JP5909778B2 - Dispersion - Google Patents
Dispersion Download PDFInfo
- Publication number
- JP5909778B2 JP5909778B2 JP2012135319A JP2012135319A JP5909778B2 JP 5909778 B2 JP5909778 B2 JP 5909778B2 JP 2012135319 A JP2012135319 A JP 2012135319A JP 2012135319 A JP2012135319 A JP 2012135319A JP 5909778 B2 JP5909778 B2 JP 5909778B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- carbon nanotube
- dispersant
- nanotube aggregate
- aggregate
- 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.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 title claims description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 154
- 239000002041 carbon nanotube Substances 0.000 claims description 143
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 143
- 239000002270 dispersing agent Substances 0.000 claims description 74
- 150000001412 amines Chemical class 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 40
- 239000002612 dispersion medium Substances 0.000 claims description 27
- 230000008961 swelling Effects 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 18
- -1 acyclic ethers Chemical class 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000001298 alcohols Chemical group 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 33
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- 238000000034 method Methods 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000002245 particle Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 125000002524 organometallic group Chemical group 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000012018 catalyst precursor Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
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- 230000003993 interaction Effects 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
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- 150000003839 salts Chemical class 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
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- 229940091250 magnesium supplement Drugs 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
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- 239000011324 bead Substances 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229960000869 magnesium oxide Drugs 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MXSORXOBAXRPQY-UHFFFAOYSA-N Cl(=O)(=O)O.Cl(=O)(=O)(=O)O.Cl(=O)(=O)O Chemical compound Cl(=O)(=O)O.Cl(=O)(=O)(=O)O.Cl(=O)(=O)O MXSORXOBAXRPQY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
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- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
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- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
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- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
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- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、分散媒にカーボンナノチューブ集合体を分散させてなる分散体に関する。 The present invention relates to a dispersion obtained by dispersing a carbon nanotube aggregate in a dispersion medium.
カーボンナノチューブに代表される筒状の形状を持った炭素材料は、その直径は数ｎｍから数１００ｎｍで、長さは数１０ｎｍから１ｍｍであり、アスペクト比が大きく、高い導電性、機械的強度を有することから、燃料電池、電極、電磁波シールド材、導電性樹脂、電界放出ディスプレー（ＦＥＤ）用部材、水素を始めとする各種ガスの吸蔵材料などの機能性材料として、エレクトロニクス、エネルギー分野等の幅広い分野への利用が期待されている。 A carbon material having a cylindrical shape typified by carbon nanotubes has a diameter of several nanometers to several hundreds of nanometers, a length of several tens of nanometers to 1 mm, a large aspect ratio, high electrical conductivity, and mechanical strength. As a functional material such as fuel cells, electrodes, electromagnetic shielding materials, conductive resins, field emission display (FED) members, and various gas storage materials such as hydrogen, a wide range of electronics, energy fields, etc. Expected to be used in fields.
通常、カーボンナノチューブは隣接するカーボンナノチューブ同士が絡まり合った凝集物（以下、カーボンナノチューブ集合体と称する）として得られる。一般に、カーボンナノチューブを使用する場合には、溶液中に微分散していることが好ましい。しかし、カーボンナノチューブそのものは、親水性液体にも疎水性液体にも分散しにくいのが現状である。 Usually, carbon nanotubes are obtained as aggregates (hereinafter referred to as carbon nanotube aggregates) in which adjacent carbon nanotubes are entangled with each other. In general, when carbon nanotubes are used, it is preferable that they are finely dispersed in a solution. However, at present, the carbon nanotubes themselves are difficult to disperse in both hydrophilic and hydrophobic liquids.
現在まで、様々な方法で分散やインキ化を試みた検討がなされている（例えば、特許文献１、特許文献２等参照）。これらの文献では、カーボンナノチューブを分散させるための分散剤の検討や、カーボンナノチューブ自体を化学修飾して易分散化（特許文献３等参照）等が検討されている。また、カーボンナノチューブの合成に使用した触媒を、除去等の為の酸性処理を行わずに、塩基性を示すカーボンナノチューブを用いて、分散性、分散安定性を改善する検討（特許文献４等参照）もなされているが、いずれも満足できるものではなく、未だ十分な分散性、分散安定性に優れた分散体が得られていないため、導電材料等への展開が困難であるのが現状である。 To date, various attempts have been made to attempt dispersion or ink formation (see, for example, Patent Document 1 and Patent Document 2). In these documents, investigation of a dispersing agent for dispersing carbon nanotubes, easy dispersion by chemically modifying the carbon nanotubes themselves (see Patent Document 3 and the like), and the like are studied. In addition, the catalyst used for the synthesis of the carbon nanotube is not subjected to an acid treatment for removal or the like, and the carbon nanotube showing basicity is used to improve the dispersibility and dispersion stability (see Patent Document 4 etc.) However, none of these are satisfactory, and a dispersion excellent in dispersibility and dispersion stability has not yet been obtained. is there.
本発明は、凝集しやすい、筒状の形状を持ったカーボンナノチューブ集合体、特に膨潤性に優れるカーボンナノチューブ集合体を有機溶媒等の分散媒に均一に分散させて、沈殿を生じなく、低粘度であり、また保存経時後でも粘度変化が小さく、沈殿を生じない、保存安定性が良好な分散体を提供することにある。 The present invention is an aggregate of carbon nanotubes having a cylindrical shape that easily aggregates, and in particular, a carbon nanotube aggregate having excellent swelling properties is uniformly dispersed in a dispersion medium such as an organic solvent, so that precipitation does not occur and low viscosity is obtained. It is another object of the present invention to provide a dispersion having a good storage stability, in which the viscosity change is small even after storage, and no precipitation occurs.
本発明者らは、上記課題を解決すべく鋭意検討した結果、膨潤率が５以上であるカーボンナノチューブ集合体と、酸価を有する分散剤またはアミン価を有する分散剤、および／または酸価を有する分散剤とアミン価を有する分散剤の組み合わせとを、有機溶媒等の分散媒に分散してなる分散体が、極めて良好な分散性、保存安定性を示すことを見いだしたものである。 As a result of intensive studies to solve the above problems, the present inventors have determined that the aggregate of carbon nanotubes having a swelling ratio of 5 or more, a dispersant having an acid value or a dispersant having an amine value, and / or an acid value. The present inventors have found that a dispersion obtained by dispersing a dispersant having an amine value and a dispersant having an amine value in a dispersion medium such as an organic solvent exhibits extremely good dispersibility and storage stability.
すなわち本発明は、カーボンナノチューブ集合体と、アミン価を有する分散剤（Ａ）および／または酸価を有する分散剤（Ｂ）とを、分散媒に分散させてなる分散体であって、カーボンナノチューブ集合体の膨潤率が５以上であり、アミン価を有する分散剤（Ａ）の固形分のアミン価が５〜１００ｍｇＫＯＨ／ｇであり、酸価を有する分散剤（Ｂ）の固形分が５〜１２０ｍｇＫＯＨ／ｇであることを特徴とする分散体に関する。 That is, the present invention is a dispersion obtained by dispersing a carbon nanotube aggregate and a dispersant (A) having an amine value and / or a dispersant (B) having an acid value in a dispersion medium, The swelling ratio of the aggregate is 5 or more, the amine content of the dispersant (A) having an amine value is 5 to 100 mg KOH / g, and the solid content of the dispersant (B) having an acid value is 5 to 5 mg It is related with the dispersion characterized by being 120 mgKOH / g.
また本発明は、分散媒が、アルコール類、炭化水素類、環式及び非環式エーテル類、モノカルボン酸エステル・ジ又はポリカルボン酸エステル等のカルボン酸エステル類、エーテルエステル類、ラクトン類、アルデヒド及びケトン類、酸アミド類、アミン類、および、ラクタム類から選ばれる１種または２種以上の有機溶媒を混合した分散媒であることを特徴とする、上記記載の分散体に関する。 In the present invention, the dispersion medium may be an alcohol, a hydrocarbon, a cyclic or acyclic ether, a carboxylic acid ester such as a monocarboxylic acid ester / di- or polycarboxylic acid ester, an ether ester, a lactone, The dispersion according to the above, which is a dispersion medium obtained by mixing one or more organic solvents selected from aldehydes and ketones, acid amides, amines, and lactams.
また本発明は、膨潤率が５以上であるカーボンナノチューブ集合体のアミン吸着量が５〜５００μｍｏｌ／ｇ、且つ酸吸着量が１〜１００μｍｏｌ／ｇであることを特徴とする、上記記載の分散体に関する。 Further, the present invention provides the dispersion described above, wherein the carbon nanotube aggregate having a swelling rate of 5 or more has an amine adsorption amount of 5 to 500 μmol / g and an acid adsorption amount of 1 to 100 μmol / g. About.
本発明によって得られるカーボンナノチューブ集合体の分散体は、低粘度で沈殿物が生じなく、分散媒中に極めて良好な分散性を示した。また、保存経時することによる粘度変化が小さく、また沈殿も生じなく、良好な保存安定性を示し、導電用材料等への展開が期待される。 The carbon nanotube aggregate dispersion obtained by the present invention had a low viscosity and no precipitates, and showed very good dispersibility in the dispersion medium. In addition, the change in viscosity due to aging is small, precipitation does not occur, good storage stability is exhibited, and development to conductive materials and the like is expected.
以下に本発明の分散体の各構成要素について説明する。 Hereinafter, each component of the dispersion of the present invention will be described.
［カーボンナノチューブ集合体］
本発明の分散体に用いる、膨潤率が５以上のカーボンナノチューブ集合体（以下、単にカーボンナノチューブ集合体と称する）について説明する。
[Aggregate of carbon nanotubes]
A carbon nanotube aggregate having a swelling ratio of 5 or more (hereinafter simply referred to as a carbon nanotube aggregate) used in the dispersion of the present invention will be described.
本発明の分散体に用いるカーボンナノチューブ集合体は、５以上の膨潤率を有することで、容易にほぐれ易く、また分散性に優れ、少ない配合量で高い導電性を有する材料を提供できる。ここで、カーボンナノチューブ集合体がほぐれるとは、該集合体中の絡まっているカーボンナノチューブ間の距離が大きくなることであり、ほぐれ易さとは、該集合体中のカーボンナノチューブ間に樹脂や溶媒等の分散媒体を容易に取り込み、カーボンナノチューブ同士の距離が大きくなることにより集合体が膨潤して大きくなることであると考えられるものである。そこで、本発明の分散体に用いるカーボンナノチューブ集合体のほぐれ易さの指標として、室温におけるメタノール中での膨潤率で表した。 Since the aggregate of carbon nanotubes used in the dispersion of the present invention has a swelling ratio of 5 or more, the carbon nanotube aggregate can be easily loosened, has excellent dispersibility, and can provide a material having high conductivity with a small amount. Here, the loosening of the carbon nanotube aggregate means that the distance between the entangled carbon nanotubes in the aggregate increases, and the ease of loosening means that a resin, a solvent, etc. between the carbon nanotubes in the aggregate. It is considered that the aggregate is swollen and becomes larger when the dispersion medium is easily taken in and the distance between the carbon nanotubes is increased. Therefore, the swelling ratio in methanol at room temperature was expressed as an index of the ease of loosening of the carbon nanotube aggregate used in the dispersion of the present invention.
膨潤率は、下記で示した方法で測定し、式（１）により算出した。 The swelling rate was measured by the method shown below and calculated by the formula (1).
直径３５ｍｍ×高さ７８ｍｍのガラス瓶に、メタノール４０ｃｃと評価用のカーボンナノチューブ粉体０．２ｇを量り取り、室温で６０分放置後溶媒中のカーボンナノチューブ集合体の高さを測定し、分散処理前の高さとした。ＢＲＡＮＳＯＮ製 超音波分散機 ＳＯＮＩＦＩＥＲ ＭＯＤＥＬ４５０Ｄを用いて、出力５Ｗで３０分処理し、６０分静置した後、溶媒中のカーボンナノチューブ集合体の高さを測定し、超音波分散処理後の高さとした。
膨潤率＝超音波分散処理後の高さ÷分散処理前の高さ ・・・・式（１）
Weigh 40 cc of methanol and 0.2 g of carbon nanotube powder for evaluation into a glass bottle with a diameter of 35 mm and a height of 78 mm, leave it at room temperature for 60 minutes, measure the height of the aggregate of carbon nanotubes in the solvent, and before dispersion treatment And the height. Using a ultrasonic dispersion machine SONIFIER MODEL450D manufactured by BRANSON, processed for 30 minutes at an output of 5 W, allowed to stand for 60 minutes, and then measured the height of the aggregate of carbon nanotubes in the solvent to obtain the height after ultrasonic dispersion treatment. .
Swelling ratio = height after ultrasonic dispersion treatment / height before dispersion treatment (1)
本発明の分散体に用いるカーボンナノチューブ集合体の膨潤率は５以上であることが重要であり、更に好ましくは１０以上である。膨潤率が５未満であると、分散媒体を容易に取り込み難く、優れた分散性、保存安定性が得られない。一方、膨潤率が５０以上であると、該集合体を形成するカーボンナノチューブのアスペクト比（カーボンナノチューブの直径に対する長さの比）が小さくなり、優れた導電性が得られにくくなる場合があり、膨潤率は５０未満であることがより好ましい。 It is important that the carbon nanotube aggregate used in the dispersion of the present invention has a swelling ratio of 5 or more, more preferably 10 or more. When the swelling ratio is less than 5, it is difficult to easily incorporate the dispersion medium, and excellent dispersibility and storage stability cannot be obtained. On the other hand, when the swelling ratio is 50 or more, the aspect ratio of the carbon nanotubes forming the aggregate (the ratio of the length to the diameter of the carbon nanotubes) is small, and it may be difficult to obtain excellent conductivity. The swelling rate is more preferably less than 50.
本発明の分散体に用いるカーボンナノチューブ集合体は、膨潤率５以上、より好ましくは膨潤率５以上５０未満の特性を有しているものである。 The aggregate of carbon nanotubes used in the dispersion of the present invention has a characteristic of a swelling ratio of 5 or more, more preferably a swelling ratio of 5 or more and less than 50.
次に、本発明の分散体に用いるカーボンナノチューブ集合体の表面官能基の推量方法について説明する。 Next, a method for estimating the surface functional group of the carbon nanotube aggregate used in the dispersion of the present invention will be described.
一般的に、カーボンナノチューブ集合体の表面には、酸性を呈する部位と塩基性を呈する部位が存在することが知られている。 In general, it is known that there are acidic sites and basic sites on the surface of an aggregate of carbon nanotubes.
更に、カーボンナノチューブの製造には金属化合物が触媒として使用され、カーボンナノチューブを生成後、硝酸や硫酸などの強酸で洗浄し、カーボンナノチューブから触媒として用いた金属化合物を取り除くことを行うことにより、カーボンナノチューブの表面はさらに酸化されて酸性を呈する官能基量が増大することも知られており、必要に応じて強酸洗浄を行っても良い。 Furthermore, a metal compound is used as a catalyst in the production of carbon nanotubes, and after carbon nanotubes are produced, they are washed with a strong acid such as nitric acid or sulfuric acid to remove the metal compound used as a catalyst from the carbon nanotubes. It is also known that the surface of the nanotube is further oxidized to increase the amount of functional groups exhibiting acidity, and strong acid cleaning may be performed as necessary.
また、酸性を呈する部位や塩基性を呈する部位の量を推量することは、カーボンナノチューブ集合体を分散安定化させるのに用いる分散剤を選択する際に有用であることが知られている。 In addition, it is known that estimating the amount of acidic sites or basic sites is useful when selecting a dispersant used to disperse and stabilize a carbon nanotube aggregate.
一般的に、酸性を呈する部位の量を推量する時は、カーボンナノチューブ集合体のアミン吸着量を用いて、塩基性を呈する部位の量を推量する時は酸吸着量を用いて推量することができることが知られている。 In general, when estimating the amount of sites exhibiting acidity, the amount of amine adsorption of the aggregate of carbon nanotubes can be used, and when estimating the amount of sites exhibiting basicity, the amount of acid adsorption can be estimated. It is known that it can be done.
後記で説明する本発明に用いる分散剤は、カーボンナノチューブ集合体の酸性を呈する部位に対しては、分散剤中のアミン価を有する部位が吸着しやすく、また塩基性を呈する部位に対しては、分散体中の酸価を有する部位が吸着しやすいと考えられる。 The dispersant used in the present invention, which will be described later, is easy to adsorb the portion having an amine value in the dispersant to the portion exhibiting the acidity of the carbon nanotube aggregate, and to the portion exhibiting basicity. It is considered that the portion having an acid value in the dispersion is easily adsorbed.
本発明の分散体に用いるカーボンナノチューブ集合体のアミン吸着量と酸吸着量は、色材, ６７ [９], ５４７−５５４ (１９９４)に記載の方法に則り、アミン吸着量は、被吸着アミン物質としてｎ−ヘキシルアミンを用いて、酸吸着量は、被吸着酸物質として酢酸を用いて測定した場合と定義し、次のようにして測定した。 The amine adsorption amount and the acid adsorption amount of the carbon nanotube aggregate used in the dispersion of the present invention are in accordance with the method described in Coloring Materials, 67 [9], 547-554 (1994). Using n-hexylamine as a substance, the amount of acid adsorption was defined as a case where it was measured using acetic acid as an adsorbed acid substance, and was measured as follows.
アミン吸着量は、密閉できるガラス容器に、測定する試料２ｇを測り取り、０．０２ｍｏｌ／ｌのｎ−ヘキシルアミン（吸着物質）のプロピレングリコールモノメチルエーテルアセテート溶液３０ｍｌ加えた。容器に栓をして超音波洗浄機に１時間かけ、カーボンナノチューブ集合体の表面に吸着物質を吸着させた。遠心分離機にかけてカーボンナノチューブ集合体を沈降させ上澄み液を得た。上澄み液を１５ｍｌ採取し、０．０２ｍｏｌ／ｌの過塩素酸ジオキサン溶液にて残存したｎ−ヘキシルアミンを電位差滴定装置により逆滴定した。ブランクを測定し、定量してアミン吸着量が得られた。 The amine adsorption amount was obtained by measuring 2 g of a sample to be measured in a glass container that can be sealed, and adding 30 ml of a propylene glycol monomethyl ether acetate solution of 0.02 mol / l of n-hexylamine (adsorbent). The container was stoppered and placed in an ultrasonic cleaner for 1 hour to adsorb the adsorbed material on the surface of the carbon nanotube aggregate. The aggregate of carbon nanotubes was settled through a centrifuge to obtain a supernatant. 15 ml of the supernatant was collected, and n-hexylamine remaining in a 0.02 mol / l dichlorate perchlorate solution was back titrated with a potentiometric titrator. A blank was measured and quantified to obtain an amine adsorption amount.
酸吸着量は、吸着物質として０．０２ｍｏｌ／ｌの酢酸のプロピレングリコールモノメチルエーテルアセテート溶液を、逆滴定に０．０２ｍｏｌ／ｌの水酸化カリウムのエタノール溶液を用いた他はアミン吸着量の測定と同様にして測定した。ブランクを測定し、定量して酸吸着量が得られた。 The amount of acid adsorbed was determined by measuring the amount of adsorbed amine except that 0.02 mol / l acetic acid in propylene glycol monomethyl ether acetate was used as the adsorbing substance, and 0.02 mol / l potassium hydroxide in ethanol was used for back titration. The measurement was performed in the same manner. A blank was measured and quantified to obtain an acid adsorption amount.
本発明の分散体に用いる前記のカーボンナノチューブ集合体は、膨潤率が５以上であることに加えて、アミン吸着量が、５〜５００μｍｏｌ／ｇである。アミン吸着量が５μｍｏｌ／ｇ未満であると、後述する分散剤中のアミン価を有する部位との相互作用が小さくなり、分散性、保存安定性が劣る。一方、５００μｍｏｌ／ｇより大きいと、後述する分散剤中のアミン価を有する部位との相互作用が強くなりすぎること、且つ酸価を有する部位との反発が強くなりすぎることにより、分散が困難となる。より好ましくは１０〜３００μｍｏｌ／ｇであり、更に好ましくは２０〜２５０μｍｏｌ／ｇである。 The aggregate of carbon nanotubes used in the dispersion of the present invention has an amine adsorption amount of 5 to 500 μmol / g in addition to a swelling ratio of 5 or more. When the amine adsorption amount is less than 5 μmol / g, the interaction with a site having an amine value in the dispersant described later is reduced, and the dispersibility and storage stability are poor. On the other hand, if it is larger than 500 μmol / g, the interaction with the site having the amine value in the dispersant described later becomes too strong, and the repulsion with the site having the acid value becomes too strong, making dispersion difficult. Become. More preferably, it is 10-300 micromol / g, More preferably, it is 20-250 micromol / g.
また、本発明の分散体に用いる前記の膨潤率が５以上のカーボンナノチューブ集合体の酸吸着量は、１〜１００μｍｏｌ／ｇである。酸吸着量が１μｍｏｌ／ｇ未満であると、後述する分散剤中の酸価を有する部位との相互作用が小さくなり、分散安定性が劣る。一方、１００μｍｏｌ／ｇより大きいと、後述する分散剤中の酸価を有する部位との相互作用が大きすぎること、且つアミン価を有する部位との反発が強くなりすぎることにより、分散が困難となる。より好ましくは３〜８０μｍｏｌ／ｇであり、更に好ましくは５〜７０μｍｏｌ／ｇである。 Further, the acid adsorption amount of the carbon nanotube aggregate having a swelling ratio of 5 or more used in the dispersion of the present invention is 1 to 100 μmol / g. When the acid adsorption amount is less than 1 μmol / g, the interaction with the portion having an acid value in the dispersant described later is reduced, and the dispersion stability is inferior. On the other hand, when it is larger than 100 μmol / g, the interaction with the site having the acid value in the dispersant described later is too large, and the repulsion with the site having the amine value becomes too strong, making dispersion difficult. . More preferably, it is 3-80 micromol / g, More preferably, it is 5-70 micromol / g.
次に、本発明の分散体に用いる、前記の膨潤率が５以上のカーボンナノチューブ集合体を得るためのカーボンナノチューブ合成用触媒（Ｃ）（以下、単にカーボンナノチューブ合成用触媒（Ｃ）または触媒（Ｃ）と称する）について説明する。 Next, a catalyst for carbon nanotube synthesis (C) (hereinafter simply referred to as catalyst for carbon nanotube synthesis (C) or catalyst) for obtaining a carbon nanotube aggregate having a swelling ratio of 5 or more, which is used in the dispersion of the present invention. C)) will be described.
カーボンナノチューブ合成用触媒（Ｃ）は、膨潤率を制御する重要な因子であり、組成、物性と作成条件を最適化することが重要である。 The catalyst for carbon nanotube synthesis (C) is an important factor for controlling the swelling rate, and it is important to optimize the composition, physical properties and preparation conditions.
本発明の分散体に用いるカーボンナノチューブ集合体を得るためのカーボンナノチューブ合成用触媒（Ｃ）は、鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機酸塩と、マグネシウムおよびアルミニウムの少なくともいずれか1つ以上の担体成分の金属元素を含む水溶性の有機酸塩、および／または、担体成分の金属元素の水酸化物と、必要に応じて、モリブデンを含む水溶性の金属塩とを、水溶液中に溶解、ないし担体成分の金属元素の水酸化物は、水に分散して混合し、１００〜２００℃の温度で、溶媒を除去、固形化し、さらに空気中で微細化処理して、平均粒径（Ｄ５０）が５０μｍ以下の触媒前駆体を作成した後、前記触媒前駆体を、酸素の存在下、焼成温度３５０〜５５０℃の範囲で加熱し、冷却した後、得られた焼成物を粉砕して、平均粒径（Ｄ５０）が、０．１〜５μｍの範囲とすることが好ましい。 The carbon nanotube synthesis catalyst (C) for obtaining the aggregate of carbon nanotubes used in the dispersion of the present invention is a water-soluble catalyst containing a metal element as an active component of at least one of iron, cobalt and nickel. An organic acid salt, a water-soluble organic acid salt containing a metal element of at least one of magnesium and aluminum as a carrier component, and / or a metal element hydroxide as a carrier component, and if necessary, A water-soluble metal salt containing molybdenum is dissolved in an aqueous solution, or a metal element hydroxide as a carrier component is dispersed and mixed in water, and the solvent is removed and solidified at a temperature of 100 to 200 ° C. Further, the catalyst precursor having an average particle size (D50) of 50 μm or less is prepared by further refinement in air, and then the catalyst precursor is calcined at 350 to 550 in the presence of oxygen. Was heated in the range of, after cooling, and grinding the resulting fired product, average particle size (D50) of, is preferably in the range of 0.1 to 5 [mu] m.
本発明の分散体に用いるカーボンナノチューブ集合体を得るためのカーボンナノチューブ合成用触媒（Ｃ）において、活性成分である、鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機金属塩と、担体成分である、マグネシウムおよびアルミニウムの少なくともいずれか１つ以上の担体成分の金属元素を含む水溶性の有機金属塩、または前記担体成分の金属元素を含む水酸化物との割合は、得られるカーボンナノチューブ合成用触媒（Ｃ）中の、前記活性成分と前記担体成分との合計１００モル％に対する前記活性成分の含有割合が５０〜８０％であることが好ましい。 In the carbon nanotube synthesis catalyst (C) for obtaining the aggregate of carbon nanotubes used in the dispersion of the present invention, the active element is an active component metal element of at least one of iron, cobalt, and nickel And a water-soluble organometallic salt containing a metal element of at least one of magnesium and aluminum as a carrier component, or water containing a metal element of the carrier component The ratio of the active component to the oxide for carbon nanotube synthesis (C) is preferably 50 to 80% with respect to 100 mol% of the total of the active component and the carrier component. .
また、前記活性成分の活性度を向上させる助触媒成分としての酸化モリブデンの原料となるモリブデンを含む水溶性の金属塩の割合は、得られる触媒中の前記活性成分の１００モル％に対して１モル％〜２０モル％であることが好ましい。 Moreover, the ratio of the water-soluble metal salt containing molybdenum as a raw material of molybdenum oxide as a promoter component for improving the activity of the active component is 1 with respect to 100 mol% of the active component in the obtained catalyst. It is preferable that it is mol%-20 mol%.
本発明に用いるカーボンナノチューブ集合体を製造するためのカーボンナノチューブ合成用触媒（Ｃ）は、以下（１）〜（３）の工程を経て得られるものである。 The carbon nanotube synthesis catalyst (C) for producing the carbon nanotube aggregate used in the present invention is obtained through the following steps (1) to (3).
前記のカーボンナノチューブ合成用触媒（Ｃ）の工程（１）は、鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機金属塩と、マグネシウムおよびアルミニウムの少なくともいずれか１つ以上の担体成分の金属元素を含む水溶性の有機金属塩、または前記担体成分の金属元素を含む水酸化物とを、水溶媒中に溶解および／または分散し、混合する工程である。 Step (1) of the carbon nanotube synthesis catalyst (C) includes a water-soluble organometallic salt containing a metal element of at least one of active ingredients of iron, cobalt and nickel, magnesium and aluminum. The water-soluble organometallic salt containing the metal element of at least one of the carrier components or the hydroxide containing the metal element of the carrier component is dissolved and / or dispersed in an aqueous solvent and mixed. It is a process.
工程（１）において、鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機金属塩は、触媒の活性成分としての、それぞれ酸化鉄、酸化コバルト、および、酸化ニッケルの原料となる。また、水溶性のマグネシウムの有機金属塩や水分散性のマグネシウム、および、アルミニウムの水酸化物は、前記活性成分の担体としてのマグネシア、および、アルミナの原料となる。 In the step (1), the water-soluble organometallic salt containing the metal element of at least one of active components of iron, cobalt, and nickel is converted into iron oxide, cobalt oxide, And it becomes a raw material of nickel oxide. Further, water-soluble magnesium organic metal salt, water-dispersible magnesium, and aluminum hydroxide serve as raw materials for magnesia and alumina as the active ingredient carrier.
活性成分の鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機金属塩は、例えば酢酸塩、クエン酸塩等を例示できる。これらは１種を単独で用いてもよく、２種以上を混合して用いても良い。中でも、コバルト化合物塩とニッケル化合物塩については無水酢酸塩、酢酸塩水和物、クエン酸塩が、鉄化合物塩についてはクエン酸塩、クエン酸鉄アンモニウム塩が水溶性の点において好ましい。 Examples of the water-soluble organometallic salt containing at least one active element metal element of iron, cobalt, and nickel as active ingredients include acetate, citrate, and the like. These may be used alone or in combination of two or more. Among them, anhydrous cobalt acetate, acetate hydrate and citrate are preferable for the cobalt compound salt and nickel compound salt, and citrate and iron ammonium citrate are preferable for the iron compound salt in terms of water solubility.
担体成分の原料であるマグネシウムおよびアルミニウムの少なくともいずれか１つ以上の担体成分の金属元素を含む水溶性の有機金属塩、または前記担体成分の金属元素を含む水酸化物としては、例えば酢酸マグネシウム、水酸化マグネシウム、水酸化アルミニウムを例示できる。 Examples of the water-soluble organometallic salt containing a metal element of at least one carrier component of magnesium and aluminum, which are raw materials of the carrier component, or the hydroxide containing the metal element of the carrier component include, for example, magnesium acetate, Examples thereof include magnesium hydroxide and aluminum hydroxide.
触媒の製造に用いる前記活性成分の水溶性の有機金属塩と、前記担体成分の水溶性の有機金属塩は、水に溶解させて混合する。また、活性成分の有機金属塩と担体成分の有機金属塩は、所定量を混合してから水に溶解させてもよく、また、それぞれを単独で水に溶解させてから、所定量を混合しても良い。また、水に溶解させる時に、溶解性を向上させるために、水が沸騰しない範囲で加熱しても良い。 The water-soluble organometallic salt of the active ingredient used for the production of the catalyst and the water-soluble organometallic salt of the carrier ingredient are dissolved in water and mixed. The organic metal salt of the active component and the organic metal salt of the carrier component may be mixed in a predetermined amount and then dissolved in water, or each may be dissolved in water alone and then mixed in a predetermined amount. May be. Moreover, when dissolving in water, in order to improve the solubility, heating may be performed in a range where water does not boil.
また、担体成分の水分散性のマグネシウムおよびアルミニウムの水酸化物は、単独で所定量を水に分散した後、前記活性成分と混合してもよく、また、前記活性成分と所定量を混合してから水に分散させても良い。 Further, the water-dispersible magnesium and aluminum hydroxides of the carrier component may be mixed with the active ingredient after being dispersed in water alone, and the active ingredient may be mixed with the predetermined amount. Then, it may be dispersed in water.
更に、水分散させる際に、ビーズミル分散機等を使用して、微細分散を行っても良い。 Furthermore, when dispersing in water, fine dispersion may be performed using a bead mill disperser or the like.
工程（１）に、さらにモリブデンを含む水溶性の金属塩を、溶液中に含有することもできる。モリブデンを含む水溶性の金属塩は、前記触媒活性成分の活性度を向上させる助触媒成分としての酸化モリブデンの原料となる。モリブデンを含む水溶性の金属塩は、前記活性成分および／または前記担体成分と所定量を混合してから水に溶解させても良く、また、前記助触媒成分を単独で水に溶解させてから、前記活性成分および／または前記担体成分と混合しても良い。 In step (1), a water-soluble metal salt containing molybdenum can also be contained in the solution. The water-soluble metal salt containing molybdenum serves as a raw material for molybdenum oxide as a promoter component that improves the activity of the catalytically active component. The water-soluble metal salt containing molybdenum may be dissolved in water after mixing a predetermined amount with the active component and / or the carrier component, or after the promoter component is dissolved in water alone. , And may be mixed with the active ingredient and / or the carrier ingredient.
モリブデンを含む水溶性の金属塩は、例えばモリブデン酸アンモニウム、モリブデン酸ナトリウム、モリブデン酸カリウム、モリブデン酸リチウム、リンモリブデン酸等を例示できる。 Examples of the water-soluble metal salt containing molybdenum include ammonium molybdate, sodium molybdate, potassium molybdate, lithium molybdate, and phosphomolybdic acid.
次に、前記のカーボンナノチューブ合成用触媒の工程（２）について説明する。 Next, step (2) of the carbon nanotube synthesis catalyst will be described.
工程（２）は、工程（１）で得られた、鉄、コバルト、および、ニッケルの少なくともいずれか１つ以上の活性成分の金属元素を含む水溶性の有機金属塩と、マグネシウムおよびアルミニウムの少なくともいずれか１つ以上の担体成分の金属元素を含む水溶性の有機金属塩、または前記担体成分の金属元素を含む水酸化物とを、水溶媒中に溶解および／または分散し、混合した溶液を、空気雰囲気下で、もしくは窒素、アルゴン等の不活性ガス雰囲気下で１００〜２００℃の範囲の温度で、乾燥して水分を除去して固形化し、さらに空気中で微細化処理して、平均粒径（Ｄ５０）が５０μｍ以下の触媒前駆体を作製する工程である。 Step (2) includes at least one of a water-soluble organometallic salt containing at least one active element metal element of iron, cobalt, and nickel obtained in step (1), and magnesium and aluminum. A solution obtained by dissolving and / or dispersing a water-soluble organometallic salt containing the metal element of any one or more carrier components or a hydroxide containing the metal element of the carrier component in an aqueous solvent, and mixing them. In an air atmosphere or in an inert gas atmosphere such as nitrogen or argon at a temperature in the range of 100 to 200 ° C., drying to remove moisture, solidifying, and further refinement in air, This is a step of producing a catalyst precursor having a particle size (D50) of 50 μm or less.
ここで、粉体の平均粒径（Ｄ５０）は、Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製の粉体粒度分布計ｍａｓｔｅｒｓｉｚｅｒ２０００を用いて乾式で測定し、積算（累積）重量百分率で積算値５０％の粒度を平均粒径（Ｄ５０）として算出した。 Here, the average particle diameter (D50) of the powder is measured by a dry method using a powder particle size distribution meter mastersizer 2000 manufactured by Malvern Instruments, and the average particle diameter is 50% of the integrated value (accumulated) weight percentage. Calculated as (D50).
工程（２）の触媒前駆体を製造する際に、乾燥して水分を除去するときの温度が重要であり、好ましくは１００℃以上２００℃以下である。 In producing the catalyst precursor in the step (2), the temperature at which the moisture is removed by drying is important, and is preferably 100 ° C. or higher and 200 ° C. or lower.
乾燥時の温度が２００℃を超えてしまうと、乾燥と同時に有機酸塩の一部で分解が起こり、前記の活性成分の担体としてのマグネシア、および、アルミナの原料となる、水溶性のマグネシウムの有機金属塩と均一に混合することができなくなるか、あるいは、水分散性のマグネシウム、および、アルミニウムの水酸化物の分散体表面に均一に存在することができなくなるため、乾燥して水分を除去して固形化した時に触媒の活性成分が微細に均一に存在できなくなるため好ましくない。 When the temperature at the time of drying exceeds 200 ° C., decomposition occurs in part of the organic acid salt simultaneously with drying, and magnesia as a carrier of the active ingredient and water-soluble magnesium as a raw material of alumina It cannot be uniformly mixed with the organometallic salt, or it cannot be uniformly present on the surface of the water-dispersible magnesium and aluminum hydroxide dispersion, so it is dried to remove moisture Then, the active component of the catalyst cannot be present finely and uniformly when solidified, which is not preferable.
一方、乾燥温度が１００℃未満であると、水分の乾燥に長時間かかるため、量産をする上で好ましくない。また、水分が残存していると、後述の微細化処理が難しく、触媒前駆体に適度の空気を含むことが難しくなってしまうため好ましくない。 On the other hand, if the drying temperature is less than 100 ° C., it takes a long time to dry the moisture, which is not preferable for mass production. In addition, if moisture remains, it is not preferable because the later-described refinement process is difficult, and it becomes difficult to contain appropriate air in the catalyst precursor.
工程（２）において、触媒前駆体を製造するときに、乾燥して水分を除去するときの温度は、好ましくは１００℃以上２００℃以下であるが、より好ましくは１２０℃以上１７０℃以下である。触媒前駆体を量産する際は、短時間で乾燥するように、できるだけ高温の雰囲気下が好ましいが、一方、高温の雰囲気下では、乾燥と同時に有機金属塩の一部で分解が起こり易いため、できるだけ低温の雰囲気下での乾燥が好ましい。１２０℃以上１７０℃以下の温度範囲は、短時間での乾燥性と有機金属塩の分解の起こり難さをいずれも満足する。 In the step (2), when producing the catalyst precursor, the temperature when drying to remove moisture is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 170 ° C. or lower. . When mass-producing the catalyst precursor, an atmosphere as high as possible is preferable so that the catalyst precursor is dried in a short time. On the other hand, in a high-temperature atmosphere, decomposition is likely to occur in part of the organometallic salt simultaneously with drying. Drying in an atmosphere as low as possible is preferred. The temperature range of 120 ° C. or more and 170 ° C. or less satisfies both the drying property in a short time and the difficulty of decomposition of the organometallic salt.
工程（２）において、乾燥して水分を除去して固形化した後、さらに微細化処理して、平均粒径（Ｄ５０）が５０μｍ以下の触媒前駆体を得ることが好ましい。 In the step (2), it is preferable to obtain a catalyst precursor having an average particle size (D50) of 50 μm or less by drying and removing water to solidify, and further finely processing.
前記の触媒前駆体は、乾燥して水分を除去して固形化した後、微細化処理することにより製造されるが、５０μｍ以下の平均粒径（Ｄ５０）まで微細化することにより、適度の空気を含むことができるようになる為、後述の工程（３）の触媒前駆体を焼成するときに、活性成分と担持成分双方の有機金属塩の有機化合物部位を効率的に分解させて消失させることができるようになる。一方、乾燥して水分を除去して固形化した後、微細化処理しないで焼成処理する、あるいは、５０μｍ以下の平均粒径（Ｄ５０）まで微細化処理しないで焼成を行うと、有機金属塩の有機化合物部位が完全に分解消失しないで、多量の炭素質不純物が触媒中に残り、カーボンナノチューブにおける異物の原因となり、また担体成分への活性成分粒子の均一担持が不十分となるため好ましくない。 The catalyst precursor is produced by drying to remove moisture and solidifying, followed by refinement treatment. By refinement to an average particle size (D50) of 50 μm or less, moderate air can be obtained. Therefore, when the catalyst precursor in the step (3) described below is calcined, the organic compound sites of the organometallic salt of both the active component and the supported component are efficiently decomposed and eliminated. Will be able to. On the other hand, after drying and solidifying by removing moisture, baking is performed without refining treatment, or baking is performed without refining to an average particle size (D50) of 50 μm or less. Since the organic compound site does not completely decompose and disappear, a large amount of carbonaceous impurities remain in the catalyst, causing foreign matters in the carbon nanotubes, and the active component particles are not uniformly supported on the carrier component.
工程（２）において、平均粒径（Ｄ５０）が５０μｍ以下の触媒前駆体を作成することが好ましいが、より好ましくは１μｍ以上３０μｍ以下である。平均粒径（Ｄ５０）が小さい方がより多くの空気を含むことができるようになる為、後述の工程（３）の触媒前駆体を焼成するときに、有機金属塩の有機化合物部位をより効率的に分解させて消失させることができる。一方、平均粒径（Ｄ５０）が１μｍ未満であると、工程（３）の焼成時に浮遊してしまい、結果として周囲の焼成雰囲気の汚染や焼成物の収率低下を起こしてしまうため、平均粒径（Ｄ５０）は大きい方が望ましい。１μｍ以上３０μｍ以下の平均粒径（Ｄ５０）は、工程（３）の焼成時の効率的な分解と汚染や収率低下の問題をいずれも満足する。 In the step (2), it is preferable to prepare a catalyst precursor having an average particle size (D50) of 50 μm or less, more preferably 1 μm or more and 30 μm or less. The smaller the average particle size (D50), the more the air can be contained. Therefore, when the catalyst precursor in step (3) described later is fired, the organic compound portion of the organometallic salt is more efficient. It can be decomposed and disappear. On the other hand, if the average particle size (D50) is less than 1 μm, it floats during firing in step (3), resulting in contamination of the surrounding firing atmosphere and a decrease in the yield of the fired product. A larger diameter (D50) is desirable. An average particle diameter (D50) of 1 μm or more and 30 μm or less satisfies both the problems of efficient decomposition, contamination, and yield reduction during firing in step (3).
工程（２）において、触媒前駆体製造時の微細化処理手段としては特に制限はないが、少量の場合は乳鉢を用いて、一度に多量を処理する場合は、ピンミル、ハンマーミル、パルペライザー、ターボミル、クリプトロンＫＴＭ等の機械式粉砕機、ジェットミル等の衝突式粉砕機を用いることができる。 In the step (2), there is no particular limitation on the means for refining the catalyst precursor, but in the case of a small amount, a mortar is used. When a large amount is processed at once, a pin mill, hammer mill, pulverizer, turbo mill A mechanical pulverizer such as Kryptron KTM or a collision pulverizer such as a jet mill can be used.
次に、前記のカーボンナノチューブ合成用触媒の工程（３）について説明する。 Next, the step (3) of the carbon nanotube synthesis catalyst will be described.
工程（３）は、工程（２）で得られた前記触媒前駆体を、酸素の存在下、焼成温度３５０〜５５０℃の範囲で加熱し、冷却した後、得られた焼成物を粉砕して平均粒径（Ｄ５０）が５μｍ以下のカーボンナノチューブ合成用触媒を得る工程である。 In the step (3), the catalyst precursor obtained in the step (2) is heated in the range of 350 to 550 ° C. in the presence of oxygen and cooled, and then the obtained fired product is pulverized. In this step, a carbon nanotube synthesis catalyst having an average particle size (D50) of 5 μm or less is obtained.
工程（３）において、触媒前駆体を焼成するとき、焼成雰囲気として酸素の存在下、空気中ないし空気と窒素混合雰囲気を用いることが重要である。酸素の欠乏雰囲気下での焼成では、活性成分と担持成分に由来する有機金属塩の有機化合物部位が完全に分解消失しないで、多量の炭素質不純物（以下、残炭分と称する）が触媒中に残り、カーボンナノチューブにおける異物の原因となり、また担体成分への活性成分粒子の均一担持が不十分となるため好ましくない。 In the step (3), when the catalyst precursor is calcined, it is important to use an air or nitrogen / air mixture atmosphere in the presence of oxygen as a calcining atmosphere. In the calcination in an oxygen-deficient atmosphere, the organic compound portion of the organometallic salt derived from the active component and the supported component is not completely decomposed and lost, and a large amount of carbonaceous impurities (hereinafter referred to as residual carbon content) are contained in the catalyst This is not preferable because it causes foreign matters in the carbon nanotubes, and the active component particles are not uniformly supported on the carrier component.
工程（３）において、焼成は、３５０℃以上５５０℃以下で行われることが好ましい。焼成温度が５５０℃よりも高いと活性成分の金属元素が焼結してしまい、３５０℃よりも低いと有機金属塩の有機化合物部位が未分解となり、多量の残炭分が触媒中に残り、カーボンナノチューブにおける異物の原因となり、また担体成分への活性成分粒子の均一担持が不十分となるため好ましくない。 In the step (3), firing is preferably performed at 350 ° C. or higher and 550 ° C. or lower. If the firing temperature is higher than 550 ° C, the metal element of the active component is sintered, and if it is lower than 350 ° C, the organic compound portion of the organometallic salt becomes undecomposed, and a large amount of residual carbon remains in the catalyst. This is not preferable because it causes foreign matters in the carbon nanotubes and the active component particles are not uniformly supported on the carrier component.
工程（３）において、焼成は、より好ましくは３５０℃以上５００℃以下、さらに好ましくは３７０℃以上４７０℃以下である。有機金属塩の有機化合物部位は燃焼により、分解・気化し、排出され、残炭分が望ましい範囲まで少なくなるには、できるだけ高温の雰囲気下で焼成することが好ましい。一方、高温の雰囲気下では活性成分の金属元素が焼結を起こしてしまい、後述のカーボンナノチューブ析出反応の効率が低下してしまう可能性があること、および急激な析出反応が起こるため生成するカーボンナノチューブの絡まりが大きくなり、分散性に劣るカーボンナノチューブ集合体となってしまうため好ましくない。 In the step (3), the firing is more preferably 350 ° C. or more and 500 ° C. or less, and further preferably 370 ° C. or more and 470 ° C. or less. The organic compound portion of the organometallic salt is preferably fired in an atmosphere as high as possible in order to decompose, vaporize and discharge by combustion, and to reduce the residual carbon content to a desired range. On the other hand, the active element metal element may sinter in a high-temperature atmosphere, which may reduce the efficiency of the carbon nanotube precipitation reaction described later, and the carbon produced due to the rapid precipitation reaction. Since the entanglement of the nanotubes becomes large and the carbon nanotube aggregate is inferior in dispersibility, it is not preferable.
焼結を起こさせないためには、できるだけ低温の雰囲気下で焼成することが好ましい。３７０℃以上４７０℃以下の温度範囲は、この残炭分と焼結のいずれも満足する。 In order not to cause sintering, it is preferable to fire in an atmosphere as low as possible. A temperature range of 370 ° C. or higher and 470 ° C. or lower satisfies both the residual carbon content and sintering.
工程（３）の焼成により、活性成分は鉄、コバルト、および、ニッケルのいずれかの酸化物、担体成分はマグネシア、および、アルミナのいずれかとなり、前記の鉄、コバルト、および、ニッケルのいずれかの酸化物が、前記のマグネシア、および、アルミナのいずれかに担持された触媒が得られる。 As a result of the firing in step (3), the active component is any oxide of iron, cobalt and nickel, the support component is either magnesia or alumina, and any one of the above iron, cobalt and nickel Thus, a catalyst in which the oxide is supported on either magnesia or alumina is obtained.
工程（３）において、このようにして得られた焼成物を更に微粉砕して平均粒径（Ｄ５０）が５μｍ以下の微粒子状の触媒とすることが好ましく、より好ましくは０．１μｍ以上５μｍ以下である。 In the step (3), it is preferable to further pulverize the fired product thus obtained to obtain a fine particle catalyst having an average particle size (D50) of 5 μm or less, more preferably 0.1 μm to 5 μm. It is.
工程（３）の微粉砕手段としては特に制限はないが、少量の場合は乳鉢を用いて、一度に多量を処理する場合は、ピンミル、ハンマーミル、パルペライザー、ジェットミル等を用いることができる。また、微粉砕後に分級機を用いることにより、粒度分布を調整することが好ましい。例えば、このジェットミルによる微粉砕時に、圧縮気体（通常、空気もしくは窒素が用いられる。）の圧力を制御するか、後段への分級機設置により粉砕粒度を調整して、所望の粒径の微粒子状触媒を得ることができる。分級機としては、エルボージェット分級機、気流式分級機、回転式分級機等を用いることができる。 The fine pulverizing means in step (3) is not particularly limited, but a mortar can be used for a small amount, and a pin mill, a hammer mill, a pulverizer, a jet mill or the like can be used for treating a large amount at a time. Moreover, it is preferable to adjust the particle size distribution by using a classifier after fine pulverization. For example, fine particles having a desired particle size can be obtained by controlling the pressure of compressed gas (usually air or nitrogen) during fine pulverization by the jet mill or adjusting the pulverization particle size by installing a classifier at the subsequent stage. A catalyst can be obtained. As the classifier, an elbow jet classifier, an airflow classifier, a rotary classifier, or the like can be used.
この様に、工程（１）〜（３）を経ることによって、本発明の分散体に用いる前記カーボンナノチューブ集合体を製造するための前記カーボンナノチューブ合成用触媒（Ｃ）が得られる。 Thus, the said carbon nanotube synthesis catalyst (C) for manufacturing the said carbon nanotube aggregate used for the dispersion of this invention is obtained by passing through process (1)-(3).
次に、得られた前記のカーボンナノチューブ合成用触媒（Ｃ）を使用し、本発明の分散体に用いる前記のカーボンナノチューブ集合体（Ｄ）の製造方法について説明する。 Next, a method for producing the carbon nanotube aggregate (D) used in the dispersion of the present invention using the obtained carbon nanotube synthesis catalyst (C) will be described.
本発明の分散体に用いる前記のカーボンナノチューブ集合体（Ｄ）を製造するには、触媒として前記のカーボンナノチューブ合成用触媒を用いて、炭素源としての原料ガスを加熱下、この触媒に接触させて、カーボンナノチューブの析出反応を行い製造する。 In order to produce the carbon nanotube aggregate (D) used for the dispersion of the present invention, the above-mentioned catalyst for carbon nanotube synthesis is used as a catalyst, and a raw material gas as a carbon source is brought into contact with this catalyst under heating. Then, the carbon nanotubes are produced by a precipitation reaction.
カーボンナノチューブの炭素源としての原料ガスとしては、従来公知の任意のものを使用でき、例えば、炭素を含むガスとしてメタンやエチレン、プロパン、ブタン、アセチレンなどの炭化水素や、一酸化炭素、メタノールやエタノール、プロパノール、イソプロパノール、ブタノールなどのアルコールなどを用いることができるが、特に使い易さ等の理由により、プロパン、ブタンやエタノールを用いることが好ましい。 As a source gas as a carbon source of the carbon nanotube, any conventionally known gas can be used. For example, as a gas containing carbon, hydrocarbons such as methane, ethylene, propane, butane, acetylene, carbon monoxide, methanol, Alcohols such as ethanol, propanol, isopropanol, and butanol can be used, but propane, butane and ethanol are preferably used for reasons such as ease of use.
また、必要に応じて、還元雰囲気下で活性化した後、又は還元性ガスと共にカーボンナノチューブ原料ガスと接触させて製造することが好ましい。活性化時における還元性ガスは、水素（Ｈ2）、アンモニア等を用いることができるが、特にＨ2が好ましく、その濃度は、原料ガス濃度１００体積％に対して０．１〜１００体積％、特に１〜１００体積％であることが好ましい。還元性ガスの濃度が０．１体積％未満であると、濃度が薄すぎて還元性ガスの効果が期待できない。１００体積％を超える濃度だと相対的に原料ガスが少なくなり、カーボンナノチューブ集合体の収率が低下してしまうため好ましくない。 Moreover, it is preferable to manufacture after making it activate in a reducing atmosphere as needed, or making it contact with carbon nanotube raw material gas with a reducing gas. As the reducing gas at the time of activation, hydrogen (H 2 ), ammonia or the like can be used, but H 2 is particularly preferable, and the concentration thereof is 0.1 to 100% by volume with respect to 100% by volume of the raw material gas. In particular, it is preferably 1 to 100% by volume. If the concentration of the reducing gas is less than 0.1% by volume, the concentration is too thin and the effect of the reducing gas cannot be expected. If the concentration exceeds 100% by volume, the amount of raw material gas is relatively reduced, and the yield of the aggregate of carbon nanotubes is unfavorable.
前記のカーボンナノチューブ集合体（Ｄ）を製造する方式としては、前記のカーボンナノチューブ合成用触媒（Ｃ）を、大気圧より減圧した雰囲気で原料ガスを導入する方式（以下、減圧法とする）でも良く、あるいは、大気圧下で原料ガスを導入する方式（以下、常圧法とする）でも良い。 As a method for producing the carbon nanotube aggregate (D), the carbon nanotube synthesis catalyst (C) may be a method in which a raw material gas is introduced in an atmosphere depressurized from atmospheric pressure (hereinafter referred to as a depressurization method). Alternatively, a method of introducing a source gas under atmospheric pressure (hereinafter referred to as an atmospheric pressure method) may be used.
減圧法は、減圧が可能で、外部ヒーターで加熱が可能な反応管内に、前記のカーボンナノチューブ合成用触媒（Ｃ）を設置し、反応管内部の空気を真空ポンプで吸引して減圧後、窒素やアルゴン等の不活性ガスを導入して、更に吸引して減圧することで、反応管内の酸素濃度を０．１％以下とした後、所定の反応温度で炭化水素ガス、必要に応じて水素ガス等の還元性ガスを混合して反応管内に導入してカーボンナノチューブ集合体（Ｄ）を製造する方式である。 In the depressurization method, the above-mentioned catalyst for carbon nanotube synthesis (C) is installed in a reaction tube that can be depressurized and heated by an external heater, and the air inside the reaction tube is sucked with a vacuum pump and depressurized. Introducing an inert gas such as argon or the like, and further reducing the pressure by suction to reduce the oxygen concentration in the reaction tube to 0.1% or less, and then at a predetermined reaction temperature, a hydrocarbon gas, and optionally hydrogen In this method, a reducing gas such as a gas is mixed and introduced into a reaction tube to produce a carbon nanotube aggregate (D).
常圧法は、常圧にて、窒素やアルゴン等の不活性ガスを導入して、反応管内部の空気を不活性ガスで置換して、反応管内の酸素濃度を０．１％以下とした後、所定の反応温度で炭化水素ガス、必要に応じて水素ガス等の還元性ガスを混合して反応管内に導入してカーボンナノチューブ集合体を製造する方式である。 In the normal pressure method, after introducing an inert gas such as nitrogen or argon at normal pressure and replacing the air inside the reaction tube with an inert gas, the oxygen concentration in the reaction tube is reduced to 0.1% or less. This is a method for producing a carbon nanotube aggregate by mixing a hydrocarbon gas at a predetermined reaction temperature and, if necessary, a reducing gas such as hydrogen gas into a reaction tube.
前記のカーボンナノチューブ合成用触媒（Ｃ）を用いて、前記のカーボンナノチューブ集合体（Ｄ）を製造する温度については、５００〜１０００℃の範囲で析出反応を行うことが好ましく、より好ましくは６００〜９００℃の範囲である。温度が５００℃未満であると、析出反応がほとんど起こらずカーボンナノチューブ集合体が製造できない。温度が１０００℃を超えると、前記得られたカーボンナノチューブ合成用触媒中の活性成分の焼結が発生し、カーボンナノチューブ析出反応の効率が低下してしまうこと、および急激な析出反応が起こるためカーボンナノチューブの絡まりが大きくなり、分散性に劣るカーボンナノチューブ集合体となってしまうため好ましくない。温度が６００〜９００℃は、ほぐれ易さを満足する。 About the temperature which manufactures the said carbon nanotube aggregate (D) using the said catalyst for carbon nanotube synthesis | combination (C), it is preferable to perform precipitation reaction in the range of 500-1000 degreeC, More preferably, 600- The range is 900 ° C. If the temperature is lower than 500 ° C., the precipitation reaction hardly occurs and the carbon nanotube aggregate cannot be produced. When the temperature exceeds 1000 ° C., sintering of the active component in the obtained catalyst for carbon nanotube synthesis occurs, and the efficiency of the carbon nanotube precipitation reaction decreases, and a rapid precipitation reaction occurs. Since the entanglement of the nanotubes becomes large and the carbon nanotube aggregate is inferior in dispersibility, it is not preferable. A temperature of 600 to 900 ° C. satisfies the ease of loosening.
原料ガスの供給量は、従来公知の任意の値から、適宜選択し決定すれば良いが、反応圧力は、減圧法の場合は大気圧以下圧力１００Ｐａ以上が好ましい。圧力が１００Ｐａ未満であると原料ガスが少なく、収率が低下してしまうため好ましくない。 The supply amount of the source gas may be appropriately selected and determined from any conventionally known value, but the reaction pressure is preferably an atmospheric pressure or lower and a pressure of 100 Pa or higher in the case of a decompression method. If the pressure is less than 100 Pa, the amount of raw material gas is small and the yield decreases, which is not preferable.
常圧法の場合は、常圧以上４０ｋＰａ以下、特に常圧以上３０ｋＰａ以下とすることが好ましい。反応時間は、反応温度や触媒と原料ガスとの接触比率に応じて任意に設定されるが、通常０．５〜６時間程度である。本発明での反応速度は反応開始から約１時間で最大となり、その後、徐々に失速して反応開始から５〜５．５時間で停止する。従って、反応時間は０．５〜６時間の範囲で管理することが好ましい。 In the case of the normal pressure method, the pressure is preferably set to normal pressure to 40 kPa, particularly normal pressure to 30 kPa. The reaction time is arbitrarily set according to the reaction temperature and the contact ratio between the catalyst and the raw material gas, but is usually about 0.5 to 6 hours. In the present invention, the reaction rate reaches its maximum at about 1 hour from the start of the reaction, and then gradually decreases and stops at 5 to 5.5 hours from the start of the reaction. Therefore, the reaction time is preferably managed in the range of 0.5 to 6 hours.
反応終了後の原料ガス置換には、アルゴンガスや窒素等の不活性ガスを用いることが好ましい。 It is preferable to use an inert gas such as argon gas or nitrogen for the replacement of the raw material gas after completion of the reaction.
［分散剤（Ａ），（Ｂ）］
次に、本発明の分散体に用いる分散剤（Ａ）、（Ｂ）について説明する。
[Dispersant (A), (B)]
Next, the dispersants (A) and (B) used in the dispersion of the present invention will be described.
本発明の分散体に用いるアミン価を有する分散剤（Ａ）は、固形分のアミン価が５〜１００ｍｇＫＯＨ／ｇであることが重要であり、より好ましくはアミン価を有し酸価を有しない分散剤である。固形分のアミン価が５ｍｇＫＯＨ／ｇ未満であると、前記のカーボンナノチューブ集合体が有する酸性を呈する部位との相互作用が小さくなり、分散安定性が劣る。一方、１００ｍｇＫＯＨ／ｇより大きいと、酸性を呈する部位との相互作用が大きすぎて、分散が困難となる。また、アミン価と酸価の両方を有する分散剤であると、後述の酸価を有する分散剤（Ｂ）と併用する場合、分散剤（Ａ）と分散剤（Ｂ）同士の相互作用が強くなり、分散剤（Ａ）と分散剤（Ｂ）が凝集してしまって分散剤の効果が小さくなるため、アミン価を有し酸価を有しない分散剤であることが好ましい。 In the dispersant (A) having an amine value used in the dispersion of the present invention, it is important that the amine value of the solid content is 5 to 100 mgKOH / g, more preferably an amine value and no acid value. It is a dispersant. If the amine value of the solid content is less than 5 mgKOH / g, the interaction with the acidic part of the aggregate of carbon nanotubes becomes small, and the dispersion stability is poor. On the other hand, when it is larger than 100 mgKOH / g, the interaction with the acidic part is too large and dispersion becomes difficult. Further, when the dispersant has both an amine value and an acid value, when used in combination with the dispersant (B) having an acid value described later, the interaction between the dispersant (A) and the dispersant (B) is strong. Thus, since the dispersant (A) and the dispersant (B) are aggregated to reduce the effect of the dispersant, a dispersant having an amine value and no acid value is preferable.
本発明の分散体に用いる酸価を有する分散剤（Ｂ）は、固形分の酸価が５〜１２０ｍｇＫＯＨ／ｇであることが重要であり、より好ましくは酸価を有しアミン価を有しない分散剤である。固形分の酸価が５ｍｇＫＯＨ／ｇ未満であると、前記のカーボンナノチューブ集合体が有する塩基性を呈する部位との相互作用が小さくなり、分散安定性が劣る。一方、１２０ｍｇＫＯＨ／ｇより大きいと、塩基性を呈する部位との相互作用が大きすぎて、分散が困難となる。また、酸価とアミン価の両方を有する分散剤であると、前記のアミン価を有する分散剤（Ａ）と併用する場合、分散剤（Ａ）と分散剤（Ｂ）同士の相互作用が強くなり、分散剤（Ａ）と分散剤（Ｂ）が凝集してしまって分散剤の効果が小さくなるため、酸価を有しアミン価を有しない分散剤であることが好ましい。 In the dispersant (B) having an acid value used in the dispersion of the present invention, it is important that the acid value of the solid content is 5 to 120 mgKOH / g, more preferably an acid value and no amine value. It is a dispersant. When the acid value of the solid content is less than 5 mgKOH / g, the interaction with the basic portion of the carbon nanotube aggregate is small, and the dispersion stability is poor. On the other hand, when it is larger than 120 mgKOH / g, the interaction with the basic portion is too large and dispersion becomes difficult. Further, when the dispersant has both an acid value and an amine value, when used in combination with the dispersant (A) having the amine value, the interaction between the dispersant (A) and the dispersant (B) is strong. Therefore, since the dispersant (A) and the dispersant (B) are aggregated to reduce the effect of the dispersant, it is preferable that the dispersant has an acid value and no amine value.
ここで、本発明に用いる分散剤の固形分のアミン価は、ＡＳＴＭ Ｄ ２０７４の方法に準拠し、測定した全アミン価（ｍｇＫＯＨ／ｇ）を固形分換算した値である。 Here, the amine value of the solid content of the dispersant used in the present invention is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content in accordance with the method of ASTM D 2074.
また、本発明に用いる分散剤の固形分の酸価は、ＪＩＳ Ｋ ００７０の電位差滴定法に準拠し、測定した酸価（ｍｇＫＯＨ／ｇ）を固形分換算した値である。 The acid value of the solid content of the dispersant used in the present invention is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.
本発明に使用するアミン価を有する分散剤（Ａ）としては、具体的には市販の分散剤であるＤＩＳＰＥＲＢＹＫ−２０００（固形分のアミン価 １０ｍｇＫＯＨ／ｇ）、ＤＩＰＥＲＢＹＫ−１６７（固形分のアミン価 ２５ｍｇＫＯＨ／ｇ）、ＢＹＫ−９０７７（固形分のアミン価（固形分のアミン価 ４９ｍｇＫＯＨ／ｇ）以上ビックケミー・ジャパン（株）社製、ＴＥＧＯ Ｄｉｓｐｅｒｓ７１０（固形分のアミン価 ８６ｍｇＫＯＨ／ｇ）以上エポニックデグサ・ジャパン（株）社製等を例示できる。 As the dispersant (A) having an amine value used in the present invention, specifically, a commercially available dispersant, DISPERBYK-2000 (solid content amine value 10 mgKOH / g), DIPERBYK-167 (solid content amine value) 25 mgKOH / g), BYK-9077 (solid content amine value (solid content amine value 49 mgKOH / g) or more, manufactured by Big Chemie Japan Co., Ltd., TEGO Dispers 710 (solid content amine value 86 mgKOH / g) or more, Eponic Degussa -Japan Co., Ltd. product etc. can be illustrated.
また、本発明に使用する酸価を有する分散剤（Ｂ）としては、具体的には市販の分散剤であるアジスパーＰＮ−４１１（固形分の酸価 ６ｍｇＫＯＨ／ｇ）以上味の素ファインテクノ（株）社製、ＤＩＳＰＥＲＢＹＫ−２０９６（固形分の酸価 ４０ｍｇＫＯＨ／ｇ）以上ビックケミー・ジャパン（株）社製、ＴＥＧＯ Ｄｉｓｐｅｒｓ６３０（固形分の酸価 １００ｍｇＫＯＨ／ｇ）以上エポニックデグサ・ジャパン（株）社製等を例示できる。 In addition, as the dispersant (B) having an acid value used in the present invention, specifically, Ajisper PN-411 (solid acid value 6 mgKOH / g) or more, which is a commercially available dispersant, Ajinomoto Fine Techno Co., Ltd. DISPERBYK-2096 (solid acid value 40 mgKOH / g) or more, manufactured by Big Chemie Japan Co., Ltd., TEGO Dispers630 (solid acid value 100 mgKOH / g) or more, manufactured by Eponic Degussa Japan Co., Ltd. Can be illustrated.
分散剤（Ａ）および／または分散剤（Ｂ）は、前記のカーボンナノチューブ集合体と、分散媒と共に所定量を測り取り、予備混合をしてもよく、また、分散媒と共に所定量を測り取り、分散媒に溶解させた後、前記のカーボンナノチューブ集合体を測り取り、予備混合をしても良い。また、分散剤（Ａ）と分散剤（Ｂ）を併用する場合、分散剤（Ａ）と分散剤（Ｂ）の混合順は問わず、どちらを先に予備混合しても良い。 The dispersant (A) and / or the dispersant (B) may be measured in a predetermined amount together with the aggregate of carbon nanotubes and the dispersion medium, and may be premixed, or the predetermined amount may be measured together with the dispersion medium. The carbon nanotube aggregate may be measured after being dissolved in a dispersion medium and premixed. Moreover, when using a dispersing agent (A) and a dispersing agent (B) together, regardless of the mixing order of a dispersing agent (A) and a dispersing agent (B), whichever may be pre-mixed first.
分散剤（Ａ）および／または分散剤（Ｂ）は、入手できる溶液または固形品をそのまま使用することも、必要に応じて分散剤を溶解できる溶媒に予め溶解させてから使用することもできるが、溶解性や前記のカーボンナノチューブ集合体と均一に相互作用させるためには、予め分散媒で希釈溶解させておくことが好ましい。 As the dispersant (A) and / or the dispersant (B), an available solution or solid product can be used as it is, or it can be used after dissolving in advance in a solvent capable of dissolving the dispersant, if necessary. In order to uniformly interact with the solubility and the carbon nanotube aggregate, it is preferable to dilute and dissolve in a dispersion medium in advance.
［分散媒］
本発明で言う分散媒とは、アミン価を５ｍｇＫＯＨ／ｇ以上有する分散剤および／または酸価を５ｍｇＫＯＨ／ｇ以上有する分散剤を溶解し、かつカーボンナノチューブ集合体を分散できる分散媒であれば、特に種類は問わない。具体的には、次の（ｉ）〜（ｘｉ）を例示することができる。
（ｉ）アルコール、特にメタノール、エタノール、ブタノール、エチルヘキサノール、デカノール、イソトリデシルアルコール、ベンジルアルコール、プロパルジルアルコール、オレイルアルコール、リノレイルアルコール、オキソ−加工アルコール、ネオペンチルアルコール、シクロヘキサノール、脂肪アルコールのような直鎖、分枝又は環式の一価又は多価アルコール、及び、グリコールのようなジオール及びポリオール；
（ｉｉ）２−メトキシエタノール、モノフェニルヂグリコール、フェニルエタノール、エチレングリコール、及びポリプロピレングリコールのようなエーテルアルコール；
（ｉｉｉ）トルエン、キシレンのような炭化水素、脂肪族及び／若しくは脂環式ベンジン画分、クロロホルム及びトリクロロエタンのような塩素化炭化水素；
（ｉｖ）エーテル、特にジオキサン、テトラヒドロフラン、及びポリアルキレングリコールジアルキルエーテルのような環式及び非環式エーテル；
（ｖ）カルボン酸エステル、特にエチルアセテート及びブチルアセテートのようなモノカルボン酸エステル、及びＣ２〜Ｃ４時カルボン酸のジアルキルエステルにようなのジカルボン酸又はポリカルボン酸エステル（「二塩基エステル」）；
（ｖｉ）エーテルエステル、特にエチルグリコールアセテート及びプロピレングリコールモノメチルエーテルアセテートのようなアルキルグリコールエステル；
（ｖｉｉ）ブチロラクトンのようなラクトン；
（ｖｉｉｉ）可塑剤、特にフタレート；
（ｉｘ）メチルイソブチルケトン、シクロヘキサノン、メチルエチルケトン及びアセトンのようなアルデヒド及びケトン；
（ｘ）ジメチルホルムアミドのような酸アミド；
（ｘｉ）Ｎ−メチルピロリドン；及び上述した分散媒体の混合物
この中で、樹脂の溶解性や取扱い性などの観点より、メチルエチルケトンのようなケトン類や酢酸エチルのようなカルボン酸エステルが好ましい。
[Dispersion medium]
The dispersion medium referred to in the present invention is a dispersion medium that dissolves a dispersant having an amine value of 5 mgKOH / g or more and / or a dispersant having an acid value of 5 mgKOH / g or more and can disperse a carbon nanotube aggregate. The type is not particularly limited. Specifically, the following (i) to (xi) can be exemplified.
(I) alcohols, in particular methanol, ethanol, butanol, ethyl hexanol, decanol, isotridecyl alcohol, benzyl alcohol, propargyl alcohol, oleyl alcohol, linoleyl alcohol, oxo-processed alcohol, neopentyl alcohol, cyclohexanol, fat Linear, branched or cyclic mono- or polyhydric alcohols such as alcohols, and diols and polyols such as glycols;
(Ii) ether alcohols such as 2-methoxyethanol, monophenyldiglycol, phenylethanol, ethylene glycol, and polypropylene glycol;
(Iii) hydrocarbons such as toluene, xylene, aliphatic and / or alicyclic benzine fractions, chlorinated hydrocarbons such as chloroform and trichloroethane;
(Iv) ethers, especially cyclic and acyclic ethers such as dioxane, tetrahydrofuran, and polyalkylene glycol dialkyl ethers;
(V) Carboxylic acid esters, in particular monocarboxylic acid esters such as ethyl acetate and butyl acetate, and dicarboxylic or polycarboxylic acid esters such as C2-C4 dialkyl esters of carboxylic acids ("dibasic esters");
(Vi) ether esters, especially alkyl glycol esters such as ethyl glycol acetate and propylene glycol monomethyl ether acetate;
(Vii) a lactone such as butyrolactone;
(Viii) plasticizers, especially phthalates;
(Ix) Aldehydes and ketones such as methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone and acetone;
(X) an acid amide such as dimethylformamide;
(Xi) N-methylpyrrolidone; and a mixture of the above-described dispersion media Among them, ketones such as methyl ethyl ketone and carboxylic acid esters such as ethyl acetate are preferable from the viewpoint of the solubility and handling properties of the resin.
［分散方法］
分散媒に、炭素材料を分散させる工程としては、特に限定はなく、公知の方法が用いられる。具体的には、例えば、ビーズミル分散法等のメディア分散法；超音波分散法、ロールミル分散法等のメディアレス分散法等が挙げられる。このうち、分散安定性等の点から、好ましくはロールミル分散法又はビーズミル分散法であり、特に好ましくはビーズミル分散法である。
[Distribution method]
The step of dispersing the carbon material in the dispersion medium is not particularly limited, and a known method is used. Specific examples include a media dispersion method such as a bead mill dispersion method; a medialess dispersion method such as an ultrasonic dispersion method and a roll mill dispersion method. Among these, from the viewpoint of dispersion stability, the roll mill dispersion method or the bead mill dispersion method is preferable, and the bead mill dispersion method is particularly preferable.
以下、実施例によって本発明を具体的に説明するが、本発明は実施例に特に限定されるものではない。なお、実施例中、「部」は「重量部」、「％」は「重量％」を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.
実施例中の表２〜９中の略称（溶剤・分散媒）は以下に示すとおりである。
・ＰＧＭＡｃ：プロピレングリコールモノメチルエーテルアセテート
・ＭＥＫ：メチルエチルケトン
Abbreviations (solvents / dispersion media) in Tables 2 to 9 in the Examples are as shown below.
-PGMAc: Propylene glycol monomethyl ether acetate-MEK: Methyl ethyl ketone
（製造例１）［カーボンナノチューブ合成用触媒（Ｃ）の製造］
酢酸コバルト・四水和物２００部、酢酸マグネシウム・四水和物１７２部、七モリブデン酸六アンモニウム・四水和物３．５部をビーカーに量り取り、精製水を１４８８部加えて、完全に溶解するまで攪拌した。耐熱性容器に移し替え、電気オーブンを用いて、雰囲気温度１５０±５℃の温度で６０分乾燥させ水分を蒸発させた後、乳鉢で粉砕して平均粒径（Ｄ５０）２０μｍの触媒（Ｃ）前駆体を得た。得られた触媒（Ｃ）前駆体３００部を耐熱容器に量り取り、マッフル炉にて、空気中４５０℃±５℃雰囲気下で６０分焼成した後、乳鉢で粉砕して平均粒径（Ｄ５０）２μｍの触媒（Ｃ）を得た。
(Production Example 1) [Production of carbon nanotube synthesis catalyst (C)]
Weigh 200 parts of cobalt acetate tetrahydrate, 172 parts of magnesium acetate tetrahydrate, 3.5 parts of hexaammonium hexamolybdate tetrahydrate into a beaker, add 1488 parts of purified water, Stir until dissolved. Transfer to a heat-resistant container and dry using an electric oven at an ambient temperature of 150 ± 5 ° C. for 60 minutes to evaporate the water, and then pulverize in a mortar to obtain a catalyst (C) having an average particle diameter (D50) of 20 μm A precursor was obtained. 300 parts of the obtained catalyst (C) precursor was weighed into a heat-resistant container, calcined in a muffle furnace in an atmosphere of 450 ° C. ± 5 ° C. for 60 minutes, and then pulverized in a mortar to obtain an average particle diameter (D50) A 2 μm catalyst (C) was obtained.
（製造例２）［カーボンナノチューブ集合体（Ｄ−１）の製造］
減圧が可能で、外部ヒーターで加熱可能な横型反応管の中央部に、製造例１で得られた触媒（Ｃ）１．０ｇ を散布した石英ガラス製耐熱皿を設置した。横型反応管中の空気を真空ポンプにて１×１０3Ｐａまで減圧後、アルゴンガスを８×１０4Ｐａまで注入し、再度真空ポンプにて1×１０3Ｐａまで減圧する、を２回繰り返して、横型反応管中の酸素濃度を０．１体積％以下とした。1×１０3Ｐａに保ちながら外部ヒーターにて加熱し、横型反応管の中心部が８５０℃まで加熱した。合成温度８５０±５℃に保ち、ブタン／プロパン混合ガスを注入し、３×１０4Ｐａ〜６×１０4Ｐａに反応管内の圧力を維持しながら３時間反応させてカーボンナノチューブ集合体を製造した。合成終了後、反応管内のガスをアルゴンガスで置換し、２００℃以下の温度で取り出し、カーボンナノチューブ集合体を得た。得られたカーボンナノチューブ集合体は、４０メッシュの金網で粉砕ろ過して、製造例２のカーボンナノチューブ集合体（Ｄ−１）の粉体を得た。
(Production Example 2) [Production of carbon nanotube aggregate (D-1)]
A quartz glass bakeware sprinkled with 1.0 g of the catalyst (C) obtained in Production Example 1 was placed in the center of a horizontal reaction tube that can be decompressed and heated with an external heater. The pressure in the horizontal reaction tube is reduced to 1 × 10 3 Pa with a vacuum pump, argon gas is injected to 8 × 10 4 Pa, and the pressure is reduced to 1 × 10 3 Pa again with a vacuum pump. Thus, the oxygen concentration in the horizontal reaction tube was set to 0.1% by volume or less. Heating was performed with an external heater while maintaining the pressure at 1 × 10 3 Pa, and the central portion of the horizontal reaction tube was heated to 850 ° C. Maintaining the synthesis temperature 850 ± 5 ° C., poured butane / propane mixed gas to produce a carbon nanotube aggregate by 3 hours while maintaining the pressure in the reaction tube to 3 × 10 4 Pa~6 × 10 4 Pa . After completion of the synthesis, the gas in the reaction tube was replaced with argon gas and taken out at a temperature of 200 ° C. or less to obtain a carbon nanotube aggregate. The obtained carbon nanotube aggregate was pulverized and filtered with a 40-mesh wire mesh to obtain a carbon nanotube aggregate (D-1) powder of Production Example 2.
（製造例３）［カーボンナノチューブ集合体（Ｄ−２）の製造］
ある程度まで加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、製造例１で得られた触媒（Ｃ）１．０ｇ を散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気をして、反応管内の空気をアルゴンガスで置換し、横型反応管中の酸素濃度を０．１体積％以下とした。外部ヒーターにて加熱し、横型反応管の中心部が７５０℃まで加熱した。合成温度７５０±５℃に保ち、ブタン／プロパン混合ガスを毎分１リットルの速度で注入し、３時間分反応させてカーボンナノチューブ集合体を製造した。合成終了後、反応管内のガスをアルゴンガスで置換し、２００℃以下の温度で取り出し、カーボンナノチューブ集合体を得た。得られたカーボンナノチューブ集合体は、４０メッシュの金網で粉砕ろ過して、製造例３のカーボンナノチューブ集合体（Ｄ−２）の粉体を得た。
(Production Example 3) [Production of carbon nanotube aggregate (D-2)]
A quartz glass bakeware in which 1.0 g of the catalyst (C) obtained in Production Example 1 is sprayed in the center of a horizontal reaction tube that can be pressurized to a certain extent and can be heated with an external heater and has an internal volume of 10 liters. Was installed. The air was exhausted while injecting argon gas, and the air in the reaction tube was replaced with argon gas, so that the oxygen concentration in the horizontal reaction tube was 0.1 vol% or less. It heated with the external heater and the center part of the horizontal reaction tube heated to 750 degreeC. While maintaining the synthesis temperature at 750 ± 5 ° C., a butane / propane mixed gas was injected at a rate of 1 liter per minute and reacted for 3 hours to produce a carbon nanotube aggregate. After completion of the synthesis, the gas in the reaction tube was replaced with argon gas and taken out at a temperature of 200 ° C. or less to obtain a carbon nanotube aggregate. The obtained carbon nanotube aggregate was pulverized and filtered with a 40-mesh wire mesh to obtain a carbon nanotube aggregate (D-2) powder of Production Example 3.
（製造例４）［カーボンナノチューブ集合体（Ｄ−３）の製造］
ある程度まで加圧可能で、反応器の外側に設けられたヒーターで加熱可能な、内容積が８０リットルの縦型反応器の内部にシリコン基板を設置し、該シリコン基板上に、製造例１で得られた触媒（Ｃ）１０ｇを散布した。反応器内にアルゴンガスを注入しながら排気をして、反応器内の空気をアルゴンガスで置換し、酸素濃度を０．１体積％以下とした。反応器の外側ヒーターで加熱し、反応器内部温度を６５０℃まで加熱した。合成温度６５０±５℃に保ち、ブタン／プロパン混合ガスを毎分５リットルの速度で注入し、３時間反応させてカーボンナノチューブ集合体を製造した。合成終了後、反応器内のガスをアルゴンガスで置換し、２００℃以下の温度で取り出し、カーボンナノチューブ集合体を得た。得られたカーボンナノチューブ集合体は、４０メッシュの金網で粉砕ろ過して、製造例４のカーボンナノチューブ集合体（Ｄ−３）の紛体を得た。
(Production Example 4) [Production of carbon nanotube aggregate (D-3)]
A silicon substrate is placed inside a vertical reactor that can be pressurized to a certain extent and can be heated by a heater provided outside the reactor and has an internal volume of 80 liters. 10 g of the obtained catalyst (C) was sprayed. The reactor was evacuated while injecting argon gas, the air in the reactor was replaced with argon gas, and the oxygen concentration was adjusted to 0.1% by volume or less. The reactor was heated by an outer heater, and the reactor internal temperature was heated to 650 ° C. While maintaining the synthesis temperature at 650 ± 5 ° C., a butane / propane mixed gas was injected at a rate of 5 liters per minute and reacted for 3 hours to produce a carbon nanotube aggregate. After completion of the synthesis, the gas in the reactor was replaced with argon gas and taken out at a temperature of 200 ° C. or lower to obtain a carbon nanotube aggregate. The obtained carbon nanotube aggregate was pulverized and filtered with a 40-mesh wire mesh to obtain a carbon nanotube aggregate (D-3) in Production Example 4.
（製造例５）［カーボンナノチューブ集合体（Ｄ−４）の製造］
市販のＣＮａｎｏ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ製カーボンナノチューブＦｌｏＴｕｂｅ９０００−Ｍを用いて、４０メッシュの金網で粉砕ろ過して、製造例５のカーボンナノチューブ集合体（Ｄ−４）の粉末を得た。
(Production Example 5) [Production of carbon nanotube aggregate (D-4)]
Using commercially available carbon nanotubes FloTube 9000-M manufactured by CNano Technology Limited, the carbon nanotube aggregate (D-4) of Production Example 5 was obtained by pulverizing and filtering with a 40-mesh wire mesh.
表１に、実施例中に用いたカーボンナノチューブ集合体（Ｄ−１〜Ｄ−４）の膨潤率、アミン吸着量、酸吸着量を示した。 Table 1 shows the swelling ratio, amine adsorption amount, and acid adsorption amount of the carbon nanotube aggregates (D-1 to D-4) used in the examples.
表１
（製造例６）［分散剤溶液の製造］
市販の分散剤であるＤＩＳＰＥＲＢＹＫ−２０００、ＤＩＳＰＥＲＢＹＫ−１６７、ＢＹＫ−９０７７、ＤＩＳＰＥＲＢＹＫ−２０９６、ＤＩＳＰＥＲＢＹＫ−１１１，ＤＩＳＰＥＲＢＹＫ−１０９（以上ビックケミー・ジャパン株式会社）、ＴＥＧＯ Ｄｉｓｐｅｒｓ７１０、ＴＥＧＯ Ｄｉｓｐｅｒｓ６１０、ＴＥＧＯ Ｄｉｓｐｅｒｓ６３０（以上エポニックデグサ・ジャパン株式会社）、アジスパーＰＮ−４１１（以上味の素ファインテクノ株式会社）を、表２〜３で示した配合比でプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＡｃ）で希釈し、固形分４０％の分散剤溶液Ｅ−１〜３、Ｅ−５〜１０を得た。なお、分散剤溶液Ｅ−４については、希釈前の固形分が３５％であり、希釈しないで用いた。
(Production Example 6) [Production of Dispersant Solution]
DISPERBYK-2000, DISPERBYK-167, BYK-9077, DISPERBYK-2096, DISPERBYK-111, DISPERBYK-109 (above Big Chemie Japan Co., Ltd.), TEGO Dispers710, TEGO Dispers610is, TEGO Diss610, TEGO Diss610, EPO Degussa Japan Co., Ltd.), Ajisper PN-411 (Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate (PGMAc) at the blending ratios shown in Tables 2-3, and a dispersant having a solid content of 40% Solutions E-1 to E3 and E-5 to 10 were obtained. The dispersant solution E-4 had a solid content before dilution of 35% and was used without dilution.
表２
表３
（実施例１）
７０ｃｃガラス瓶に、製造例６にて製造した分散剤（Ａ）溶液Ｅ−１を１．８８部、カーボンナノチューブ集合体Ｄ−１を０．７５部、分散媒（メチルエチルケトン）２７．３７部を配合し、２ｍｍφジルコニアビーズ部を加えスキャンデックスで３時間分散し、カーボンナノチューブ集合体の分散体を調製した。
(Example 1)
Into a 70 cc glass bottle, 1.88 parts of the dispersant (A) solution E-1 produced in Production Example 6 is blended, 0.75 parts of the carbon nanotube aggregate D-1 and 27.37 parts of the dispersion medium (methyl ethyl ketone) are blended. Then, a 2 mmφ zirconia bead portion was added and dispersed with a scandex for 3 hours to prepare a carbon nanotube aggregate dispersion.
（実施例２〜６）
表４に示した分散剤（Ａ）溶液の種類および配合量、カーボンナノチューブ集合体の種類、分散媒の配合量に変更した以外は実施例１と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Examples 2 to 6)
The dispersion of the carbon nanotube aggregate was changed in the same manner as in Example 1 except that the type and blending amount of the dispersant (A) solution shown in Table 4 were changed to the kind of the carbon nanotube aggregate and the blending amount of the dispersion medium. Prepared.
表４
（実施例７）
７０ｃｃガラス瓶に、製造例６にて製造した分散剤（Ｂ）溶液Ｅ−６を１．８８部、カーボンナノチューブ集合体Ｄ−１を０．７５部、分散媒（メチルエチルケトン）２７．３７部を配合し、２ｍｍφジルコニアビーズ部を加えスキャンデックスで３時間分散し、カーボンナノチューブ集合体の分散体を調製した。
(Example 7)
In a 70 cc glass bottle, 1.88 parts of the dispersant (B) solution E-6 produced in Production Example 6, 0.75 parts of the carbon nanotube aggregate D-1 and 27.37 parts of a dispersion medium (methyl ethyl ketone) are blended. Then, a 2 mmφ zirconia bead portion was added and dispersed with a scandex for 3 hours to prepare a carbon nanotube aggregate dispersion.
（実施例８〜１１）
表５に示した分散剤（Ｂ）溶液の種類およびカーボンナノチューブ集合体の種類に変更した以外は実施例７と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Examples 8 to 11)
A carbon nanotube aggregate dispersion was prepared in the same manner as in Example 7 except that the type of the dispersant (B) solution and the type of carbon nanotube aggregate shown in Table 5 were changed.
表５
（実施例１２）
７０ｃｃガラス瓶に、製造例６にて製造した分散剤（Ａ）溶液Ｅ−２を０．９４部、分散剤（Ｂ）溶液Ｅ−７を０．９４部、カーボンナノチューブ集合体Ｄ−１を０．７５部、分散媒（メチルエチルケトン）２７．３部を配合し、２ｍｍφジルコニアビーズ部を加えスキャンデックスで３時間分散し、カーボンナノチューブ集合体の分散体を調製した。
Example 12
In a 70 cc glass bottle, 0.94 part of the dispersant (A) solution E-2 produced in Production Example 6, 0.94 part of the dispersant (B) solution E-7, and 0 of the carbon nanotube aggregate D-1 .75 parts and 27.3 parts of a dispersion medium (methyl ethyl ketone) were added, 2 mmφ zirconia bead parts were added, and the mixture was dispersed with a scandex for 3 hours to prepare a carbon nanotube aggregate dispersion.
（実施例１３〜１５）
表６に示した分散剤（Ａ）溶液の種類および分散剤（Ｂ）溶液の種類、カーボンナノチューブ集合体の種類に変更した以外は実施例１２と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Examples 13 to 15)
A dispersion of carbon nanotube aggregates was prepared in the same manner as in Example 12 except that the types of dispersant (A) solution and dispersant (B) solution shown in Table 6 were changed to the types of carbon nanotube aggregates. Prepared.
表６
（比較例１〜６）
表７に示した分散剤（Ａ）溶液の種類および配合量、カーボンナノチューブ集合体の種類、分散媒の配合量に変更した以外は実施例１と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Comparative Examples 1-6)
The dispersion of the carbon nanotube aggregate was changed in the same manner as in Example 1 except that the type and blending amount of the dispersant (A) solution shown in Table 7 were changed to the kind of the carbon nanotube aggregate and the blending amount of the dispersion medium. Prepared.
表７
（比較例７〜１１）
表８に示した分散剤（Ｂ）溶液の種類およびカーボンナノチューブ集合体の種類に変更した以外は実施例７と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Comparative Examples 7 to 11)
A carbon nanotube aggregate dispersion was prepared in the same manner as in Example 7 except that the type of the dispersant (B) solution and the type of carbon nanotube aggregate shown in Table 8 were changed.
表８
（比較例１２〜１４）
表９に示した分散剤（Ａ）溶液の種類および分散剤（Ｂ）溶液の種類、カーボンナノチューブ集合体の種類に変更した以外は実施例１２と同様にして、カーボンナノチューブ集合体の分散体を調製した。
(Comparative Examples 12-14)
A dispersion of carbon nanotube aggregates was prepared in the same manner as in Example 12 except that the types of dispersant (A) solution and dispersant (B) solution shown in Table 9 were changed to the types of carbon nanotube aggregates. Prepared.
表９
［カーボンナノチューブ集合体の分散体評価方法および結果］
本発明のカーボンナノチューブ分散組成物の分散状態の評価は、溶剤中で分散したカーボンナノチューブ分散組成物の分散状態（沈殿の有無、粘度、経時安定性）で行った。
・初期粘度：カーボンナノチューブ分散組成物を、分散後室温で１日静置後、 ２５℃に調整し、Ｅ型粘度計ＲＥ−８０（東機産業社製）にて測定した。
・沈殿の有無：目視で沈殿の有無を確認し、全く沈殿の無いものを○、僅かに 沈殿が見られるものを△、沈殿の多いものを×とした。
・経時安定性：カーボンナノチューブ分散組成物を、４０℃１ヶ月経時保存し た後、上記と同様にして、沈殿の有無、経時粘度を測定した。経時粘度につ いては、初期粘度からの変化が１０％以内を◎、１０〜３０％以内を○、３ ０〜１００％以内を△、それ以上の変化または増粘して粘度が測定不能にな った場合を×とした。
[Method for evaluating dispersion of carbon nanotube aggregate and results]
Evaluation of the dispersion state of the carbon nanotube dispersion composition of the present invention was performed based on the dispersion state of the carbon nanotube dispersion composition dispersed in a solvent (presence of precipitation, viscosity, stability over time).
Initial viscosity: After dispersion, the carbon nanotube dispersion composition was allowed to stand at room temperature for 1 day, adjusted to 25 ° C., and measured with an E-type viscometer RE-80 (manufactured by Toki Sangyo Co., Ltd.).
-Presence / absence of precipitation: The presence / absence of precipitation was confirmed by visual inspection. The case where there was no precipitation was indicated as ◯, the case where slight precipitation was observed was indicated as △, and the case where precipitation was large was indicated as ×.
-Stability over time: After the carbon nanotube dispersion composition was stored for one month at 40 ° C, the presence or absence of precipitation and the viscosity over time were measured in the same manner as described above. As for the viscosity over time, the change from the initial viscosity is within 10%, the 10-30% is within ◯, the within 30-100% is within △, and the viscosity is not measurable due to further change or thickening. The case where there was nothing was set as x.
表１０に、実施例１〜１５のカーボンナノチューブ集合体の分散体評価結果（分散１日後および４０℃３０日経時後）を示した。 Table 10 shows the dispersion evaluation results of the carbon nanotube aggregates of Examples 1 to 15 (one day after dispersion and after 30 days at 40 ° C.).
表１０
表１１に、比較例１〜１４のカーボンナノチューブ集合体の分散体評価結果（分散１日後および４０℃３０日経時後）を示した。 Table 11 shows the evaluation results of the carbon nanotube aggregates of Comparative Examples 1 to 14 (after 1 day of dispersion and after 30 days of 40 ° C.).
表１１
表１０より、実施例１〜１５で得られたカーボンナノチューブ集合体の分散体は、表１１で得られた比較例１〜１４と比較して、分散1日後および４０℃３０日経時後で良好な分散安定性を有していることが分かる。 From Table 10, the dispersion of carbon nanotube aggregates obtained in Examples 1 to 15 was better after 1 day of dispersion and after 30 days at 40 ° C. than Comparative Examples 1 to 14 obtained in Table 11. It can be seen that it has excellent dispersion stability.
以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は本発明の範囲に含まれる。 As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.
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