JP6175700B2 - CNT dispersion - Google Patents
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- JP6175700B2 JP6175700B2 JP2011094925A JP2011094925A JP6175700B2 JP 6175700 B2 JP6175700 B2 JP 6175700B2 JP 2011094925 A JP2011094925 A JP 2011094925A JP 2011094925 A JP2011094925 A JP 2011094925A JP 6175700 B2 JP6175700 B2 JP 6175700B2
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- 239000006185 dispersion Substances 0.000 title claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000002270 dispersing agent Substances 0.000 claims description 59
- 239000000084 colloidal system Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 12
- 239000008119 colloidal silica Substances 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 description 154
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 139
- 229910021393 carbon nanotube Inorganic materials 0.000 description 139
- 239000000243 solution Substances 0.000 description 30
- 238000009210 therapy by ultrasound Methods 0.000 description 20
- 238000004220 aggregation Methods 0.000 description 17
- 230000002776 aggregation Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 238000004062 sedimentation Methods 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000002612 dispersion medium Substances 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Description
本発明は、ＣＮＴ（カーボンナノチューブ）を液中で分散させたＣＮＴ分散液に関する。 The present invention relates to C NT dispersion obtained by dispersing CNT (carbon nanotube) in the liquid.
ＣＮＴは、電界放出特性、機械的強度、電気伝導性、熱伝導性、化学的安定性等において優れた特性を有する。そのため、ＣＮＴを含む材料は、電界放出型ディスプレイ（ＦＥＤ）、透明電極、燃料電池、導電性樹脂、ヒートシンク、宇宙エレベータ、化学センサ等、様々な用途において期待されている。 CNTs have excellent characteristics in field emission characteristics, mechanical strength, electrical conductivity, thermal conductivity, chemical stability, and the like. Therefore, a material containing CNT is expected in various applications such as a field emission display (FED), a transparent electrode, a fuel cell, a conductive resin, a heat sink, a space elevator, and a chemical sensor.
ＣＮＴを含む材料を製造するとき、ＣＮＴが分散媒中で安定に分散している分散液（ＣＮＴ分散液）を調製する必要がある。ＣＮＴを分散媒中で安定に分散させるために、ＣＮＴを酸で処理する方法（非特許文献１参照）、ＣＮＴをプラズマで処理する方法（特許文献１参照）、界面活性剤を添加する方法（特許文献２参照）等が提案されている。 When producing a material containing CNTs, it is necessary to prepare a dispersion (CNT dispersion) in which CNTs are stably dispersed in a dispersion medium. In order to stably disperse CNT in a dispersion medium, a method of treating CNT with an acid (see Non-Patent Document 1), a method of treating CNT with plasma (see Patent Document 1), and a method of adding a surfactant ( Patent Document 2) has been proposed.
しかしながら、ＣＮＴを酸やプラズマで処理すると、ＣＮＴ表面に欠陥を形成し、ＣＮＴが元来有している優れた特性（電気伝導性、熱伝導性、機械強度等）を低下させてしまう。 However, when CNTs are treated with acid or plasma, defects are formed on the surface of the CNTs, and the excellent characteristics (electric conductivity, thermal conductivity, mechanical strength, etc.) inherent to the CNTs are reduced.
また、従来の界面活性剤（通常、ドデシル硫酸ナトリウム等の有機系材料）を添加する方法では、分散媒中におけるＣＮＴ濃度が高い場合、ＣＮＴを安定に分散できず、ＣＮＴの凝集や沈降が生じてしまう。 In addition, when a conventional surfactant (usually an organic material such as sodium dodecyl sulfate) is added, if the CNT concentration in the dispersion medium is high, the CNT cannot be stably dispersed, and CNT aggregation and sedimentation occur. End up.
本発明は以上の点に鑑みなされたものであり、ＣＮＴの特性を低下させず、分散媒中でＣＮＴを安定に分散させることができるＣＮＴ分散液を提供することを目的とする。 The present invention is intended is been made in consideration of these circumstances, without reducing the properties of the CNT, and an object thereof is to provide a C NT dispersion can be stably dispersed CNT in the dispersion medium.
