JP5800232B2 - Graphite thin film and manufacturing method thereof - Google Patents
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本発明は、板状の黒鉛粒子を含有する黒鉛薄膜およびその製造方法に関する。 The present invention relates to a graphite thin film containing plate-like graphite particles and a method for producing the same.
黒鉛粒子は、熱伝導性、導電性、機械的強度など様々な特性に優れており、このような黒鉛粒子からなる薄膜は、様々な分野において、導電体材料や熱伝導体材料などとして注目されている。しかしながら、黒鉛粒子は凝集しやすく、従来の黒鉛薄膜は必ずしも十分な特性を有するものではなかった。 Graphite particles are excellent in various properties such as thermal conductivity, electrical conductivity, and mechanical strength, and thin films made of such graphite particles are attracting attention as conductor materials and thermal conductor materials in various fields. ing. However, graphite particles tend to aggregate, and conventional graphite thin films do not always have sufficient characteristics.
そこで、従来から、薄片化した黒鉛粒子を水などの溶媒に分散させ、この分散液を用いて黒鉛塗膜を形成する方法が提案されている。例えば、特開２０１１−１８４２６４号公報（特許文献１）には、黒鉛とアルカリ金属の水酸化物と水とを混合してアルカリ性の水分散液を調製することによって、前記黒鉛を薄片化し、この薄片化された黒鉛を含む水分散液を基板上に塗布、乾燥させて薄片化黒鉛を含む薄膜を製造する方法が開示されている。また、特開２０１１−３２１５６号公報（特許文献２）には、高品質、高配向性のグラファイト結晶を水などの溶媒中で撹拌して前記グラファイト結晶の表面からグラファイト層を剥離してグラフェンを含む溶液を調製し、この溶液を基板上に塗布、乾燥させて薄膜を製造する方法が開示されている。しかしながら、これらの方法において調製した薄片化黒鉛やグラフェンは、水分散液中や溶液中で凝集しやすく、得られた黒鉛薄膜の特性も未だ十分なものではなかった。 Therefore, conventionally, a method has been proposed in which exfoliated graphite particles are dispersed in a solvent such as water and a graphite coating film is formed using this dispersion. For example, in Japanese Patent Application Laid-Open No. 2011-184264 (Patent Document 1), graphite is exfoliated by mixing an alkali metal hydroxide and water to prepare an alkaline aqueous dispersion. A method for producing a thin film containing exfoliated graphite by applying an aqueous dispersion containing exfoliated graphite on a substrate and drying the substrate is disclosed. Japanese Patent Laid-Open No. 2011-32156 (Patent Document 2) describes that graphene is separated from the surface of the graphite crystal by stirring a high-quality, highly-oriented graphite crystal in a solvent such as water. A method for producing a thin film by preparing a solution containing the solution, applying the solution on a substrate, and drying the solution is disclosed. However, exfoliated graphite and graphene prepared by these methods tend to aggregate in an aqueous dispersion or solution, and the characteristics of the obtained graphite thin film have not been sufficient.
また、特許文献２には、高品質、高配向性のグラファイト結晶を濃硫酸などを含む溶液中に浸漬して前記グラファイト結晶の表面を酸化しながらグラファイト層を剥離してグラフェンを含む溶液を調製し、この溶液を基板上に塗布、乾燥させて薄膜を製造する方法も開示されている。しかしながら、グラファイト結晶の表面を酸化するとグラファイト構造の一部が破壊されやすく、黒鉛粒子の本来の特性に比べて、薄膜の特性が低下する傾向があった。 Patent Document 2 prepares a solution containing graphene by detaching a graphite layer while oxidizing the surface of the graphite crystal by immersing a high quality, highly oriented graphite crystal in a solution containing concentrated sulfuric acid. In addition, a method of manufacturing a thin film by applying this solution on a substrate and drying it is also disclosed. However, when the surface of the graphite crystal is oxidized, a part of the graphite structure is easily broken, and the characteristics of the thin film tend to be lower than the original characteristics of the graphite particles.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、薄片化した黒鉛粒子を凝集させずに黒鉛薄膜を製造する方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a method for producing a graphite thin film without agglomerating the exfoliated graphite particles.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、黒鉛粒子、特定の芳香族ビニル共重合体、過酸化水素化物を混合して粉砕処理を施すことによって得られる微細化板状黒鉛粒子を有機溶媒に分散させ、この分散液を用いて黒鉛薄膜を作製することによって、複数の前記微細化板状黒鉛粒子が凝集せずに板面方向に連続的に接触することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a fine plate obtained by mixing and pulverizing graphite particles, a specific aromatic vinyl copolymer, and a hydrogen peroxide. It has been found that a plurality of the above-mentioned fine plate-like graphite particles are continuously contacted in the plate surface direction without agglomeration by dispersing the graphite particles in an organic solvent and preparing a graphite thin film using this dispersion. The present invention has been completed.
すなわち、本発明の黒鉛薄膜は、水酸基、カルボキシル基およびエポキシ基からなる群から選択される少なくとも１種の官能基が表面に結合している板状黒鉛粒子と、前記官能基を介して前記板状黒鉛粒子に吸着した、下記式（１）：
−（ＣＨ２−ＣＨＸ）− （１）
（式（１）中、Ｘはフェニル基、ナフチル基、アントラセニル基またはピレニル基を表し、これらの基は置換基を有していてもよい。）
で表されるビニル芳香族モノマー単位と、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルイミダゾール類、ビニルピリジン類、無水マレイン酸およびマレイミド類からなる群から選択される少なくとも１種のモノマーから誘導されるモノマー単位とを含有する芳香族ビニル共重合体とを備える微細化板状黒鉛粒子を含有し、
複数の該微細化板状黒鉛粒子が板面方向に連続的に接触して配置されていることを特徴とするものである。また、このような本発明の黒鉛粒子においては、前記微細化板状黒鉛粒子の板面と前記黒鉛薄膜の膜面とが平行であることが好ましい。
That is, the graphite thin film of the present invention includes plate-like graphite particles having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and an epoxy group bonded to the surface, and the plate via the functional group. The following formula (1) adsorbed on the graphite particles:
- (CH 2 -CHX) - ( 1)
(In formula (1), X represents a phenyl group, a naphthyl group, an anthracenyl group, or a pyrenyl group, and these groups may have a substituent.)
Selected from the group consisting of a vinyl aromatic monomer unit represented by : (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, vinylimidazoles, vinylpyridines, maleic anhydride and maleimides Containing refined plate-like graphite particles comprising an aromatic vinyl copolymer containing monomer units derived from at least one monomer ,
A plurality of the fine plate-like graphite particles are arranged in continuous contact with each other in the plate surface direction. In the graphite particles of the present invention, the plate surface of the fine plate-like graphite particles and the film surface of the graphite thin film are preferably parallel.
本発明の黒鉛粒子の製造方法は、水酸基、カルボキシル基およびエポキシ基からなる群から選択される少なくとも１種の官能基が表面に結合している板状黒鉛粒子と、前記官能基を介して前記板状黒鉛粒子に吸着した、下記式（１）：
−（ＣＨ２−ＣＨＸ）− （１）
（式（１）中、Ｘはフェニル基、ナフチル基、アントラセニル基またはピレニル基を表し、これらの基は置換基を有していてもよい。）
で表されるビニル芳香族モノマー単位と、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルイミダゾール類、ビニルピリジン類、無水マレイン酸およびマレイミド類からなる群から選択される少なくとも１種のモノマーから誘導されるモノマー単位とを含有する芳香族ビニル共重合体とを備える微細化板状黒鉛粒子および有機溶媒を含有する板状黒鉛粒子分散液からなる有機層を形成する層形成工程と、
該有機層から前記有機溶媒を除去して、複数の前記微細化板状黒鉛粒子が板面方向に連続的に接触して配置されている黒鉛薄膜を形成する溶媒除去工程と、
を含むことを特徴とする方法である。前記層形成工程においては、前記微細化板状黒鉛粒子の板面と前記有機層の表面とが平行となるように、前記有機層を形成することが好ましい。
Method for producing a graphite particle of the present invention, a hydroxyl group, a plate-like graphite particles of at least one functional group selected from the group consisting of carboxyl group and an epoxy group is bonded to a surface, said through said functional group The following formula (1) adsorbed on the plate-like graphite particles:
- (CH 2 -CHX) - ( 1)
(In formula (1), X represents a phenyl group, a naphthyl group, an anthracenyl group, or a pyrenyl group, and these groups may have a substituent.)
Selected from the group consisting of a vinyl aromatic monomer unit represented by : (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, vinylimidazoles, vinylpyridines, maleic anhydride and maleimides Layer for forming an organic layer comprising fine plate-like graphite particles comprising an aromatic vinyl copolymer containing a monomer unit derived from at least one monomer and a plate-like graphite particle dispersion containing an organic solvent Forming process;
Removing the organic solvent from the organic layer to form a graphite thin film in which a plurality of the fine plate-like graphite particles are continuously contacted in the plate surface direction; and
It is the method characterized by including. In the layer forming step, it is preferable to form the organic layer so that the plate surface of the fine plate-like graphite particles and the surface of the organic layer are parallel to each other.
