JP4066754B2 - Magnetic substance-containing resin fine particles and method for producing the same - Google Patents
Magnetic substance-containing resin fine particles and method for producing the same Download PDFInfo
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- JP4066754B2 JP4066754B2 JP2002267619A JP2002267619A JP4066754B2 JP 4066754 B2 JP4066754 B2 JP 4066754B2 JP 2002267619 A JP2002267619 A JP 2002267619A JP 2002267619 A JP2002267619 A JP 2002267619A JP 4066754 B2 JP4066754 B2 JP 4066754B2
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- Japan
- Prior art keywords
- resin fine
- fine particles
- magnetic substance
- particles
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000005291 magnetic effect Effects 0.000 title claims description 70
- 239000000126 substance Substances 0.000 title claims description 53
- 239000011347 resin Substances 0.000 title claims description 49
- 229920005989 resin Polymers 0.000 title claims description 49
- 239000010419 fine particle Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 230000005298 paramagnetic effect Effects 0.000 claims description 11
- 239000006249 magnetic particle Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000002296 dynamic light scattering Methods 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 230000002794 monomerizing effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- -1 iron ions Chemical class 0.000 description 22
- 239000004094 surface-active agent Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000000696 magnetic material Substances 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IZHVBANLECCAGF-UHFFFAOYSA-N 2-hydroxy-3-(octadecanoyloxy)propyl octadecanoate Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCCCCCCCCCCC IZHVBANLECCAGF-UHFFFAOYSA-N 0.000 description 2
- PCGDWIWUQDHQLK-UHFFFAOYSA-N 2-morpholin-4-yl-5-nitrobenzaldehyde Chemical compound O=CC1=CC([N+](=O)[O-])=CC=C1N1CCOCC1 PCGDWIWUQDHQLK-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004064 cosurfactant Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000011553 magnetic fluid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229930015698 phenylpropene Natural products 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VEJIQHRMIYFYPS-UHFFFAOYSA-N (3-phenyl-1,2-oxazol-5-yl)boronic acid Chemical compound O1C(B(O)O)=CC(C=2C=CC=CC=2)=N1 VEJIQHRMIYFYPS-UHFFFAOYSA-N 0.000 description 1
- FONWXYJNYDZEEY-UPHRSURJSA-N (z)-4-(hydroxymethylamino)-4-oxobut-2-enoic acid Chemical compound OCNC(=O)\C=C/C(O)=O FONWXYJNYDZEEY-UPHRSURJSA-N 0.000 description 1
- ZWUBFMWIQJSEQS-UHFFFAOYSA-N 1,1-bis(ethenyl)cyclohexane Chemical compound C=CC1(C=C)CCCCC1 ZWUBFMWIQJSEQS-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- OSUBTVWFZGWNKI-XOKGJFMYSA-N 1,3-bis[(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC(\C=C\C)=C1 OSUBTVWFZGWNKI-XOKGJFMYSA-N 0.000 description 1
- BHPDNFUVYQFFNK-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrole-2,5-dione Chemical compound OCN1C(=O)C=CC1=O BHPDNFUVYQFFNK-UHFFFAOYSA-N 0.000 description 1
- DIOFTWYEZJWBHO-UHFFFAOYSA-N 1-dodecoxy-4-ethenoxy-1,4-dioxobutane-2-sulfonic acid Chemical compound CCCCCCCCCCCCOC(=O)C(CC(=O)OC=C)S(O)(=O)=O DIOFTWYEZJWBHO-UHFFFAOYSA-N 0.000 description 1
- YEBQUUKDSJCPIX-UHFFFAOYSA-N 12h-benzo[a]thioxanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4SC3=CC=C21 YEBQUUKDSJCPIX-UHFFFAOYSA-N 0.000 description 1
- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 description 1
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical compound N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- IHAYMIVQKCTBBS-UHFFFAOYSA-N 2-[2-(2-hydroxyethyl)phenyl]ethanol Chemical compound OCCC1=CC=CC=C1CCO IHAYMIVQKCTBBS-UHFFFAOYSA-N 0.000 description 1
- DXWHZJXKTHGHQF-UHFFFAOYSA-N 2-butyl-6-(butylamino)benzo[de]isoquinoline-1,3-dione Chemical compound O=C1N(CCCC)C(=O)C2=CC=CC3=C2C1=CC=C3NCCCC DXWHZJXKTHGHQF-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- MHJFWPOZAIOCQL-UHFFFAOYSA-N 2-phenylpropan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)C(=O)OOC(C)(C)C1=CC=CC=C1 MHJFWPOZAIOCQL-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
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CBNSBRVOBGWOBM-UHFFFAOYSA-N 3-(5-chlorobenzoxazol-2-yl)-7-diethylaminocoumarin Chemical compound ClC1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 CBNSBRVOBGWOBM-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、磁性体含有樹脂微粒子、特には平均粒径が小さく、粒径分布が狭く、かつ磁性体含有率が高い粒子に関するものである。このような磁性体含有樹脂簿粒子は、診断薬担体、細胞分離担体、核酸分離担体、タンパク質分離担体、ドラッグデリバリー担体、磁性インク等の用途において有用なものである。
【０００２】
【従来技術】
粒子内部に磁性体が存在する磁性体含有樹脂微粒子の合成方法としては、１）懸濁重合法を用いるもの、２）乳化重合法を用いるもの（例えば、特許文献１参照）、３）ミニエマルジョン重合法を用いるもの（例えば、非特許文献１参照）が知られている。
【０００３】
しかしながら、懸濁重合を用いた場合、一般的には粒径分布が広くなる上、通常、得られる粒子は平均粒径が１μｍを超える様な大きなものである（例えば、特許文献２参照。）。
