JP2005162877A - Carbon nanotube-dispersed polar organic solvent and method for producing the same - Google Patents
Carbon nanotube-dispersed polar organic solvent and method for producing the same Download PDFInfo
- Publication number
- JP2005162877A JP2005162877A JP2003403504A JP2003403504A JP2005162877A JP 2005162877 A JP2005162877 A JP 2005162877A JP 2003403504 A JP2003403504 A JP 2003403504A JP 2003403504 A JP2003403504 A JP 2003403504A JP 2005162877 A JP2005162877 A JP 2005162877A
- Authority
- JP
- Japan
- Prior art keywords
- carbon nanotube
- carbon nanotubes
- organic solvent
- polar organic
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000003495 polar organic solvent Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 title abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 111
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 111
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 49
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 49
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 47
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001408 amides Chemical class 0.000 claims abstract description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 39
- 239000002109 single walled nanotube Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 230000000717 retained effect Effects 0.000 claims description 9
- 238000000149 argon plasma sintering Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000013339 polymer-based nanocomposite Substances 0.000 abstract description 7
- 239000012046 mixed solvent Substances 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 17
- 238000000981 high-pressure carbon monoxide method Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002071 nanotube Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、アミド系有機溶媒及びポリビニルピロリドン（ＰＶＰ）からなるカーボンナノチューブ分散溶液及びその製造方法に関する。特に、カーボンナノチューブをポリマー系ナノコンポジットなどの各種用途への応用を可能にするためのカーボンナノチューブ分散有機溶媒及びその製造方法に関する。 The present invention relates to a carbon nanotube dispersion solution comprising an amide organic solvent and polyvinylpyrrolidone (PVP) and a method for producing the same. In particular, the present invention relates to a carbon nanotube-dispersed organic solvent for enabling application of carbon nanotubes to various uses such as polymer-based nanocomposites and a method for producing the same.
近年発見されたカーボンナノチューブは直径１μｍ以下の太さのチューブ状材料であり、理想的なものとしては炭素６角網目の面がチューブの軸に平行な管を形成し、さらにこの管が多重になることもある。このカーボンナノチューブは炭素ででき６角網目の数や、チューブの太さによって異なる性質を有し、将来の機械的及び機能的材料として期待されている。 Recently discovered carbon nanotubes are tube-shaped materials with a diameter of 1 μm or less. Ideally, the carbon hexagonal mesh surface forms a tube parallel to the axis of the tube. Sometimes. This carbon nanotube is made of carbon and has different properties depending on the number of hexagonal meshes and the thickness of the tube, and is expected as a future mechanical and functional material.
カーボンナノチューブを用いてこのような機械的及び機能的材料を製造する際には、カーボンナノチューブが均一に分散された溶媒を用いることが有益である。例えば、カーボンナノチューブが均一に分散された溶媒にポリマーを溶かすことによってカーボンナノチューブがポリマーマトリックスに均一に分散したナノコンポジットを製造することができる。また、カーボンナノチューブが均一に分散された溶媒の有する低い散乱性を利用して光学機器として用いることができる。さらに分散液の精製によってトランジスタ等の電子装置、電子放出装置や二次電池を製造する際にも利用される。例えば、炭素微粒子を用いたエミッタの形成方法としては、炭素微粒子を溶媒に分散した懸濁液を作成し、キャスト、スクリーン印刷、インクジェットなどの印刷技術を用いて基板となる支持部材上に懸濁液のパターンを形成した後、溶媒を乾燥して所望の形状を得ている。 When producing such mechanical and functional materials using carbon nanotubes, it is beneficial to use a solvent in which carbon nanotubes are uniformly dispersed. For example, a nanocomposite in which carbon nanotubes are uniformly dispersed in a polymer matrix can be produced by dissolving the polymer in a solvent in which carbon nanotubes are uniformly dispersed. Further, it can be used as an optical device by utilizing the low scattering property of a solvent in which carbon nanotubes are uniformly dispersed. Furthermore, it is also used when manufacturing electronic devices such as transistors, electron emission devices and secondary batteries by refining the dispersion. For example, as a method of forming an emitter using carbon fine particles, a suspension in which carbon fine particles are dispersed in a solvent is prepared and suspended on a support member serving as a substrate by using a printing technique such as casting, screen printing, or inkjet. After forming the liquid pattern, the solvent is dried to obtain the desired shape.
一般に、カーボンナノチューブ分散用の溶媒としては、水溶性溶媒や有機溶媒あるいはそれらの混合溶媒が利用できることが知られている。例えば、水、酸性溶液、アルカリ性溶液、アルコール、エーテル、石油エーテル、ベンゼン、酢酸エチル、クロロホルム、イソプロピルアルコール、エタノール、アセトン、トルエン等が使用できる旨開示されている（下記、特許文献１参照）。 In general, it is known that a water-soluble solvent, an organic solvent, or a mixed solvent thereof can be used as a solvent for dispersing carbon nanotubes. For example, it is disclosed that water, acidic solution, alkaline solution, alcohol, ether, petroleum ether, benzene, ethyl acetate, chloroform, isopropyl alcohol, ethanol, acetone, toluene and the like can be used (see Patent Document 1 below).
しかしながら、未だ、十分にカーボンナチューブを溶媒に分散する方法は確立されていない。これはカーボンナノチューブ相互の凝集力（ファンデルワールス力）によって、束状及び縄状になってしまうためである。また、カーボンナノチューブの原子レベルでの滑らかな表面が溶媒に対する親和性を低下する要因となっている。したがって、カーボンナノチューブの特異で有用な性質にもかかわらず、これを均一に分散したポリマー系ナノコンポジットなどを製造することは極めて困難であり、カーボンナノチューブの各種用途への応用を事実上困難にしている。 However, a method for sufficiently dispersing carbon nanotubes in a solvent has not yet been established. This is because the carbon nanotubes become bundles and ropes due to the cohesive force (van der Waals force). In addition, the smooth surface at the atomic level of the carbon nanotube is a factor that reduces the affinity for the solvent. Therefore, in spite of the unique and useful properties of carbon nanotubes, it is extremely difficult to produce polymer nanocomposites and the like in which they are uniformly dispersed, making it practically difficult to apply carbon nanotubes to various applications. Yes.
これまでに、カーボンナノチューブの溶媒に対する分散性を改善するために様々な試みがなされているが、必ずしも十分な効果を得ていない。 Various attempts have been made so far to improve the dispersibility of carbon nanotubes in a solvent, but sufficient effects have not been obtained.
まず、超音波をかけながらカーボンナノチューブをアセトン中に分散させる方法（下記、特許文献２参照）が提案されている。しかし、超音波を照射している間は分散できても照射が終了するとカーボンナノチューブの凝集が始まり、カーボンナチューブの濃度が高くなると凝集してしまうということが起きてしまう。 First, a method of dispersing carbon nanotubes in acetone while applying ultrasonic waves (see Patent Document 2 below) has been proposed. However, even though it can be dispersed while the ultrasonic wave is irradiated, the carbon nanotubes start to aggregate when the irradiation ends, and when the concentration of the carbon nanotube increases, the carbon nanotubes aggregate.