ＣＮＴ分散剤は、シリカコロイド、及び／又は遷移金属の酸化物のコロイドを含むことを特徴とする。
このＣＮＴ分散剤を用いれば、ＣＮＴを分散媒中で安定に分散させることができる。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。
The CNT dispersant is characterized by containing a colloid of silica and / or a colloid of an oxide of a transition metal.
The use of CNT dispersant this may be stably disperse CNT in a dispersion medium. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
ＣＮＴ分散剤の使用方法としては、例えば、ＣＮＴ分散剤と、ＣＮＴの粉末とを混合する方法がある。また、ＣＮＴ分散剤と、ＣＮＴを含む分散液とを混合してもよい。 The use of C NT dispersants, for example, a method of mixing a C NT dispersant, a powder of CNT. Further, a C NT dispersant may be mixed with a dispersion containing a CNT.
ＣＮＴ分散剤におけるコロイド粒子の粒径は、１〜１１０ｎｍの範囲が好適である。この範囲内であることにより、ＣＮＴの分散性が一層向上する。
また、ＣＮＴ分散剤におけるコロイド粒子の濃度は、０．０５〜３０重量％の範囲が好適である。０．０５重量％以上であることにより、ＣＮＴの分散性が一層向上する。また、３０重量％以下であることにより、コロイド粒子がゲル化しにくい。イオン交換により作製したシリカコロイドを含むＣＮＴ分散剤の場合は、０．０５〜５重量％の範囲が好適である。
The particle size of the colloidal particles in C NT dispersant range 1~110nm are preferred. By being in this range, the dispersibility of CNT is further improved.
The concentration of colloidal particles in the CNT dispersant is preferably in the range of 0.05 to 30% by weight. The dispersibility of CNT improves further by being 0.05 weight% or more. Further, the colloidal particles are hardly gelled by being 30% by weight or less. In the case of a CNT dispersant containing silica colloid prepared by ion exchange, a range of 0.05 to 5% by weight is suitable.
前記遷移金属の酸化物としては、例えば、ジルコニア、セリア、チタニア、及び酸化亜鉛から成る群から選ばれる１種以上が挙げられる。これらのコロイド粒子は、アルミナのコロイド粒子よりも、ＣＮＴの分散性が一層高い。 Examples of the transition metal oxide include one or more selected from the group consisting of zirconia, ceria, titania, and zinc oxide. These colloidal particles have higher CNT dispersibility than alumina colloidal particles.
ＣＮＴ分散剤におけるｐＨは、７以下であることが好ましい。この範囲内であることにより、ＣＮＴの分散性が一層向上する。
ＣＮＴ分散剤に含まれる分散媒としては、例えば、水、ＩＰＡ、エチレングリコール等が挙げられる。
PH in C NT dispersant is preferably 7 or less. By being in this range, the dispersibility of CNT is further improved.
As the dispersion medium contained in the C NT dispersants, for example, water, IPA, and ethylene glycol.
ＣＮＴ分散剤（シリカコロイドを含むもの）は、例えば、以下のように製造することができる。まず、ケイ酸ソーダ（１〜５号ケイ酸ソーダ、高純度ケイ酸ソーダ）を、ＳｉＯ2濃度が１〜５重量％となるように希釈する。この希釈したケイ酸ソーダを、強酸性陽イオン交換樹脂に通す。このとき、ケイ酸ソーダのＮａイオンがＨイオンに置換される。その結果、シリカゾル（活性ケイ酸）が得られる。このシリカゾルを、シリカコロイドを含むＣＮＴ分散剤とすることができる。また、硫酸とケイ酸ソーダとから調製した酸性シリカゾル等も、シリカコロイドを含むＣＮＴ分散剤とすることができる。 A CNT dispersant (containing a silica colloid) can be produced, for example, as follows. First, sodium silicate (No. 1-5 sodium silicate, high-purity sodium silicate) is diluted so that the SiO 2 concentration becomes 1 to 5% by weight. The diluted sodium silicate is passed through a strongly acidic cation exchange resin. At this time, sodium ions of sodium silicate are replaced with H ions. As a result, silica sol (active silicic acid) is obtained. This silica sol can be used as a CNT dispersant containing silica colloid. An acidic silica sol prepared from sulfuric acid and sodium silicate can also be used as a CNT dispersant containing a silica colloid.
