JPH02240105A - Production of aqueous resin particle - Google Patents
Production of aqueous resin particleInfo
- Publication number
- JPH02240105A JPH02240105A JP1059823A JP5982389A JPH02240105A JP H02240105 A JPH02240105 A JP H02240105A JP 1059823 A JP1059823 A JP 1059823A JP 5982389 A JP5982389 A JP 5982389A JP H02240105 A JPH02240105 A JP H02240105A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- resin particles
- polymerization initiator
- polymerizable monomer
- dissolve
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 22
- 239000012736 aqueous medium Substances 0.000 claims abstract description 17
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 25
- 239000003995 emulsifying agent Substances 0.000 abstract description 11
- 125000002091 cationic group Chemical group 0.000 abstract description 9
- 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 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 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 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 229920006317 cationic polymer Polymers 0.000 description 22
- 239000003094 microcapsule Substances 0.000 description 20
- -1 0-methylstyrene Chemical compound 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000011162 core material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007771 core particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 241000721047 Danaus plexippus Species 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007869 azo polymerization initiator Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- XQBHAZDVLGNSOJ-UHFFFAOYSA-N 1-(4-ethenylphenyl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(C=C)C=C1 XQBHAZDVLGNSOJ-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000013441 quality evaluation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 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
- BJQFWAQRPATHTR-UHFFFAOYSA-N 1,2-dichloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1Cl BJQFWAQRPATHTR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- YXJYLMQTEUGGKT-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane penta-1,4-dien-3-one Chemical class C(=C)C(=O)C=C.C(C(C)C)OC=C YXJYLMQTEUGGKT-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-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
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- DJLHXXNSHHGFLB-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C(C)=C DJLHXXNSHHGFLB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
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Abstract
Description
〔産業上の利用分野]
本発明は水性媒体中で正極性に帯電する水性樹脂粒子の
製造法に関する.更に詳しくは、水溶性重合開始剤を用
いることのない無乳化剤乳化重合法いわゆるソープフリ
ー乳化重合法による水性樹脂粒子の新規製造法に関する
。
[従来の技術]
従来、水性樹脂粒子の製造方法としては、(1)界面活
性剤を使用して行う乳化重合法による樹脂粒子の製造方
法。
(2)水溶性の重合開始剤を用いるソープフリー乳化重
合法による水性樹脂粒子の製造方法。
(3)親水性の重合性単量体及び水溶性の重合開始剤を
用いるソープフリー乳化重合法による水性樹脂粒子の製
造方法.
(4)水溶性の高分子乳化剤を用いる水性樹脂粒子の製
造方法.
等がある.
このうち(1)および(4)では界面活性剤や高分子乳
化剤を完全に除去することが困難で、得られた水性樹脂
を使う際に、これらの残留物が問題となる。
また(2)では使用できる重合開始剤が3〜4種に限ら
れ、重合反応の条件も限定されるので、所望の特性の粒
子がが得られないことがある。例えば電子写真用のマイ
クロカプセルトナー粒子を製造した場合、粒子に対する
電荷の付与が充分におこなえず、電子写真の画像濃度に
問題が生じたりする.
(3)では親水性の重合単量体と、スチレンやメタクリ
ル酸メチルなどの疎水性単量体とを共重合させて均一な
ボリマーを得るのが難しいという問題がある.
〔発明が解決しようとする課題]
本発明の目的は乳化重合法の改良にある.本発明の他の
目的は、通常の乳化剤を使用することなく、また、水溶
性の重合開始剤も使用することなく、更には水溶性の高
分子乳化剤等をも使用しないことを特徴とする水性樹脂
粒子の製造方法を提供することにある.
本発明の他の目的はマイクロカプセルトナー用樹脂粒子
の製造方法を提供することにある.本発明の他の目的は
、通常の乳化剤を使用することなく、また、水溶性の重
合開始剤も使用することなく、更には水溶性の高分子乳
化剤をも使用しないことを特徴とし、マイクロカプセル
トナーの殻材として用いた場合に帯電特性にすぐれ、欠
損部分のない耐久性および耐熱性にすぐれた水性樹脂粒
子の製造方法を提供することにある。
[課題を解決するための手段及び作用1本発明者は鋭意
研究の結果、少なくとも重合性単量体、該単量体に溶解
し正に帯電する重合体(以下、カチオン性重合体と称す
)、カーボンブラック、及び該単量体に溶解し水性媒体
には溶解しない重合開始剤からなる単量体組成物を該水
性媒体中でpot〜6の条件で重合することを特徴とす
る水性樹脂粒子の製造方法により前記本発明の目的が達
成されることを見出した.
以下、本発明を更に詳細に説明する。以下の記載におい
て、量比を表わす「%」及び「部」は特に断わらない限
り重量規準とする。
本発明に用いられる重合性単量体を以下に記す.
すなわち、例えば、スチレン、0−メチルスチレン、潅
−メチルスチレン、p−メチルスチレン、p−メトキシ
スチレン、p−フェニルスチレン、p−クロルスチレン
、3.4−ジクロルスチレン、p一エチルスチレン、2
.4−ジメチルスチレン、p一ロープチルスチレン、p
−tert−プチルスチレン、p−n−へキシルスチレ
ン、p−n−才クチルスチレン、p−n−ノニルスチレ
ン、p−n一デシルスチレン、p−n−ドデシルスチレ
ン、等のスチレンおよびその誘導体.エチレン、ブロビ
レン、ブチレン、イソブチレンなどのエチレン不飽和モ
ノ才レフィン類;塩化ビニル、塩化ビニリデン、臭化ビ
ニル、弗化ビニルなどのハロゲン化ビニル類:酢酸ビニ
ル、ブロビオン酸ビニル、ベンゾエ酸ビニルなどのビニ
ルエステル類メタクリル酸メチル、メタクリル酸エチル
、メタクリル酸プロビル、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n−オクチル、メ
タクリル酸ドデシル、メタクリル酸−2−エチルヘキシ
ル、メタクリル酸ステアリル、メタクリル酸フェニル、
アクリル酸メチル、アクリル酸エチル、アクリル酸n−
ブチル、アクリル酸イソブチル、アクリル酸プロビル、
アクリル酸ローオクチル、アクリル酸ドデシル、アクリ
ル酸2−エチルヘキシル、アクリル酸ステアリル、アク
リル酸2−クロルエチル、アクリル酸フェニルなどのア
クリル酸エステル類;ビニルメチルエーテル、ビニルエ
チルエーテル、ビニルイソブチルエーテルなどのビニル
エーテル類;ビニルメチルケトン、ビニルへキシルケト
ン、メチルイソブロベニルヶトンなどのビニルケトン類
;ビニルナフタリン類,アクリロニトリル、メタクリ口
ニトリル、アクリルアミドなどのアクリル酸もしくはメ
タクリル酸誘導体などがある.
