JP6440963B2 - Method for producing coagulated spinning structure - Google Patents
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- JP6440963B2 JP6440963B2 JP2014083399A JP2014083399A JP6440963B2 JP 6440963 B2 JP6440963 B2 JP 6440963B2 JP 2014083399 A JP2014083399 A JP 2014083399A JP 2014083399 A JP2014083399 A JP 2014083399A JP 6440963 B2 JP6440963 B2 JP 6440963B2
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- 238000009987 spinning Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000006185 dispersion Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 26
- 230000015271 coagulation Effects 0.000 claims description 24
- 238000005345 coagulation Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000002229 CNT20 Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002109 single walled nanotube Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003833 bile salt Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UWTATZPHSA-M malate ion Chemical compound [O-]C(=O)[C@H](O)CC(O)=O BJEPYKJPYRNKOW-UWTATZPHSA-M 0.000 description 1
- 229940006477 nitrate ion Drugs 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Description
本発明は、凝集紡糸構造体の製造方法に関し、詳しくはポリマーフリーの凝集紡糸構造体の製造方法に関する。 The present invention relates to a method for producing an agglomerated spinning structure, and more particularly to a method for producing a polymer-free agglomerated spinning structure.
カーボンナノチューブ（CNT）を含む凝集紡糸構造体は、優れた導電性と機械強度を得ることが期待されるため、様々な製造方法が提案されている。 Aggregated spinning structures containing carbon nanotubes (CNTs) are expected to obtain excellent electrical conductivity and mechanical strength, and various production methods have been proposed.
例えば、特許文献１はＣＮＴ分散液をポリマーを含む凝固浴に吐出して凝集紡糸構造体を得ているが、この方法では凝集液に含まれるポリマーが凝集紡糸構造体に残存するため、導電性が低下する。 For example, Patent Document 1 obtains an agglomerated spinning structure by discharging a CNT dispersion liquid into a coagulation bath containing a polymer, but in this method, the polymer contained in the agglomerated liquid remains in the agglomerated spinning structure, so Decreases.
特許文献２は、CNT分散液を強酸又は強アルカリの凝固浴に吐出して凝集紡糸構造体を製造する方法を開示しているが、CNTは強酸又は強アルカリによってダメージを受けるため、得られる凝集紡糸構造体の性能が低下する。 Patent Document 2 discloses a method for producing an agglomerated spun structure by discharging a CNT dispersion liquid into a coagulation bath of strong acid or strong alkali. However, since CNT is damaged by strong acid or strong alkali, the obtained agglomeration is disclosed. The performance of the spinning structure is reduced.
特許文献３〜５は、CNT分散液もしくは凝集液に有機溶媒を使用して凝集紡糸構造体を製造しているが、得られた凝集紡糸構造体は導電性のさらなる向上が望まれる。 In Patent Documents 3 to 5, an aggregated spinning structure is produced using an organic solvent in a CNT dispersion or aggregating liquid, and the obtained aggregated spinning structure is desired to further improve conductivity.
本発明は、導電性に優れた凝集紡糸構造体の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the aggregation spinning structure excellent in electroconductivity.
本発明は、以下の凝集紡糸構造体の製造方法を提供するものである。
項１． カーボンナノチューブと界面活性剤を含む分散液を凝固浴に吐出する、凝集紡糸構造体の製造方法であって、前記分散液及び凝固浴のｐＨはいずれも３〜１１であり、前記分散液及び凝固浴の溶媒はいずれも水であり、前記分散液と凝固浴のいずれかに塩類を含むことを特徴とする凝集紡糸構造体の製造方法。
項２． 前記界面活性剤がアニオン界面活性剤である、項１に記載の凝集紡糸構造体の製造方法。
項３． 上記塩類がアルカリ金属またはアルカリ土類金属を含む少なくとも１種の水溶性塩である項１又は２に記載の凝集紡糸構造体の製造方法。
項４． 上記塩類が塩化ナトリウム、塩化カルシウム、塩化マグネシウム又はリン酸二水素ナトリウムであることを特徴とする項３に記載の凝集紡糸構造体の製造方法。
The present invention provides the following method for producing an agglomerated spinning structure.
Item 1. A method for producing an agglomerated spinning structure in which a dispersion containing carbon nanotubes and a surfactant is discharged to a coagulation bath, wherein the pH of the dispersion and the coagulation bath is 3 to 11, and the dispersion and coagulation The solvent for the bath is water, and a salt is contained in either the dispersion or the coagulation bath.