次に、界面活性剤を用いることも提案されている。界面活性剤としては、非イオン系界面活性剤であるＴｅｒｇｉｔｏｌ（商標）ＮＰ７を用いて超音波処理することが提案されているが、カーボンナノチューブの配合量を増加させると、カーボンナノチューブが凝集してしまい、均一な分散が得られない旨報告されている。（下記非特許文献１参照
）また、単層ナノチューブを陰イオン性界面活性剤ＳＤＳ水溶液中で超音波処理することにより、カーボンナノチューブ表面の疎水性と界面活性剤の疎水部を吸着させ、外側に親水部を形成して水溶液中に分散することも報告されているが（下記非特許文献２参照）、水溶性溶媒であるため、例えば、ポリマー系ナノコンポジットに応用する際、適用できる高分子は水溶性高分子に限られてしまい、応用範囲に限界がある。同様に、界面活性剤の替わりに水溶性高分子ＰＶＰの疎水部分をカーボンナノチューブの表面につける方法も提案されているが、やはり水溶性高分子であって応用範囲は限られている（下記非特許文献３参照）。
カーボンナノチューブを均一に分散した溶媒を用いると、カーボンナノチューブの特異な性質を利用して多様な用途へ応用が可能であるが、カーボンナノチューブ相互の凝集力、及び表面の親和力の低さから、均一に分散した溶媒を得ることは困難となっている。特に、ポリマーにカーボンナノチューブを分散させることができれば、カーボンナノチューブの分散したポリマー系ナノコンポジット得られ、極めて有用である。しかしながら、ポリマーの溶媒として多用されている極性有機溶媒へのカーボンナノチューブの分散が極めて有用であるにもかかわらず、これまでに、このような極性有機溶媒に効果的に分散させることには成功していない。 If a solvent in which carbon nanotubes are uniformly dispersed is used, it can be applied to various applications using the unique properties of carbon nanotubes. However, it is uniform because of the low cohesion between carbon nanotubes and the low surface affinity. It is difficult to obtain a solvent dispersed in the solution. In particular, if carbon nanotubes can be dispersed in a polymer, a polymer-based nanocomposite in which carbon nanotubes are dispersed is obtained, which is extremely useful. However, even though the dispersion of carbon nanotubes in a polar organic solvent, which is widely used as a solvent for polymers, is extremely useful, it has so far been successfully dispersed in such a polar organic solvent. Not.
したがって、本発明の目的は、ポリマー溶媒として有用な極性有機溶媒にカーボンナノチューブを有効に分散させることができる分散溶媒を得ることにある。 Accordingly, an object of the present invention is to obtain a dispersion solvent capable of effectively dispersing carbon nanotubes in a polar organic solvent useful as a polymer solvent.
本発明は、アミド系極性有機溶媒、特に、ＮＭＰ（Ｎメチルピロリドン）及びポリビニルピロリドンからなる混合溶媒が、カーボンナノチューブの優れた分散剤としての機能を発揮することを見出したものである。 The present invention has been found that an amide polar organic solvent, in particular, a mixed solvent composed of NMP (N methylpyrrolidone) and polyvinylpyrrolidone exhibits an excellent function as a dispersant for carbon nanotubes.
この際、カーボンナノチューブを分散するには、超音波処理をする必要がある。超音波処理は、アミド系極性有機溶媒及びポリビニルピロリドン（ＰＶＰ）の混合溶媒を作製した後、カーボンナノチューブを分散する際に適用する。 At this time, in order to disperse the carbon nanotubes, it is necessary to perform ultrasonic treatment. The ultrasonic treatment is applied when carbon nanotubes are dispersed after preparing a mixed solvent of an amide polar organic solvent and polyvinylpyrrolidone (PVP).
ポリビニルピロリドン（ＰＶＰ）は、カーボンナノチューブの表面に吸着し、カーボンナノチューブを包むいわゆるラッピング効果を有する。したがって、カーボンナノチューブの再凝集を防止する働きがあるものと考えられる。 Polyvinyl pyrrolidone (PVP) has a so-called wrapping effect that is adsorbed on the surface of the carbon nanotube and encapsulates the carbon nanotube. Therefore, it is considered that the carbon nanotubes have a function of preventing reaggregation.
これによって、カーボンナノチューブを利用したポリマー系ナノコンポジットの製造に極めて有利な方法が提供でき、また、光散乱の低減を利用した光学機器への応用等も可能となる。
本発明は、具体的には、次の構成からなる。
As a result, it is possible to provide a method that is extremely advantageous for the production of polymer-based nanocomposites using carbon nanotubes, and it is also possible to apply to optical devices using the reduction of light scattering.
Specifically, the present invention has the following configuration.
（１）カーボンナノチューブ、アミド系極性有機溶媒及びポリビニルピロリドリン（ＰＶＰ）からなるカーボンナノチューブ分散溶液。
（２）アミド系極性有機溶媒がＮ−メチルピロリドン（ＮＭＰ）であることを特徴とする上記（１）に記載のカーボンナノチューブ分散溶液。
（３）ポリビニルピロリドン（ＰＶＰ）の添加量が０．１〜１０％であることを特徴とする上記（１）又は（２）に記載のカーボンナノチューブ分散溶液。
（４）ポリビニルピロリドン（ＰＶＰ）の分子量が、２万〜５００万であることを特徴とする上記（１）ないし（３）のいずれかに記載のカーボンナノチューブ分散溶液。
（５）カーボンナノチューブが単層カーボンナノチューブ（ＳＷＮＴ）であることを特徴とする上記（１）ないし（４）のいずれかに記載のカーボンナノチューブ分散溶液。
（６）カーボンナノチューブとして、保留粒子径０．１〜３．０μｍのフィルター処理によって微細なカーボンナノチューブのみを含むことを特徴とする上記（１）ないし（５）のいずれかに記載のカーボンナノチューブ分散溶液。
（７）ポリマー系ナノコンポジットにおけるカーボンナノチューブの均一分散のために使用される上記（１）ないし（６）のいずれかに記載のカーボンナノチューブ分散溶液。
（８）光散乱性が減少していることを特徴とする上記（１）ないし（７）のいずれかに記載のカーボンナノチューブ分散溶液。
（９）アミド系極性有機溶媒及びポリビニルピロリドリン混合溶液に、超音波処理を行いながらカーボンナノチューブを混合分散することを特徴とするカーボンナノチューブ分散溶液の製造方法。
（１０）アミド系極性有機溶媒及びポリビニルピロリドリン混合溶液に、超音波処理を行いながらカーボンナノチューブを混合した後、保留粒子径０．１〜３．０μｍのフィルター処理することによって微細なカーボンナノチューブのみを含む溶液とすることを特徴とするカーボンナノチューブ分散溶液の製造方法。
(1) A carbon nanotube dispersion solution comprising carbon nanotubes, an amide-based polar organic solvent, and polyvinylpyrrolidolin (PVP).
(2) The carbon nanotube dispersion solution as described in (1) above, wherein the amide polar organic solvent is N-methylpyrrolidone (NMP).
(3) The carbon nanotube dispersion solution described in (1) or (2) above, wherein the addition amount of polyvinylpyrrolidone (PVP) is 0.1 to 10%.
(4) The carbon nanotube dispersion solution according to any one of (1) to (3) above, wherein the molecular weight of polyvinylpyrrolidone (PVP) is 20,000 to 5,000,000.
(5) The carbon nanotube dispersion solution described in any one of (1) to (4) above, wherein the carbon nanotube is a single-walled carbon nanotube (SWNT).
(6) The carbon nanotube dispersion according to any one of the above (1) to (5), wherein the carbon nanotube contains only fine carbon nanotubes by a filter treatment with a reserved particle diameter of 0.1 to 3.0 μm. solution.