重合に際して、次のような架橋剤を存在させて重合し、
架橋重合体としてもよい.
ジビニルベンゼン、ジビニルナフタレン、ジビニルエー
テル、ジビニルスルホン、ジエチレングリコールジメタ
クリレート、トリエチレングリコールジメタクリレート
、エチレングリコールジメタクリレート、ポリエチレン
グリコールジメタクリレート、ジエチレングリコールジ
アクリレート、トリエチレングリコールジアクリレート
、1.3−ブチレングリコールジメタクリレート、l,
6ーヘキサングリコールジメタクリレート、ネオベンチ
ルグリコールジメタクリレート、ジプロピレングリコー
ルジメタクリレート、ボリブロビレングリコールジメタ
クリレート、2.2゜ビス(4−メタクリ口キシジエト
キシフェニル)ブロバン、2.2゛ビス(4−アクリロ
キシジエトキシフェニル)ブロバン、トリメチロールブ
ロバントリメタクリレート、トリメチロールブロバント
リアクリレート、テトラメチロールメタンテトラアクリ
レート、ジブロムネオベンチルグリコールジメタクリレ
ート、一般の架橋剤を適宜用いることができる.上記、
単量体に溶解するカチオン性重合体は、以下に記す正に
帯電する重合性単量体(以下、カチオン性単量体と称す
)を含有する.すなわち、例えば、(メタ)アクリル酸
ジメチルアミノエチル、(メタ)アクリル酸ジエチルア
ミノエチル、ビニルピリジン、ビニルイミダゾール、ジ
メチルアミノメチルスチレン等であり、これらのカチオ
ン性単量体においては、メチル基、エチル基、ブチル基
あるいはベンジル基等で4級アンモニウム化されていて
もよい.
上記、カチオン性単量体と共重合しつる重合性単量体と
しては、例えば、スチレン、0−メチルスチレン、m−
メチルスチレン、p−メチルスチレン、p−メトキシス
チレン、p−フェニルスチレン、p−クロルスチレン、
3.4−ジクロルスチレン、p一エチルスチレン、2.
4−ジメチルスチレン、p−n−プチルスチレン、 p
−tert−プチルスチレン、p−n−へキシルスチレ
ン、p−n−才クチルスチレン、p−n−ノニルスチレ
ン、p−n−デシルスチレン、p−n−ドデシルスチレ
ン、等のスチレンおよびその誘導体;エチレン、プロピ
レン、ブチレン、イソブチレンなどのエチレン不飽和モ
ノオレフィン類;塩化ビニル、塩化ビニリデン、臭化ビ
ニル、弗化ビニルなどのハロゲン化ビニル類;酢酸ビニ
ル、ブロビオン酸ビニル、ベンゾエ酸ビニルなどのビニ
ルエステル類;メタクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸プロビル、メタクリル酸ローブチル、
メタクリル酸イソブチル、メタクリル酸n−オクチル、
メタクリル酸ドデシル、メタクリル酸−2−エチルヘキ
シル、メタクリル酸ステアリル、メタクリル酸フェニル
、アクリル酸メチル、アクリル酸エチル、アクリル酸n
−ブチル、アクリル酸イソブチル、アクリル酸プロビル
、アクリル酸n−オクチル、アクリル酸ドデシル、アク
リル酸2−エチルヘキシル、アクリル酸ステアリル、ア
クリル酸2−クロルエチル、アクリル酸フェニルなどの
アクリル酸エステル類;ビニルメチルエーテル、ビニル
エチルエーテル、ビニルイソブチルエーテルなどのビニ
ルエーテル類;ビニルメチルケトン、ビニルへキシルケ
トン、メチルイソブロベニルケトンなどのビニルケトン
類;ビニルナフタリン類:アクリロニトリル、メタクリ
口ニトリル、アクリルアミドなどのアクリル酸もしくは
メタクリル酸誘導体などがある.
カチオン性重合体は例えばアゾ系重合開始剤を用いた有
機溶媒中での溶液重合により製造される.すなわち上記
カチオン性単量体、上記カチオン性単量体と共重合しつ
る重合性単量体、およびアゾ系重合開始剤を有機溶媒中
で重合させる.
ここでアゾ系重合開始剤としては、たとえば1.1’−
アゾビス(シクロヘキサンー!一カルポニトリル)、
2.2゜−アゾビスイソブチロニトリル、2,2゜−ア
ゾビス(2.4−ジメチルバレ口ニトリル)等が用いら
れる。上記有機溶媒としては、例えばトルエン、キシレ
ン等の芳香族、アルコール類、ケトン類等が用いられる
.一般的には芳香族、とくにトルエンが好ましく用いら
れる.
カチオン性重合体中の、前記カチオン性単量体の割合は
、3〜80%が好ましく、更に好ましくは7〜70%で
ある.これは、カチオン性単量体が3%未満では充分な
正帯電性を付与することはできないためであり、80%
以上含有する場合には充分な正帯電性を付与することは
できても水性媒体に対する溶解性が強くなり、本発明の
目的を達成することはできない.
本発明において、カチオン性重合体と前記重合性単量体
とを、前者が5〜80%となるよう混合するのが好まし
く、更に好ましくはlO〜70%含有する場合である。
カチオン性重合体の含有量が5%未満では水性樹脂粒子
に充分な正帯電性を付与することはできないためであり
、80%以上混合した場合には、カチオン性重合体と重
合性単量体との混合物の粘度が高くなりすぎ、実際上、
水性樹脂粒子を得ることはできない.
