JP2011063762A - Metal composite organic resin particle and manufacturing method for metal composite organic resin particle - Google Patents
Metal composite organic resin particle and manufacturing method for metal composite organic resin particle Download PDFInfo
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- JP2011063762A JP2011063762A JP2009217310A JP2009217310A JP2011063762A JP 2011063762 A JP2011063762 A JP 2011063762A JP 2009217310 A JP2009217310 A JP 2009217310A JP 2009217310 A JP2009217310 A JP 2009217310A JP 2011063762 A JP2011063762 A JP 2011063762A
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- Prior art keywords
- metal
- organic resin
- resin particles
- composite organic
- metal composite
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 360
- 229920005989 resin Polymers 0.000 title claims abstract description 212
- 239000011347 resin Substances 0.000 title claims abstract description 212
- 239000002905 metal composite material Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 137
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000003505 polymerization initiator Substances 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 150000004703 alkoxides Chemical class 0.000 claims description 15
- 239000002612 dispersion medium Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 230000001603 reducing effect Effects 0.000 claims description 6
- 229920006037 cross link polymer Polymers 0.000 claims description 5
- 239000002609 medium Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 32
- 238000002156 mixing Methods 0.000 description 30
- 239000011246 composite particle Substances 0.000 description 20
- -1 alkyl sulfate sulfonate Chemical class 0.000 description 18
- 239000008199 coating composition Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 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 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- NKELEQZBIMMAPC-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.ClC1=CC=C(C=C)C=C1 NKELEQZBIMMAPC-UHFFFAOYSA-N 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- 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
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OHANIVUMXFQWIQ-UHFFFAOYSA-N CCO.CCO.CCO.CCCCCCCCCCCCOS(O)(=O)=O Chemical compound CCO.CCO.CCO.CCCCCCCCCCCCOS(O)(=O)=O OHANIVUMXFQWIQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- PCCNIENXBRUYFK-UHFFFAOYSA-O azanium;cerium(4+);pentanitrate Chemical compound [NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PCCNIENXBRUYFK-UHFFFAOYSA-O 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、粒子径が極めて均一な金属複合有機樹脂粒子に関する。また、本発明は、該金属複合有機樹脂粒子の製造方法に関する。 The present invention relates to metal composite organic resin particles having a very uniform particle diameter. Moreover, this invention relates to the manufacturing method of this metal composite organic resin particle.
近年、金属、金属酸化物又は金属塩を有機樹脂バインダーに分散させて得られる塗工組成物が、例えば、基板等の上に塗工された後、乾燥、脱脂、焼成工程を経ることにより、電極材料、色素増感太陽電池用電極、透明電極、触媒担体、電子材料用セラミックス、紫外線吸収剤、熱線反射材料等の様々な構造体を得るために用いられている。このような構造体が、広い表面積、高い平滑性、緻密性等を有し、高い電極効率、触媒効率、透明性等を得るためには、塗工組成物中で、更には、得られる構造体中で、金属、金属酸化物又は金属塩を極めて均一に分散させる必要がある。 In recent years, a coating composition obtained by dispersing a metal, a metal oxide or a metal salt in an organic resin binder, for example, after being coated on a substrate or the like, is subjected to drying, degreasing, and firing steps, It is used to obtain various structures such as electrode materials, dye-sensitized solar cell electrodes, transparent electrodes, catalyst carriers, ceramics for electronic materials, ultraviolet absorbers, heat ray reflective materials and the like. Such a structure has a large surface area, high smoothness, denseness, etc., and in order to obtain high electrode efficiency, catalyst efficiency, transparency, etc., in the coating composition, further, the structure obtained It is necessary to disperse the metal, metal oxide or metal salt very uniformly in the body.
金属、金属酸化物又は金属塩を有機樹脂バインダーに分散させる方法として、例えば、粉砕又は析出法により得られた金属等の固体粉末と、有機樹脂バインダーと、有機溶剤とを３本ロール、ビーズミル等の混練装置を用いて分散させる方法が挙げられる。
しかしながら、この方法では、非常に過酷な混練条件を用いなければ金属等の固体粉末を極めて均一に分散させることは困難である。また、この方法で得られた塗工組成物は貯蔵安定性が悪く、使用する前に再度混練して金属等の固体粉末を再分散させる必要があり、生産性に問題がある。
As a method for dispersing a metal, metal oxide or metal salt in an organic resin binder, for example, a solid powder such as metal obtained by pulverization or precipitation, an organic resin binder, and an organic solvent in three rolls, a bead mill, etc. And a method of dispersing using a kneading apparatus.
However, in this method, it is difficult to disperse a solid powder such as a metal very uniformly unless very severe kneading conditions are used. Moreover, the coating composition obtained by this method has poor storage stability, and it is necessary to knead again before use to redisperse a solid powder such as metal, resulting in a problem in productivity.
これに対して、金属等の固体粉末の代わりに、重合性モノマーと金属等の固体粉末とを溶媒中に分散させ、重合を行うことにより得られる金属複合有機樹脂粒子を用いる方法が検討されている。
例えば、特許文献１には、所定の磁性体微粒子を分散させた単量体を含む重合組成物を、懸濁保護剤の存在下、水性溶媒中で攪拌して所定の大きさの油滴に分散し、この状態で懸濁重合を行なって所定の磁性重合体粒子を得る方法が記載されている。特許文献１に記載のような金属複合有機樹脂粒子においては、有機樹脂が金属等の固体粉末を取り囲んでいることから、このような金属複合有機樹脂粒子は有機樹脂バインダーとの相溶性が高く、塗工組成物中で良好に分散することができる。そのため、金属等の固体粉末もまた、塗工組成物中で良好な分散状態をとることができる。
しかしながら、従来、金属複合有機樹脂粒子は形状及び粒子径にばらつきがあることから、金属等の固体粉末が充分に均一に分散した塗工組成物を得ることは困難であった。
On the other hand, instead of solid powder such as metal, a method using metal composite organic resin particles obtained by dispersing a polymerizable monomer and solid powder such as metal in a solvent and performing polymerization has been studied. Yes.
For example, in Patent Document 1, a polymerization composition containing a monomer in which predetermined magnetic fine particles are dispersed is stirred in an aqueous solvent in the presence of a suspension protective agent to form oil droplets of a predetermined size. A method is described in which predetermined magnetic polymer particles are obtained by dispersing and performing suspension polymerization in this state. In the metal composite organic resin particles as described in Patent Document 1, since the organic resin surrounds a solid powder such as metal, such metal composite organic resin particles have high compatibility with the organic resin binder, It can be dispersed well in the coating composition. Therefore, solid powders such as metals can also be well dispersed in the coating composition.
However, conventionally, since metal composite organic resin particles have variations in shape and particle diameter, it has been difficult to obtain a coating composition in which a solid powder such as metal is sufficiently uniformly dispersed.
また、別の金属複合有機樹脂粒子として、例えば、重合性油溶性モノマーとシランカップリング剤とを共存反応、重合させることで得られる金属複合有機樹脂粒子も挙げられる。
しかしながら、この方法で得られる金属複合有機樹脂粒子では、含有する金属がケイ素に限定され、また、金属系成分比率が有機樹脂に比較して高々５％程度と少ないことが問題である。
Moreover, as another metal composite organic resin particle, the metal composite organic resin particle obtained by co-reacting and polymerizing a polymerizable oil-soluble monomer and a silane coupling agent is mentioned, for example.
However, in the metal composite organic resin particles obtained by this method, the metal contained is limited to silicon, and the metal component ratio is at most about 5% lower than that of the organic resin.
本発明は、粒子径が極めて均一な金属複合有機樹脂粒子を提供することを目的とする。また、本発明は、該金属複合有機樹脂粒子の製造方法を提供することを目的とする。 An object of the present invention is to provide metal composite organic resin particles having a very uniform particle diameter. Moreover, an object of this invention is to provide the manufacturing method of this metal composite organic resin particle.
本発明は、金属、金属酸化物又は金属塩を多孔質有機樹脂粒子の細孔内に有する金属複合有機樹脂粒子であって、前記多孔質有機樹脂は、個数基準粒子径の変動係数が１０％以下である金属複合有機樹脂粒子である。
以下、本発明を詳述する。
The present invention is a metal composite organic resin particle having a metal, a metal oxide or a metal salt in the pores of the porous organic resin particle, wherein the porous organic resin has a coefficient of variation of the number-based particle diameter of 10%. It is the following metal composite organic resin particle.
The present invention is described in detail below.
本発明者らは、金属、金属酸化物又は金属塩を、所定の個数基準粒子径の変動係数を有する多孔質有機樹脂粒子の細孔内に有することにより、粒子径が極めて均一な金属複合有機樹脂粒子が得られることを見出した。本発明者らは、該金属複合有機樹脂粒子を用いることにより、例えば、金属、金属酸化物又は金属塩が極めて均一に分散した塗工組成物を得ることができ、このような塗工組成物を用いることにより、例えば、金属、金属酸化物又は金属塩が極めて均一に分散した構造体を容易に製造できることを見出し、本発明を完成させるに至った。 The present inventors have provided a metal, a metal oxide, or a metal salt in the pores of a porous organic resin particle having a coefficient of variation of a predetermined number-based particle diameter, whereby a metal composite organic having a very uniform particle diameter. It has been found that resin particles can be obtained. By using the metal composite organic resin particles, the present inventors can obtain, for example, a coating composition in which a metal, a metal oxide, or a metal salt is dispersed very uniformly, and such a coating composition. For example, it has been found that a structure in which a metal, a metal oxide or a metal salt is dispersed extremely uniformly can be easily produced, and the present invention has been completed.
本発明の金属複合有機樹脂粒子は、金属、金属酸化物又は金属塩を多孔質有機樹脂粒子の細孔内に有する。
上記多孔質有機樹脂粒子の平均粒子径は特に限定されないが、好ましい下限が０．５μｍ、好ましい上限が５０μｍである。上記多孔質有機樹脂粒子の平均粒子径が０．５μｍ未満であると、得られる金属複合有機樹脂粒子を用いて製造した構造体において、金属、金属酸化物又は金属塩の含有量が低下することがある。上記多孔質有機樹脂粒子の平均粒子径が５０μｍを超えると、得られる金属複合有機樹脂粒子は、塗工組成物中での分散性が低下することがあり、このような塗工組成物を用いて製造した構造体は、金属、金属酸化物又は金属塩の分散性が低下することがある。上記多孔質有機樹脂粒子の平均粒子径は、より好ましい下限が１μｍ、より好ましい上限が３０μｍである。
The metal composite organic resin particles of the present invention have metal, metal oxide or metal salt in the pores of the porous organic resin particles.
The average particle diameter of the porous organic resin particles is not particularly limited, but a preferable lower limit is 0.5 μm and a preferable upper limit is 50 μm. When the average particle diameter of the porous organic resin particles is less than 0.5 μm, the content of metal, metal oxide or metal salt in the structure produced using the obtained metal composite organic resin particles is reduced. There is. When the average particle diameter of the porous organic resin particles exceeds 50 μm, the resulting metal composite organic resin particles may have reduced dispersibility in the coating composition, and such a coating composition is used. In the structure manufactured in this manner, the dispersibility of the metal, metal oxide or metal salt may be lowered. A more preferable lower limit of the average particle diameter of the porous organic resin particles is 1 μm, and a more preferable upper limit is 30 μm.