(7) The carbon nanotube dispersion solution according to any one of (1) to (6), which is used for uniform dispersion of carbon nanotubes in a polymer nanocomposite.
(8) The carbon nanotube dispersion solution as described in any one of (1) to (7) above, wherein the light scattering property is reduced.
(9) A method for producing a carbon nanotube dispersion solution, wherein carbon nanotubes are mixed and dispersed in an amide polar organic solvent and polyvinylpyrrolidolin mixed solution while performing ultrasonic treatment.
(10) After mixing carbon nanotubes with ultrasonic treatment in an amide polar organic solvent and polyvinylpyrrolidolin mixed solution, only fine carbon nanotubes are obtained by filtering with a retained particle diameter of 0.1 to 3.0 μm. A method for producing a carbon nanotube dispersion solution, wherein
本発明で用いられるアミド系極性有機溶媒としては、具体的には、ジメチルホルムアミド（ＤＭＦ），ジエチルホルムアミド、ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）などのいずれも用いることができるが、特に好ましくは、Ｎ−メチルピロリドン（ＮＭＰ）を用いるとよい。これらは、多くの有機物（低級炭化水素を除く）、無機物、極性ガスおよび高分子、特に、ポリアミド、ポリイミド、ポリエステル、ポリウレタン、アクリル樹脂をとかすことができる。したがって、カーボンナノチューブをこれらの溶媒に均一に分散することができれば、その分散液にこれらの高分子材料をとかすことによってカーボンナノチューブが均一に分散したポリマー系ナノコンポジットを得ることができる。 As the amide polar organic solvent used in the present invention, specifically, any of dimethylformamide (DMF), diethylformamide, dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and the like can be used. Particularly preferably, N-methylpyrrolidone (NMP) is used. These can dissolve many organic substances (excluding lower hydrocarbons), inorganic substances, polar gases and polymers, especially polyamides, polyimides, polyesters, polyurethanes and acrylic resins. Therefore, if the carbon nanotubes can be uniformly dispersed in these solvents, a polymer-based nanocomposite in which the carbon nanotubes are uniformly dispersed can be obtained by dissolving these polymer materials in the dispersion.
本発明で用いられるカーボンナノチューブには、多層のもの（マルチウォール・カーボンナノチューブ、「ＭＷＮＴ」と呼ばれる）から単層のもの（シングルウォール・カーボンナノチューブ、「ＳＷＮＴ」と呼ばれる）まで、それぞれ目的に応じて使うことができる。本発明においては、好ましくは、シングルウォール・カーボンナノチューブが用いられる。用いるＳＷＮＴの製造方法としては、特に制限されるものではなく、触媒を用いる熱分解法（気相成長法と類似の方法）、アーク放電法、レーザー蒸発法、及びＨｉＰｃｏ法（Ｈｉｇｈ−ｐｒｅｓｓｕｒｅ ｃａｒｂｏｎ ｍｏｎｏｘｉｄｅ ｐｒｏｃｅｓｓ）等、従来公知のいずれの製造方法を採用いても構わない。 Carbon nanotubes used in the present invention vary from multi-walled ones (multi-wall carbon nanotubes, called “MWNT”) to single-walled ones (single-wall carbon nanotubes, called “SWNT”) depending on the purpose. Can be used. In the present invention, single wall carbon nanotubes are preferably used. The production method of SWNT to be used is not particularly limited, and a thermal decomposition method using a catalyst (a method similar to the vapor phase growth method), an arc discharge method, a laser evaporation method, and a HiPco method (High-pressure carbon monoxide). Any conventionally known manufacturing method such as process) may be employed.
以下に、レーザー蒸着法により、本発明に好適なシングルウォール・カーボンナノチューブを作成する手法について例示する。原料として、グラファイトパウダーと、ニッケルおよびコバルト微粉末混合ロッドを用意した。この混合ロッドを６６５ｈＰａ（５００Ｔｏｒｒ）のアルゴン雰囲気下、電気炉により１，２５０℃に加熱し、そこに３５０ｍＪ／ＰｕｌｓｅのＮｄ：ＹＡＧレーザーの第二高調波パルスを照射し、炭素と金属微粒子を蒸発させることにより、シングルウォール・カーボンナノチューブを作製した。 Hereinafter, a method for producing a single wall carbon nanotube suitable for the present invention by laser vapor deposition will be exemplified. As raw materials, graphite powder and nickel and cobalt fine powder mixing rods were prepared. This mixing rod is heated to 1,250 ° C. by an electric furnace in an argon atmosphere of 665 hPa (500 Torr), and irradiated with a second harmonic pulse of 350 mJ / Pulse Nd: YAG laser to evaporate carbon and metal fine particles. By doing so, a single wall carbon nanotube was produced.
以上の作製方法は、あくまで典型例であり、金属の種類、ガスの種類、電気炉の温度、レーザーの波長等を変更しても差し支えない。また、レーザー蒸着法以外の作製法、例えば、ＨｉＰｃｏ法、ＣＶＤ法、アーク放電法、一酸化炭素の熱分解法、微細な空孔中に有機分子を挿入して熱分解するテンプレート法、フラーレン・金属共蒸着法等、他の手法によって作製されたシングルウォールナノチューブを使用しても差し支えない。 The above manufacturing method is merely a typical example, and the metal type, gas type, electric furnace temperature, laser wavelength, and the like may be changed. Also, methods other than laser vapor deposition, such as HiPco, CVD, arc discharge, pyrolysis of carbon monoxide, template method in which organic molecules are inserted into fine vacancies, fullerene, Single wall nanotubes produced by other methods such as metal co-evaporation may be used.
また、カーボンナノチューブの配合量は、使用目的によっても異なるが、分散性が得られる限り特に限定されるものではない。ＳＷＮＴを用いて、ＮMＰ及びポリビニルピロリドン（ＰＶＰ）の混合溶液に分散した場合、最大０．０５％まで分散することができる。特に好ましくは、０．００５から０．０５％までがよい。 Further, the blending amount of the carbon nanotubes varies depending on the purpose of use, but is not particularly limited as long as dispersibility is obtained. When SWNT is used and dispersed in a mixed solution of NMP and polyvinylpyrrolidone (PVP), it can be dispersed up to 0.05%. Particularly preferred is 0.005 to 0.05%.
本発明で使用される超音波は、２０ｋＨｚ，１５０Ｗ及び２８ｋＨｚ，１４０Ｗを用い、約１時間処理することによって良好な分散効果を得ることができたが、本発明の超音波の条件はこれに限定されるものではない。配合されるカーボンナノチューブの量、アミド系極性有機溶媒の種類等によって、適宜、定めることが可能である。 The ultrasonic waves used in the present invention were 20 kHz, 150 W and 28 kHz, 140 W, and a good dispersion effect could be obtained by processing for about 1 hour, but the ultrasonic conditions of the present invention are limited to this. Is not to be done. It can be appropriately determined depending on the amount of carbon nanotubes to be blended, the type of amide polar organic solvent, and the like.