Item 2. Item 2. The method for producing an agglomerated spinning structure according to Item 1, wherein the surfactant is an anionic surfactant.
Item 3. Item 3. The method for producing an aggregated spinning structure according to Item 1 or 2, wherein the salt is at least one water-soluble salt containing an alkali metal or an alkaline earth metal.
Item 4. Item 4. The method for producing an agglomerated spinning structure according to Item 3, wherein the salt is sodium chloride, calcium chloride, magnesium chloride, or sodium dihydrogen phosphate.
本発明によれば、導電性に優れたカーボンナノチューブの凝集紡糸構造体を得ることができる。 According to the present invention, an agglomerated spinning structure of carbon nanotubes excellent in conductivity can be obtained.
本発明に用いられるカーボンナノチューブは、グラフェンシートが筒形に巻いた形状から成る炭素系材料であり、その周壁の構成数から単層カーボンナノチューブ（ＳＷＮＴ）と多層カーボンナノチューブ（ＭＷＮＴ）とに大別され、また、グラフェンシートの構造の違いからカイラル（らせん）型、ジグザグ型、およびアームチェア型に分けられるなど、各種のものが知られている。本発明には、このような所謂カーボンナノチューブと称されるものであれば、いずれのタイプのカーボンナノチューブも用いることができる。一般的には、アスペクト比が大きく分子間力の大きな単層カーボンナノチューブがＣＮＴ糸が形成し易い。例えば、アスペクト比が１０２以上、好ましくは５×１０２以上のカーボンナノチューブが挙げられる。カーボンナノチューブの長さの上限は、特に限定されないが、例えば10μm程度である。好ましいカーボンナノチューブは、単層ナノチューブ（ＳＷＮＴ）であり、直噴熱分解合成法（DIPS法）、改良直噴熱分解合成法（eDIPS法）により製造されたカーボンナノチューブがより好ましく、eDIPS法により製造されたカーボンナノチューブが特に好ましい。 The carbon nanotube used in the present invention is a carbon-based material having a shape in which a graphene sheet is wound in a cylindrical shape, and is roughly classified into single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) from the number of peripheral walls. In addition, various types are known, such as being divided into a chiral type, a zigzag type, and an armchair type due to the difference in the structure of the graphene sheet. Any type of carbon nanotube can be used in the present invention as long as it is referred to as such a so-called carbon nanotube. In general, single-walled carbon nanotubes having a large aspect ratio and a large intermolecular force tend to form CNT yarns. For example, carbon nanotubes having an aspect ratio of 10 2 or more, preferably 5 × 10 2 or more can be mentioned. The upper limit of the length of the carbon nanotube is not particularly limited, but is about 10 μm, for example. The preferred carbon nanotube is a single-walled nanotube (SWNT), more preferably a carbon nanotube produced by a direct injection pyrolysis synthesis method (DIPS method) or an improved direct injection pyrolysis synthesis method (eDIPS method), and produced by an eDIPS method. The carbon nanotubes made are particularly preferred.
カーボンナノチューブは、界面活性剤の水溶液に分散される。界面活性剤としては、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤のいずれを使用してもよい。 Carbon nanotubes are dispersed in an aqueous solution of a surfactant. As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant may be used.
ノニオン界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックコポリマーなどが挙げられ、具体的にはポリ（オキシエチレン）オクチルフェニルエーテル（例えば、Ｔｒｉｔｏｎ（登録商標）Ｘ−１００）、ポリオキシエチレンソルビタンモノラウラート（例えば、Ｔｗｅｅｎ（登録商標） ２０）などが挙げられる。 Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene Fatty acid esters, polyoxyethylene polyoxypropylene block copolymers and the like, specifically, poly (oxyethylene) octylphenyl ether (for example, Triton (registered trademark) X-100), polyoxyethylene sorbitan monolaurate (for example, , Tween (registered trademark) 20) and the like.