上記多孔質有機樹脂粒子の個数基準粒子径の変動係数は、上限が１０％である。上記多孔質有機樹脂粒子の個数基準粒子径の変動係数が１０％を超えると、得られる金属複合有機樹脂粒子は、粒子径の均一性が低下し、このような金属複合有機樹脂粒子を用いて製造した構造体は、金属、金属酸化物又は金属塩の分散性が低下する。上記多孔質有機樹脂粒子の個数基準粒子径の変動係数は、好ましい上限が７％、より好ましい上限が５％である。
なお、本明細書中、多孔質有機樹脂粒子の平均粒子径と、個数基準粒子径の変動係数とは、以下のようにして求められる。
多孔質有機樹脂粒子について、走査型電子顕微鏡により１視野に約１００個が観察できる倍率で観察し、任意に選択した５０個の多孔質有機樹脂粒子についてノギスを用いて最長径を測定する。得られた最長径の数平均値を多孔質有機樹脂粒子の平均粒子径とする。多孔質有機樹脂粒子の個数基準粒子径の変動係数（ＣＶ１）は、得られた平均粒子径ｍ１と標準偏差σ１から、下記式（１）により算出することができる。
ＣＶ１＝σ１／ｍ１×１００（％） （１）
The upper limit of the coefficient of variation of the number-based particle diameter of the porous organic resin particles is 10%. When the coefficient of variation in the number-based particle diameter of the porous organic resin particles exceeds 10%, the resulting metal composite organic resin particles have a reduced particle diameter uniformity, and such metal composite organic resin particles are used. In the manufactured structure, the dispersibility of the metal, metal oxide, or metal salt is lowered. As for the coefficient of variation of the number-based particle diameter of the porous organic resin particles, a preferable upper limit is 7%, and a more preferable upper limit is 5%.
In the present specification, the average particle diameter of the porous organic resin particles and the coefficient of variation of the number-based particle diameter are obtained as follows.
The porous organic resin particles are observed with a scanning electron microscope at a magnification at which about 100 particles can be observed in one field of view, and the longest diameter of 50 arbitrarily selected porous organic resin particles is measured using calipers. The number average value of the obtained longest diameter is defined as the average particle diameter of the porous organic resin particles. The variation coefficient (CV 1 ) of the number-based particle diameter of the porous organic resin particles can be calculated from the obtained average particle diameter m 1 and standard deviation σ 1 by the following formula (1).
CV 1 = σ 1 / m 1 × 100 (%) (1)
上記多孔質有機樹脂粒子を製造する方法は特に限定されないが、シード重合法が好ましい。
上記シード重合法は特に限定されないが、非架橋ポリマーを含有する種粒子を、水を含有する分散媒中に分散させた種粒子分散液と、ラジカル重合性モノマーと、油溶性溶剤と、油溶性重合開始剤とを混合し、上記種粒子に上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とを吸収させて膨潤粒子液滴の分散液を調製する工程と、上記膨潤粒子液滴中の上記ラジカル重合性モノマーを重合させる工程とを有する方法（以下、方法（１）ともいう）が好ましい。
以下、上記方法（１）について説明する。
A method for producing the porous organic resin particles is not particularly limited, but a seed polymerization method is preferable.
The seed polymerization method is not particularly limited, but a seed particle dispersion in which seed particles containing a non-crosslinked polymer are dispersed in a dispersion medium containing water, a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble solvent. Mixing a polymerization initiator, absorbing the radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator in the seed particles to prepare a dispersion of swollen particle droplets; and And a method of polymerizing the radical polymerizable monomer in the swollen particle droplets (hereinafter also referred to as method (1)) is preferable.
Hereinafter, the method (1) will be described.
上記方法（１）では、まず、非架橋ポリマーを含有する種粒子を、水を含有する分散媒中に分散させた種粒子分散液と、ラジカル重合性モノマーと、油溶性溶剤と、油溶性重合開始剤とを混合し、上記種粒子に上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とを吸収させて膨潤粒子液滴の分散液を調製する工程を行う。
なお、上記方法（１）では、非架橋ポリマーを含有する種粒子を、水を含有する分散媒中に分散させた種粒子分散液を調製する工程を別途行ってもよい。
In the above method (1), first, a seed particle dispersion in which seed particles containing a non-crosslinked polymer are dispersed in a dispersion medium containing water, a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble polymerization. An initiator is mixed, and the seed particles are allowed to absorb the radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator to prepare a dispersion of swollen particle droplets.
In the method (1), a step of preparing a seed particle dispersion in which seed particles containing a non-crosslinked polymer are dispersed in a dispersion medium containing water may be separately performed.
上記非架橋ポリマーを構成する非架橋性モノマーは特に限定されず、例えば、スチレン、メタクリル酸メチル、メタクリル酸−ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸、アクリル酸メチル、アクリル酸−ｎ−ブチル、アクリル酸イソブチル、アクリル酸等が挙げられる。 The non-crosslinkable monomer constituting the non-crosslinked polymer is not particularly limited. For example, styrene, methyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid, methyl acrylate, n-butyl acrylate, Examples thereof include isobutyl acrylate and acrylic acid.
上記種粒子は、非架橋性モノマーを重合して非架橋ポリマーを構成する際に、少量の架橋性モノマーを併用してもよい。少量の架橋性モノマーを併用することにより、得られる種粒子の強度が向上する。上記架橋性モノマーは特に限定されず、例えば、ジビニルベンゼン、エチレングリコールジメタクリレート等が挙げられる。
上記架橋性モノマーを配合する場合、上記非架橋性モノマーと上記架橋性モノマーとの合計に占める上記架橋性モノマーの配合量は特に限定されないが、好ましい上限は５重量％である。上記架橋性モノマーの配合量が５重量％を超えると、得られる種粒子へのラジカル重合性モノマー等の吸収性が低下し、膨潤粒子液滴が形成されないことがある。上記架橋性モノマーの配合量のより好ましい上限は１重量％である。
The seed particles may be used in combination with a small amount of a crosslinkable monomer when the noncrosslinkable monomer is polymerized to form a noncrosslinked polymer. By using a small amount of a crosslinkable monomer in combination, the strength of the seed particles obtained is improved. The crosslinkable monomer is not particularly limited, and examples thereof include divinylbenzene and ethylene glycol dimethacrylate.
When the crosslinkable monomer is blended, the blending amount of the crosslinkable monomer in the total of the non-crosslinkable monomer and the crosslinkable monomer is not particularly limited, but a preferable upper limit is 5% by weight. When the blending amount of the crosslinkable monomer exceeds 5% by weight, the absorbability of the radically polymerizable monomer or the like to the obtained seed particles may be reduced, and swollen particle droplets may not be formed. A more preferred upper limit of the amount of the crosslinkable monomer is 1% by weight.
上記種粒子の重量平均分子量は特に限定されないが、好ましい上限は５０万である。上記種粒子の重量平均分子量が５０万を超えると、得られる種粒子へのラジカル重合性モノマー等の吸収性が低下し、膨潤粒子液滴が形成されないことがある。上記種粒子の重量平均分子量のより好ましい上限は１０万である。
また、上記種粒子の重量平均分子量の下限は特に限定されないが、１０００未満であると、実質的に粒子を形成できないことがある。
The weight average molecular weight of the seed particles is not particularly limited, but a preferable upper limit is 500,000. If the weight average molecular weight of the seed particles exceeds 500,000, the absorbability of the radical polymerizable monomer or the like to the seed particles obtained may be reduced, and swollen particle droplets may not be formed. A more preferable upper limit of the weight average molecular weight of the seed particles is 100,000.
Further, the lower limit of the weight average molecular weight of the seed particles is not particularly limited, but if it is less than 1000, particles may not be formed substantially.
上記種粒子の形状は特に限定されないが、球状であることが好ましい。上記種粒子の形状が球状でない場合には、ラジカル重合性モノマー等を吸収する際に等方的な膨潤がなされず、得られる多孔質有機樹脂粒子の形状にばらつきが生じることがある。 The shape of the seed particles is not particularly limited, but is preferably spherical. When the shape of the seed particles is not spherical, isotropic swelling may not occur when the radical polymerizable monomer or the like is absorbed, and the resulting porous organic resin particles may vary in shape.
上記種粒子の平均粒子径は特に限定されないが、好ましい下限は目的とする多孔質有機樹脂粒子の平均粒子径の１／１０、好ましい上限は目的とする多孔質有機樹脂粒子の平均粒子径の１／１．０５である。上記種粒子の平均粒子径が目的とする多孔質有機樹脂粒子の平均粒子径の１／１０未満であると、所望の多孔質有機樹脂粒子の粒子径を得るために、吸収性能の限界を超えた多くのラジカル重合性モノマー等を吸収する必要があり、吸収残りが発生したり、得られる多孔質有機樹脂粒子の個数基準粒子径の変動係数が増大したりすることがある。上記種粒子の平均粒子径が目的とする多孔質有機樹脂粒子の平均粒子径の１／１．０５を超えると、ごく微量のラジカル重合性モノマー等しか吸収する余地がなく、高い空隙率を有する多孔質有機樹脂粒子が得られないことがある。上記種粒子の平均粒子径は、目的とする多孔質有機樹脂粒子の平均粒子径の１／８以上であることがより好ましく、１／１．５以下であることがより好ましい。 The average particle diameter of the seed particles is not particularly limited, but the preferable lower limit is 1/10 of the average particle diameter of the target porous organic resin particles, and the preferable upper limit is 1 of the average particle diameter of the target porous organic resin particles. /1.05. When the average particle size of the seed particles is less than 1/10 of the average particle size of the target porous organic resin particles, the limit of the absorption performance is exceeded in order to obtain the desired particle size of the porous organic resin particles. In addition, it is necessary to absorb a large amount of radically polymerizable monomers and the like, which may result in residual absorption or increase in the coefficient of variation of the number-based particle diameter of the obtained porous organic resin particles. When the average particle size of the seed particles exceeds 1 / 1.05 of the average particle size of the target porous organic resin particles, there is no room for absorbing a very small amount of radically polymerizable monomer and the like, and the porosity is high. Porous organic resin particles may not be obtained. The average particle diameter of the seed particles is more preferably 1/8 or more, and more preferably 1 / 1.5 or less, of the average particle diameter of the target porous organic resin particles.
上記種粒子は、体積基準粒子径の変動係数の好ましい上限が３０％である。上記種粒子の体積基準粒子径の変動係数が３０％を超えると、膨潤した種粒子の粒子径が均一にならず、得られる多孔質有機樹脂粒子の個数基準粒子径の変動係数が増大することがある。上記種粒子の体積基準粒子径の変動係数のより好ましい上限は、２０％である。
なお、本明細書中、種粒子の平均粒子径とは、粒子径測定装置により測定される体積平均粒子径を意味する。また、種粒子の体積基準粒子径の変動係数（ＣＶ２）は、得られた平均粒子径ｍ２と標準偏差σ２から、下記式（２）により算出することができる。
ＣＶ２＝σ２／ｍ２×１００（％） （２）
In the seed particles, the preferable upper limit of the coefficient of variation of the volume-based particle diameter is 30%. When the variation coefficient of the volume-based particle diameter of the seed particles exceeds 30%, the particle diameter of the swollen seed particles is not uniform, and the variation coefficient of the number-based particle diameter of the obtained porous organic resin particles is increased. There is. A more preferable upper limit of the coefficient of variation of the volume-based particle diameter of the seed particles is 20%.
