JP5898565B2 - Method for reducing surface resistance of transparent conductive carbon film laminate - Google Patents
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本発明は、実際の製造プロセスへの応用が可能な大面積のグラフェンのドーピング方法に関する。 The present invention relates to a method for doping large-area graphene that can be applied to an actual manufacturing process.
グラフェンは高い透明性と電気移動度を兼ね備えており、タッチパネル、太陽電池、有機ＥＬ用透明導電膜や電極材料として注目されている。特に近年のスマートフォン市場の拡大を受け、スマートフォン用タッチパネル用透明導電膜としての利用が注目されている。 Graphene has high transparency and electric mobility, and has attracted attention as a touch panel, a solar cell, a transparent conductive film for organic EL, and an electrode material. In particular, in response to the recent expansion of the smartphone market, the use as a transparent conductive film for smartphone touch panels has attracted attention.
タッチパネル用の大面積グラフェンを作成するには、熱およびプラズマＣＶＤでグラフェンを銅、ニッケル箔上に作製するか、酸化グラフェンを基板に塗布して還元する方法がある。これらの方法では大面積のグラフェン膜が比較的簡便に作成できる。しかし、表面抵抗値が１０3〜１０5Ｏｈｍ／ｓｑ．程度であり、現状のグラフェン合成手法だけではタッチパネル用透明導電膜の要求特性を満たすことは厳しい。 In order to create large-area graphene for a touch panel, there is a method in which graphene is produced on copper or nickel foil by heat and plasma CVD, or graphene oxide is applied to a substrate and reduced. With these methods, a large-area graphene film can be formed relatively easily. However, the surface resistance value is 10 3 to 10 5 Ohm / sq. However, it is difficult to satisfy the required characteristics of the transparent conductive film for touch panel only with the current graphene synthesis method.
このような状況から、グラフェンの表面抵抗を下げるためのドーピング法が多数検討されている。濃硝酸を使用するグラフェンのドーピング方法が報告されている（非特許文献１）。この方法によりグラフェンの表面抵抗は減少するが、使用する試薬が危険であり、安全対策のための設備が必要となる。また濃硝酸は、使用できる基板が限定され、デバイス作成後には腐食など悪影響が懸念される。塩化金（ＩＩＩ）のニトロメタン溶液を使用する方法も報告されている（非特許文献１）。この方法もドーピング効果が高いことが報告されているが、高価な塩化金と可燃性が非常に高いニトロメタンを多量に使用するため、実際の工業プロセスで使用することは難しい。他にも有機分子などを付着させる方法も報告されているが、希ガス雰囲気化で電気抵抗だけを評価したもの、高配向熱分解黒鉛（ＨＯＰＧ）から剥離した数μｍ程度の非常に小さなグラフェンを用いて電気特性だけを評価しただけのものである（非特許文献２）。さらにこれらの文献では、ドーピング前後のグラフェンの透過率変化に関して詳細に調べていない。実際のタッチパネル用透明導電膜では、ドーピングによる基板の着色、透過率の低下は致命的である。このように、グラフェン透明導電膜の透過率を損なわず、表面抵抗を下げる方法の開発が目下の急務である。 Under such circumstances, many doping methods for reducing the surface resistance of graphene have been studied. A graphene doping method using concentrated nitric acid has been reported (Non-patent Document 1). Although the surface resistance of graphene is reduced by this method, the reagent used is dangerous and equipment for safety measures is required. Concentrated nitric acid is limited in the substrates that can be used, and there is a concern about adverse effects such as corrosion after device fabrication. A method using a nitromethane solution of gold (III) chloride has also been reported (Non-patent Document 1). Although this method is also reported to have a high doping effect, it is difficult to use it in an actual industrial process because it uses a large amount of expensive gold chloride and highly flammable nitromethane. Other methods of attaching organic molecules have also been reported, but only a small gas graphene of about several μm peeled from highly oriented pyrolytic graphite (HOPG) was evaluated based on the evaluation of electrical resistance only in a rare gas atmosphere. It is only used to evaluate only the electric characteristics (Non-Patent Document 2). Furthermore, these documents do not examine in detail the transmittance change of graphene before and after doping. In an actual transparent conductive film for a touch panel, coloring of the substrate due to doping and a decrease in transmittance are fatal. Thus, there is an urgent need to develop a method for reducing the surface resistance without impairing the transmittance of the graphene transparent conductive film.
本発明は前述の従来技術が包含する課題に鑑み、大面積グラフェンの透過率を低下させることなく表面抵抗を下げられる、実際の製造プロセスへの応用可能なドーピング方法を提供することである。 The present invention provides a doping method applicable to an actual manufacturing process, in which surface resistance can be reduced without reducing the transmittance of large-area graphene, in view of the problems involved in the above-described conventional technology.
本発明者らは前述の課題を解決するため、鋭意研究を重ねた。
すなわち本発明は、以下の通りである。
１）基板（Ａ）上の透明導電性炭素膜（Ｂ）に、薄膜活性化層（Ｃ）を設けることを特徴とする透明導電性炭素膜積層体の表面抵抗の低下方法。
２）基板（Ａ）として、金属、金属酸化物、ガラス、シリコンウエハ、ＳｉＣウエハ、およびポリマーフィルムからなる群より選択される材料からなることを特徴とする、１）に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
３）透明導電性炭素膜（Ｂ）が、厚さ０．１〜１０００ｎｍ、面積０．１ｃｍ2以上のものであることを特徴とする、１）または２）に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
４）薄膜活性化層（Ｃ）の厚さが０．０１〜１０００ｎｍであることを特徴とする、１）〜３）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
５）薄膜活性化層（Ｃ）の屈折率が透明導電炭素膜（Ｂ）よりも低いことを特徴とする、１）〜４）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
６）薄膜活性化層（Ｃ）を作成する際に、シランカップリング剤を使用することを特徴とする、１）〜５）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
７）シランカップリング剤として、下記化学式（Ｉ）、（ＩＩ）または（ＩＩＩ）
In order to solve the above-mentioned problems, the present inventors have conducted extensive research.
That is, the present invention is as follows.
1) A method for reducing the surface resistance of a transparent conductive carbon film laminate, comprising providing a thin film activation layer (C) on a transparent conductive carbon film (B) on a substrate (A).
2) The transparent conductive carbon according to 1), wherein the substrate (A) is made of a material selected from the group consisting of metal, metal oxide, glass, silicon wafer, SiC wafer, and polymer film. A method for reducing the surface resistance of a film laminate.
3) The transparent conductive carbon film (B) has a thickness of 0.1 to 1000 nm and an area of 0.1 cm 2 or more, and the transparent conductive carbon film laminate according to 1) or 2) A method of reducing the surface resistance of the body.
4) The thickness of the thin film activated layer (C) is 0.01 to 1000 nm, and the surface resistance of the transparent conductive carbon film laminate according to any one of 1) to 3) Lowering method.
5) The transparent conductive carbon film laminate according to any one of 1) to 4), wherein the refractive index of the thin film activated layer (C) is lower than that of the transparent conductive carbon film (B). Method for reducing surface resistance.
6) The surface of the transparent conductive carbon film laminate according to any one of 1) to 5), wherein a silane coupling agent is used when forming the thin film activation layer (C). How to reduce resistance.
7) As a silane coupling agent, the following chemical formula (I), (II) or (III)
〔但しＸは加水分解性基である。Ｒ1，Ｒ2、Ｒ3は、それぞれ同一または異なって、水素原子の一部または全部がフッ素原子で置換されていてもよい炭素数１〜１８の炭化水素基を表す。〕で示されるシランカップリング剤を少なくとも１種類以上含むことを特徴とする、６）に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
８）薄膜活性化層（Ｃ）上の接触角が６０〜１５０°であることを特徴とする、請求項１〜７）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
９）（Ａ）〜（Ｃ）からなる積層体の光線透過率が７０％以上であることを特徴とする、１）〜８）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
１０）（Ａ）、（Ｂ）からなる積層体と、（Ａ）〜（Ｃ）からなる積層体の透過率の差が１０％以下であることを特徴とする、１）〜９）のいずれか１項に記載の透明導電性炭素膜積層体の表面抵抗の低下方法。
１１）１）〜１０）１０のいずれか１項に記載の製造方法により得られた透明導電性炭素膜積層体。
[However, X is a hydrolyzable group. R 1 , R 2 and R 3 are the same or different and each represents a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms. The method for reducing the surface resistance of the transparent conductive carbon film laminate according to 6), comprising at least one silane coupling agent represented by the formula:
8) The surface resistance of the transparent conductive carbon film laminate according to any one of claims 1 to 7, wherein a contact angle on the thin film activation layer (C) is 60 to 150 °. Method of lowering.
9) The transparent conductive carbon film laminate according to any one of 1) to 8) above, wherein the laminate comprising (A) to (C) has a light transmittance of 70% or more. Method for reducing surface resistance.
10) Any one of 1) to 9), wherein the difference in transmittance between the laminate comprising (A) and (B) and the laminate comprising (A) to (C) is 10% or less. The method for decreasing the surface resistance of the transparent conductive carbon film laminate according to claim 1.
11) The transparent conductive carbon film laminated body obtained by the manufacturing method of any one of 1) -10) 10.
本発明者らによる鋭意研究の結果、基板（Ａ）に転写したグラフェン（Ｂ）を、下記化学式（I）、（II）、（II）で表されるシランカップリング剤と減圧条件で共存させることにより、グラフェン（Ｂ）の表面に薄膜活性化層（Ｃ）を作成させ、ドーピングすることを見出した。 As a result of intensive studies by the present inventors, the graphene (B) transferred to the substrate (A) is allowed to coexist with the silane coupling agent represented by the following chemical formulas (I), (II), and (II) under reduced pressure conditions. Thus, the inventors have found that a thin film activation layer (C) is formed on the surface of graphene (B) and doping is performed.
本発明により、グラフェンの透過率を下げることなく大面積のグラフェンに対してドーピングが可能となり、低抵抗のタッチパネル用のグラフェン透明導電膜を作成できる。 According to the present invention, it is possible to dope a large area of graphene without lowering the transmittance of graphene, and a graphene transparent conductive film for a low-resistance touch panel can be created.
以下に本発明の詳細について述べる。 Details of the present invention will be described below.