また、本発明の黒鉛粒子の製造方法においては、前記層形成工程において前記有機層を水面上に形成し、前記溶媒除去工程において前記黒鉛薄膜を水面上に形成することがより好ましく、前記水面上に形成された黒鉛薄膜を膜面方向に圧縮する工程をさらに含むことがより好ましい。 In the method for producing graphite particles of the present invention, it is more preferable that the organic layer is formed on the water surface in the layer forming step, and the graphite thin film is formed on the water surface in the solvent removing step. More preferably, the method further includes a step of compressing the graphite thin film formed in the film surface direction.
本発明の複合体は、このような本発明の黒鉛薄膜が基板上に配置されていることを特徴とするものである。このような本発明の複合体は、前記本発明の黒鉛薄膜の製造方法を用いて基板上に黒鉛薄膜を形成することによって製造することができる。また、前記本発明の黒鉛薄膜の製造方法を用いて黒鉛薄膜を水面上に形成した後、該黒鉛薄膜を基板上に写し取ることによって製造することもできる。 The composite of the present invention is characterized in that such a graphite thin film of the present invention is disposed on a substrate. Such a composite of the present invention can be produced by forming a graphite thin film on a substrate using the method for producing a graphite thin film of the present invention. Moreover, after forming a graphite thin film on the water surface using the method for producing a graphite thin film of the present invention, the graphite thin film can be copied on a substrate.
なお、本発明にかかる微細化板状黒鉛粒子を用いることによって、微細化された板状黒鉛粒子が凝集することなく、板面方向に連続的に接触している黒鉛薄膜が形成される理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、黒鉛粒子は、本来、有機溶媒との相互作用が小さく、凝集しやすいものであるため、有機溶媒中に高度に分散させることは困難であった。 In addition, the reason why the graphite thin film continuously contacting in the plate surface direction is formed without agglomeration of the refined plate-like graphite particles by using the refined plate-like graphite particles according to the present invention. Although not necessarily certain, the present inventors infer as follows. That is, the graphite particles originally have a small interaction with the organic solvent and are likely to aggregate, so that it was difficult to highly disperse in the organic solvent.
一方、本発明にかかる微細化板状黒鉛粒子においては、微細化された板状の黒鉛粒子に前記芳香族ビニル共重合体が吸着しているため、板状黒鉛粒子間の凝集力が低下し、有機溶媒中への分散性が向上すると推察される。さらに、芳香族ビニル共重合体の吸着性が安定しているため、微細化板状黒鉛粒子の分散安定性も向上すると推察される。そして、このような微細化板状黒鉛粒子の分散安定性は、乾燥などにより有機溶媒除去する過程においても保持されていると推察される。その結果、本発明にかかる微細化板状黒鉛粒子を含有する分散液を基板上に塗布し、塗膜を乾燥させた場合、微細化板状黒鉛粒子が均一に分散している状態で有機溶媒が除去されるため、微細化板状黒鉛粒子は、凝集しにくく、さらに、板面が塗膜の表面と平行となるように配向しやすいため、板面方向に連続的に接触した状態が形成され、本発明の黒鉛薄膜が得られると推察される。 On the other hand, in the refined plate-like graphite particles according to the present invention, since the aromatic vinyl copolymer is adsorbed on the refined plate-like graphite particles, the cohesive force between the plate-like graphite particles is reduced. It is presumed that the dispersibility in an organic solvent is improved. Furthermore, since the adsorptivity of the aromatic vinyl copolymer is stable, it is presumed that the dispersion stability of the fine plate-like graphite particles is also improved. And it is guessed that the dispersion stability of such refined plate-like graphite particles is maintained even in the process of removing the organic solvent by drying or the like. As a result, when the dispersion containing the fine plate-like graphite particles according to the present invention is applied on the substrate and the coating film is dried, the organic solvent is in a state where the fine plate-like graphite particles are uniformly dispersed. Therefore, the refined plate-like graphite particles are less likely to agglomerate and are more easily oriented so that the plate surface is parallel to the surface of the coating film, thus forming a state of continuous contact in the plate surface direction. It is speculated that the graphite thin film of the present invention is obtained.
また、本発明にかかる微細化板状黒鉛粒子の分散液を水面上にゆっくり滴下すると、前記微細化板状黒鉛粒子は、疎水性であるため、水中には沈降せず、有機溶媒とともに水面上に浮遊する。また、この疎水性により、微細化板状黒鉛粒子は、板面が水面と平行となるように配向すると推察される。そして、このような状態で、有機溶媒が蒸発などにより除去されると、水面上では微細化板状黒鉛粒子同士が、板面と水面との平行状態を維持したまま、集合するため、複数の微細化板状黒鉛粒子が板面方向に連続的に接触した状態が形成され、本発明の黒鉛薄膜が得られると推察される。 In addition, when the dispersion of the fine plate-like graphite particles according to the present invention is slowly dropped onto the water surface, the fine plate-like graphite particles are hydrophobic, so that they do not settle in the water, and together with the organic solvent on the water surface. To float. Further, it is presumed that, due to this hydrophobicity, the refined plate-like graphite particles are oriented so that the plate surface is parallel to the water surface. In such a state, when the organic solvent is removed by evaporation or the like, the fine plate-like graphite particles gather on the water surface while maintaining the parallel state between the plate surface and the water surface. It is inferred that a state in which the fine plate-like graphite particles are continuously contacted in the plate surface direction is formed, and the graphite thin film of the present invention is obtained.
さらに、本発明の黒鉛薄膜が、酸化により微細化された黒鉛粒子からなる薄膜に比べて優れた導電性および熱伝導性を示す理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の黒鉛薄膜においては、本発明にかかる微細化板状黒鉛粒子中の板状黒鉛粒子が構造欠陥の少ないもの（ラマンスペクトルにおけるＤバンドのピークがほとんど観測されないもの）であるため、グラファイト構造が保持され、黒鉛本来の特性がそのまま発現すると推察される。一方、黒鉛粒子を酸化により微細化する場合、黒鉛粒子の表面だけでなく、内部まで酸化することによって十分に微細化することが可能となる。しかしながら、黒鉛粒子を内部まで酸化すると粒子の微細化とともにグラファイト構造の一部が破壊される傾向にある。このため、酸化により微細化された黒鉛粒子においては、グラファイト構造に起因する特性、例えば、導電性、熱伝導性などの黒鉛本来の特性が低下すると推察される。 Furthermore, the reason why the graphite thin film of the present invention exhibits superior conductivity and thermal conductivity compared to a thin film made of graphite particles refined by oxidation is not necessarily clear, but the present inventors have as follows. I guess. That is, in the graphite thin film of the present invention, the plate-like graphite particles in the refined plate-like graphite particles according to the present invention have few structural defects (those in which the peak of the D band in the Raman spectrum is hardly observed) It is presumed that the graphite structure is maintained and the original characteristics of graphite are expressed as they are. On the other hand, when the graphite particles are refined by oxidation, the graphite particles can be sufficiently refined by oxidizing not only the surface of the graphite particles but also the inside. However, when the graphite particles are oxidized to the inside, there is a tendency that a part of the graphite structure is destroyed as the particles become finer. For this reason, in graphite particles refined | miniaturized by oxidation, it is guessed that the characteristic resulting from a graphite structure, for example, the intrinsic characteristics of graphite, such as electroconductivity and thermal conductivity, deteriorates.
本発明によれば、微細化された複数の板状黒鉛粒子が板面方向に連続的に接触している黒鉛薄膜を得ることが可能となる。 According to the present invention, it is possible to obtain a graphite thin film in which a plurality of refined plate-like graphite particles are continuously in contact in the plate surface direction.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明にかかる微細化板状黒鉛粒子について説明する。本発明にかかる微細化板状黒鉛粒子は、板状黒鉛粒子とこの板状黒鉛粒子に吸着した芳香族ビニル共重合体とを備えるものである。 First, the refined plate-like graphite particles according to the present invention will be described. The refined plate-like graphite particles according to the present invention comprise plate-like graphite particles and an aromatic vinyl copolymer adsorbed on the plate-like graphite particles.
前記板状黒鉛粒子は、特に制限されず、例えば、グラファイト構造を有する公知の黒鉛（人造黒鉛、天然黒鉛（例えば、鱗片状黒鉛、塊状黒鉛、土状黒鉛））をグラファイト構造が破壊されないように粉砕することによって得られるものである。 The plate-like graphite particles are not particularly limited. For example, a known graphite having a graphite structure (artificial graphite, natural graphite (for example, flaky graphite, lump graphite, earthy graphite)) is not destroyed. It is obtained by grinding.