本発明で用いられるポリビニルピロリドン（ＰＶＰ）の配合量は、カーボンナノチューブの配合量によって適宜定めることができるが、好ましくは分散溶媒中０．１〜１０％配合するとよい。ポリビニルピロリドンは、カーボンナノチューブの表面に吸着し、カーボンナノチューブを包むいわゆるラッピング効果を有することが知られている。本発明では、ポリビニルピロリドンのこのようなラッピング効果を利用して、カーボンナノチューブの凝集を防止することができる。カーボンナノチューブの配合量に対してポリビニルピロリドンの配合量が低すぎると、十分なラッピング効果が得られず、ナノチューブどうしの凝集が起きてしまう。 The blending amount of polyvinyl pyrrolidone (PVP) used in the present invention can be appropriately determined depending on the blending amount of the carbon nanotubes, but preferably 0.1 to 10% in the dispersion solvent. Polyvinyl pyrrolidone is known to have a so-called wrapping effect that is adsorbed on the surface of the carbon nanotube and encapsulates the carbon nanotube. In the present invention, the wrapping effect of polyvinyl pyrrolidone can be used to prevent the carbon nanotubes from aggregating. If the blending amount of polyvinylpyrrolidone is too low relative to the blending amount of carbon nanotubes, a sufficient wrapping effect cannot be obtained, causing aggregation of the nanotubes.
本発明で用いられるポリビニルピロリドン（ＰＶＰ）の分子量は特に限定されるものではなく、一般には２万〜５００万であれば、十分な凝集防止効果を得ることができるが、好ましくは２０万〜２００万がよい。ナノチューブの分子量が非常に大きいため、分子量が小さすぎるとＰＶＰが十分にナノチューブをラッピングすることができない。また、分子量が大きすぎると溶媒中におけるＰＶＰの分子運動が低下し、十分にナノチューブをラッピングすることができない。 The molecular weight of the polyvinyl pyrrolidone (PVP) used in the present invention is not particularly limited, and generally 20,000 to 5,000,000 can provide a sufficient aggregation preventing effect, but preferably 200,000 to 200. Everything is good. Since the molecular weight of the nanotube is very large, if the molecular weight is too small, the PVP cannot sufficiently wrap the nanotube. On the other hand, if the molecular weight is too large, the molecular motion of PVP in the solvent is lowered and the nanotubes cannot be sufficiently wrapped.
本発明で使用されるフィルターは、ガラス繊維フィルター、メンブランフィルターなどが用いられる。その際、フィルターの保留粒子径は、目的に応じて適宜定めることができる。保留粒子径とは、ＪＩＳ ３８０１で規定された硫酸バリウムなどを自然ろ過したときの漏洩粒子径により求めたものであるが、実質的には、フィルターの平均孔径に相当する。例えば、光散乱の低減を利用した光学機器に応用する場合、フィルターの保留粒子径は小さいほどよいが、一般には保留粒子径０．１〜３．０μｍのものを用いることができる。 A glass fiber filter, a membrane filter, etc. are used for the filter used by this invention. At that time, the retained particle diameter of the filter can be appropriately determined according to the purpose. The reserved particle diameter is obtained from the leaked particle diameter when barium sulfate or the like specified in JIS 3801 is naturally filtered, and substantially corresponds to the average pore diameter of the filter. For example, when applied to an optical device using light scattering reduction, the smaller the retained particle diameter of the filter, the better. In general, a filter having a retained particle diameter of 0.1 to 3.0 μm can be used.
本発明にしたがって、カーボンナノチューブをアミド系極性有機溶媒及びポリビニルピロリドンからなる混合溶液に、超音波を照射しつつ溶解させると、カーボンナノチューブが均一に分散した分散溶媒が得ることができる。この溶液は、調製後１ヶ月を経過してもカーボンナノチューブが凝集することなく、長時間安定である。 According to the present invention, when a carbon nanotube is dissolved in a mixed solution composed of an amide polar organic solvent and polyvinylpyrrolidone while irradiating with ultrasonic waves, a dispersion solvent in which the carbon nanotubes are uniformly dispersed can be obtained. This solution is stable for a long time without agglomeration of carbon nanotubes even after one month from the preparation.
このように、本発明は、アミド系極性有機溶媒及びポリビニルピロリドンの混合溶液を用いることによって、カーボンナノチューブが凝集せずに均一に分散することができ、カーボンナノチューブ材料の様々な分野への応用が可能となる。 As described above, according to the present invention, by using a mixed solution of an amide polar organic solvent and polyvinyl pyrrolidone, the carbon nanotubes can be uniformly dispersed without agglomeration, and the carbon nanotube material can be applied to various fields. It becomes possible.
以下の実施例に示されるように、単層カーボンナノチューブ０．００５〜０．０５％を、ＮＭＰ溶液にポリビニルピロリドンを０．１〜１０％混合した溶液に超音波を照射することによって、カーボンナノチューブの分散性に極めて優れた極性有機溶媒を得ることができる。 As shown in the following examples, carbon nanotubes were irradiated by irradiating 0.005 to 0.05% single-walled carbon nanotubes with a solution obtained by mixing 0.1 to 10% polyvinyl pyrrolidone in an NMP solution. A polar organic solvent having extremely excellent dispersibility can be obtained.
ＨｉＰｃｏ法（高圧一酸化炭素法）により製作されたＳＷＮＴ（１ｍｇ）を、ＮＭＰ（Ｎ−メチルピロリドン）溶媒１０ｇと平均分子量１３０万のポリビニルピロリドン（ＰＶＰ）粉末１００ｍｇを加えた溶液に溶解し、超音波（２０ｋＨｚ）で１時間処理した後、攪拌した後、５０℃で１２時間熟成したところ、沈殿のない黒濁の液を得た。次に、このカーボンナノチューブ分散溶液を２つに分離し、ガラス繊維濾紙（ＧＣ−５０、保留粒子径０．５μｍ）およびメンブレンフィルター（ＦＲ−１００、孔径１μｍ）で濾過し、濾過液が黒色かどうか調べたところ、ともに黒色であることがわかった。これらの溶液は、３０日後もカーボンナノチューブが凝集沈殿することなく安定に存在した。 SWNT (1 mg) produced by the HiPco method (high pressure carbon monoxide method) was dissolved in a solution containing 10 g of NMP (N-methylpyrrolidone) solvent and 100 mg of polyvinylpyrrolidone (PVP) powder having an average molecular weight of 1.3 million. After being treated with sonic waves (20 kHz) for 1 hour and then stirred, the mixture was aged at 50 ° C. for 12 hours to obtain a black turbid liquid without precipitation. Next, this carbon nanotube dispersion solution is separated into two and filtered with glass fiber filter paper (GC-50, retained particle diameter 0.5 μm) and membrane filter (FR-100, pore diameter 1 μm). I checked it and found that both were black. These solutions existed stably without aggregation and precipitation of the carbon nanotubes even after 30 days.
実施例１と同様のプロセスをＰＶＰの配合量を変えて行った。ＨｉＰｃｏ法（高圧一酸化炭素法）により製作されたＳＷＮＴ（１ｍｇ）を、ＮＭＰ（Ｎ−メチルピロリドン）溶媒１０ｇと平均分子量１３０万のポリビニルピロリドン（ＰＶＰ）粉末５０ｍｇを加えて溶解し、超音波（２０ｋＨｚ）で１時間処理した後、攪拌した後、５０℃で１２時間熟成したところ、沈殿のない黒濁の液を得た。次に、このカーボンナノチューブ分散溶液を２つに分離し、ガラス繊維濾紙（ＧＣ−５０、保留粒子径０．５μｍ）およびメンブレンフィルター（ＦＲ−１００、孔径１μｍ）で濾過し、濾過液が黒色かどうか調べたところ、ともに黒色であることがわかった。これらの溶液は、３０日後もカーボンナノチューブが凝集沈殿することなく安定に存在した。 A process similar to that of Example 1 was performed by changing the blending amount of PVP. SWNT (1 mg) produced by the HiPco method (high-pressure carbon monoxide method) was dissolved by adding 10 g of NMP (N-methylpyrrolidone) solvent and 50 mg of polyvinylpyrrolidone (PVP) powder having an average molecular weight of 1.3 million, and ultrasonic ( (20 kHz) for 1 hour, followed by stirring, and then aging at 50 ° C. for 12 hours to obtain a black turbid liquid without precipitation. Next, this carbon nanotube dispersion solution is separated into two and filtered with glass fiber filter paper (GC-50, retained particle diameter 0.5 μm) and membrane filter (FR-100, pore diameter 1 μm). I checked it and found that both were black. These solutions existed stably without aggregation and precipitation of the carbon nanotubes even after 30 days.