本発明において、カチオン性重合体の分子量はGPCに
よる重量平均分子量測定で、2000〜1000000
にある場合であり、好ましくは、5000〜50000
0となる場合である.カチ才ン性重合体の重量平均分子
量が2000未満では水性媒体に対する溶解性が強くな
り本発明の目的を達成することはできないし、 100
0000以上では実質上、重合性単量体に溶解、混合す
ることが不可能である.本発明において用いられるカー
ボンブラックとしてはラジカル重合反応を阻害すること
の少ないものであればあらゆる種類のものを用いること
ができる.また該カーボンブラックは前記重合性単量体
組成物中で良好な分散状態とするためにあらかじめ粉砕
することができ、例えば前記カチオン性重合体と混線を
行うこと、あるいは、上記重合性単量体組成物と混合後
機械的な外力を加え分散する等の処理を行うことができ
る.
本発明に用いるカーボンブラックとして例えば、モナー
ク1300、同1100、同l000、同900、同8
80、同800、同700、モーガルL1 リーガル4
00R、同660R,同500R,同330R、同30
0R,同99R1バルカンXC−728,エルフテック
ス8、エルフテックス12(以上、キャボット社製)、
ラーベン5000、同7000、同5750,同525
0、同3500、同2000、同l500、同l250
、同l200、同1l70、同1040、同l035、
同!000、コンダクテック40−220、同975、
同900、同SC(以上、コロンビャン・カーボン社製
)等を挙げることができる。
上記カーボンブラックは前記重合性単量体100部に対
して0.1〜20部含まれるのが好ましく、更には、
0.1〜8部含まれる場合が好ましい。含有量が20部
以上となるのは重合反応への影響が強く反応をいちじる
しく阻害し、0.1部未満では本発明の目的の一つであ
るマイクロカプセルトナーの殻材に用いた場合、帯電特
性の改良、向上効果がみられない.
本発明において用いられる水性媒体には溶解しない重合
開始剤には、次に示すものがある。
すなわち、例えば、 1.1’−アゾビス(シクロヘキ
サン−1一カルポニトリル)、2.2゜−アゾビスイソ
ブチロニトリル、 2.2゜−アゾビス(2.4−ジメ
チルバレ口ニトリル)、 2.2゜−アゾビス(4−メ
トキシ−2,4−ジメチルバレ口ニトリル)、ジクミル
ペルオキシド、ジラウロイルベルオキシド、ペンゾイル
ベルオキシド、トルイルペルオキシド、クロロペンゾイ
ルペルオキシド等を挙げることができ、これらの重合開
始剤は重合性単量体及びカチオン性重合体の混合物中に
0.1〜20%となるよう添加するのが好ましく、更に
好ましくは0.5〜15%添加する場合である.もし、
重合開始剤の添加量が0.1%未満では重合反応を完結
することは困難であり、20%以上添加する場合には重
合反応を制御することが困難である.
本発明において、水性媒体のp}Iは20℃で測定して
、1〜6の間にある場合が好ましく、pH1未満となる
ような強酸性下であっても、pH6となる弱酸性下でも
本発明の水性樹脂粒子を安定に製造することはできない
。なお、水性媒体のpHは塩酸、酢酸等で調整するのが
好ましく、緩衝液を用いてpHの安定化をはかってもよ
い.
本発明の水性樹脂粒子は500μm〜0.Olμmの間
で任意の粒径で調整することができるが、好ましくは1
00μI11〜0.01μmの粒径にすることであり、
更に好ましくは50μl11〜0.1μmの粒径にする
ことである.
本発明の水性樹脂は水性媒体に対して50%以下であれ
ば任意の固形分濃度で調整することができるが、好まし
くは5〜35%の固形分濃度で調製する場合である.固
形分濃度が50%以上となると重合性単量体の重合反応
に基く発熱が大きくなり制御することが困難となり、さ
らには樹脂粒子間の凝集によるスケールの発生が多くな
り問題となる.
なお、本発明において、水性媒体に溶解しない重合開始
剤とは20℃で水性媒体への溶解度を測定した場合に1
%以下になることを意味する。
本発明の方法をマイクロカプセルトナーの製造に適用す
る場合、水性樹脂粒子はマイクロカプセルの芯材粒子1
00部に対して0.1〜50部、好ましくは1〜30部
用いられる.もし、粒子が0、1部未満であれば、実質
上芯材粒子のカプセル化は行なわれず、水性樹脂粒子が
50部以上ではカプセル化時に芯材粒子同志の凝集が著
しくマイクロカプセルトナーとしては実用上使用できな
い.壁材粒子と芯材粒子との粒径比率は芯材粒子の粒径
を1とするならば1/1000〜!/!の間にあればよ
く、さらに好ましくは!/500〜1/2の間にある場
合である.もし、水性樹脂粒子と芯材粒子との粒径比率
カ月/1000より小さくなる場合、すなわち水性樹脂
粒子が小さすぎる場合は芯材粒子の表面にカプセル壁を
形成することはできてもマイクロカプセルトナーとして
は耐久性、保存性が著しく劣るし、1/1より大きくな
る場合、すなわち水性樹脂粒子が大きすぎる場合は、芯
材粒子の表面に水性樹脂粒子が付着できても緻密で強固
なカプセル壁を形成することはなく、これもまた耐久性
が著しく劣ることになる.