In the present specification, the average particle diameter of the seed particles means a volume average particle diameter measured by a particle diameter measuring device. Further, the variation coefficient (CV 2 ) of the volume-based particle diameter of the seed particles can be calculated from the obtained average particle diameter m 2 and standard deviation σ 2 by the following formula (2).
CV 2 = σ 2 / m 2 × 100 (%) (2)
上記種粒子を製造する方法は特に限定されず、例えば、ソープフリー乳化重合、乳化重合、分散重合等の方法が挙げられる。 The method for producing the seed particles is not particularly limited, and examples thereof include methods such as soap-free emulsion polymerization, emulsion polymerization, and dispersion polymerization.
上記分散媒は、水を含有する分散媒であれば特に限定されず、水、又は、水にメタノール、エタノール等の水溶性有機溶剤を添加した混合分散媒等が挙げられる。
上記分散媒は、必要に応じて、分散剤を含有してもよい。上記分散剤は特に限定されず、例えば、アルキル硫酸スルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸トリエタノールアミン、ポリオキシエチレンアルキルエーテル、ポリビニルアルコール等が挙げられる。
The dispersion medium is not particularly limited as long as it contains water, and examples thereof include water or a mixed dispersion medium in which a water-soluble organic solvent such as methanol or ethanol is added to water.
The dispersion medium may contain a dispersant as necessary. The dispersant is not particularly limited, and examples thereof include alkyl sulfate sulfonate, alkyl benzene sulfonate, alkyl sulfate triethanolamine, polyoxyethylene alkyl ether, and polyvinyl alcohol.
上記種粒子分散液における上記種粒子の配合量は特に限定されず、好ましい下限は０．１重量％、好ましい上限は５０重量％である。上記種粒子の配合量が０．１重量％未満であると、多孔質有機樹脂粒子の生産効率が低くなることがある。上記種粒子の配合量が５０重量％を超えると、種粒子が凝集してしまうことがある。上記種粒子の配合量のより好ましい下限は０．５重量％、より好ましい上限は３０重量％である。 The blending amount of the seed particles in the seed particle dispersion is not particularly limited, and a preferable lower limit is 0.1% by weight and a preferable upper limit is 50% by weight. When the blending amount of the seed particles is less than 0.1% by weight, the production efficiency of the porous organic resin particles may be lowered. If the blended amount of the seed particles exceeds 50% by weight, the seed particles may aggregate. A more preferable lower limit of the blending amount of the seed particles is 0.5% by weight, and a more preferable upper limit is 30% by weight.
上記ラジカル重合性モノマーは特に限定されず、例えば、単官能性モノマー、多官能性モノマーが挙げられる。
上記単官能性モノマーは特に限定されず、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、クミル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、パルミチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸、グリシジル（メタ）アクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート等の極性基含有（メタ）アクリル系モノマー、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−クロロスチレン等のスチレン系モノマー、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、塩化ビニル、塩化ビニリデン等のハロゲン含有モノマー、ビニルピリジン、２−アクリロイルオキシエチルフタル酸、イタコン酸、フマル酸、エチレン、プロピレン等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
なかでも、重合する際の反応性が良好であることから、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリル酸等のアクリル系モノマーが好ましい。
The radical polymerizable monomer is not particularly limited, and examples thereof include a monofunctional monomer and a polyfunctional monomer.
The monofunctional monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate, myristyl Alkyl (meth) acrylates such as (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, glycidyl (meth) Polar group-containing (meth) acrylic monomers such as acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene Styrene monomers such as vinyl, vinyl esters such as vinyl acetate and vinyl propionate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, vinyl pyridine, 2-acryloyloxyethylphthalic acid, itaconic acid, fumaric acid, ethylene, propylene, etc. Is mentioned. These may be used alone or in combination of two or more.
Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylic acid because of good reactivity during polymerization Acrylic monomers such as are preferred.
上記多官能性モノマーは、得られる多孔質有機樹脂粒子の収縮を抑制し、耐圧縮強度を改善する目的で添加される。上記多官能性モノマーは特に限定されず、例えば、ジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、ヘキサ（メタ）アクリレート、ジアリル化合物、トリアリル化合物、ジビニル化合物等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The polyfunctional monomer is added for the purpose of suppressing the shrinkage of the resulting porous organic resin particles and improving the compression resistance. The polyfunctional monomer is not particularly limited. For example, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate, diallyl compound, triallyl compound, divinyl Compounds and the like. These may be used alone or in combination of two or more.
上記ジ（メタ）アクリレートは特に限定されず、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート等が挙げられる。
上記トリ（メタ）アクリレートは特に限定されず、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。
上記テトラ（メタ）アクリレートは特に限定されず、例えば、テトラメチロールプロパンテトラ（メタ）アクリレート等が挙げられる。
上記ジビニル化合物は特に限定されず、例えば、ジビニルベンゼン等が挙げられる。
これらのラジカル重合性モノマーは単独で用いてもよく、２種以上を併用してもよい。
The di (meth) acrylate is not particularly limited. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Examples include trimethylolpropane di (meth) acrylate.
The tri (meth) acrylate is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.
The tetra (meth) acrylate is not particularly limited, and examples thereof include tetramethylolpropane tetra (meth) acrylate.
The divinyl compound is not particularly limited, and examples thereof include divinylbenzene.
These radically polymerizable monomers may be used alone or in combination of two or more.
上記油溶性溶剤は、油溶性であり、かつ、上記ラジカル重合性モノマーと反応しなければ特に限定されない。
本明細書において、油溶性とは、ｌｏｇＰｏｗ（オクタノール／水分配係数）が０以上であることを意味する。例えば、溶剤のｌｏｇＰｏｗは、以下のように求められる。
ｎ−オクタノールと水とを充分に混合した混合液を２４時間放置した後、混合液に溶剤を加えてさらに混合する。その後、オクタノール相中に含まれる溶剤の濃度（Ｃｏ）と水相中に含まれる溶剤の濃度（Ｃｗ）とをガスクロマトグラフィーにより測定し、得られたＣｏ及びＣｗを用いて、下記式（３）からｌｏｇＰｏｗを算出できる。
ｌｏｇＰｏｗ＝ｌｏｇ（Ｃｏ／Ｃｗ） （３）
The oil-soluble solvent is not particularly limited as long as it is oil-soluble and does not react with the radical polymerizable monomer.
In the present specification, oil-soluble means that logPow (octanol / water partition coefficient) is 0 or more. For example, the logPow of the solvent is obtained as follows.
After leaving the mixed liquid in which n-octanol and water are sufficiently mixed for 24 hours, a solvent is added to the mixed liquid and further mixed. Thereafter, the concentration of the solvent contained in the octanol phase (Co) and the concentration of the solvent contained in the aqueous phase (Cw) were measured by gas chromatography. Using the obtained Co and Cw, the following formula (3 ) To calculate logPow.
logPow = log (Co / Cw) (3)
また、上記油溶性溶剤は、水に難溶性（２３℃における水への溶解度が２０重量％以下）であることが好ましい。 The oil-soluble solvent is preferably hardly soluble in water (the solubility in water at 23 ° C. is 20% by weight or less).
上記油溶性溶剤は特に限定されず、例えば、トルエン、キシレン等の芳香族炭化水素や、ヘプタン、イソオクタン等の脂肪族炭化水素や、シクロヘキサン等の環状炭化水素や、メチルイソブチルケトン等のケトン類や、酢酸エチル等のエステル類等が挙げられる。これらの油溶性溶剤は単独で用いてもよく、２種以上を併用してもよい。 The oil-soluble solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as heptane and isooctane, cyclic hydrocarbons such as cyclohexane, ketones such as methyl isobutyl ketone, And esters such as ethyl acetate. These oil-soluble solvents may be used alone or in combination of two or more.
上記油溶性溶剤の配合量は、目的とする多孔質有機樹脂粒子の粒子径により適宜調整すればよいが、上記ラジカル重合性モノマー１００重量部に対する好ましい下限は１０重量部、好ましい上限は３００重量部である。上記油溶性溶剤の配合量が１０重量部未満であると、得られる多孔質有機樹脂粒子にほとんど孔が形成されないことがある。上記油溶性溶剤の配合量が３００重量部を超えると、得られる多孔質有機樹脂粒子の強度が著しく低下することがある。上記油溶性溶剤の配合量のより好ましい下限は２０重量部、より好ましい上限は２００重量部である。 The blending amount of the oil-soluble solvent may be appropriately adjusted depending on the particle diameter of the target porous organic resin particles, but the preferred lower limit with respect to 100 parts by weight of the radical polymerizable monomer is 10 parts by weight, and the preferred upper limit is 300 parts by weight. It is. When the blending amount of the oil-soluble solvent is less than 10 parts by weight, almost no pores may be formed in the obtained porous organic resin particles. When the blending amount of the oil-soluble solvent exceeds 300 parts by weight, the strength of the obtained porous organic resin particles may be significantly reduced. A more preferred lower limit of the amount of the oil-soluble solvent is 20 parts by weight, and a more preferred upper limit is 200 parts by weight.
上記油溶性重合開始剤は、ラジカル重合を開始させるための開始剤であり、かつ、油溶性であれば特に限定されない。また、上記油溶性重合開始剤は、水に難溶性（２３℃における水への溶解度が２０重量％以下）であることが好ましい。
上記油溶性重合開始剤として、例えば、ベンゾイルパーオキサイド等の過酸化物や、アゾビスイソブチロニトリル等のアゾ化合物等が挙げられる。これらの油溶性重合開始剤は単独で用いてもよく、２種以上を併用してもよい。
The oil-soluble polymerization initiator is not particularly limited as long as it is an initiator for initiating radical polymerization and is oil-soluble. The oil-soluble polymerization initiator is preferably hardly soluble in water (the solubility in water at 23 ° C. is 20% by weight or less).
Examples of the oil-soluble polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. These oil-soluble polymerization initiators may be used alone or in combination of two or more.
上記油溶性重合開始剤の配合量は特に限定されず、上記ラジカル重合性モノマー１００重量部に対する好ましい下限は０．０１重量部、好ましい上限は２０重量部である。上記油溶性重合開始剤の配合量が０．０１重量部未満であると、多孔質有機樹脂粒子が形成されないことがある。上記油溶性重合開始剤の配合量が２０重量部を超えて配合してもほとんど反応には寄与せず、ブリードアウト等の原因となることがある。上記油溶性重合開始剤の配合量のより好ましい下限は０．１重量部、より好ましい上限は１０重量部である。 The blending amount of the oil-soluble polymerization initiator is not particularly limited, and a preferable lower limit with respect to 100 parts by weight of the radical polymerizable monomer is 0.01 part by weight, and a preferable upper limit is 20 parts by weight. When the blending amount of the oil-soluble polymerization initiator is less than 0.01 part by weight, porous organic resin particles may not be formed. Even if the blending amount of the oil-soluble polymerization initiator exceeds 20 parts by weight, it hardly contributes to the reaction and may cause bleeding out. The more preferable lower limit of the amount of the oil-soluble polymerization initiator is 0.1 part by weight, and the more preferable upper limit is 10 parts by weight.