本発明のＣＮＴ分散液は、上述したＣＮＴ分散剤と、ＣＮＴとを含むことを特徴とする。本発明のＣＮＴ分散液は、上述したＣＮＴ分散剤を含むことにより、ＣＮＴを分散媒中で安定に分散させることができる。 The CNT dispersion liquid of the present invention includes the CNT dispersant described above and CNT. The CNT dispersion liquid of the present invention can stably disperse CNTs in a dispersion medium by including the above-described CNT dispersant.
ＣＮＴ分散液におけるコロイド粒子の濃度は、０．０５〜３０重量％の範囲である。０．０５重量％以上であることにより、ＣＮＴの分散性が一層向上する。また、３０重量％以下であることにより、コロイド粒子がゲル化しにくい。イオン交換により作製したシリカコロイドを含むＣＮＴ分散液の場合は、０．０５〜５重量％の範囲が好適である。 The concentration of colloidal particles in the CNT dispersion is in the range of 0.05 to 30% by weight. The dispersibility of CNT improves further by being 0.05 weight% or more. Further, the colloidal particles are hardly gelled by being 30% by weight or less. In the case of a CNT dispersion containing silica colloid prepared by ion exchange, a range of 0.05 to 5% by weight is suitable.
本発明のＣＮＴ分散液におけるｐＨは、７以下である。この範囲内であることにより、ＣＮＴの分散性が一層向上する。
本発明のＣＮＴ分散液における分散媒は、ＣＮＴ分散剤に含まれていた分散媒であってもよいし、それとは別に加えられた分散媒であってもよいし、ＣＮＴ分散剤に含まれていた分散媒と他の分散剤との混合物であってもよい。
The pH in the CNT dispersion of the present invention is 7 or less . By being in this range, the dispersibility of CNT is further improved.
The dispersion medium in the CNT dispersion liquid of the present invention may be a dispersion medium contained in the CNT dispersion agent, or may be a dispersion medium added separately from the dispersion medium, or may be contained in the CNT dispersion agent. It may be a mixture of a dispersion medium and other dispersant.
本発明のＣＮＴ分散液は、例えば、ＣＮＴ分散剤と、ＣＮＴとを混合させることで製造できる。混合後、分散処理（例えば、超音波処理、機械的な攪拌処理等）を行うことが好ましい。分散処理を行うことにより、ＣＮＴの分散性が一層向上する。 The CNT dispersion of the present invention can be produced, for example, by mixing a CNT dispersant and CNT. After mixing, it is preferable to perform a dispersion treatment (for example, ultrasonic treatment, mechanical stirring treatment, etc.). By performing the dispersion treatment, the dispersibility of the CNTs is further improved.
本発明の実施形態を説明する。 An embodiment of the present invention will be described.
１．ＣＮＴ分散剤の製造
５号ケイ酸ナトリウム水溶液(SiO2濃度25.6重量％、モル比3.7)を、SiO2濃度が１重量％となるようにイオン交換水で希釈した。この希釈したケイ酸ナトリウム溶液を、カラムに充てんした強酸性陽イオン交換樹脂に通液することで、SiO2濃度1重量％のシリカコロイド溶液(ｐＨ3.9)を調製した。このシリカコロイド溶液を、ＣＮＴ分散剤１Ａとする。
1. Production of CNT dispersing agent No. 5 sodium silicate aqueous solution (SiO 2 concentration 25.6 wt%, molar ratio 3.7) was diluted with ion-exchanged water so that the SiO 2 concentration became 1 wt%. The diluted sodium silicate solution was passed through a strongly acidic cation exchange resin packed in a column to prepare a silica colloid solution (pH 3.9) having a SiO 2 concentration of 1% by weight. This silica colloid solution is designated as CNT dispersant 1A.
また、3ｇのＣＮＴ分散剤１Ａに、イオン交換水27ｇを加えて希釈することにより、SiO2濃度0.1重量％のシリカコロイド溶液(ｐＨ5.2)を調製した。このシリカコロイド溶液を、ＣＮＴ分散剤１Ｂとする。 Further, a silica colloid solution (pH 5.2) having a SiO 2 concentration of 0.1% by weight was prepared by adding and diluting 27 g of ion exchange water to 3 g of the CNT dispersant 1A. This silica colloid solution is designated as CNT dispersant 1B.