芯材粒子の平均粒径は1〜30μmであればよく、さら
に好ましくは5〜20μmの範囲にある場合である.[Industrial Application Field] The present invention relates to a method for producing aqueous resin particles that are positively charged in an aqueous medium. More specifically, the present invention relates to a new method for producing aqueous resin particles by an emulsifier-free emulsion polymerization method, so-called soap-free emulsion polymerization method, which does not use a water-soluble polymerization initiator. [Prior Art] Conventionally, methods for producing aqueous resin particles include (1) a method for producing resin particles by emulsion polymerization using a surfactant; (2) A method for producing aqueous resin particles by a soap-free emulsion polymerization method using a water-soluble polymerization initiator. (3) A method for producing aqueous resin particles by a soap-free emulsion polymerization method using a hydrophilic polymerizable monomer and a water-soluble polymerization initiator. (4) Method for producing water-based resin particles using a water-soluble polymer emulsifier. etc. Among these, in (1) and (4), it is difficult to completely remove the surfactant and polymer emulsifier, and their residue poses a problem when using the resulting aqueous resin. In addition, in (2), the usable polymerization initiators are limited to 3 to 4 types, and the conditions for the polymerization reaction are also limited, so particles with desired characteristics may not be obtained. For example, when microcapsule toner particles for electrophotography are manufactured, sufficient charge cannot be imparted to the particles, resulting in problems with image density in electrophotography. In (3), there is a problem in that it is difficult to obtain a uniform polymer by copolymerizing a hydrophilic monomer with a hydrophobic monomer such as styrene or methyl methacrylate. [Problems to be Solved by the Invention] The purpose of the present invention is to improve the emulsion polymerization method. Another object of the present invention is to provide an aqueous polymerization method which is characterized in that it does not use ordinary emulsifiers, does not use water-soluble polymerization initiators, and does not use water-soluble polymer emulsifiers, etc. The purpose of this invention is to provide a method for producing resin particles. Another object of the present invention is to provide a method for producing resin particles for microcapsule toner. Another object of the present invention is to use microcapsules without using ordinary emulsifiers, without using water-soluble polymerization initiators, and without using water-soluble polymer emulsifiers. It is an object of the present invention to provide a method for producing aqueous resin particles that have excellent charging characteristics when used as a toner shell material, have no defective parts, and have excellent durability and heat resistance. [Means and Effects for Solving the Problems 1] As a result of intensive research, the present inventor has discovered that at least a polymerizable monomer and a positively charged polymer dissolved in the monomer (hereinafter referred to as a cationic polymer) , carbon black, and a monomer composition consisting of a polymerization initiator that dissolves in the monomer but does not dissolve in the aqueous medium, is polymerized in the aqueous medium under conditions of pot to 6. It has been found that the above-mentioned object of the present invention can be achieved by the manufacturing method. The present invention will be explained in more detail below. In the following description, "%" and "part" expressing quantitative ratios are based on weight unless otherwise specified. The polymerizable monomers used in the present invention are described below. That is, for example, styrene, 0-methylstyrene, di-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2
.. 4-dimethylstyrene, p-rope-dimethylstyrene, p
Styrene and its derivatives such as -tert-butylstyrene, pn-hexylstyrene, pn-cutylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, etc. Ethylenically unsaturated monoolefins such as ethylene, brobylene, butylene, and isobutylene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; Vinyls such as vinyl acetate, vinyl brobionate, and vinyl benzoate. Esters methyl methacrylate, ethyl methacrylate, probyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Methyl acrylate, ethyl acrylate, n-acrylate
Butyl, isobutyl acrylate, probyl acrylate,
Acrylic acid esters such as low octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isobrobenyl ketone; Acrylic acid or methacrylic acid derivatives such as vinyl naphthalenes, acrylonitrile, methacrylonitrile, and acrylamide. During polymerization, polymerization is carried out in the presence of the following crosslinking agent,
It may also be a crosslinked polymer. Divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate ,l,
6-hexane glycol dimethacrylate, neobentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polybrobylene glycol dimethacrylate, 2.2゜bis(4-methacryloxydiethoxyphenyl)broban, 2.2゛bis( 4-Acryloxydiethoxyphenyl)broban, trimethylolbroban trimethacrylate, trimethylolbroban triacrylate, tetramethylolmethanetetraacrylate, dibromneobentylglycol dimethacrylate, and general crosslinking agents can be used as appropriate. the above,
The cationic polymer dissolved in the monomer contains the positively charged polymerizable monomer (hereinafter referred to as cationic monomer) described below. That is, for example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, vinylpyridine, vinylimidazole, dimethylaminomethylstyrene, etc. In these cationic monomers, methyl group, ethyl group , may be quaternary ammoniumated with a butyl group, benzyl group, etc. Examples of the above-mentioned polymerizable monomer that copolymerizes with the cationic monomer include styrene, 0-methylstyrene, m-
Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene,
3.4-dichlorostyrene, p-ethylstyrene, 2.
4-dimethylstyrene, p-n-butylstyrene, p
- Styrene and its derivatives such as tert-butylstyrene, pn-hexylstyrene, pn-butylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; Vinyl esters such as vinyl acetate, vinyl brobionate, and vinyl benzoate Class; methyl methacrylate, ethyl methacrylate, provil methacrylate, loubyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid n
- Acrylic acid esters such as butyl, isobutyl acrylate, probyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether , vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isobrobenyl ketone; vinyl naphthalenes: acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylic nitrile, acrylamide, etc. and so on. Cationic polymers are produced, for example, by solution polymerization in organic solvents using an azo polymerization initiator. That is, the cationic monomer, a polymerizable monomer that copolymerizes with the cationic monomer, and an azo polymerization initiator are polymerized in an organic solvent. Here, as the azo polymerization initiator, for example, 1.1'-
Azobis (cyclohexane! monocarponitrile),
2.2°-azobisisobutyronitrile, 2,2°-azobis(2.4-dimethylbaretonitrile), etc. are used. Examples of the organic solvent used include aromatics such as toluene and xylene, alcohols, and ketones. Generally, aromatic compounds, particularly toluene, are preferably used. The proportion of the cationic monomer in the cationic polymer is preferably 3 to 80%, more preferably 7 to 70%. This is because if the cationic monomer content is less than 3%, sufficient positive chargeability cannot be imparted;
If the content is above, the solubility in an aqueous medium becomes strong even though sufficient positive chargeability can be imparted, making it impossible to achieve the object of the present invention. In the present invention, it is preferable to mix the cationic polymer and the polymerizable monomer so that the former becomes 5 to 80%, more preferably 1O to 70%. This is because if the content of the cationic polymer is less than 5%, sufficient positive chargeability cannot be imparted to the aqueous resin particles, and if the content is more than 80%, the cationic polymer and the polymerizable monomer The viscosity of the mixture with
It is not possible to obtain water-based resin particles. In the present invention, the molecular weight of the cationic polymer is 2,000 to 1,000,000 as determined by weight average molecular weight measurement by GPC.
