JP4544581B2 - Carbon nanofiber and method for producing the same - Google Patents
Carbon nanofiber and method for producing the same Download PDFInfo
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本発明は、カーボンナノファイバーとその製造方法に関し、詳しくは、カーボンナノファイバーの表面に無機微粒子が存在しているカーボンナノファイバーに関する。 The present invention relates to a carbon nanofiber and a method for producing the same, and more particularly to a carbon nanofiber in which inorganic fine particles are present on the surface of the carbon nanofiber.
一般に、繊維状炭素のうち直径が１００ｎｍのオーダー前後のものをカーボンナノファイバーと呼び、直径が１０ｎｍのオーダー前後にまで小さくなるとカーボンナノチューブと呼ばれる（非特許文献１）。 In general, fibrous carbon having a diameter of around 100 nm is called a carbon nanofiber, and when the diameter is reduced to around 10 nm, it is called a carbon nanotube (Non-Patent Document 1).
カーボンナノファイバーは、樹脂材料への導電性の付与・機械的性質の向上を目的として添加するフィラーとして有用な材料であり、最近では、燃料電池の電極材料やガス吸蔵材料としても期待される材料である。 Carbon nanofibers are useful as fillers added for the purpose of imparting electrical conductivity to resin materials and improving mechanical properties. Recently, carbon nanofibers are also expected as fuel cell electrode materials and gas storage materials. It is.
しかし、カーボンナノファイバー同士が分子間力によって凝集する傾向が強く、フィラーとして用いる場合は、カーボンナノファイバー表面を改質して樹脂材料への分散性を向上しなければならないことが知られていた。 However, carbon nanofibers tend to aggregate due to intermolecular forces, and when used as fillers, it was known that the surface of carbon nanofibers must be modified to improve dispersibility in resin materials. .
カーボンナノファイバーの表面を改質して分散性を向上した例としては、表面に官能基を導入する方法や表面をポリマーで被覆する方法（特許文献１）がある。 Examples of improving the dispersibility by modifying the surface of the carbon nanofiber include a method of introducing a functional group on the surface and a method of coating the surface with a polymer (Patent Document 1).
しかし、これらの方法では、改質が進むほどカーボンナノファイバー本来の表面積が減少してしまい、カーボンナノファイバーの表面特性を活用した用途開発に大きな制限を与えることになることが知られている。 However, these methods are known to reduce the original surface area of the carbon nanofibers as the modification progresses, and greatly limit the development of applications utilizing the surface characteristics of the carbon nanofibers.
本発明は、上記の従来の問題点を解決する、カーボンナノファイバーを得ることにあり、カーボンナノファイバー表面に無機微粒子が存在しているカーボンナノファイバーとその製造方法を提供することにある。 An object of the present invention is to provide a carbon nanofiber in which inorganic fine particles are present on the surface of the carbon nanofiber and a method for producing the same.
本発明の第１の要旨は、酸化珪素、酸化チタン、酸化アルミニウム、酸化亜鉛、酸化ジルコニウム、窒化珪素、窒化チタン、窒化アルミニウム、窒化亜鉛、窒化ジルコニウム、炭化珪素、炭化チタン、炭化アルミニウム、炭化亜鉛、炭化ジルコニウムからなる群から選ばれる１種以上の無機微粒子が表面に存在しているカーボンナノファイバーである。 The first gist of the present invention is silicon oxide, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, silicon nitride, titanium nitride, aluminum nitride, zinc nitride, zirconium nitride, silicon carbide, titanium carbide, aluminum carbide, zinc carbide. Carbon nanofibers having one or more inorganic fine particles selected from the group consisting of zirconium carbide on the surface.
第２の要旨は、繊維軸方向断面では、熱分解性ポリマーからなるマトリックス相中に熱炭化性ポリマーからなる島状独立層が筋状に相分離した構造を有し、繊維軸に垂直方向断面では、マトリックス相の中に直径１００ｎｍ以下の島状独立相が点在している相分離構造を有する前駆体繊維であって、マトリックス相中に無機微粒子を分散された前駆体繊維を、空気中で２００〜３００℃の温度で処理して、熱炭化性ポリマーを耐炎化し、さらに不活性雰囲気中で無機微粒子の組成および形態が変化しない温度で熱炭化性ポリマー炭素化する、カーボンナノファイバーの製造方法にある。 The second gist is that the cross section in the direction of the fiber axis has a structure in which the island-like independent layer made of the thermo-carbonizable polymer is phase-separated in the matrix phase made of the thermodegradable polymer, and the cross section is perpendicular to the fiber axis. Then, a precursor fiber having a phase separation structure in which island-like independent phases having a diameter of 100 nm or less are scattered in the matrix phase, and the precursor fiber in which inorganic fine particles are dispersed in the matrix phase, Of carbon nanofibers, which is treated at a temperature of 200 to 300 ° C. to make the thermally carbonizable polymer flame resistant and further carbonized at a temperature at which the composition and form of the inorganic fine particles do not change in an inert atmosphere. Is in the way.
