JP2020152891A - Polymer-coated silicon particle - Google Patents
Polymer-coated silicon particle Download PDFInfo
- Publication number
- JP2020152891A JP2020152891A JP2019181160A JP2019181160A JP2020152891A JP 2020152891 A JP2020152891 A JP 2020152891A JP 2019181160 A JP2019181160 A JP 2019181160A JP 2019181160 A JP2019181160 A JP 2019181160A JP 2020152891 A JP2020152891 A JP 2020152891A
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- JP
- Japan
- Prior art keywords
- polymer
- poly
- silicon particles
- polyacrylate
- silicon
- 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
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- 229920000642 polymer Polymers 0.000 title claims abstract description 133
- 239000011856 silicon-based particle Substances 0.000 title claims abstract description 132
- 229910052710 silicon Inorganic materials 0.000 claims description 102
- 229920000058 polyacrylate Polymers 0.000 claims description 59
- 229920000193 polymethacrylate Polymers 0.000 claims description 42
- -1 2-ethylhexyl Chemical group 0.000 claims description 29
- 229920002125 Sokalan® Polymers 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 239000004584 polyacrylic acid Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 8
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- YSKIQSYEHUCIFO-UHFFFAOYSA-M lithium;4-ethenylbenzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 YSKIQSYEHUCIFO-UHFFFAOYSA-M 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910020175 SiOH Inorganic materials 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 229920001688 coating polymer Polymers 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 claims description 4
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 4
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001496 poly(N,N'-methylenebisacrylamide) polymer Polymers 0.000 claims description 3
- 229920003991 poly(N-tert-butyl acrylamide) Polymers 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 229920000779 poly(divinylbenzene) Polymers 0.000 claims description 3
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 15
- 239000012776 electronic material Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 95
- 239000010703 silicon Substances 0.000 description 95
- 239000002002 slurry Substances 0.000 description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000002245 particle Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 239000011324 bead Substances 0.000 description 12
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000002407 reforming Methods 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000006011 modification reaction Methods 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
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- WUEOIYLQFLWYKV-UHFFFAOYSA-N 1-phenylbut-1-ene-2-sulfonic acid Chemical compound CCC(S(O)(=O)=O)=CC1=CC=CC=C1 WUEOIYLQFLWYKV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
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- GXCDLJXPZVCHBX-UHFFFAOYSA-N 3-methylpent-1-yn-3-yl carbamate Chemical compound CCC(C)(C#C)OC(N)=O GXCDLJXPZVCHBX-UHFFFAOYSA-N 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ZVBJPHBJAKGQAI-UHFFFAOYSA-N [Li].C(=CC1=CC=CC=C1)S(=O)(=O)O Chemical compound [Li].C(=CC1=CC=CC=C1)S(=O)(=O)O ZVBJPHBJAKGQAI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XDIJWRHVEDUFGP-UHFFFAOYSA-N azanium;2-phenylethenesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 XDIJWRHVEDUFGP-UHFFFAOYSA-N 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- DPLUMPJQXVYXBH-UHFFFAOYSA-N n,n-diethyl-2-phenylethenamine Chemical compound CCN(CC)C=CC1=CC=CC=C1 DPLUMPJQXVYXBH-UHFFFAOYSA-N 0.000 description 1
- UTKONZMCFKGKAR-UHFFFAOYSA-N n,n-diethyl-2-phenylprop-1-en-1-amine Chemical compound CCN(CC)C=C(C)C1=CC=CC=C1 UTKONZMCFKGKAR-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は、電子材料、電池等に用いられるポリマー被覆シリコンに関する。 The present invention relates to polymer-coated silicon used in electronic materials, batteries and the like.
粒径がナノメートルオーダーまで微細化されたシリコンナノ粒子は、高効率ＬＥＤや太陽電池、リチウムイオン二次電池等に用いられている。例えば太陽電池にシリコンナノ粒子を塗布することにより、シリコンナノ粒子から太陽電池材料へのエネルギー移動を可能として変換効率が向上する（例えば特許文献１、非特許文献１参照）。また、シリコンはリチウムイオン二次電池の負極材として黒鉛の１０倍以上の理論容量を持つため、次世代の負極材料として期待されている。シリコンは充放電の際に大きく体積変化するため、粒子の崩壊を防いで電池寿命を向上させるためにシリコンナノ粒子が有用である（例えば非特許文献２参照）。 Silicon nanoparticles whose particle size has been refined to the nanometer order are used in high-efficiency LEDs, solar cells, lithium-ion secondary batteries, and the like. For example, by applying silicon nanoparticles to a solar cell, energy transfer from the silicon nanoparticles to the solar cell material is possible and conversion efficiency is improved (see, for example, Patent Document 1 and Non-Patent Document 1). Further, since silicon has a theoretical capacity of 10 times or more that of graphite as a negative electrode material for a lithium ion secondary battery, it is expected as a next-generation negative electrode material. Since silicon changes its volume significantly during charging and discharging, silicon nanoparticles are useful for preventing particle decay and improving battery life (see, for example, Non-Patent Document 2).
様々な用途で用いられるシリコンナノ粒子であるが、活性な粒子表面の保護が大きな課題である。ナノサイズ化により表面原子数の割合が増し、バルクシリコンに比して表面活性が非常に大きく容易に酸化される。解決策の一つとして、シリコンナノ粒子の表面修飾が挙げられる。ナノ粒子表面をフッ酸等の強力な酸でエッチングし、アルキル基で置換して被覆層を形成することでシリコンナノ粒子の安定性が向上することが知られている（例えば特許文献２参照）。アルキル基による置換は表面保護として有効であるが、フッ酸等の強力な酸を必要とし実際の使用の際に大きな問題がある。また、置換基による被覆層の膜厚はせいぜい１０ｎｍ程度であり非常に薄い。 Although silicon nanoparticles are used for various purposes, protection of the active particle surface is a major issue. Nanosize increases the proportion of surface atoms and has a much higher surface activity than bulk silicon and is easily oxidized. One of the solutions is surface modification of silicon nanoparticles. It is known that the stability of silicon nanoparticles is improved by etching the surface of the nanoparticles with a strong acid such as hydrofluoric acid and substituting with an alkyl group to form a coating layer (see, for example, Patent Document 2). .. Substitution with an alkyl group is effective as surface protection, but requires a strong acid such as hydrofluoric acid, which poses a big problem in actual use. Further, the film thickness of the coating layer due to the substituent is at most about 10 nm, which is very thin.
このような背景のもと、フッ酸等の強力な酸を用いることなく、シリコンナノ粒子の周囲を１０ｎｍ以上の厚みで均一に被覆する方法が求められている。球状のシリコンナノ粒子にポリスチレンを被覆する方法が最近報告されているが、適用できるシリコンナノ粒子形状が球状に限られ、かつ、シリコン粒子の平均粒径が１００ｎｍ以下と小さく、シリコン同士の分散性が非常に悪く凝集している（例えば非特許文献３参照）。異方性を持ったシリコンナノ粒子の周囲を均一かつ分散性良く化学種で被覆する方法は知られていない。 Against this background, there is a demand for a method of uniformly coating the periphery of silicon nanoparticles with a thickness of 10 nm or more without using a strong acid such as hydrofluoric acid. Recently, a method of coating spherical silicon nanoparticles with polystyrene has been reported, but the applicable silicon nanoparticles shape is limited to spheres, the average particle size of the silicon particles is as small as 100 nm or less, and the dispersibility between silicons is small. Is very poorly aggregated (see, for example, Non-Patent Document 3). There is no known method of uniformly and dispersively coating the periphery of anisotropic silicon nanoparticles with a chemical species.
従って、本発明が解決しようとする課題は、電子材料や電池等に用いることができる、シリコンナノ粒子の周囲がポリマーで被覆されたポリマー被覆シリコンナノ粒子を提供することにある。 Therefore, an object to be solved by the present invention is to provide polymer-coated silicon nanoparticles in which the periphery of the silicon nanoparticles is coated with a polymer, which can be used for electronic materials, batteries and the like.
本発明者らは、種々検討の結果、以下の構成によって上記課題を解決できることを見出した。
（１）
シリコン粒子のメディアン径（Ｄ５０）が１００〜１０００ｎｍであるポリマー被覆シリコン粒子。
（２）
シリコン粒子の表面が改質されている（１）に記載のポリマー被覆シリコン粒子。
（３）
シリコン粒子がＳｉＯ２、Ｓｉ（Ｉ）Ｏ、Ｓｉ（ＩＩ）Ｏ、Ｓｉ（ＩＩＩ）Ｏ、またはＳｉＯＨを介してポリマーと結合している（１）又は（２）に記載のポリマー被覆シリコン粒子。
（４）
シリコン粒子の平均長径度が４以下である（１）〜（３）のいずれかに記載のポリマー被覆シリコン粒子。
（５）
シリコン粒子に対する被覆ポリマーの体積比が１以上である（１）〜（４）のいずれかに記載のポリマー被覆シリコン粒子。
（６）
１つのポリマー内に含まれる平均シリコン粒子数が４以下である（１）〜（５）のいずれかに記載のポリマー被覆シリコン粒子。
（７）
Ｄ５０が２００〜１２００ｎｍである（１）〜（６）のいずれかに記載のポリマー被覆シリコン粒子。
（８）
被覆ポリマーが、ポリスチレン、ポリメタクリル酸、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ｎ−プロピル、ポリメタクリル酸イソプロピル、ポリメタクリル酸ｎ−ブチル、ポリメタクリル酸ｓｅｃ−ブチル、ポリメタクリル酸イソブチル、ポリメタクリル酸ｔｅｒｔ−ブチル、ポリメタクリル酸２−エチルへキシル、ポリメタクリル酸イソボニル、ポリメタクリル酸ベンジル、ポリメタクリル酸２−ヒドロキシエチル、ポリメタクリル酸ヒドロキシプロピル、ポリメタクリル酸ヒドロキシブチル、ポリメタクリル酸トリエチレングリコ−ルなどのポリメタクリル酸系、ポリイタコン酸無水物、ポリイタコン酸、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ｎ−プロピル、ポリアクリル酸イソプロピル、ポリアクリル酸ｎ−ブチル、ポリアクリル酸ｓｅｃ−ブチル、ポリアクリル酸イソブチル、ポリアクリル酸ｔｅｒｔ−ブチル、ポリアクリル酸２−エチルへキシル、ポリアクリル酸イソボルニル、ポリアクリル酸ベンジル、ポリアクリル酸フェニル、ポリアクリル酸グリシジル、ポリアクリル酸２−ヒドロキシエチル、ポリアクリル酸ヒドロキシプロピル、ポリアクリル酸ヒドロキシブチルなどのポリアクリル酸系、ポリメタクリルアミド、ポリ（Ｎ−メチルアクリルアミド）、ポリ（Ｎ、Ｎ’−ジメチルアクリルアミド）、ポリ（Ｎ−ｔｅｒｔ−ブチルメタクリルアミド）、ポリ（Ｎ−ｎ−ブチルメタクリルアミド）、ポリ（Ｎ−メチロ−ルメタクリルアミド）、ポリ（Ｎ−エチロ−ルメタクリルアミド）などのポリメタクリルアミド系、ポリ（Ｎ，Ｎ’−メチレンビスアクリルアミド）、ポリＮ−イソプロピルアクリルアミド）、ポリ（Ｎ−ｔｅｒｔ−ブチルアクリルアミド）、ポリ（Ｎ−ｎ−ブチルアクリルアミド）、ポリ（Ｎ−メチロ−ルアクリルアミド）、ポリ（Ｎ−エチロ−ルアクリルアミド）などのポリアクリルアミド系、ポリ安息香酸ビニル、ポリジエチルアミノスチレン、ポリジエチルアミノアルファ−メチルスチレン、ポリ（ｐ−ビニルベンゼンスルホン酸）、ポリ（ｐ−ビニルベンゼンスルホン酸ナトリウム塩）、ポリ（ｐ−ビニルベンゼンスルホン酸リチウム塩）、ポリジビニルベンゼン、ポリ酢酸ビニル、ポリ酢酸ブチル、ポリ塩化ビニル、ポリフッ化ビニル、ポリ臭化ビニル、ポリ無水マレイン酸、ポリ（Ｎ−フェニルマレイミド）、ポリ（Ｎ−ブチルマレイミド）、ポリ（Ｎ−ビニルピロリドン）、ポリ（Ｎ−ビニルカルバゾ−ル）、ポリアクリロニトリル、ポリアニリン、ポリピロ−ル、ウレタン重合に用いられるポリオ−ル系又はイソシアネ−ト系からなる群から選ばれる１種以上のモノマーの単独重合体又は共重合体である（１）〜（７）のいずれかに記載のポリマー被覆シリコン粒子。
As a result of various studies, the present inventors have found that the above problems can be solved by the following configurations.