, preferably 5,000 to 50,000
This is the case when it becomes 0. If the weight average molecular weight of the cationic polymer is less than 2,000, the solubility in an aqueous medium will be strong and the object of the present invention cannot be achieved;
0,000 or more, it is virtually impossible to dissolve and mix with the polymerizable monomer. As the carbon black used in the present invention, any type of carbon black can be used as long as it does not inhibit the radical polymerization reaction. Further, the carbon black can be pulverized in advance to obtain a good dispersion state in the polymerizable monomer composition, for example, by cross-mixing with the cationic polymer, or by mixing the carbon black with the polymerizable monomer composition. After mixing with the composition, it can be processed by applying external mechanical force to disperse it. Examples of the carbon black used in the present invention include Monarch 1300, Monarch 1100, Monarch 1000, Monarch 900, and Monarch 8.
80, 800, 700, Mogul L1 Legal 4
00R, 660R, 500R, 330R, 30
0R, 99R1 Vulcan XC-728, Elftex 8, Elftex 12 (all manufactured by Cabot),
Raven 5000, 7000, 5750, 525
0, 3500, 2000, 1500, 250
, same 1200, same 1170, same 1040, same 1035,
same! 000, Conductec 40-220, 975,
Examples include the same 900 and the same SC (manufactured by Columbian Carbon Co., Ltd.). The carbon black is preferably contained in an amount of 0.1 to 20 parts based on 100 parts of the polymerizable monomer, and further,
It is preferable that it is contained in an amount of 0.1 to 8 parts. If the content is 20 parts or more, it will have a strong influence on the polymerization reaction and will significantly inhibit the reaction, while if it is less than 0.1 part, it will not be charged when used in the shell material of microcapsule toner, which is one of the objects of the present invention. No improvement or improvement effect on characteristics was observed. Polymerization initiators that are not soluble in the aqueous medium used in the present invention include the following. That is, for example, 1.1'-azobis(cyclohexane-1-carponitrile), 2.2°-azobisisobutyronitrile, 2.2°-azobis(2.4-dimethylvalenitrile), 2.2 Examples of polymerization initiators include ゜-azobis(4-methoxy-2,4-dimethylbaretonitrile), dicumyl peroxide, dilauroyl peroxide, penzoyl peroxide, tolyl peroxide, and chloropenzoyl peroxide. It is preferable to add it to the mixture of the cationic monomer and the cationic polymer in an amount of 0.1 to 20%, more preferably 0.5 to 15%. if,
If the amount of the polymerization initiator added is less than 0.1%, it is difficult to complete the polymerization reaction, and if the amount of the polymerization initiator added is 20% or more, it is difficult to control the polymerization reaction. In the present invention, it is preferable that p}I of the aqueous medium is between 1 and 6 when measured at 20°C, and even under strong acidity where the pH is less than 1 or under weak acidity where the pH is 6. The aqueous resin particles of the present invention cannot be stably produced. Note that the pH of the aqueous medium is preferably adjusted with hydrochloric acid, acetic acid, etc., and a buffer solution may be used to stabilize the pH. The aqueous resin particles of the present invention are 500 μm to 0.0 μm. The particle size can be adjusted to any size between 1 μm and preferably 1 μm.
The particle size is 00 μI11 to 0.01 μm,
More preferably, the particle size is 50 μl and 11 to 0.1 μm. The aqueous resin of the present invention can be prepared at any solid content concentration of 50% or less based on the aqueous medium, but is preferably prepared at a solid content concentration of 5 to 35%. When the solid content concentration exceeds 50%, heat generation due to the polymerization reaction of the polymerizable monomer increases and becomes difficult to control, and furthermore, scale formation due to aggregation between resin particles increases, which becomes a problem. In addition, in the present invention, a polymerization initiator that does not dissolve in an aqueous medium has a solubility in an aqueous medium of 1 when measured at 20°C.
% or less. When the method of the present invention is applied to the production of microcapsule toner, the aqueous resin particles are the core particles 1 of the microcapsules.
0.1 to 50 parts, preferably 1 to 30 parts. If the amount of particles is less than 0 or 1 part, the core particles will not be encapsulated substantially, and if the amount of aqueous resin particles is more than 50 parts, the core particles will agglomerate among themselves during encapsulation, making it unsuitable for practical use as a microcapsule toner. Cannot be used above. If the particle size of the core material particles is 1, the particle size ratio of the wall material particles and the core material particles is 1/1000 ~! /! It is good if it is between, and more preferably! /500 to 1/2. If the particle size ratio of the aqueous resin particles to the core particles is smaller than 1/1000, that is, if the aqueous resin particles are too small, a capsule wall can be formed on the surface of the core particles, but the microcapsule toner However, if the size is larger than 1/1, that is, if the aqueous resin particles are too large, even if the aqueous resin particles can adhere to the surface of the core material particles, the capsule wall will not be dense and strong. This also results in significantly lower durability. The average particle diameter of the core material particles may be in the range of 1 to 30 μm, more preferably in the range of 5 to 20 μm.
以下、実施例によって本発明をさらに具体的に説明する
。
カチオン性重合体(1)の合成
メタクリル酸ジメチルアミンエチル lO部スチレン
90部2.2゜−アゾビ
スイソブチロニトリル IO部上記、重合性単量体組
成物5. 0kgをトルエン12.OI2と混合し、2
0βの容器に入れ攪拌する。重合開始剤が完全に溶解し
、均一溶液となったのを確認し、窒素を流しながら、攪
拌下、78℃まで徐々に加熱する.78℃に達したなら
ばその温度で6時間重合反応を行い、ついで、溶媒のト
ルエンが還流するまで加熱し、1時間その状態に保つ。
その後、溶媒を未反応の重合性単量体とともに留去して
濃縮する。さらに120℃で24時間減圧乾燥すること
により、カチオン性重合体(1)を得た。
尚、元素分析を行なった結果、メタクリル酸ジメチルア
ミノエチルが9.7%含有されていることがわかった。
カチオン性重合体(2)の合成
メタクリル酸ジエチルアミノエチル 8部メタクリル
酸メチル 92部2.2゜−アゾビス
イソブチロニトリル 5部上記重合性単量体組成物を
用いた以外はカチオン性重合体(1)と同様にして、重
合体を得た.これを本発明のカチオン性重合体(2)と
する.尚、元素分析を行なった結果、メタクリル酸ジエ
チルアミノエチルは8.4%含有されていることがわか
った.