このような板状黒鉛粒子の厚さとしては特に制限はないが、０．３〜２０００ｎｍが好ましく、０．３〜１０００ｎｍがより好ましく、０．３〜１００ｎｍが特に好ましく、１〜１００ｎｍが最も好ましい。また、板状黒鉛粒子の平面方向の大きさとしては特に制限はないが、例えば、長軸方向の長さ（長径）としては０．０１〜５００μｍが好ましく、０．１〜１００μｍがより好ましく、１〜５０μｍが特に好ましく、短軸方向の長さ（短径）としては０．０１〜５００μｍが好ましく、０．１〜１００μｍがより好ましく、０．３〜５０μｍが特に好ましい。 The thickness of such plate-like graphite particles is not particularly limited, but is preferably 0.3 to 2000 nm, more preferably 0.3 to 1000 nm, particularly preferably 0.3 to 100 nm, and most preferably 1 to 100 nm. . Further, the size of the plate-like graphite particles in the planar direction is not particularly limited. For example, the length in the major axis direction (major axis) is preferably 0.01 to 500 μm, more preferably 0.1 to 100 μm, The length in the minor axis direction (minor axis) is preferably 0.01 to 500 μm, more preferably 0.1 to 100 μm, and particularly preferably 0.3 to 50 μm.
また、本発明にかかる板状黒鉛粒子の表面には、水酸基、カルボキシル基、エポキシ基などの官能基が結合（より好ましくは共有結合）していることが好ましい。このような官能基は、本発明にかかる芳香族ビニル共重合体との親和性を有するものであり、芳香族ビニル共重合体の板状黒鉛粒子への吸着量が増大し、本発明にかかる微細化板状黒鉛粒子は有機溶媒中への分散性が高くなる傾向にある。その結果、このような微細化板状黒鉛粒子を含有する分散液を用いて黒鉛薄膜を作製する場合において、微細化板状黒鉛粒子の凝集が十分に抑制され、微細化板状黒鉛粒子が均一に配置した黒鉛薄膜が得られる傾向にある。 Moreover, it is preferable that functional groups such as a hydroxyl group, a carboxyl group, and an epoxy group are bonded (more preferably covalently bonded) to the surface of the plate-like graphite particles according to the present invention. Such a functional group has an affinity with the aromatic vinyl copolymer according to the present invention, and the adsorption amount of the aromatic vinyl copolymer to the plate-like graphite particles is increased, and the present invention is applied. The fine plate-like graphite particles tend to be highly dispersible in an organic solvent. As a result, in the case of producing a graphite thin film using a dispersion containing such refined plate-like graphite particles, aggregation of the refined plate-like graphite particles is sufficiently suppressed, and the refined plate-like graphite particles are uniform. There is a tendency to obtain a graphite thin film disposed on the surface.
このような官能基は、板状黒鉛粒子の表面近傍（好ましくは、表面から深さ１０ｎｍまでの領域）の全炭素原子の５０％以下（より好ましくは２０％以下、特に好ましくは１０％以下）の炭素原子に結合していることが好ましい。官能基が結合している炭素原子の割合が前記上限を超えると、板状黒鉛粒子は、親水性が増大するため、芳香族ビニル共重合体との親和性が低下する傾向にある。また、官能基が結合している炭素原子の割合の下限としては特に制限はないが、０．０１％以上が好ましい。なお、水酸基などの前記官能基はＸ線光電子分光法（ＸＰＳ）により定量することができ、粒子表面から深さ１０ｎｍまでの領域に存在する官能基の量を測定することができる。なお、板状黒鉛粒子の厚さが１０ｎｍ以下の場合には、板状黒鉛粒子の全領域に存在する官能基の量が測定される。 Such a functional group is 50% or less (more preferably 20% or less, particularly preferably 10% or less) of the total carbon atoms in the vicinity of the surface of the plate-like graphite particles (preferably, a region from the surface to a depth of 10 nm). It is preferable that it is bonded to the carbon atom. When the ratio of the carbon atom to which the functional group is bonded exceeds the upper limit, the plate-like graphite particles tend to have a low affinity with the aromatic vinyl copolymer because the hydrophilicity increases. Moreover, there is no restriction | limiting in particular as a minimum of the ratio of the carbon atom which the functional group has couple | bonded, However 0.01% or more is preferable. The functional group such as a hydroxyl group can be quantified by X-ray photoelectron spectroscopy (XPS), and the amount of the functional group present in a region from the particle surface to a depth of 10 nm can be measured. In addition, when the thickness of the plate-like graphite particles is 10 nm or less, the amount of functional groups present in the entire region of the plate-like graphite particles is measured.
本発明にかかる微細化板状黒鉛粒子を構成する芳香族ビニル共重合体は、下記式（１）：
−（ＣＨ２−ＣＨＸ）− （１）
（式（１）中、Ｘはフェニル基、ナフチル基、アントラセニル基またはピレニル基を表し、これらの基は置換基を有していてもよい。）
で表されるビニル芳香族モノマー単位と他のモノマー単位とを含有するものである。
The aromatic vinyl copolymer composing the fine plate-like graphite particles according to the present invention has the following formula (1):
- (CH 2 -CHX) - ( 1)
(In formula (1), X represents a phenyl group, a naphthyl group, an anthracenyl group, or a pyrenyl group, and these groups may have a substituent.)
The vinyl aromatic monomer unit represented by these and other monomer units are contained.
このような芳香族ビニル共重合体において、前記ビニル芳香族モノマー単位は黒鉛粒子に対する吸着性を示し、他のモノマー単位は有機溶媒および黒鉛粒子表面近傍の官能基との親和性を示す。したがって、このような芳香族ビニル共重合体は、板状黒鉛粒子に吸着して板状黒鉛粒子同士の凝集力を低下させるとともに板状黒鉛粒子に有機溶媒との親和性を付与し、板状黒鉛粒子を有機溶媒中に高度に分散させることが可能となる。 In such an aromatic vinyl copolymer, the vinyl aromatic monomer unit exhibits adsorptivity to the graphite particles, and the other monomer units exhibit affinity with the organic solvent and functional groups near the surface of the graphite particles. Therefore, such an aromatic vinyl copolymer is adsorbed on the plate-like graphite particles to reduce the cohesive force between the plate-like graphite particles and gives the plate-like graphite particles an affinity with an organic solvent. It becomes possible to highly disperse graphite particles in an organic solvent.
また、上述したように、ビニル芳香族モノマー単位は黒鉛粒子に吸着しやすいため、ビニル芳香族モノマー単位の含有率が高い共重合体ほど、板状黒鉛粒子への吸着量が増大し、本発明にかかる微細化板状黒鉛粒子は有機溶媒中への分散性が高くなる傾向にある。ビニル芳香族モノマー単位の含有量としては、芳香族ビニル共重合体全体に対して１０〜９８質量％が好ましく、３０〜９８質量％がより好ましく、５０〜９５質量％が特に好ましい。ビニル芳香族モノマー単位の含有量が前記下限未満になると、芳香族ビニル共重合体の板状黒鉛粒子への吸着量が低下し、微細化板状黒鉛粒子の有機溶媒中での分散性が低下する傾向にある。ビニル芳香族モノマー単位の含有量が前記上限を超えると、板状黒鉛粒子に有機溶媒との親和性が付与されず、微細化板状黒鉛粒子の有機溶媒中での分散性が低下する傾向にある。 Further, as described above, since the vinyl aromatic monomer unit is easily adsorbed on the graphite particles, the higher the vinyl aromatic monomer unit content, the more the amount of adsorption to the plate-like graphite particles, and the present invention. The refined plate-like graphite particles tend to be highly dispersible in an organic solvent. As content of a vinyl aromatic monomer unit, 10-98 mass% is preferable with respect to the whole aromatic vinyl copolymer, 30-98 mass% is more preferable, 50-95 mass% is especially preferable. When the content of the vinyl aromatic monomer unit is less than the lower limit, the adsorption amount of the aromatic vinyl copolymer to the plate-like graphite particles is lowered, and the dispersibility of the fine plate-like graphite particles in the organic solvent is lowered. Tend to. If the content of the vinyl aromatic monomer unit exceeds the upper limit, the plate-like graphite particles are not given affinity with the organic solvent, and the dispersibility of the fine plate-like graphite particles in the organic solvent tends to decrease. is there.
前記式（１）中のＸで表される基が有していてもよい置換基としては、アミノ基、カルボキシル基、カルボン酸エステル基、水酸基、アミド基、イミノ基、グリシジル基、アルコキシ基（例えば、メトキシ基）、カルボニル基、イミド基、リン酸エステル基などが挙げられ、中でも、微細化板状黒鉛粒子の有機溶媒中での分散性が向上するという観点から、メトキシ基などのアルコキシ基が好ましく、メトキシ基がより好ましい。 Examples of the substituent that the group represented by X in the formula (1) may have include an amino group, a carboxyl group, a carboxylic ester group, a hydroxyl group, an amide group, an imino group, a glycidyl group, an alkoxy group ( For example, a methoxy group), a carbonyl group, an imide group, a phosphate ester group, and the like. Among them, an alkoxy group such as a methoxy group is preferred from the viewpoint of improving dispersibility of the fine plate-like graphite particles in an organic solvent. Are preferable, and a methoxy group is more preferable.