上記種粒子分散液と、上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とを混合すると、上記種粒子に上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とが吸収されて、均一な膨潤粒子液滴が形成される。 When the seed particle dispersion, the radically polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator are mixed, the radically polymerizable monomer, the oil-soluble solvent, and the oil are mixed with the seed particles. The soluble polymerization initiator is absorbed and uniform swollen particle droplets are formed.
上記種粒子分散液と、上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とを混合する際には、上記ラジカル重合性モノマーと、上記油溶性溶剤と、上記油溶性重合開始剤とを直接上記種粒子分散液に加えて混合してもよいが、いったん水を含有する分散媒に添加して乳化液を調製し、該乳化液を上記種粒子分散液に加えて混合する方法が好ましい。いったん乳化液としてから加えることにより、上記ラジカル重合性モノマー等をより均一に上記種粒子に吸収させることができる。
上記ラジカル重合性モノマー、上記油溶性溶剤、上記油溶性重合開始剤は、これらの混合物の乳化液を調製して上記種粒子分散液に加えて混合してもよいし、各々の乳化液を別個に調製して上記種粒子分散液に加えて混合してもよい。
When mixing the seed particle dispersion, the radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator, the radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble solvent are mixed. A polymerization initiator may be added directly to the seed particle dispersion and mixed, but once added to a dispersion medium containing water, an emulsion is prepared, and the emulsion is added to the seed particle dispersion. A method of mixing is preferred. Once added as an emulsion, the radically polymerizable monomer and the like can be more uniformly absorbed by the seed particles.
The radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator may be prepared by preparing an emulsion of these mixtures and mixing them in addition to the seed particle dispersion. And may be mixed in addition to the seed particle dispersion.
上記ラジカル重合性モノマー等の乳化液の分散媒は特に限定されず、上記種粒子分散液に用いた分散媒と同じ分散媒であってもよく、異なる分散媒であってもよい。
また、上記ラジカル重合性モノマー等の乳化液の分散媒は、乳化剤を含有することが好ましい。上記乳化剤は特に限定されず、例えば、アルキル硫酸スルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸トリエタノールアミン、ポリオキシエチレンアルキルエーテル、ポリビニルアルコール等が挙げられる。
更に、上記ラジカル重合性モノマー等の乳化液と上記種粒子分散液とを混合する際には、上記乳化液の全量を一括で加えて混合してもよいし、分割して加えて混合してもよい。分割して加える場合には、滴下することにより添加してもよい。
The dispersion medium of the emulsion liquid such as the radical polymerizable monomer is not particularly limited, and may be the same dispersion medium as that used in the seed particle dispersion liquid or a different dispersion medium.
Moreover, it is preferable that the dispersion medium of emulsion liquids, such as the said radically polymerizable monomer, contains an emulsifier. The emulsifier is not particularly limited, and examples thereof include alkyl sulfate sulfonate, alkyl benzene sulfonate, alkyl sulfate triethanolamine, polyoxyethylene alkyl ether, and polyvinyl alcohol.
Furthermore, when mixing the emulsion of the above radical polymerizable monomer and the seed particle dispersion, the whole amount of the emulsion may be added and mixed all at once, or added and mixed separately. Also good. When adding by dividing | segmenting, you may add by dripping.
上記種粒子に対する油性成分の添加量は特に限定されないが、上記種粒子１００重量部に対する好ましい下限は１５重量部、好ましい上限は１００，０００重量部である。上記油性成分の添加量が１５重量部未満であると、ごく微量の油性成分しか吸収する余地がなく、高い空隙率を有する多孔質有機樹脂粒子が得られないことがある。上記油性成分の添加量が１００，０００重量部を超えると、上記種粒子に吸収し切れない上記油性成分が発生し、中実微粒子等の混入の原因となることがある。上記油性成分の添加量のより好ましい下限は２３０重量部、より好ましい上限は５０，０００重量部である。
なお、油性成分は、ラジカル重合性モノマー、油溶性溶剤、及び、油溶性重合開始剤を構成成分とする。
The amount of the oil component added to the seed particles is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the seed particles is 15 parts by weight, and a preferable upper limit is 100,000 parts by weight. When the amount of the oily component added is less than 15 parts by weight, there is no room for absorbing a very small amount of the oily component, and porous organic resin particles having a high porosity may not be obtained. When the added amount of the oily component exceeds 100,000 parts by weight, the oily component that cannot be absorbed by the seed particles is generated, which may cause mixing of solid fine particles and the like. The more preferable lower limit of the addition amount of the oil component is 230 parts by weight, and the more preferable upper limit is 50,000 parts by weight.
The oil component includes a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble polymerization initiator as constituent components.
上記方法（１）では、次いで、得られた膨潤粒子液滴中の上記ラジカル重合性モノマーを重合させる工程を行う。
上記ラジカル重合性モノマーを重合させることにより、上記油溶性溶剤と、上記ラジカル重合性モノマーを重合することにより得られたポリマーとからなるポリマー粒子分散液が得られる。なお、重合は、上記油溶性重合開始剤の種類等に従って、光を照射したり、加熱したりすることにより開始することができる。
In the method (1), a step of polymerizing the radical polymerizable monomer in the obtained swollen particle droplet is then performed.
By polymerizing the radical polymerizable monomer, a polymer particle dispersion comprising the oil-soluble solvent and a polymer obtained by polymerizing the radical polymerizable monomer is obtained. In addition, superposition | polymerization can be started by irradiating light or heating according to the kind etc. of said oil-soluble polymerization initiator.
更に、得られたポリマー粒子を、遠心分離と純水添加とを繰り返し行って洗浄し、上記油溶性溶剤を揮発させることにより、上述した範囲の平均粒子径と、個数基準粒子径の変動係数とを有する多孔質有機樹脂粒子が得られる。このような多孔質有機樹脂粒子を用いることにより、粒子径が極めて均一な金属複合有機樹脂粒子が得られる。 Further, the obtained polymer particles are washed by repeatedly performing centrifugation and addition of pure water, and the oil-soluble solvent is volatilized to obtain an average particle size in the above-described range and a coefficient of variation of the number-based particle size. Porous organic resin particles having the following are obtained. By using such porous organic resin particles, metal composite organic resin particles having a very uniform particle diameter can be obtained.
上記金属、金属酸化物又は金属塩は特に限定されないが、周期律表２ａ〜４ｂ族のうちの少なくとも１種の金属、又は、該金属からなる金属酸化物若しくは金属塩であることが好ましい。
上記金属として、具体的には、例えば、白金、金、パラジウム、ニッケル、銅等が挙げられる。上記金属酸化物として、具体的には、例えば、酸化セリウム、酸化チタン、酸化ケイ素、酸化亜鉛、ジルコニア、酸化鉄、酸化マグネシウム、酸化銅、酸化コバルト、酸化インジウム、酸化アルミニウム、酸化亜鉛、酸化錫等が挙げられる。上記金属塩として、具体的には、例えば、水酸化セリウム、水酸化チタン、水酸化マグネシウム、炭酸カルシウム、硫酸バリウム、水酸化（ＩＩ）鉄、水酸化（ＩＩＩ）鉄、水酸化ニッケル、硫酸銅、水酸化亜鉛、水酸化アルミニウム等が挙げられる。
Although the said metal, a metal oxide, or a metal salt is not specifically limited, It is preferable that they are at least 1 sort (s) of the periodic table 2a-4b group, or the metal oxide or metal salt which consists of this metal.
Specific examples of the metal include platinum, gold, palladium, nickel, and copper. Specific examples of the metal oxide include cerium oxide, titanium oxide, silicon oxide, zinc oxide, zirconia, iron oxide, magnesium oxide, copper oxide, cobalt oxide, indium oxide, aluminum oxide, zinc oxide, and tin oxide. Etc. Specific examples of the metal salt include cerium hydroxide, titanium hydroxide, magnesium hydroxide, calcium carbonate, barium sulfate, (II) iron hydroxide, (III) iron hydroxide, nickel hydroxide, and copper sulfate. , Zinc hydroxide, aluminum hydroxide and the like.
上記金属、金属酸化物又は金属塩の含有量は特に限定されないが、好ましい下限が金属複合有機樹脂粒子全体の５重量％、好ましい上限が金属複合有機樹脂粒子全体の９０重量％である。上記金属、金属酸化物又は金属塩の含有量が５重量％未満であると、得られる金属複合有機樹脂粒子を用いて、導電性、熱線反射性等の所望とする性能を充分に有する構造体を製造できないことがある。上記金属、金属酸化物又は金属塩の含有量が９０重量％を超えると、得られる金属複合有機樹脂粒子は、塗工組成物中での分散性が低下することがあり、このような塗工組成物を用いて製造した構造体は、金属、金属酸化物又は金属塩の分散性が低下することがある。上記金属、金属酸化物又は金属塩の含有量は、より好ましい下限が金属複合有機樹脂粒子全体の１０重量％、より好ましい上限が金属複合有機樹脂粒子全体の７０重量％である。 Although content of the said metal, a metal oxide, or a metal salt is not specifically limited, A preferable minimum is 5 weight% of the whole metal composite organic resin particle, and a preferable upper limit is 90 weight% of the whole metal composite organic resin particle. When the content of the metal, metal oxide or metal salt is less than 5% by weight, the structure having sufficient performance such as conductivity and heat ray reflectivity using the obtained metal composite organic resin particles May not be manufactured. When the content of the metal, metal oxide or metal salt exceeds 90% by weight, the resulting metal composite organic resin particles may have reduced dispersibility in the coating composition. In the structure manufactured using the composition, the dispersibility of the metal, metal oxide, or metal salt may be lowered. As for the content of the metal, metal oxide or metal salt, a more preferred lower limit is 10% by weight of the whole metal composite organic resin particles, and a more preferred upper limit is 70% by weight of the whole metal composite organic resin particles.
本発明の金属複合有機樹脂粒子は、金属、金属酸化物又は金属塩を多孔質有機樹脂粒子の細孔内に有することから、有機樹脂バインダーとの相溶性が高く、塗工組成物中で良好に分散することができる。更に、本発明の金属複合有機樹脂粒子は粒子径が極めて均一であることから、本発明の金属複合有機樹脂粒子を用いることで、金属、金属酸化物又は金属塩が極めて均一に分散した塗工組成物を得ることができ、このような塗工組成物を用いることで、金属、金属酸化物又は金属塩が極めて均一に分散した構造体を容易に製造することができる。
また、本発明の金属複合有機樹脂粒子を含有する塗工組成物は、金属、金属酸化物又は金属塩の凝集が抑制され、貯蔵安定性にも優れることから、使用する前に再度混練して再分散する必要がない。
Since the metal composite organic resin particles of the present invention have a metal, metal oxide or metal salt in the pores of the porous organic resin particles, the compatibility with the organic resin binder is high, and the coating composition is good. Can be dispersed. Furthermore, since the metal composite organic resin particles of the present invention have a very uniform particle size, the use of the metal composite organic resin particles of the present invention allows a coating in which metal, metal oxide or metal salt is dispersed extremely uniformly. A composition can be obtained, and by using such a coating composition, a structure in which a metal, a metal oxide, or a metal salt is dispersed extremely uniformly can be easily produced.
In addition, the coating composition containing the metal composite organic resin particles of the present invention suppresses aggregation of metal, metal oxide or metal salt and is excellent in storage stability. There is no need to redistribute.