アニオン界面活性剤としては、アルキルベンゼンスルホン酸塩（例えば、ドデシルベンゼンスルホン酸ナトリウム等）、アルキルアルコール硫酸エステル塩（例えば、ドデシル硫酸ナトリウム等）、アルキルジフェニルエーテルジスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム、ジアルキルスルホコハク酸ナトリウム、アルキルアリルスルホコハク酸ナトリウム、Ｎ−ラウロイルサルコシンナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸エステルナトリウム、（メタ）アクリロイルポリオキシアルキレン硫酸エステルナトリウム、アルキルアルコールリン酸エステル塩、胆汁酸塩(例えばコール酸ナトリウム、デオキシコール酸ナトリウムなど)が挙げられ、コール酸ナトリウムなどの胆汁酸塩が好ましく例示される。 Examples of the anionic surfactant include alkylbenzene sulfonate (for example, sodium dodecylbenzenesulfonate), alkyl alcohol sulfate (for example, sodium dodecyl sulfate), sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate. , Sodium dialkylsulfosuccinate, sodium alkylallylsulfosuccinate, sodium N-lauroyl sarcosine, sodium polyoxyethylene alkylphenyl ether sulfate, sodium (meth) acryloyl polyoxyalkylene sulfate, alkyl alcohol phosphate, bile salt ( For example, sodium cholate, sodium deoxycholate, etc.), such as sodium cholate Shirusanshio are preferably exemplified.
カチオン界面活性剤としては、テトラアルキルアンモニウムハライド、アルキルピリジニウムハライド、アルキルイミダゾリンハライドなどが挙げられる。 Examples of cationic surfactants include tetraalkylammonium halides, alkylpyridinium halides, and alkyl imidazoline halides.
両性界面活性剤としては、アルキルベタイン、アルキルイミダゾリニウムベタイン、レシチンなどが挙げられる。 Examples of amphoteric surfactants include alkyl betaines, alkyl imidazolinium betaines, and lecithin.
好ましい界面活性剤はノニオン界面活性剤であり、より好ましくは胆汁酸塩である。 A preferred surfactant is a nonionic surfactant, more preferably a bile salt.
分散液、凝固浴の溶媒はいずれも水である。有機溶媒は廃液処理の問題があり本来使用しない方が望ましいものであるが、溶媒として水を使用する本発明は導電性に優れた凝集紡糸構造体を得ることができる。本発明の特徴の１つは、分散液と凝固浴の両方の溶媒を水にしたことである。 Both the dispersion and the coagulation bath solvent are water. The organic solvent has a problem of waste liquid treatment and is desirably not used originally. However, the present invention using water as a solvent can obtain an aggregated spinning structure excellent in conductivity. One feature of the present invention is that the solvent of both the dispersion and the coagulation bath is water.
本発明では、分散液と凝固浴のいずれか一方もしくは両方に塩類を添加する。分散液と凝固浴の両方に塩類が含まれない場合、凝集紡糸構造体を得ることができない。塩類は無機塩及び有機塩のいずれでもよいが、無機塩類が好ましい。塩類は水溶性である。塩類は、アルカリ金属塩、アルカリ土類金属塩が好ましく、より好ましくはナトリウム塩、カリウム塩、リチウム塩、カルシウム塩、マグネシウム塩、バリウム塩、ストロンチウム塩が挙げられ、さらに好ましくはナトリウム塩、カルシウム塩、マグネシウム塩が挙げられる。塩類のアニオンとしては、塩素イオン、フッ素イオン、臭素イオン、ヨウ素イオン、硫酸イオン、亜硫酸イオン、リン酸イオン、硝酸イオン、亜硝酸イオン、メタンスルホン酸イオン、ベンゼンスルホン酸イオン、トルエンスルホン酸イオン、クエン酸イオン、シュウ酸イオン、リンゴ酸イオン、酒石酸イオン、マレイン酸イオン、フマル酸イオン、酢酸イオンなどが挙げられる。 In the present invention, salts are added to one or both of the dispersion and the coagulation bath. When salts are not included in both the dispersion and the coagulation bath, an agglomerated spun structure cannot be obtained. The salt may be either an inorganic salt or an organic salt, but is preferably an inorganic salt. Salts are water soluble. The salt is preferably an alkali metal salt or alkaline earth metal salt, more preferably a sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt or strontium salt, still more preferably a sodium salt or calcium salt. And magnesium salts. Salt anions include chlorine ion, fluorine ion, bromine ion, iodine ion, sulfate ion, sulfite ion, phosphate ion, nitrate ion, nitrite ion, methanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, Examples include citrate ion, oxalate ion, malate ion, tartrate ion, maleate ion, fumarate ion, acetate ion and the like.