本発明は、カーボンナノチューブ本来の物性を低下することなく溶液への分散性を向上したカーボンナノファイバーであり、本発明の製造方法によれば、生産性よく、工業的に高い品質と歩留で前記カーボンナノファイバーを製造することができるので、カーボンナノファイバーの用途拡大に極めて有用である。 The present invention is a carbon nanofiber having improved dispersibility in a solution without deteriorating the original physical properties of the carbon nanotube. According to the production method of the present invention, the productivity is high, and the industrially high quality and yield. Since the said carbon nanofiber can be manufactured, it is very useful for the use expansion of a carbon nanofiber.
『カーボンナノファイバー』
本発明のカーボンナノファイバーは、カーボンナノファイバー表面に酸化珪素、酸化チタン、酸化アルミニウム、酸化亜鉛、酸化ジルコニウム、窒化珪素、窒化チタン、窒化アルミニウム、窒化亜鉛、窒化ジルコニウム、炭化珪素、炭化チタン、炭化アルミニウム、炭化亜鉛、炭化ジルコニウムからなる群から選ばれる１種以上の無機微粒子が単層または複数層の形態で物理的または化学的に表面に付着していることが必要である。
無機微粒子の付着量は、カーボンナノファイバーの大きさに比して無機微粒子の大きさが小さい場合は、後述する被覆率という数値で表すことができる。
"Carbon nanofiber"
The carbon nanofiber of the present invention has silicon oxide, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, silicon nitride, titanium nitride, aluminum nitride, zinc nitride, zirconium nitride, silicon carbide, titanium carbide, carbonized carbon nanofiber surface. It is necessary that one or more inorganic fine particles selected from the group consisting of aluminum, zinc carbide, and zirconium carbide are physically or chemically attached to the surface in the form of a single layer or multiple layers.
The adhesion amount of the inorganic fine particles can be expressed by a numerical value called a coverage described later when the size of the inorganic fine particles is smaller than the size of the carbon nanofibers.
無機微粒子が被覆率３％以上であれば、無機微粒子を介しての分散性の向上が十分に期待でき、また９５％以下であれば、カーボンナノファイバーの表面積の減少によるカーボンナノファイバー本来の物性低下が起こらない。 If the inorganic fine particle coverage is 3% or more, sufficient improvement in dispersibility through the inorganic fine particle can be expected, and if it is 95% or less, the original physical properties of the carbon nanofiber due to the decrease in the surface area of the carbon nanofiber. There is no decline.
『カーボンナノファイバーの製造方法』
以下に、本発明のカーボンナノファイバーの製造方法について説明する。
＜前駆体繊維＞
本発明の製造方法では、前駆体繊維として、繊維軸方向断面では、熱分解性ポリマーからなるマトリックス相中に熱炭化性ポリマーからなる島状独立層が筋状に相分離した構造を有し、繊維軸に垂直方向断面では、マトリックス相の中に直径１００ｎｍ以下の島状独立相が点在している相分離構造を有する前駆体繊維であって、マトリックス相中に無機微粒子を分散された前駆体繊維を用いる。
"Production method of carbon nanofiber"
Below, the manufacturing method of the carbon nanofiber of this invention is demonstrated.
<Precursor fiber>
In the production method of the present invention, the precursor fiber has a structure in which the island-shaped independent layer made of the thermocarbonizable polymer is phase-separated in a matrix phase made of the thermally decomposable polymer in the fiber axial direction cross section, A precursor fiber having a phase separation structure in which island-like independent phases having a diameter of 100 nm or less are scattered in a matrix phase in a cross section in a direction perpendicular to the fiber axis, the precursor having inorganic fine particles dispersed in the matrix phase Use body fibers.
＜前駆体繊維のモルフォロジー＞
本発明においては、ポリマーブレンド繊維である前駆体繊維のモルフォロジー制御が最大の技術のポイントである。すなわち、前駆体繊維のモルフォロジーが繊維軸方向に沿って筋状相分離構造を有し、且つ、繊維軸垂直方向断面にマトリックス相の中に直径１００ｎｍ以下の島状独立相が点在している相分離構造を有することが必要である。また、島状に分散した筋状構造体は部分的に結節されていてもよいが、筋状部分の長さは１０μｍ以上であることが必要である。
<Morphology of precursor fibers>
In the present invention, the most important technical point is the morphology control of the precursor fiber which is a polymer blend fiber. That is, the morphology of the precursor fiber has a streaky phase separation structure along the fiber axis direction, and island-like independent phases having a diameter of 100 nm or less are scattered in the matrix phase in the cross section in the fiber axis vertical direction. It is necessary to have a phase separation structure. In addition, the streak-like structures dispersed in islands may be partially knotted, but the length of the streak-like part needs to be 10 μm or more.