又、懸濁重合でも平均粒径が小さな粒子を得た例はあるが（例えば、特許文献３参照。）、特定のモノマー種を用いる必要があり、スチレン等の汎用性のあるモノマーでは分散性が悪いものしか得られていない。
【０００４】
従って、粒径分布が広いことに起因する安定な磁力を持つ均一な粒子を得られないと言う問題に加え、粒子径が大きいことによる重量当たりの磁力が弱いという問題またはモノマー種が限定されると言う問題から診断等の分野で実用化するに当たっては未だ不十分であった。
また、乳化重合の場合、粒径の小さい樹脂微粒子は得られやすいものの、そのメカニズム的に、反応液内で磁性体粒子がミセル中に移動し、取り込まれる必要がある。従って、この場合、樹脂微粒子内の磁性体含有量が低くなるため、未だ磁気沈降性の良好な磁性ポリマー粒子を再現性よく得るには至っていない。
【０００５】
さらに、非特許文献１には、ミニエマルション重合法を用いて酸化鉄をポリスチレン粒子にカプセル化した写真が掲載されているものの、その具体的製法は記載されておらず、また、その写真を見る限りでは、酸化鉄コロイドは粒子の一部分が表面に偏っているため、鉄イオンの溶出の可能性もあり、実用化には未だ不十分なものと考えられる。
【０００６】
【特許文献１】
特公平３−５７９２１号公報
【特許文献２】
特開平１０−８７７１１号公報（第４頁、合成例１）
【特許文献３】
特開平９−２０８７８８号公報（第６頁〜第８頁）
【非特許文献１】
K.Landfester, Macromol. Rapid Commun.（2001）,22,p.896-936
【０００７】
【発明が解決しようとする課題】
以上のように、従来の製造法で得られる磁性体含有ポリマー粒子は、その粒子径、粒径分布、磁性体含有量及び磁力等の点において未だ不十分であり、実用性は低いものであった。
従って、本発明の課題は、平均粒径が小さく、単分散性の高く、加えて、小粒径であっても磁石に容易に引きつけられる、磁力の強い磁性体含有樹脂微粒子を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは上記課題を解決するために、鋭意検討した結果、ミニエマルジョン重合法を用いて磁性体含有樹脂微粒子を製造するに当たり、予め、有機溶媒中に常磁性体粒子を分散させた分散液を用いると、小粒径で粒径分布も狭く、且つ、磁性体含有率の高い磁性体含有樹脂微粒子を得ることができることを見出し、本発明を完成するに至った。すなわち、本発明の要旨は、動的光散乱法により測定した重量平均粒径が０．２〜１μｍであり、同じく動的光散乱法により測定した数平均粒径に対する該重量平均粒径の比が１．２未満の樹脂微粒子であって、該樹脂微粒子を構成する樹脂がエチレン性不飽和結合を有する化合物の重合体であって過硫酸塩からなる重合開始剤の残基を有すると共に、該樹脂微粒子中に常磁性体粒子を１０重量％以上含有し、且つ、電子顕微鏡による観察で樹脂微粒子表面に磁性体粒子の露出が認められないことを特徴とする磁性体含有樹脂微粒子及びその製造方法に存する。
【０００９】
【発明の実施の形態】
以下、本発明の磁性体含有樹脂微粒子について詳細に説明する。
１，磁性体含有樹脂微粒子
本発明の磁性体含有樹脂微粒子は、重量平均粒径が０．２〜１μｍであり、動的光散乱法により測定した数平均粒径に対する重量平均粒径との比１．２未満であり、かつ、樹脂微粒子中の常磁性体粒子含有量が１０重量％以上のものである。
上記の平均粒径は、例えば、ハネウェル社製「Microtrack UPA」等の一般的な動的光散乱装置を用いて測定することができる。
粒径分布は、数平均粒径に対する重量平均粒径との比（Dw/Dn）で表すことができ、好ましくは１．１未満であり、より好ましくは１．０５未満である。
【００１０】
（磁性体）
本発明の磁性体含有樹脂微粒子中に含まれる常磁性体粒子は、目的に応じて任意に使用できるが、磁性体粒子に５０００エールステッドの強い磁場をかけた後、ゼロ磁場に戻したときの磁化（残留磁化）が５０００エールステッドの磁場のときの磁化（飽和磁化）の１／３以下となる磁性体が好ましく、例えば四三酸化鉄（Fe3O4）、γ-重三二酸化鉄（γ-Fe2O3）等の各種フェライト類；鉄、マンガン、コバルト等の金属、若しくはそれらの合金などが挙げられる。診断等の用途では樹脂微粒子の磁力が強いものが要求される傾向にあるため、これらのうち強磁性体に分類されるものの方が好ましく、より好ましくはフェライト類であり、特にはFe3O4が好ましい。
【００１１】
常磁性体粒子の粒径は、目的とする上記樹脂微粒子の粒径より小さいものを用いる。ここで、磁性体が樹脂微粒子の表面に露出することを避けるためには、通常、５０ｎｍ以下、好ましくは３０ｎｍ以下、より好ましくは２０ｎｍ以下の粒径の磁性体を用いる。一方で、磁性体粒子が小さくなればなるほど、ミニエマルション液滴の中に安定に磁性体粒子を分散させるのが難しくなることから、通常、３ｎｍ以上、好ましくは５ｎｍ以上、より好ましくは６ｎｍ以上のものを用いる。
【００１２】
上記磁性体の市販品の例としては、磁性流体 フェリコロイドHC-50（タイホー工業）、ＨＸ―２０（シグマハイケミカル）等が挙げられる。
樹脂微粒子中の上記磁性体粒子の含有率としては、ポリマー重量に対して１０重量％以上含有される。十分な磁気応答性を発現するためには磁性体含有量が高い方が好ましく、好ましくは含有率が２０重量％以上であり、より好ましくは２５重量％以上であり、さらに好ましくは３０重量％以上である。一方で、磁性体が樹脂微粒子の表面に露出することを避けるために磁性体含有率は、通常、７０重量％以下であり、好ましくは６０重量％以下であり、特に好ましくは５０重量％以下である。
【００１３】
２，磁性体含有樹脂微粒子の製造方法
上述の磁性体含有樹脂微粒子は、予め、脂肪族炭化水素系溶媒を含有する有機溶媒中に常磁性体粒子を分散させた分散液を用いてミニエマルジョン重合を行うこと、すなわち、脂肪族炭化水素系溶媒を含有する有機溶媒中に常磁性体粒子を分散させた分散液とモノマーとして用いるエチレン性不飽和結合を有する化合物とを接触させた後、これらを水中で微分散させ、さらに該モノマーを重合させることにより製造することができる。
【００１４】
上記常磁性体粒子を分散させる有機溶媒としては、脂肪族炭化水素系溶媒を含有しており、磁性体を溶解する等の悪影響を与えず、且つモノマーと混合可能なものであれば特に限定されない。
上記脂肪族炭化水素系溶媒としては、少なくともペンタン、ヘキサン、ヘプタン、イソブタン、イソペンタン等の直鎖、分岐若しくは環状のものが挙げられ、炭素数５〜２０の直鎖又は分岐のものであり、特に好ましくは炭素数５〜７のものである。また、上述の脂肪族炭化水素系溶媒は単独でも、それらを混合したものを用いても良い。
【００１５】
上記混合溶媒の代表例としては、ケロシンが挙げられる。
この場合、常磁性体粒子を分散させる有機溶媒中における脂肪族炭化水素系溶媒の含有割合としては、全有機溶媒量にも依存するが、通常、５０重量％以上、好ましくは６０重量％以上、より好ましくは７０重量％以上、更に好ましくは８０重量％以上、特に好ましくは９０重量％以上である。
【００１６】
有機溶媒の使用量は、通常、磁性体に対して重量で０．１％以上、好ましくは１％以上、特に好ましくは１０％以上の範囲で用いられる。但し、有機溶媒が多すぎるとミニエマルジョン重合後の残存溶媒の除去が必要となる等、操作が煩雑になるため、用いる溶媒の沸点にもよるが、通常、５００％以下、好ましくは３００％以下、特に好ましくは２５０％以下である。このとき、沸点が高い溶媒を用いる場合はより少ない量を用いるのが好ましい。
【００１７】
さらに、沸点が高い溶媒を用いる場合は、分散液をモノマーと接触させる時点で下記に例示するような界面活性剤、特には反応性界面活性剤の共存下で接触させるのが好ましい。
上記磁性体分散液を得るための好ましい具体的な方法としては、市販の磁性流体を任意の温度、例えば６０℃以上１５０℃以下、好ましくは１２０℃以下の温度で処理し、溶媒を揮発させた後、ヘキサンを加え、磁性体を再分散させる方法が挙げられる。
【００１８】
上記で得られる磁性体の分散液をモノマーと接触させ一般的なミニエマルジョン重合の手法を用いることにより、本発明の磁性体含有樹脂微粒子を製造することができる。
すなわち、磁性体分散液とモノマーとして用いるエチレン性不飽和結合を有する化合物とを接触させ、水中に微分散させた後、該モノマーを重合させるものである。
【００１９】
（エチレン性不飽和結合を有する化合物）
本発明でモノマーとして用いられるエチレン性不飽和結合を有する化合物としては、重合可能なモノマーであれば制限なく使用することが出来る。ラジカル重合において用いられるモノマーの具体例としては、スチレン、クロルスチレン、α-メチルスチレン、ジビニルベンゼン、ビニルトルエン等の重合性不飽和芳香族類；（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸などの重合性不飽和カルボン酸類；スチレンスルホン酸ソーダ等の重合性不飽和スルホン酸もしくはその塩；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸-ｎ-ブチル、（メタ）アクリル酸-２-ヒドロキシエチル、（メタ）アクリル酸グリシジル、エチレングリコール-ジ-（メタ）アクリル酸エステル、（メタ）アクリル酸トリブロモフェニル等の重合性カルボン酸エステル類；（メタ）アクリロニトリル、（メタ）アクロレイン、（メタ）アクリルアミド、メチレンビス（メタ）アクリルアミド、ブタジエン、イソプレン、酢酸ビニル、ビニルピリジン、Ｎ-ビニルピロリドン、塩化ビニル、塩化ビニリデン、臭化ビニル等の不飽和カルボン酸アミド類、重合性不飽和ニトリル類、ハロゲン化ビニル類、共役ジエン類；ポリスチレン、ポリエチレングリコール、ポリメチルメタクリレートのなどの高分子量セグメントに、ビニル基、メタクリロイル基、ジヒドロキシル基などの重合可能な官能基を持つマクロモノマー類などが挙げられる。
【００２０】
また、本発明で用いられるモノマーは付加重合で用いられるようなモノマーも使用できる。重付加に用いられるモノマーの具体例としては、ジフェニルメタンジイソシアナート、ナフタレンジイソシアナート、トリレンジイソシアナート、テトラメチルキシレンジイソシアナート、キシレンジイソシアナート、ジシクロヘキサンジイソシアナート、ジシクロヘキシルメタンジイソシアナート、ヘキサメチレンジイソシアナート、イソホロンジイソシアナートのような脂肪族又は芳香族イソシアナート類、ケテン類、エポキシ基含有化合物類、ビニル基含有化合物類が挙げられ、また、上記化合物群と反応させるモノマーとしては、活性化水素を有する官能基、具体例としては水酸基又はアミノ基を有する化合物が挙げられ、具体的には、エチレングリコール、ジエチレングリコール、プロピレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、メチレングリコシド、しょ糖、ビス（ヒドロキシエチル）ベンゼンのようなポリオール類；エチレンジアミン、ヘキサメチレンジアミン、N,N'-ジイソプロピルメチレンジアミン、N,N'-ジ-sec-ブチル-p-フェニレンジアミン、1,3,5-トリアミノベンゼンのようなポリアミン類；オキシム類などが挙げられる。