好ましい塩類としては、塩化ナトリウム、塩化カリウム、塩化リチウム、塩化カルシウム、塩化マグネシウム、臭化ナトリウム、臭化カリウム、臭化カルシウム、臭化マグネシウム、硫酸ナトリウム、硫酸カリウム、硝酸ナトリウム、硝酸カリウム、硝酸カルシウム、硝酸マグネシウム、リン酸ナトリウム、リン酸一水素二ナトリウム、リン酸二水素一ナトリウム、リン酸ナトリウム、リン酸一水素二ナトリウム、リン酸二水素一ナトリウム、リン酸カリウム、リン酸一水素二カリウム、リン酸二水素一カリウム、リン酸カリウム、リン酸一水素二カリウム、リン酸二水素一カリウムなどが挙げられる。 Preferred salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, calcium nitrate, Magnesium nitrate, sodium phosphate, disodium monohydrogen phosphate, monosodium dihydrogen phosphate, sodium phosphate, disodium monohydrogen phosphate, monosodium dihydrogen phosphate, potassium phosphate, dipotassium monohydrogen phosphate, Examples thereof include monopotassium dihydrogen phosphate, potassium phosphate, dipotassium monohydrogen phosphate, and monopotassium dihydrogen phosphate.
塩類の濃度は、分散液中では０〜２５質量％程度、好ましくは０〜２０質量％程度であり、凝固浴中では０〜４０質量％程度、好ましくは０〜３５質量％程度である。塩類は単独で或いは２種以上の塩類を組み合わせて分散液及び／又は凝固浴に溶解される。凝固浴又は分散液中に塩類が含まれるので、分散液を吐出後の凝固浴には塩類が含まれる。分散液を吐出後の凝固浴中の塩類濃度は０．５〜４０質量％程度、好ましくは１〜３５質量％程度である。塩類は、分散液のみ或いは凝固液のみに含まれていてもよいので、分散液と凝固液の塩類濃度の下限は各々０質量％であるが、塩類を含む分散液／凝固液の塩類濃度の下限は、０．５質量％程度、好ましくは１質量％程度であり、上限は、４０質量％程度、好ましくは３５質量％程度である。 The concentration of the salt is about 0 to 25% by mass in the dispersion, preferably about 0 to 20% by mass, and about 0 to 40% by mass in the coagulation bath, preferably about 0 to 35% by mass. The salts are dissolved in the dispersion and / or the coagulation bath alone or in combination of two or more salts. Since salts are contained in the coagulation bath or dispersion, the coagulation bath after discharging the dispersion contains salts. The salt concentration in the coagulation bath after discharging the dispersion is about 0.5 to 40% by mass, preferably about 1 to 35% by mass. Since the salts may be contained only in the dispersion liquid or only in the coagulation liquid, the lower limit of the salt concentration of the dispersion liquid and the coagulation liquid is 0% by mass, respectively. The lower limit is about 0.5% by mass, preferably about 1% by mass, and the upper limit is about 40% by mass, preferably about 35% by mass.
分散液中のカーボンナノチューブの量は、溶媒１００ｍｌあたり５〜１５００ｍｇ程度、好ましくは１０〜１２００ｍｇ程度である。 The amount of carbon nanotubes in the dispersion is about 5 to 1500 mg, preferably about 10 to 1200 mg per 100 ml of solvent.
分散液中の界面活性剤の量は、０.０５〜５質量％程度、好ましくは０.１〜２質量％程度である。 The amount of the surfactant in the dispersion is about 0.05 to 5% by mass, preferably about 0.1 to 2% by mass.
本発明の分散液は、シリンジ、紡糸口金などから凝固浴中に吐出され、ＣＮＴ糸から構成される凝集紡糸構造体を形成する。凝集紡糸構造体は水に浸漬・洗浄して界面活性剤と塩類を十分に除去する。浸漬時間は2時間以上、好ましくは24時間以上である。この水中の浸漬工程により界面活性剤と塩類は除去される。 The dispersion of the present invention is discharged from a syringe, a spinneret, or the like into a coagulation bath to form an aggregated spinning structure composed of CNT yarns. The coagulated spinning structure is immersed in water and washed to sufficiently remove the surfactant and salts. The immersion time is 2 hours or longer, preferably 24 hours or longer. Surfactant and salts are removed by this immersion step in water.
得られた凝集紡糸構造体は、そのままもしくは張力をかけながら乾燥することもでき、必要に応じてさらに延伸して延伸糸とすることができる。乾燥時に、延伸工程に供することにより、延伸糸とすることができる。延伸率は、5〜70％程度、好ましくは10〜50％程度である。 The obtained agglomerated spun structure can be dried as it is or under tension, and can be further drawn into a drawn yarn as necessary. A stretched yarn can be obtained by subjecting it to a stretching step during drying. The stretching ratio is about 5 to 70%, preferably about 10 to 50%.