そして、前記マトリックス相ポリマーの主成分が熱分解性ポリマーからなり、且つ、前記島状独立相の主成分がアクリロニトリル系ポリマーからなり、マトリックス相に無機微粒子が含まれることが必要である。 The main component of the matrix phase polymer is made of a thermally decomposable polymer, the main component of the island-like independent phase is made of an acrylonitrile polymer, and the matrix phase needs to contain inorganic fine particles.
このような前駆体繊維を得るには、特開２００３−３３６１３０公報、特開２００４−３６０３８公報および特開２００４−３６０５８公報に開示されている方法を用いることができる。そして、前駆体繊維のモルフォロジーは、得られた前駆体繊維の縦断面および横断面の超薄切片を作製し、透過型電子顕微鏡（ＴＥＭ）で観察することにより確認できる。 In order to obtain such a precursor fiber, the methods disclosed in JP2003-336130A, JP200436038A and JP200436058A can be used. The morphology of the precursor fiber can be confirmed by preparing ultra-thin sections of the obtained precursor fiber having a longitudinal section and a transverse section and observing with a transmission electron microscope (TEM).
（熱分解性ポリマーについて）
本発明では、熱分解性ポリマーの重量平均分子量は、３万〜３００万であることが好ましい。熱分解性ポリマーとしてはメタクリレート系ポリマーのホモポリマーおよび／または共重合体が好ましく、例えばポリメタクリル酸メチルのホモポリマーおよび／または他のモノマーとの共重合体を用いることができる。
(About thermally decomposable polymers)
In the present invention, the weight average molecular weight of the thermally decomposable polymer is preferably 30,000 to 3,000,000. As the thermally decomposable polymer, a homopolymer and / or copolymer of a methacrylate polymer is preferable. For example, a homopolymer of polymethyl methacrylate and / or a copolymer with another monomer can be used.
熱分解性ポリマーの共重合成分モノマーとしては、特に制限は無いが、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピルなどに代表されるアクリル酸エステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｎ−ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ラウリル、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ジエチルアミノエチルなどの代表されるメタクリル酸エステル類、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、アクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、スチレン、ビニルトルエン、酢酸ビニル、塩化ビニル、塩化ビニリデン、臭化ビニル、臭化ビニリデン、フッ化ビニル、フッ化ビニリデンなどの不飽和モノマー類であり、さらに染色性改良などの目的によっては、ｐ−スルホフェニルメタリルエーテル、メタリルスルホン酸、アリルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸及びこれらのアルカリ金属塩などが挙げられる。 The copolymerizable component monomer of the thermally decomposable polymer is not particularly limited. For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, Acrylic acid esters such as hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-methacrylic acid 2- Representative methacrylic esters such as hydroxyethyl, hydroxypropyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, N-methylol Unsaturated monomers such as rilamide, diacetone acrylamide, styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride, etc. Depending on the purpose, p-sulfophenyl methallyl ether, methallyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali metal salts thereof may be used.
＜熱炭化性ポリマー＞
本発明に使用する熱炭化性ポリマーは、炭素化されるポリマーであれば特に制限はなくたとえばポリアクリロニトリル、セルロース類、ポリイミド類、ポリ塩化ビニリデン、ポリビニルアルコール、ポリジビニルベンゼンなどが挙げられるが、中でも重量平均分子量３万〜３００万のアクリロニトリル系ポリマーが好ましい。直径１００ｎｍ以下で長さ１０μｍ以上の筋状構造を形成しやすくするためには、重量平均分子量は１０万〜２００万の範囲がさらに好ましい。
<Thermocarbonizable polymer>
The thermally carbonizable polymer used in the present invention is not particularly limited as long as it is a carbonized polymer, and examples thereof include polyacrylonitrile, celluloses, polyimides, polyvinylidene chloride, polyvinyl alcohol, and polydivinylbenzene. An acrylonitrile-based polymer having a weight average molecular weight of 30,000 to 3,000,000 is preferable. In order to easily form a streak structure having a diameter of 100 nm or less and a length of 10 μm or more, the weight average molecular weight is more preferably in the range of 100,000 to 2,000,000.
＜アクリロニトリル系ポリマー＞
アクリロニトリル系ポリマーとしてはアクリロニトリルのホモポリマーおよび／または他のモノマーとの共重合体を用いることができる。この場合、炭素化を良好に行う目的で共重合体中のアクリロニトリル単位は、９０モル％以上であることが好ましい。
<Acrylonitrile polymer>
As the acrylonitrile-based polymer, homopolymers of acrylonitrile and / or copolymers with other monomers can be used. In this case, the acrylonitrile unit in the copolymer is preferably 90 mol% or more for the purpose of good carbonization.
アクリロニトリル系ポリマーの共重合成分モノマーとしては、特に制限は無いが、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピルなどに代表されるアクリル酸エステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｎ−ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ラウリル、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ジエチルアミノエチルなどの代表されるメタクリル酸エステル類、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、アクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、スチレン、ビニルトルエン、酢酸ビニル、塩化ビニル、塩化ビニリデン、臭化ビニル、臭化ビニリデン、フッ化ビニル、フッ化ビニリデンなどの不飽和モノマー類であり、さらに染色性改良などの目的によっては、ｐ−スルホフェニルメタリルエーテル、メタリルスルホン酸、アリルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸及びこれらのアルカリ金属塩などが挙げられる。 The copolymerization component monomer of the acrylonitrile polymer is not particularly limited. For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acrylic Acrylic acid esters represented by hydroxypropyl acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-hydroxy methacrylate Representative methacrylic acid esters such as ethyl, hydroxypropyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, N-methyl Unsaturated monomers such as roll acrylamide, diacetone acrylamide, styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride, and further improve dyeability Depending on the purpose, p-sulfophenylmethallyl ether, methallylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and alkali metal salts thereof may be used.
アクリロニトリル系ポリマーの共重合成分モノマーとして、炭素化工程における環化反応を促進する目的でカルボン酸基を有するモノマーやアクリルアミド系モノマーを用いることが好ましい。このようなカルボン酸基を有するモノマーとしては、メタクリル酸やイタコン酸が好ましい。又、アクリルアミド系モノマーとしてはアクリルアミドが好ましい。 As the copolymerization component monomer for the acrylonitrile-based polymer, a monomer having a carboxylic acid group or an acrylamide-based monomer is preferably used for the purpose of promoting the cyclization reaction in the carbonization step. As the monomer having such a carboxylic acid group, methacrylic acid and itaconic acid are preferable. As the acrylamide monomer, acrylamide is preferable.
＜相分離のサイズを制御するための第三成分＞
相分離のサイズを制御し安定化する目的で、界面活性剤、微粒子、グラフトポリマー、ブロックポリマー等を添加することにより相分離界面の界面張力を低下しても良い。第三成分を添加することにより、紡糸原液中での炭化性ポリマーの相分離サイズを小さくしかつ安定化できるので、前駆体繊維中で筋状に分散した炭化性ポリマーの直径を小さくするのに有効である。
<Third component for controlling the size of phase separation>
For the purpose of controlling and stabilizing the size of the phase separation, the surface tension of the phase separation interface may be lowered by adding a surfactant, fine particles, graft polymer, block polymer or the like. By adding the third component, the phase separation size of the carbonized polymer in the spinning dope can be reduced and stabilized, so that the diameter of the carbonized polymer dispersed in the precursor fiber in a streak can be reduced. It is valid.
そのような場合には、アクリロニトリル系ポリマーと熱分解性ポリマーを成分とするグラフトポリマーおよび／またはブロックポリマーを添加する方法が好ましい。グラフトポリマー又はブロックポリマーの特性としては、特に制限は無いが重量平均分子量は１００万以下、グラフト鎖長またはブロック鎖長は重量平均分子量で５０万以下が好ましい。 In such a case, a method of adding a graft polymer and / or a block polymer containing an acrylonitrile-based polymer and a thermally decomposable polymer as components is preferable. The characteristics of the graft polymer or block polymer are not particularly limited, but the weight average molecular weight is preferably 1,000,000 or less, and the graft chain length or block chain length is preferably 500,000 or less in terms of weight average molecular weight.
本発明で使用する前駆体繊維においては、マトリックス相である熱分解性ポリマー中に無機微粒子を５〜４０質量％含むことが好ましい。無機微粒子を分散相として隣接する炭化性ポリマーの間に存在させることにより、無機微粒子が焼成過程で炭化性ポリマーに物理的または／および化学的に付着したカーボンナノファイバーが得られる。無機微粒子は、炭化性ポリマー同士の融着を防ぐ役割も果している。 In the precursor fiber used by this invention, it is preferable that 5-40 mass% of inorganic fine particles are included in the thermally decomposable polymer which is a matrix phase. By allowing the inorganic fine particles to be present as a dispersed phase between adjacent carbonized polymers, carbon nanofibers in which the inorganic fine particles are physically or / and chemically attached to the carbonized polymer during the firing process can be obtained. The inorganic fine particles also play a role of preventing fusion between the carbonized polymers.
＜紡糸と紡糸溶剤＞
本発明で使用する前駆体繊維は、溶融紡糸法または溶液紡糸法により得ることができる。溶液紡糸の方法としては、例えば乾式紡糸法、乾湿式紡糸法、湿式紡糸法が挙げられる。紡糸原液の溶剤としては熱分解性ポリマーとアクリロニトリル系ポリマーの両者を溶解する溶剤であることが要求される以外には特に制限は無く、例えばジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシドが挙げられる。前駆体繊維は、このような溶液紡糸法によって通常のアクリル繊維と同様の紡糸工程で製造することができる。
<Spinning and spinning solvent>
The precursor fiber used in the present invention can be obtained by a melt spinning method or a solution spinning method. Examples of the solution spinning method include a dry spinning method, a dry and wet spinning method, and a wet spinning method. The solvent for the spinning solution is not particularly limited except that it is required to be a solvent that dissolves both the thermally decomposable polymer and the acrylonitrile-based polymer, and examples thereof include dimethylformamide, dimethylacetamide, and dimethylsulfoxide. The precursor fiber can be produced by the same spinning process as that of a normal acrylic fiber by such a solution spinning method.
＜焼成条件＞
本発明の製造方法では、前記前駆体繊維を、空気中で２００〜３００℃の温度で処理して、熱炭化性ポリマーを耐炎化し、さらに不活性雰囲気中で無機微粒子の組成および形態が変化しない温度で熱炭化性ポリマー炭素化する。
<Baking conditions>
In the production method of the present invention, the precursor fiber is treated in air at a temperature of 200 to 300 ° C. to make the thermally carbonizable polymer flame resistant, and the composition and form of the inorganic fine particles do not change in an inert atmosphere. Thermal carbonization polymer carbonizes at temperature.
『カーボンナノファイバーの存在の確認』
本発明のカーボンナノファイバーの存在は、電界放出型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて確認できる。無機微粒子の径が１０〜２０ｎｍである焼成品ならば加速電圧５．０ｋＶ、観察倍率１００，０００倍の条件で観察すれば上記無機微粒子がカーボンナノファイバー表面に存在していることが確認できる。被覆率は、上記と同条件で観察して得た平面画像から、カーボンナノファイバー部の面積とその上に存在している無機微粒子部の面積から求めることができる。
“Confirmation of the existence of carbon nanofibers”
The presence of the carbon nanofiber of the present invention can be confirmed using a field emission scanning electron microscope (FE-SEM). In the case of a fired product having an inorganic fine particle diameter of 10 to 20 nm, it can be confirmed that the inorganic fine particle is present on the surface of the carbon nanofiber when observed under conditions of an acceleration voltage of 5.0 kV and an observation magnification of 100,000. The coverage can be determined from the area of the carbon nanofiber part and the area of the inorganic fine particle part existing on the plane image obtained by observation under the same conditions as described above.
また、焼成によって無機微粒子の組成が変化していないことを確かめるには、カーボンナノファイバーを分解せずに無機微粒子のみを分解させる酸やアルカリで処理したのち、それを上記と同条件で観察して無機微粒子が除去されたことを確認すればよい。 In order to confirm that the composition of the inorganic fine particles is not changed by firing, after treating with an acid or alkali that decomposes only the inorganic fine particles without decomposing the carbon nanofibers, it is observed under the same conditions as above. It is sufficient to confirm that the inorganic fine particles have been removed.
＜カーボンナノファイバーから無機微粒子を取り除きカーボンナノファイバーを得る方法＞
本発明のカーボンナノファイバーから無機微粒子を取り除きカーボンナノファイバーを得るには、カーボンナノファイバーを分解せずに無機微粒子のみを分解させる酸やアルカリで処理すれば得られる。たとえば無機微粒子に酸化珪素を選んだ場合は熱アルカリやフッ化水素で酸化珪素を溶解すればカーボンナノファイバーが取り出せる。
<Method of obtaining carbon nanofibers by removing inorganic fine particles from carbon nanofibers>
In order to obtain the carbon nanofiber by removing the inorganic fine particles from the carbon nanofiber of the present invention, the carbon nanofiber can be obtained by treating with an acid or alkali that decomposes only the inorganic fine particles without decomposing the carbon nanofibers. For example, when silicon oxide is selected as the inorganic fine particles, carbon nanofibers can be taken out by dissolving the silicon oxide with hot alkali or hydrogen fluoride.
気相法で得られるカーボンナノファイバーには内部に金属触媒が含まれ、これを除去するにはカーボンナノファイバーを損傷することになる。これに対し本発明では無機微粒子がカーボンナノファイバーの表面にあるため、これの除去においてカーボンナノファイバーの損傷は少ない。したがって得られるカーボンナノファイバーの品質においては気相法よりも優位である。 The carbon nanofiber obtained by the vapor phase method contains a metal catalyst inside, and removing this will damage the carbon nanofiber. On the other hand, in the present invention, since the inorganic fine particles are present on the surface of the carbon nanofiber, the carbon nanofiber is hardly damaged in the removal thereof. Therefore, the quality of the obtained carbon nanofiber is superior to the gas phase method.
以下に実施例を挙げて本発明を更に詳細に説明する。
本実施例において、「質量部」及び「質量％」は、それぞれ、単に「部」及び「％」を記した。
Hereinafter, the present invention will be described in more detail with reference to examples.
In this example, “parts by mass” and “% by mass” are simply “parts” and “%”, respectively.
『原料ポリマー』
＜合成例１＞グラフトコポリマーの合成
冷却管、熱電対、窒素導入口及び攪拌装置を備えたセパラブルフラスコに、アニオン系乳化剤（花王製ラテムルＡＳＫ、固形分２８％）３．０部（固形分）、蒸留水２９０部を仕込み、窒素雰囲気下に温水浴中で６０℃まで加熱した。次いで、硫酸第一鉄０．０００４部、エチレンジアミン四酢酸二ナトリウム塩０．００１２部、ロンガリット１．０部を蒸留水５部に溶かして加え、その後メチルメタクリレート５０部、ｔ−ブチルヒドロパーオキサイド０．２５部、ｎ−オクチルメルカプタン０．５部からなる単量体混合物１を９０分かけて滴下した。その後６０分間攪拌し、第一段目の重合を完了した。
"Raw polymer"
<Synthesis Example 1> Synthesis of Graft Copolymer In a separable flask equipped with a cooling tube, a thermocouple, a nitrogen inlet and a stirrer, 3.0 parts of an anionic emulsifier (Kao Latemul ASK, solid content 28%) (solid content) ), 290 parts of distilled water was charged and heated to 60 ° C. in a warm water bath under a nitrogen atmosphere. Next, 0.0004 parts of ferrous sulfate, 0.0012 parts of ethylenediaminetetraacetic acid disodium salt and 1.0 part of Rongalite are dissolved in 5 parts of distilled water and added, and then 50 parts of methyl methacrylate and 0 parts of t-butyl hydroperoxide are added. Monomer mixture 1 consisting of .25 parts and n-octyl mercaptan 0.5 parts was added dropwise over 90 minutes. The mixture was then stirred for 60 minutes to complete the first stage polymerization.
このエマルション中に、硫酸第一鉄０．０００４部、エチレンジアミン四酢酸二ナトリウム塩０．００１２部、ロンガリット１．０部を、蒸留水５部に溶かして加え、その後アクリロニトリル４６．７部、アクリルアミド３部、メタクリル酸０．３部、ｔ−ブチルヒドロパーオキサイド０．２５部、ｎ−オクチルメルカプタン０．５部からなる単量体混合物２を９０分かけて滴下した。その後６０分間攪拌し、第二段目の重合を完了した。 In this emulsion, 0.0004 part of ferrous sulfate, 0.0012 part of ethylenediaminetetraacetic acid disodium salt and 1.0 part of Rongalite are dissolved in 5 parts of distilled water, and then 46.7 parts of acrylonitrile, acrylamide 3 Monomer mixture 2 consisting of 1 part, 0.3 part of methacrylic acid, 0.25 part of t-butyl hydroperoxide and 0.5 part of n-octyl mercaptan was added dropwise over 90 minutes. The mixture was then stirred for 60 minutes to complete the second stage polymerization.
得られたエマルションの固形分を測定したところ２４．２％であった。このエマルションを希硫酸水溶液中に注ぎ、生じた沈殿物を乾燥し、グラフトコポリマーＧ−１を得た。 The solid content of the obtained emulsion was measured and found to be 24.2%. This emulsion was poured into dilute sulfuric acid aqueous solution, and the resulting precipitate was dried to obtain graft copolymer G-1.
＜合成例２＞アクリロニトリル系ポリマーの合成
水とジメチルアセトアミドの混合溶媒中で２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）を開始剤とし、アクリロニトリル単位１００％からなる超高分子量アクリロニトリル系ポリマーを得た。このポリマーの重量平均分子量は５０万であった。
<Synthesis Example 2> Synthesis of acrylonitrile-based polymer In a mixed solvent of water and dimethylacetamide, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) is used as an initiator, and an ultra-compound composed of 100% acrylonitrile units. A high molecular weight acrylonitrile-based polymer was obtained. The weight average molecular weight of this polymer was 500,000.
『評価方法』
＜モルフォロジー観察＞
（前駆体繊維）
前駆体繊維を電子顕微鏡用のエポキシ系樹脂で包埋硬化して、繊維軸と平行または垂直方向の断面が得られるようにトリミング、面出しした後、ダイヤモンドナイフを装着したミクロトームにより約７０ｎｍの厚さの切片を切り出した。得られた切片を電子顕微鏡観察用のメッシュに載せ、日立（株）Ｈ−７６００透過型電子顕微鏡により、加速電圧８０ｋＶの条件で観察した。
"Evaluation methods"
<Morphological observation>
(Precursor fiber)
The precursor fiber was embedded and cured with an epoxy resin for an electron microscope, trimmed and surfaced so that a cross section parallel or perpendicular to the fiber axis was obtained, and then a thickness of about 70 nm was obtained by a microtome equipped with a diamond knife. A section was cut out. The obtained slice was placed on a mesh for observation with an electron microscope, and observed with a Hitachi H-7600 transmission electron microscope under an acceleration voltage of 80 kV.
＜カーボンナノファイバー＞
カーボンナノファイバーを乳鉢で破砕したものを日本電子（株）ＪＳＭ−７４００Ｆ電界放出型電子顕微鏡（ＦＥ−ＳＥＭ）で加速電圧５．０ｋＶで観察した。
<Carbon nanofiber>
The carbon nanofibers crushed with a mortar were observed with an acceleration voltage of 5.0 kV with a JSM-7400F field emission electron microscope (FE-SEM).