【００２１】
上記モノマーは、単独で用いても良いし、２種以上を混合して用いても良い。
このうち、好ましくはラジカル重合において用いられるモノマーであり、より好ましくはスチレン類、又は、（メタ）アクリル酸及びそのエステル類であり、更に好ましくはスチレン、（メタ）アクリル酸、（メタ）アクリル酸のＣ1〜Ｃ4アルキルエステル又は（メタ）アクリル酸グリシジルである。
【００２２】
また、上記モノマーの他、架橋剤となりうる多官能性化合物を共存させても良い。
該多官能性化合物としては、例えば、Ｎ-メチロールアクリルアミド、Ｎ-エタノールアクリルアミド、Ｎ-プロパノールアクリルアミド、Ｎ-メチロールマレイミド、Ｎ-エチロールマレイミド、Ｎ-メチロールマレインアミド酸、Ｎ-メチロールマレインアミド酸エステル、ビニル芳香族酸のＮ-アルキロールアミド（例えばＮ-メチロール-ｐ-ビニルベンズアミド等）、Ｎ-（イソブトキシメチル）アクリルアミド等が挙げられる。さらに、上述のモノマーのうち、ジビニルベンゼン、ジビニルナフタレン、ジビニルシクロヘキサン、１，３-ジプロペニルベンゼン、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、ジエチレングリコールジ（メタ）アクリレート、ブチレングリコール、トリメチロールエタントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等の多官能性モノマー類は、架橋剤としても使用することが出来る。
【００２３】
（界面活性剤）
ミニエマルジョン重合においては、モノマーの液滴を水中に安定的に微分散させるために、界面活性剤及び共界面活性剤の共存下で分散を行う。
本発明で使用する界面活性剤としては、従来のラテックス重合に使用できるものであれば特に制限されない。例えば、アニオン系界面活性剤としては、ドデシルベンゼンスルホネート、デシルベンゼンスルホネート、ウンデシルベンゼンスルホネート、トリデシルベンゼンスルホネート、ノニルベンゼンスルホネート並びにこれらのナトリウム、カリウム、アンモニウム塩などが挙げられ、カチオン系界面活性剤としては、セチルトリメチルアンモニウムプロミド、塩化ヘキサデシルピリジニウム、塩化ヘキサデシルトリメチルアンモニウム等が挙げられる。また、ノニオン系界面活性剤としては、ポリビニルアルコールの他、各種のものが市販されており、例えば、ユニオンカーバイド社製の「Ｔｒｉｔｏｎ」（Ｘ-１００、Ｘ-１１４、Ｘ-３０５、Ｎ-１０１）、アイ・シー・アイ社製の「Ｔｗｅｅｎ」（２０、４０、６０、８０、８５）、アイ・シー・アイ社製の「Ｂｒｉｊ」（３５、５８、７６、９８）、シェル社製の「Ｎｏｎｉｄｅｔ」（Ｐ-４０）、ローヌ・プーラン社製の「Ｉｇｅｐｏｌ」（ＣＯ５３０、ＣＯ６３０、ＣＯ７２０、ＣＯ７３０）等が挙げられる。
【００２４】
このうち好ましくはアニオン性界面活性剤である。
また、前記油溶性モノマーと重合可能なアニオン、カチオン、ノニオン反応性界面活性剤を用いることもできる。その反応性界面活性剤における反応基として、例えば、ビニル基、アリル基、（メタ）アクリロイル基等のエチレン性不飽和基を有するものであるのが好ましい。それらの反応性界面活性剤としては、前記反応性基を有する限り、通常の界面活性能を有するものであれば良く、例えば、特開平９−２７９０７３号公報等に記載されるものがあげられ、具体的には、例えば、ラウリル（アリルベンゼン）スルホン酸塩、ラウリルスチレンスルホン酸塩、ステアリル（アリルベンゼン）スルホン酸塩、ステアリルスチレンスルホン酸塩等のアルキルベンゼンスルホン酸塩類、およびそれらのポリエチレンオキサイド付加物類、ラウリルアリルスルホ琥珀酸エステル、ラウリルビニルスルホ琥珀酸エステル、ステアリルアリルスルホ琥珀酸エステル、ステアリルビニルスルホ琥珀酸エステル等のアルキルスルホ琥珀酸エステル類、及びそれらのポリエチレンオキサイド付加物類、（メタ）アクリル酸ラウリルスルホン酸塩、オレイルスルホン酸塩等のアルキルまたはアルケニルスルホン酸塩類、（メタ）アクリル酸ステアリル硫酸塩、オレイル硫酸塩等のアルキル又はアルケニル硫酸塩類、及びそれらのポリエチレンオキサイド付加物類等ののアニオン性界面活性剤、ラウリルトリアリルアンモニウムクロライド、ステアリルトリアリルアンモニウムクロライド、ジステアリルジアリルアンモニウムクロライド等の第４級アンモニウム塩類等のカチオン性界面活性剤、ポリエチレングリコールオクチル（アリルフェニル）エーテル、ポリエチレングリコールノニル（アリルフェニル）エーテル、ポリエチレングリコールオレイルフェニルエーテル等のポリエチレングリコールアルキル又はアルケニルフェニルエーテル類、モノステアリル酸モノアリルグリセリル、ジステアリン酸モノアリルグリセリル等のグリセリン脂肪酸エステル類、及びそれらのポリエチレンオキサイド付加物類、モノステアリン酸モノアリルソルビタン、トリステアリン酸モノアリルソルビタン等のソルビタン脂肪酸エステル類、及びそれらのポリエチレンオキサイド付加物類、ポリエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート等の（メタ）アクリル酸のポリエチレンオキサイドエステル類等のノニオン性界面活性剤等を挙げることができる。
【００２５】
尚、これらの反応性界面活性剤は、前記アニオン性界面活性剤としては、例えば、第一工業製薬社より「アクアロン ＨＳ−１０」、日本乳化剤社より「Ａｎｔｏｘ−ＭＳ−６０」、「ＲＡ−１０００シリーズ」、「Ａｎｔｏｘ−ＭＳ−２Ｎ」、旭電化工業社より「アデカリアソープ ＳＥ−１０Ｎ」、花王社より「テラムル Ｓ−１８０Ａ」、三洋化成工業社より「エレミノール ＪＳ−２」等の商品名で、また、前記カチオン性界面活性剤としては、例えば、日本乳化剤社より「ＲＦ―７５１」等の商品名で、又、前記ノニオン性界面活性剤としては、例えば、旭電化工業社より「アデカリアソープ ＮＥ−１０」、日本油脂社より「ブレンマー ＰＥ−２００」、「ブレンマー ＰＥ−３５０」、「ブレンマー ＰＥ−４００」等の商品名で、それぞれ市販されている。
【００２６】
上記界面活性剤は、単独で用いても良いし、２種以上を混合して用いても良い。
界面活性剤の使用量としてはモノマー１００重量部に対し、０．０１重量部以上、好ましくは０．１重量部以上であり、特に好ましくは０．５重量部以上である。また、通常、５０重量部以下、好ましくは３０重量部以下の範囲で用いられる。
【００２７】
（共界面活性剤）
本発明で用いられる共界面活性剤としてはミニエマルジョン重合で一般的に用いられているものであれば特に限定されないが、具体的には（ａ）ヘキサデカン、スクアラン、シクロオクタン等のＣ8〜Ｃ30の直鎖、分岐鎖、環状アルカン類、（ｂ）ステアリルメタクリレート、ドデシルメタクリレート等のＣ8〜Ｃ30アルキルアクリレート、（ｃ）セチルアルコール等のＣ8〜Ｃ30アルキルアルコール、（ｄ）ドデシルメルカプタン等のＣ8〜Ｃ30アルキルチオール、（ｅ）ポリウレタン、ポリエステル、ポリスチレン等のポリマー類（ｆ）その他、長鎖脂肪族又は芳香族カルボン酸類、長鎖脂肪族又は芳香族カルボン酸エステル類、長鎖脂肪族又は芳香族アミン類、ケトン類、ハロゲン化アルカン類、シラン類、シロキサン類、イソシアネート類などが挙げられる。過酸化ラウロイルなどの長鎖の油溶性開始剤を使用することもできる。このうち好ましくは、炭素数が１２以上のものであり、より好ましくは炭素数１２〜２０のアルカン類である。
【００２８】
また、油溶性染料やベンゾチオキサンテン、キサンテン、クマリン、ナフタルイミド、ベンゾキサンテン、ペリレン、アクリジンなどの各種の蛍光染料（または蛍光増白剤）などの有機化合物であっても、水に対する溶解度が０．０１ｇ/L以下であり、油溶性モノマーに可溶であれば使用することが可能である。その具体例としては、ソルベントブルー、ソルベントレッド、ソルベントオレンジ、ソルベントグリーン、蛍光増白剤「UVITEX OB(2,5-thiphenediylbis(5-tert-butyl-1,3-benzoxazole, Chiba Speciality Chemicals社製)、クマリン系黄色蛍光染料「MACROLEX Fluorescent Yellow 10GN」（Solvent Yellow 160:1, BAYER社製）、クマリン系赤色蛍光染料「MACROLEX Fluorescent Red G」（BAYER社製）、その他「Basic Red1」（BASFよりBasonyl Red 482として市販のカチオンRhodamine F5G染料）、「Basic Violet11」（BASFよりBasonyl Red 560として市販のBasic Violet 11:1のカチオンRhodamine B染料）、「Basic Yellow 40」（Ciba-GigyよりMaxilon Brilliant Flavine 10GFFとして市販のノニオンCoumarin染料）、「Solvent Yellow 43」（Day-Glo Color社よりHudson Yellowとして市販のノニオンNaphthalimide染料）、「Solvent Yellow 44」（Day-Glo Color社よりAlberta Yellowとして市販のノニオンCoumarine染料）、「Solvent Yellow 160」（Day-Glo Color社よりPotomac Yellowとして市販のノニオンCoumarine染料）等が挙げられる。
【００２９】
さらには、ジシアノピニル系、アゾ系（例えば、ピリドンアゾ系、ジスアゾ系、トリスアゾ系、ベンゼンアゾ系、ヘテロ環アゾ系なそ）、キノフタロン系、アミノピラゾール系、メチン系、ジシアノイミダゾール系、インドアニリン系、フタロシアニン系も好適に使用しうる。これらの中では、アゾ系、フタロシアニン系、アントラキノン系が好ましく、これらの染料は、２種以上を混合して使用してもよい。
上記共界面活性剤の使用量は、モノマーに対して通常０．１〜１００重量％の範囲から選択される。
【００３０】
（重合開始剤）
本発明で使用可能なラジカル系重合開始剤の例としては、例えば２，２’-アゾビスイソブチロニトリル、２，２’- アゾビス-（２-メチルプロパンニトリル） 、２，２’-アゾビス-（２，４-ジメチルペンタンニトリル） 、２，２’-アゾビス-（２-メチルブタンニトリル） 、１，１’-アゾビス-（シクロヘキサンカルボニトリル） 、２，２’- アゾビス-（２，４-ジメチル-４-メトキシバレロニトリル） 、２，２’- アゾビス-（２，４-ジメチルバレロニトリル）、２，２’-アゾビス-（２-アミジノプロパン）ヒドロクロリド等のアゾ（アゾビスニトリル）タイプの開始剤、過酸化ベンゾイル、クメンヒドロペルオキシド、過酸化水素、過酸化アセチル、過酸化ラウロイル、過硫酸塩（例えば過硫酸アンモニウム）、過酸エステル（例えばｔ-ブチルペルオクテート、α-クミルペルオキシピバレート及びｔ-ブチルペルオクテート）等の過酸化物タイプの開始剤が挙げられる。