吐出する際のシリンジ、紡糸口金などの口径は、１０〜２０００μｍ程度、好ましくは２０〜１５００μｍ程度である。この口径を調節することにより凝集紡糸構造体の径を調節することができる。 The diameters of the syringe, the spinneret, etc. when discharging are about 10 to 2000 μm, preferably about 20 to 1500 μm. The diameter of the aggregated spinning structure can be adjusted by adjusting the diameter.
凝固浴の温度は特に限定されないが、通常５〜５０℃程度、好ましくは室温程度の温度であればよい。吐出された凝集紡糸構造体は１分以上、例えば５分以上凝固浴中に維持してもよく、塩類、界面活性剤を除去するために水または有機溶剤に浸漬してもよい。 The temperature of the coagulation bath is not particularly limited, but is usually about 5 to 50 ° C., preferably about room temperature. The discharged agglomerated spinning structure may be maintained in the coagulation bath for 1 minute or longer, for example 5 minutes or longer, and may be immersed in water or an organic solvent in order to remove salts and surfactants.
延伸後は、必要に応じて乾燥することによりＣＮＴ延伸糸を得ることができる。 After drawing, a CNT drawn yarn can be obtained by drying as necessary.
凝集紡糸構造体の導電率は、1700〜1000000 S/cm程度、好ましくは1800〜600000 S/cm程度である。 The electrical conductivity of the aggregated spinning structure is about 1700 to 100000 S / cm, preferably about 1800 to 600000 S / cm.
以下、本発明を実施例及び比較例を用いてより詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples and comparative examples.
（実施例1）
e-Dips法により製造された単層カーボンナノチューブ(以下、eDips-CNTと記述する) 20mgとコール酸ナトリウム(SC) 120mgを9.86ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 1)
20 mg of single-walled carbon nanotubes manufactured by the e-Dips method (hereinafter referred to as eDips-CNT) and 120 mg of sodium cholate (SC) are added to 9.86 g of water, and the condition is 35 ° C for 30 minutes using a sonic stirrer And then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から5%塩化カルシウム水溶液中に注入することによりCNT糸の形状にした。 The obtained dispersion liquid was injected into a 5% calcium chloride aqueous solution from an injection nozzle (inner diameter: 1.25 mm) to form a CNT yarn.
5%塩化カルシウム水溶液中にて1日間放置した後、水に置換し３日以上浸漬した。 After being left in a 5% calcium chloride aqueous solution for 1 day, it was replaced with water and immersed for 3 days or more.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
ＣＮＴ糸の導電率は２００３Ｓ／ｃｍであった。 The conductivity of the CNT yarn was 2003 S / cm.
上記と同様の作製方法で得られたeDips-CNT分散液を１０％塩化カルシウム水溶液、２０％塩化カルシウム水溶液、３０％塩化カルシウム水溶液中に注入し、上記と同様の方法によりＣＮＴ糸を得た。得られたＣＮＴ糸の導電率はそれぞれ１９２８Ｓ／ｃｍ、２４５１Ｓ／ｃｍ、２９０７Ｓ／ｃｍであった。 The eDips-CNT dispersion obtained by the same production method as described above was poured into 10% calcium chloride aqueous solution, 20% calcium chloride aqueous solution and 30% calcium chloride aqueous solution, and CNT yarn was obtained by the same method as above. The electrical conductivity of the obtained CNT yarn was 1928 S / cm, 2451 S / cm, and 2907 S / cm, respectively.
（実施例2）
eDips-CNT 20mgとSC 120mgを9.86ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 2)
eDips-CNT 20 mg and SC 120 mg were added to 9.86 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から25%塩化ナトリウム水溶液中に注入することによりCNT糸の形状にした。 The obtained dispersion was injected into a 25% aqueous sodium chloride solution from an injection nozzle (inner diameter 1.25 mm) to form a CNT yarn.
25%塩化ナトリウム水溶液中にて１日間放置した後、イソプロピルアルコールに置換し1日放置した後、水に置換し1日以上浸漬した。 After being left in a 25% aqueous solution of sodium chloride for 1 day, it was replaced with isopropyl alcohol, left for 1 day, then replaced with water and immersed for 1 day or longer.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
ＣＮＴ糸の導電率は４４３８Ｓ／ｃｍであった。 The conductivity of the CNT yarn was 4438 S / cm.