実施例１と同様のプロセスをＰＶＰの平均分子量を変えて行った。ＨｉＰｃｏ法（高圧一酸化炭素法）により製作されたＳＷＮＴ（１ｍｇ）を、ＮＭＰ（Ｎ−メチルピロリドン）溶媒１０ｇと平均分子量３万５千のポリビニルピロリドン（ＰＶＰ）粉末１００ｍｇを加えて溶解し、超音波（２０ｋＨｚ）で１時間処理した後、攪拌した後、５０℃で１２時間熟成したところ、沈殿のない黒濁の液を得た。次に、このカーボンナノチューブ分散溶液を２つに分離し、ガラス繊維濾紙（ＧＣ−５０、保留粒子径０．５μｍ）およびメンブレンフィルター（ＦＲ−１００、孔径１μｍ）で濾過し、濾過液が黒色かどうか調べたところ、ともに黒色であることがわかったが、いずれも実施例１よりも薄色となった。これらの溶液は、３０日後もカーボンナノチューブが凝集沈殿することなく安定に存在した。 A process similar to that of Example 1 was performed by changing the average molecular weight of PVP. SWNT (1 mg) produced by HiPco method (high pressure carbon monoxide method) was dissolved by adding 10 g of NMP (N-methylpyrrolidone) solvent and 100 mg of polyvinylpyrrolidone (PVP) powder having an average molecular weight of 35,000, After being treated with sonic waves (20 kHz) for 1 hour and then stirred, the mixture was aged at 50 ° C. for 12 hours to obtain a black turbid liquid without precipitation. Next, this carbon nanotube dispersion solution is separated into two and filtered with glass fiber filter paper (GC-50, retained particle diameter 0.5 μm) and membrane filter (FR-100, pore diameter 1 μm). As a result, it was found that both were black, but both were lighter than Example 1. These solutions existed stably without aggregation and precipitation of the carbon nanotubes even after 30 days.
実施例１と同様のプロセスをレーザー蒸着法で製作したカーボンナノチューブで行った。レーザー蒸着法で製作したＳＷＮＴ（１ｍｇ）を、ＮＭＰ（Ｎ−メチルピロリドン）溶媒１０ｇと平均分子量１３０万のポリビニルピロリドン（ＰＶＰ）粉末１００ｍｇを加えて溶解し、超音波（２０ｋＨｚ）で１時間処理した後、攪拌した後、５０℃で１２時間熟成したところ、沈殿のない黒濁の液を得た。次に、このカーボンナノチューブ分散溶液を２つに分離し、ガラス繊維濾紙（ＧＣ−５０、保留粒子径０．５μｍ）およびメンブレンフィルター（ＦＲ−１００、孔径１μｍ）で濾過し、濾過液が黒色かどうか調べたところ、ともに黒色であることがわかった。これらの溶液は、３０日後もカーボンナノチューブが凝集沈殿することなく安定に存在した。 A process similar to that in Example 1 was performed on carbon nanotubes manufactured by laser vapor deposition. SWNT (1 mg) produced by the laser deposition method was dissolved by adding 10 g of NMP (N-methylpyrrolidone) solvent and 100 mg of polyvinylpyrrolidone (PVP) powder having an average molecular weight of 1.3 million, and treated with ultrasonic waves (20 kHz) for 1 hour. After stirring, the mixture was aged at 50 ° C. for 12 hours to obtain a black turbid liquid without precipitation. Next, this carbon nanotube dispersion solution is separated into two and filtered with glass fiber filter paper (GC-50, retained particle diameter 0.5 μm) and membrane filter (FR-100, pore diameter 1 μm). I checked it and found that both were black. These solutions existed stably without aggregation and precipitation of the carbon nanotubes even after 30 days.
実施例１ないし４で得られたカーボンナノチューブ分散溶液をそれぞれ、ブロック共重合ポリイミドのＮＭＰ溶液に混合し、ドクターブレード法により薄膜を形成した。それぞれの薄膜を光学顕微鏡で観察したところ、ナノチューブの凝集体は観察されなかった。また、それぞれの薄膜について、顕微ラマン測定および可視・近赤外光吸収スペクトル測定を行ったところ、ナノチューブのラマンシグナルおよび光吸収が検出された。このように、本発明で得られたカーボンナノチューブ分散溶液を用いることによって、ＳＷＮＴをポリマーに均一に分散できることが確認できた。 Each of the carbon nanotube dispersion solutions obtained in Examples 1 to 4 was mixed with an NMP solution of block copolymerized polyimide, and a thin film was formed by a doctor blade method. When each thin film was observed with an optical microscope, aggregates of nanotubes were not observed. Further, when each thin film was subjected to microscopic Raman measurement and visible / near-infrared light absorption spectrum measurement, Raman signals and light absorption of the nanotubes were detected. Thus, it was confirmed that the SWNTs can be uniformly dispersed in the polymer by using the carbon nanotube dispersion solution obtained in the present invention.
実施例１ないし４で得られたカーボンナノチューブ分散溶液の光散乱性をそれぞれ、動的光散乱測定装置によって確認したところ、極めて低い光散乱性を有することが確認できた。
（比較例１）
When the light scattering properties of the carbon nanotube dispersions obtained in Examples 1 to 4 were confirmed by a dynamic light scattering measurement device, it was confirmed that they had extremely low light scattering properties.
(Comparative Example 1)
実施例１と同様のプロセスをＰＶＰを用いずに行った。ＨｉＰｃｏ法（高圧一酸化炭素法）により製作されたＳＷＮＴ（１ｍｇ）を、ＮＭＰ（Ｎ−メチルピロリドン）溶媒１０ｇに入れて混合し、超音波（２０ｋＨｚ）で１時間処理したところ、黒濁の液を得た。 The same process as in Example 1 was performed without using PVP. When SWNT (1 mg) produced by the HiPco method (high pressure carbon monoxide method) was mixed in 10 g of NMP (N-methylpyrrolidone) solvent and treated with ultrasound (20 kHz) for 1 hour, a blackish liquid Got.
次に、黒濁したカーボンナノチューブ分散溶液を２つに分離し、ガラス繊維濾紙（ＧＡ−１００、保留粒子径１．０μｍ）及びガラス繊維濾紙（ＧＣ−５０、保留粒子径０．５μｍ）で濾過し、濾過液が黒色かどうか調べたところ、ともに透明であった。これらの液では、カーボンナノチューブが凝集しており、濾紙を通過しなかったことがわかる。 Next, the black turbid carbon nanotube dispersion solution is separated into two and filtered with glass fiber filter paper (GA-100, retention particle diameter 1.0 μm) and glass fiber filter paper (GC-50, retention particle diameter 0.5 μm). When the filtrate was examined for black color, both were transparent. In these liquids, it can be seen that the carbon nanotubes aggregated and did not pass through the filter paper.
本発明よって、カーボンナノチューブが均一に分散した極性有機溶媒が提供できるため、カーボンナノチューブを利用したポリマー系ナノコンポジットの製造、光散乱の低減を利用した光学機器への応用、電子放出用装置の製造など、多様な用途へのカーボンナノチューブ材料の製造が可能となる。
According to the present invention, it is possible to provide a polar organic solvent in which carbon nanotubes are uniformly dispersed. Therefore, production of polymer-based nanocomposites using carbon nanotubes, application to optical devices using reduction of light scattering, and manufacture of electron emission devices. For example, it is possible to manufacture carbon nanotube materials for various applications.
Claims (10)
A solution containing only fine carbon nanotubes by mixing carbon nanotubes with amide polar organic solvent and polyvinylpyrrolidone mixed solution while performing ultrasonic treatment, and then filtering with a retention particle diameter of 0.1 to 3.0 μm A method for producing a carbon nanotube dispersion solution.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003403504A JP4182215B2 (en) | 2003-12-02 | 2003-12-02 | Carbon nanotube-dispersed polar organic solvent and method for producing the same |
| US10/580,809 US7682590B2 (en) | 2003-11-27 | 2004-11-16 | Carbon nanotube dispersed polar organic solvent and method for producing the same |
| PCT/JP2004/017332 WO2005052053A1 (en) | 2003-11-27 | 2004-11-16 | Polar organic solvent containing dispersed carbon nanotube and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003403504A JP4182215B2 (en) | 2003-12-02 | 2003-12-02 | Carbon nanotube-dispersed polar organic solvent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005162877A true JP2005162877A (en) | 2005-06-23 |
| JP4182215B2 JP4182215B2 (en) | 2008-11-19 |
Family
ID=34726796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003403504A Expired - Lifetime JP4182215B2 (en) | 2003-11-27 | 2003-12-02 | Carbon nanotube-dispersed polar organic solvent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4182215B2 (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023149A (en) * | 2005-07-15 | 2007-02-01 | National Institute Of Advanced Industrial & Technology | Polyimide in which carbon nanotube is dispersed and conductivity is controlled |
| JP2007056136A (en) * | 2005-08-24 | 2007-03-08 | Mitsubishi Electric Corp | Carbon nanotube dispersion, its manufacturing method, carbon nanotube paste for printing and electron discharge source |
| JP2007182546A (en) * | 2005-12-06 | 2007-07-19 | Mitsubishi Rayon Co Ltd | Carbon nanotube-containing composition, composite and manufacturing process of those |
| JP2008024761A (en) * | 2006-07-19 | 2008-02-07 | Sumitomo Bakelite Co Ltd | Method for producing resin varnish and the resultant resin varnish |
| JP2008024522A (en) * | 2006-07-15 | 2008-02-07 | Toray Ind Inc | Carbon nanotube dispersion, its production method, and electroconductive material using it |
| JP2008138039A (en) * | 2006-11-30 | 2008-06-19 | Mitsubishi Materials Corp | Carbon nanofiber-dispersed polyimide varnish and coating film thereof |
| FR2915109A1 (en) * | 2007-04-20 | 2008-10-24 | Arkema France | PROCESS FOR PREPARING AN ALCOHOLIC SUSPENSION OF CARBON NANOTUBES AND SUSPENSION THUS OBTAINED |
| WO2009081986A1 (en) | 2007-12-26 | 2009-07-02 | Nano Carbon Technologies Co., Ltd. | Planar heating element obtained using dispersion of fine carbon fibers in water and process for producing the planar heating element |
| US7682590B2 (en) | 2003-11-27 | 2010-03-23 | National Institute Of Advanced Industrial Science And Technology | Carbon nanotube dispersed polar organic solvent and method for producing the same |
| WO2011065395A1 (en) | 2009-11-25 | 2011-06-03 | 日産化学工業株式会社 | Carbon nano-tube dispersant |
| WO2011108530A1 (en) * | 2010-03-01 | 2011-09-09 | 国立大学法人九州大学 | Particle coated with carbon nanotubes, and method for producing same |
| WO2012096317A1 (en) | 2011-01-12 | 2012-07-19 | 保土谷化学工業株式会社 | Thermosetting-resin-containing liquid having dispersed fine carbon fibers, and molded thermoset resin obtained therefrom |
| JP5019152B2 (en) * | 2004-01-20 | 2012-09-05 | 独立行政法人産業技術総合研究所 | Carbon nanotube-dispersed polyimide composition |
| JP2012245441A (en) * | 2011-05-25 | 2012-12-13 | Nissan Chem Ind Ltd | Carbon nanotube dispersant |
| JP2013036021A (en) * | 2011-07-08 | 2013-02-21 | Ube Industries Ltd | Carbon nanotube dispersant including polyamic acid |
| US8591771B2 (en) | 2006-04-14 | 2013-11-26 | Samsung Electronics Co., Ltd. | Dispersed solution of carbon nanotubes and method of preparing the same |
| KR20140031327A (en) | 2011-05-25 | 2014-03-12 | 닛산 가가쿠 고교 가부시키 가이샤 | Highly branched polymer and dispersant for carbon nanotubes |
| JPWO2012114590A1 (en) * | 2011-02-23 | 2014-07-07 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery electrode, method for producing the same, and non-aqueous electrolyte secondary battery |
| JP2014181140A (en) * | 2013-03-18 | 2014-09-29 | Ube Ind Ltd | Fine carbon fiber dispersion liquid and method for producing the same |
| WO2015029949A1 (en) | 2013-08-27 | 2015-03-05 | 日産化学工業株式会社 | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| US9892817B2 (en) | 2011-05-25 | 2018-02-13 | Nissan Chemical Industries, Ltd. | Conductive composition, and conductive complex |
| JP2018024788A (en) * | 2016-08-10 | 2018-02-15 | Ｋｊケミカルズ株式会社 | Adhesiveness improver for carbon material and composite material using the same |
| WO2019208637A1 (en) | 2018-04-26 | 2019-10-31 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and use for same |
| WO2019230820A1 (en) | 2018-06-01 | 2019-12-05 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube, carbon nanotube liquid dispersion, and use thereof |
| WO2020004095A1 (en) | 2018-06-28 | 2020-01-02 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and usage therefor |
| WO2020051970A1 (en) | 2018-09-14 | 2020-03-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented thin film, manufacturing method therefor and application thereof |
| WO2020054210A1 (en) | 2018-09-14 | 2020-03-19 | ダイキン工業株式会社 | Composition and multilayer body |
| WO2021080006A1 (en) | 2019-10-24 | 2021-04-29 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion liquid for nonaqueous electrolyte secondary battery, resin composition using same, mixture slurry, membrane electrode, and nonaqueous electrolyte secondary battery |
| WO2021152875A1 (en) | 2020-01-31 | 2021-08-05 | 東洋インキＳｃホールディングス株式会社 | Dispersing agent, conductive material dispersion, and slurry for electrode film |
| WO2021220773A1 (en) | 2020-04-27 | 2021-11-04 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, method for producing same, composition for secondary battery electrodes using same, electrode membrane, secondary battery and vehicle |
| WO2022009915A1 (en) | 2020-07-07 | 2022-01-13 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotubes, carbon nanotube dispersion liquid, and nonaqueous electrolyte secondary battery using same |
| WO2022050328A1 (en) | 2020-09-03 | 2022-03-10 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, conductive material dispersion containing binder resin, slurry for electrode membranes, electrode membrane and nonaqueous electrolyte secondary battery |
| WO2022050329A1 (en) | 2020-09-03 | 2022-03-10 | 東洋インキＳｃホールディングス株式会社 | Dispersion of electrically conductive material, dispersion of binder resin-containing electrically conductive material, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery |
| WO2022075387A1 (en) | 2020-10-09 | 2022-04-14 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and use thereof |
| WO2022102727A1 (en) | 2020-11-16 | 2022-05-19 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion, carbon nanotube resin composition, mixture slurry, electrode membrane, non-aqueous electrolyte secondary battery, and method for manufacturing mixture slurry |
| EP4186857A1 (en) | 2021-11-26 | 2023-05-31 | Nanocyl S.A. | Carbon nanotube dispersion, method for obtaining it and use of it in electrode materials |
-
2003
- 2003-12-02 JP JP2003403504A patent/JP4182215B2/en not_active Expired - Lifetime
Cited By (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7682590B2 (en) | 2003-11-27 | 2010-03-23 | National Institute Of Advanced Industrial Science And Technology | Carbon nanotube dispersed polar organic solvent and method for producing the same |
| JP5019152B2 (en) * | 2004-01-20 | 2012-09-05 | 独立行政法人産業技術総合研究所 | Carbon nanotube-dispersed polyimide composition |
| JP2007023149A (en) * | 2005-07-15 | 2007-02-01 | National Institute Of Advanced Industrial & Technology | Polyimide in which carbon nanotube is dispersed and conductivity is controlled |
| JP2007056136A (en) * | 2005-08-24 | 2007-03-08 | Mitsubishi Electric Corp | Carbon nanotube dispersion, its manufacturing method, carbon nanotube paste for printing and electron discharge source |
| JP2007182546A (en) * | 2005-12-06 | 2007-07-19 | Mitsubishi Rayon Co Ltd | Carbon nanotube-containing composition, composite and manufacturing process of those |
| US8591771B2 (en) | 2006-04-14 | 2013-11-26 | Samsung Electronics Co., Ltd. | Dispersed solution of carbon nanotubes and method of preparing the same |
| JP2008024522A (en) * | 2006-07-15 | 2008-02-07 | Toray Ind Inc | Carbon nanotube dispersion, its production method, and electroconductive material using it |
| JP2008024761A (en) * | 2006-07-19 | 2008-02-07 | Sumitomo Bakelite Co Ltd | Method for producing resin varnish and the resultant resin varnish |
| JP2008138039A (en) * | 2006-11-30 | 2008-06-19 | Mitsubishi Materials Corp | Carbon nanofiber-dispersed polyimide varnish and coating film thereof |
| FR2915109A1 (en) * | 2007-04-20 | 2008-10-24 | Arkema France | PROCESS FOR PREPARING AN ALCOHOLIC SUSPENSION OF CARBON NANOTUBES AND SUSPENSION THUS OBTAINED |
| WO2008145910A2 (en) * | 2007-04-20 | 2008-12-04 | Arkema France | Method for preparing an alcoholic suspension of carbon nanotubes and suspension thus obtained |
| WO2008145910A3 (en) * | 2007-04-20 | 2009-10-15 | Arkema France | Method for preparing an alcoholic suspension of carbon nanotubes and suspension thus obtained |
| WO2009081986A1 (en) | 2007-12-26 | 2009-07-02 | Nano Carbon Technologies Co., Ltd. | Planar heating element obtained using dispersion of fine carbon fibers in water and process for producing the planar heating element |
| WO2011065395A1 (en) | 2009-11-25 | 2011-06-03 | 日産化学工業株式会社 | Carbon nano-tube dispersant |
| US9123893B2 (en) | 2009-11-25 | 2015-09-01 | Nissan Chemical Industries, Ltd. | Carbon nano-tube dispersant |
| WO2011108530A1 (en) * | 2010-03-01 | 2011-09-09 | 国立大学法人九州大学 | Particle coated with carbon nanotubes, and method for producing same |
| WO2012096317A1 (en) | 2011-01-12 | 2012-07-19 | 保土谷化学工業株式会社 | Thermosetting-resin-containing liquid having dispersed fine carbon fibers, and molded thermoset resin obtained therefrom |
| JPWO2012114590A1 (en) * | 2011-02-23 | 2014-07-07 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery electrode, method for producing the same, and non-aqueous electrolyte secondary battery |
| KR20140031327A (en) | 2011-05-25 | 2014-03-12 | 닛산 가가쿠 고교 가부시키 가이샤 | Highly branched polymer and dispersant for carbon nanotubes |
| JP2012245441A (en) * | 2011-05-25 | 2012-12-13 | Nissan Chem Ind Ltd | Carbon nanotube dispersant |
| US9892817B2 (en) | 2011-05-25 | 2018-02-13 | Nissan Chemical Industries, Ltd. | Conductive composition, and conductive complex |
| US10138323B2 (en) | 2011-05-25 | 2018-11-27 | Nissan Chemical Industries, Ltd. | Highly branched polymer and dispersant for carbon nanotubes |
| JP2013036021A (en) * | 2011-07-08 | 2013-02-21 | Ube Industries Ltd | Carbon nanotube dispersant including polyamic acid |
| JP2014181140A (en) * | 2013-03-18 | 2014-09-29 | Ube Ind Ltd | Fine carbon fiber dispersion liquid and method for producing the same |
| WO2015029949A1 (en) | 2013-08-27 | 2015-03-05 | 日産化学工業株式会社 | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| KR20160045792A (en) | 2013-08-27 | 2016-04-27 | 닛산 가가쿠 고교 가부시키 가이샤 | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| KR20160149324A (en) | 2013-08-27 | 2016-12-27 | 닛산 가가쿠 고교 가부시키 가이샤 | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| US11326010B2 (en) | 2013-08-27 | 2022-05-10 | Nissan Chemical Industries, Ltd. | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| EP3695899A1 (en) | 2013-08-27 | 2020-08-19 | Nissan Chemical Corporation | Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material |
| JP2018024788A (en) * | 2016-08-10 | 2018-02-15 | Ｋｊケミカルズ株式会社 | Adhesiveness improver for carbon material and composite material using the same |
| KR20210003144A (en) | 2018-04-26 | 2021-01-11 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion and its use |
| WO2019208637A1 (en) | 2018-04-26 | 2019-10-31 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and use for same |
| WO2019230820A1 (en) | 2018-06-01 | 2019-12-05 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube, carbon nanotube liquid dispersion, and use thereof |
| US11286164B2 (en) | 2018-06-01 | 2022-03-29 | Toyo Ink Sc Holdings Co., Ltd. | Carbon nanotube, carbon nanotube dispersion, and use thereof |
| KR20210013704A (en) | 2018-06-01 | 2021-02-05 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube, carbon nanotube dispersion and use thereof |
| WO2020004095A1 (en) | 2018-06-28 | 2020-01-02 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and usage therefor |
| US11923546B2 (en) | 2018-06-28 | 2024-03-05 | Toyo Ink Sc Holdings Co., Ltd. | Carbon nanotube dispersion and use thereof |
| KR20210013224A (en) | 2018-06-28 | 2021-02-03 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion and its use |
| KR20230058188A (en) | 2018-06-28 | 2023-05-02 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion and usage therefor |
| WO2020051970A1 (en) | 2018-09-14 | 2020-03-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented thin film, manufacturing method therefor and application thereof |
| US11225581B2 (en) | 2018-09-14 | 2022-01-18 | Suzhou Institute Of Nano-Tech And Nano-Bionics (Sinano), Chinese Academy Of Sciences | Carbon nanotube aligned film as well as preparation method and application thereof |
| WO2020054210A1 (en) | 2018-09-14 | 2020-03-19 | ダイキン工業株式会社 | Composition and multilayer body |
| KR20210041605A (en) | 2018-09-14 | 2021-04-15 | 다이킨 고교 가부시키가이샤 | Composition and laminate |
| WO2021080006A1 (en) | 2019-10-24 | 2021-04-29 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion liquid for nonaqueous electrolyte secondary battery, resin composition using same, mixture slurry, membrane electrode, and nonaqueous electrolyte secondary battery |
| KR20220088742A (en) | 2019-10-24 | 2022-06-28 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion for non-aqueous electrolyte secondary battery, resin composition using same, mixture slurry, electrode film, and non-aqueous electrolyte secondary battery |
| KR20220133928A (en) | 2020-01-31 | 2022-10-05 | 토요잉크Sc홀딩스주식회사 | Dispersant, conductive material dispersion, and slurry for electrode film |
| US11827830B2 (en) | 2020-01-31 | 2023-11-28 | Toyo Ink Sc Holdings Co., Ltd. | Dispersant, conductive material dispersion and slurry for electrode film |
| WO2021152875A1 (en) | 2020-01-31 | 2021-08-05 | 東洋インキＳｃホールディングス株式会社 | Dispersing agent, conductive material dispersion, and slurry for electrode film |
| WO2021220773A1 (en) | 2020-04-27 | 2021-11-04 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, method for producing same, composition for secondary battery electrodes using same, electrode membrane, secondary battery and vehicle |
| KR20230007337A (en) | 2020-04-27 | 2023-01-12 | 토요잉크Sc홀딩스주식회사 | Conductive material dispersion and its manufacturing method, and composition for secondary battery electrode using the same, electrode film, secondary battery, vehicle |
| WO2022009915A1 (en) | 2020-07-07 | 2022-01-13 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotubes, carbon nanotube dispersion liquid, and nonaqueous electrolyte secondary battery using same |
| KR20230034966A (en) | 2020-07-07 | 2023-03-10 | 토요잉크Sc홀딩스주식회사 | Carbon nanotubes, carbon nanotube dispersions, non-aqueous electrolyte secondary batteries using them |
| KR20220042364A (en) | 2020-09-03 | 2022-04-05 | 토요잉크Sc홀딩스주식회사 | Conductive material dispersion, binder resin-containing conductive material dispersion, electrode film slurry, electrode film, and non-aqueous electrolyte secondary battery |
| US11469421B2 (en) | 2020-09-03 | 2022-10-11 | Toyo Ink Sc Holdings Co., Ltd. | Conductive material dispersion, binder resin-containing conductive material dispersion, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery |
| KR20220044731A (en) | 2020-09-03 | 2022-04-11 | 토요잉크Sc홀딩스주식회사 | Conductive material dispersion, binder resin-containing conductive material dispersion, electrode film slurry, electrode film, and non-aqueous electrolyte secondary battery |
| US11658303B2 (en) | 2020-09-03 | 2023-05-23 | Toyo Ink Sc Holdings Co., Ltd. | Conductive material dispersion, binder resin-containing conductive material dispersion, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery |
| WO2022050329A1 (en) | 2020-09-03 | 2022-03-10 | 東洋インキＳｃホールディングス株式会社 | Dispersion of electrically conductive material, dispersion of binder resin-containing electrically conductive material, slurry for electrode film, electrode film, and non-aqueous electrolyte secondary battery |
| WO2022050328A1 (en) | 2020-09-03 | 2022-03-10 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, conductive material dispersion containing binder resin, slurry for electrode membranes, electrode membrane and nonaqueous electrolyte secondary battery |
| WO2022075387A1 (en) | 2020-10-09 | 2022-04-14 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion and use thereof |
| KR20230084248A (en) | 2020-10-09 | 2023-06-12 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion and its use |
| WO2022102727A1 (en) | 2020-11-16 | 2022-05-19 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube dispersion, carbon nanotube resin composition, mixture slurry, electrode membrane, non-aqueous electrolyte secondary battery, and method for manufacturing mixture slurry |
| KR20230107202A (en) | 2020-11-16 | 2023-07-14 | 토요잉크Sc홀딩스주식회사 | Carbon nanotube dispersion, carbon nanotube resin composition, mixture slurry, electrode film, non-aqueous electrolyte secondary battery, and method for preparing mixture slurry |
| EP4186857A1 (en) | 2021-11-26 | 2023-05-31 | Nanocyl S.A. | Carbon nanotube dispersion, method for obtaining it and use of it in electrode materials |
| WO2023094550A1 (en) | 2021-11-26 | 2023-06-01 | Nanocyl Sa | Improved catalyst for mwcnt production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4182215B2 (en) | 2008-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4182215B2 (en) | Carbon nanotube-dispersed polar organic solvent and method for producing the same | |
| US7682590B2 (en) | Carbon nanotube dispersed polar organic solvent and method for producing the same | |
| JP3837557B2 (en) | Carbon nanotube dispersion solution and method for producing the same | |
| EP2464698B1 (en) | Solvent-based and water-based carbon nanotube inks with removable additives | |
| US11643328B2 (en) | Method of producing surface-treated carbon nanostructures | |
| Shirazi et al. | Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization | |
| KR100881317B1 (en) | Carbon nanotube-carbon nanohorn complex and method for producing the same | |
| JP4182214B2 (en) | Carbon nanotube dispersed polar organic solvent | |
| Manivannan et al. | Dispersion of single-walled carbon nanotubes in aqueous and organic solvents through a polymer wrapping functionalization | |
| JP2008274502A (en) | Fine carbon fiber aggregate for redispersion and method for producing the same | |
| JP2008517863A (en) | Improved ozonolysis of carbon nanotubes | |
| JP2005290292A (en) | Saturable absorber of carbon nanotube-dispersed polyimide | |
| Adenuga et al. | Preparation of water soluble carbon nanotubes and assessment of their biological activity in embryonic zebrafish | |
| Stancu et al. | Purification of multiwall carbon nanotubes obtained by AC arc discharge method | |
| JPWO2017115708A1 (en) | Fibrous carbon nanostructure dispersion | |
| Chiu et al. | Chemical modification of multiwalled carbon nanotube with the liquid phase method | |
| Manivannan et al. | Fabrication and effect of post treatment on flexible single-walled carbon nanotube films | |
| JP6275743B2 (en) | Solvent-based and water-based carbon nanotube inks with removable additives | |
| JP2007231127A (en) | Liquid crystalline compound-carbon nanotube composite material and method for producing the same composite material | |
| JPWO2017104772A1 (en) | Fibrous carbon nanostructure dispersion | |
| JP4761183B2 (en) | Carbon nanotube-dispersed polyimide and method for producing the same | |
| JP2003205499A (en) | Porous carbon nano-structure and its manufacturing method | |
| JP4452804B2 (en) | Optical element | |
| JP2006219358A (en) | Nanocarbon and method for producing the nanocarbon | |
| KR101249403B1 (en) | Nanocomposite membranes and method for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050616 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080507 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080704 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080805 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4182215 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |