JP2012020924A - Method for manufacturing graphite particle dispersion, and graphite particle dispersion - Google Patents
Method for manufacturing graphite particle dispersion, and graphite particle dispersion Download PDFInfo
- Publication number
- JP2012020924A JP2012020924A JP2011134160A JP2011134160A JP2012020924A JP 2012020924 A JP2012020924 A JP 2012020924A JP 2011134160 A JP2011134160 A JP 2011134160A JP 2011134160 A JP2011134160 A JP 2011134160A JP 2012020924 A JP2012020924 A JP 2012020924A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- graphite particle
- membered ring
- particle dispersion
- ring skeleton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 185
- 239000010439 graphite Substances 0.000 title claims abstract description 184
- 239000002245 particle Substances 0.000 title claims abstract description 151
- 239000006185 dispersion Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003586 protic polar solvent Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 abstract 3
- 238000005336 cracking Methods 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 description 15
- 238000009830 intercalation Methods 0.000 description 15
- -1 graphite Chemical class 0.000 description 13
- 239000000138 intercalating agent Substances 0.000 description 7
- 229910021382 natural graphite Inorganic materials 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007800 oxidant agent Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- LLLWMXQKXWIRDZ-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one Chemical compound C=CN1CCCC1=O.C=CN1CCCC1=O LLLWMXQKXWIRDZ-UHFFFAOYSA-N 0.000 description 2
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical compound CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 description 2
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 description 2
- ORNUPNRNNSVZTC-UHFFFAOYSA-N 2-vinylthiophene Chemical compound C=CC1=CC=CS1 ORNUPNRNNSVZTC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000011835 quiches Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NOYVOSGVFSEKPR-UHFFFAOYSA-N 2-Pentylthiophene Chemical compound CCCCCC1=CC=CS1 NOYVOSGVFSEKPR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- BLDGTTBQSUTRDG-UHFFFAOYSA-N 2-octadecyl-1h-pyrrole Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CN1 BLDGTTBQSUTRDG-UHFFFAOYSA-N 0.000 description 1
- QUKGVEYDVQUXJG-UHFFFAOYSA-N 2-octyl-1h-pyrrole Chemical compound CCCCCCCCC1=CC=CN1 QUKGVEYDVQUXJG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- MZJUGRUTVANEDW-UHFFFAOYSA-N bromine fluoride Chemical compound BrF MZJUGRUTVANEDW-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- YVIVRJLWYJGJTJ-UHFFFAOYSA-N gamma-Valerolactam Chemical compound CC1CCC(=O)N1 YVIVRJLWYJGJTJ-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
本発明は、黒鉛粒子分散液の製造方法及び黒鉛粒子分散液に関する。 The present invention relates to a method for producing a graphite particle dispersion and a graphite particle dispersion.
従来から、黒鉛粒子をフィラ−として用いることが広く検討されており、更に、黒鉛粒子をより良好な分散状態で分散させる技術の開発も検討されている。特許文献１には、例えば、カ−ボンブラックを溶媒に対して５〜２５重量％、ポリビニルピロリドン（ＰＶＰ）をカ−ボンブラックに対して２０〜６０重量％の割合で含み、かつ、式（１）：３００≦Ｔ2／Ｄ50≦５５０（式中、Ｔ２は当該分散液のスピン−スピン緩和時間（ｍｓ）、Ｄ50は当該分散液中のカ−ボンブラックのメディアン径（μｍ）を示す。）を満たすカ−ボンブラック分散液が開示されている。 Conventionally, the use of graphite particles as fillers has been widely studied, and further development of a technique for dispersing graphite particles in a better dispersion state has been studied. Patent Document 1 includes, for example, 5 to 25% by weight of carbon black with respect to the solvent and 20 to 60% by weight of polyvinyl pyrrolidone (PVP) with respect to the carbon black, and a formula ( 1): 300 ≦ T 2 / D 50 ≦ 550 (where T2 is the spin-spin relaxation time (ms) of the dispersion, D 50 is the median diameter (μm) of carbon black in the dispersion) A carbon black dispersion satisfying the above is disclosed.
そして、特許文献１には、溶媒としてＮ−メチルピロリドンを用いることが好ましく、カ−ボンブラックのメディアン径Ｄ50が０．１２〜０．２０μｍであることが記載されている。 Patent Document 1 describes that N-methylpyrrolidone is preferably used as a solvent, and that the median diameter D 50 of carbon black is 0.12 to 0.20 μm.
しかしながら、特許文献１に記載の技術によると、使用する有機溶媒が限定されるという問題があった。 However, according to the technique described in Patent Document 1, there is a problem that the organic solvent to be used is limited.
一方、近年、グラファイトをその層面で剥離して薄片化した薄片化黒鉛をフィラ−として用いる試みもなされている。例えば、特許文献２には、酸化グラファイトを熱的に剥離させた変性グラファイト酸化物材料が提案されている。そして、特許文献２には、実施例において、ＤＭＦ、ＮＭＰ、１，２−ジクロロベンゼン又はニトロメタンを溶媒として用いると、安定した分散液が得られることが記載されている。 On the other hand, in recent years, an attempt has been made to use exfoliated graphite obtained by exfoliating graphite on its layer surface as a filler. For example, Patent Document 2 proposes a modified graphite oxide material obtained by thermally exfoliating graphite oxide. Patent Document 2 describes that, in the examples, when DMF, NMP, 1,2-dichlorobenzene or nitromethane is used as a solvent, a stable dispersion can be obtained.
しかしながら、特許文献２に記載の技術によると、グラファイトに変性処理や熱処理を加えているので、得られる変性グラファイト酸化物材料は、グラファイト本来の性質が損なわれているという問題がある。 However, according to the technique described in Patent Document 2, since the graphite is subjected to a modification treatment or a heat treatment, the obtained modified graphite oxide material has a problem that the original properties of graphite are impaired.
本発明は、黒鉛粒子がその本来の性質を損なうことなくプロトン性極性溶媒中に均一に分散してなる黒鉛粒子分散液の製造方法及びこの方法を用いて得られた黒鉛粒子分散液を提供する。 The present invention provides a method for producing a graphite particle dispersion in which graphite particles are uniformly dispersed in a protic polar solvent without impairing its original properties, and a graphite particle dispersion obtained by using this method. .
本発明の黒鉛粒子分散液の製造方法は、黒鉛粒子が凝集している黒鉛粒子凝集体と、プロトン性極性溶媒と、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、及び／又は、水素結合可能部位を有する五員環骨格を含む線状重合体とを混合して混合物を作製する混合工程と、上記混合物を撹拌して黒鉛粒子凝集体を解砕して黒鉛粒子とし、この黒鉛粒子を上記プロトン性極性溶媒中に分散させて黒鉛粒子分散液を作製する分散工程とを含むことを特徴とする。 The method for producing a graphite particle dispersion of the present invention comprises a graphite particle aggregate in which graphite particles are aggregated, a protic polar solvent, a compound having a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, and / or Or, a mixing step of preparing a mixture by mixing a linear polymer containing a five-membered ring skeleton having a hydrogen bondable site, and stirring the mixture to disintegrate the graphite particle aggregates into graphite particles, And a dispersion step of dispersing the graphite particles in the protic polar solvent to produce a graphite particle dispersion.
先ず、本発明では、黒鉛粒子凝集体と、プロトン性極性溶媒と、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、及び／又は、水素結合可能部位を有する五員環骨格を含む線状重合体とを混合して混合物を作製する（混合工程）。 First, in the present invention, a graphite particle aggregate, a protic polar solvent, a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, and / or a five-membered ring skeleton having a hydrogen bondable site are provided. The mixed linear polymer is mixed to prepare a mixture (mixing step).
上記プロトン性極性溶媒としては、特に限定されず、例えば、１−ブタノール、１−プロパノール、メタノール、エタノールなどのアルコ−ル、酢酸、蟻酸などのカルボン酸、水などが挙げられ、誘電率が適正（極性が適正）という理由から、１−ブタノール、１−プロパノール、メタノール、エタノール、酢酸及び蟻酸からなる群から選ばれた少なくとも一種の化合物が好ましい。なお、プロトン性極性溶媒は、単独で用いられても二種以上が併用されてもよい。 The protic polar solvent is not particularly limited, and examples thereof include alcohols such as 1-butanol, 1-propanol, methanol and ethanol, carboxylic acids such as acetic acid and formic acid, water, and the like. For the reason (polarity is appropriate), at least one compound selected from the group consisting of 1-butanol, 1-propanol, methanol, ethanol, acetic acid and formic acid is preferred. In addition, a protic polar solvent may be used independently or 2 or more types may be used together.
黒鉛粒子凝集体は黒鉛粒子が凝集してなる。黒鉛粒子としては、黒鉛、膨張黒鉛、黒鉛層間化合物などの黒鉛化合物、黒鉛化合物をその層面（グラフェンシート）間において剥離し薄片化して得られる薄片化黒鉛の何れであってもよい。本発明において、グラフェンシートとは炭素六角網平面からなる１枚のシート状物をいう。なお、黒鉛に官能基が化学的に結合してしても、或いは、黒鉛に官能基が弱い相互作用により疑似的に結合していてもよい。 The graphite particle aggregate is formed by aggregation of graphite particles. The graphite particles may be any of graphite compounds such as graphite, expanded graphite, and graphite intercalation compounds, and exfoliated graphite obtained by exfoliating and exfoliating a graphite compound between its layer surfaces (graphene sheets). In the present invention, the graphene sheet refers to a single sheet-like material composed of a carbon hexagonal mesh plane. Note that a functional group may be chemically bonded to graphite, or a functional group may be artificially bonded to graphite due to weak interaction.
黒鉛としては、粒子全体で単一の多層構造を有する黒鉛が好ましく、例えば、天然黒鉛、キッシュ黒鉛、高配向性熱分解黒鉛などが挙げられる。天然黒鉛とキッシュ黒鉛は、各層面（基本層）が略単一の方位を有する単独の結晶又はその集合体であり、高配向性熱分解黒鉛の各層面（基本層）は異なる方位を有する多数の小さな結晶の集合体である。 As the graphite, graphite having a single multilayer structure as a whole is preferable, and examples thereof include natural graphite, quiche graphite, and highly oriented pyrolytic graphite. Natural graphite and quiche graphite are single crystals or aggregates in which each layer surface (basic layer) has a substantially single orientation, and each layer surface (basic layer) of highly oriented pyrolytic graphite has many different orientations. It is an aggregate of small crystals.
膨張黒鉛としては従来公知のものが用いられる。膨張黒鉛の製造方法としては、公知の方法が用いられ、例えば、硫酸と硝酸との混合水溶液中に天然黒鉛を浸漬した後、天然黒鉛を混合水溶液から取り出して水洗して残余化合物とする。この残余化合物を急速加熱して、天然黒鉛の層面間に進入した化合物の分解によって天然黒鉛の層面間の間隔を拡げて天然黒鉛を膨張させる膨張黒鉛の製造方法などが挙げられる。 Conventionally known expanded graphite is used. As a method for producing expanded graphite, a known method is used. For example, after immersing natural graphite in a mixed aqueous solution of sulfuric acid and nitric acid, the natural graphite is taken out from the mixed aqueous solution and washed with water to obtain a residual compound. Examples include a method for producing expanded graphite in which the residual compound is rapidly heated and the natural graphite is expanded by expanding the interval between the natural graphite layers by decomposing the compound that has entered between the natural graphite layers.
黒鉛層間化合物は、上記黒鉛の層面間にインターカレーターを挿入することによって形成されている。黒鉛層間化合物における黒鉛の層面間に挿入されるインターカレーターとしては、特に限定されず、例えば、酸、酸化剤、金属、金属塩、気体、ハロゲン化合物などが挙げられ、高圧条件を用いることなく黒鉛層間化合物を生成することができるので、酸と酸化剤との混合物が好ましい。インターカレーターは単独で用いられても二種以上が併用されてもよい。 The graphite intercalation compound is formed by inserting an intercalator between the graphite layer surfaces. The intercalator inserted between the graphite layer surfaces in the graphite intercalation compound is not particularly limited, and examples thereof include acids, oxidants, metals, metal salts, gases, halogen compounds, and the like, without using high-pressure conditions. Since an intercalation compound can be formed, a mixture of an acid and an oxidizing agent is preferred. An intercalator may be used independently or 2 or more types may be used together.
酸としては、例えば、硝酸、塩酸、硫酸、カルボン酸、クロム酸、リン酸、ヨウ素酸などが挙げられる。酸化剤としては、例えば、硝酸カリウム、硝酸セリウムアンモニウム、過塩素酸、過マンガン酸塩などが挙げられる。金属としては、例えば、カリウム、ナトリウムなどが挙げられる。金属塩としては、例えば、塩化銅、塩化鉄、塩化ナトリウム、塩化カリウム、硫酸銅、酢酸ナトリウムなどが挙げられる。気体としては、例えば、水素などが挙げられる。ハロゲン化合物としては、例えば、塩化ヨウ素、塩化臭素、臭化ヨウ素、フッ化ヨウ素、フッ化臭素、フッ化塩素、フッ素、塩素、塩化アルミニウムなどが挙げられる。 Examples of the acid include nitric acid, hydrochloric acid, sulfuric acid, carboxylic acid, chromic acid, phosphoric acid, iodic acid and the like. Examples of the oxidizing agent include potassium nitrate, cerium ammonium nitrate, perchloric acid, permanganate and the like. Examples of the metal include potassium and sodium. Examples of the metal salt include copper chloride, iron chloride, sodium chloride, potassium chloride, copper sulfate, sodium acetate and the like. Examples of the gas include hydrogen. Examples of the halogen compound include iodine chloride, bromine chloride, iodine bromide, iodine fluoride, bromine fluoride, chlorine fluoride, fluorine, chlorine, and aluminum chloride.
黒鉛の層面間にインターカレーターを挿入して黒鉛層間化合物を製造する方法としては、公知の方法を採用することができ、例えば、黒鉛をインターカレーターの溶液に分散させて、分散液中において黒鉛とインターカレーターとを反応させて黒鉛層間化合物を製造する方法、黒鉛と気体状のインターカレーターとを高圧下にて反応させて黒鉛層間化合物を製造する方法、酸化剤を用いてＨｕｍｍｅｒｓ−Ｏｆｆｅｍａｎ法によって黒鉛層間化合物を製造する方法などが挙げられ、酸化剤を用いてＨｕｍｍｅｒｓ−Ｏｆｆｅｍａｎ法によって黒鉛層間化合物を製造する方法が好ましい。 As a method for producing a graphite intercalation compound by inserting an intercalator between graphite layer surfaces, a known method can be adopted. For example, graphite is dispersed in an intercalator solution, and graphite and A method for producing a graphite intercalation compound by reacting with an intercalator, a method for producing a graphite intercalation compound by reacting graphite and a gaseous intercalator under high pressure, and a graphite by a Hummers-Offeman method using an oxidizing agent. The method of manufacturing an intercalation compound etc. are mentioned, The method of manufacturing a graphite intercalation compound by the Hummers-Offeman method using an oxidizing agent is preferred.
上述の要領で製造された黒鉛層間化合物に薄層化処理を施して、黒鉛層間化合物をその層面間において剥離して原料黒鉛よりも薄層化させて薄片化黒鉛としておくことが好ましい。黒鉛層間化合物に施す薄層化処理としては、例えば、黒鉛層間化合物にマイクロ波又は超音波を照射する方法、黒鉛層間化合物に物理的に応力を加えて黒鉛層間化合物を粉砕する方法などが挙げられる。 It is preferable that the graphite intercalation compound produced as described above is subjected to a thinning treatment, and the graphite intercalation compound is peeled between the layer surfaces so as to be thinner than the raw graphite to obtain exfoliated graphite. Examples of the thinning treatment applied to the graphite intercalation compound include a method of irradiating the graphite intercalation compound with microwaves or ultrasonic waves, and a method of physically applying stress to the graphite intercalation compound to pulverize the graphite intercalation compound. .
黒鉛化合物において、レーザー光回折法により粒度分布を測定した場合に５０％体積平均径として得られる値は、小さいと、黒鉛化合物を薄片化して得られる薄片化黒鉛において異方性が得られないことがあり、大きいと、黒鉛化合物の薄片化が進行しにくいことがあるので、０．１〜５０μｍが好ましい。 In graphite compounds, when the particle size distribution is measured by the laser diffraction method, the value obtained as the 50% volume average diameter is small, and anisotropy cannot be obtained in exfoliated graphite obtained by exfoliating graphite compounds. If it is large, flaking of the graphite compound may not proceed easily, so 0.1 to 50 μm is preferable.
なお、レーザー光回折法により粒度分布を測定した場合に５０％体積平均径として得られる値が２０μｍ未満である黒鉛化合物は、例えば、ＳＥＣカ−ボン社から商品名「ＳＮＯ−１５」などのＳＮＯシリ−ズにて、中越黒鉛工業所から商品名「ＣＸ−３０００」にて、伊藤黒鉛社からＣＮＰ−シリ−ズにて、ＸＧＳｉｅｎｃｅ社から商品名「ＸＧｎＰ−５」にて市販されている。 In addition, when the particle size distribution is measured by the laser light diffraction method, a graphite compound having a value obtained as a 50% volume average diameter of less than 20 μm is, for example, SNO such as “SNO-15” from SEC Carbon. The series is commercially available under the trade name “CX-3000” from Chuetsu Graphite Industries Co., Ltd. under the name “CNP-Series” from Ito Graphite Co., Ltd. and under the trade name “XGnP-5” from the company XGSience.
なお、黒鉛粒子が凝集してなる黒鉛粒子凝集体は、例えば、ＸＧＳｃｉｅｎｃｅ社から商品名「ｘＧｎＰ」シリ−ズ、Ａｎｇｓｔｒｏｍ Ｍａｔｅｒｉａｌｓ社から商品名「Ｎ」シリ−ズにて市販されている。 The graphite particle aggregate obtained by agglomerating graphite particles is commercially available, for example, from XGS Science under the trade name “xGnP” series and from Angstrom Materials under the trade name “N” series.
混合物を作製する際において、黒鉛粒子凝集体の量は、少ないと、黒鉛粒子分散液が黒鉛粒子に起因した機能を発揮しないことがあり、多いと、黒鉛粒子分散液中の黒鉛粒子が再度、凝集してしまうことがあるので、プロトン性極性溶媒１００重量部に対して０．１〜１．５重量部が好ましく、０．１〜１重量部がより好ましい。 In preparing the mixture, if the amount of the graphite particle aggregate is small, the graphite particle dispersion may not exhibit the function due to the graphite particles, and if large, the graphite particles in the graphite particle dispersion again Since it may aggregate, 0.1-1.5 weight part is preferable with respect to 100 weight part of protic polar solvent, and 0.1-1 weight part is more preferable.
混合物を作製するにあたって、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、又は、水素結合可能部位を有する五員環骨格を含む線状重合体のいずれか一方或いは双方が用いられる。水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、並びに、水素結合可能部位を有する五員環骨格を含む線状重合体は、水素結合可能部位を有する五員環骨格を有していることからプロトン性極性溶媒と水素結合を形成してプロトン性極性溶媒中に良好に溶解する。 In preparing the mixture, either one or both of a compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group, or a linear polymer having a five-membered ring skeleton having a hydrogen-bondable site is used. . A compound having a 5-membered ring skeleton having a hydrogen-bondable site and an alkyl group, and a linear polymer containing a 5-membered ring skeleton having a hydrogen-bondable site have a 5-membered ring skeleton having a hydrogen-bondable site. Therefore, it forms a hydrogen bond with the protic polar solvent and dissolves well in the protic polar solvent.
更に、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物は、アルキル基を有している一方、黒鉛粒子凝集体を構成している黒鉛粒子はその表面に極性基を有しておらず、疎水性であることから、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物のアルキル基によって黒鉛粒子凝集体が包まれた状態となる。 Further, a compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group has an alkyl group, while the graphite particles constituting the graphite particle aggregate have a polar group on the surface thereof. In addition, since it is hydrophobic, the graphite particle aggregate is encased by the alkyl group of the compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group.
又、上述の通り、黒鉛粒子凝集体を構成している黒鉛粒子はその表面に極性基を有しておらず、疎水性であることから、水素結合可能部位を有する五員環骨格を含む線状重合体の主鎖によって黒鉛粒子凝集体が包まれた状態となる。 In addition, as described above, the graphite particles constituting the graphite particle aggregate do not have a polar group on the surface and are hydrophobic, and therefore, a line including a five-membered ring skeleton having a hydrogen bondable site. The aggregate of graphite particles is encased by the main chain of the polymer.
この状態において、後述するように混合物を撹拌することによって、混合物中において、黒鉛粒子凝集体の黒鉛粒子に対して相互作用を有している、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、及び／又は、水素結合可能部位を有する五員環骨格を含む線状重合体が互いに相対位置を変化させ、それらの相対変位によって黒鉛粒子凝集体に剥離力を付与し、黒鉛粒子凝集体を解砕し、黒鉛粒子とすることができる。 In this state, by stirring the mixture as will be described later, in the mixture, the five-membered ring skeleton having a hydrogen-bondable site and an alkyl group having an interaction with the graphite particles of the graphite particle aggregates. And / or a linear polymer containing a five-membered ring skeleton having a hydrogen-bondable site changes relative positions to each other, and gives a peeling force to the graphite particle aggregate by their relative displacement. Aggregates can be crushed into graphite particles.
そして、黒鉛粒子凝集体を解砕して得られる黒鉛粒子の表面は、黒鉛粒子凝集体の場合と同様に、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物のアルキル基、又は、水素結合可能部位を有する五員環骨格を含む線状重合体の主鎖のいずれか一方或いは双方によって包まれた状態となり、黒鉛粒子は、プロトン性極性溶媒中にて凝集することなく均一に分散した状態となる。 And the surface of the graphite particles obtained by pulverizing the graphite particle aggregate is, as in the case of the graphite particle aggregate, an alkyl group of a compound having a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, or And a state in which the main chain of the linear polymer containing a five-membered ring skeleton having a hydrogen-bondable site is enclosed by one or both of them, and the graphite particles are uniformly agglomerated in a protic polar solvent. It becomes a distributed state.
上述した水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物としては、水素結合可能部位を有する五員環骨格とアルキル基とを有しておればよい。 The compound having a 5-membered ring skeleton having a hydrogen-bondable site and an alkyl group only needs to have a 5-membered ring skeleton having a hydrogen-bondable site and an alkyl group.
上記水素結合可能部位を有する五員環骨格とは、電気陰性度の高い原子を含む五員環骨格をいい、電気陰性度の高い原子をヘテロ原子として含む五員環骨格が好ましい。なお、電気陰性度の高い原子とは、例えば、酸素、窒素、硫黄などをいう。 The five-membered ring skeleton having a hydrogen bondable site refers to a five-membered ring skeleton containing an atom having a high electronegativity, and preferably a five-membered ring skeleton containing an atom having a high electronegativity as a heteroatom. In addition, an atom with high electronegativity means oxygen, nitrogen, sulfur, etc., for example.
上記アルキル基としては、炭素数が４〜４０であるアルキル基が好ましく、炭素数が４〜１０であるアルキル基がより好ましい。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、オクタデシル基などが挙げられ、メチル基、エチル基、ブチル基、オクチル基が好ましい。 The alkyl group is preferably an alkyl group having 4 to 40 carbon atoms, and more preferably an alkyl group having 4 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, octadecyl, and the like. And a methyl group, an ethyl group, a butyl group, and an octyl group are preferable.
水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物としては、ピロリドン系化合物、ピロ−ル系化合物及びチオフェン系化合物からなる群から選ばれた少なくとも一種の化合物が好ましい。ピロリドン系化合物、ピロ−ル系化合物及びチオフェン系化合物は何れもアルキル基を有している。 The compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group is preferably at least one compound selected from the group consisting of pyrrolidone compounds, pyrrole compounds, and thiophene compounds. The pyrrolidone compound, the pyrrole compound, and the thiophene compound all have an alkyl group.
ピロリドン系化合物としては、例えば、１−ブチル−２−ピロリドン、１−エチル−２−ピロリドン、１−メチル−２−ピロリドン、１−ｎ−オクチル−２−ピロリドン、４、４−ペンタメチレン−２−ピロリドン、５−メチル−２−ピロリドンなどが挙げられる。 Examples of pyrrolidone compounds include 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-n-octyl-2-pyrrolidone and 4,4-pentamethylene-2. -Pyrrolidone, 5-methyl-2-pyrrolidone and the like.
又、ピロ−ル系化合物としては、特に限定されず、例えば、メチルピロ−ル、エチルピロ−ル、オクチルピロ−ル、オクタデシルピロ−ルなどが挙げられる。なお、例えば、１−エチルピロールは、東京化成工業社から市販されている。 The pyrrole compound is not particularly limited, and examples thereof include methyl pyrrole, ethyl pyrrole, octyl pyrrole, and octadecyl pyrrole. For example, 1-ethylpyrrole is commercially available from Tokyo Chemical Industry.
更に、上記チオフェン系化合物としては、特に限定されず、例えば、メチルチオフェン、エチルチオフェン、ペンチルチオフェンなどが挙げられる。なお、２−エチルチオフェンは、東京化成工業社製から市販されている。 Furthermore, the thiophene compound is not particularly limited, and examples thereof include methylthiophene, ethylthiophene, pentylthiophene, and the like. Note that 2-ethylthiophene is commercially available from Tokyo Chemical Industry Co., Ltd.
水素結合可能部位を有する五員環骨格を含む線状重合体について説明する。水素結合可能部位を有する五員環骨格を含む線状重合体の主鎖としては、特に限定されず、例えば、ビニル重合体、ポリエステル、ポリアミドが好ましく、ビニル重合体がより好ましい。そして、水素結合可能部位を有する五員環骨格を含む線状重合体は、その側鎖に水素結合可能部位を有する五員環骨格を有している。水素結合可能部位を有する五員環骨格を含む線状重合体において、水素結合可能部位を有する五員環骨格とは、電気陰性度の高い原子を含む五員環骨格をいい、電気陰性度の高い原子をヘテロ原子として含む五員環骨格が好ましい。なお、電気陰性度の高い原子とは、例えば、酸素、窒素、硫黄などをいう。そして、線状高分子の主鎖と、水素結合可能部位を有する五員環骨格との化学結合としては、共有結合、イオン結合などが挙げられるが、共有結合が好ましい。 A linear polymer containing a five-membered ring skeleton having a hydrogen-bondable site will be described. The main chain of the linear polymer containing a five-membered ring skeleton having a hydrogen bondable site is not particularly limited, and for example, vinyl polymers, polyesters, and polyamides are preferable, and vinyl polymers are more preferable. A linear polymer including a five-membered ring skeleton having a hydrogen bondable site has a five-membered ring skeleton having a hydrogen bondable site in its side chain. In a linear polymer including a five-membered ring skeleton having a hydrogen-bondable site, the five-membered ring skeleton having a hydrogen-bondable site refers to a five-membered ring skeleton containing an atom having a high electronegativity. A five-membered ring skeleton containing a high atom as a hetero atom is preferred. In addition, an atom with high electronegativity means oxygen, nitrogen, sulfur, etc., for example. The chemical bond between the main chain of the linear polymer and the five-membered ring skeleton having a hydrogen bondable site includes a covalent bond and an ionic bond, and a covalent bond is preferable.
水素結合可能部位を有する五員環骨格を含む線状重合体は、例えば、水素結合可能部位を有する五員環骨格及びラジカル重合性不飽和二重結合を有する単量体をラジカル重合することによって製造することができる。 A linear polymer containing a five-membered ring skeleton having a hydrogen-bondable site is obtained by radical polymerization of, for example, a monomer having a five-membered ring skeleton having a hydrogen-bondable site and a radically polymerizable unsaturated double bond. Can be manufactured.
水素結合可能部位を有する五員環骨格及びラジカル重合性不飽和二重結合を有する単量体としては、特に限定されないが、ビニルピロリドン（１−ビニル−２−ピロリドン）、２−ビニル−１Ｈピロール、２−ビニルチオフェンなどが挙げられ、ビニルピロリドン（１−ビニル−２−ピロリドン）が好ましい。 The monomer having a five-membered ring skeleton having a hydrogen-bondable site and a radically polymerizable unsaturated double bond is not particularly limited, but vinyl pyrrolidone (1-vinyl-2-pyrrolidone), 2-vinyl-1H pyrrole. , 2-vinylthiophene and the like, and vinylpyrrolidone (1-vinyl-2-pyrrolidone) is preferable.
水素結合可能部位を有する五員環骨格を含む線状重合体としては、例えば、ポリビニルピロリドン（ポリ（１−ビニル−２−ピロリドン））、ポリ（２−ビニル−１Ｈピロール）、ポリ（２−ビニルチオフェン）などが挙げられる。なお、水素結合可能部位を有する五員環骨格を含む線状重合体は単独で用いられても二種以上が併用されてもよい。 Examples of the linear polymer having a five-membered ring skeleton having a hydrogen bondable site include polyvinyl pyrrolidone (poly (1-vinyl-2-pyrrolidone)), poly (2-vinyl-1H pyrrole), poly (2- Vinylthiophene) and the like. In addition, the linear polymer containing the five-membered ring skeleton having a hydrogen bondable site may be used alone or in combination of two or more.
水素結合可能部位を有する五員環骨格及びラジカル重合性不飽和二重結合を有する単量体は、他の単量体と共重合させてもよい。共重合可能な単量体としては、特に限定されず、例えば、スチレン、メタクリル酸、アクリル酸、アクリロニトリルなどのビニル系化合物が挙げられる。なお、共重合可能な単量体は、単独で用いられても二種以上が併用されてもよい。 A monomer having a five-membered ring skeleton having a hydrogen-bondable site and a radically polymerizable unsaturated double bond may be copolymerized with another monomer. The copolymerizable monomer is not particularly limited, and examples thereof include vinyl compounds such as styrene, methacrylic acid, acrylic acid, and acrylonitrile. In addition, the monomer which can be copolymerized may be used independently, or 2 or more types may be used together.
水素結合可能部位を有する五員環骨格を含む線状重合体の重量平均分子量は、小さいと、黒鉛粒子凝集体の解砕が不充分となることがあり或いは黒鉛粒子分散液中における黒鉛粒子の分散性が低下することがあり、大きいと、黒鉛粒子分散液の粘度が高くなりすぎてゲル状態となることがあるので、１０００〜１０００００が好ましく、１００００〜５００００がより好ましい。なお、水素結合可能部位を有する五員環骨格を含む線状重合体の重量平均分子量は、流量０．８ミリリットル／ｍ、温度４０℃、注入量２０マイクロリットルの条件下においてゲル浸透クロマトグラフィ−を用いて測定された値をいう。 If the weight average molecular weight of the linear polymer containing a five-membered ring skeleton having a hydrogen bondable site is small, the graphite particle aggregate may not be sufficiently crushed, or the graphite particles in the graphite particle dispersion may not be crushed. The dispersibility may be lowered, and if it is large, the viscosity of the graphite particle dispersion becomes too high and may be in a gel state, so 1000 to 100,000 is preferable, and 10,000 to 50,000 is more preferable. The weight average molecular weight of the linear polymer containing a five-membered ring skeleton having a hydrogen bondable site was determined by gel permeation chromatography under the conditions of a flow rate of 0.8 ml / m, a temperature of 40 ° C., and an injection amount of 20 microliters. The value measured using.
混合物を作製する際において、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、並びに、水素結合可能部位を有する五員環骨格を含む線状重合体の総量は、少ないと、黒鉛粒子凝集体の解砕効果が低下し或いは得られる黒鉛粒子分散液中における黒鉛粒子の分散性が低下することがあり、多いと、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物自体、及び、水素結合可能部位を有する五員環骨格を含む線状重合体自体が凝集することがあるので、プロトン性極性溶媒１００重量部に対して０．０５〜２０重量部が好ましく、０．１〜５重量部がより好ましい。 In preparing the mixture, if the total amount of the compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group, and the linear polymer containing the five-membered ring skeleton having a hydrogen-bondable site is small, graphite A compound having a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, which may reduce the disintegration effect of the particle aggregate or may lower the dispersibility of the graphite particles in the resulting graphite particle dispersion. Since the linear polymer itself containing a five-membered ring skeleton having a hydrogen bondable site itself may aggregate, 0.05 to 20 parts by weight is preferable with respect to 100 parts by weight of the protic polar solvent. More preferably, it is 1 to 5 parts by weight.
混合物を作製する際において、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物の量は、少ないと、黒鉛粒子凝集体の解砕効果が低下し或いは得られる黒鉛粒子分散液中における黒鉛粒子の分散性が低下することがあり、多いと、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物自体が凝集することがあるので、プロトン性極性溶媒１００重量部に対して０．０５〜２０重量部が好ましく、０．１〜５重量部がより好ましい。 In preparing the mixture, if the amount of the compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group is small, the crushing effect of the graphite particle aggregate is reduced or obtained in the resulting graphite particle dispersion. The dispersibility of the graphite particles may be reduced, and in many cases, the compound itself having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group may aggregate. Therefore, with respect to 100 parts by weight of the protic polar solvent 0.05-20 weight part is preferable and 0.1-5 weight part is more preferable.
混合物を作製する際において、水素結合可能部位を有する五員環骨格を含む線状重合体の量は、少ないと、黒鉛粒子凝集体の解砕効果が低下し或いは得られる黒鉛粒子分散液中における黒鉛粒子の分散性が低下することがあり、多いと、水素結合可能部位を有する五員環骨格を含む線状重合体自体が凝集することがあるので、プロトン性極性溶媒１００重量部に対して０．０５〜２０重量部が好ましく、０．１〜５重量部がより好ましい。 In preparing the mixture, if the amount of the linear polymer containing a five-membered ring skeleton having a hydrogen bondable site is small, the crushing effect of the graphite particle aggregate is reduced or obtained in the obtained graphite particle dispersion. The dispersibility of the graphite particles may be reduced, and in many cases, the linear polymer itself containing a five-membered ring skeleton having a hydrogen-bondable site may aggregate. Therefore, with respect to 100 parts by weight of the protic polar solvent 0.05-20 weight part is preferable and 0.1-5 weight part is more preferable.
黒鉛粒子凝集体と、プロトン性極性溶媒と、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、又は、水素結合可能部位を有する五員環骨格を含む線状重合体のいずれか一方或いは双方とを混合して混合物を作製する（混合工程）が、混合物の作製にあたっては、黒鉛粒子凝集体と、プロトン性極性溶媒と、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、又は、水素結合可能部位を有する五員環骨格を含む線状重合体のいずれか一方或いは双方とが混合されておればよく、各成分が均一に混合されている必要はないが、各成分が均一に混合されていることが好ましい。 Either a graphite particle aggregate, a protic polar solvent, a compound having a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, or a linear polymer having a five-membered ring skeleton having a hydrogen bondable site One or both are mixed to prepare a mixture (mixing step). In preparing the mixture, a graphite particle aggregate, a protic polar solvent, a five-membered ring skeleton having a hydrogen-bondable site, and an alkyl group are used. It is sufficient that either one or both of the compound or the linear polymer containing a five-membered ring skeleton having a hydrogen bondable site is mixed, and it is not necessary that each component is uniformly mixed. It is preferable that each component is mixed uniformly.
黒鉛粒子凝集体と、プロトン性極性溶媒と、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、又は、水素結合可能部位を有する五員環骨格を含む線状重合体のいずれか一方或いは双方とを混合して得られる混合物を撹拌して黒鉛粒子凝集体を解砕して黒鉛粒子とし、この黒鉛粒子をプロトン性極性溶媒中に分散させて黒鉛粒子分散液を得ることができる（分散工程）。 Either a graphite particle aggregate, a protic polar solvent, a compound having a five-membered ring skeleton having a hydrogen bondable site and an alkyl group, or a linear polymer having a five-membered ring skeleton having a hydrogen bondable site A mixture obtained by mixing one or both can be stirred to break up the graphite particle aggregates into graphite particles, and the graphite particles can be dispersed in a protic polar solvent to obtain a graphite particle dispersion. (Dispersing step).
混合物を撹拌する方法としては、汎用の撹拌装置を用いて混合物を撹拌すればよく、このような撹拌装置としては、特に限定されず、例えば、ナノマイザー、超音波照射装置、ボールミル、サンドミル、バスケットミル、三本ロールミル、プラネタリーミキサー、ビーズミル、ホモジナイザーなどが挙げられ、黒鉛粒子凝集体に物理的な付加が加わらないことから、超音波照射装置が好ましい。 As a method of stirring the mixture, the mixture may be stirred using a general-purpose stirring device. Such a stirring device is not particularly limited, and examples thereof include a nanomizer, an ultrasonic irradiation device, a ball mill, a sand mill, and a basket mill. , A three-roll mill, a planetary mixer, a bead mill, a homogenizer, and the like, and an ultrasonic irradiation apparatus is preferable because no physical addition is added to the graphite particle aggregate.
混合物に超音波を照射する際の照射条件としては、周波数２６〜３８ｋＨｚ、出力４００〜６００Ｗの超音波を混合物に３０〜３００分に亘って照射することが好ましい。 As irradiation conditions for irradiating the mixture with ultrasonic waves, it is preferable to irradiate the mixture with ultrasonic waves having a frequency of 26 to 38 kHz and an output of 400 to 600 W for 30 to 300 minutes.
混合物を撹拌することによって、プロトン性極性溶媒中に水素結合を形成することによって均一に溶解した、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物、又は、水素結合可能部位を有する五員環骨格を含む線状重合体のいずれか一方或いは双方を介して黒鉛粒子凝集体に解砕力が加えられて黒鉛粒子凝集体は解砕され、黒鉛粒子となり、この黒鉛粒子は、水素結合可能部位を有する五員環骨格及びアルキル基を有する化合物のアルキル基、又は、水素結合可能部位を有する五員環骨格を含む線状重合体の主鎖のいずれか一方或いは双方によって表面が被覆された状態となっており、プロトン性極性溶媒中に安定的に分散している。よって、得られる黒鉛粒子分散液は、プロトン性極性溶媒中に黒鉛粒子が均一に分散した状態となっている。 A compound having a five-membered ring skeleton having a hydrogen-bondable site and an alkyl group, or a hydrogen-bondable site, which is uniformly dissolved by forming a hydrogen bond in a protic polar solvent by stirring the mixture A crushing force is applied to the graphite particle aggregate via one or both of the linear polymers containing a five-membered ring skeleton, and the graphite particle aggregate is crushed into graphite particles. These graphite particles can be hydrogen-bonded. The surface is coated with either or both of the alkyl group of the compound having a 5-membered ring skeleton having a moiety and an alkyl group, or the main chain of a linear polymer having a 5-membered ring skeleton having a hydrogen-bondable moiety. It is in a state and is stably dispersed in the protic polar solvent. Therefore, the obtained graphite particle dispersion is in a state where the graphite particles are uniformly dispersed in the protic polar solvent.
黒鉛粒子分散液中に分散している黒鉛粒子において、粒度分布測定装置によって測定された個数分布平均値として求められる平均粒子径は、小さいと、黒鉛粒子の比表面積が大きくなりすぎて再凝集する可能性があり、大きいと、黒鉛粒子分散液中において黒鉛粒子が沈殿する可能性があるので、０．５〜１０μｍが好ましい。なお、粒度分布測定装置は、例えば、Ｐａｒｔｉｃｌｅ Ｓｉｚｉｎｇ Ｓｙｓｔｅｍｓ社から商品名「ＡｃｃｕＳｉｚｅｒ７８０」にて市販されている。 In the graphite particles dispersed in the graphite particle dispersion, if the average particle size obtained as the average number distribution measured by the particle size distribution analyzer is small, the specific surface area of the graphite particles becomes too large and re-aggregates. There is a possibility, and if it is large, graphite particles may be precipitated in the graphite particle dispersion, so 0.5 to 10 μm is preferable. The particle size distribution measuring apparatus is commercially available, for example, from Particle Sizing Systems under the trade name “Acucizer 780”.
黒鉛粒子分散液中に分散している黒鉛粒子において、透過型電子顕微鏡で観察される厚みは、薄いと、黒鉛粒子の比表面積が大きくなりすぎて再凝集する可能性があり、厚いと、黒鉛粒子分散液中において黒鉛粒子が沈殿する可能性があるので、１〜３００ｎｍが好ましい。なお、黒鉛粒子の厚みとは、黒鉛粒子の面積が最も大きくなる方向から見た時の黒鉛粒子の表面に対して直交する方向の黒鉛粒子の最大寸法をいう。透過型電子顕微鏡で観察される黒鉛粒子の厚みとは、透過型電子顕微鏡で観察した任意の１０視野に存在する全ての黒鉛粒子の厚みを測定し、黒鉛粒子の厚みの相加平均値をいう。 In the graphite particles dispersed in the graphite particle dispersion, if the thickness observed with a transmission electron microscope is thin, the specific surface area of the graphite particles may become too large and re-aggregate. Since graphite particles may precipitate in the particle dispersion, 1 to 300 nm is preferable. The thickness of the graphite particles refers to the maximum dimension of the graphite particles in the direction orthogonal to the surface of the graphite particles when viewed from the direction in which the area of the graphite particles is the largest. The thickness of the graphite particles observed with a transmission electron microscope refers to the arithmetic average value of the thickness of the graphite particles by measuring the thickness of all the graphite particles present in any 10 visual fields observed with the transmission electron microscope. .
透過型電子顕微鏡としては、例えば、日立製作所から商品名「Ｓ−８００」にて市販されているＦＥ−ＳＥＭ（Field Emission Scanning Micro Scope）が挙げられる。 Examples of the transmission electron microscope include FE-SEM (Field Emission Scanning Microscope) commercially available from Hitachi, Ltd. under the trade name “S-800”.
そして、上述のようにして得られた黒鉛粒子分散液と合成樹脂とを混合することによって、黒鉛粒子が合成樹脂中に均一に分散してなる樹脂組成物を作製することができる。このような合成樹脂としては、例えば、エポキシ樹脂、ポリウレタン、ポリイミド、ポリスチレン、ＡＢＳ樹脂、ポリエチレン、ＥＶＡ樹脂、ポリプロピレン、ポリアミド、ポリカーボネート、ポリエステル、ポリフェニレンエーテルなどが挙げられ、ポリプロピレンが好ましい。 Then, by mixing the graphite particle dispersion obtained as described above and the synthetic resin, a resin composition in which the graphite particles are uniformly dispersed in the synthetic resin can be produced. Examples of such a synthetic resin include epoxy resin, polyurethane, polyimide, polystyrene, ABS resin, polyethylene, EVA resin, polypropylene, polyamide, polycarbonate, polyester, polyphenylene ether, and the like, and polypropylene is preferable.
本発明の黒鉛粒子分散液の製造方法は、上述の如き構成を有しているので、黒鉛粒子凝集体を解砕してなる黒鉛粒子がその本来の性質を損なわれることなくプロトン性極性溶媒中に分散されてなる黒鉛粒子分散液を容易に製造することができる。 Since the method for producing a graphite particle dispersion of the present invention has the above-described configuration, graphite particles obtained by pulverizing graphite particle aggregates can be contained in a protic polar solvent without impairing their original properties. It is possible to easily produce a graphite particle dispersion in which the graphite particles are dispersed.
次に本発明の実施例を説明するが、本発明は下記実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to the following examples.
（実施例１）
スクリュー管中にエタノール１００重量部を供給した上で、このエタノール中に、黒鉛粒子凝集体（薄片化黒鉛の凝集体、ＸＧＳｃｉｅｎｃｅ社製 商品名「ＸＧｎＰ−５」、）１重量部を供給した後にポリビニルピロリドン（ポリ（１−ビニル−２−ピロリドン）、和光純薬工業社製、重量平均分子量：４００００）１重量部を供給して混合物とした。なお、エタノールに供給する前の黒鉛粒子凝集体は、その個数分布平均値として求められる平均粒子径が４．８０μｍであった。
Example 1
After supplying 100 parts by weight of ethanol into a screw tube and supplying 1 part by weight of graphite particle aggregate (aggregated flake graphite, trade name “XGnP-5” manufactured by XScience) into this ethanol 1 part by weight of polyvinylpyrrolidone (poly (1-vinyl-2-pyrrolidone), manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 40000) was supplied to prepare a mixture. In addition, the average particle diameter calculated | required as the number distribution average value of the graphite particle aggregate before supplying to ethanol was 4.80 micrometers.
超音波照射装置（株式会社カイジョー社製 商品名「ＰＨＥＮＩＸ II ２６ｋＨｚ」）を用いて、混合物に周波数２６ｋＨｚ、出力６００Ｗの条件下にて超音波を６０分間に亘って照射して、黒鉛粒子凝集体を解砕してなる黒鉛粒子がエタノール中に分散してなる黒鉛粒子分散液を得た。 Using an ultrasonic irradiation device (trade name “PHENIX II 26 kHz” manufactured by Kaijo Co., Ltd.), the mixture was irradiated with ultrasonic waves for 60 minutes under conditions of a frequency of 26 kHz and an output of 600 W. A graphite particle dispersion was obtained in which graphite particles obtained by pulverizing were dispersed in ethanol.
（実施例２）
混合物への超音波の照射時間を２４０分としたこと以外は実施例１と同様にして黒鉛粒子分散液を得た。
(Example 2)
A graphite particle dispersion was obtained in the same manner as in Example 1 except that the duration of ultrasonic irradiation to the mixture was 240 minutes.
（実施例３）
ポリビニルピロリドンを５重量部としたこと以外は実施例１と同様にして黒鉛粒子分散液を得た。
(Example 3)
A graphite particle dispersion was obtained in the same manner as in Example 1 except that 5 parts by weight of polyvinylpyrrolidone was used.
（実施例４）
混合物への超音波の照射時間を２４０分としたこと、ポリビニルピロリドンを５重量部としたこと以外は実施例１と同様にして黒鉛粒子分散液を得た。
Example 4
A graphite particle dispersion was obtained in the same manner as in Example 1 except that the irradiation time of ultrasonic waves to the mixture was 240 minutes and that polyvinylpyrrolidone was 5 parts by weight.
（比較例１）
ポリビニルピロリドンを用いなかったこと以外は実施例１と同様にして黒鉛粒子分散液を得た。
(Comparative Example 1)
A graphite particle dispersion was obtained in the same manner as in Example 1 except that polyvinylpyrrolidone was not used.
（比較例２）
エタノールの代わりにアセトンを用いたこと以外は実施例１と同様にして黒鉛粒子分散液を得た。
(Comparative Example 2)
A graphite particle dispersion was obtained in the same manner as in Example 1 except that acetone was used instead of ethanol.
得られた黒鉛粒子分散液中の黒鉛粒子における個数分布平均値として求められる平均粒子径を粒度分布測定装置（Ｐａｒｔｉｃｌｅ Ｓｉｚｉｎｇ Ｓｙｓｔｅｍｓ社製 商品名「ＡｃｃｕＳｉｚｅｒ７８０」）を用いて測定し、その結果を表１に示した。なお、比較例１及び比較例２については、黒鉛粒子分散液中の黒鉛粒子における個数分布平均値として求められる平均粒子径が大きいことから、黒鉛粒子凝集体を解砕してなる黒鉛粒子は殆ど存在していないものと推定された。 The average particle diameter obtained as the average number distribution of graphite particles in the obtained graphite particle dispersion was measured using a particle size distribution measuring apparatus (trade name “AccurSizer780” manufactured by Particle Sizing Systems), and the results are shown in Table 1. It was shown to. In Comparative Example 1 and Comparative Example 2, since the average particle size obtained as the average number distribution of the graphite particles in the graphite particle dispersion is large, almost all graphite particles obtained by pulverizing the graphite particle aggregates are used. It was estimated that it did not exist.
又、得られた黒鉛粒子分散液において、黒鉛粒子の厚みを透過型電子顕微鏡（日本電子社製 商品名「ＪＥＭ−２１００ＦＥＦ」）を用いて測定し、その結果を表１に示した。なお、比較例１、２については黒鉛粒子が殆ど存在していないと推定されたので、黒鉛粒子の厚みの測定は行わなかった。 In the obtained graphite particle dispersion, the thickness of the graphite particles was measured using a transmission electron microscope (trade name “JEM-2100FEF” manufactured by JEOL Ltd.), and the results are shown in Table 1. In Comparative Examples 1 and 2, since it was estimated that almost no graphite particles were present, the thickness of the graphite particles was not measured.
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