本発明の金属複合有機樹脂粒子の用途は特に限定されないが、例えば、本発明の金属複合有機樹脂粒子、有機樹脂バインダー、溶剤等を混合して塗工組成物を作製し、該塗工組成物を用いて、電極材料、色素増感太陽電池用電極、透明電極、触媒担体、電子材料用セラミックス、紫外線吸収剤、熱線反射材料等を製造することができる。本発明の金属複合有機樹脂粒子を用いることで、これらの構造体は、金属、金属酸化物又は金属塩が極めて均一に分散していることから、広い表面積、高い平滑性、緻密性等を有し、高い電極効率、触媒効率、透明性等を得ることができる。 The use of the metal composite organic resin particles of the present invention is not particularly limited. For example, a coating composition is prepared by mixing the metal composite organic resin particles of the present invention, an organic resin binder, a solvent, and the like. Can be used to produce electrode materials, dye-sensitized solar cell electrodes, transparent electrodes, catalyst carriers, ceramics for electronic materials, ultraviolet absorbers, heat ray reflective materials, and the like. By using the metal composite organic resin particles of the present invention, these structures have a large surface area, high smoothness, denseness, and the like because the metal, metal oxide, or metal salt is dispersed extremely uniformly. In addition, high electrode efficiency, catalyst efficiency, transparency, and the like can be obtained.
本発明の金属複合有機樹脂粒子を製造する方法は特に限定されないが、水を主成分とする媒体中に多孔質有機樹脂粒子と金属イオンとを共存させた分散液を調製する工程と、前記金属イオンを中和、還元若しくは酸化するか、又は、前記金属イオンの溶解度を低下させることにより、前記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程とを有する方法が好ましい。このような本発明の金属複合有機樹脂粒子の製造方法もまた、本発明の１つである（第１の本発明の金属複合有機樹脂粒子の製造方法）。
また、本発明の金属複合有機樹脂粒子を製造する方法として、多孔質有機樹脂粒子と金属アルコキシドとを共存させた分散液を調製する工程と、前記金属アルコキシドを加水分解及び／又は脱水縮合することにより、前記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程とを有する方法も好ましい。このような本発明の金属複合有機樹脂粒子の製造方法もまた、本発明の１つである（第２の本発明の金属複合有機樹脂粒子の製造方法）。
The method for producing the metal composite organic resin particles of the present invention is not particularly limited, but the step of preparing a dispersion in which porous organic resin particles and metal ions coexist in a medium mainly composed of water; A step of precipitating a metal, a metal oxide, or a metal salt in the pores of the porous organic resin particles by neutralizing, reducing, or oxidizing the ions, or reducing the solubility of the metal ions. The method is preferred. Such a method for producing metal composite organic resin particles of the present invention is also one aspect of the present invention (method for producing metal composite organic resin particles of the first present invention).
Moreover, as a method for producing the metal composite organic resin particles of the present invention, a step of preparing a dispersion in which porous organic resin particles and a metal alkoxide coexist, and hydrolysis and / or dehydration condensation of the metal alkoxide. And a step of depositing metal, metal oxide or metal salt in the pores of the porous organic resin particles. Such a method for producing metal composite organic resin particles of the present invention is also one aspect of the present invention (method for producing metal composite organic resin particles of the second present invention).
第１の本発明の金属複合有機樹脂粒子の製造方法では、まず、水を主成分とする媒体中に上述した多孔質有機樹脂粒子と金属イオンとを共存させた分散液を調製する工程を行う。
上記水を主成分とする媒体は、水を主成分としていれば特に限定されず、例えば、水や、エタノール、メタノール、イソプロパノール、アセトン等と水との混合物等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
In the method for producing metal composite organic resin particles according to the first aspect of the present invention, first, a step of preparing a dispersion in which the above-described porous organic resin particles and metal ions coexist in a medium containing water as a main component is performed. .
The medium containing water as a main component is not particularly limited as long as it contains water as a main component, and examples thereof include water and a mixture of water, ethanol, methanol, isopropanol, acetone, and the like. These may be used alone or in combination of two or more.
上記分散液中の上記多孔質有機樹脂粒子の配合量は特に限定されないが、好ましい下限が０．５重量％、好ましい上限が５０重量％である。上記多孔質有機樹脂粒子の配合量が０．５重量％未満であると、上記多孔質有機樹脂粒子の細孔外で析出する金属、金属酸化物又は金属塩の量が増加し、分散性が悪化することがある。上記多孔質有機樹脂粒子の配合量が５０重量％を超えると、多孔質有機樹脂粒子が凝集することがある。上記分散液中の上記多孔質有機樹脂粒子の配合量は、より好ましい下限が１重量％、より好ましい上限が３０重量％である。 The blending amount of the porous organic resin particles in the dispersion is not particularly limited, but a preferred lower limit is 0.5% by weight and a preferred upper limit is 50% by weight. When the amount of the porous organic resin particles is less than 0.5% by weight, the amount of the metal, metal oxide or metal salt precipitated outside the pores of the porous organic resin particles is increased, and the dispersibility is increased. May get worse. When the blending amount of the porous organic resin particles exceeds 50% by weight, the porous organic resin particles may aggregate. As for the compounding quantity of the said porous organic resin particle in the said dispersion liquid, a more preferable minimum is 1 weight% and a more preferable upper limit is 30 weight%.
上記金属イオンは、本発明の金属複合有機樹脂粒子に含まれる上記金属、金属酸化物又は金属塩を形成する金属のイオンであれば特に限定されず、具体的には、例えば、パラジウムイオン、ニッケルイオン、セリウムイオン、白金イオン、金イオン、セリウムイオン、亜鉛イオン、ジルコニウムイオン、鉄イオン、マグネシウムイオン、銅イオン、コバルトイオン、アルミニウムイオン、錫イオン等が挙げられる。 The metal ion is not particularly limited as long as it is a metal ion that forms the metal, metal oxide, or metal salt contained in the metal composite organic resin particles of the present invention. Specifically, for example, palladium ion, nickel Examples include ions, cerium ions, platinum ions, gold ions, cerium ions, zinc ions, zirconium ions, iron ions, magnesium ions, copper ions, cobalt ions, aluminum ions, and tin ions.
上記分散液中の上記金属イオンの配合量は特に限定されないが、好ましい下限が０．００１モル％、好ましい上限が１０モル％である。上記金属イオンの配合量が０．００１モル％未満であると、得られる金属複合有機樹脂粒子は、金属、金属酸化物又は金属塩の含有量が低下することがある。上記金属イオンの配合量が１０モル％を超えると、上記多孔質有機樹脂粒子の細孔外で析出する金属、金属酸化物又は金属塩の量が増加し、得られる金属複合有機樹脂粒子との分離が困難になることがある。上記分散液中の上記金属イオンの配合量は、より好ましい下限が０．０１モル％、より好ましい上限が５モル％である。 The compounding amount of the metal ions in the dispersion is not particularly limited, but a preferable lower limit is 0.001 mol% and a preferable upper limit is 10 mol%. When the blending amount of the metal ions is less than 0.001 mol%, the metal composite organic resin particles obtained may have a reduced content of metal, metal oxide or metal salt. When the amount of the metal ions exceeds 10 mol%, the amount of metal, metal oxide or metal salt precipitated outside the pores of the porous organic resin particles increases, and the resulting metal composite organic resin particles Separation may be difficult. As for the compounding quantity of the said metal ion in the said dispersion liquid, a more preferable minimum is 0.01 mol% and a more preferable upper limit is 5 mol%.
上記分散液を調製する方法は特に限定されず、例えば、上記多孔質有機樹脂粒子を分散させた分散液と、上記金属イオンを含有する溶液とを混合する方法、上記多孔質有機樹脂粒子の乾燥体と、上記金属イオンを含有する溶液とを混合する方法、上記多孔質有機樹脂粒子を分散させた分散液と、上記金属イオンからなる金属塩の乾燥体とを混合する方法等が挙げられる。
なお、上記分散液には、上記多孔質有機樹脂粒子の分散性を向上させるために、界面活性剤等の他の添加剤が添加されてもよい。
The method for preparing the dispersion is not particularly limited. For example, a method of mixing the dispersion in which the porous organic resin particles are dispersed and a solution containing the metal ions, drying of the porous organic resin particles. And a solution containing the metal ions, a dispersion in which the porous organic resin particles are dispersed, and a dried metal salt made of the metal ions.
In addition, in order to improve the dispersibility of the said porous organic resin particle, other additives, such as surfactant, may be added to the said dispersion liquid.
第１の本発明の金属複合有機樹脂粒子の製造方法では、次いで、上記金属イオンを中和、還元若しくは酸化するか、又は、上記金属イオンの溶解度を低下させることにより、上記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程を行う。これにより、粒子径が極めて均一な金属複合有機樹脂粒子が得られる。
上記金属イオンを中和する方法は特に限定されず、例えば、塩化マグネシウム水溶液に水酸化ナトリウムを添加する、硝酸セリウムにアンモニアを添加する、炭酸ナトリウム水溶液に二酸化炭素を添加する、塩化カルシウム水溶液に炭酸ナトリウムを添加する等の酸性物質にアルカリ性物質を添加したり、アルカリ性物質に酸性物質を添加したりする方法等が挙げられる。
上記金属イオンを還元する方法は特に限定されず、例えば、アンモニア等の還元剤を反応させる方法等が挙げられる。
In the method for producing metal composite organic resin particles according to the first aspect of the present invention, the porous organic resin particles are then neutralized, reduced or oxidized, or the solubility of the metal ions is reduced. A step of precipitating a metal, metal oxide or metal salt in the pores. Thereby, metal composite organic resin particles having a very uniform particle diameter can be obtained.
The method for neutralizing the metal ions is not particularly limited. For example, sodium hydroxide is added to an aqueous magnesium chloride solution, ammonia is added to cerium nitrate, carbon dioxide is added to an aqueous sodium carbonate solution, carbonic acid is added to an aqueous calcium chloride solution. Examples thereof include a method of adding an alkaline substance to an acidic substance such as adding sodium or adding an acidic substance to an alkaline substance.
The method for reducing the metal ion is not particularly limited, and examples thereof include a method of reacting a reducing agent such as ammonia.
第２の本発明の金属複合有機樹脂粒子の製造方法では、まず、上述した多孔質有機樹脂粒子と金属アルコキシドとを共存させた分散液を調製する工程を行う。 In the method for producing metal composite organic resin particles of the second aspect of the present invention, first, a step of preparing a dispersion in which the above-described porous organic resin particles and metal alkoxide coexist is performed.
上記分散液中の上記多孔質有機樹脂粒子の配合量は特に限定されず、第１の本発明の金属複合有機樹脂粒子の製造方法で用いられた配合量と同様の配合量を用いることができる。 The blending amount of the porous organic resin particles in the dispersion is not particularly limited, and a blending amount similar to the blending amount used in the method for producing metal composite organic resin particles of the first invention can be used. .
上記金属アルコキシドは、本発明の金属複合有機樹脂粒子に含まれる上記金属、金属酸化物又は金属塩を形成する金属のアルコキシドであれば特に限定されず、具体的には、例えば、オルトテトラケイ酸エチル、チタンテトライソプロポキシド等が挙げられる。 The metal alkoxide is not particularly limited as long as it is a metal alkoxide that forms the metal, metal oxide, or metal salt contained in the metal composite organic resin particles of the present invention. Specifically, for example, orthotetrasilicate Examples thereof include ethyl and titanium tetraisopropoxide.