カチオン性重合体(3)の合成
ジメチルアミノメチルスチレン 15部スチレン
85部過酸化ベンゾイル
3部上記、重合性単量体組成物5
. 0kgをトルエン12.oj2と混合し、20氾の
容器に入れ攪拌する。重合開始剤が完全に溶解し、均一
溶液となったのを確認し、窒素を流しながら、攪拌下、
80゜Cまで徐々に加熱する。80℃に達したならばそ
の温度で10時間重合反応を行い、ついで、溶媒のトル
エンが還流するまで加熱し、1時間その状態に保つ。
その後、溶媒を未反応の重合性単量体とともに留去して
濃縮する。さらに120℃で24時間減圧乾燥すること
により、カチオン性重合体(3)を得た。
尚、元素分析を行なった結果、ジメチルアミンメチルス
チレンが15.1%含有されていることがわかった.
カチオン性重合体(4)の合成
ビニルイミダゾール 30部スチレン
70部t,t’−アゾビ
ス(シクロヘキサン 5部−1一カルポニトリル)
上記、重合性単量体組成物5. 0kgをトルエン15
,Oβと混合し、30℃の容器に入れ攪拌する。重合開
始剤が完全に溶解し、均一溶液となったのを確認したな
らば窒素を流しながら、攪・拌下、95℃まで徐々に加
熱する。95℃に達したならばその温度で8時間重合反
応を行い、ついで、溶媒のトルエンが還流するまで加熱
し、1時間その状態に保つ.その後、溶媒を未反応の重
合性単量体とともに留去して濃縮する。さらに120℃
で24時間減圧乾燥することにより、カチオン性重合体
(4)を得た。
尚、元素分析を行なった結果、ビニルイミダゾールが2
9.2%含有されていることがわかった.水性樹脂粒子
(1)の製造
カチオン性重合体(1) 50部スチ
レン 48部ジビニルベン
ゼン 2部2.2゜−アゾビス(2
.4−ジメチル 5部バレロニトリル)
ラーベン3500 1部(
コロンビャ・カーボン社製)
容量lOI2の反応容器に塩酸によりpH2.0に調整
したイオン交換水5βを投入する.室温で攪拌下、上記
重合性単量体溶液組成物2. 0kgを20分かけて滴
下すると、乳白色の乳化物を得る。ついで、60℃まで
加熱し、その温度で8時間保持し、さらに80℃まで加
熱して1時間保った後に室温まで冷却する.得られた樹
脂粒子水溶液は100メッシュのふるいを通過させて、
若干量生成する樹脂粒子凝集物を除去した.これを本発
明の水性樹脂粒子(1)とする.
尚、コールターN4型により測定した平均粒径は0。4
0±0.09μmであった.また、一定量の水性樹脂粒
子液を濃縮、乾固することで求めた固形分量は28.1
%、重合収率は97.8%であった。
水性樹脂粒子(2)の製造
カチオン性重合体(2) 20部スチ
レン 70部アクリル酸エ
チル 8部ジビニルベンゼン
2部コンダクテック40−220
0. 1部(コロンビャ・カーボン社製)
上記単量体組成物を周囲を冷却したサンドミルに投入し
、10時間カーボンブラックの混合、分散を行なった.
次に、重合開始剤である2,2゛−アゾビスイソブチロ
ニトリル5部を加え、溶解した.容量10βの反応容器
に塩酸によりpH2.0に調整したイオン交換水5℃を
投入する。室温で攪拌下、上記重合性単量体溶液組成物
1. 0kgを20分かけて滴下すると、乳白色の乳化
物を得る.ついで、78℃まで加熱し、その温度で8時
間保持し、さらに90℃まで加熱して1時間保った後に
室温まで冷却する.得られた樹脂粒子水溶液は100メ
ッシュのふるいを通過させて、若干量生成する樹脂粒子
凝集物を除去した.これを本発明の水性樹脂粒子(2)
とする.
尚、コールターN4型により測定した平均粒径は0.1
5±0.02μmであった。また、一定量の水性樹脂粒
子液を濃縮、乾固することで求めた固形分量は16.1
%、重合収率は97,1%であった.マイクロカプセル
トナー(1)の製造(応用例)ポリエステル(組成、テ
レフタル酸:イソフタル酸:エチレングリコール:トリ
メチロールプロパン=45:10:30:15) 1
00部磁性体 60部低
分子量ボリブロビレン 6部(三洋化成工
業製ビスコール660P)からなる混合物をロールで加
熱混練した。これを放冷した後に粗砕し、さらにジェッ
トミルによる微粉砕及び風力分級機による分級を行なっ
て、体積平均粒径11.6μmの芯材粒子(1)を得た
。
この芯材粒子100部に対して本発明の水性樹脂粒子(
1)を固形分に換算して!5部を混合分散した.次に、
スブレイドライアーにより、入口温度160℃、出口温
度90℃の条件でスブレイ乾燥を行ない、芯材粒子の周
囲に前記エマルジョン構成共重合体を主体とする架橋樹
脂被覆層を設けた。これを本発明のマイクロカプセルト
ナー(1)とする。
このようにして得られたカプセルトナー(1)にコロイ
ダルシリ力(アエロジルR−972)を添加し、NP−
3525 (キヤノン製)にて1000枚の画出しを行
なったところ、充分な画像濃度、現像耐久性を有するこ
とを確認した.
また熱定着性を詳しく見る目的で前記複写装置の定着部
のみを別に用意し、別途作成した転写紙上の未定着画像
をこの別定着器で定着させたところ、広い温度範囲でオ
フセット現象も発生せず定着性も優れていた.
更にこのカプセルトナーな45℃の雰囲気に長時間放置
したが、プロツキング.ケーキングは見られなかった.
マイクロカプセルトナー(2)の製造(応用例)スチレ
ン・プチルアクリレート・
ジビニルベンゼン共重合体
(組成比?7: 22.5: o.s) 1
00部磁性体 60部低
分子量ポリブロビレン 8部(三洋化成工
業製ビスコール660P)からなる芯材粒子を用いて、
水性樹脂(2)を用いた以外は実施例lと同様にしてマ
イクロカプセルトナー(2)を得た.マイクロカプセル
トナー(11 と同様の画出し評価及びブロッキング試
験を行なったところ良好な結果を得た.
マイクロカプセルトナー(3)の製造(応用例)マイク
ロカプセルトナー(1)の製造で用いた芯材粒子とアエ
ロジル#300とを混合、攪拌し、その表面なシリカで
被覆した.この芯材粒子1. 0kgを含むスラリ−1
0kgを204の容器に入れ室温で攪拌した.次にシリ
カが解離してアニオンとして作用する様に水相のpHを
調整した.
上記芯材粒子(+)の懸濁分散液中に水性樹脂粒子(1
)を150g含む微粒子分散液を攪拌下添加した.1時
間攪拌を継続した後に50℃まで加熱し、2時間その温
度に保った.
室温まで冷却後、濾別.乾燥した.電子顕微鏡を用いて
該粒子の表面を観察したところ、壁材粒子により被覆さ
れているのを確認した.これをマイクロカプセルトナー
(3)とする.マイクロカプセルトナー(1)と同様の
画出し評価及び、ブロッキング試験を行なったところ良
好な結果を得た.
比較例l
水性樹脂粒子(1)の製造例において、水系媒体である
イオン交換水をpH7.6に調整した以外は全く同様に
して水性樹脂粒子の製造を試みた.重合性単量体溶液組
成物の水相への分散状態はきわめて不安定であり、水性
樹脂粒子を得ることはできなかった.
比較応用例
水性樹脂粒子(1)の製造例において、乳化剤としてド
デシルベンゼンスルホン酸ナトリウム塩を0,5部加え
、水相のpllを調整しなかった以外は全く同様にして
重合を行ない、比較用水性樹脂粒子(2)を得た.
この比較用樹脂粒子(2)を用いた以外はマイクロカプ
セル(1)の製造と同様にして、スプレードライ法によ
り比較用マイクロカプセルトナーな得、画出しおよび耐
久評価を行なったところ、画像濃度はきわめて低いもの
であった.Hereinafter, the present invention will be explained in more detail with reference to Examples. Synthesis of Cationic Polymer (1) Dimethylamine ethyl methacrylate 10 parts Styrene 90 parts 2.2°-Azobisisobutyronitrile 10 parts Above polymerizable monomer composition 5. 0kg to toluene 12. Mix with OI2, 2
Pour into a 0β container and stir. After confirming that the polymerization initiator has completely dissolved to form a homogeneous solution, gradually heat the solution to 78°C while stirring and flowing nitrogen. Once the temperature reaches 78°C, the polymerization reaction is carried out at that temperature for 6 hours, and then heated until the solvent toluene refluxes and kept in that state for 1 hour. Thereafter, the solvent is distilled off along with the unreacted polymerizable monomer to concentrate. Further, by drying under reduced pressure at 120° C. for 24 hours, a cationic polymer (1) was obtained. As a result of elemental analysis, it was found that 9.7% of dimethylaminoethyl methacrylate was contained. Synthesis of cationic polymer (2) Diethylaminoethyl methacrylate 8 parts Methyl methacrylate 92 parts 2.2°-Azobisisobutyronitrile 5 parts Cationic polymers except for the above polymerizable monomer composition were used A polymer was obtained in the same manner as in (1). This is referred to as the cationic polymer (2) of the present invention. As a result of elemental analysis, it was found that the content of diethylaminoethyl methacrylate was 8.4%. Synthesis of cationic polymer (3) Dimethylaminomethylstyrene 15 parts Styrene 85 parts Benzoyl peroxide 3 parts Above polymerizable monomer composition 5
.. 0kg to toluene 12. Mix with oj2 and stir in a 20ml container. After confirming that the polymerization initiator was completely dissolved and a homogeneous solution was formed, the solution was stirred while flowing nitrogen.
Gradually heat to 80°C. Once the temperature reaches 80°C, the polymerization reaction is carried out at that temperature for 10 hours, and then heated until the solvent toluene refluxes and kept in that state for 1 hour. Thereafter, the solvent is distilled off along with the unreacted polymerizable monomer to concentrate. Further, by drying under reduced pressure at 120° C. for 24 hours, a cationic polymer (3) was obtained. As a result of elemental analysis, it was found that 15.1% of dimethylamine methylstyrene was contained. Synthesis of cationic polymer (4) Vinylimidazole 30 parts Styrene 70 parts t,t'-azobis(cyclohexane 5 parts - 1-carponitrile) Above polymerizable monomer composition 5. 0kg to toluene 15
, Oβ, and stirred in a container at 30°C. After confirming that the polymerization initiator has completely dissolved to form a homogeneous solution, the solution is gradually heated to 95° C. while flowing nitrogen and stirring. Once the temperature reached 95°C, the polymerization reaction was carried out at that temperature for 8 hours, then heated until the solvent toluene refluxed and kept in that state for 1 hour. Thereafter, the solvent is distilled off along with the unreacted polymerizable monomer to concentrate. Further 120℃
By drying under reduced pressure for 24 hours, a cationic polymer (4) was obtained. Furthermore, as a result of elemental analysis, vinylimidazole was found to be 2
It was found that the content was 9.2%. Production of aqueous resin particles (1) Cationic polymer (1) 50 parts Styrene 48 parts Divinylbenzene 2 parts 2.2°-azobis(2
.. 4-dimethyl 5 parts Valeronitrile) Raben 3500 1 part (
(manufactured by Columbia Carbon) Pour 5β of ion-exchanged water adjusted to pH 2.0 with hydrochloric acid into a reaction vessel with a capacity of 1OI2. While stirring at room temperature, the polymerizable monomer solution composition 2. When 0 kg is added dropwise over 20 minutes, a milky white emulsion is obtained. Next, heat to 60°C, hold at that temperature for 8 hours, further heat to 80°C, hold for 1 hour, and then cool to room temperature. The resulting resin particle aqueous solution was passed through a 100 mesh sieve,
A small amount of resin particle aggregates were removed. This is referred to as the aqueous resin particle (1) of the present invention. In addition, the average particle diameter measured by Coulter N4 type is 0.4
It was 0±0.09 μm. In addition, the solid content determined by concentrating and drying a certain amount of aqueous resin particle liquid was 28.1
%, and the polymerization yield was 97.8%. Production of water-based resin particles (2) Cationic polymer (2) 20 parts styrene 70 parts ethyl acrylate 8 parts divinylbenzene
Part 2 Conductec 40-220
0. 1 part (manufactured by Columbia Carbon) The above monomer composition was placed in a sand mill whose surroundings were cooled, and carbon black was mixed and dispersed for 10 hours.