(1)
Polymer-coated silicon particles having a median diameter (D50) of the silicon particles of 100 to 1000 nm.
(2)
The polymer-coated silicon particles according to (1), wherein the surface of the silicon particles is modified.
(3)
The polymer-coated silicon particles according to (1) or (2), wherein the silicon particles are bonded to the polymer via SiO 2 , Si (I) O, Si (II) O, Si (III) O, or SiOH.
(4)
The polymer-coated silicon particles according to any one of (1) to (3), wherein the average major axis of the silicon particles is 4 or less.
(5)
The polymer-coated silicon particles according to any one of (1) to (4), wherein the volume ratio of the coated polymer to the silicon particles is 1 or more.
(6)
The polymer-coated silicon particles according to any one of (1) to (5), wherein the average number of silicon particles contained in one polymer is 4 or less.
(7)
The polymer-coated silicon particles according to any one of (1) to (6), wherein D50 is 200 to 1200 nm.
(8)
The coating polymers are polystyrene, polymethacrylic acid, polymethylmethacrylate, ethylpolymethacrylate, n-propylpolymethacrylate, isopropylpolymethacrylate, n-butylpolymethacrylate, sec-butyl polymethacrylate, isobutyl polymethacrylate. , Polymethacrylate tert-butyl, polymethacrylate 2-ethylhexyl, polymethacrylate isobonyl, polymethacrylate benzyl, polymethacrylate 2-hydroxyethyl, polymethacrylate hydroxypropyl, polymethacrylate hydroxybutyl, polymethacrylate Polymethacrylic acid such as triethyleneglycol, polyitaconic acid anhydride, polyitaconic acid, polyacrylic acid, methyl polyacrylate, ethyl polyacrylate, n-propyl polyacrylate, isopropyl polyacrylate, n polyacrylic acid -Butyl, sec-butyl polyacrylate, isobutyl polyacrylate, tert-butyl polyacrylate, 2-ethylhexyl polyacrylate, isobornyl polyacrylate, benzyl polyacrylate, phenyl polyacrylate, glycidyl polyacrylate , Polyacrylic acid-based such as 2-hydroxyethyl polyacrylate, hydroxypropyl polyacrylate, hydroxybutyl polyacrylate, polymethacrylate, poly (N-methylacrylamide), poly (N, N'-dimethylacrylamide), Polymethacrylamides such as poly (N-tert-butylmethacrylate), poly (Nn-butylmethacrylate), poly (N-methylolmethacrylate), poly (N-ethylolmethacrylate), Poly (N, N'-methylenebisacrylamide), poly N-isopropylacrylamide), poly (N-tert-butylacrylamide), poly (Nn-butylacrylamide), poly (N-methylolacrylamide), poly Polyacrylamides such as (N-Etylol acrylamide), Vinyl Polybenzoate, Polydiethylaminostyrene, Polydiethylaminoalpha-Methylstyrene, Poly (p-vinylbenzenesulfonic acid), Poly (sodium salt of p-vinylbenzenesulfonate) ), Poly (p-vinylbenzene sulfonic acid lithium salt), polydivinylbenzene, polyvinyl acetate, butyl polyacetate, polyvinyl chloride, polyvinyl fluoride, polyvinyl bromide, polymaleic anhydride, poly (N-phenylma) Reimide), poly (N-butylmaleimide), poly (N-vinylpyrrolidone), poly (N-vinylcarbazol), polyacrylonitrile, polyaniline, polypyrrole, polyol-based or isocyanate used for urethane polymerization. The polymer-coated silicon particles according to any one of (1) to (7), which are homopolymers or copolymers of one or more monomers selected from the group consisting of systems.
本発明によれば、シリコンの酸化が抑制されたＤ５０が１００〜１０００ｎｍであるシリコン粒子の周囲がポリマーで被覆された、ポリマー被覆シリコン粒子を提供することができる。 According to the present invention, it is possible to provide polymer-coated silicon particles in which the periphery of silicon particles having a D50 of 100 to 1000 nm in which oxidation of silicon is suppressed is coated with a polymer.
以下に、本発明のポリマー被覆シリコン粒子について、本発明の一例を示しながら詳述する。ただし、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更して実施することができる。 The polymer-coated silicon particles of the present invention will be described in detail below with reference to an example of the present invention. However, the scope of the present invention is not limited to these explanations, and other than the following examples, the scope of the present invention can be appropriately modified and implemented as long as the gist of the present invention is not impaired.
本発明のポリマー被覆シリコン粒子は、少なくともシリコンとポリマーとを含み、シリコン粒子がポリマーに被覆されているものである。ここでいう被覆されている状態とは、図１で示すようにシリコン粒子の表面被覆率が８０％以上である状態を言う。表面被覆率は、例えば、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ；以下、ＴＥＭと称する。）写真を視覚的に検査することにより評価することができる。 The polymer-coated silicon particles of the present invention contain at least silicon and a polymer, and the silicon particles are coated with a polymer. The coated state here means a state in which the surface coverage of the silicon particles is 80% or more as shown in FIG. The surface coverage can be evaluated, for example, by visually inspecting a transmission electron microscope (Transmission Electron Microscope; hereinafter referred to as TEM) photograph.
本発明のポリマー被覆シリコン粒子におけるシリコンは、純度が９８重量％程度の汎用グレ−ドの金属シリコン、純度が２〜４Ｎのケミカルグレ−ドの金属シリコン、塩素化して蒸留精製した４Ｎより高純度のポリシリコン、単結晶成長法による析出工程を経た超高純度の単結晶シリコン、もしくはそれらに周期表１３族もしくは１５族元素をド−ピングして、ｐ型又はｎ型としたもの、半導体製造プロセスで発生したウエハの研磨や切断の屑、プロセスで不良となった廃棄ウエハなど、汎用グレ−ドの金属シリコン以上の純度のものであれば特に限定されない。シリコンは、純度２〜４Ｎの金属シリコンであることが好ましい。 The silicon in the polymer-coated silicon particles of the present invention has a higher purity than general-purpose grade metallic silicon having a purity of about 98% by weight, chemical grade metallic silicon having a purity of 2 to 4N, and 4N obtained by chlorination and distillation purification. Polysilicon, ultra-high-purity single-crystal silicon that has undergone a precipitation step by the single crystal growth method, or a p-type or n-type product obtained by doping them with Group 13 or Group 15 elements of the periodic table, semiconductor manufacturing. There is no particular limitation as long as the purity is higher than that of general-purpose grade metallic silicon, such as wafer polishing and cutting scraps generated in the process, and waste wafers that have become defective in the process. The silicon is preferably metallic silicon having a purity of 2 to 4N.
本発明のポリマー被覆シリコン粒子におけるシリコン粒子の粒径（Ｄ５０：５０％体積粒径）は、１００〜１０００ｎｍであり、好ましくは１２０ｎｍ〜８００ｎｍであり、特に好ましくは１２０〜６００ｎｍであり、より好ましくは１５０〜４００ｎｍである。 The particle size (D50: 50% volumetric particle size) of the silicon particles in the polymer-coated silicon particles of the present invention is 100 to 1000 nm, preferably 120 nm to 800 nm, particularly preferably 120 to 600 nm, and more preferably. It is 150 to 400 nm.
Ｄ５０は、レ−ザ−回折散乱法により測定した累積粒度分布において微粒側から累積５０％の粒径に該当する。粒径の測定に際しては、シリコン粒子やポリマー被覆シリコン粒子を液体に加えて超音波等を利用しながら激しく混合することで分散液を作製し、作製した分散液を装置に測定サンプルとして導入し、粒径の測定を行えばよい。 D50 corresponds to a cumulative particle size of 50% from the fine particle side in the cumulative particle size distribution measured by the laser diffraction scattering method. When measuring the particle size, silicon particles or polymer-coated silicon particles are added to the liquid and mixed vigorously using ultrasonic waves to prepare a dispersion, and the prepared dispersion is introduced into the apparatus as a measurement sample. The particle size may be measured.
本発明のポリマー被覆シリコン粒子では、シリコンとポリマーの密着性を向上できることから、シリコン粒子の表面が改質されていることが好ましく、具体的には、シリコン粒子がＳｉＯ２、Ｓｉ（Ｉ）Ｏ、Ｓｉ（ＩＩ）Ｏ、Ｓｉ（ＩＩＩ）Ｏ、またはＳｉＯＨを介してポリマーと結合していることが好ましい。ＳｉＯ２、Ｓｉ（Ｉ）Ｏ、Ｓｉ（ＩＩ）Ｏ、Ｓｉ（ＩＩＩ）Ｏ、またはＳｉＯＨの存在および組成は、例えばＸ線光電分光法などの分析手法により測定できる。 In the polymer-coated silicon particles of the present invention, the surface of the silicon particles is preferably modified because the adhesion between the silicon and the polymer can be improved. Specifically, the silicon particles are SiO 2 , Si (I) O. , Si (II) O, Si (III) O, or SiOH, which are preferably bonded to the polymer. The presence and composition of SiO 2 , Si (I) O, Si (II) O, Si (III) O, or SiOH can be measured by analytical techniques such as X-ray photoelectric spectroscopy.