（実施例１）
ＰＭＭＡ樹脂（三菱レイヨン製ダイヤナールＢＲ−８５）１０部、アクリロニトリル系ポリマー５部、グラフトコポリマー１．５部、及びジメチルアセトアミド分散シリカゾル（日産化学製ＤＭＡＣ−ＳＴ 酸化珪素含量２０％、酸化珪素粒子径１０〜２０ｎｍ）２０部及びジメチルアセトアミド６４部を１３０℃で６０分よく撹拌しながら加熱溶解し、続いて、ホモジナイザー（特殊機化工業製Ｔ．Ｋ．ホモミクサー）で３０分処理した。得られた溶液は、固形分２０％のジメチルアセトアミド溶液で、固形分の内訳はＰＭＭＡ樹脂４８％、アクリロニトリル系ポリマー２４％、グラフトコポリマー８％及び酸化珪素２０％である。この溶液を紡糸原液とし（温度３０℃）、直径０．３５ｍｍ、孔数５０の口金を用いて、一旦空気中に吐出し、約５ｍｍの空間を通して、濃度４０％、温度２０℃のジメチルアセトアミド水溶液に吐出し、紡糸ドラフトが１０となるように引き取り凝固糸となした。これを温水中で５倍延伸しながら洗浄・脱溶剤した後、１％アミノシリコン系油剤溶液中に浸漬し、１７５℃の加熱ローラーにて乾燥緻密化した。続いて、０．２ＭＰａの加圧水蒸気中で２倍延伸して、単糸繊度が１．７ｄｔｅｘの前駆体繊維を得た。
Example 1
10 parts of PMMA resin (Mitsubishi Rayon Dianal BR-85), 5 parts of acrylonitrile polymer, 1.5 parts of graft copolymer, and dimethylacetamide-dispersed silica sol (Nissan Chemical DMAC-ST silicon oxide content 20%, silicon oxide particle size 10 parts by weight (10 to 20 nm) and 64 parts of dimethylacetamide were heated and dissolved at 130 ° C. with good stirring for 60 minutes, and then treated with a homogenizer (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) for 30 minutes. The obtained solution was a dimethylacetamide solution having a solid content of 20%, and the breakdown of the solid content was 48% PMMA resin, 24% acrylonitrile polymer, 8% graft copolymer and 20% silicon oxide. This solution was used as a spinning dope (temperature 30 ° C.), and was once discharged into the air using a die having a diameter of 0.35 mm and a hole number of 50, and a dimethylacetamide aqueous solution having a concentration of 40% and a temperature of 20 ° C. through a space of about 5 mm. And was drawn so that the spinning draft was 10 to obtain a coagulated yarn. This was washed and desolvated while being stretched 5 times in warm water, then immersed in a 1% aminosilicone oil solution and dried and densified with a 175 ° C. heating roller. Subsequently, the fiber was stretched twice in a pressurized water vapor of 0.2 MPa to obtain a precursor fiber having a single yarn fineness of 1.7 dtex.
得られた前駆体繊維のモルフォロジーは、酸化珪素粒子が分散したＰＭＭＡ樹脂のマトリックス相中にアクリロニトリル系ポリマーが島状に独立分散しており、分散相の直径は１０〜１００ｎｍで繊維軸方向の長さは１０〜３０μｍ以上であった。 The morphology of the obtained precursor fiber is as follows. The acrylonitrile-based polymer is independently dispersed in an island shape in the matrix phase of the PMMA resin in which silicon oxide particles are dispersed, the diameter of the dispersed phase is 10 to 100 nm, and the length in the fiber axis direction is long. The thickness was 10 to 30 μm or more.
得られた前駆体繊維を２０ｃｍに固定し、空気中２５０℃で６０分間処理して耐炎化糸を得た。得られた耐炎化糸をメノウ鉢中でＭＥＫを滴下しながら剪断を加えて静置したのち沈降物を回収し自然乾燥した。 The obtained precursor fiber was fixed to 20 cm and treated in air at 250 ° C. for 60 minutes to obtain a flameproof yarn. The flameproofed yarn obtained was left to stand by adding shear while dropping MEK in an agate bowl, and then the sediment was recovered and air dried.
乾燥物を引き続き窒素雰囲気下最高温度１０００℃にて６０分間処理し焼成品をえた。電界放出型電子顕微鏡観察の結果、径が１０〜２０ｎｍの微粒子が被覆率１０〜３０％で存在するカーボンナノファイバーが確認された。この微粒子が存在するカーボンナノファバーを加熱フッ化水素５０％水溶液中で重量減少がなくなるまで処理したものを電界放出型電子顕微鏡観察した結果、微粒子が除去されたカーボンナノファイバーを得た。よって焼成品は酸化珪素微粒子複合カーボンナノファイバーであることが確認された。 The dried product was subsequently treated in a nitrogen atmosphere at a maximum temperature of 1000 ° C. for 60 minutes to obtain a baked product. As a result of observation with a field emission electron microscope, carbon nanofibers in which fine particles having a diameter of 10 to 20 nm were present at a coverage of 10 to 30% were confirmed. As a result of observing the carbon nanofabric in which the fine particles are present in a heated hydrogen fluoride 50% aqueous solution until the weight reduction is eliminated, the carbon nanofibers from which the fine particles have been removed were obtained. Therefore, it was confirmed that the fired product was a silicon oxide fine particle composite carbon nanofiber.
（比較例１）
実施例１の乾燥物を窒素雰囲気下最高温度１５５０℃にて６０分間処理して焼成品を得た。得られた焼成品を電界放出型電子顕微鏡観察した結果、カーボンナノファイバー表面には径が１０〜２０ｎｍの微粒子が確認できなかった。
(Comparative Example 1)
The dried product of Example 1 was treated at a maximum temperature of 1550 ° C. for 60 minutes in a nitrogen atmosphere to obtain a fired product. As a result of observing the obtained fired product with a field emission electron microscope, fine particles having a diameter of 10 to 20 nm could not be confirmed on the surface of the carbon nanofiber.
本発明によれば、直径１００ｎｍ以下のカーボンナノファイバーの表面に粒径１００ｎｍ以下の無機微粒子が存在する無機微粒子複合カーボンナノファイバーが工業的に高い品質と歩留で得られる。 According to the present invention, an inorganic fine particle composite carbon nanofiber in which inorganic fine particles having a particle diameter of 100 nm or less are present on the surface of a carbon nanofiber having a diameter of 100 nm or less can be obtained with industrially high quality and yield.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11131321A (en) * | 1997-10-30 | 1999-05-18 | Mitsubishi Rayon Co Ltd | Microparticle-containing phase-separated fiber and its production |
| JPH11222718A (en) * | 1998-02-09 | 1999-08-17 | Mitsubishi Rayon Co Ltd | Extremely extrafine acrylic fiber aggregate |
| JP2003300717A (en) * | 2002-02-07 | 2003-10-21 | Toray Ind Inc | Carbon nanotube precursor fiber, carbon nanotube and method for manufacturing the same |
| JP2003336130A (en) * | 2002-03-15 | 2003-11-28 | Mitsubishi Rayon Co Ltd | Carbon fiber, carbon nanofiber obtained from the same and method of production for carbon fiber and precursor fiber for the same |
| JP2004036038A (en) * | 2002-07-03 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Precursor fiber of carbon fiber, method for producing carbon fiber by using the same, and filament-shaped carbon nanofiber obtained from the carbon fiber |
| JP2004036058A (en) * | 2002-07-05 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Carbon fiber, carbon fibril obtained therefrom, method for producing the carbon fiber and precursor fiber thereof |
| JP2004043993A (en) * | 2002-07-09 | 2004-02-12 | Mitsubishi Rayon Co Ltd | Method for producing carbon fiber precursor and carbon fiber obtained from the carbon fiber precursor |
| JP2005097792A (en) * | 2003-09-25 | 2005-04-14 | Kuraray Co Ltd | Ultrafine carbon fiber and method for producing the same |
-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11131321A (en) * | 1997-10-30 | 1999-05-18 | Mitsubishi Rayon Co Ltd | Microparticle-containing phase-separated fiber and its production |
| JPH11222718A (en) * | 1998-02-09 | 1999-08-17 | Mitsubishi Rayon Co Ltd | Extremely extrafine acrylic fiber aggregate |
| JP2003300717A (en) * | 2002-02-07 | 2003-10-21 | Toray Ind Inc | Carbon nanotube precursor fiber, carbon nanotube and method for manufacturing the same |
| JP2003336130A (en) * | 2002-03-15 | 2003-11-28 | Mitsubishi Rayon Co Ltd | Carbon fiber, carbon nanofiber obtained from the same and method of production for carbon fiber and precursor fiber for the same |
| JP2004036038A (en) * | 2002-07-03 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Precursor fiber of carbon fiber, method for producing carbon fiber by using the same, and filament-shaped carbon nanofiber obtained from the carbon fiber |
| JP2004036058A (en) * | 2002-07-05 | 2004-02-05 | Mitsubishi Rayon Co Ltd | Carbon fiber, carbon fibril obtained therefrom, method for producing the carbon fiber and precursor fiber thereof |
| JP2004043993A (en) * | 2002-07-09 | 2004-02-12 | Mitsubishi Rayon Co Ltd | Method for producing carbon fiber precursor and carbon fiber obtained from the carbon fiber precursor |
| JP2005097792A (en) * | 2003-09-25 | 2005-04-14 | Kuraray Co Ltd | Ultrafine carbon fiber and method for producing the same |
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