【００３１】
レドックス系開始剤としては、例えば、アスコルビン酸／硫酸鉄（ＩＩ）／ペルオキシ二硫酸ナトリウム、第三ブチルヒドロペルオキシド／二亜硫酸ナトリウム、第三ブチルヒドロペルオキシド／Ｎａヒドロキシメタンスルフィン酸が挙げられる。なお、個々の成分、例えば還元成分は、混合物、例えばヒドロキシメタンスルフィン酸のナトリウム塩と二亜硫酸ナトリウムとの混合物であってもよい。
重合開始剤の使用量は、モノマーに対し、通常０．１〜３０ｗｔ％の範囲から選択され、これらの重合開始剤は磁性体含有モノマーエマルジョン作成時に添加しておいても良いし、磁性体含有モノマーエマルジョン作製後に添加しても良い。
【００３２】
（反応様式）
上記磁性体分散液とモノマーとの接触・水分散に当たっては、１）磁性体分散液にエチレン性不飽和化合物を加えた後、該混合液を水中に加え、微分散させる方法、２）磁性体分散液とエチレン性不飽和化合物とを同時に水中に加えた後、微分散させる方法、３）磁性体分散液を水に分散させた後、エチレン性不飽和化合物を加えた後、さらに分散させる方法等、任意の反応様式を取ることができるが、好ましくは上記１）の方法であり、斯かるミニエマルションの調製は、公知の方法を利用し、共界面活性剤を含有する磁性体分散モノマー溶液（Ａ液）と界面活性剤の水溶液（Ｂ液）とを高いせん断力を有するせん断混合装置によって均一に乳化する方法で行うことが好ましい。
【００３３】
また、せん断混合装置としては、例えば、ピストンホモジナイザー、マイクロ流動化装置（Microfluidizer：登録商標）、超音波分散機などが使用される。斯かる粒子径は、使用する界面活性剤の量・乳化するモノマー量によって調節することが出来る。
次いで、本発明の製造方法においては、上記の方法でミニエマルジョンを調整した後、重合開始剤の存在下にミニエマルションの重合を行う。
【００３４】
重合開始剤は、前記のＡ液およびＢ液の何れに添加してもよい。重合温度は、通常、３０〜９５℃、好ましくは５０〜９５℃の範囲から選択される。また、重合時間は通常５〜６時間以上反応させれば十分である。
重合後の粒子は、透析法、遠心分離法、イオン交換樹脂による精製等、一般的な単離精製方法を用い、得ることができる。具体的には、透析法は、重合後の粒子を半透膜である透析チューブに入れ、外部を純水にすることにより透析操作を行い精製を行う方法であり、遠心分離法は、遠心分離操作により粒子を沈降させ、上澄みを取り除いた後に、純水に置換することで精製する方法であり、イオン交換樹脂による精製法は、イオン交換樹脂を通すことにより精製を行う方法である。このうち、最も簡単な方法は遠心分離法であるが、最も効果の高い方法はイオン交換樹脂法である。
【００３５】
本発明の磁性体含有樹脂微粒子は、上述のモノマーを適宜選択することにより、用途に応じた適当な表面修飾を行うこともできる。
具体的には、アクリル酸。メタクリル酸等のカルボキシル基を持つモノマーを共重合モノマーとして用いた場合には、粒子表面にある該モノマー由来のカルボキシル基とタンパク質のアミノ基を共有結合させることでタンパク質を固定化することができる。
【００３６】
また、グリシジルメタクリレートを用いた場合には、粒子表面にある該モノマー由来のエポキシ基に直接タンパク質を固定化してもよいし、このエポキシ基にカルボキシル基やアミノ基を導入してからタンパク質を共有結合させることもできる。
さらに、上記のエポキシ基を導入した粒子表面に、末端にアミノ基やカルボキシル基を有するポリエチレングリコールのオリゴマー・ポリマーを固定化し、タンパク質の非特異吸着を抑制してから目的のタンパク質のみを固定化することもできる。
【００３７】
【実施例】
以下に、実施例を示し、さらに詳しく本発明について説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。
実施例１
磁性流体「フェリコロイドＨＣ５０」（タイホー工業（株）製）１．０ｇ（磁性体０．５ｇ含有）をインキュベーター中で８０℃にて１２時間乾燥し、０．３ｇのケロシンを除去して、濃縮された超常磁性体０．７ｇを得た。濃縮後の磁性体にスチレン３ｇ、ヘキサデカン０．２３ｇ、重合性界面活性剤「ＮＥ−２０（旭電化工業社製）」０．０１ｇを入れ、さらにカップ型ソニケーターで処理することで、超常磁性体のモノマー分散液を得た（以下、A液と称する。）。
【００３８】
水１０ｇにドデシルベンゼンスルホン酸ナトリウム０．０６ｇ、過硫酸アンモニウム０．０５ｇを溶解させた（以下、Ｂ液と称する。）。
Ｂ液中にA液を入れ、超音波破砕機（タイテック社製ＶＰ−３０Ｓ，目盛り５）を用い、氷冷下で１０分間処理することで磁性体を含むミニエマルション液滴を作製した。
【００３９】
このミニエマルション溶液を窒素雰囲気下、７０℃で、２１．５時間重合することで、磁性体含有樹脂微粒子を得た。重量法で求めた転化率は約９８％であり、動的光散乱法（大塚電子社製、Photal PAR-IIIS）で測定した平均粒径はＤｎ５０６．６nm， Ｄｗ ５２９．０nm であり、その粒度分布Dw/Dnは１．０４４であった。
【００４０】
重合後のフラスコ内には、ほとんど沈殿物は観察されなかった。この磁性体含有樹脂微粒子は磁石DYNAL MPC-M (Magnetic Particle Concentration for eppendorf microtubes)によって容易に吸引・回収することができた。また、回収された磁性体含有樹脂微粒子は、磁石を取り除くと水中に容易に再分散できた。
FE-TEMにより磁性体含有樹脂微粒子の磁性体は粒子のほぼ中央に存在しており、磁性体粒子は樹脂微粒子表面には露出していないことが確認できた。
【００４１】
実施例２
磁性流体「フェリコロイドＨＣ５０」（タイホー工業（株）製）３．０ｇ（磁性体１．５ｇ含有）をインキュベーター中で８０℃にて１２時間乾燥し、０．９ｇのケロシンを除去して、濃縮された超常磁性体２．１ｇを得た。これにヘキサン０．５ｇを入れ、カップ型ソニケーターを用いて超常磁性体を分散させた。この分散液にスチレン３ｇ、ヘキサデカン０．２３ｇを入れ、さらにカップ型ソニケーターで処理することで、超常磁性体のモノマー分散液を得た（以下、A液と称する。）。
【００４２】
水１０ｇにドデシルベンゼンスルホン酸ナトリウム０．０６ｇと過硫酸アンモニウム０．０５ｇを溶解させた（以下、Ｂ液と称する。）。
Ｂ液中にA液を入れ、超音波破砕機（タイテック社製ＶＰ−３０Ｓ，目盛り５）を用い、氷冷下で１０分間処理することで磁性体を含むミニエマルション液滴を作製した。
【００４３】
このミニエマルション溶液を窒素雰囲気下、７０℃で、１８時間重合することで、磁性体含有樹脂微粒子を得た。重量法で求めた転化率は約９０％であり、動的光散乱法（大塚電子社製、Photal PAR-IIIS）で測定した平均粒径はDn 280.2 nm ，Dw 291.7 nmであり、その粒径分布Dw/Dnは1.041であった。
【００４４】
重合後のフラスコ内には、ほとんど沈殿物は観察されなかった。ＴＧ−ＤＴＡ分析で求めた樹脂微粒子中の磁性体の含有率は３２％であり、仕込みの磁性体のほぼ９６％が樹脂微粒子中に取り込まれた。
この磁性体含有樹脂微粒子は磁石DYNAL MPC-M (Magnetic Particle Concentration for eppendorf microtubes)によって容易に吸引・回収することができた。また、回収された磁性体含有樹脂微粒子は、磁石を取り除くと水中に容易に再分散できた。
【００４５】
FE-TEMにより磁性体含有樹脂微粒子の磁性体は粒子のほぼ中央に存在しており、磁性体粒子は樹脂微粒子表面には露出していないことが確認できた。
【００４６】
【発明の効果】
本発明によれば、平均粒径が小さく、粒径分布が狭く、かつ磁性体含有率が高い粒子を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to magnetic substance-containing resin fine particles, particularly particles having a small average particle diameter, a narrow particle size distribution, and a high magnetic substance content. Such magnetic substance-containing resin particles are useful in applications such as diagnostic drug carriers, cell separation carriers, nucleic acid separation carriers, protein separation carriers, drug delivery carriers, magnetic inks, and the like.
[0002]
[Prior art]
As a method for synthesizing the magnetic substance-containing resin fine particles in which a magnetic substance is present inside the particle, 1) using a suspension polymerization method, 2) using an emulsion polymerization method (see, for example, Patent Document 1), and 3) a miniemulsion. Those using a polymerization method (for example, see Non-Patent Document 1) are known.
[0003]
However, when suspension polymerization is used, the particle size distribution is generally wide, and the obtained particles are usually large particles having an average particle size exceeding 1 μm (see, for example, Patent Document 2). .