上記分散液中の上記金属アルコキシドの配合量は特に限定されないが、好ましい下限が０．００１モル％、好ましい上限が１０モル％である。上記金属アルコキシドの配合量が０．００１モル％未満であると、得られる金属複合有機樹脂粒子は、金属、金属酸化物又は金属塩の含有量が低下することがある。上記金属アルコキシドの配合量が１０モル％を超えると、上記多孔質有機樹脂粒子の細孔外で析出する金属、金属酸化物又は金属塩の量が増加し、得られる金属複合有機樹脂粒子との分離が困難になることがある。上記分散液中の上記金属アルコキシドの配合量は、より好ましい下限が０．０１モル％、より好ましい上限が５モル％である。 Although the compounding quantity of the said metal alkoxide in the said dispersion liquid is not specifically limited, A preferable minimum is 0.001 mol% and a preferable upper limit is 10 mol%. When the blending amount of the metal alkoxide is less than 0.001 mol%, the metal composite organic resin particles obtained may have a reduced content of metal, metal oxide or metal salt. When the amount of the metal alkoxide exceeds 10 mol%, the amount of metal, metal oxide or metal salt precipitated outside the pores of the porous organic resin particles increases, and the resulting metal composite organic resin particles Separation may be difficult. As for the compounding quantity of the said metal alkoxide in the said dispersion liquid, a more preferable minimum is 0.01 mol% and a more preferable upper limit is 5 mol%.
上記分散液を調製する方法は特に限定されず、例えば、上記多孔質有機樹脂粒子を分散させた分散液と、上記金属アルコキシドを含有する溶液とを混合する方法、上記多孔質有機樹脂粒子の乾燥粉体と、上記金属アルコキシドを含有する溶液とを混合する方法、上記多孔質有機樹脂粒子の乾燥粉体をエタノール等の水と容易に分散する水以外の溶媒に分散させた多孔質有機樹脂粒子分散液と、上記金属アルコキシドを含有する溶液とを混合する方法等が挙げられる。
なお、上記分散液には、上記多孔質有機樹脂粒子の分散性を向上させるために、界面活性剤等の他の添加剤が添加されてもよい。
The method for preparing the dispersion is not particularly limited. For example, a method of mixing the dispersion in which the porous organic resin particles are dispersed and a solution containing the metal alkoxide, drying the porous organic resin particles. A method of mixing powder and a solution containing the metal alkoxide, porous organic resin particles in which a dry powder of the porous organic resin particles is dispersed in a solvent other than water, such as ethanol, which is easily dispersed Examples include a method of mixing the dispersion and a solution containing the metal alkoxide.
In addition, in order to improve the dispersibility of the said porous organic resin particle, other additives, such as surfactant, may be added to the said dispersion liquid.
第２の本発明の金属複合有機樹脂粒子の製造方法では、次いで、上記金属アルコキシドを加水分解及び／又は脱水縮合することにより、上記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程を行う。これにより、粒子径が極めて均一な金属複合有機樹脂粒子が得られる。
上記加水分解及び／又は脱水縮合する方法は特に限定されず、例えば、アンモニアを反応させる方法、硝酸を反応させる方法等が挙げられる。
In the method for producing metal composite organic resin particles of the second aspect of the present invention, the metal alkoxide is then hydrolyzed and / or dehydrated to condense a metal, a metal oxide or a metal oxide in the pores of the porous organic resin particles. A step of depositing a metal salt is performed. Thereby, metal composite organic resin particles having a very uniform particle diameter can be obtained.
The method for the hydrolysis and / or dehydration condensation is not particularly limited, and examples thereof include a method of reacting ammonia and a method of reacting nitric acid.
第１及び第２の本発明の金属複合有機樹脂粒子の製造方法では、上述のようにして金属複合有機樹脂粒子を得た後、更に、得られた金属複合有機樹脂粒子に対して各工程を繰り返して行ってもよい。
より具体的には、例えば、第１の本発明の金属複合有機樹脂粒子の製造方法により得られた金属複合有機樹脂粒子と、新たな金属イオンとを、水を主成分とする媒体中に共存させた分散液を調製する工程を行い、次いで、上記新たな金属イオンを中和、還元又は酸化することにより、多孔質有機樹脂粒子の細孔内に新たな金属、金属酸化物又は金属塩を析出させる工程を行ってもよい。
In the method for producing metal composite organic resin particles of the first and second present invention, after obtaining the metal composite organic resin particles as described above, each step is further performed on the obtained metal composite organic resin particles. You may repeat.
More specifically, for example, the metal composite organic resin particles obtained by the method for producing metal composite organic resin particles of the first invention and a new metal ion coexist in a medium containing water as a main component. A step of preparing the dispersed liquid, and then neutralizing, reducing, or oxidizing the new metal ions to form new metal, metal oxide, or metal salt in the pores of the porous organic resin particles. You may perform the process to make it precipitate.
また、第１及び第２の本発明の金属複合有機樹脂粒子の製造方法では、上述のようにして金属複合有機樹脂粒子を得た後、析出した金属、金属酸化物又は金属塩を、更に酸化してもよい。
上記酸化する方法は特に限定されず、例えば、金属複合有機樹脂粒子を空気中で加熱する方法等が挙げられる。
Moreover, in the manufacturing method of the metal composite organic resin particle of 1st and 2nd this invention, after obtaining a metal composite organic resin particle as mentioned above, the metal, metal oxide, or metal salt which precipitated is further oxidized. May be.
The method for oxidizing is not particularly limited, and examples thereof include a method of heating metal composite organic resin particles in air.
第１及び第２の本発明の金属複合有機樹脂粒子の製造方法によれば、粒子径が極めて均一な、本発明の金属複合有機樹脂粒子が得られる。本発明の金属複合有機樹脂粒子を用いることで、金属、金属酸化物又は金属塩が極めて均一に分散した塗工組成物を得ることができ、このような塗工組成物を用いることで、金属、金属酸化物又は金属塩が極めて均一に分散した構造体を容易に製造することができる。 According to the first and second methods for producing metal composite organic resin particles of the present invention, the metal composite organic resin particles of the present invention having a very uniform particle diameter can be obtained. By using the metal composite organic resin particles of the present invention, it is possible to obtain a coating composition in which a metal, a metal oxide or a metal salt is extremely uniformly dispersed. By using such a coating composition, a metal In addition, a structure in which a metal oxide or a metal salt is dispersed extremely uniformly can be easily produced.
本発明によれば、粒子径が極めて均一な金属複合有機樹脂粒子を提供することができる。また、本発明によれば、該金属複合有機樹脂粒子の製造方法を提供することができる。 According to the present invention, metal composite organic resin particles having a very uniform particle diameter can be provided. Moreover, according to this invention, the manufacturing method of this metal composite organic resin particle can be provided.
（実施例１）
（多孔質有機樹脂粒子の製造）
スチレン１００重量部、過硫酸カリウム３重量部、ｎ−オクチルメルカプタン２５重量部、水２５００重量部を混合し、攪拌しながら７０℃で２４時間反応させて、体積平均粒子径０．５μｍ、体積基準粒子径の変動係数１５％、かつ、球状の非架橋のポリスチレン粒子が１．５重量％の濃度で水に分散された種粒子分散液を調製した。
Example 1
(Manufacture of porous organic resin particles)
100 parts by weight of styrene, 3 parts by weight of potassium persulfate, 25 parts by weight of n-octyl mercaptan, and 2500 parts by weight of water were mixed and reacted at 70 ° C. for 24 hours with stirring, volume average particle diameter 0.5 μm, volume basis A seed particle dispersion was prepared in which a coefficient of variation in particle diameter of 15% and spherical non-crosslinked polystyrene particles were dispersed in water at a concentration of 1.5% by weight.
ラジカル重合性モノマーとしてジビニルベンゼン１００重量部、油溶性溶剤としてノルマルヘプタン３０重量部、及び、油溶性重合開始剤として過酸化ベンゾイル１重量部を均一に溶解した混合液に、乳化剤としてラウリル硫酸トリエタノールアミン２重量部と水とを加えて混合し、乳化液を調製した。 100 parts by weight of divinylbenzene as a radical polymerizable monomer, 30 parts by weight of normal heptane as an oil-soluble solvent, and 1 part by weight of benzoyl peroxide as an oil-soluble polymerization initiator are mixed in a mixed solution in which lauryl sulfate triethanol is used as an emulsifier. An emulsion was prepared by adding 2 parts by weight of amine and water and mixing.
得られた種粒子分散液と、ポリスチレン粒子重量の２００倍の油性成分となるように乳化液とを混合し、２４時間撹拌して、ラジカル重合性モノマー、油溶性溶剤、油溶性重合開始剤を吸収した種粒子の膨潤粒子液滴の分散液を得た。なお、油性成分は、ラジカル重合性モノマー、油溶性溶剤、及び、油溶性重合開始剤を構成成分とする。
得られた膨潤粒子液滴の分散液を撹拌しながら８５℃で、１０時間反応させることにより、ヘプタンとポリジビニルベンゼンとからなるポリマー粒子分散液を得た。得られたポリマー粒子について、遠心分離と純水添加とを繰り返し行って洗浄し、真空乾燥してヘプタンを揮発させて、多孔質有機樹脂粒子を作製した。
The obtained seed particle dispersion is mixed with an emulsified liquid so as to be an oily component 200 times the weight of polystyrene particles, and stirred for 24 hours to give a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble polymerization initiator. A dispersion of swollen particle droplets of absorbed seed particles was obtained. The oil component includes a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble polymerization initiator as constituent components.
The obtained dispersion liquid of swollen particle droplets was reacted at 85 ° C. for 10 hours with stirring to obtain a polymer particle dispersion liquid composed of heptane and polydivinylbenzene. The obtained polymer particles were washed by repeated centrifugation and addition of pure water, and vacuum-dried to volatilize heptane to produce porous organic resin particles.
得られた多孔質有機樹脂粒子について、走査型電子顕微鏡により１視野に約１００個が観察できる倍率で観察し、任意に選択した５０個の多孔質有機樹脂粒子についてノギスを用いて最長径を測定した。得られた最長径の数平均値を平均粒子径とし、上記式（１）により個数基準粒子径の変動係数を算出したところ、平均粒子径は３．２μｍ、個数基準粒子径の変動係数は２．５％であった。 The obtained porous organic resin particles are observed with a scanning electron microscope at a magnification at which about 100 particles can be observed in one field of view, and the arbitrarily selected 50 porous organic resin particles are measured for the longest diameter using calipers. did. The number average value of the obtained longest diameter was taken as the average particle diameter, and the variation coefficient of the number-based particle diameter was calculated by the above formula (1). The average particle diameter was 3.2 μm, and the variation coefficient of the number-based particle diameter was 2 .5%.
（金属複合有機樹脂粒子及び塗工体の製造）
得られた多孔質有機樹脂粒子のエタノール分散液と、界面活性剤水溶液と、硫酸パラジウムと、２−アミノピリジン水溶液とを混合して、多孔質有機樹脂粒子が３重量％、パラジウムイオンが１モル％で共存した分散液を調製した。この分散液に対して、ジメチルアミンボランを添加することにより還元を行い、パラジウムが多孔質有機樹脂粒子の細孔内に析出したパラジウム複合粒子を作製した。
得られたパラジウム複合粒子１０重量部と、エチルセルロース３０重量部と、トルエン３０重量部と、メチルエチルケトン（ＭＥＫ）３０重量部とを、３本ロールで５分間混練し、バーコーターにより乾燥厚み２０μｍとなるように塗工し、乾燥させて、塗工体を作製した。
(Manufacture of metal composite organic resin particles and coated bodies)
An ethanol dispersion of the obtained porous organic resin particles, a surfactant aqueous solution, palladium sulfate, and a 2-aminopyridine aqueous solution were mixed to obtain 3% by weight of porous organic resin particles and 1 mol of palladium ions. A dispersion coexisting in% was prepared. The dispersion was reduced by adding dimethylamine borane to produce palladium composite particles in which palladium was precipitated in the pores of the porous organic resin particles.
10 parts by weight of the obtained palladium composite particles, 30 parts by weight of ethyl cellulose, 30 parts by weight of toluene, and 30 parts by weight of methyl ethyl ketone (MEK) are kneaded for 5 minutes with three rolls, and a dry thickness of 20 μm is obtained by a bar coater. The coated body was coated and dried to prepare a coated body.
（実施例２）
（金属複合有機樹脂粒子及び塗工体の製造）
実施例１で得られたパラジウム複合粒子を、硫酸ニッケル水溶液に投入し、パラジウム複合粒子が３重量％、ニッケルイオンが１モル％で共存した分散液を調製した。この分散液に対して、ホスフィン酸ナトリウムを添加することにより還元を行い、ニッケルが多孔質有機樹脂粒子の細孔内に析出したニッケル複合粒子を作製した。
得られたニッケル複合粒子を用いたこと以外は実施例１と同様にして、塗工体を作製した。
(Example 2)
(Manufacture of metal composite organic resin particles and coated bodies)
The palladium composite particles obtained in Example 1 were put into a nickel sulfate aqueous solution to prepare a dispersion in which palladium composite particles coexisted at 3 wt% and nickel ions at 1 mol%. The dispersion was reduced by adding sodium phosphinate to produce nickel composite particles in which nickel was precipitated in the pores of the porous organic resin particles.
A coated body was produced in the same manner as in Example 1 except that the obtained nickel composite particles were used.
（実施例３）
（金属複合有機樹脂粒子及び塗工体の製造）
実施例１で得られた多孔質有機樹脂粒子の水分散液と、別途作製した硝酸アンモニウムセリウム（ＩＶ）水溶液とを混合して、多孔質有機樹脂粒子が３重量％、セリウムイオンが１モル％で共存した分散液を調製した。この分散液に対して、アンモニアを添加することにより還元を行い、水酸化セリウムが多孔質有機樹脂粒子の細孔内に析出した水酸化セリウム複合粒子を作製した。
得られた水酸化セリウム複合粒子を用いたこと以外は実施例１と同様にして、塗工体を作製した。
(Example 3)
(Manufacture of metal composite organic resin particles and coated bodies)
The aqueous dispersion of porous organic resin particles obtained in Example 1 and a separately prepared aqueous solution of ammonium cerium (IV) nitrate were mixed so that the porous organic resin particles were 3 wt% and the cerium ions were 1 mol%. A coexisting dispersion was prepared. The dispersion was reduced by adding ammonia to produce cerium hydroxide composite particles in which cerium hydroxide was precipitated in the pores of the porous organic resin particles.
A coated body was produced in the same manner as in Example 1 except that the obtained cerium hydroxide composite particles were used.
（実施例４）
（金属複合有機樹脂粒子及び塗工体の製造）
実施例３で得た水酸化セリウム複合粒子を、空気中で、１５０℃で２４時間加熱することにより、酸化セリウムが多孔質有機樹脂粒子の細孔内に析出した酸化セリウム複合粒子を作製した。
得られた酸化セリウム複合粒子を用いたこと以外は実施例１と同様にして、塗工体を作製した。
Example 4
(Manufacture of metal composite organic resin particles and coated bodies)
The cerium hydroxide composite particles obtained in Example 3 were heated in air at 150 ° C. for 24 hours to produce cerium oxide composite particles in which cerium oxide was precipitated in the pores of the porous organic resin particles.
A coated body was produced in the same manner as in Example 1 except that the obtained cerium oxide composite particles were used.
（実施例５）
（金属複合有機樹脂粒子及び塗工体の製造）
実施例１で得られた多孔質有機樹脂粒子の水分散液と、別途作製したオルトテトラケイ酸エチルのエタノール溶液と混合して、多孔質有機樹脂粒子が３重量％、オルトテトラケイ酸エチルが１モル％で共存した分散液を調製した。この分散液に対して、アンモニアを添加することにより加水分解を行い、酸化ケイ素が多孔質有機樹脂粒子の細孔内に析出した酸化ケイ素複合粒子を作製した。
得られた酸化ケイ素複合粒子を用いたこと以外は実施例１と同様にして、塗工体を作製した。
(Example 5)
(Manufacture of metal composite organic resin particles and coated bodies)
The aqueous dispersion of the porous organic resin particles obtained in Example 1 and an ethanol solution of ethyl orthotetrasilicate prepared separately were mixed to obtain 3% by weight of porous organic resin particles and ethyl orthotetrasilicate. A dispersion coexisting at 1 mol% was prepared. The dispersion was hydrolyzed by adding ammonia to produce silicon oxide composite particles in which silicon oxide was precipitated in the pores of the porous organic resin particles.
A coated body was produced in the same manner as in Example 1 except that the obtained silicon oxide composite particles were used.
（実施例６）
（金属複合有機樹脂粒子及び塗工体の製造）
実施例１で得られた多孔質有機樹脂粒子の水分散液と、別途作製したチタンテトライソプロポキシドのエタノール溶液と混合して、多孔質有機樹脂粒子が３重量％、チタンテトライソプロポキシドが１モル％で共存した分散液を調製した。この分散液に対して、硝酸を添加することにより加水分解を行い、酸化チタンが多孔質有機樹脂粒子の細孔内に析出した酸化チタン複合粒子を作製した。
得られた酸化チタン複合粒子を用いたこと以外は実施例１と同様にして、塗工体を作製した。
(Example 6)
(Manufacture of metal composite organic resin particles and coated bodies)
The aqueous dispersion of the porous organic resin particles obtained in Example 1 was mixed with an ethanol solution of titanium tetraisopropoxide separately prepared, so that the porous organic resin particles were 3% by weight and the titanium tetraisopropoxide was A dispersion coexisting at 1 mol% was prepared. The dispersion was hydrolyzed by adding nitric acid to produce titanium oxide composite particles in which titanium oxide was precipitated in the pores of the porous organic resin particles.
A coated body was produced in the same manner as in Example 1 except that the obtained titanium oxide composite particles were used.
（比較例１）
（塗工体の製造）
平均粒子径２０ｎｍの酸化チタン１０重量部と、エチルセルロース３０重量部と、トルエン３０重量部と、ＭＥＫ３０重量部とを、３本ロールで１時間混練し、バーコーターにより乾燥厚み２０μｍとなるように塗工し、乾燥させて、塗工体を作製した。
(Comparative Example 1)
(Manufacture of coated bodies)
10 parts by weight of titanium oxide having an average particle diameter of 20 nm, 30 parts by weight of ethyl cellulose, 30 parts by weight of toluene, and 30 parts by weight of MEK are kneaded with three rolls for 1 hour, and applied to a dry thickness of 20 μm with a bar coater. And dried to produce a coated body.
（比較例２）
（金属複合有機樹脂粒子及び塗工体の製造）
平均粒径２０ｎｍの酸化チタン３０重量部を、スチレン３０重量部、ジビニルベンゼン４０重量部、過酸化ベンゾイル１重量部からなる油性物質に分散させた分散液を調製した。この分散液を、イオン交換水４００重量部、ポリビニルアルコール１重量部を溶解させた水系溶液に懸濁させ、懸濁重合を行うことにより、酸化チタン複合粒子を作製した。
得られた酸化チタン複合粒子１０重量部と、エチルセルロース３０重量部と、トルエン３０重量部と、ＭＥＫ３０重量部とを、３本ロールで５分間混練し、バーコーターにより乾燥厚み２０μｍとなるように塗工し、乾燥させて、塗工体を作製した。
(Comparative Example 2)
(Manufacture of metal composite organic resin particles and coated bodies)
A dispersion was prepared by dispersing 30 parts by weight of titanium oxide having an average particle diameter of 20 nm in an oily substance composed of 30 parts by weight of styrene, 40 parts by weight of divinylbenzene, and 1 part by weight of benzoyl peroxide. This dispersion was suspended in an aqueous solution in which 400 parts by weight of ion-exchanged water and 1 part by weight of polyvinyl alcohol were dissolved, and suspension polymerization was performed to produce titanium oxide composite particles.
10 parts by weight of the obtained titanium oxide composite particles, 30 parts by weight of ethyl cellulose, 30 parts by weight of toluene, and 30 parts by weight of MEK were kneaded with three rolls for 5 minutes, and applied with a bar coater to a dry thickness of 20 μm. And dried to produce a coated body.
（比較例３）
（金属複合有機樹脂粒子及び塗工体の製造）
スチレン４０重量部、ジビニルベンゼン３０重量部、シランカップリング剤（ＫＢＭ５１０３、アクリル基含有シランカップリング剤）３０重量部、過酸化ベンゾイル１重量部からなる油性物質を、イオン交換水４００重量部、ポリビニルアルコール１重量部を溶解させた水系溶液に懸濁させ、懸濁重合を行うことにより、有機ケイ素複合粒子を作製した。
得られた有機ケイ素複合粒子１０重量部と、エチルセルロース３０重量部と、トルエン３０重量部と、ＭＥＫ３０重量部とを、３本ロールで５分間混練し、バーコーターにより乾燥厚み２０μｍとなるように塗工し、乾燥させて、塗工体を作製した。
(Comparative Example 3)
(Manufacture of metal composite organic resin particles and coated bodies)
An oily substance consisting of 40 parts by weight of styrene, 30 parts by weight of divinylbenzene, 30 parts by weight of a silane coupling agent (KBM5103, acrylic group-containing silane coupling agent), 1 part by weight of benzoyl peroxide, 400 parts by weight of ion-exchanged water, polyvinyl Organosilicon composite particles were prepared by suspending in an aqueous solution in which 1 part by weight of alcohol was dissolved and performing suspension polymerization.
10 parts by weight of the obtained organosilicon composite particles, 30 parts by weight of ethyl cellulose, 30 parts by weight of toluene, and 30 parts by weight of MEK are kneaded with three rolls for 5 minutes, and coated with a bar coater to a dry thickness of 20 μm. And dried to produce a coated body.