また、0.3ｇのＣＮＴ分散剤１Ａに、イオン交換水29.7ｇを加えて希釈することにより、SiO2濃度0.01重量％のシリカコロイド溶液(ｐＨ5.6)を調製した。このシリカコロイド溶液を、ＣＮＴ分散剤１Ｃとする。 Further, 29.7 g of ion exchange water was added to 0.3 g of CNT dispersant 1A and diluted to prepare a silica colloid solution (pH 5.6) having a SiO 2 concentration of 0.01 wt%. This silica colloid solution is designated as CNT dispersant 1C.
また、ＣＮＴ分散剤１ＡのｐＨを、1mol/lの塩酸を加えることで、1.5、2.5、3.4にそれぞれ調整した。ｐＨが1.5であるシリカコロイド溶液をＣＮＴ分散剤１Ｄとし、ｐＨが2.5であるシリカコロイド溶液をＣＮＴ分散剤１Ｅとし、ｐＨが3.4であるシリカコロイド溶液をＣＮＴ分散剤１Ｆとする。また、ＣＮＴ分散剤１ＡのｐＨを、0.1mol/lのアンモニア水を用いて、4.5、5.5、6.4にそれぞれ調整した。ｐＨが4.5であるシリカコロイド溶液をＣＮＴ分散剤１Ｇとし、ｐＨが5.5であるシリカコロイド溶液をＣＮＴ分散剤１Ｈとし、ｐＨが6.4であるシリカコロイド溶液をＣＮＴ分散剤１Ｉとする。 Further, the pH of the CNT dispersant 1A was adjusted to 1.5, 2.5, and 3.4 by adding 1 mol / l hydrochloric acid, respectively. A silica colloid solution having a pH of 1.5 is referred to as CNT dispersant 1D, a silica colloid solution having a pH of 2.5 is referred to as CNT dispersant 1E, and a silica colloid solution having a pH of 3.4 is referred to as CNT dispersant 1F. Further, the pH of the CNT dispersant 1A was adjusted to 4.5, 5.5, and 6.4 using 0.1 mol / l ammonia water, respectively. A silica colloid solution having a pH of 4.5 is referred to as CNT dispersant 1G, a silica colloid solution having a pH of 5.5 is referred to as CNT dispersant 1H, and a silica colloid solution having a pH of 6.4 is referred to as CNT dispersant 1I.
また、市販のシリカコロイド溶液である、日産化学工業製のシリカゾルスノーテックスOXS(ｐＨ2〜4、粒径4〜6ｎｍ、SiO2濃度10重量％)、スノーテックスOS(ｐＨ2〜4、粒径8〜11ｎｍ、SiO2濃度20重量％)、スノーテックスOUP(ｐＨ2〜4、粒径40〜100ｎｍ、SiO2濃度15重量％)を、それぞれ、ＣＮＴ分散剤１Ｊ、１Ｋ、１Ｌとする。 In addition, commercially available silica colloid solutions, silica sol snowtex OXS (pH 2-4, particle size 4-6 nm, SiO 2 concentration 10% by weight) manufactured by Nissan Chemical Industries, Snowtex OS (pH 2-4, particle size 8-8) 11 nm, SiO 2 concentration 20% by weight) and Snowtex OUP (pH 2-4, particle size 40-100 nm, SiO 2 concentration 15% by weight) are designated as CNT dispersants 1J, 1K, 1L, respectively.
なお、本実施例における各ＣＮＴ分散剤の概略を表１に示す。 In addition, Table 1 shows an outline of each CNT dispersant in this example.
また、表１には、後述する実施例２〜７で調製する各ＣＮＴ分散剤の概略も示す。
２. ＣＮＴ分散液の製造
30ｇのＣＮＴ分散剤１Ａに、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。ＣＮＴとしては、図１（ａ）に示すＶＧＣＦ−Ｈ（Vapor Grown Carbon Fiber、昭和電工製）と図１（ｂ）に示すＶＧＣＦ−Ｘ（Vapor Grown Carbon Fiber、昭和電工製）を、それぞれ用いた。ＶＧＣＦ−Ｈは直径150ｎｍ、長さ6μｍのＣＮＴである。また、ＶＧＣＦ−Ｘは、直径15ｎｍ、長さ３μｍのＣＮＴである。なお、後述する実施例２以降でも、同様のＣＮＴを用いた。
Table 1 also shows an outline of each CNT dispersant prepared in Examples 2 to 7 described later.
2. Production of CNT dispersion
0.15 g of CNT was added to 30 g of CNT dispersant 1A and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. As CNT, VGCF-H (Vapor Grown Carbon Fiber, Showa Denko) shown in FIG. 1A and VGCF-X (Vapor Grown Carbon Fiber, Showa Denko) shown in FIG. . VGCF-H is a CNT having a diameter of 150 nm and a length of 6 μm. VGCF-X is a CNT having a diameter of 15 nm and a length of 3 μm. Similar CNTs were used in Example 2 and later described later.
また、ＣＮＴ分散剤１Ａの代わりに、ＣＮＴ分散剤１Ｂ〜１Ｌをそれぞれ用いて、上と同様に、ＣＮＴ分散液を得た。
得られた各ＣＮＴ分散液を、超音波処理後、24時間静置し、凝集や沈降が生じたかを確認した。その結果を上記表１に示す。表１において「○」は凝集や沈降が生じないことを表し、「×」は凝集や沈降が生じたことを表す。
Moreover, the CNT dispersion liquid was obtained similarly to the above using each of the CNT dispersants 1B to 1L instead of the CNT dispersant 1A.
Each obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment to confirm whether aggregation or sedimentation occurred. The results are shown in Table 1 above. In Table 1, “◯” indicates that aggregation or sedimentation does not occur, and “x” indicates that aggregation or sedimentation has occurred.
また、30ｇのＣＮＴ分散剤１Ａに、1.5ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。このＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降がないことを確認した。 Further, 1.5 g of CNT was added to 30 g of CNT dispersant 1A, and ultrasonic treatment was performed for 20 minutes to obtain a CNT dispersion. Even if this CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, it was confirmed that there was no aggregation or sedimentation.
また、30ｇのＣＮＴ分散剤１Ａに、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た後、アンモニア水を用いて、このＣＮＴ分散液のｐＨを9.5に調整した。その後、２４時間静置しても、凝集や沈降は生じなかった。 In addition, 0.15 g of CNT was added to 30 g of CNT dispersant 1A, subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion, and then the pH of this CNT dispersion was adjusted to 9.5 using aqueous ammonia. It was adjusted. Then, even if it left still for 24 hours, aggregation and sedimentation did not arise.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
なお、ＣＮＴ分散剤１ＡのｐＨを、0.1mol/Lのアンモニア水を用いて、7.4、8.6、9.5としてから、上と同様にＣＮＴを添加し、20分間の超音波処理を行ったところ、ｐＨが酸性である場合に比べて、凝集や沈降が生じ易かった。 The pH of the CNT dispersant 1A was adjusted to 7.4, 8.6, and 9.5 using 0.1 mol / L ammonia water, and CNT was added in the same manner as above, followed by ultrasonic treatment for 20 minutes. Aggregation and sedimentation were more likely to occur than when the solution was acidic.
日産化学工業製のジルコニアコロイド溶液(ｐＨ2.9、粒径80〜110ｎｍ、ZrO2濃度30重量％)を、ＣＮＴ分散剤２とする。
30ｇのＣＮＴ分散剤２に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。得られたＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降は生じなかった。
A zirconia colloidal solution (pH 2.9, particle size 80 to 110 nm, ZrO 2 concentration 30% by weight) manufactured by Nissan Chemical Industries is used as CNT dispersant 2.
0.15 g of CNT was added to 30 g of CNT dispersant 2 and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. Even when the obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, no aggregation or sedimentation occurred.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
日産化学工業製のセリアコロイド溶液(ｐＨ3.1、粒径30〜80ｎｍ、CeO2濃度20重量％)を、ＣＮＴ分散剤３とする。
30ｇのＣＮＴ分散剤３に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。得られたＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降は生じなかった。
A ceria colloid solution (pH 3.1, particle size 30 to 80 nm, CeO 2 concentration 20% by weight) manufactured by Nissan Chemical Industries is used as the CNT dispersant 3.
0.15 g of CNT was added to 30 g of CNT dispersant 3 and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. Even when the obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, no aggregation or sedimentation occurred.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
0.2mol/lの硝酸亜鉛水溶液とアンモニア水とを、それぞれ100ml調製した後に混合した。この結果得られた沈殿物を3000ｒｐｍで10分間遠心分離させ、未反応成分を除去した。これにエチレングリコール（ＥＧ）を溶媒として添加して、40℃で24時間静置して酸化亜鉛コロイド溶液を得た。この酸化亜鉛コロイド溶液をＣＮＴ分散剤４とする。ＣＮＴ分散剤４における酸化亜鉛の濃度は8重量％であり、ＣＮＴ分散剤４のｐＨは5.7である。 100 ml each of 0.2 mol / l aqueous zinc nitrate solution and aqueous ammonia were prepared and then mixed. The resulting precipitate was centrifuged at 3000 rpm for 10 minutes to remove unreacted components. Ethylene glycol (EG) was added to this as a solvent, and allowed to stand at 40 ° C. for 24 hours to obtain a zinc oxide colloid solution. This zinc oxide colloid solution is used as CNT dispersant 4. The concentration of zinc oxide in the CNT dispersant 4 is 8% by weight, and the pH of the CNT dispersant 4 is 5.7.
30ｇのＣＮＴ分散剤４に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。得られたＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降は生じなかった。 0.15 g of CNT was added to 30 g of CNT dispersant 4 and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. Even when the obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, no aggregation or sedimentation occurred.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
シリカコロイド粒子が、分散媒であるイソプロピルアルコール(ＩＰＡ)中に分散しているコロイド溶液を、ＣＮＴ分散剤５とする。シリカコロイド粒子は、ＣＮＴ分散剤１Ａにおけるシリカコロイド粒子と同様のものである。また、ＣＮＴ分散剤５におけるシリカ濃度は30重量％である。 A colloidal solution in which silica colloid particles are dispersed in isopropyl alcohol (IPA) as a dispersion medium is referred to as a CNT dispersant 5. The silica colloid particles are the same as the silica colloid particles in the CNT dispersant 1A. The silica concentration in the CNT dispersant 5 is 30% by weight.
30ｇのＣＮＴ分散剤５に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。得られたＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降は生じなかった。 0.15 g of CNT was added to 30 g of CNT dispersant 5 and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. Even when the obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, no aggregation or sedimentation occurred.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成してしまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, defects are not formed on the CNT surface unlike the method of treating CNT with acid or plasma.
酸化チタン（TiO2）コロイド粒子が、分散媒であるＩＰＡ中に分散しているコロイド溶液を、ＣＮＴ分散剤６とする。ＣＮＴ分散剤６における酸化チタン濃度は10重量％である。 A colloidal solution in which titanium oxide (TiO 2 ) colloidal particles are dispersed in IPA as a dispersion medium is referred to as CNT dispersant 6. The titanium oxide concentration in the CNT dispersant 6 is 10% by weight.
30ｇのＣＮＴ分散剤６に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行い、ＣＮＴ分散液を得た。得られたＣＮＴ分散液を、超音波処理後、24時間静置しても、凝集や沈降は生じなかった。 0.15 g of CNT was added to 30 g of CNT dispersant 6 and subjected to ultrasonic treatment for 20 minutes to obtain a CNT dispersion. Even when the obtained CNT dispersion was allowed to stand for 24 hours after ultrasonic treatment, no aggregation or sedimentation occurred.
以上のように、本実施例のＣＮＴ分散液は、ＣＮＴを安定に分散させることができた。また、ＣＮＴを酸やプラズマで処理する方法のように、ＣＮＴ表面に欠陥を形成しまうことがない。 As described above, the CNT dispersion liquid of this example was able to stably disperse CNTs. In addition, unlike the method of treating CNT with acid or plasma, no defects are formed on the CNT surface.