このようなビニル芳香族モノマー単位としては、例えば、スチレンモノマー単位、ビニルナフタレンモノマー単位、ビニルアントラセンモノマー単位、ビニルピレンモノマー単位、ビニルアニソールモノマー単位、ビニル安息香酸エステルモノマー単位、アセチルスチレンモノマー単位などが挙げられ、中でも、微細化板状黒鉛粒子の有機溶媒中での分散性が向上するという観点から、スチレンモノマー単位、ビニルナフタレンモノマー単位、ビニルアニソールモノマー単位が好ましい。 Examples of such vinyl aromatic monomer units include styrene monomer units, vinyl naphthalene monomer units, vinyl anthracene monomer units, vinyl pyrene monomer units, vinyl anisole monomer units, vinyl benzoate ester monomer units, and acetyl styrene monomer units. Among them, a styrene monomer unit, a vinyl naphthalene monomer unit, and a vinyl anisole monomer unit are preferable from the viewpoint of improving dispersibility of the fine plate-like graphite particles in an organic solvent.
本発明にかかる芳香族ビニル共重合体を構成する他のモノマー単位としては特に制限はないが、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルイミダゾール類、ビニルピリジン類、無水マレイン酸およびマレイミド類からなる群から選択される少なくとも１種のモノマーから誘導されるモノマー単位が好ましい。このような他のモノマー単位を含む芳香族ビニル共重合体を用いることによって、微細化板状黒鉛粒子は有機溶媒との親和性が向上し、有機溶媒中に高度に分散させることが可能となる。 Although there is no restriction | limiting in particular as another monomer unit which comprises the aromatic vinyl copolymer concerning this invention, (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, vinylimidazoles, vinylpyridines Monomer units derived from at least one monomer selected from the group consisting of maleic anhydride and maleimides are preferred. By using such an aromatic vinyl copolymer containing other monomer units, the affinity of the fine plate-like graphite particles with the organic solvent is improved, and it becomes possible to highly disperse in the organic solvent. .
前記（メタ）アクリレート類としては、アルキル（メタ）アクリレート、置換アルキル（メタ）アクリレート（例えば、ヒドロキシアルキル（メタ）アクリレート、アミノアルキル（メタ）アクリレート）などが挙げられる。前記（メタ）アクリルアミド類としては、（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミドなどが挙げられる。 Examples of the (meth) acrylates include alkyl (meth) acrylate, substituted alkyl (meth) acrylate (for example, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate), and the like. Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide and the like.
前記ビニルイミダゾール類としては、１−ビニルイミダゾールなどが挙げられる。前記ビニルピリジン類としては、２−ビニルピリジン、４−ビニルピリジンなどが挙げられる。前記マレイミド類としては、マレイミド、アルキルマレイミド、アリールマレイミドなどが挙げられる。 Examples of the vinylimidazoles include 1-vinylimidazole. Examples of the vinyl pyridines include 2-vinyl pyridine and 4-vinyl pyridine. Examples of the maleimides include maleimide, alkyl maleimide, aryl maleimide and the like.
このような他のモノマーのうち、微細化板状黒鉛粒子の有機溶媒中での分散性が向上するという観点から、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アミノアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド、２−ビニルピリジン、４−ビニルピリジン、アリールマレイミドが好ましく、ヒドロキシアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド、２−ビニルピリジン、アリールマレイミドがより好ましく、フェニルマレイミドが特に好ましい。 Among such other monomers, from the viewpoint of improving the dispersibility of the fine plate-like graphite particles in an organic solvent, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, 2-vinylpyridine, 4-vinylpyridine and arylmaleimide are preferred, and hydroxyalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, 2-vinylpyridine and arylmaleimide are preferred. More preferred is phenylmaleimide, particularly preferred.
本発明にかかる微細化板状黒鉛粒子において、前記芳香族ビニル共重合体の数平均分子量としては特に制限はないが、１千〜１００万が好ましく、５千〜１０万がより好ましい。芳香族ビニル共重合体の数平均分子量が前記下限未満になると、黒鉛粒子に対する吸着能が低下する傾向にあり、他方、前記上限を超えると、有機溶媒への溶解性が低下したり、粘度が著しく上昇して取り扱いが困難になる傾向にある。なお、芳香族ビニル共重合体の数平均分子量は、ゲルパーミエーションクロマトグラフィ（カラム：Ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０５ＬおよびＳｈｏｄｅｘ ＧＰＣ Ｋ−８００ＲＬ（ともに、昭和電工（株）製）、溶離液：クロロホルム）により測定し、標準ポリスチレンで換算した値である。 In the fine plate-like graphite particles according to the present invention, the number average molecular weight of the aromatic vinyl copolymer is not particularly limited, but is preferably 1,000 to 1,000,000, and more preferably 5,000 to 100,000. If the number average molecular weight of the aromatic vinyl copolymer is less than the lower limit, the adsorptivity to the graphite particles tends to be reduced. On the other hand, if the upper limit is exceeded, the solubility in an organic solvent is reduced or the viscosity is decreased. It tends to rise significantly and become difficult to handle. The number average molecular weight of the aromatic vinyl copolymer was measured by gel permeation chromatography (column: Shodex GPC K-805L and Shodex GPC K-800RL (both manufactured by Showa Denko KK), eluent: chloroform). It is a value converted with standard polystyrene.
また、本発明にかかる微細化板状黒鉛粒子においては、前記芳香族ビニル共重合体としてランダム共重合体を用いても、ブロック共重合体を用いてもよいが、微細化板状黒鉛粒子の有機溶媒中での分散性が向上するという観点から、ブロック共重合体を用いることが好ましい。 In the refined plate-like graphite particles according to the present invention, a random copolymer or a block copolymer may be used as the aromatic vinyl copolymer. From the viewpoint of improving dispersibility in an organic solvent, it is preferable to use a block copolymer.
本発明にかかる微細化板状黒鉛粒子において、前記芳香族ビニル共重合体の含有量としては、前記板状黒鉛粒子１００質量部に対して１０−７〜１０−１質量部が好ましく、１０−５〜１０−２質量部がより好ましい。芳香族ビニル共重合体の含有量が前記下限未満になると、板状黒鉛粒子への芳香族ビニル共重合体の吸着が不十分なため、微細化板状黒鉛粒子の有機溶媒中での分散性が低下する傾向にあり、他方、前記上限を超えると、板状黒鉛粒子に直接吸着していない芳香族ビニル共重合体が存在する傾向にある。 In fine plate-like graphite particles according to the present invention, the content of the aromatic vinyl copolymer, preferably 10 -7 to 10 -1 parts by weight with respect to the plate-like graphite particles 100 parts by weight, 10 - 5 -10 -2 parts by mass is more preferable. When the content of the aromatic vinyl copolymer is less than the lower limit, the adsorption of the aromatic vinyl copolymer to the plate-like graphite particles is insufficient, so that the dispersibility of the fine plate-like graphite particles in an organic solvent is reduced. On the other hand, when the upper limit is exceeded, an aromatic vinyl copolymer that is not directly adsorbed on the plate-like graphite particles tends to exist.
このような板状黒鉛粒子とこれに吸着した芳香族ビニル共重合体とを備える微細化板状黒鉛粒子は、以下のようにして製造することができる。すなわち、本発明にかかる微細化板状黒鉛粒子は、原料の黒鉛粒子、前記式（１）で表されるビニル芳香族モノマー単位を含有する芳香族ビニル共重合体、過酸化水素化物、および有機溶媒を混合し、得られた混合物に粉砕処理を施し、必要に応じて、ろ過などによって有機溶媒を除去することによって得ることができる。 The refined plate-like graphite particles comprising such plate-like graphite particles and the aromatic vinyl copolymer adsorbed thereto can be produced as follows. That is, the fine plate-like graphite particles according to the present invention include raw material graphite particles, an aromatic vinyl copolymer containing a vinyl aromatic monomer unit represented by the formula (1), a hydrogen peroxide, and an organic material. It can be obtained by mixing the solvent, subjecting the resulting mixture to pulverization, and removing the organic solvent by filtration or the like, if necessary.
原料として用いられる黒鉛粒子（以下、「原料黒鉛粒子」という）としては、グラファイト構造を有する公知の黒鉛（人造黒鉛、天然黒鉛（例えば、鱗片状黒鉛、塊状黒鉛、土状黒鉛））が挙げられ、中でも、粉砕することによって前記範囲の厚さを有する板状黒鉛粒子となるものが好ましい。このような原料黒鉛粒子の粒子径としては特に制限はないが、０．０１〜５ｍｍが好ましく、０．１〜１ｍｍがより好ましい。 Examples of graphite particles used as a raw material (hereinafter referred to as “raw material graphite particles”) include known graphite having a graphite structure (artificial graphite, natural graphite (eg, flake graphite, massive graphite, earthy graphite)). Especially, what becomes the plate-like graphite particle | grains which have the thickness of the said range by grind | pulverizing is preferable. Although there is no restriction | limiting in particular as a particle diameter of such a raw material graphite particle, 0.01-5 mm is preferable and 0.1-1 mm is more preferable.