（実施例3）
eDips-CNT 20mgとSC 120mg、塩化ナトリウム２ｇを１０ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 3)
eDips-CNT 20 mg, SC 120 mg and sodium chloride 2 g were added to 10 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から水に注入することによりCNT糸の形状にした。 The obtained dispersion was poured into water from an injection nozzle (inner diameter 1.25 mm) to form a CNT yarn.
水に1日間放置した後、さらにはイソプロピルアルコールに置換し1日浸漬した後、水に置換し1日以上浸漬した。 After leaving it in water for 1 day, it was further replaced with isopropyl alcohol and immersed for 1 day, then replaced with water and immersed for 1 day or more.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
導電率は２１４９Ｓ／ｃｍであった。 The conductivity was 2149 S / cm.
（実施例４）
eDips-CNT 20mgとSC 120mg、塩化ナトリウム１ｇを１０ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 4)
eDips-CNT 20 mg, SC 120 mg, and sodium chloride 1 g were added to 10 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から5%塩化カルシウム水溶液中に注入することによりCNT糸の形状にした。 The obtained dispersion liquid was injected into a 5% calcium chloride aqueous solution from an injection nozzle (inner diameter: 1.25 mm) to form a CNT yarn.
5%塩化カルシウム水溶液中にて1日間放置した後、イソプロピルアルコールに置換し1日放置した後、水に置換し1日以上浸漬した。 After being left in a 5% calcium chloride aqueous solution for 1 day, it was replaced with isopropyl alcohol, left for 1 day, then replaced with water and immersed for 1 day or longer.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
ＣＮＴ糸の導電率は１８０１Ｓ／ｃｍであった。 The conductivity of the CNT yarn was 1801 S / cm.
（実施例５）
eDips-CNT 20mgとSC 120mgを9.86ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 5)
eDips-CNT 20 mg and SC 120 mg were added to 9.86 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から5%塩化マグネシウム水溶液中に注入することによりCNT糸の形状にした。 The obtained dispersion was injected into a 5% magnesium chloride aqueous solution from an injection nozzle (inner diameter 1.25 mm) to form a CNT yarn.
5%塩化マグネシウム水溶液中にて１日間放置した後、イソプロピルアルコールに置換し1日放置した後、水に置換し1日以上浸漬した。 After leaving in a 5% magnesium chloride aqueous solution for 1 day, it was replaced with isopropyl alcohol, left for 1 day, then replaced with water and immersed for 1 day or more.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
ＣＮＴ糸の導電率は２４４６Ｓ／ｃｍであった。 The conductivity of the CNT yarn was 2446 S / cm.
（実施例６）
eDips-CNT 20mgとSC 120mgを9.86ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Example 6)
eDips-CNT 20 mg and SC 120 mg were added to 9.86 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から5%リン酸二水素ナトリウム水溶液に注入することによりCNT糸の形状にした。 The obtained dispersion was injected into a 5% sodium dihydrogen phosphate aqueous solution from an injection nozzle (inner diameter 1.25 mm) to form a CNT yarn.
5%リン酸二水素ナトリウム水溶液にて１日間放置した後、イソプロピルアルコールに置換し1日放置した後、水に置換し1日以上浸漬した。 After being left in a 5% aqueous solution of sodium dihydrogen phosphate for 1 day, it was replaced with isopropyl alcohol, left for 1 day, then replaced with water and immersed for 1 day or longer.
水中から取り出したeDips-CNT糸を湿潤(wet)状態で一端を治具で固定し、荷重をかけて乾燥させながらＣＮＴ糸を得た。 One end of the eDips-CNT yarn taken out from the water was fixed with a jig in a wet state, and a CNT yarn was obtained while drying by applying a load.
（比較例１）
eDips-CNT 20mgとSC 120mgを9.86ｇの水に加え、ソニックスターラーを用いて30分間35℃の条件で撹拌し、次いで超音波ホモジナイザーで処理し、eDips-CNT分散液を得た。
(Comparative Example 1)
eDips-CNT 20 mg and SC 120 mg were added to 9.86 g of water, stirred for 30 minutes at 35 ° C. using a sonic stirrer, and then treated with an ultrasonic homogenizer to obtain an eDips-CNT dispersion.
得られた分散液を注入ノズル(内径1.25mm)から水に注入したが、糸の形状にはならなかった。 The obtained dispersion was poured into water from an injection nozzle (inner diameter 1.25 mm), but it did not take the shape of a thread.
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