（比較例４）
（多孔質有機樹脂粒子の製造）
ジビニルベンゼン１００重量部、ノルマルヘプタン３０重量部、過酸化ベンゾイル１重量部を溶解させて油系溶液とし、イオン交換水９００重量部、ポリビニルアルコール５重量部を溶解させた水系溶液に添加し、超音波ホモジナイザーにより１０分間乳化させた。セパラブルフラスコに乳化液を投入し、７５℃１２時間反応させて多孔質有機樹脂粒子スラリーを得た。吸引濾過により水系溶液を概略除去し、更にイオン交換水を加えて吸引濾過を繰り返し、イオン交換水で洗浄されたウェットケーキ状の多孔質有機樹脂粒子を得た。得られたウェットケーキを７０℃の熱風オーブンにて２４時間乾燥させ、多孔質有機樹脂粒子を作製した。
(Comparative Example 4)
(Manufacture of porous organic resin particles)
100 parts by weight of divinylbenzene, 30 parts by weight of normal heptane, and 1 part by weight of benzoyl peroxide are dissolved to obtain an oil-based solution, which is added to an aqueous solution in which 900 parts by weight of ion-exchanged water and 5 parts by weight of polyvinyl alcohol are dissolved. The mixture was emulsified with a sonic homogenizer for 10 minutes. The emulsified liquid was put into a separable flask and reacted at 75 ° C. for 12 hours to obtain a porous organic resin particle slurry. The aqueous solution was roughly removed by suction filtration, and ion exchange water was further added and suction filtration was repeated to obtain wet cake-like porous organic resin particles washed with ion exchange water. The obtained wet cake was dried in a hot air oven at 70 ° C. for 24 hours to produce porous organic resin particles.
得られた多孔質有機樹脂粒子について、走査型電子顕微鏡により１視野に約１００個が観察できる倍率で観察し、任意に選択した５０個の多孔質有機樹脂粒子についてノギスを用いて最長径を測定した。得られた最長径の数平均値を平均粒径とし、上記式（１）により個数基準粒子径の変動係数を算出たところ、平均粒子径は３μｍ、個数基準粒子径の変動係数は４５％であった。 The obtained porous organic resin particles are observed with a scanning electron microscope at a magnification at which about 100 particles can be observed in one field of view, and the arbitrarily selected 50 porous organic resin particles are measured for the longest diameter using calipers. did. The number average value of the obtained longest diameter was taken as the average particle diameter, and the variation coefficient of the number-based particle diameter was calculated by the above formula (1). The average particle diameter was 3 μm, and the variation coefficient of the number-based particle diameter was 45%. there were.
（金属複合有機樹脂粒子及び塗工体の製造）
得られた多孔質有機樹脂粒子を用いたこと以外は実施例５と同様にして、酸化ケイ素が多孔質有機樹脂粒子の細孔内に析出した酸化ケイ素複合粒子、及び、塗工体を作製した。
(Manufacture of metal composite organic resin particles and coated bodies)
Except having used the obtained porous organic resin particle, it carried out similarly to Example 5, and produced the silicon oxide composite particle in which the silicon oxide precipitated in the pore of the porous organic resin particle, and the coating body. .
（評価）
実施例、比較例で得られた金属複合有機樹脂粒子、塗工体について、以下の評価を行った。結果を表１に示す。
(Evaluation)
The following evaluation was performed about the metal composite organic resin particle and coating body which were obtained by the Example and the comparative example. The results are shown in Table 1.
（１）金属複合有機樹脂粒子の平均粒子径、個数基準粒子径の変動係数
得られた金属複合有機樹脂粒子について、走査型電子顕微鏡により１視野に約１００個が観察できる倍率で観察し、任意に選択した５０個の金属複合有機樹脂粒子についてノギスを用いて最長径を測定した。得られた最長径の数平均値を金属複合有機樹脂粒子の平均粒子径とした。金属複合有機樹脂粒子の個数基準粒子径の変動係数（ＣＶ３）は、得られた平均粒子径ｍ３と標準偏差σ３から、下記式（４）により算出した。
ＣＶ３＝σ３／ｍ３×１００（％） （４）
(1) Coefficient of variation of average particle diameter and number-based particle diameter of metal composite organic resin particles The obtained metal composite organic resin particles were observed with a scanning electron microscope at a magnification capable of observing about 100 particles in one field of view. The longest diameter was measured using calipers for the 50 metal composite organic resin particles selected in the above. The number average value of the longest diameters obtained was defined as the average particle diameter of the metal composite organic resin particles. The coefficient of variation (CV 3 ) of the number-based particle diameter of the metal composite organic resin particles was calculated from the obtained average particle diameter m 3 and standard deviation σ 3 by the following formula (4).
CV 3 = σ 3 / m 3 × 100 (%) (4)
（２）金属、金属酸化物又は金属塩の粒子径
得られた金属複合有機樹脂粒子をエポキシ樹脂に包埋し、ウルトラミクロトームで断面切片を採取した後、この断面切片について、ＴＥＭ／ＥＤＳ装置にて元素マッピング画像を得た。得られた元素マッピング画像１０点の金属、金属酸化物又は金属塩の個数平均粒子径を算出することにより、金属、金属酸化物又は金属塩の粒子径を評価した。
(2) Particle size of metal, metal oxide or metal salt The obtained metal composite organic resin particles were embedded in an epoxy resin, and a cross section was taken with an ultramicrotome. The element mapping image was obtained. The particle diameter of the metal, metal oxide or metal salt was evaluated by calculating the number average particle diameter of the obtained 10 element mapping images of metal, metal oxide or metal salt.
（３）金属、金属酸化物又は金属塩の含有量（金属複合有機樹脂粒子）
得られた金属複合有機樹脂粒子を約１ｇはかりとり、８００℃のマッフル炉で５時間加熱した。加熱前後の重量から、下記式（５）により、金属複合有機樹脂粒子全体に占める金属、金属酸化物又は金属塩の含有量を算出した。
含有量＝（１−（加熱後の粒子重量／加熱前の粒子重量））×１００（重量％） （５）
(3) Content of metal, metal oxide or metal salt (metal composite organic resin particles)
About 1 g of the obtained metal composite organic resin particles was weighed and heated in an 800 ° C. muffle furnace for 5 hours. From the weight before and after heating, the content of the metal, metal oxide or metal salt in the entire metal composite organic resin particles was calculated from the following formula (5).
Content = (1- (Particle weight after heating / Particle weight before heating)) × 100 (wt%) (5)
（４）金属、金属酸化物又は金属塩の分散性
得られた塗工体について、ウルトラミクロトームで断面切片を採取した後、この断面切片について、ＴＥＭ／ＥＤＳ装置にて元素マッピング画像を得た。得られた元素マッピング画像１μｍ四方中の元素粒子の数、元素粒子径、凝集の数から、金属、金属酸化物又は金属塩の分散性を評価した。３００ｎｍ以上の粒子又は凝集が存在する場合を「×」、存在しない場合を「○」とし、３００ｎｍ以上の粒子又は凝集が存在せず、かつ、金属複合有機樹脂粒子の凝集が存在しない場合を「◎」とした。
(4) Dispersibility of metal, metal oxide, or metal salt After obtaining a cross section of the obtained coated body with an ultramicrotome, an element mapping image was obtained for the cross section with a TEM / EDS apparatus. The dispersibility of the metal, metal oxide, or metal salt was evaluated from the number of element particles, element particle diameter, and number of aggregation in the obtained element mapping image 1 μm square. The case where particles of 300 nm or more or agglomeration are present is “x”, the case where they are not present is “◯”, the case where there is no particle or agglomeration of 300 nm or more, and the agglomeration of metal composite organic resin particles is not present “ ◎ ”.
（５）金属、金属酸化物又は金属塩の含有量（塗工体）
得られた塗工体について、塗膜をはがして約１ｇはかりとり、８００℃のマッフル炉で５時間加熱した。加熱前後の重量から、下記式（６）により、塗膜に占める金属、金属酸化物又は金属塩の含有量を算出した。
含有量＝（１−（加熱後の塗膜重量／加熱前の塗膜重量））×１００（重量％） （６）
(5) Content of metal, metal oxide or metal salt (coating body)
About 1 g of the obtained coated body was peeled off and weighed, and heated in an muffle furnace at 800 ° C. for 5 hours. From the weight before and after the heating, the content of the metal, metal oxide or metal salt in the coating film was calculated by the following formula (6).
Content = (1− (weight of coating film after heating / weight of coating film before heating)) × 100 (% by weight) (6)
本発明によれば、粒子径が極めて均一な金属複合有機樹脂粒子を提供することができる。また、本発明によれば、該金属複合有機樹脂粒子の製造方法を提供することができる。 According to the present invention, metal composite organic resin particles having a very uniform particle diameter can be provided. Moreover, according to this invention, the manufacturing method of this metal composite organic resin particle can be provided.
Claims (7)
前記多孔質有機樹脂粒子は、個数基準粒子径の変動係数が１０％以下である
ことを特徴とする金属複合有機樹脂粒子。 Metal composite organic resin particles having metal, metal oxide or metal salt in the pores of the porous organic resin particles,
The porous organic resin particles have a coefficient of variation in number-based particle diameter of 10% or less.
非架橋ポリマーを含有する種粒子を、水を含有する分散媒中に分散させた種粒子分散液と、ラジカル重合性モノマーと、油溶性溶剤と、油溶性重合開始剤とを混合し、前記種粒子に前記ラジカル重合性モノマーと、前記油溶性溶剤と、前記油溶性重合開始剤とを吸収させて膨潤粒子液滴の分散液を調製する工程と、
前記膨潤粒子液滴中の前記ラジカル重合性モノマーを重合させる工程とを有する
方法により得られることを特徴とする請求項１、２又は３記載の金属複合有機樹脂粒子。 Porous organic resin particles
A seed particle dispersion in which seed particles containing a non-crosslinked polymer are dispersed in a dispersion medium containing water, a radical polymerizable monomer, an oil-soluble solvent, and an oil-soluble polymerization initiator are mixed, and the seeds are mixed. A step of making the particles absorb the radical polymerizable monomer, the oil-soluble solvent, and the oil-soluble polymerization initiator to prepare a dispersion of swollen particle droplets;
The metal composite organic resin particle according to claim 1, 2 or 3, wherein the metal composite organic resin particle is obtained by a method comprising polymerizing the radical polymerizable monomer in the swollen particle droplet.
水を主成分とする媒体中に多孔質有機樹脂粒子と金属イオンとを共存させた分散液を調製する工程と、
前記金属イオンを中和、還元若しくは酸化するか、又は、前記金属イオンの溶解度を低下させることにより、前記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程とを有する
ことを特徴とする金属複合有機樹脂粒子の製造方法。 A method for producing the metal composite organic resin particles according to claim 1, 2, 3, 4 or 5,
Preparing a dispersion in which porous organic resin particles and metal ions coexist in a water-based medium;
A step of precipitating a metal, a metal oxide or a metal salt in the pores of the porous organic resin particles by neutralizing, reducing or oxidizing the metal ions or reducing the solubility of the metal ions; The manufacturing method of the metal composite organic resin particle characterized by having.
多孔質有機樹脂粒子と金属アルコキシドとを共存させた分散液を調製する工程と、
前記金属アルコキシドを加水分解及び／又は脱水縮合することにより、前記多孔質有機樹脂粒子の細孔内に金属、金属酸化物又は金属塩を析出させる工程とを有する
ことを特徴とする金属複合有機樹脂粒子の製造方法。 A method for producing the metal composite organic resin particles according to claim 1, 2, 3, 4 or 5,
Preparing a dispersion in which porous organic resin particles and metal alkoxide coexist;
A metal composite organic resin comprising a step of precipitating a metal, a metal oxide or a metal salt in the pores of the porous organic resin particles by hydrolyzing and / or dehydrating and condensing the metal alkoxide. Particle production method.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |