sheet having radiation sensitivity is a functional sheet made of one or more resins selected from polyepoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate. Structure oriented carbon nanotube film composite sheet. 易溶解性を有する機能性シートが、溶媒または溶媒蒸気にさらすことによって、溶解または軟化する機能性シートであることを特徴とする請求項１〜６のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The orientation of the three-layer structure according to any one of claims 1 to 6, wherein the functional sheet having easy solubility is a functional sheet that dissolves or softens when exposed to a solvent or solvent vapor. Carbon nanotube film composite sheet. 易溶解性を有する機能性シートが、ポリビニルアルコールおよびポリエチレンオキサイドから選ばれた単独または複数の樹脂からなる機能性シートであることを特徴とする請求項１４記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The oriented carbon nanotube film having a three-layer structure according to claim 14, wherein the functional sheet having easy solubility is a functional sheet made of one or more resins selected from polyvinyl alcohol and polyethylene oxide. Composite sheet. 化学反応性を有する機能性シートが、化学反応性物質にさらすことによって、溶解、軟化または硬化する機能性シートであることを特徴とする請求項１〜６のいずれかに記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The functional sheet having chemical reactivity is a functional sheet that dissolves, softens or hardens when exposed to a chemically reactive substance. An oriented carbon nanotube film composite sheet. 化学反応性を有する機能性シートが、エポキシ樹脂およびキシレン樹脂から選ばれた単独または複数の樹脂からなる機能性シートであることを特徴とする請求項１６記載の三層構造の配向性カーボンナノチューブ膜複合シート。   The oriented carbon nanotube film having a three-layer structure according to claim 16, wherein the functional sheet having chemical reactivity is a functional sheet made of one or a plurality of resins selected from an epoxy resin and a xylene resin. Composite sheet. 第一の機能性シートに固定化した配向性カーボンナノチューブ膜の表面に第二の機能性シートを接触させ固定化する工程と、該配向性カーボンナノチューブ膜の形状を崩さずに、該配向性カーボンナノチューブ膜と該第一の機能性シートとを剥離する工程から成ることを特徴とする、配向性カーボンナノチューブ膜の固定化方法。   A step of bringing the second functional sheet into contact with the surface of the oriented carbon nanotube film immobilized on the first functional sheet, and fixing the oriented carbon nanotube film without breaking the shape of the oriented carbon nanotube film; A method for immobilizing an oriented carbon nanotube film, comprising the step of peeling the nanotube film and the first functional sheet. 第一の機能性シートに固定化した配向性カーボンナノチューブ膜の表面に第二の機能性シートの前駆体とを接触させ、該第二の機能性シートを硬化形成することにより、該配向性カーボンナノチューブ膜を固定化する工程と、該配向性カーボンナノチューブ膜の形状を崩さずに、該配向性カーボンナノチューブ膜と該第一の機能性シートとを剥離する工程から成ることを特徴とする、配向性カーボンナノチューブ膜の固定化方法。   By contacting the precursor of the second functional sheet with the surface of the oriented carbon nanotube film immobilized on the first functional sheet, and curing the second functional sheet, the oriented carbon An orientation comprising: a step of fixing a nanotube film; and a step of peeling the orientation carbon nanotube film and the first functional sheet without breaking the shape of the orientation carbon nanotube film. Method for fixing carbon nanotube film. 第一または第二の機能性シートが、接着性、熱接着性、照射感受性、易溶解性、および化学反応性から選ばれた単独または複数の機能を有するシートであることを特徴とする、請求項１８または１９記載の配向性カーボンナノチューブ膜の固定化方法。   The first or second functional sheet is a sheet having a single function or a plurality of functions selected from adhesiveness, thermal adhesiveness, irradiation sensitivity, easy solubility, and chemical reactivity. Item 20. A method for immobilizing an oriented carbon nanotube film according to Item 18 or 19. 第一および第二の機能性シートが接着性シートで、該第一の接着性シートの接着力が該第二の接着性シートの接着力よりも弱いことを特徴とする、請求項１８または１９記載の配向性カーボンナノチューブ膜の固定化方法。   The first and second functional sheets are adhesive sheets, and the adhesive strength of the first adhesive sheet is weaker than the adhesive strength of the second adhesive sheet. The method for immobilizing an oriented carbon nanotube film as described.
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