本発明で用いることのできる基板（Ａ）としては、金属、金属酸化物、金属窒化物、金属酸窒化物などの無機材料の基体が挙げられる。例えば、ガラス、セラミックス、金属、シリコンウエハ、ＳｉＣなどがあげられる。ほかの基板例として、ポリビニルフェノール（ＰＶＰ）、ポリスチレン（ＰＳ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリビニルアルコール（ＰＶＡ）、ポリ塩化ビニル（ＰＶＣ）、ポリフッ化ビニリデン（ＰＶＤＦ、なおＶＤＦは登録商標）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリイミド（ＰＩ）、エポキシ樹脂、ポリジメチルシロキサン（ＰＤＭＳ）、ブタジエンゴム等のプラスチック基板が挙げられる。これら基板はバルクまたは薄膜として使用してもよいし、ガラス、プラスチックフィルム、セラミックス、金属、あるいはシリコンウエハなどの基板の最表面に配置してもよい。以上の無機材料や有機材料等の基体を張り合わせたり、積層したりして用いてもよい。 Examples of the substrate (A) that can be used in the present invention include substrates of inorganic materials such as metals, metal oxides, metal nitrides, and metal oxynitrides. For example, glass, ceramics, metal, silicon wafer, SiC and the like can be mentioned. Examples of other substrates include polyvinylphenol (PVP), polystyrene (PS), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF, VDF is a registered trademark), Examples thereof include plastic substrates such as polytetrafluoroethylene (PTFE), polyimide (PI), epoxy resin, polydimethylsiloxane (PDMS), and butadiene rubber. These substrates may be used as a bulk or a thin film, and may be disposed on the outermost surface of a substrate such as glass, plastic film, ceramics, metal, or silicon wafer. Substrates such as the above inorganic materials and organic materials may be laminated or laminated.
透明導電性炭素膜（Ｂ）の合成方法として特に限定はしないが、グラファイト薄膜、グラファイト薄膜の剥離法、表面波プラズマＣＶＤ法、熱ＣＶＤ法、ＲＦプラズマＣＶＤ法、リモートプラズマＣＶＤ法、インバータプラズマＣＶＤ法、ＳｉＣの加熱による合成法、酸化グラフェンの還元等、その他従来公知の方法または上記方法を一つ以上組み合わせてもよい。特に表面波プラズマＣＶＤ法、熱ＣＶＤ法、ＲＦプラズマＣＶＤ法、リモートプラズマＣＶＤ法、インバータプラズマＣＶＤ法で作成した透明導電性炭素膜が、膜の均一性が高いことからより好ましい。 The method for synthesizing the transparent conductive carbon film (B) is not particularly limited, but it is not limited to graphite thin film, graphite thin film peeling method, surface wave plasma CVD method, thermal CVD method, RF plasma CVD method, remote plasma CVD method, inverter plasma CVD. One or more of the above-mentioned methods or other conventionally known methods such as a method, a synthesis method by heating SiC, or reduction of graphene oxide may be used. In particular, a transparent conductive carbon film prepared by a surface wave plasma CVD method, a thermal CVD method, an RF plasma CVD method, a remote plasma CVD method, or an inverter plasma CVD method is more preferable because of high film uniformity.
透明導電性炭素膜（Ｂ）の厚みは０．０１ｎｍ〜１０００ｎｍが好ましく、炭素膜の透明性を考慮すると０．１〜１０ｎｍが好ましく、０．３〜５ｎｍがより好ましい。 The thickness of the transparent conductive carbon film (B) is preferably 0.01 nm to 1000 nm, and considering the transparency of the carbon film, 0.1 to 10 nm is preferable, and 0.3 to 5 nm is more preferable.
透明導電性炭素膜（Ｂ）は透明導電膜として使用することを考慮すると、面積０．１ｃｍ2以上であることが好ましい。 In consideration of using the transparent conductive carbon film (B) as a transparent conductive film, the area is preferably 0.1 cm 2 or more.
薄膜活性化層（Ｃ）とは、透明導電性炭素膜（Ｂ）に対してドーピングする役割を果たし、かつ（Ｂ）の表面抵抗を下げ、光線透過率を低下させない、連続または不連続な膜と定義する。 The thin film activation layer (C) is a continuous or discontinuous film that plays a role of doping the transparent conductive carbon film (B) and does not lower the surface resistance of (B) and reduce the light transmittance. It is defined as
活性化層（Ｃ）の厚みは、０．０１〜１０００ｎｍ以下が好ましく、透明導電性炭素膜組成物の透過率を下げないことを考えると０．１ｎｍ〜２００ｎｍであることがより好ましい。 The thickness of the activation layer (C) is preferably 0.01 to 1000 nm or less, and more preferably 0.1 to 200 nm in view of not reducing the transmittance of the transparent conductive carbon film composition.
活性化層（Ｃ）の屈折率は、反射抑制を考慮すると透明導電性炭素膜（Ｂ）より低いことが好ましい。 The refractive index of the activation layer (C) is preferably lower than that of the transparent conductive carbon film (B) in consideration of reflection suppression.
炭素膜表面に上記活性化層（Ｃ）を形成する方法として特に限定はしないが、ディッピング法、スピンコート法、バーコート法、スプレー法、エアレススプレー法、ダイコート法、ロールコート法、フローコート法、そして真空中でシランカップリング剤の蒸気に晒す真空蒸着法などがあげられる。通常シランカップリング剤中の加水分解性基Ｘが系中の水分と加水分解反応を起こしポリマー化やオリゴマー化が進行するため、できる限り空気や水分に接触しない方法が望まれることから、真空中でシランカップリング剤の蒸気に晒す真空蒸着法が特に好ましい。 The method for forming the activated layer (C) on the surface of the carbon film is not particularly limited, but dipping method, spin coating method, bar coating method, spray method, airless spray method, die coating method, roll coating method, flow coating method. And vacuum deposition in which the silane coupling agent is exposed to vapor in vacuum. Since a hydrolyzable group X in a silane coupling agent usually undergoes a hydrolysis reaction with water in the system and polymerization and oligomerization proceed, a method that does not come into contact with air and moisture as much as possible is desired. Particularly preferred is a vacuum deposition method in which the silane coupling agent is exposed to vapor.
本発明の化学式（Ｉ）、（ＩＩ）または（ＩＩＩ）におけるＲ1，Ｒ2、Ｒ3は、それぞれ同一または異なって、水素原子の一部または全部がフッ素原子で置換されていてもよい炭素数１〜１８の炭化水素基を表す。 R 1 , R 2 , and R 3 in the chemical formula (I), (II), or (III) of the present invention are the same or different, and a carbon atom in which some or all of the hydrogen atoms may be substituted with fluorine atoms The hydrocarbon group of number 1-18 is represented.
また上記化学式（Ｉ）、（ＩＩ）、（ＩＩＩ）における官能基Ｒ1、Ｒ2、Ｒ3は、それぞれ同一または異なって、水素原子の一部がフッ素原子で置換されていてもよい炭素数１〜１２の炭化水素基を表すことが好ましい。 The functional groups R 1 , R 2 , and R 3 in the above chemical formulas (I), (II), and (III) are the same or different, and the number of carbon atoms that may be partially substituted with fluorine atoms. It preferably represents 1 to 12 hydrocarbon groups.
さらに上記化学式（Ｉ）、（ＩＩ）、（ＩＩＩ）における官能基Ｒ1、Ｒ2、Ｒ3は、それぞれ同一または異なって、独立して、アルキル基、アリール基などを表わす。アルキル基としては、炭素数１〜１８の置換もしくは無置換のものを示し、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｎ−ヘキシル基、トリフルオロメチル基、トリフルオロエチル基などを挙げることができる。アリール基としては炭素数６〜２０の置換もしくは無置換のものを示し、例えば、フェニル基、１−ナフチル基、２−ナフチル基、４−メチルフェニル基、３−メチルフェニル基、２−メチルフェニル基、４−エチルフェニル基、３−エチルフェニル基、４−メトキシフェニル基、３−メトキシフェニル基、２−メトキシフェニル基、４−ニトロフェニル基、４−フェニルフェニル基、４−クロロフェニル基、４−ブロモフェニル基などを挙げることができる。他の官能基としては、炭素数７〜２０の置換もしくは無置換のものを示し、ベンジル基、４−メチルベンジル基、３−メチルベンジル基、２−メチルベンジル基、４−メトキシベンジル基、３−メトキシベンジル基、２−メトキシベンジル基、１−フェニルエチル基、２−フェニルエチル基、１−（４−メチルフェニル）エチル基、１−（４−メトキシフェニル）エチル基、３−フェニルプロピル基、２−フェニルプロピル基等を挙げることができる。中でもＲ1として好ましくはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、オクタデシル基、フェニル基、シクロヘキシル基、シクロペンチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ-トリデカフルオロ−ｎ−オクチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ-ヘプタデカフルオロデシル基、２−シアノエチル基メチル基、フェニル基、４−メチルフェニル基であり、さらに好ましくはフェニル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ-トリデカフルオロ−ｎ−オクチル基、トリクロロ(１Ｈ，１Ｈ，２Ｈ，２Ｈ-ヘプタデカフルオロデシル)基である。Ｒ2、Ｒ3として好ましくはメチル基、エチル基、フェニル基であり、さらに好ましくはメチル基、エチル基である。メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、オクタデシル基、フェニル基、シクロヘキシル基、シクロペンチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ-トリデカフルオロ-n-オクチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ-ヘプタデカフルオロデシル基、2-シアノエチル基である。 Furthermore, the functional groups R 1 , R 2 and R 3 in the chemical formulas (I), (II) and (III) are the same or different and each independently represents an alkyl group, an aryl group or the like. Examples of the alkyl group include substituted or unsubstituted ones having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include a butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a trifluoromethyl group, and a trifluoroethyl group. The aryl group is a substituted or unsubstituted group having 6 to 20 carbon atoms, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl. Group, 4-ethylphenyl group, 3-ethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-nitrophenyl group, 4-phenylphenyl group, 4-chlorophenyl group, 4 -A bromophenyl group etc. can be mentioned. Other functional groups are substituted or unsubstituted having 7 to 20 carbon atoms, such as benzyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-methoxybenzyl group, 3 -Methoxybenzyl group, 2-methoxybenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1- (4-methylphenyl) ethyl group, 1- (4-methoxyphenyl) ethyl group, 3-phenylpropyl group And 2-phenylpropyl group. Among them, R 1 is preferably methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, octadecyl group, phenyl group, cyclohexyl group, cyclopentyl group, 1H, 1H, 2H, 2H- Tridecafluoro-n-octyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group, 2-cyanoethyl group methyl group, phenyl group, 4-methylphenyl group, more preferably phenyl group, 1H, 1H , 2H, 2H-tridecafluoro-n-octyl group, trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) group. R 2 and R 3 are preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group. Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, octadecyl group, phenyl group, cyclohexyl group, cyclopentyl group, 1H, 1H, 2H, 2H-tridecafluoro-n- An octyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group and 2-cyanoethyl group.
本発明の化学式（Ｉ）、（ＩＩ）または（ＩＩＩ）におけるＸは加水分解性基である。 X in the chemical formula (I), (II) or (III) of the present invention is a hydrolyzable group.
上記化学式（Ｉ）、（ＩＩ）、（ＩＩＩ）における官能基Ｘとしてはハロゲン原子またはアルコキシ基が好ましい。例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子、アルコキシ基、アセトキシ基などを挙げることができる。入手性などを考慮すると、塩素原子、アルコキシ基が特に好ましい。 The functional group X in the chemical formulas (I), (II), and (III) is preferably a halogen atom or an alkoxy group. For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, an acetoxy group, etc. can be mentioned. In view of availability, a chlorine atom and an alkoxy group are particularly preferable.
本発明の薄膜活性層（Ｃ）の接触角は、透明導電性炭素膜（Ｂ）の接触角が８０〜９５°であるため、濡れ性の問題を考慮すると薄膜活性層（Ｃ）表面は６０〜１５０°が好ましく、８０〜１２０°がより好ましい。 The contact angle of the thin film active layer (C) of the present invention is that the contact angle of the transparent conductive carbon film (B) is 80 to 95 °. ˜150 ° is preferable, and 80 to 120 ° is more preferable.
本発明の透明導電性炭素膜組成物（Ａ）、（Ｂ）や組成物（Ａ）〜（Ｃ）の透過率は、透明導電膜としての使用を考慮すると７０％以上が好ましく、さらには８０％以上がより好ましい。 The transmittance of the transparent conductive carbon film compositions (A) and (B) and the compositions (A) to (C) of the present invention is preferably 70% or more in consideration of use as a transparent conductive film, and more preferably 80 % Or more is more preferable.
本発明においては、透明導電性炭素膜組成物（Ａ），（Ｂ）と組成物（Ａ）〜（Ｃ）透過率の差は小さければ小さいほど透明導電性炭素膜組成物の透過率を損なわない良いドーピング方法であり、その差が１０％以下であることが好ましく、５％以下であることがより好ましい。 In this invention, the transmittance | permeability of a transparent conductive carbon film composition is impaired, so that the difference of the transparent conductive carbon film composition (A), (B) and the composition (A)-(C) transmittance is small. A good doping method, and the difference is preferably 10% or less, more preferably 5% or less.
以下、実施例を挙げ、本発明を説明するが、本発明の主旨を越えない限り、実施例に限定されるものではない。また比較例、実施例中で使用する表面プラズマＣＶＤで合成したグラフェンは以下の非公開特許に従い製造した。
1. “透明導電性炭素膜の製造方法及び透明導電性炭素膜”， 金載浩，石原正統，古賀義紀，津川和夫，長谷川雅考，飯島澄男，山田貴尋，特願2011- 041749 ，2011/02/28．
2. “透明導電性炭素膜の製造方法及び透明導電性炭素膜”， 金載浩，石原正統，古賀義紀，津川和夫，長谷川雅考，飯島澄男，山田貴尋，特願2011-009616，2011/01/20．
3. “透明導電性炭素膜の製造方法及び透明導電性炭素膜”，金載浩，石原正統，古賀義紀，津川和夫，長谷川雅考，飯島澄男，山田貴壽，特願2010-200901，2010/09/08.
4. “透明導電性炭素膜の製造方法及び透明導電性炭素膜”，金載浩，石原正統，古賀義紀，津川和夫，長谷川雅考，飯島澄男，特願2010-060055，2010/03/17.
5. “透明導電膜積層体の製造方法および透明導電膜積層体”石原正統，金載浩，山田貴壽、古賀義紀，長谷川雅考，特願2011-103370, 2011/05/06.
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, unless it exceeds the main point of this invention, it is not limited to an Example. Moreover, the graphene synthesized by surface plasma CVD used in the comparative examples and examples was manufactured according to the following non-public patents.
1. “Transparent Conductive Carbon Film Manufacturing Method and Transparent Conductive Carbon Film”, Hiroshi Kanami, Masanori Ishihara, Yoshinori Koga, Kazuo Tsugawa, Masanori Hasegawa, Sumio Iijima, Takahiro Yamada, Japanese Patent Application 2011-041749, 2011/02 / 28.
2. “Method of manufacturing transparent conductive carbon film and transparent conductive carbon film”, Hiroshi Kane, Masanori Ishihara, Yoshinori Koga, Kazuo Tsukawa, Masanori Hasegawa, Sumio Iijima, Takahiro Yamada, Japanese Patent Application 2011-009616, 2011/01 / 20.
3. “Transparent Conductive Carbon Film Manufacturing Method and Transparent Conductive Carbon Film”, Hiroshi Kane, Masanori Ishihara, Yoshinori Koga, Kazuo Tsugawa, Masanori Hasegawa, Sumio Iijima, Takaaki Yamada, Japanese Patent Application 2010-200901, 2010/09 / 08.
4. “Manufacturing method of transparent conductive carbon film and transparent conductive carbon film”, Hiroshi Kanami, Masanori Ishihara, Yoshinori Koga, Kazuo Tsukawa, Masanori Hasegawa, Sumio Iijima, Japanese Patent Application 2010-060055, 2010/03/17.
5. “Method for producing transparent conductive film laminate and transparent conductive film laminate”, Masanori Ishihara, Hiroshi Kane, Takaaki Yamada, Yoshinori Koga, Masanori Hasegawa, Japanese Patent Application 2011-103370, 2011/05/06.
＜比較例１＞グラフェン付石英基板の製造
表面プラズマＣＶＤ法により作成した銅箔グラフェン（グラフェン層数１０層程度、大きさ２５ｘ２５ｍｍ）を純水中に浸した後、超音波洗浄機で１分処理し、グラフェン上の炭素粒子や製膜中に付着した埃を除去した。この銅箔グラフェンを乾燥した後、弱剥離シート（「Ｅ−ＭＡＳＫR ＴＷ１００」日東電工（株）製）を気泡がつかないように貼りあわせた。貼りあわせたフィルムを１０％塩化鉄（和光純薬（株）製）水溶液に浸潤させ銅箔をエッチングした。この時グラフェンは弱剥離シート側に転写される。このグラフェン付保護シートを溶融石英板（２ｃｍｘ２ｃｍ、厚み１ｍｍ、（株）アトック製）に貼りあわせ、２日間室温にて乾燥させた。乾燥を確認した後、弱剥離シートを除去してグラフェンを石英板に転写した。転写したグラフェン組成物の表面抵抗を４端子４探針法抵抗測定機（「ロレスタＧＰ ＭＣＰ−Ｔ６００型」（株）三菱アナリテック製）、透過率はヘイズメーター（「ＮＤＨ５０００ＳＰ」，日本電色工業（株）製）で測定した。結果を表１に示す。
<Comparative example 1> Manufacture of a quartz substrate with graphene Copper foil graphene (number of graphene layers of about 10 layers, size: 25x25 mm) prepared by surface plasma CVD method is immersed in pure water, and then treated with an ultrasonic cleaner for 1 minute Then, carbon particles on the graphene and dust adhered during film formation were removed. After the copper foil graphene was dried, a weak release sheet (“E-MASKR TW100” manufactured by Nitto Denko Corporation) was attached so as not to cause bubbles. The laminated film was immersed in a 10% aqueous solution of iron chloride (manufactured by Wako Pure Chemical Industries, Ltd.) to etch the copper foil. At this time, the graphene is transferred to the weak release sheet side. This protective sheet with graphene was attached to a fused quartz plate (2 cm × 2 cm, thickness 1 mm, manufactured by Atock Co., Ltd.) and dried at room temperature for 2 days. After confirming the drying, the weak release sheet was removed and the graphene was transferred to the quartz plate. The surface resistance of the transferred graphene composition was measured using a 4-terminal 4-probe resistance measuring machine ("Loresta GP MCP-T600 type" manufactured by Mitsubishi Analitech Co., Ltd.), and the transmittance was a haze meter ("NDH5000SP", Nippon Denshoku Industries Co., Ltd.) (Made by Co., Ltd.). The results are shown in Table 1.
＜比較例２＞グラフェン付ＰＥＴ基板の製造
使用した基板をＰＥＴにした以外は、比較例１に記載の石英基板と同様に実験を行った。結果を表１に示す。
<Comparative Example 2> Manufacture of graphene-attached PET substrate An experiment was conducted in the same manner as the quartz substrate described in Comparative Example 1 except that the substrate used was PET. The results are shown in Table 1.
＜比較例３＞グラフェン付ＰＭＭＡ基板の製造
表面プラズマＣＶＤ法により作成した銅箔グラフェン（グラフェン層数１０層程度、大きさ２５ｘ２５ｍｍ）を純水中に浸した後、超音波洗浄機で１分処理し、グラフェン上の炭素粒子や製膜中に付着した埃を除去した。この銅箔グラフェンを乾燥した後、２０重量％濃度のポリメタクリル酸メチル（ＰＭＭＡ、東京化成（株）製）クロロホルム溶液をガラス棒で塗布した。このポリマー付銅箔を１４０℃で１時間加熱処理をした。貼りあわせたフィルムの銅箔背面をサンドペーパで研磨し、過剰のＰＭＭＡを除去した。このフィルムを１０％塩化鉄（和光純薬（株）製）水溶液に浸潤させ銅箔をエッチングした。この時グラフェンはＰＭＭＡ側に転写される。エッチングしたフィルムを純水で３回洗浄した後、ＰＥＴフィルムで掬い上げて乾燥させた。このグラフェン組成物の表面抵抗を４端子４探針法抵抗測定機（「ロレスタＧＰ ＭＣＰ−Ｔ６００型」（株）三菱アナリテック製）、透過率はヘイズメーター（「ＮＤＨ５０００ＳＰ」，日本電色工業（株）製）で測定した。結果を表１に示す。
<Comparative Example 3> Manufacture of graphene-attached PMMA substrate After immersing copper foil graphene (number of graphene layers of about 10 layers, size: 25 x 25 mm) prepared by surface plasma CVD in pure water, it was treated with an ultrasonic cleaner for 1 minute Then, carbon particles on the graphene and dust adhered during film formation were removed. After the copper foil graphene was dried, a 20% strength by weight polymethyl methacrylate (PMMA, manufactured by Tokyo Chemical Industry Co., Ltd.) chloroform solution was applied with a glass rod. This polymer-attached copper foil was heat-treated at 140 ° C. for 1 hour. The copper foil back surface of the bonded film was polished with sandpaper to remove excess PMMA. The film was infiltrated with a 10% iron chloride (Wako Pure Chemical Industries, Ltd.) aqueous solution to etch the copper foil. At this time, the graphene is transferred to the PMMA side. The etched film was washed three times with pure water, then scooped up with PET film and dried. The surface resistance of this graphene composition was measured using a 4-terminal 4-probe resistance measuring machine (“Loresta GP MCP-T600 type” (manufactured by Mitsubishi Analitech Co., Ltd.)), and the transmittance was a haze meter (“NDH5000SP”, Nippon Denshoku Industries ( Measured by the company). The results are shown in Table 1.
＜比較例４＞グラフェン付ＣＹＴＯＰ基板の製造
表面プラズマＣＶＤ法により作成した銅箔グラフェン（グラフェン層数１０層程度、大きさ２５ｘ２５ｍｍ）を純水中に浸した後、超音波洗浄機で１分処理し、グラフェン上の炭素粒子や製膜中に付着した埃を除去した。この銅箔グラフェンを乾燥した後、アモルファスフッ素樹脂ＣＹＴＯＰ（「Ｍシリーズ」旭硝子（株）製）をガラス棒で塗布した。この銅箔を１４０℃で１時間加熱処理をした。貼りあわせたフィルムの銅箔背面をサンドペーパで研磨し、過剰のフッ素系ポリマーを除去した。このフィルムを１０％塩化鉄（和光純薬（株）製）水溶液に浸潤させ銅箔をエッチングした。この時グラフェンはＣＹＴＯＰ側に転写される。エッチングしたフィルムを純水で３回洗浄した後、ＰＥＴフィルムで掬い上げて乾燥させた。このグラフェン組成物の表面抵抗を４端子４探針法抵抗測定機（「ロレスタＧＰ ＭＣＰ−Ｔ６００型」（株）三菱アナリテック製）、透過率はヘイズメーター（「ＮＤＨ５０００ＳＰ」，日本電色工業（株）製）で測定した。結果を表１に示す。
<Comparative Example 4> Manufacture of CYTOP substrate with graphene Copper foil graphene (number of graphene layers of about 10 layers, size: 25x25 mm) created by surface plasma CVD method is immersed in pure water, and then treated with an ultrasonic cleaner for 1 minute Then, carbon particles on the graphene and dust adhered during film formation were removed. After drying the copper foil graphene, an amorphous fluororesin CYTOP (“M series” manufactured by Asahi Glass Co., Ltd.) was applied with a glass rod. This copper foil was heat-treated at 140 ° C. for 1 hour. The back surface of the copper foil of the bonded film was polished with sandpaper to remove excess fluorine-based polymer. The film was infiltrated with a 10% iron chloride (Wako Pure Chemical Industries, Ltd.) aqueous solution to etch the copper foil. At this time, the graphene is transferred to the CYTOP side. The etched film was washed three times with pure water, then scooped up with PET film and dried. The surface resistance of this graphene composition was measured using a 4-terminal 4-probe resistance measuring machine (“Loresta GP MCP-T600 type” (manufactured by Mitsubishi Analitech Co., Ltd.)), and the transmittance was a haze meter (“NDH5000SP”, Nippon Denshoku Industries ( Measured by Co., Ltd.). The results are shown in Table 1.
＜比較例５＞グラフェン付エポキシ基板の製造
表面プラズマＣＶＤ法により作成した銅箔グラフェン（グラフェン層数１０層程度、大きさ２５ｘ２５ｍｍ）を純水中に浸した後、超音波洗浄機で１分処理し、グラフェン上の炭素粒子や製膜中に付着した埃を除去した。この銅箔グラフェンを乾燥した後、弱剥離シート（「E-MASKRTW100シリーズ」日東電工（株）製）を気泡がつかないように貼りあわせた。貼りあわせたフィルムを１０％塩化鉄（和光純薬（株）製）水溶液に浸潤させ銅箔をエッチングした。この時グラフェンは弱剥離シート側に転写される。この積層フィルムにエポキシ樹脂（「クリスタルレジン」日清レジン（株）製）1ｍＬをバーコーダーで塗布し、０．５ＭＰaで３時間、５０℃で終夜反応させ、硬化させた。この時グラフェンはエポキシ樹脂側に転写される。エッチングしたフィルムを純水で3回洗浄した後、ＰＥＴフィルムで掬い上げて乾燥させた。このグラフェン組成物の表面抵抗を４端子４探針法抵抗測定機（「ロレスタＧＰ ＭＣＰ−Ｔ６００型」（株）三菱アナリテック製）、透過率はヘイズメーター（「ＮＤＨ５０００ＳＰ」，日本電色工業（株）製）で測定した。結果を表１に示す。
<Comparative Example 5> Manufacture of epoxy substrate with graphene Copper foil graphene (number of graphene layers of about 10 layers, size: 25 x 25 mm) prepared by surface plasma CVD method is immersed in pure water, and then treated with an ultrasonic cleaner for 1 minute Then, carbon particles on the graphene and dust adhered during film formation were removed. After the copper foil graphene was dried, a weak release sheet (“E-MASKRTW100 series” manufactured by Nitto Denko Corporation) was attached so as not to cause bubbles. The laminated film was immersed in a 10% aqueous solution of iron chloride (manufactured by Wako Pure Chemical Industries, Ltd.) to etch the copper foil. At this time, the graphene is transferred to the weak release sheet side. 1 mL of an epoxy resin (“Crystal Resin” manufactured by Nissin Resin Co., Ltd.) was applied to the laminated film with a bar coder, and reacted at 0.5 MPa for 3 hours at 50 ° C. overnight to be cured. At this time, the graphene is transferred to the epoxy resin side. The etched film was washed three times with pure water, then scooped up with PET film and dried. The surface resistance of this graphene composition was measured using a 4-terminal 4-probe resistance measuring machine (“Loresta GP MCP-T600 type” (manufactured by Mitsubishi Analitech Co., Ltd.)), and the transmittance was a haze meter (“NDH5000SP”, Nippon Denshoku Industries ( Measured by Co., Ltd.). The results are shown in Table 1.
次に、グラフェンのドーピング方法の実施例を示す。
（実施例１）ＦＴＳによるグラフェンのドーピング実験(石英)
比較例１のグラフェン付石英基板の作成方法に従って調整したグラフェンを、減圧乾燥オーブンに入れ、減圧下(１０3Ｐａ程度)、１００ ℃で一時間乾燥した。乾燥後グラフェンフィルムをデシケーターに入れた。デシケーター内に０．２ ｍＬのＴｒｉｃｈｌｏｒｏ− （１Ｈ，１Ｈ，２Ｈ，２Ｈ−ｔｒｉｄｅｃａｆｌｕｏｒｏ−ｎ−ｏｃｔｙｌ）ｓｉｌａｎｅ（以後ＦＴＳ）（東京化成（株）製）をガラス製シャーレに入れてデシケーターの蓋をし、室温、減圧条件(１０3Ｐａ程度)にて表面処理を行った。反応終了後、デシケーターからサンプルを取り出し、グラフェン積層体の表面抵抗を４端子４探針法抵抗測定機（「ロレスタＧＰ ＭＣＰ−Ｔ６００型」（株）三菱アナリテック製）、透過率、ヘイズはヘイズメーター（「ＮＤＨ５０００ＳＰ」，日本電色工業（株）製）、接触角計は（「ＤＭｓ−４００Ｈｉ」協和界面化学（株）製） にて測定した。結果を表１に示す。
Next, an example of a graphene doping method will be described.
Example 1 Graphene Doping Experiment with FTS (Quartz)
Graphene prepared according to the method for producing a graphene-attached quartz substrate of Comparative Example 1 was placed in a vacuum drying oven and dried at 100 ° C. for 1 hour under reduced pressure (about 10 3 Pa). After drying, the graphene film was placed in a desiccator. Place 0.2 mL of Trichloro- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (hereinafter FTS) (manufactured by Tokyo Chemical Industry Co., Ltd.) in a glass petri dish and cover the desiccator. Surface treatment was performed at room temperature under reduced pressure conditions (about 10 3 Pa). After completion of the reaction, a sample was taken out from the desiccator, and the surface resistance of the graphene laminate was measured using a 4-terminal 4-probe resistance measuring instrument (“Loresta GP MCP-T600 type” manufactured by Mitsubishi Analitech Co., Ltd.), transmittance, haze haze A meter (“NDH5000SP”, manufactured by Nippon Denshoku Industries Co., Ltd.) and a contact angle meter (“DMs-400Hi” manufactured by Kyowa Interface Chemical Co., Ltd.) were used. The results are shown in Table 1.
（実施例２）ＦＴＳによるグラフェンのドーピング実験（ＰＥＴ）
比較例２で作成したグラフェン付ＰＥＴ基板を実施例１と同様の方法でドーピングを行った。結果を表１に示す。
Example 2 Graphene Doping Experiment with FTS (PET)
The graphene-coated PET substrate prepared in Comparative Example 2 was doped by the same method as in Example 1. The results are shown in Table 1.
（実施例３）ＦＴＳによるグラフェンのドーピング実験（ＰＭＭＡ）
比較例３で作成したグラフェン付ＰＭＭＡ基板を実施例１と同様の方法でドーピングを行った。結果を表１に示す。
(Example 3) Graphene doping experiment by FTS (PMMA)
The PMMA substrate with graphene prepared in Comparative Example 3 was doped by the same method as in Example 1. The results are shown in Table 1.
（実施例４）ＦＴＳによるグラフェンのドーピング実験（ＣＹＴＯＰ）
比較例２で作成したグラフェン付ＣＹＴＯＰ基板を実施例１と同様の方法でドーピングを行った。結果を表１に示す。
(Example 4) Graphene doping experiment by FTS (CYTOP)
The graphene-attached CYTOP substrate prepared in Comparative Example 2 was doped by the same method as in Example 1. The results are shown in Table 1.
（実施例５）ＦＴＳによるグラフェンのドーピング実験（Ｅｐｏｘｙ）
比較例２で作成したグラフェン付エポキシ基板を実施例１と同様の方法でドーピングを行った。結果を表１に示す。
(Example 5) Graphene doping experiment by FTS (Epoxy)
The graphene-attached epoxy substrate prepared in Comparative Example 2 was doped by the same method as in Example 1. The results are shown in Table 1.
上記比較例１〜５および実施例１〜５に記載したグラフェン積層体の接触角、表面抵抗、透過率を表１にまとめた。 Table 1 shows the contact angle, surface resistance, and transmittance of the graphene laminates described in Comparative Examples 1 to 5 and Examples 1 to 5.
比較例１〜５と比較し、実施例１〜６についてはその表面抵抗は減少している。また透過率はドーピング前後で大きく変化しておらず１０％以下である。 Compared with Comparative Examples 1-5, about Examples 1-6, the surface resistance is reducing. Further, the transmittance is not greatly changed before and after doping and is 10% or less.
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