まず、前記実施例１と同様にして、SiO2濃度1重量％のシリカコロイド溶液を調製した。次に、このSiO2濃度1重量％のシリカコロイド溶液をイオン交換水で希釈して、SiO2濃度0.25重量％のシリカコロイド溶液を調製した。このSiO2濃度0.25重量％のシリカコロイド溶液を、ＣＮＴ分散剤７とする。なお、ＣＮＴ分散剤７におけるシリカ濃度は、後述する比較例４におけるアルミナ濃度と同じである。 First, in the same manner as in Example 1, a silica colloid solution having a SiO 2 concentration of 1% by weight was prepared. Next, this silica colloid solution having a SiO 2 concentration of 1% by weight was diluted with ion-exchanged water to prepare a silica colloid solution having a SiO 2 concentration of 0.25% by weight. This silica colloid solution having a SiO 2 concentration of 0.25 wt% is used as the CNT dispersant 7. Note that the silica concentration in the CNT dispersant 7 is the same as the alumina concentration in Comparative Example 4 described later.
上記のように調製したＣＮＴ分散剤７の30ｇに、0.15ｇのＣＮＴを添加し、分散処理（超音波処理）を行った。分散処理後、24時間静置しても、凝集や沈降は生じなかった。
（比較例１）
30ｇの塩酸水溶液（ｐＨ2.5）に、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行った。その後24時間静置すると、凝集や沈降が生じた。
0.15 g of CNT was added to 30 g of the CNT dispersant 7 prepared as described above, and dispersion treatment (ultrasonic treatment) was performed. Even after 24 hours of dispersion treatment, no aggregation or sedimentation occurred.
(Comparative Example 1)
0.15 g of CNT was added to 30 g of hydrochloric acid aqueous solution (pH 2.5) and subjected to ultrasonic treatment for 20 minutes. After standing for 24 hours, aggregation and sedimentation occurred.
（比較例２）
30ｇのＩＰＡに、0.15ｇのＣＮＴを添加し、20分間の超音波処理を行った。その後24時間静置すると、凝集や沈降が生じた。
(Comparative Example 2)
0.15 g of CNT was added to 30 g of IPA, and sonication was performed for 20 minutes. After standing for 24 hours, aggregation and sedimentation occurred.
（比較例３）
ドデシル硫酸ナトリウムの(ＳＤＳ)の1重量％溶液40ｇに、2ｇのＣＮＴを添加し、20分間の超音波処理を行った。その後24時間静置すると、凝集や沈降が生じた。また、ＳＤＳ溶液は、超音波処理時に、泡を発生させた。
(Comparative Example 3)
2 g of CNT was added to 40 g of a 1 wt% solution of sodium dodecyl sulfate (SDS), and sonication was performed for 20 minutes. After standing for 24 hours, aggregation and sedimentation occurred. The SDS solution generated bubbles during the ultrasonic treatment.
（比較例４）
Al2O3濃度0.25重量％のアルミナコロイド溶液を調製した。このアルミナ濃度は、前記実施例７におけるシリカ濃度と同じである。上記のアルミナコロイド溶液30ｇに、0.15gのＣＮＴを添加し、分散処理（超音波処理）を行った。その後24時間静置すると、凝集や沈降が生じた。
(Comparative Example 4)
An alumina colloid solution having an Al 2 O 3 concentration of 0.25% by weight was prepared. This alumina concentration is the same as the silica concentration in Example 7. 0.15 g of CNT was added to 30 g of the above-mentioned alumina colloid solution, and dispersion treatment (sonication) was performed. After standing for 24 hours, aggregation and sedimentation occurred.
尚、本発明は前記実施形態になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。 In addition, this invention is not limited to the said embodiment at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.
Claims (2)
ｐＨが３．４以上７以下であり、
前記シリカコロイドの濃度が０．０５〜３０重量％であることを特徴とするＣＮＴ分散液。 A CNT dispersant containing silica colloid, and CNT,
pH is 3.4 or more and 7 or less,
CNT dispersion concentration of the colloidal silica is characterized in that Ru 0.05 to 30 wt% der.
前記シリカコロイドの濃度が０．０５〜０．２５重量％であることを特徴とするＣＮＴ分散液。A CNT dispersion liquid, wherein the concentration of the silica colloid is 0.05 to 0.25% by weight.
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