Next, 5 parts of 2,2'-azobisisobutyronitrile, a polymerization initiator, was added and dissolved. Ion-exchange water adjusted to pH 2.0 with hydrochloric acid at 5° C. is charged into a reaction vessel having a capacity of 10β. While stirring at room temperature, the polymerizable monomer solution composition 1. When 0 kg is added dropwise over 20 minutes, a milky white emulsion is obtained. Next, heat to 78°C, hold at that temperature for 8 hours, further heat to 90°C, hold for 1 hour, and then cool to room temperature. The resulting resin particle aqueous solution was passed through a 100 mesh sieve to remove a small amount of resin particle aggregates. This is the aqueous resin particle (2) of the present invention.
Suppose that In addition, the average particle diameter measured by Coulter N4 type is 0.1
It was 5±0.02 μm. In addition, the solid content determined by concentrating and drying a certain amount of aqueous resin particle liquid was 16.1
%, and the polymerization yield was 97.1%. Production of microcapsule toner (1) (application example) Polyester (composition, terephthalic acid: isophthalic acid: ethylene glycol: trimethylolpropane = 45:10:30:15) 1
A mixture consisting of 00 parts magnetic material 60 parts low molecular weight polypropylene 6 parts (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.) was heated and kneaded with a roll. After allowing it to cool, it was coarsely crushed, and further finely pulverized using a jet mill and classified using an air classifier to obtain core particles (1) having a volume average particle diameter of 11.6 μm. The aqueous resin particles of the present invention (
Convert 1) to solid content! 5 parts were mixed and dispersed. next,
A spray dryer was used to perform spray drying at an inlet temperature of 160° C. and an outlet temperature of 90° C., and a crosslinked resin coating layer mainly composed of the emulsion-constituting copolymer was provided around the core material particles. This is referred to as the microcapsule toner (1) of the present invention. Colloidal Siriyoku (Aerosil R-972) was added to the capsule toner (1) thus obtained, and NP-
3525 (manufactured by Canon) and it was confirmed that the image had sufficient image density and development durability. In addition, in order to examine the thermal fixability in detail, we prepared a separate fixing unit for the copying machine and used this separate fixing unit to fix an unfixed image on a separately prepared transfer paper, and no offset phenomenon occurred over a wide temperature range. The adhesion properties were also excellent. Furthermore, when this capsule toner was left in an atmosphere of 45°C for a long time, no blockage occurred. No caking was observed. Production of microcapsule toner (2) (application example) Styrene/butyl acrylate/divinylbenzene copolymer (composition ratio: 7:22.5: o.s) 1
Using core material particles consisting of 00 parts magnetic material 60 parts low molecular weight polypropylene 8 parts (Viscol 660P manufactured by Sanyo Chemical Industries),
Microcapsule toner (2) was obtained in the same manner as in Example 1 except that aqueous resin (2) was used. Good results were obtained when the same image quality evaluation and blocking test as for microcapsule toner (11) were conducted. Production of microcapsule toner (3) (application example) Core used in the production of microcapsule toner (1) The core material particles and Aerosil #300 were mixed and stirred, and the surface thereof was coated with silica.Slurry 1 containing 1.0 kg of the core material particles
0 kg was placed in a 204 container and stirred at room temperature. Next, the pH of the aqueous phase was adjusted so that the silica dissociated and acted as an anion. The aqueous resin particles (1
) was added under stirring. After continuing stirring for 1 hour, it was heated to 50°C and kept at that temperature for 2 hours. After cooling to room temperature, filter. It was dry. When the surface of the particles was observed using an electron microscope, it was confirmed that the particles were covered with wall material particles. This is called microcapsule toner (3). Good results were obtained when the same image quality evaluation and blocking test as for Microcapsule Toner (1) were conducted. Comparative Example 1 An attempt was made to produce aqueous resin particles in exactly the same manner as in the production example of aqueous resin particles (1) except that the aqueous medium, ion-exchanged water, was adjusted to pH 7.6. The dispersion state of the polymerizable monomer solution composition in the aqueous phase was extremely unstable, and it was not possible to obtain aqueous resin particles. Comparative Application Example Polymerization was carried out in exactly the same manner as in the production example of aqueous resin particles (1) except that 0.5 parts of sodium dodecylbenzenesulfonate was added as an emulsifier and the PLL of the aqueous phase was not adjusted. Aqueous resin particles (2) were obtained. The comparative microcapsule toner was evaluated for yield, image quality, and durability by spray drying in the same manner as the production of microcapsules (1) except that the comparative resin particles (2) were used. was extremely low.
本発明により、通常の乳化剤、水溶性の重合開始剤、更
には水溶性の高分子乳化剤等をも使用しないことを特徴
とし、特にマイクロカプセルトナー用樹脂粒子の製造に
適した水性樹脂粒子の製造方法が提供された.
特許出願人 キヤノン株式会社According to the present invention, water-based resin particles are produced that are characterized in that they do not use ordinary emulsifiers, water-soluble polymerization initiators, or even water-soluble polymer emulsifiers, and are particularly suitable for producing resin particles for microcapsule toners. A method was provided. Patent applicant Canon Inc.
Claims (1)
電する重合体、カーボンブラック及び該単量体に溶解し
水性媒体には溶解しない重合開始剤からなる単量体組成
物を該水性媒体中でpH1〜6の条件で重合することを
特徴とする水性樹脂粒子の製造方法。1) A monomer composition consisting of at least a polymerizable monomer, a positively charged polymer that dissolves in the monomer, carbon black, and a polymerization initiator that dissolves in the monomer but does not dissolve in an aqueous medium. A method for producing aqueous resin particles, which comprises polymerizing in the aqueous medium at a pH of 1 to 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1059823A JPH02240105A (en) | 1989-03-14 | 1989-03-14 | Production of aqueous resin particle |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1059823A JPH02240105A (en) | 1989-03-14 | 1989-03-14 | Production of aqueous resin particle |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02240105A true JPH02240105A (en) | 1990-09-25 |
Family
ID=13124335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1059823A Pending JPH02240105A (en) | 1989-03-14 | 1989-03-14 | Production of aqueous resin particle |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02240105A (en) |
-
1989
- 1989-03-14 JP JP1059823A patent/JPH02240105A/en active Pending
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