また、原料黒鉛粒子を構成する板状黒鉛粒子の表面には、水酸基、カルボキシル基、エポキシ基などの官能基が結合（好ましくは共有結合）していることが好ましい。前記官能基は前記芳香族ビニル共重合体との親和性を有するものであり、芳香族ビニル共重合体の板状黒鉛粒子への吸着量が増大し、得られる微細化板状黒鉛粒子は有機溶媒中への分散性が高くなる傾向にある。 Moreover, it is preferable that functional groups such as a hydroxyl group, a carboxyl group, and an epoxy group are bonded (preferably covalently bonded) to the surface of the plate-like graphite particles constituting the raw graphite particles. The functional group has an affinity for the aromatic vinyl copolymer, the amount of adsorption of the aromatic vinyl copolymer to the plate-like graphite particles increases, and the obtained fine plate-like graphite particles are organic. The dispersibility in the solvent tends to be high.
このような官能基は、板状黒鉛粒子の表面近傍（好ましくは、表面から深さ１０ｎｍまでの領域）の全炭素原子の５０％以下（より好ましくは２０％以下、特に好ましくは１０％以下）の炭素原子に結合していることが好ましい。官能基が結合している炭素原子の割合が前記上限を超えると、板状黒鉛粒子は、親水性が増大するため、芳香族ビニル共重合体との親和性が低下する傾向にある。また、官能基が結合している炭素原子の割合の下限としては特に制限はないが、０．０１％以上が好ましい。 Such a functional group is 50% or less (more preferably 20% or less, particularly preferably 10% or less) of the total carbon atoms in the vicinity of the surface of the plate-like graphite particles (preferably, a region from the surface to a depth of 10 nm). It is preferable that it is bonded to the carbon atom. When the ratio of the carbon atom to which the functional group is bonded exceeds the upper limit, the plate-like graphite particles tend to have a low affinity with the aromatic vinyl copolymer because the hydrophilicity increases. Moreover, there is no restriction | limiting in particular as a minimum of the ratio of the carbon atom which the functional group has couple | bonded, However 0.01% or more is preferable.
また、過酸化水素化物としては、カルボニル基を有する化合物（例えば、ウレア、カルボン酸（安息香酸、サリチル酸など）、ケトン（アセトン、メチルエチルケトンなど）、カルボン酸エステル（安息香酸メチル、サリチル酸エチルなど））と過酸化水素との錯体；四級アンモニウム塩、フッ化カリウム、炭酸ルビジウム、リン酸、尿酸などの化合物に過酸化水素が配位したものなどが挙げられる。このような過酸化水素化物は、本発明にかかる微細化板状黒鉛粒子を製造する際に酸化剤として作用し、原料黒鉛粒子のグラファイト構造を破壊せずに、炭素層間の剥離を容易にするものである。すなわち、過酸化水素化物が炭素層間に侵入して層表面を酸化しながら劈開を進行させ、同時に芳香族ビニル共重合体が劈開した炭素層間に侵入して劈開面を安定化させ、層間剥離が促進される。その結果、板状黒鉛粒子の表面に前記芳香族ビニル共重合体が吸着して、微細化板状黒鉛粒子を有機溶媒中に高度に分散させることが可能となる。 Further, as the hydrogen peroxide, a compound having a carbonyl group (for example, urea, carboxylic acid (benzoic acid, salicylic acid, etc.), ketone (acetone, methyl ethyl ketone, etc.), carboxylic acid ester (methyl benzoate, ethyl salicylate, etc.)) And a complex of hydrogen peroxide with quaternary ammonium salts, potassium fluoride, rubidium carbonate, phosphoric acid, uric acid, and the like. Such a hydrogen peroxide acts as an oxidant when producing fine plate-like graphite particles according to the present invention, and facilitates peeling between carbon layers without destroying the graphite structure of the raw graphite particles. Is. That is, hydrogen peroxide enters between the carbon layers to oxidize the surface of the layer, and proceeds with cleavage. At the same time, the aromatic vinyl copolymer penetrates into the cleaved carbon layer and stabilizes the cleavage surface. Promoted. As a result, the aromatic vinyl copolymer is adsorbed on the surface of the plate-like graphite particles, and the fine plate-like graphite particles can be highly dispersed in the organic solvent.
本発明にかかる微細化板状黒鉛粒子を製造する際に用いられる有機溶媒としては特に制限はないが、ジメチルホルムアミド（ＤＭＦ）、クロロホルム、ジクロロメタン、クロロベンゼン、ジクロロベンゼン、Ｎ−メチルピロリドン（ＮＭＰ）、ヘキサン、トルエン、ジオキサン、プロパノール、γ−ピコリン、アセトニトリル、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルアセトアミド（ＤＭＡＣ）が好ましく、ジメチルホルムアミド（ＤＭＦ）、クロロホルム、ジクロロメタン、クロロベンゼン、ジクロロベンゼン、Ｎ−メチルピロリドン（ＮＭＰ）、ヘキサン、トルエンがより好ましい。 The organic solvent used in producing the fine plate-like graphite particles according to the present invention is not particularly limited, but dimethylformamide (DMF), chloroform, dichloromethane, chlorobenzene, dichlorobenzene, N-methylpyrrolidone (NMP), Hexane, toluene, dioxane, propanol, γ-picoline, acetonitrile, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC) are preferred, dimethylformamide (DMF), chloroform, dichloromethane, chlorobenzene, dichlorobenzene, N-methylpyrrolidone (NMP) More preferred are hexane and toluene.
本発明にかかる微細化板状黒鉛粒子を製造する場合、先ず、前記原料黒鉛粒子と前記芳香族ビニル共重合体と前記過酸化水素化物と前記有機溶媒とを混合する（混合工程）。前記原料黒鉛粒子の混合量としては、有機溶媒１Ｌ当たり０．１〜５００ｇ／Ｌが好ましく、１０〜２００ｇ／Ｌがより好ましい。原料黒鉛粒子の混合量が前記下限未満になると、有機溶媒の消費量が増大し、経済的に不利となる傾向にあり、他方、前記上限を超えると液の粘度が上昇して取り扱いが困難となる傾向にある。 When manufacturing the refined plate-like graphite particles according to the present invention, first, the raw material graphite particles, the aromatic vinyl copolymer, the hydrogen peroxide, and the organic solvent are mixed (mixing step). The mixing amount of the raw graphite particles is preferably 0.1 to 500 g / L, more preferably 10 to 200 g / L, per liter of the organic solvent. If the mixing amount of the raw material graphite particles is less than the lower limit, the consumption of the organic solvent tends to increase, which tends to be economically disadvantageous.On the other hand, if the upper limit is exceeded, the viscosity of the liquid increases and handling is difficult. Tend to be.
また、前記芳香族ビニル共重合体の混合量としては、前記原料黒鉛粒子１００質量部に対して０．１〜１０００質量部が好ましく、０．１〜２００質量部がより好ましい。芳香族ビニル共重合体の混合量が前記下限未満になると、芳香族ビニル共重合体の板状黒鉛粒子への吸着量が減少し、微細化板状黒鉛粒子の有機溶媒中での分散性が低下する傾向にあり、他方、前記上限を超えると、芳香族ビニル共重合体が有機溶媒に溶解しなくなるとともに、液の粘度が上昇して取り扱いが困難となる傾向にある。 Moreover, as a mixing amount of the said aromatic vinyl copolymer, 0.1-1000 mass parts is preferable with respect to 100 mass parts of said raw material graphite particles, and 0.1-200 mass parts is more preferable. When the mixing amount of the aromatic vinyl copolymer is less than the lower limit, the adsorption amount of the aromatic vinyl copolymer to the plate-like graphite particles is reduced, and the dispersibility of the fine plate-like graphite particles in the organic solvent is reduced. On the other hand, when the upper limit is exceeded, the aromatic vinyl copolymer does not dissolve in the organic solvent, and the viscosity of the liquid tends to increase, making it difficult to handle.
また、前記過酸化水素化物の混合量としては、前記原料黒鉛粒子１００質量部に対して０．１〜５００質量部が好ましく、１〜１００質量部がより好ましい。前記過酸化水素化物の混合量が前記下限未満になると、微細化板状黒鉛粒子の有機溶媒中での分散性が低下する傾向にあり、他方、前記上限を超えると、原料黒鉛粒子が過剰に酸化され、微細化板状黒鉛粒子の導電性および熱伝導性が低下する傾向にある。 Further, the mixing amount of the hydrogen peroxide is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the raw graphite particles. When the mixing amount of the hydrogen peroxide is less than the lower limit, the dispersibility of the fine plate-like graphite particles in the organic solvent tends to be lowered. On the other hand, when the upper limit is exceeded, the raw graphite particles are excessive. Oxidized, and the conductivity and thermal conductivity of the fine plate-like graphite particles tend to decrease.