In addition, although there is an example in which particles having a small average particle diameter are obtained even by suspension polymerization (see, for example, Patent Document 3), it is necessary to use a specific monomer type. Only bad ones have been obtained.
[0004]
Therefore, in addition to the problem that uniform particles having a stable magnetic force due to the wide particle size distribution cannot be obtained, the problem that the magnetic force per weight due to the large particle size is weak or the monomer type is limited. Because of this problem, it was still insufficient for practical use in the field of diagnosis.
In the case of emulsion polymerization, resin fine particles having a small particle diameter can be easily obtained, but it is necessary for the magnetic particles to move into the micelles in the reaction solution due to the mechanism. Therefore, in this case, since the content of the magnetic substance in the resin fine particles is low, it has not yet been possible to obtain magnetic polymer particles with good magnetic precipitation with good reproducibility.
[0005]
Furthermore, Non-Patent Document 1 discloses a photograph in which iron oxide is encapsulated in polystyrene particles using a mini-emulsion polymerization method, but its specific production method is not described, and the photograph is seen. As far as the iron oxide colloid is concerned, since some of the particles are biased toward the surface, there is a possibility of elution of iron ions, which is considered to be insufficient for practical use.
[0006]
[Patent Document 1]
Japanese Examined Patent Publication No. 3-57921
[Patent Document 2]
JP-A-10-87711 (Page 4, Synthesis Example 1)
[Patent Document 3]
JP-A-9-208788 (pages 6 to 8)
[Non-Patent Document 1]
K. Landfester, Macromol. Rapid Commun. (2001), 22, p. 896-936
[0007]
[Problems to be solved by the invention]
As described above, the magnetic substance-containing polymer particles obtained by the conventional production method are still insufficient in terms of the particle diameter, particle size distribution, magnetic substance content, magnetic force, etc., and their practicality is low. It was.
Accordingly, an object of the present invention is to provide magnetic substance-containing resin fine particles with a strong magnetic force that have a small average particle size, high monodispersibility, and that are easily attracted to a magnet even with a small particle size. is there.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, the present inventors have intensively studied. As a result, in the production of the magnetic substance-containing resin fine particles using the miniemulsion polymerization method, the dispersion in which the paramagnetic particles are dispersed in an organic solvent in advance. When the liquid was used, it was found that magnetic substance-containing resin fine particles having a small particle diameter, a narrow particle size distribution, and a high magnetic substance content can be obtained, and the present invention has been completed. That is, the gist of the present invention is that the weight average particle diameter measured by the dynamic light scattering method is 0.2 to 1 μm, and the ratio of the weight average particle diameter to the number average particle diameter also measured by the dynamic light scattering method. Is a resin fine particle of less than 1.2, and the resin constituting the resin fine particle is A polymer of a compound having an ethylenically unsaturated bond, It has a residue of a polymerization initiator composed of a persulfate, contains 10% by weight or more of paramagnetic particles in the resin fine particles, and observation of the magnetic particles on the surface of the resin fine particles is observed by an electron microscope. The present invention resides in a magnetic substance-containing resin fine particle and a method for producing the same.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the magnetic substance-containing resin fine particles of the present invention will be described in detail.
1, Magnetic substance-containing resin fine particles
The magnetic substance-containing resin fine particles of the present invention have a weight average particle diameter of 0.2 to 1 μm, and a ratio of the weight average particle diameter to the number average particle diameter measured by a dynamic light scattering method is less than 1.2, In addition, the content of paramagnetic particles in the resin fine particles is 10% by weight or more.
The average particle diameter can be measured using a general dynamic light scattering apparatus such as “Microtrack UPA” manufactured by Honeywell.
The particle size distribution can be represented by the ratio (Dw / Dn) of the weight average particle size to the number average particle size, and is preferably less than 1.1, more preferably less than 1.05.
[0010]
(Magnetic material)
The paramagnetic particles contained in the magnetic substance-containing resin fine particles of the present invention can be arbitrarily used depending on the purpose, but when a strong magnetic field of 5000 aersted is applied to the magnetic particles, the magnetic particles are returned to zero magnetic field. A magnetic material whose magnetization (residual magnetization) is 1/3 or less of the magnetization (saturation magnetization) when the magnetic field is 5000 aersted is preferable. For example, iron trioxide (Fe Three O Four ), Γ-heavy ferric oxide (γ-Fe 2 O Three ) And the like; metals such as iron, manganese and cobalt, or alloys thereof. In applications such as diagnostics, resin particles having a strong magnetic force tend to be required, so among them, those classified as ferromagnetic materials are preferable, ferrites are more preferable, and Fe is particularly preferable. Three O Four Is preferred.
[0011]
The particle diameter of the paramagnetic particles is smaller than that of the target resin fine particles. Here, in order to avoid exposure of the magnetic substance to the surface of the resin fine particles, a magnetic substance having a particle diameter of usually 50 nm or less, preferably 30 nm or less, more preferably 20 nm or less is used. On the other hand, the smaller the magnetic particles, the more difficult it is to stably disperse the magnetic particles in the mini-emulsion droplets, so usually 3 nm or more, preferably 5 nm or more, more preferably 6 nm or more. Use things.
[0012]
Examples of commercially available magnetic materials include ferrofluid ferricolloid HC-50 (Taiho Industries) and HX-20 (Sigma High Chemical).
The content of the magnetic particles in the resin fine particles is 10% by weight or more based on the polymer weight. In order to develop sufficient magnetic responsiveness, the content of the magnetic substance is preferably high, preferably the content is 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight or more. It is. On the other hand, the magnetic substance content is usually 70% by weight or less, preferably 60% by weight or less, and particularly preferably 50% by weight or less in order to prevent the magnetic substance from being exposed on the surface of the resin fine particles. is there.
[0013]
2. Method for producing magnetic substance-containing resin fine particles
The above-mentioned magnetic substance-containing resin fine particles are obtained by performing miniemulsion polymerization using a dispersion in which paramagnetic particles are dispersed in an organic solvent containing an aliphatic hydrocarbon solvent in advance, that is, aliphatic hydrocarbons. After contacting a dispersion in which paramagnetic particles are dispersed in an organic solvent containing a system solvent with a compound having an ethylenically unsaturated bond used as a monomer, these are finely dispersed in water. It can be produced by polymerization.
[0014]
The organic solvent in which the paramagnetic particles are dispersed is not particularly limited as long as it contains an aliphatic hydrocarbon solvent and does not adversely affect the dissolution of the magnetic substance and can be mixed with the monomer. .
Examples of the aliphatic hydrocarbon solvent include linear, branched or cyclic solvents such as at least pentane, hexane, heptane, isobutane and isopentane. Preferably, it is a C5-C7 thing. Moreover, the above-mentioned aliphatic hydrocarbon solvents may be used singly or as a mixture thereof.
[0015]
A representative example of the mixed solvent is kerosene.
In this case, the content ratio of the aliphatic hydrocarbon solvent in the organic solvent in which the paramagnetic particles are dispersed depends on the total amount of the organic solvent, but is usually 50% by weight or more, preferably 60% by weight or more, More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more, Most preferably, it is 90 weight% or more.
[0016]
The amount of the organic solvent used is usually 0.1% or more, preferably 1% or more, particularly preferably 10% or more by weight with respect to the magnetic substance. However, if the amount of the organic solvent is too large, the operation becomes complicated, for example, it is necessary to remove the residual solvent after miniemulsion polymerization. Especially preferably, it is 250% or less. At this time, when a solvent having a high boiling point is used, it is preferable to use a smaller amount.
[0017]
Further, when a solvent having a high boiling point is used, it is preferable to contact in the presence of a surfactant as exemplified below, particularly a reactive surfactant, when the dispersion is brought into contact with the monomer.
As a preferable specific method for obtaining the magnetic dispersion liquid, a commercially available magnetic fluid was treated at an arbitrary temperature, for example, a temperature of 60 ° C. or higher and 150 ° C. or lower, preferably 120 ° C. or lower, and the solvent was volatilized. Thereafter, hexane is added to redisperse the magnetic material.
[0018]
The magnetic substance-containing resin fine particles of the present invention can be produced by bringing the dispersion of the magnetic substance obtained above into contact with a monomer and using a general technique of miniemulsion polymerization.
That is, a magnetic dispersion and a compound having an ethylenically unsaturated bond used as a monomer are brought into contact with each other and finely dispersed in water, and then the monomer is polymerized.
[0019]
(Compound having an ethylenically unsaturated bond)
As the compound having an ethylenically unsaturated bond used as a monomer in the present invention, any polymerizable monomer can be used without limitation. Specific examples of monomers used in radical polymerization include polymerizable unsaturated aromatics such as styrene, chlorostyrene, α-methylstyrene, divinylbenzene, vinyltoluene; (meth) acrylic acid, itaconic acid, maleic acid, fumar Polymerizable unsaturated carboxylic acids such as acids; polymerizable unsaturated sulfonic acids such as sodium styrene sulfonate or salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, Polymerizable carboxylic acid esters such as (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid glycidyl, ethylene glycol-di- (meth) acrylic acid ester, (meth) acrylic acid tribromophenyl; Acrylonitrile, (meth) acrolein, (meth) acrylamide, methylenebis (meta Unsaturated carboxylic acid amides such as acrylamide, butadiene, isoprene, vinyl acetate, vinyl pyridine, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, vinyl bromide, polymerizable unsaturated nitriles, vinyl halides, conjugated dienes Macromolecules having a polymerizable functional group such as a vinyl group, a methacryloyl group or a dihydroxyl group in a high molecular weight segment such as polystyrene, polyethylene glycol or polymethyl methacrylate.
[0020]
Moreover, the monomer used by this invention can also use a monomer used by addition polymerization. Specific examples of monomers used for polyaddition include diphenylmethane diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, tetramethylxylene diisocyanate, xylene diisocyanate, dicyclohexane diisocyanate, dicyclohexylmethane diisocyanate. , Aliphatic or aromatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, ketenes, epoxy group-containing compounds, vinyl group-containing compounds, and monomers to be reacted with the above compound group These include functional groups having activated hydrogen, and specific examples include compounds having a hydroxyl group or an amino group. Specific examples include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6- Polyols such as xylenediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, methyleneglycoside, sucrose, bis (hydroxyethyl) benzene; ethylenediamine, hexamethylenediamine, N, N'-diisopropylmethylenediamine, N, N ' -Polyamines such as -di-sec-butyl-p-phenylenediamine and 1,3,5-triaminobenzene; oximes and the like.
[0021]
The said monomer may be used independently and may be used in mixture of 2 or more types.
Of these, monomers used in radical polymerization are preferable, styrenes, or (meth) acrylic acid and esters thereof are more preferable, and styrene, (meth) acrylic acid, (meth) acrylic acid are more preferable. C 1 ~ C Four Alkyl ester or glycidyl (meth) acrylate.
[0022]
In addition to the above monomers, a polyfunctional compound that can serve as a crosslinking agent may coexist.
Examples of the polyfunctional compound include N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide, N-methylol maleimide, N-ethylol maleimide, N-methylol maleamic acid, N-methylol maleamic acid ester. N-alkylolamides of vinyl aromatic acids (for example, N-methylol-p-vinylbenzamide), N- (isobutoxymethyl) acrylamide and the like. Furthermore, among the above-mentioned monomers, divinylbenzene, divinylnaphthalene, divinylcyclohexane, 1,3-dipropenylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butylene glycol, Polyfunctional monomers such as trimethylolethane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate can also be used as a crosslinking agent.
[0023]
(Surfactant)
In miniemulsion polymerization, dispersion is performed in the presence of a surfactant and a co-surfactant in order to stably finely disperse monomer droplets in water.
The surfactant used in the present invention is not particularly limited as long as it can be used for conventional latex polymerization. Examples of anionic surfactants include dodecyl benzene sulfonate, decyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonyl benzene sulfonate, and sodium, potassium, and ammonium salts thereof, and cationic surfactants. Examples thereof include cetyltrimethylammonium promide, hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride, and the like. In addition to polyvinyl alcohol, various types of nonionic surfactants are commercially available. For example, “Triton” (X-100, X-114, X-305, N-101 manufactured by Union Carbide Corporation) is available. ), "Tween" (20, 40, 60, 80, 85) manufactured by ICC, "Brij" (35, 58, 76, 98) manufactured by ICC, manufactured by Shell “Nonidet” (P-40), “Igepol” (CO530, CO630, CO720, CO730) manufactured by Rhône-Poulenc.
[0024]
Of these, anionic surfactants are preferred.
An anion, cation, or nonionic reactive surfactant that can be polymerized with the oil-soluble monomer can also be used. The reactive group in the reactive surfactant preferably has an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth) acryloyl group. Those reactive surfactants may be those having ordinary surface activity as long as they have the reactive group, and examples include those described in JP-A-9-279073, Specifically, for example, alkylbenzene sulfonates such as lauryl (allylbenzene) sulfonate, lauryl styrene sulfonate, stearyl (allyl benzene) sulfonate, stearyl styrene sulfonate, and their polyethylene oxide adducts , Alkylsulfosuccinates such as lauryl allyl sulfosuccinate, lauryl vinyl sulfosuccinate, stearyl allyl sulfosuccinate, stearyl vinyl sulfosuccinate, and their polyethylene oxide adducts (meth) Lauryl acrylate Anionic properties of alkyl or alkenyl sulfonates such as phonates and oleyl sulfonates, alkyl or alkenyl sulfates such as stearyl sulfate (meth) acrylate and oleyl sulfate, and their polyethylene oxide adducts Surfactants, cationic surfactants such as quaternary ammonium salts such as lauryl triallyl ammonium chloride, stearyl triallyl ammonium chloride, distearyl diallyl ammonium chloride, polyethylene glycol octyl (allylphenyl) ether, polyethylene glycol nonyl (allyl) Phenyl) ether, polyethylene glycol alkyl or alkenyl phenyl ethers such as polyethylene glycol oleyl phenyl ether, monoallyl monostearyl acid Glycerin fatty acid esters such as lysyl and monoallyl glyceryl distearate, and polyethylene oxide adducts thereof, sorbitan fatty acid esters such as monoallyl sorbitan monostearate and monoallyl sorbitan tristearate, and polyethylene oxide adducts thereof And nonionic surfactants such as polyethylene oxide esters of (meth) acrylic acid such as polyethylene glycol mono (meth) acrylate and polyethylene glycol di (meth) acrylate.
[0025]
These reactive surfactants include, for example, “AQUALON HS-10” from Daiichi Kogyo Seiyaku Co., Ltd., “Antox-MS-60”, “RA- Products such as “1000 Series”, “Antox-MS-2N”, “Adekaria Soap SE-10N” from Asahi Denka Kogyo Co., “Teramulu S-180A” from Kao Corporation, “Eleminol JS-2” from Sanyo Kasei Kogyo Co., Ltd. In addition, as the cationic surfactant, for example, a product name such as “RF-751” from Nippon Emulsifier Co., Ltd., and as the nonionic surfactant, for example, from Asahi Denka Kogyo Co., Ltd., “ “ADEKA rear soap NE-10”, from Nippon Oil & Fats Co., Ltd. under the trade names “Blemmer PE-200”, “Blemmer PE-350”, “Blemmer PE-400”, etc. Each are commercially available.
[0026]
The said surfactant may be used independently and may be used in mixture of 2 or more types.
The amount of the surfactant used is 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and particularly preferably 0.5 parts by weight or more with respect to 100 parts by weight of the monomer. Further, it is usually used in an amount of 50 parts by weight or less, preferably 30 parts by weight or less.
[0027]
(Co-surfactant)
The cosurfactant used in the present invention is not particularly limited as long as it is generally used in miniemulsion polymerization. Specifically, (a) C such as hexadecane, squalane, cyclooctane, etc. 8 ~ C 30 (B) C such as stearyl methacrylate, dodecyl methacrylate, etc. 8 ~ C 30 C such as alkyl acrylate and (c) cetyl alcohol 8 ~ C 30 C such as alkyl alcohol and (d) dodecyl mercaptan 8 ~ C 30 (E) Polymers such as (e) polyurethane, polyester, polystyrene, etc. (f) other, long chain aliphatic or aromatic carboxylic acids, long chain aliphatic or aromatic carboxylic esters, long chain aliphatic or aromatic amines , Ketones, halogenated alkanes, silanes, siloxanes, isocyanates and the like. Long chain oil soluble initiators such as lauroyl peroxide can also be used. Of these, those having 12 or more carbon atoms are preferred, and alkanes having 12 to 20 carbon atoms are more preferred.
[0028]
Even if it is an organic compound such as oil-soluble dyes and various fluorescent dyes (or fluorescent brighteners) such as benzothioxanthene, xanthene, coumarin, naphthalimide, benzoxanthene, perylene, and acridine, the solubility in water is 0. If it is 0.01 g / L or less and is soluble in an oil-soluble monomer, it can be used. Specific examples include Solvent Blue, Solvent Red, Solvent Orange, Solvent Green, and fluorescent whitening agent UVITEX OB (2,5-thiphenediylbis (5-tert-butyl-1,3-benzoxazole, manufactured by Chiba Specialty Chemicals) , Coumarin yellow fluorescent dye "MACROLEX Fluorescent Yellow 10GN" (Solvent Yellow 160: 1, manufactured by BAYER), Coumarin red fluorescent dye "MACROLEX Fluorescent Red G" (manufactured by BAYER), others "Basic Red1" (BASF from Basylyl Cationic Rhodamine F5G dye commercially available as Red 482), "Basic Violet 11" (Basic Violet 11: 1 cationic Rhodamine B dye commercially available as BASONyl Red 560 from BASF), "Basic Yellow 40" (Maxilon Brilliant Flavine 10GFF from Ciba-Gigy) Nonionic Coumarin dye commercially available as “Solvent Yellow 43” (nonionic Naphthalimide dye commercially available as Hudson Yellow from Day-Glo Color), “Solvent Yellow 44” (available as Alberta Yellow from Day-Glo Color) Nonionic Coumarine dyes), "Solvent Yellow 160" (commercially available nonionic Coumarine dyes as Day-Glo Color Corp. from Potomac Yellow), and the like.
[0029]
Furthermore, dicyanopinyl, azo (for example, pyridone azo, disazo, trisazo, benzeneazo, heterocyclic azo, etc.), quinophthalone, aminopyrazole, methine, dicyanoimidazole, indoaniline, phthalocyanine A system can also be suitably used. Among these, azo, phthalocyanine, and anthraquinone are preferable, and these dyes may be used in combination of two or more.
The usage-amount of the said co-surfactant is normally selected from the range of 0.1 to 100 weight% with respect to a monomer.
[0030]
(Polymerization initiator)
Examples of the radical polymerization initiator that can be used in the present invention include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2-methylpropanenitrile), 2,2′-azobis. -(2,4-dimethylpentanenitrile), 2,2'-azobis- (2-methylbutanenitrile), 1,1'-azobis- (cyclohexanecarbonitrile), 2,2'-azobis- (2,4 -Dimethyl-4-methoxyvaleronitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (2-amidinopropane) hydrochloride, etc. azo (azobisnitrile) Types of initiators, benzoyl peroxide, cumene hydroperoxide, hydrogen peroxide, acetyl peroxide, lauroyl peroxide, persulfates (eg, ammonium persulfate), peracid esters (eg, t-butyl peroxide) And peroxide type initiators such as tate, α-cumyl peroxypivalate and t-butyl peroctate).
[0031]
Examples of the redox initiator include ascorbic acid / iron (II) sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, and tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid. In addition, each component, for example, a reducing component, may be a mixture, for example, a mixture of sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
The amount of the polymerization initiator used is usually selected from the range of 0.1 to 30 wt% with respect to the monomer, and these polymerization initiators may be added at the time of preparing the magnetic substance-containing monomer emulsion, or contain the magnetic substance. You may add after monomer emulsion preparation.
[0032]
(Reaction format)
In the contact / water dispersion of the magnetic dispersion liquid and the monomer, 1) a method in which an ethylenically unsaturated compound is added to the magnetic dispersion liquid, and then the mixture is added to water and finely dispersed. A method in which a dispersion and an ethylenically unsaturated compound are simultaneously added to water and then finely dispersed. 3) A method in which a magnetic dispersion is dispersed in water and then an ethylenically unsaturated compound is added, followed by further dispersion. Arbitrary reaction modes can be taken, but the method of 1) above is preferred, and the preparation of such a miniemulsion utilizes a known method, and a magnetic dispersion monomer solution containing a cosurfactant It is preferable to carry out by a method of uniformly emulsifying (A liquid) and an aqueous surfactant solution (B liquid) with a shear mixing device having a high shearing force.
[0033]
As the shear mixing device, for example, a piston homogenizer, a microfluidizer (registered trademark), an ultrasonic disperser, or the like is used. Such particle diameter can be adjusted by the amount of the surfactant used and the amount of the monomer to be emulsified.
Next, in the production method of the present invention, after the miniemulsion is prepared by the above method, the miniemulsion is polymerized in the presence of a polymerization initiator.
[0034]
The polymerization initiator may be added to any of the liquid A and liquid B described above. The polymerization temperature is usually selected from the range of 30 to 95 ° C, preferably 50 to 95 ° C. The polymerization time is usually sufficient for 5 to 6 hours or more.
The particles after polymerization can be obtained by using a general isolation and purification method such as dialysis, centrifugation, or purification using an ion exchange resin. Specifically, the dialysis method is a method in which the particles after polymerization are put into a dialysis tube that is a semipermeable membrane and the outside is purified by performing dialysis operation with pure water. After the particles are settled by operation and the supernatant is removed, purification is performed by replacing with pure water. The purification method using an ion exchange resin is a method of performing purification by passing the ion exchange resin. Of these, the simplest method is the centrifugal separation method, but the most effective method is the ion exchange resin method.
[0035]
The magnetic substance-containing resin fine particles of the present invention can be subjected to appropriate surface modification depending on the application by appropriately selecting the above-mentioned monomers.
Specifically, acrylic acid. When a monomer having a carboxyl group such as methacrylic acid is used as a copolymerization monomer, the protein can be immobilized by covalently bonding the carboxyl group derived from the monomer on the particle surface to the amino group of the protein.
[0036]
When glycidyl methacrylate is used, the protein may be directly immobilized on the epoxy group derived from the monomer on the particle surface, or the protein is covalently bonded after introducing a carboxyl group or amino group into the epoxy group. It can also be made.
Furthermore, a polyethylene glycol oligomer / polymer having an amino group or a carboxyl group at the end is immobilized on the surface of the particle having the epoxy group introduced thereinto, and only the target protein is immobilized after suppressing nonspecific adsorption of the protein. You can also.
[0037]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
Example 1
1.0 g (containing 0.5 g of magnetic substance) of the magnetic fluid “Ferricolloid HC50” (made by Taiho Kogyo Co., Ltd.) is dried in an incubator at 80 ° C. for 12 hours to remove 0.3 g of kerosene and concentrate. 0.7 g of the obtained superparamagnetic material was obtained. By adding 3 g of styrene, 0.23 g of hexadecane and 0.01 g of a polymerizable surfactant “NE-20 (manufactured by Asahi Denka Kogyo Co., Ltd.)” to the concentrated magnetic body, and further treating with a cup-type sonicator, a superparamagnetic body A monomer dispersion was obtained (hereinafter referred to as “A solution”).
[0038]
0.06 g of sodium dodecylbenzenesulfonate and 0.05 g of ammonium persulfate were dissolved in 10 g of water (hereinafter referred to as “Liquid B”).
Liquid A was put into liquid B, and a miniemulsion droplet containing a magnetic material was prepared by processing for 10 minutes under ice cooling using an ultrasonic crusher (VP-30S manufactured by Taitec Co., Ltd., scale 5).
[0039]
This mini-emulsion solution was polymerized in a nitrogen atmosphere at 70 ° C. for 21.5 hours to obtain magnetic substance-containing resin fine particles. The conversion obtained by the gravimetric method was about 98%, and the average particle diameters measured by the dynamic light scattering method (Photal PAR-IIIS, manufactured by Otsuka Electronics Co., Ltd.) were Dn506.6 nm and Dw 529.0 nm. The distribution Dw / Dn was 1.044.
[0040]
Almost no precipitate was observed in the flask after polymerization. The magnetic substance-containing resin fine particles could be easily attracted and collected by a magnet DYNAL MPC-M (Magnetic Particle Concentration for Eppendorf microtubes). The recovered magnetic substance-containing resin fine particles could be easily redispersed in water when the magnet was removed.
It was confirmed by FE-TEM that the magnetic substance of the magnetic substance-containing resin fine particles was present at almost the center of the particle, and the magnetic substance particles were not exposed on the surface of the resin fine particle.
[0041]
Example 2
3. Ferrocolloid HC50 (manufactured by Taiho Kogyo Co., Ltd.) 3.0 g (containing 1.5 g of magnetic material) is dried in an incubator at 80 ° C. for 12 hours to remove 0.9 g of kerosene and concentrate 2.1 g of the obtained superparamagnetic material was obtained. To this was added 0.5 g of hexane, and the superparamagnetic material was dispersed using a cup-type sonicator. The dispersion was charged with 3 g of styrene and 0.23 g of hexadecane, and further treated with a cup-type sonicator to obtain a superparamagnetic monomer dispersion (hereinafter referred to as A solution).
[0042]
0.06 g of sodium dodecylbenzenesulfonate and 0.05 g of ammonium persulfate were dissolved in 10 g of water (hereinafter referred to as “Liquid B”).
Liquid A was put into liquid B, and mini-emulsion droplets containing a magnetic material were prepared by processing for 10 minutes under ice cooling using an ultrasonic crusher (VP-30S manufactured by Taitec Co., Ltd., scale 5).
[0043]
This miniemulsion solution was polymerized at 70 ° C. for 18 hours in a nitrogen atmosphere to obtain magnetic substance-containing resin fine particles. The conversion obtained by the gravimetric method is about 90%, and the average particle diameters measured by the dynamic light scattering method (Photal PAR-IIIS, manufactured by Otsuka Electronics Co., Ltd.) are Dn 280.2 nm and Dw 291.7 nm. The distribution Dw / Dn was 1.041.
[0044]
Almost no precipitate was observed in the flask after polymerization. The content of the magnetic substance in the resin fine particles determined by TG-DTA analysis was 32%, and almost 96% of the charged magnetic substance was taken into the resin fine particles.
The magnetic substance-containing resin fine particles could be easily attracted and collected by a magnet DYNAL MPC-M (Magnetic Particle Concentration for Eppendorf microtubes). The recovered magnetic substance-containing resin fine particles could be easily redispersed in water when the magnet was removed.
[0045]
It was confirmed by FE-TEM that the magnetic substance of the magnetic substance-containing resin fine particles was present at almost the center of the particle, and the magnetic substance particles were not exposed on the surface of the resin fine particle.
[0046]
【The invention's effect】
According to the present invention, particles having a small average particle size, a narrow particle size distribution, and a high magnetic substance content can be obtained.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002267619A JP4066754B2 (en) | 2002-09-13 | 2002-09-13 | Magnetic substance-containing resin fine particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002267619A JP4066754B2 (en) | 2002-09-13 | 2002-09-13 | Magnetic substance-containing resin fine particles and method for producing the same |
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| JP4066754B2 true JP4066754B2 (en) | 2008-03-26 |
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| JP2007528286A (en) * | 2003-07-03 | 2007-10-11 | エルジー・ケム・リミテッド | Method for producing microcapsules through miniemulsion polymerization |
| KR100572400B1 (en) * | 2004-05-11 | 2006-04-24 | 재단법인서울대학교산학협력재단 | Plastic molded article using semiconductor nanoparticle encapsulated vinyl polymer particles and manufacturing method thereof |
| JP5517419B2 (en) * | 2007-06-28 | 2014-06-11 | キヤノン株式会社 | Composite particle and method for producing the same |
| JP5147452B2 (en) | 2008-02-26 | 2013-02-20 | キヤノン株式会社 | Target substance detection method and kit using magnetic biosensor |
| JP2009229736A (en) | 2008-03-21 | 2009-10-08 | Fuji Xerox Co Ltd | Magnetic polymer particle for magnetic latent image development, its manufacturing method, liquid development agent for magnetic latent image, cartridge, and image forming device |
| DE102009042036B4 (en) * | 2009-09-17 | 2016-09-01 | Institut für Bioprozess- und Analysenmesstechnik e.V. | Use of a light-curing, biocompatible and biodegradable polymer blend |
| JP7693331B2 (en) * | 2021-02-26 | 2025-06-17 | キヤノン株式会社 | Method for producing polymer particles |
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