本発明のポリマー被覆シリコン粒子におけるシリコン粒子の平均長径度は４以下であることが好ましく、特に好ましくは３以下である。長径度がこの範囲にあることで、シリコン粒子の端部までポリマーで被覆しやすくなる。 The average major axis of the silicon particles in the polymer-coated silicon particles of the present invention is preferably 4 or less, and particularly preferably 3 or less. When the major axis is in this range, it becomes easy to cover the edges of the silicon particles with the polymer.
長径度は、一つの粒子について（長径度）＝（長径）／（短径）で定義される。シリコン粒子の長径度を測定する方法として、例えば、図１に示すようなＴＥＭ画像において、各粒子内のシリコン粒子の長径と短径を画像処理で計測する方法が挙げられる。シリコン平均長径度は、例えば、ＴＥＭ画像内の２０個以上の粒子について求めた長径度の平均を算出することで求められる。 The major axis is defined as (major axis) = (major axis) / (minor axis) for one particle. As a method of measuring the major axis of the silicon particles, for example, in the TEM image as shown in FIG. 1, a method of measuring the major axis and the minor axis of the silicon particles in each particle by image processing can be mentioned. The silicon average major axis is obtained, for example, by calculating the average major axis obtained for 20 or more particles in the TEM image.
本発明のポリマー被覆シリコン粒子ではシリコン粒子に対する被覆ポリマーの体積比が１以上であることが好ましく、特に好ましくは３以上である。 In the polymer-coated silicon particles of the present invention, the volume ratio of the coated polymer to the silicon particles is preferably 1 or more, and particularly preferably 3 or more.
シリコン粒子に対する被覆ポリマーの体積比の算出方法として、以下の方法が挙げられる。 Examples of the method for calculating the volume ratio of the coated polymer to the silicon particles include the following methods.
まず、得られたポリマー被覆シリコン粒子のＴＥＭ画像の上に透明シートを２枚重ね、１枚のシートにはシリコンに相当する部分をペンで模写し、もう１枚のシートにはポリマーに相当する部分をペンで模写する。透明シートとしては作業性が良いことから、ＯＨＰシート（オーバーヘッドプロジェクター用シート）を用いる。計測する粒子数としては多いほど良いが、作業性の観点から１０粒子以上、好ましくは２０粒子以上計測する。次に、それぞれの画像をＪＰＥＧやＴＩＦＦデータに変換し、Ｎａｎｏ Ｈｕｎｔｅｒ ＮＳ２Ｋ−Ｐｒｏ（ナノシステム株式会社）を用いて２値化し、シリコン部分とポリマー部分それぞれの総面積を算出する。次に、シリコン粒子の総面積を計測個数で割ることで、シリコン粒子１個の平均面積（ＳＳｉ、ｎｍ２）を算出し、シリコン粒子１個の平均体積（ＶＳｉ、ｎｍ３）＝（４／３）×ＳＳｉ×√（ＳＳｉ／π）の式からシリコン粒子１個の平均体積を算出する。さらに、ポリマーの総面積を計測個数で割ることで、１つの複合粒子に含まれるポリマー部分の面積（ＳＰＳ、ｎｍ２）を求め、ＳＳｉとＳｐｓを加算することで複合粒子１個の面積（Ｓ）を算出する。その後、複合粒子１個の平均体積（Ｖ、ｎｍ３）＝（４／３）×Ｓ×√（Ｓ／π）の式から複合粒子１個の平均体積を算出する。複合粒子１個に含まれるポリマー部分の体積（Ｖｐｓ、ｎｍ３）はＶｐｓ＝Ｖ−ＶＳｉから算出できる。最後にＶｐｓをＶＳｉで割ることで、シリコン粒子に対する被覆ポリマーの体積比を算出することができる。 First, two transparent sheets are laminated on the TEM image of the obtained polymer-coated silicon particles, the portion corresponding to silicon is copied on one sheet with a pen, and the other sheet corresponds to polymer. Copy the part with a pen. Since the transparent sheet has good workability, an OHP sheet (overhead projector sheet) is used. The larger the number of particles to be measured, the better, but from the viewpoint of workability, 10 or more particles, preferably 20 or more particles are measured. Next, each image is converted into JPEG or TIFF data, binarized using Nano Hunter NS2K-Pro (Nanosystem Co., Ltd.), and the total area of each of the silicon portion and the polymer portion is calculated. Next, the average area of one silicon particle (S Si , nm 2 ) is calculated by dividing the total area of the silicon particles by the measured number, and the average volume of one silicon particle (V Si , nm 3 ) = ( The average volume of one silicon particle is calculated from the formula of 4/3) × S Si × √ (S Si / π). Furthermore, the area of the polymer portion (S PS , nm 2 ) contained in one composite particle is obtained by dividing the total area of the polymer by the number of measured particles, and S Si and Sps are added to obtain one composite particle. The area (S) is calculated. Then, the average volume of one composite particle is calculated from the formula of the average volume (V, nm 3 ) = (4/3) × S × √ (S / π) of one composite particle. The volume (V ps , nm 3 ) of the polymer portion contained in one composite particle can be calculated from V ps = VV Si . Finally, by dividing V ps by V Si , the volume ratio of the coated polymer to the silicon particles can be calculated.
本発明のポリマー被覆シリコン粒子では、シリコン同士の凝集を防止できることから、１つのポリマー内に含まれる平均シリコン粒子数は４以下であることが好ましく、特に好ましくは２以下である。 In the polymer-coated silicon particles of the present invention, the average number of silicon particles contained in one polymer is preferably 4 or less, and particularly preferably 2 or less, because aggregation of silicon can be prevented.
１つのポリマー内に含まれる平均シリコン粒子数を測定する手法として、例えばポリマー被覆シリコン粒子のＴＥＭ画像を視覚的に検査する方法が挙げられる。図２に示すようにポリマー被覆シリコン粒子が２０個以上映ったＴＥＭ画像を用意し、各ポリマー内に含まれるシリコン粒子の個数を計上し、その平均を計算することで１つのポリマー内に含まれる平均シリコン粒子数を求めることができる。測定のばらつきを小さくするために、２０個以上のポリマーについて調べることが好ましい。 As a method of measuring the average number of silicon particles contained in one polymer, for example, a method of visually inspecting a TEM image of polymer-coated silicon particles can be mentioned. As shown in FIG. 2, a TEM image showing 20 or more polymer-coated silicon particles is prepared, the number of silicon particles contained in each polymer is counted, and the average thereof is calculated to be included in one polymer. The average number of silicon particles can be obtained. It is preferable to investigate 20 or more polymers in order to reduce measurement variability.
本発明のポリマー被覆シリコン粒子のＤ５０は２００〜１２００ｎｍであることが好ましく、特に好ましくは２６０〜１０００ｎｍである。ポリマー被覆シリコンの粒径がこの範囲にあることで粒子同士が凝集しにくくなる。 The D50 of the polymer-coated silicon particles of the present invention is preferably 200 to 1200 nm, particularly preferably 260 to 1000 nm. When the particle size of the polymer-coated silicon is in this range, the particles are less likely to aggregate with each other.
本発明のポリマー被覆シリコン粒子における被覆ポリマーとしては、ポリスチレン、ポリメタクリル酸、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ｎ−プロピル、ポリメタクリル酸イソプロピル、ポリメタクリル酸ｎ−ブチル、ポリメタクリル酸ｓｅｃ−ブチル、ポリメタクリル酸イソブチル、ポリメタクリル酸ｔｅｒｔ−ブチル、ポリメタクリル酸２−エチルへキシル、ポリメタクリル酸イソボニル、ポリメタクリル酸ベンジル、ポリメタクリル酸２−ヒドロキシエチル、ポリメタクリル酸ヒドロキシプロピル、ポリメタクリル酸ヒドロキシブチル、ポリメタクリル酸トリエチレングリコ−ルなどのポリメタクリル酸系、ポリイタコン酸無水物、ポリイタコン酸、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ｎ−プロピル、ポリアクリル酸イソプロピル、ポリアクリル酸ｎ−ブチル、ポリアクリル酸ｓｅｃ−ブチル、ポリアクリル酸イソブチル、ポリアクリル酸ｔｅｒｔ−ブチル、ポリアクリル酸２−エチルへキシル、ポリアクリル酸イソボルニル、ポリアクリル酸ベンジル、ポリアクリル酸フェニル、ポリアクリル酸グリシジル、ポリアクリル酸２−ヒドロキシエチル、ポリアクリル酸ヒドロキシプロピル、ポリアクリル酸ヒドロキシブチルなどのポリアクリル酸系、ポリメタクリルアミド、ポリ（Ｎ−メチルアクリルアミド）、ポリ（Ｎ、Ｎ’−ジメチルアクリルアミド）、ポリ（Ｎ−ｔｅｒｔ−ブチルメタクリルアミド）、ポリ（Ｎ−ｎ−ブチルメタクリルアミド）、ポリ（Ｎ−メチロ−ルメタクリルアミド）、ポリ（Ｎ−エチロ−ルメタクリルアミド）などのポリメタクリルアミド系、ポリ（Ｎ，Ｎ’−メチレンビスアクリルアミド）、ポリＮ−イソプロピルアクリルアミド）、ポリ（Ｎ−ｔｅｒｔ−ブチルアクリルアミド）、ポリ（Ｎ−ｎ−ブチルアクリルアミド）、ポリ（Ｎ−メチロ−ルアクリルアミド）、ポリ（Ｎ−エチロ−ルアクリルアミド）などのポリアクリルアミド系、ポリ安息香酸ビニル、ポリジエチルアミノスチレン、ポリジエチルアミノアルファ−メチルスチレン、ポリ（ｐ−ビニルベンゼンスルホン酸）、ポリ（ｐ−ビニルベンゼンスルホン酸ナトリウム塩）、ポリ（ｐ−ビニルベンゼンスルホン酸リチウム塩）、ポリジビニルベンゼン、ポリ酢酸ビニル、ポリ酢酸ブチル、ポリ塩化ビニル、ポリフッ化ビニル、ポリ臭化ビニル、ポリ無水マレイン酸、ポリ（Ｎ−フェニルマレイミド）、ポリ（Ｎ−ブチルマレイミド）、ポリ（Ｎ−ビニルピロリドン）、ポリ（Ｎ−ビニルカルバゾ−ル）、ポリアクリロニトリル、ポリアニリン、ポリピロ−ル、ウレタン重合に用いられるポリオ−ル系又はイソシアネ−ト系からなる群から選ばれる１種以上のモノマーの単独重合体又は共重合体等が挙げられ、好ましくはポリスチレン、ポリメタクリル酸、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ｎ−プロピル、ポリメタクリル酸イソプロピル、ポリメタクリル酸ｎ−ブチル、ポリメタクリル酸ｓｅｃ−ブチル、ポリメタクリル酸イソブチル、ポリメタクリル酸ｔｅｒｔ−ブチル、ポリメタクリル酸２−エチルへキシル、ポリメタクリル酸イソボニル、ポリメタクリル酸ベンジル、ポリメタクリル酸２−ヒドロキシエチル、ポリメタクリル酸ヒドロキシプロピル、ポリメタクリル酸ヒドロキシブチル、ポリメタクリル酸トリエチレングリコ−ルなどのメチルメタクリル酸系、ポリイタコン酸無水物、ポリイタコン酸、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ｎ−プロピル、ポリアクリル酸イソプロピル、ポリアクリル酸ｎ−ブチル、ポリアクリル酸ｓｅｃ−ブチル、ポリアクリル酸イソブチル、ポリアクリル酸ｔｅｒｔ−ブチル、ポリアクリル酸２−エチルへキシル、ポリアクリル酸イソボルニル、ポリアクリル酸ベンジル、ポリアクリル酸フェニル、ポリアクリル酸グリシジル、ポリアクリル酸２−ヒドロキシエチル、ポリアクリル酸ヒドロキシプロピル、ポリアクリル酸ヒドロキシブチルなどのポリアクリル酸系、ポリアクリロニトリルからなる群から選ばれる１種以上のモノマーの単独重合体又は共重合体等であり、さらに好ましくは、ポリスチレン、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ｎ−プロピル、ポリメタクリル酸ｎ−ブチル、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ｎ−プロピル、ポリアクリル酸ｎ−ブチル、ポリアクリロニトリルからなる群から選ばれる１種以上のモノマーの単独重合体又は共重合体等であり、特に好ましくはポリスチレン、ポリメタクリル酸メチル又はポリアクリル酸メチルからなる群から選ばれる１種以上のモノマーの単独重合体又は共重合体等である。 Examples of the coating polymer in the polymer-coated silicon particles of the present invention include polystyrene, polymethacrylic acid, polymethylmethacrylate, ethylpolymethacrylate, n-propyl polymethacrylate, isopropylpolymethacrylate, n-butyl polymethacrylate, and polymethacryl. Sec-butyl acid, isobutyl polymethacrylate, tert-butyl polymethacrylate, 2-ethylhexyl polymethacrylate, isobonyl polymethacrylate, benzyl polymethacrylate, 2-hydroxyethyl polymethacrylate, hydroxypropylpolymethacrylate, Polymethacrylic acid-based materials such as hydroxybutylpolymethacrylate and triethyleneglycol methacrylate, polyitaconic acid anhydride, polyitaconic acid, polyacrylic acid, methyl polyacrylate, ethyl polyacrylate, n-propyl polyacrylate, Isopropyl polyacrylate, n-butyl polyacrylate, sec-butyl polyacrylate, isobutyl polyacrylate, tert-butyl polyacrylate, 2-ethylhexyl polyacrylate, isobornyl polyacrylate, benzyl polyacrylate, Polyacrylic acid-based such as phenyl polyacrylate, glycidyl polyacrylate, 2-hydroxyethyl polyacrylate, hydroxypropyl polyacrylate, hydroxybutyl polyacrylate, polymethacrylamide, poly (N-methylacrylamide), poly ( N, N'-dimethylacrylamide), poly (N-tert-butylmethacrylate), poly (Nn-butylmethacrylate), poly (N-methylolmethacrylate), poly (N-ethylolmethacrylate) Polymethacrylamides such as amide), poly (N, N'-methylenebisacrylamide), polyN-isopropylacrylamide), poly (N-tert-butylacrylamide), poly (Nn-butylacrylamide), poly ( Polyacrylamides such as N-methylolacrylamide) and poly (N-ethylolacrylamide), vinyl benzoate, polydiethylaminostyrene, polydiethylaminoalpha-methylstyrene, poly (p-vinylbenzenesulfonic acid), poly (Sodium salt of p-vinylbenzene sulfonic acid), poly (lithium salt of p-vinylbenzene sulfonic acid), polydivinylbenzene, polyvinyl acetate, butyl polyacetate, polyvinyl chloride, polyvinyl fluoride, poly bromide Nyl, polymaleic anhydride, poly (N-phenylmaleimide), poly (N-butylmaleimide), poly (N-vinylpyrrolidone), poly (N-vinylcarbazol), polyacrylic nitrile, polyaniline, polypyrrole, urethane Examples thereof include homopolymers or copolymers of one or more monomers selected from the group consisting of polyole-based or isocyanate-based used for polymerization, preferably polystyrene, polymethacrylic acid, polymethylmethacrylate, and the like. To polyethyl methacrylate, n-propyl polymethacrylate, isopropyl polymethacrylate, n-butyl polymethacrylate, sec-butyl polymethacrylate, isobutyl polymethacrylate, tert-butyl polymethacrylate, 2-ethyl polymethacrylate Methyl methacrylic acid such as xyl, polyisobonyl methacrylate, benzyl polymethacrylate, 2-hydroxyethyl polymethacrylate, hydroxypropylpolymethacrylate, hydroxybutylpolymethacrylate, triethyleneglycolpolymethacrylate, polyitaconic acid anhydride Things, polyitaconic acid, polyacrylic acid, methyl polyacrylic acid, ethyl polyacrylic acid, n-propyl polyacrylic acid, isopropyl polyacrylic acid, n-butyl polyacrylic acid, sec-butyl polyacrylic acid, isobutyl polyacrylic acid, Tert-butyl polyacrylate, 2-ethylhexyl polyacrylate, isobornyl polyacrylate, benzyl polyacrylate, phenyl polyacrylate, glycidyl polyacrylate, 2-hydroxyethyl polyacrylate, hydroxypropyl polyacrylate, It is a homopolymer or copolymer of one or more monomers selected from the group consisting of polyacrylic acid-based polyacrylic acid such as hydroxybutyl polyacrylic acid and polyacrylonitrile, and more preferably polystyrene, polymethyl methacrylate, and polymethacrylic. 1 selected from the group consisting of ethyl acid acid, n-propyl polymethacrylate, n-butyl polymethacrylate, methyl polyacrylate, ethyl polyacrylate, n-propyl polyacrylate, n-butyl polyacrylate, polyacrylonitrile 1 It is a homopolymer or copolymer of one or more kinds of monomers, and particularly preferably a homopolymer or copolymer of one or more kinds of monomers selected from the group consisting of polystyrene, polymethyl methacrylate or methyl polyacrylate. Is.
本発明のポリマー被覆シリコン粒子の製造方法としては、シリコン粒子をポリマーとなる高分子モノマーとを反応させ、そこに開始剤を加えることで得られる高分子モノマーのスラリーを重合することにより、ポリマー被覆シリコン粒子を得る方法が挙げられる。 In the method for producing polymer-coated silicon particles of the present invention, a polymer coating is performed by reacting the silicon particles with a polymer monomer to be a polymer and polymerizing a slurry of the polymer monomer obtained by adding an initiator thereto. Examples thereof include a method for obtaining silicon particles.
本発明のポリマー被覆シリコン粒子の製造方法では、シリコン粒子と高分子モノマーを反応させる際には、反応を促進させるために、シリコン粒子の表面を改質することが好ましい。ここでいう改質とは、表面改質剤を用いる化学反応によってシリコン粒子の表面状態を変化させ、ポリマーの被覆を容易にする工程である。表面改質剤としては、分子内にアルコキシド基、カルボキシ基、又はヒドロキシ基を含む分子、塩基および酸化剤からなる群より選ばれた１種以上の化合物を用いることが好ましく、具体的な表面改質剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニル系、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシランなどのエポキシ系、ｐ−スチリルトリメトキシシランなどのスチリル系、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシランなどのメタクリル系、３−アクリロキシプロピルトリメトキシシランなどのアクリル系、トリス−（トリメトキシシリルプロピル）イソシアヌレ−トなどのイソシアヌレ−ト系又は３−イソシアネ−トプロピルトリエトキシシランなどのイソシアネ−ト系、テトラエトキシシラン、過酸化水素、硝酸、硫酸、過マンガン酸カリウム、二クロム酸カリウム、次亜塩素酸ナトリウム、三酸化クロム、過硫酸アンモニウム、過硫酸カリウムなどの酸化剤、アンモニア、水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸カリウムなどの塩基が挙げられ、好ましくは３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、テトラエトキシシラン、過酸化水素、硝酸、アンモニア、水酸化ナトリウムの群から選ばれる１種以上、特に好ましくは３−メタクリロキシプロピルトリメトキシシラン、テトラエトキシシラン、アンモニアの群から選ばれる１種以上である。 In the method for producing polymer-coated silicon particles of the present invention, when the silicon particles are reacted with the polymer monomer, it is preferable to modify the surface of the silicon particles in order to accelerate the reaction. The modification referred to here is a step of changing the surface state of the silicon particles by a chemical reaction using a surface modifier to facilitate the coating of the polymer. As the surface modifier, it is preferable to use one or more compounds selected from the group consisting of molecules containing an alkoxide group, a carboxy group, or a hydroxy group in the molecule, a base, and an oxidizing agent, and a specific surface modification is performed. Examples of the pledge agent include vinyl-based agents such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy. Epoxy-based silanes such as 3-glycidoxypropyltriethoxysilane, styryl-based such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, methacryl such as 3-methacryloxypropyltriethoxysilane, acrylic such as 3-acryloxypropyltrimethoxysilane, isocyanurate such as tris- (trimethoxysilylpropyl) isocyanurate or 3 -Isocyanate-Isocyanates such as propyltriethoxysilane, tetraethoxysilane, hydrogen peroxide, nitrate, sulfuric acid, potassium permanganate, potassium dichromate, sodium hypochlorite, chromium trioxide, ammonium persulfate, Examples thereof include oxidizing agents such as potassium persulfate and bases such as ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate and potassium carbonate, preferably 3-methacryloxypropylmethyldimethoxysilane, 3 − One or more selected from the group of methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraethoxysilane, hydrogen peroxide, nitrate, ammonia, and sodium hydroxide. , Particularly preferably one or more selected from the group of 3-methacryloxypropyltrimethoxysilane, tetraethoxysilane, and ammonia.
表面改質剤を用いる際には、シリコン粒子１００質量部に対して表面改質剤を０．１〜８００質量部添加することが好ましい。修飾反応中の粒子の凝集を防ぐため、必要に応じてポリカルボン酸系の安定化剤を添加してもよい。修飾反応を促進するため、必要に応じてアンモニア、水酸化ナトリウム、水酸化カリウム又は炭酸水素ナトリウムなどの水に溶けてアルカリ性を示す化合物や、塩酸、硝酸、酢酸又は硫酸などの水に溶けて酸性を示す化合物などの残存反応促進剤を添加してもよい。反応性が高く、金属化合物が残存しないことから、アンモニア又は塩酸であることが好ましい。残存反応促進剤を用いる場合、シリコン粒子１００質量部に対して残存反応促進剤を０．００５〜５４質量部添加することが好ましい。反応に用いる溶媒としては表面改質剤が溶解する溶媒であればよく、水、エタノ−ル、メタノ−ル、アセトン、ジメチルホルムアミド、テトラヒドロフラン、トルエン、ヘキサン、ジクロロメタン、クロロホルムなどが挙げられ、必要に応じて混合溶媒を用いても良い。表面改質剤として３−メタクリロキシプロピルトリメトキシシラン又はテトラエトキシシランを用いてシリコン粒子表面を修飾する際には、水とエタノ−ルの混合溶媒を用いることが好ましい。該混合溶媒における各溶媒の比率は、エタノ−ル１００質量部に対して、水が１０〜１００質量部であることが好ましい。該混合溶媒中のエタノ−ルの比率がこの範囲内であることで、溶媒中のシリコン粒子が分散しやすく、なおかつ、修飾反応が十分に進みやすくなる。 When using the surface modifier, it is preferable to add 0.1 to 800 parts by mass of the surface modifier to 100 parts by mass of the silicon particles. If necessary, a polycarboxylic acid-based stabilizer may be added to prevent agglomeration of particles during the modification reaction. In order to promote the modification reaction, if necessary, it is soluble in water-soluble compounds such as ammonia, sodium hydroxide, potassium hydroxide or sodium hydrogen carbonate, and acidic in water such as hydrochloric acid, nitric acid, acetic acid or sulfuric acid. A residual reaction accelerator such as a compound showing the above may be added. Ammonia or hydrochloric acid is preferable because it has high reactivity and no metal compound remains. When the residual reaction accelerator is used, it is preferable to add 0.005 to 54 parts by mass of the residual reaction accelerator with respect to 100 parts by mass of the silicon particles. The solvent used in the reaction may be any solvent in which the surface modifier dissolves, and examples thereof include water, ethanol, methanol, acetone, dimethylformamide, tetrahydrofuran, toluene, hexane, dichloromethane, chloroform, etc. A mixed solvent may be used depending on the situation. When modifying the surface of silicon particles with 3-methacryloxypropyltrimethoxysilane or tetraethoxysilane as a surface modifier, it is preferable to use a mixed solvent of water and etanol. The ratio of each solvent in the mixed solvent is preferably 10 to 100 parts by mass of water with respect to 100 parts by mass of ethanol. When the ratio of ethanol in the mixed solvent is within this range, the silicon particles in the solvent are easily dispersed, and the modification reaction is sufficiently easy to proceed.
シリコン粒子の表面を改質した後に、必要に応じて、ボ−ルミルやビ−ズミルを用いて上記表面改質シリコン粒子を粉砕・微粒化しても良い。解砕に用いるボ−ルはジルコニア又はアルミナが好ましい。解砕時間は１〜２４時間が好ましく、より好ましくは１〜１２時間である。 After modifying the surface of the silicon particles, the surface-modified silicon particles may be pulverized and atomized by using a ball mill or a bead mill, if necessary. The ball used for crushing is preferably zirconia or alumina. The crushing time is preferably 1 to 24 hours, more preferably 1 to 12 hours.
また、表面改質シリコン粒子を粉砕・微粒化した後、必要に応じて遠心分離によりシリコン粒子表面を改質する際に用いた溶媒を水に置換してもよい。 Further, after the surface-modified silicon particles are pulverized and atomized, the solvent used for modifying the surface of the silicon particles by centrifugation may be replaced with water, if necessary.
シリコン粒子と高分子モノマーの反応中は、マグネチックスタ−ラ−、スリ−ワンモ−タ−、ホモミキサ−、インラインミキサ−、ビ−ズミル、ボ−ルミルなどの一般的な混合機や攪拌機を用い、各原料を均一に混合することが好ましい。反応温度は４０〜１００℃が好ましい。また、反応時間は０．５〜７２時間が好ましく、より好ましくは０．５〜２４時間である。反応時間がこの範囲であることで、修飾反応が十分に進行し、なおかつ、生産性が低下しにくくなる。 During the reaction between the silicon particles and the polymer monomer, a general mixer or stirrer such as a magnetic star, a three-one motor, a homomixer, an in-line mixer, a bead mill, or a ball mill is used. , It is preferable to mix each raw material uniformly. The reaction temperature is preferably 40 to 100 ° C. The reaction time is preferably 0.5 to 72 hours, more preferably 0.5 to 24 hours. When the reaction time is within this range, the modification reaction proceeds sufficiently, and the productivity is less likely to decrease.
シリコン粒子に反応させる高分子モノマーとしては、例えば、スチレン、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｓｅｃ−ブチル、メタクリル酸イソブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸２−エチルへキシル、メタクリル酸イソボニル、メタクリル酸ベンジル、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシブチル、メタクリル酸トリエチレングリコ−ルなどのメタクリル酸系、イタコン酸無水物、イタコン酸、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸ｓｅｃ−ブチル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸２−エチルへキシル、アクリル酸イソボルニル、アクリル酸ベンジル、アクリル酸フェニル、アクリル酸グリシジル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピル、アクリル酸ヒドロキシブチルなどのアクリル酸系、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ、Ｎ’−ジメチルアクリルアミド、Ｎ−ｔｅｒｔ−ブチルメタクリルアミド、Ｎ−ｎ−ブチルメタクリルアミド、Ｎ−メチロ−ルメタクリルアミド、Ｎ−エチロ−ルメタクリルアミドなどのメタクリルアミド系、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ｔｅｒｔ−ブチルアクリルアミド、Ｎ−ｎ−ブチルアクリルアミド、Ｎ−メチロ−ルアクリルアミド、Ｎ−エチロ−ルアクリルアミドなどのアクリルアミド系、安息香酸ビニル、ジエチルアミノスチレン、ジエチルアミノアルファ−メチルスチレン、ｐ−ビニルベンゼンスルホン酸、ｐ−ビニルベンゼンスルホン酸ナトリウム塩、ｐ−ビニルベンゼンスルホン酸リチウム塩、ジビニルベンゼン、酢酸ビニル、酢酸ブチル、塩化ビニル、フッ化ビニル、臭化ビニル、無水マレイン酸、Ｎ−フェニルマレイミド、Ｎ−ブチルマレイミド、Ｎ−ビニルピロリドン、Ｎ−ビニルカルバゾ−ル、アクリロニトリル、アニリン、ピロ−ル、ウレタン重合に用いられるポリオ−ル系又はイソシアネ−ト系が挙げられ、好ましくはスチレン、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｓｅｃ−ブチル、メタクリル酸イソブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸２−エチルへキシル、メタクリル酸イソボニル、メタクリル酸ベンジル、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシブチル、メタクリル酸トリエチレングリコ−ルなどのメタクリル酸系、イタコン酸無水物、イタコン酸、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸ｓｅｃ−ブチル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸２−エチルへキシル、アクリル酸イソボルニル、アクリル酸ベンジル、アクリル酸フェニル、アクリル酸グリシジル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピル、アクリル酸ヒドロキシブチルなどのアクリル酸系、アクリロニトリルであり、さらに好ましくは、スチレン、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｎ−ブチル、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｎ−ブチル、アクリロニトリル、特に好ましくはスチレン、メタクリル酸メチル又はアクリル酸メチルである。 Examples of the polymer monomer that reacts with silicon particles include styrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and methacrylic acid. Isobutyl, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isobonyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, triethylene glycol methacrylate, etc. Methacrylic acid, itaconic acid anhydride, itaconic acid, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, acrylic Acrylic acids such as tert-butyl acid, 2-ethylhexyl acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc. , Methacrylicamide, N-methylacrylamide, N, N'-dimethylacrylamide, N-tert-butylmethacrylate, Nn-butylmethacrylate, N-methylolmethacrylate, N-ethyloxylamide, etc. Methacrylic acid, N, N'-methylenebisacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylolacrylamide, N-ethylrolacrylamide and other acrylamides, Vinyl benzoate, diethylaminostyrene, diethylaminoalpha-methylstyrene, p-vinylbenzenesulfonic acid, sodium p-vinylbenzenesulfonic acid salt, lithium p-vinylbenzenesulfonic acid salt, divinylbenzene, vinyl acetate, butyl acetate, vinyl chloride, Vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazol, acryliconitrile, aniline, pyrrol, polyol system used for urethane polymerization. Alternatively, isocyanate type is mentioned, preferably styrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, meta. Isopropyl crylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isobonyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, methacryl Hydroxypropyl acid, hydroxybutyl methacrylate, triethyleneglycol methacrylate and other methacrylic acid, itaconic acid anhydride, itaconic acid, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate , N-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, glycidyl acrylate, 2 acrylate Acrylic acid-based, acrylonitrile such as −hydroxyethyl, hydroxypropyl acrylate, and hydroxybutyl acrylate, more preferably styrene, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, acrylic. Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylonitrile, particularly preferably styrene, methyl methacrylate or methyl acrylate.
用いる開始剤としては、例えば、アゾビスイソブチロニトリルなどのアゾ系化合物、過硫酸カリウム、過硫酸アンモニウム、過酸化ベンゾイル、ジイソブチリルパ−オキシド、ジ−ｎ−プロピルパ−オキシジカ−ボネ−ト、ジイソプロピルパ−オキシジカ−ボネ−ト、ジラウロイルパ−オキシド、ジベンゾイルパ−オキシド、１，１−ジ（ｔｅｒｔ−へキシルペルオキシ）シクロヘキサン、１，１−ジ（ｔｅｒｔ−ブチルペルオキシ）シクロヘキサン、ｔｅｒｔ−ブチルヒドロパ−オキシドやジイソブチリルパ−オキシド、ｔｅｒｔ−ヘキシルペルオキシイソプロピルモノカルボネ−ト、ｔｅｒｔ−ブチルペルオキシイソプロピルモノカルボネ−ト、２，５−ジ−メチル−２，５−ジ（ベンゾイルペルオキシ）ヘキサン、ｔｅｒｔ−ブチルペルオキシアセテ−ト、ジ−ｔｅｒｔ−ヘキシルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、ジイソプロピルベンゼンヒドロペルオキシド、ｔｅｒｔ−ブチルヒドロペルオキシド等の過酸化物が挙げられる。 Examples of the initiator to be used include azo compounds such as azobisisobutyronitrile, potassium persulfate, ammonium persulfate, benzoyl peroxide, diisobutyryl peroxide, di-n-propylperoxydicarbonate, and diisopropylperate. Oxydicarbonate, dilauroyl peroxide, dibenzoyl peroxide, 1,1-di (tert-hexylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, tert-butylhydroperoxide and diisobutyryl peroxide , Tert-hexyl peroxyisopropyl monocarbonate, tert-butylperoxyisopropyl monocarbonate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetate, Examples thereof include peroxides such as di-tert-hexyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide and tert-butyl hydroperoxide.
高分子モノマーのスラリーとする際に用いる溶媒としては、例えば、水、エタノ−ル、メタノ−ル、イソプロピルアルコ−ル、プロパノ−ル又はトルエンなどが挙げられ、好ましくは水、エタノ−ル又はメタノ−ル、特に好ましくは水又はエタノ−ルである。これらは１種又は２種以上用いることができる。 Examples of the solvent used in preparing the slurry of the polymer monomer include water, etanol, metanol, isopropyl alcohol, propanol, toluene and the like, and water, etanol or metanol is preferable. -Lu, especially preferably water or toluene. These can be used alone or in combination of two or more.
高分子モノマーのスラリーにおける高分子モノマーの含有量は、０．５〜２０重量％が好ましく、特に好ましくは１．５〜１０重量％である。高分子モノマーの含有量がこの範囲であることで、シリコン粒子周囲の被覆体が十分な厚みとなる。 The content of the polymer monomer in the polymer monomer slurry is preferably 0.5 to 20% by weight, particularly preferably 1.5 to 10% by weight. When the content of the polymer monomer is in this range, the coating material around the silicon particles has a sufficient thickness.
高分子モノマーのスラリーにおける開始剤の含有量は、０．０１〜３重量％が好ましく、特に好ましくは０．０１〜１重量％である。 The content of the initiator in the slurry of the polymer monomer is preferably 0.01 to 3% by weight, particularly preferably 0.01 to 1% by weight.
高分子モノマーのスラリーにおいては、シリコン粒子の分散性を向上させるため、又は重合を促進させるため、分散剤を含有することが好ましく、該分散剤としては、例えば、ポリビニルピロリドン、スチレンスルホン酸ナトリウム、スチレンスルホン酸リチウム、スチレンスルホン酸アンモニウム、スチレンスルホン酸エチルエステルなどのスチレンスルホン酸系、カルボキシスチレン、ポリアクリル酸、ポリメタクリル酸などのポリカルボン酸系、ナフタレンスルホン酸ホルマリン縮合系、ポリエチレングリコ−ル、ポリカルボン酸部分アルキルエステル系、ポリエ−テル系、ポリアルキレンポリアミン系、アルキルスルホン酸系、四級アンモニウム系、高級アルコ−ルアルキレンオキサイド系、多価アルコ−ルエステル系、アルキルポリアミン系又はポリリン酸塩系が挙げられ、好ましくはポリアクリル酸系添加剤、スチレンスルホン酸系、ポリビニルピロリドン、特に好ましくはスチレンスルホン酸系及びポリビニルピロリドンである。 The polymer monomer slurry preferably contains a dispersant in order to improve the dispersibility of the silicon particles or promote the polymerization, and the dispersant includes, for example, polyvinylpyrrolidone, sodium styrene sulfonate, and the like. Stylonate sulfonic acid type such as lithium styrene sulfonic acid, ammonium styrene sulfonic acid, ethyl styrene sulfonic acid ester, polycarboxylic acid type such as carboxystyrene, polyacrylic acid, polymethacrylic acid, naphthalene sulfonic acid formarin condensation type, polyethylene glycol , Polycarboxylic acid partial alkyl ester type, polyester type, polyalkylene polyamine type, alkyl sulfonic acid type, quaternary ammonium type, higher alcohol alkylene oxide type, polyvalent alcohol ester type, alkyl polyamine type or polyphosphate Examples thereof include salt-based additives, preferably polyacrylic acid-based additives, styrene-sulfonic acid-based additives, and polyvinylpyrrolidone, and particularly preferably styrene-sulfonic acid-based and polyvinylpyrrolidone.
高分子モノマースラリーにおける分散剤の含有量は、３重量％以下が好ましく、特に好ましくは０．００１〜２重量％である。分散剤の量がこの範囲内にあることで、シリコン粒子同士の凝集が進行しにくくなる。もしくは、シリコン粒子周囲のポリマー膜厚が薄くなりにくくなる。 The content of the dispersant in the polymer monomer slurry is preferably 3% by weight or less, particularly preferably 0.001 to 2% by weight. When the amount of the dispersant is within this range, the aggregation of the silicon particles is less likely to proceed. Alternatively, the polymer film thickness around the silicon particles is less likely to be thinned.
高分子モノマースラリーにおいては、重合を促進するために、重合促進剤を含有してもよい。該重合促進剤としては、例えば、炭酸水素ナトリウム又は水酸化カリウムなどのｐＨ調整剤が挙げられ、好ましくは炭酸水素ナトリウムである。 The polymer monomer slurry may contain a polymerization accelerator in order to promote the polymerization. Examples of the polymerization accelerator include a pH adjuster such as sodium hydrogen carbonate or potassium hydroxide, and sodium hydrogen carbonate is preferable.
本発明のポリマー被覆シリコン粒子は、高効率ＬＥＤや太陽電池等に用いることができる。 The polymer-coated silicon particles of the present invention can be used for high-efficiency LEDs, solar cells, and the like.
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
＜実施例１＞
（シリコン粉砕工程）
粒径（Ｄ５０）が７μｍのケミカルグレ−ドの金属シリコン（純度３Ｎ）をエタノ−ルに２０重量％混合し、直径０．３ｍｍのジルコニアビ−ズを用いた微粉砕湿式ビ−ズミルを９時間行い、粒径（Ｄ５０）２００ｎｍ、乾燥時のＢＥＴ比表面積が１００ｍ２／ｇのシリコンスラリーを得た。なお、ＢＥＴ比表面積は、窒素吸着によるＢＥＴ法（ＪＩＳ Ｚ ８８３０、一点法）を用いて測定された値である。
<Example 1>
(Silicon crushing process)
20% by weight of chemical grade metallic silicon (purity 3N) having a particle size (D50) of 7 μm is mixed with ethanol, and a finely pulverized wet bead mill using zirconia beads having a diameter of 0.3 mm is used. After a period of time, a silicon slurry having a particle size (D50) of 200 nm and a BET specific surface area of 100 m 2 / g when dried was obtained. The BET specific surface area is a value measured by using the BET method (JIS Z 8830, one-point method) by nitrogen adsorption.
（シリコン表面改質工程）
上記粉砕シリコンスラリーを３７ｇビ−カ−に投入し、１５分間超音波照射を行い、その後、追加エタノ−ル９４ｇを追加し、シリコンスラリーを得た。その後、ポリカルボン酸系分散剤１１ｇ、アンモニウムヒドロキシド４．５ｇ、水４０ｇを上記シリコンスラリーに添加し、マグネチックスターラーを用いて回転数２５０ｒｐｍの条件で１時間撹拌を行った。その後、テトラエトキシシラン（ＴＥＯＳ）１０ｇを上記スラリーに添加した。室温で１．５時間撹拌を行い、その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間１０分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）２５６ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
(Silicon surface reforming process)
The pulverized silicon slurry was put into a 37 g beaker and irradiated with ultrasonic waves for 15 minutes, and then 94 g of additional ethanol was added to obtain a silicon slurry. Then, 11 g of a polycarboxylic acid-based dispersant, 4.5 g of ammonium hydroxide, and 40 g of water were added to the above silicon slurry, and the mixture was stirred using a magnetic stirrer at a rotation speed of 250 rpm for 1 hour. Then, 10 g of tetraethoxysilane (TEOS) was added to the above slurry. The mixture was stirred at room temperature for 1.5 hours, and then the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 10 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 256 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
上記スラリーをシリコン固形分量が０．７９ｇとなるように秤量して丸底フラスコに移し、合計の水量が２１８ｇとなるように追加で水を添加した。フラスコ系内を窒素パ−ジした後、液温を３５℃に昇温した。その後、３−メタクリロキシプロピルトリメトキシシラン（ＭＰＳ）０．０３ｇをフラスコ内に加え、３０分間攪拌した。蒸留したスチレンモノマー５．０ｇと８ｇの水に溶解させたｐ−スチレンスルホン酸ナトリウム（ＮａＳＳ）０．０３ｇを添加し、２時間攪拌した。その後、液温を６２℃に昇温させ、８ｇの水に溶解させた過硫酸アンモニウム（ＡＰＳ）０．１１ｇを添加した。その後、還流下で１０時間加熱撹拌を続けた。得られた反応液を回転数４８００ｒｐｍ、回転時間４５分の条件で遠心分離処理し、沈殿をエタノ−ルで再分散することでポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は３４９ｎｍ、シリコン粒子の平均長径度は２．２、シリコン粒子に対する被覆ポリマーの体積比は６．３、１つのポリマー内に含まれる平均シリコン粒子数は１．４であった。
(Polymer coating process)
The slurry was weighed so that the silicon solid content was 0.79 g, transferred to a round bottom flask, and additional water was added so that the total water content was 218 g. After nitrogen charging in the flask system, the liquid temperature was raised to 35 ° C. Then, 0.03 g of 3-methacryloxypropyltrimethoxysilane (MPS) was added to the flask, and the mixture was stirred for 30 minutes. 5.0 g of distilled styrene monomer and 0.03 g of sodium p-styrene sulfonate (NaSS) dissolved in 8 g of water were added, and the mixture was stirred for 2 hours. Then, the liquid temperature was raised to 62 ° C., and 0.11 g of ammonium persulfate (APS) dissolved in 8 g of water was added. Then, heating and stirring were continued for 10 hours under reflux. The obtained reaction solution was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 45 minutes, and the precipitate was redistributed with ethanol to obtain a slurry of polymer-coated silicon. The D50 of the polymer-coated silicon particles is 349 nm, the average major axis of the silicon particles is 2.2, the volume ratio of the coated polymer to the silicon particles is 6.3, and the average number of silicon particles contained in one polymer is 1.4. It was.
＜実施例２＞
（シリコン表面改質工程）
実施例１のシリコン粉砕工程と同様の手法で得た粉砕シリコンを固形分量が１００ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計のエタノ−ル量が２５２８ｇとなるように追加でエタノ−ルを添加してシリコンスラリーを得た。その後、ポリカルボン酸系分散剤２２０ｇ、アンモニウムヒドロキシド１８０ｇ、水８００ｇを上記シリコンスラリーに添加し、攪拌羽を用いて回転数３００ｒｐｍの条件で１時間撹拌を行った。その後、ＴＥＯＳ５．２ｇを上記スラリーに添加した。室温で１．５時間撹拌を行い、その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間２５分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）２４８ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
<Example 2>
(Silicon surface reforming process)
The pulverized silicon obtained by the same method as the silicon pulverization step of Example 1 was weighed so that the solid content was 100 g, and then ultrasonic irradiation was performed for 15 minutes so that the total amount of ethaneol was 2528 g. Ethanol was additionally added to obtain a silicon slurry. Then, 220 g of a polycarboxylic acid-based dispersant, 180 g of ammonium hydroxide, and 800 g of water were added to the silicon slurry, and the mixture was stirred for 1 hour under the condition of a rotation speed of 300 rpm using a stirring blade. Then, 5.2 g of TEOS was added to the above slurry. The mixture was stirred at room temperature for 1.5 hours, and then the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 25 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 248 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
分散剤としてｐ−スチレンスルホン酸リチウム（ＬｉＳＳ）を用いる以外は実施例１と同様の方法でポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は３３２ｎｍ、シリコン粒子の平均長径度は２．２、シリコン粒子に対する被覆ポリマーの体積比は５．４、１つのポリマー内に含まれる平均シリコン粒子数は１．５であった。
(Polymer coating process)
A polymer-coated silicon slurry was obtained in the same manner as in Example 1 except that lithium p-styrene sulfonate (LiSS) was used as the dispersant. The D50 of the polymer-coated silicon particles is 332 nm, the average major axis of the silicon particles is 2.2, the volume ratio of the coated polymer to the silicon particles is 5.4, and the average number of silicon particles contained in one polymer is 1.5. It was.
＜実施例３＞
（シリコン表面改質工程）
実施例１のシリコン粉砕工程と同様の手法で得た粉砕シリコンを固形分量が４０ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計のエタノ−ル量が１０１１ｇとなるように追加でエタノ−ルを添加してシリコンスラリーを得た。その後、ポリカルボン酸系分散剤８８ｇ、アンモニウムヒドロキシド７．２ｇ、水３２０ｇを上記シリコンスラリーに添加し、攪拌羽を用いて回転数２５０ｒｐｍの条件で５時間撹拌を行った。その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間２５分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）２４３ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
<Example 3>
(Silicon surface reforming process)
The pulverized silicon obtained by the same method as the silicon pulverization step of Example 1 was weighed so that the solid content was 40 g, and then ultrasonic irradiation was performed for 15 minutes so that the total amount of ethaneol was 1011 g. Ethanol was additionally added to obtain a silicon slurry. Then, 88 g of a polycarboxylic acid-based dispersant, 7.2 g of ammonium hydroxide, and 320 g of water were added to the above silicon slurry, and the mixture was stirred using a stirring blade under the condition of a rotation speed of 250 rpm for 5 hours. Then, the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 25 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 243 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
実施例１と同様の方法でポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は２９７ｎｍ、シリコン粒子の平均長径度は２．５、シリコン粒子に対する被覆ポリマーの体積比は６．６、１つのポリマー内に含まれる平均シリコン粒子数は１．３であった。
(Polymer coating process)
A polymer-coated silicon slurry was obtained in the same manner as in Example 1. The D50 of the polymer-coated silicon particles is 297 nm, the average major axis of the silicon particles is 2.5, the volume ratio of the coated polymer to the silicon particles is 6.6, and the average number of silicon particles contained in one polymer is 1.3. It was.
＜実施例４＞
（シリコン表面改質工程）
実施例１のシリコン粉砕工程と同様の手法で得た粉砕シリコンを固形分量が５２．５ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計のエタノ−ル量が１３２７ｇとなるように追加でエタノ−ルを添加してシリコンスラリーを得た。その後、ポリカルボン酸系分散剤１１６ｇ、１０ｍｏｌ／Ｌの塩酸３．５ｇ、水４２０ｇを上記シリコンスラリーに添加し、攪拌羽を用いて回転数２５０ｒｐｍの条件で３０分間攪拌を行った。その後、ＴＥＯＳ１０５ｇを上記スラリーに添加し、液温を７０℃に昇温した。７０℃で１２時間撹拌を行い、その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間２５分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）２３８ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
<Example 4>
(Silicon surface reforming process)
The pulverized silicon obtained by the same method as the silicon pulverization step of Example 1 is weighed so that the solid content becomes 52.5 g, and then ultrasonic irradiation is performed for 15 minutes, so that the total amount of ethaneol becomes 1327 g. As described above, additional ethaneol was added to obtain a silicon slurry. Then, 116 g of a polycarboxylic acid-based dispersant, 3.5 g of 10 mol / L hydrochloric acid, and 420 g of water were added to the silicon slurry, and the mixture was stirred for 30 minutes under the condition of a rotation speed of 250 rpm using a stirring blade. Then, 105 g of TEOS was added to the above slurry to raise the liquid temperature to 70 ° C. The mixture was stirred at 70 ° C. for 12 hours, and then the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 25 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 238 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
上記スラリーをシリコン固形分量が０．７９ｇとなるように秤量して丸底フラスコに移し、合計の水量が１７５ｇとなるように追加で水を添加した。フラスコ系内を窒素パ−ジした後、液温を３５℃に昇温した。その後、３−メタクリロキシプロピルトリメトキシシラン（ＭＰＳ）０．０３ｇをフラスコ内に加え、３０分間攪拌した。蒸留したスチレンモノマー５．０ｇと８ｇの水に溶解させたポリビニルピロリドンＫ３０（ＰＶＰ）１．０ｇを添加し、２時間攪拌した。その後、液温を６０℃に昇温させ、３５ｇのエタノールに溶解させたアゾビスイソブチロニトリル（ＡＩＢＮ）８ｍｇを添加した。その後、還流下で１０時間加熱撹拌を続けた。得られた反応液を回転数４８００ｒｐｍ、回転時間４５分の条件で遠心分離処理し、沈殿をエタノ−ルで再分散することでポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は５０３ｎｍ、シリコン粒子の平均長径度は２．２、シリコン粒子に対する被覆ポリマーの体積比は５．６、１つのポリマー内に含まれる平均シリコン粒子数は１．６であった。
(Polymer coating process)
The slurry was weighed so that the silicon solid content was 0.79 g, transferred to a round bottom flask, and additional water was added so that the total water content was 175 g. After nitrogen charging in the flask system, the liquid temperature was raised to 35 ° C. Then, 0.03 g of 3-methacryloxypropyltrimethoxysilane (MPS) was added to the flask, and the mixture was stirred for 30 minutes. 5.0 g of distilled styrene monomer and 1.0 g of polyvinylpyrrolidone K30 (PVP) dissolved in 8 g of water were added, and the mixture was stirred for 2 hours. Then, the liquid temperature was raised to 60 ° C., and 8 mg of azobisisobutyronitrile (AIBN) dissolved in 35 g of ethanol was added. Then, heating and stirring were continued for 10 hours under reflux. The obtained reaction solution was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 45 minutes, and the precipitate was redistributed with ethanol to obtain a slurry of polymer-coated silicon. The D50 of the polymer-coated silicon particles is 503 nm, the average major axis of the silicon particles is 2.2, the volume ratio of the coated polymer to the silicon particles is 5.6, and the average number of silicon particles contained in one polymer is 1.6. It was.
＜実施例５＞
（シリコン粉砕工程）
粒径（Ｄ５０）が７μｍのケミカルグレ−ドの金属シリコン（純度３Ｎ）をエタノ−ルに２０重量％混合し、直径０．３ｍｍのジルコニアビ−ズを用いた微粉砕湿式ビ−ズミルを６時間行い、粒径（Ｄ５０）２８８ｎｍ、乾燥時のＢＥＴ比表面積が６８ｍ２／ｇのシリコンスラリーを得た。
<Example 5>
(Silicon crushing process)
20% by weight of a chemical grade metallic silicon (purity 3N) having a particle size (D50) of 7 μm was mixed with ethanol, and a finely pulverized wet bead mill using zirconia beads having a diameter of 0.3 mm was used. After a period of time, a silicon slurry having a particle size (D50) of 288 nm and a dry BET specific surface area of 68 m 2 / g was obtained.
（シリコン表面改質工程）
上記粉砕シリコンスラリーを固形分量が１０ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計のエタノ−ル量が２５３ｇとなるように追加でエタノ−ルを添加してシリコンスラリーを得た。その後、ポリカルボン酸系分散剤２２ｇ、アンモニウムヒドロキシド９．０ｇ、水８０ｇを上記シリコンスラリーに添加し、マグネチックスターラーを用いて回転数２５０ｒｐｍの条件で１時間撹拌を行った。その後、ＴＥＯＳ２０ｇを上記スラリーに添加した。室温で１．５時間撹拌を行い、その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間２５分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）３１７ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
(Silicon surface reforming process)
The pulverized silicon slurry is weighed so that the solid content becomes 10 g, and then ultrasonic irradiation is performed for 15 minutes, and additional ethanol is added so that the total amount of ethanol becomes 253 g to prepare the silicon slurry. Obtained. Then, 22 g of a polycarboxylic acid-based dispersant, 9.0 g of ammonium hydroxide, and 80 g of water were added to the above silicon slurry, and the mixture was stirred with a magnetic stirrer at a rotation speed of 250 rpm for 1 hour. Then, 20 g of TEOS was added to the above slurry. The mixture was stirred at room temperature for 1.5 hours, and then the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 25 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 317 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
上記スラリーをシリコン固形分量が２．７７ｇとなるように秤量して丸底フラスコに移し、合計の水量が７６５ｇとなるように追加で水を添加した。フラスコ系内を窒素パ−ジした後、液温を３５℃に昇温した。その後、ＭＰＳ０．１１ｇをフラスコ内に加え、３０分間攪拌した。蒸留したスチレンモノマー１７．５ｇと１０ｇの水に溶解させたＮａＳＳ０．０８ｇを添加し、２時間攪拌した。その後、液温を６２℃に昇温させ、１０ｇの水に溶解させたＡＰＳ０．３９ｇを添加した。その後、還流下で１０時間加熱撹拌を続けた。得られた反応液を回転数４８００ｒｐｍ、回転時間４５分の条件で遠心分離処理し、沈殿をエタノ−ルで再分散することでポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は３４８ｎｍ、シリコン粒子の平均長径度は２．３、シリコン粒子に対する被覆ポリマーの体積比は４．６、１つのポリマー内に含まれる平均シリコン粒子数は１．３であった。
(Polymer coating process)
The slurry was weighed so that the silicon solid content was 2.77 g and transferred to a round bottom flask, and additional water was added so that the total water content was 765 g. After nitrogen charging in the flask system, the liquid temperature was raised to 35 ° C. Then, 0.11 g of MPS was added into the flask, and the mixture was stirred for 30 minutes. 17.5 g of distilled styrene monomer and 0.08 g of NaSS dissolved in 10 g of water were added, and the mixture was stirred for 2 hours. Then, the liquid temperature was raised to 62 ° C., and 0.39 g of APS dissolved in 10 g of water was added. Then, heating and stirring were continued for 10 hours under reflux. The obtained reaction solution was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 45 minutes, and the precipitate was redistributed with ethanol to obtain a slurry of polymer-coated silicon. The D50 of the polymer-coated silicon particles is 348 nm, the average major axis of the silicon particles is 2.3, the volume ratio of the coated polymer to the silicon particles is 4.6, and the average number of silicon particles contained in one polymer is 1.3. It was.
＜実施例６＞
（シリコン粉砕工程）
粒径（Ｄ５０）が７μｍのケミカルグレ−ドの金属シリコン（純度３Ｎ）をエタノ−ルに２０重量％混合し、直径０．３ｍｍのジルコニアビ−ズを用いた微粉砕湿式ビ−ズミルを行い、粒径（Ｄ５０）３２５ｎｍ、乾燥時のＢＥＴ比表面積が３４ｍ２／ｇのシリコンスラリーを得た。
<Example 6>
(Silicon crushing process)
20% by weight of chemical grade metallic silicon (purity 3N) having a particle size (D50) of 7 μm is mixed with ethanol, and a finely pulverized wet bead mill using zirconia beads having a diameter of 0.3 mm is performed. A silicon slurry having a particle size (D50) of 325 nm and a dry BET specific surface area of 34 m 2 / g was obtained.
（シリコン表面改質工程）
上記粉砕シリコンスラリーを固形分量が１７．５ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計のエタノ−ル量が４４２ｇとなるように追加でエタノ−ルを添加してシリコンスラリーを得た。その後、ポリカルボン酸系分散剤３８．５ｇ、１０ｍｏｌ／Ｌの塩酸１．２ｇ、水１４０ｇを上記シリコンスラリーに添加し、攪拌羽を用いて回転数２５０ｒｐｍの条件で３０分間攪拌を行った。その後、ＴＥＯＳ３５ｇを上記スラリーに添加し、液温を７０℃に昇温した。７０℃で１２時間撹拌を行い、その後、得られたシリコンスラリーを回転数４８００ｒｐｍ、回転時間２５分の条件で遠心分離処理し、エタノ−ルで再分散した。得られたスラリーに対して、直径１．０ｍｍのジルコニアボ−ルを用いたボ−ルミルを８時間行い、粒径（Ｄ５０）３２１ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
(Silicon surface reforming process)
The pulverized silicon slurry was weighed so that the solid content was 17.5 g, and then ultrasonic irradiation was performed for 15 minutes, and additional ethaneol was added so that the total amount of ethanol was 442 g. A slurry was obtained. Then, 38.5 g of a polycarboxylic acid-based dispersant and 1.2 g of 10 mol / L hydrochloric acid and 140 g of water were added to the above silicon slurry, and the mixture was stirred for 30 minutes under the condition of a rotation speed of 250 rpm using a stirring blade. Then, 35 g of TEOS was added to the above slurry to raise the liquid temperature to 70 ° C. The mixture was stirred at 70 ° C. for 12 hours, and then the obtained silicon slurry was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 25 minutes, and redispersed with ethanol. A ball mill using a zirconia ball having a diameter of 1.0 mm was carried out on the obtained slurry for 8 hours to obtain a silicon slurry having a particle size (D50) of 321 nm. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
実施例２と同様の方法でポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は４１９ｎｍ、シリコン粒子の平均長径度は２．１、シリコン粒子に対する被覆ポリマーの体積比は５．９、１つのポリマー内に含まれる平均シリコン粒子数は１．１であった。
(Polymer coating process)
A polymer-coated silicon slurry was obtained in the same manner as in Example 2. The D50 of the polymer-coated silicon particles is 419 nm, the average major axis of the silicon particles is 2.1, the volume ratio of the coated polymer to the silicon particles is 5.9, and the average number of silicon particles contained in one polymer is 1.1. It was.
＜実施例７＞
（シリコン粉砕工程）
粒径（Ｄ５０）が７μｍのケミカルグレ−ドの金属シリコン（純度３Ｎ）を水に１７重量％混合し、直径０．３ｍｍのジルコニアビ−ズを用いた微粉砕湿式ビ−ズミルを行い、粒径（Ｄ５０）２９１ｎｍ、乾燥時のＢＥＴ比表面積が８２ｍ２／ｇのシリコンスラリーを得た。
<Example 7>
(Silicon crushing process)
Metallic silicon (purity 3N) of chemical grade having a particle size (D50) of 7 μm is mixed with water in an amount of 17% by weight, and a finely pulverized wet bead mill using zirconia beads having a diameter of 0.3 mm is performed. A silicon slurry having a diameter (D50) of 291 nm and a BET specific surface area of 82 m 2 / g when dried was obtained.
（シリコン表面改質工程）
上記粉砕シリコンスラリーを固形分量が２０ｇとなるように秤量し、その後、超音波照射を１５分間行い、合計の水量が３３３ｇとなるように追加で水を添加してシリコンスラリーを得た。その後、アンモニウムヒドロキシド０．０３６ｇ、水４ｇを上記シリコンスラリーに添加し、マグネチックスターラーを用いて回転数５００ｒｐｍの条件で１時間撹拌を行った。その後、テトラエトキシシラン（ＴＥＯＳ）４０ｇを上記スラリーに添加した。室温で５時間撹拌を行い、粒径（Ｄ５０）２９０ｎｍのシリコンスラリーを得た。
(Silicon surface reforming process)
The pulverized silicon slurry was weighed so that the solid content was 20 g, and then ultrasonic irradiation was performed for 15 minutes, and additional water was added so that the total water amount was 333 g to obtain a silicon slurry. Then, 0.036 g of ammonium hydroxide and 4 g of water were added to the above silicon slurry, and the mixture was stirred for 1 hour under the condition of a rotation speed of 500 rpm using a magnetic stirrer. Then, 40 g of tetraethoxysilane (TEOS) was added to the above slurry. The mixture was stirred at room temperature for 5 hours to obtain a silicon slurry having a particle size (D50) of 290 nm.
（ポリマー被覆工程）
上記スラリーをシリコン固形分量が７．５ｇとなるように秤量して丸底フラスコに移し、合計の水量が６０５ｇとなるように追加で水を添加した。フラスコ系内を窒素パ−ジした後、液温を３５℃に昇温した。その後、ＭＰＳ１．１ｇをフラスコ内に加え、３０分間攪拌した。蒸留したスチレンモノマー４７．２ｇと１０ｇの水に溶解させたＮａＳＳ０．２４ｇを添加し、２時間攪拌した。その後、液温を６２℃に昇温させ、４０ｇの水に溶解させたＡＰＳ１．０ｇをシリンジポンプを用いて４ｃｃ／ｈの速度で添加した。その後、還流下で１０時間加熱撹拌を続けた。得られた反応液を回転数４８００ｒｐｍ、回転時間４５分の条件で遠心分離処理し、沈殿をエタノ−ルで再分散することでポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は３４０ｎｍ、シリコン粒子の平均長径度は２．３、シリコン粒子に対する被覆ポリマーの体積比は５．５、１つのポリマー内に含まれる平均シリコン粒子数は１．４であった。
(Polymer coating process)
The slurry was weighed so that the silicon solid content was 7.5 g, transferred to a round bottom flask, and additional water was added so that the total water content was 605 g. After nitrogen charging in the flask system, the liquid temperature was raised to 35 ° C. Then, 1.1 g of MPS was added into the flask, and the mixture was stirred for 30 minutes. 47.2 g of distilled styrene monomer and 0.24 g of NaSS dissolved in 10 g of water were added, and the mixture was stirred for 2 hours. Then, the liquid temperature was raised to 62 ° C., and 1.0 g of APS dissolved in 40 g of water was added at a rate of 4 cc / h using a syringe pump. Then, heating and stirring were continued for 10 hours under reflux. The obtained reaction solution was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 45 minutes, and the precipitate was redistributed with ethanol to obtain a slurry of polymer-coated silicon. The D50 of the polymer-coated silicon particles is 340 nm, the average major axis of the silicon particles is 2.3, the volume ratio of the coated polymer to the silicon particles is 5.5, and the average number of silicon particles contained in one polymer is 1.4. It was.
＜実施例８＞
（シリコン粉砕工程）
粒径（Ｄ５０）が７μｍのケミカルグレ−ドの金属シリコン（純度３Ｎ）を水に１６重量％混合し、直径０．３ｍｍのジルコニアビ−ズを用いた微粉砕湿式ビ−ズミルを行い、粒径（Ｄ５０）２５５ｎｍ、乾燥時のＢＥＴ比表面積が６８ｍ２／ｇのシリコンスラリーを得た。
<Example 8>
(Silicon crushing process)
Metallic silicon (purity 3N) of chemical grade having a particle size (D50) of 7 μm is mixed with water in an amount of 16% by weight, and a finely pulverized wet bead mill using zirconia beads having a diameter of 0.3 mm is performed. A silicon slurry having a diameter (D50) of 255 nm and a BET specific surface area of 68 m 2 / g when dried was obtained.
（シリコン表面改質工程）
実施例７と同様の方法で、粒径（Ｄ５０）２４９ｎｍのシリコンスラリーを得た。これを回転数４８００ｒｐｍ、回転時間６０分の条件で遠心分離処理し、水で再分散した。
(Silicon surface reforming process)
A silicon slurry having a particle size (D50) of 249 nm was obtained in the same manner as in Example 7. This was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 60 minutes, and redispersed with water.
（ポリマー被覆工程）
上記スラリーをシリコン固形分量が１６ｇとなるように秤量して丸底フラスコに移し、合計の水量が１３０２ｇとなるように追加で水を添加した。フラスコ系内を窒素パ−ジした後、液温を３５℃に昇温した。その後、ＭＰＳ２．４ｇをフラスコ内に加え、３０分間攪拌した。蒸留したスチレンモノマー１０１ｇと１０ｇの水に溶解させたＮａＳＳ０．５１ｇを添加し、２時間攪拌した。その後、液温を６２℃に昇温させ、８０ｇの水に溶解させたＡＰＳ２．２ｇをシリンジポンプを用いて８ｃｃ／ｈの速度で添加した。その後、還流下で１０時間加熱撹拌を続けた。得られた反応液を回転数４８００ｒｐｍ、回転時間４５分の条件で遠心分離処理し、沈殿をエタノ−ルで再分散することでポリマー被覆シリコンのスラリーを得た。ポリマー被覆シリコン粒子のＤ５０は３１９ｎｍ、シリコン粒子の平均長径度は２．２、シリコン粒子に対する被覆ポリマーの体積比は５．８、１つのポリマー内に含まれる平均シリコン粒子数は１．４であった。
(Polymer coating process)
The slurry was weighed so that the silicon solid content was 16 g, transferred to a round bottom flask, and additional water was added so that the total water content was 1302 g. After nitrogen charging in the flask system, the liquid temperature was raised to 35 ° C. Then, 2.4 g of MPS was added to the flask and stirred for 30 minutes. 101 g of distilled styrene monomer and 0.51 g of NaSS dissolved in 10 g of water were added, and the mixture was stirred for 2 hours. Then, the liquid temperature was raised to 62 ° C., and 2.2 g of APS dissolved in 80 g of water was added at a rate of 8 cc / h using a syringe pump. Then, heating and stirring were continued for 10 hours under reflux. The obtained reaction solution was centrifuged under the conditions of a rotation speed of 4800 rpm and a rotation time of 45 minutes, and the precipitate was redistributed with ethanol to obtain a slurry of polymer-coated silicon. The D50 of the polymer-coated silicon particles is 319 nm, the average major axis of the silicon particles is 2.2, the volume ratio of the coated polymer to the silicon particles is 5.8, and the average number of silicon particles contained in one polymer is 1.4. It was.
実施例で得られたポリマー被覆シリコン粒子は、シリコンがポリマーで被覆されていることからシリコンの酸化が抑制されている。 In the polymer-coated silicon particles obtained in the examples, the oxidation of silicon is suppressed because the silicon is coated with the polymer.
＜比較例１＞
比較例１のポリマー被覆していないシリコン粒子としては、実施例１の粉砕シリコンを、ポリマー被覆していないシリコン粒子とした。
<Comparative example 1>
As the silicon particles not coated with the polymer of Comparative Example 1, the pulverized silicon of Example 1 was used as the silicon particles not coated with the polymer.
この比較例１のポリマー被覆していないシリコン粒子は、ポリマー被覆していないことから、シリコンの酸化が促進されている。 Since the non-polymer-coated silicon particles of Comparative Example 1 are not polymer-coated, the oxidation of silicon is promoted.
１ シリコン粒子
２ 被覆ポリマー
1 Silicon particles 2 Coating polymer
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