次に、前記混合工程で得られた混合物に粉砕処理を施して原料黒鉛粒子を板状黒鉛粒子に粉砕する（粉砕工程）。これにより、生成した板状黒鉛粒子の表面に前記芳香族ビニル共重合体が吸着して、有機溶媒中での分散安定性に優れた微細化板状黒鉛粒子を得ることができる。 Next, the mixture obtained in the mixing step is pulverized to pulverize the raw graphite particles into plate-like graphite particles (pulverization step). Thereby, the aromatic vinyl copolymer is adsorbed on the surface of the generated plate-like graphite particles, and fine plate-like graphite particles excellent in dispersion stability in an organic solvent can be obtained.
本発明にかかる粉砕処理としては、超音波処理（発振周波数としては１５〜４００ｋＨｚが好ましく、出力としては５００Ｗ以下が好ましい。）、ボールミルによる処理、湿式粉砕、爆砕、機械式粉砕などが挙げられる。これにより、原料黒鉛粒子のグラファイト構造を破壊させずに原料黒鉛粒子を粉砕して板状黒鉛粒子を得ることが可能となる。また、粉砕処理時の温度としては特に制限はなく、例えば、−２０〜１００℃が挙げられる。また、粉砕処理時間についても特に制限はなく、例えば、０．０１〜５０時間が挙げられる。 Examples of the pulverization treatment according to the present invention include ultrasonic treatment (oscillation frequency is preferably 15 to 400 kHz, output is preferably 500 W or less), treatment with a ball mill, wet pulverization, explosion, mechanical pulverization, and the like. This makes it possible to obtain plate-like graphite particles by pulverizing the raw graphite particles without destroying the graphite structure of the raw graphite particles. Moreover, there is no restriction | limiting in particular as temperature at the time of a grinding | pulverization process, For example, -20-100 degreeC is mentioned. Moreover, there is no restriction | limiting in particular also about pulverization processing time, For example, 0.01 to 50 hours are mentioned.
次に、本発明の黒鉛薄膜について説明する。本発明の黒鉛薄膜は、板状黒鉛粒子とこの板状黒鉛粒子に吸着した芳香族ビニル共重合体とを備える前記微細化板状黒鉛粒子を含有し、複数の前記微細化板状黒鉛粒子が板面方向に連続的に接触して配置されたものである。 Next, the graphite thin film of the present invention will be described. The graphite thin film of the present invention contains the fine plate-like graphite particles comprising plate-like graphite particles and an aromatic vinyl copolymer adsorbed on the plate-like graphite particles, and the plurality of fine plate-like graphite particles are They are arranged in continuous contact with the plate surface direction.
このような黒鉛薄膜は、例えば、以下のようにして製造することができる。すなわち、先ず、前記微細化板状黒鉛粒子と有機溶媒とを含有する板状黒鉛粒子分散液を調製する。前記有機溶媒としては、前記微細化板状黒鉛粒子を製造する際に用いられるものとして例示した有機溶媒を使用することができる。このような板状黒鉛粒子分散液において、前記微細化板状黒鉛粒子の濃度としては、有機溶媒１Ｌ当たり０．１〜２００ｇ／Ｌが好ましく、１〜１００ｇ／Ｌがより好ましい。微細化板状黒鉛粒子の濃度が前記下限未満になると、溶媒の消費量が増大し、経済的に不利になるとともに、黒鉛薄膜が形成されない傾向にあり、他方、前記上限を超えると、微細化板状黒鉛粒子の接触により分散液の濃度が上昇して流動性が低下するため、黒鉛薄膜が形成できない傾向にある。 Such a graphite thin film can be manufactured as follows, for example. That is, first, a plate-like graphite particle dispersion containing the fine plate-like graphite particles and an organic solvent is prepared. As said organic solvent, the organic solvent illustrated as what is used when manufacturing the said refined plate-like graphite particle | grains can be used. In such a plate-like graphite particle dispersion, the concentration of the fine plate-like graphite particles is preferably from 0.1 to 200 g / L, more preferably from 1 to 100 g / L, per liter of the organic solvent. When the concentration of the refined plate-like graphite particles is less than the lower limit, the consumption of the solvent increases, which is economically disadvantageous and tends not to form a graphite thin film. Since the concentration of the dispersion increases due to contact with the plate-like graphite particles and the fluidity decreases, there is a tendency that a graphite thin film cannot be formed.
次に、このような板状黒鉛粒子分散液を用いて板状黒鉛粒子分散液からなる有機層を形成する（層形成工程）。このような有機層の形成方法としては、基板上に前記板状黒鉛粒子分散液を塗布する方法が一般的であるが、本発明においては、水面上に前記板状黒鉛粒子分散液をゆっくり滴下して前記有機層を形成することもできる。これらの層形成方法においては、前記微細化板状黒鉛粒子を、その板面が前記有機層の表面と平行になるように配向させることが好ましい。これにより、前記微細化板状黒鉛粒子を、その板面が前記黒鉛薄膜の膜面と平行となるように配置することができ、膜面方向の導電性および熱伝導性に優れた黒鉛薄膜を得ることができる。また、前記層形成方法のうち、水面上に前記有機層を形成する方法によれば、板状黒鉛粒子が疎水性であることを利用して、前記微細化板状黒鉛粒子の板面と前記有機層の表面とを容易に平行にすることが可能となる。 Next, an organic layer made of the plate-like graphite particle dispersion is formed using such a plate-like graphite particle dispersion (layer forming step). As a method for forming such an organic layer, a method of applying the plate-like graphite particle dispersion on a substrate is generally used. In the present invention, the plate-like graphite particle dispersion is slowly dropped on the water surface. Thus, the organic layer can be formed. In these layer forming methods, it is preferable that the fine plate-like graphite particles are oriented so that their plate surfaces are parallel to the surface of the organic layer. Thus, the refined plate-like graphite particles can be arranged so that the plate surface thereof is parallel to the film surface of the graphite thin film, and a graphite thin film having excellent conductivity and heat conductivity in the film surface direction is obtained. Can be obtained. Moreover, according to the method of forming the organic layer on the water surface among the layer forming methods, the plate surface of the fine plate graphite particles and the plate surface are utilized by utilizing the fact that the plate graphite particles are hydrophobic. It becomes possible to make the surface of the organic layer parallel to the organic layer easily.
次に、このようにして、基板上または水面上に形成した板状黒鉛粒子分散液からなる有機層から有機溶媒を除去する（溶媒除去工程）。これにより、複数の前記微細化板状黒鉛粒子が板面方向に連続的に接触して配置されている本発明の黒鉛薄膜が基板上または水面上に形成される。有機溶媒の除去方法としては特に制限はないが、微細化された複数の板状黒鉛粒子が板面方向に連続的に接触しやすいという観点から、自然乾燥による方法が好ましい。特に、水面上に前記有機層を形成した場合には、水面を安定した状態に保ちながら有機溶媒を除去できることから、自然乾燥による方法が特に好ましい。 Next, the organic solvent is removed from the organic layer composed of the plate-like graphite particle dispersion formed on the substrate or the water surface in this way (solvent removal step). Thereby, the graphite thin film of the present invention in which a plurality of the above-mentioned fine plate-like graphite particles are arranged in continuous contact with each other in the plate surface direction is formed on the substrate or the water surface. Although there is no restriction | limiting in particular as a removal method of an organic solvent, From the viewpoint that several refined plate-like graphite particle | grains are easy to contact continuously in a plate surface direction, the method by natural drying is preferable. In particular, when the organic layer is formed on the water surface, the organic solvent can be removed while keeping the water surface in a stable state.
また、本発明の黒鉛薄膜を水面上に形成した場合には、前記水面上に形成された黒鉛薄膜を膜面方向に圧縮すること（圧縮工程）が好ましい。これにより、微細化された複数の板状黒鉛粒子が板面方向に連続的に接触している確率が高くなり、黒鉛薄膜の膜面方向の導電性および熱伝導性がさらに向上する傾向にある。 Moreover, when the graphite thin film of this invention is formed on the water surface, it is preferable to compress the graphite thin film formed on the said water surface in the film surface direction (compression process). As a result, the probability that a plurality of refined plate-like graphite particles are continuously in contact with the plate surface direction increases, and the conductivity and thermal conductivity in the film surface direction of the graphite thin film tend to further improve. .
次に、本発明の複合体について説明する、本発明の複合体は、基板と、この基板上に配置されている本発明の黒鉛薄膜とを備えるものである。上述したように、本発明の黒鉛薄膜が膜面方向の導電性および熱伝導性に優れていることから、本発明の複合体は、導電性複合体（例えば、電極複合体）や熱伝導性複合体（例えば、透明電熱ヒーター）として使用することが可能である。本発明の複合体に用いられる基板としては特に制限はないが、例えば、ガラス基板、金属板、セラミック板、半導体基板などが挙げられる。 Next, the composite of the present invention will be described. The composite of the present invention includes a substrate and the graphite thin film of the present invention disposed on the substrate. As described above, since the graphite thin film of the present invention is excellent in conductivity and thermal conductivity in the film surface direction, the composite of the present invention is a conductive composite (for example, electrode composite) or thermal conductivity. It can be used as a composite (for example, a transparent electric heater). Although there is no restriction | limiting in particular as a board | substrate used for the composite_body | complex of this invention, For example, a glass substrate, a metal plate, a ceramic board, a semiconductor substrate etc. are mentioned.
このような複合体は、上述したように、基板上に前記板状黒鉛粒子分散液を塗布し、有機溶媒を除去して基板上に直接、本発明の黒鉛薄膜を形成することによって製造することができる。また、上述したように、水面上に黒鉛薄膜を形成した場合には、基板上に黒鉛薄膜を写し取り、それを乾燥させることによって製造することができる。 As described above, such a composite is manufactured by applying the plate-like graphite particle dispersion on a substrate, removing the organic solvent, and directly forming the graphite thin film of the present invention on the substrate. Can do. As described above, when a graphite thin film is formed on the water surface, it can be produced by copying the graphite thin film on a substrate and drying it.
以下、実施例および比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
＜芳香族ビニル共重合体の数平均分子量＞
芳香族ビニル共重合体の数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィ（昭和電工（株）製「Ｓｈｏｄｅｘ ＧＰＣ１０１」）を用いて以下の条件で測定し、標準ポリスチレンで換算した。
（測定条件）
・カラム：Ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０５ＬおよびＳｈｏｄｅｘ ＧＰＣ Ｋ−８００ＲＬ（ともに、昭和電工（株）製）。
・溶離液：クロロホルム。
・測定温度：２５℃。
・サンプル濃度：０．１ｍｇ／ｍｌ。
・検出手段：ＲＩ。
<Number average molecular weight of aromatic vinyl copolymer>
The number average molecular weight (Mn) of the aromatic vinyl copolymer was measured under the following conditions using gel permeation chromatography (“Shodex GPC101” manufactured by Showa Denko KK), and converted to standard polystyrene.
(Measurement condition)
Column: Shodex GPC K-805L and Shodex GPC K-800RL (both manufactured by Showa Denko KK).
-Eluent: Chloroform.
Measurement temperature: 25 ° C.
Sample concentration: 0.1 mg / ml.
-Detection means: RI.
（調製例１）
スチレン（ＳＴ）１．８ｇ、Ｎ，Ｎ−ジメチルメタクリルアミド（ＤＭＭＡＡ）０．２ｇ、アゾビスイソブチロニトリル８ｍｇおよびトルエン７ｍｌを混合し、窒素雰囲気下、８５℃で６時間重合反応を行なった。放冷後、クロロホルム−エーテルを用いて再沈殿により精製し、０．９９ｇのＳＴ−ＤＭＭＡＡ（９：１）ランダム共重合体を得た。このＳＴ−ＤＭＭＡＡ（９：１）ランダム共重合体の数平均分子量（Ｍｎ）は、５２０００であった。
(Preparation Example 1)
Styrene (ST) (1.8 g), N, N-dimethylmethacrylamide (DMMAA) (0.2 g), azobisisobutyronitrile (8 mg) and toluene (7 ml) were mixed, and a polymerization reaction was carried out at 85 ° C. for 6 hours in a nitrogen atmosphere. . After cooling, the mixture was purified by reprecipitation using chloroform-ether to obtain 0.99 g of ST-DMMAA (9: 1) random copolymer. The number average molecular weight (Mn) of this ST-DMMAA (9: 1) random copolymer was 52,000.
黒鉛粒子（日本黒鉛工業（株）製「ＥＸＰ−Ｐ」、粒子径１００〜６００μｍ）２０ｍｇ、ウレア−過酸化水素包接錯体８０ｍｇ、前記ＳＴ−ＤＭＭＡＡ（９：１）ランダム共重合体２０ｍｇおよびＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）２ｍｌを混合し、室温で５時間超音波処理（出力：２５０Ｗ）を施して黒鉛粒子分散液を得た。この黒鉛粒子分散液をろ過し、ろ滓をＤＭＦで洗浄した後、真空乾燥して微細化板状黒鉛粒子を回収した。 20 mg of graphite particles (“EXP-P” manufactured by Nippon Graphite Industry Co., Ltd., particle size 100 to 600 μm), 80 mg of urea-hydrogen peroxide inclusion complex, 20 mg of ST-DMMAA (9: 1) random copolymer and N , N-dimethylformamide (DMF) 2 ml was mixed and subjected to ultrasonic treatment (output: 250 W) at room temperature for 5 hours to obtain a graphite particle dispersion. The graphite particle dispersion was filtered, and the filter cake was washed with DMF and then vacuum dried to recover fine plate-like graphite particles.
（実施例１）
調製例１で得られた微細化板状黒鉛粒子３ｍｇをクロロホルム１ｍｌに添加し、室温で６０分間超音波処理（出力：２５０Ｗ）を施し、微細化板状黒鉛粒子を含有する分散液を得た。
(Example 1)
3 mg of the refined plate-like graphite particles obtained in Preparation Example 1 was added to 1 ml of chloroform, and subjected to ultrasonic treatment (output: 250 W) at room temperature for 60 minutes to obtain a dispersion containing the refined plate-like graphite particles. .
直径１００ｍｍφのガラス製シャーレにイオン交換水を１ｃｍの深さで入れ、静置した。このイオン交換水の水面上に前記微細化板状黒鉛粒子を含有する分散液をゆっくりと滴下したところ、分散液は、直ちに水面上に広がり、その後、急激に水面で島状に集合し、黒鉛薄膜が形成された。この黒鉛薄膜をスライドグラス上に静かにすくい取って乾燥した。 Ion exchange water was poured into a glass petri dish having a diameter of 100 mmφ at a depth of 1 cm and allowed to stand. When the dispersion containing the fine plate-like graphite particles was slowly dropped onto the surface of the ion-exchanged water, the dispersion immediately spread on the surface of the water, and then suddenly gathered in an island shape on the surface of the water. A thin film was formed. The graphite thin film was gently scooped on a slide glass and dried.
得られた黒鉛薄膜は可視光を透過するものであった。また、この黒鉛薄膜の表面を走査型電子顕微鏡（ＳＥＭ）により観察した結果を図１Ａ〜１Ｃに示す。図１Ａ〜１Ｃに示した結果から明らかなように、複数の微細化板状黒鉛粒子が連続的に接触しており、さらに黒鉛薄膜の表面に平行に配向していることが確認された。また、この黒鉛薄膜の表面の任意の２点間（距離：１ｃｍ）の電気抵抗を、テスターを用いて室温で測定したところ、電気抵抗は１００Ωであった。 The obtained graphite thin film transmitted visible light. Moreover, the result of having observed the surface of this graphite thin film with the scanning electron microscope (SEM) is shown to FIG. As is clear from the results shown in FIGS. 1A to 1C, it was confirmed that a plurality of fine plate-like graphite particles were in continuous contact and further oriented parallel to the surface of the graphite thin film. Further, when the electric resistance between any two points (distance: 1 cm) on the surface of the graphite thin film was measured at room temperature using a tester, the electric resistance was 100Ω.
（実施例２）
実施例１と同様にして水面上に黒鉛薄膜を形成した。その後、スライドグラスを用いて膜面積が実施例１の黒鉛薄膜の８０％となるように、この黒鉛薄膜を膜面方向に圧縮した。圧縮後の黒鉛薄膜をスライドグラス上に静かにすくい取って乾燥した。
(Example 2)
A graphite thin film was formed on the water surface in the same manner as in Example 1. Then, this graphite thin film was compressed in the film surface direction so that the film area might become 80% of the graphite thin film of Example 1 using a slide glass. The compressed graphite thin film was gently scooped on a slide glass and dried.
得られた黒鉛薄膜は可視光を透過するものであった。また、この黒鉛薄膜の表面の任意の２点間（距離：１ｃｍ）の電気抵抗を、テスターを用いて室温で測定したところ、電気抵抗は７０Ωであった。 The obtained graphite thin film transmitted visible light. Further, when the electric resistance between any two points (distance: 1 cm) on the surface of the graphite thin film was measured at room temperature using a tester, the electric resistance was 70Ω.
（実施例３〜４）
クロロホルムの代わりにそれぞれ酢酸エチルまたはジクロロメタンを１ｍｌ用いた以外は実施例１と同様にして黒鉛薄膜を作製した。得られた黒鉛薄膜はいずれも可視光を透過するものであった。
(Examples 3 to 4)
A graphite thin film was prepared in the same manner as in Example 1 except that 1 ml of ethyl acetate or dichloromethane was used instead of chloroform. All of the obtained graphite thin films were transparent to visible light.
（実施例５）
実施例１と同様にして微細化板状黒鉛粒子を含有する分散液を作製した。この分散液０．１ｍｌをスライドグラス上に塗布し、自然乾燥させて黒鉛薄膜を作製した。
(Example 5)
A dispersion containing fine plate graphite particles was prepared in the same manner as in Example 1. 0.1 ml of this dispersion was applied onto a slide glass and allowed to air dry to produce a graphite thin film.
得られた黒鉛薄膜は可視光を透過するものであった。また、この黒鉛薄膜の表面を走査型電子顕微鏡（ＳＥＭ）により観察した結果を図２Ａ〜２Ｃに示す。図２Ａ〜２Ｃに示した結果から明らかなように、複数の微細化板状黒鉛粒子が連続的に接触しており、さらに黒鉛薄膜の表面に平行に配向していることが確認された。また、この黒鉛薄膜の表面の任意の２点間（距離：１ｃｍ）の電気抵抗を、テスターを用いて室温で測定したところ、電気抵抗は２４０Ωであった。 The obtained graphite thin film transmitted visible light. Moreover, the result of having observed the surface of this graphite thin film with the scanning electron microscope (SEM) is shown to FIG. As is clear from the results shown in FIGS. 2A to 2C, it was confirmed that a plurality of fine plate-like graphite particles were in continuous contact and further oriented parallel to the surface of the graphite thin film. Further, when the electric resistance between any two points (distance: 1 cm) on the surface of the graphite thin film was measured at room temperature using a tester, the electric resistance was 240Ω.
（比較例１）
黒鉛粒子（日本黒鉛工業（株）製「ＥＸＰ−Ｐ」）３ｍｇをクロロホルム１ｍｌに添加し、室温で６０分間超音波処理（出力：２５０Ｗ）を施し、黒鉛粒子を含有する分散液を得た。
(Comparative Example 1)
3 mg of graphite particles (“EXP-P” manufactured by Nippon Graphite Industry Co., Ltd.) was added to 1 ml of chloroform, and subjected to ultrasonic treatment (output: 250 W) for 60 minutes at room temperature to obtain a dispersion containing graphite particles.
前記微細化板状黒鉛粒子を含有する分散液の代わりに、この黒鉛粒子を含有する分散液を用いた以外は実施例１と同様に水面上に分散液をゆっくり滴下した。その結果、分散液は、直ちに水面上に広がったものの、その後、粒子塊が生成した。この粒子塊をスライドグラス上に静かにすくい取って乾燥した。 The dispersion was slowly dropped onto the water surface in the same manner as in Example 1 except that the dispersion containing the graphite particles was used instead of the dispersion containing the fine plate-like graphite particles. As a result, although the dispersion spread immediately on the water surface, a particle lump was formed thereafter. The particle mass was gently scooped on a slide glass and dried.
得られた粒子塊を走査型電子顕微鏡（ＳＥＭ）により観察した結果を図３Ａ〜３Ｂに示す。図３Ａ〜３Ｂに示した結果から明らかなように、粒子塊は複数の板状黒鉛粒子の集合体ではあるものの、それらは連続的には接触していなかった。また、この粒子塊の表面の任意の２点間（距離：１ｃｍ）の電気抵抗を、テスターを用いて室温で測定したところ、電気抵抗は１００ＭΩであった。 The result of having observed the obtained particle lump with the scanning electron microscope (SEM) is shown to FIG. As apparent from the results shown in FIGS. 3A to 3B, the particle lump is an aggregate of a plurality of plate-like graphite particles, but they are not in continuous contact. Moreover, when the electrical resistance between any two points (distance: 1 cm) on the surface of the particle mass was measured at room temperature using a tester, the electrical resistance was 100 MΩ.
（比較例２）
比較例１と同様にして黒鉛粒子を含有する分散液を調製した。前記微細化板状黒鉛粒子を含有する分散液の代わりに、この黒鉛粒子を含有する分散液を用いた以外は実施例５と同様にスライドグラス上に分散液を塗布し、自然乾燥させたところ、粒子塊が生成した。
(Comparative Example 2)
A dispersion containing graphite particles was prepared in the same manner as in Comparative Example 1. The dispersion was applied on a slide glass in the same manner as in Example 5 except that the dispersion containing the graphite particles was used instead of the dispersion containing the fine plate-like graphite particles, and then naturally dried. A particle mass was formed.
得られた粒子塊を走査型電子顕微鏡（ＳＥＭ）により観察した結果を図４Ａ〜４Ｂに示す。図４Ａ〜４Ｂに示した結果から明らかなように、粒子塊は複数の板状黒鉛粒子の集合体ではあるものの、それらは連続的には接触していなかった。また、この粒子塊の表面の任意の２点間（距離：１ｃｍ）の電気抵抗を、テスターを用いて室温で測定したところ、電気抵抗は１５０ＭΩであった。 The result of having observed the obtained particle lump with the scanning electron microscope (SEM) is shown to FIG. As is clear from the results shown in FIGS. 4A to 4B, although the particle mass is an aggregate of a plurality of plate-like graphite particles, they were not in continuous contact. Further, when the electric resistance between any two points (distance: 1 cm) on the surface of the particle mass was measured at room temperature using a tester, the electric resistance was 150 MΩ.
以上説明したように、本発明によれば、微細化された複数の板状黒鉛粒子が板面方向に連続的に接触している黒鉛薄膜を得ることが可能となる。 As described above, according to the present invention, it is possible to obtain a graphite thin film in which a plurality of refined plate-like graphite particles are continuously in contact in the plate surface direction.
したがって、本発明の黒鉛薄膜は、導電性や熱伝導性に優れた板状黒鉛粒子が膜表面に略平行な方向に連続的に接触した状態で形成されたものであるため、膜表面方向の導電性や熱伝導性に優れており、導電体材料や熱伝導体材料などなどとして有用である。 Therefore, the graphite thin film of the present invention is formed in a state in which plate-like graphite particles having excellent conductivity and thermal conductivity are continuously in contact with the film surface in a direction substantially parallel to the film surface. It has excellent conductivity and thermal conductivity, and is useful as a conductor material, a heat conductor material, and the like.
Claims (9)
−（ＣＨ２−ＣＨＸ）− （１）
（式（１）中、Ｘはフェニル基、ナフチル基、アントラセニル基またはピレニル基を表し、これらの基は置換基を有していてもよい。）
で表されるビニル芳香族モノマー単位と、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルイミダゾール類、ビニルピリジン類、無水マレイン酸およびマレイミド類からなる群から選択される少なくとも１種のモノマーから誘導されるモノマー単位とを含有する芳香族ビニル共重合体とを備える微細化板状黒鉛粒子を含有し、
複数の該微細化板状黒鉛粒子が板面方向に連続的に接触して配置されていることを特徴とする黒鉛薄膜。 Plate-like graphite particles having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and an epoxy group bonded to the surface, and adsorbed to the plate-like graphite particles through the functional group, (1):
- (CH 2 -CHX) - ( 1)
(In formula (1), X represents a phenyl group, a naphthyl group, an anthracenyl group, or a pyrenyl group, and these groups may have a substituent.)
Selected from the group consisting of a vinyl aromatic monomer unit represented by : (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, vinylimidazoles, vinylpyridines, maleic anhydride and maleimides Containing refined plate-like graphite particles comprising an aromatic vinyl copolymer containing monomer units derived from at least one monomer ,
A graphite thin film, wherein a plurality of the fine plate-like graphite particles are arranged in continuous contact with each other in the plate surface direction.
−（ＣＨ２−ＣＨＸ）− （１）
（式（１）中、Ｘはフェニル基、ナフチル基、アントラセニル基またはピレニル基を表し、これらの基は置換基を有していてもよい。）
で表されるビニル芳香族モノマー単位と、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルイミダゾール類、ビニルピリジン類、無水マレイン酸およびマレイミド類からなる群から選択される少なくとも１種のモノマーから誘導されるモノマー単位とを含有する芳香族ビニル共重合体とを備える微細化板状黒鉛粒子および有機溶媒を含有する板状黒鉛粒子分散液からなる有機層を形成する層形成工程と、
該有機層から前記有機溶媒を除去して、複数の前記微細化板状黒鉛粒子が板面方向に連続的に接触して配置されている黒鉛薄膜を形成する溶媒除去工程と、
を含むことを特徴とする黒鉛薄膜の製造方法。 Plate-like graphite particles having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and an epoxy group bonded to the surface, and adsorbed to the plate-like graphite particles through the functional group, (1):
- (CH 2 -CHX) - ( 1)
(In formula (1), X represents a phenyl group, a naphthyl group, an anthracenyl group, or a pyrenyl group, and these groups may have a substituent.)
Selected from the group consisting of a vinyl aromatic monomer unit represented by : (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, vinylimidazoles, vinylpyridines, maleic anhydride and maleimides Layer for forming an organic layer comprising fine plate-like graphite particles comprising an aromatic vinyl copolymer containing a monomer unit derived from at least one monomer and a plate-like graphite particle dispersion containing an organic solvent Forming process;
Removing the organic solvent from the organic layer to form a graphite thin film in which a plurality of the fine plate-like graphite particles are continuously contacted in the plate surface direction; and
A method for producing a graphite thin film, comprising:
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