JPH01962A - Method for manufacturing toner for electrophotography - Google Patents
Method for manufacturing toner for electrophotographyInfo
- Publication number
- JPH01962A JPH01962A JP62-157045A JP15704587A JPH01962A JP H01962 A JPH01962 A JP H01962A JP 15704587 A JP15704587 A JP 15704587A JP H01962 A JPH01962 A JP H01962A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- particle size
- polymer
- dispersion stabilizer
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000000034 method Methods 0.000 title description 43
- 239000000178 monomer Substances 0.000 claims description 81
- 239000006185 dispersion Substances 0.000 claims description 72
- 239000003381 stabilizer Substances 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 56
- -1 acrylic ester Chemical class 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000003086 colorant Substances 0.000 claims description 18
- 239000006247 magnetic powder Substances 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 91
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 72
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 57
- 239000000243 solution Substances 0.000 description 56
- 238000010557 suspension polymerization reaction Methods 0.000 description 56
- 238000006116 polymerization reaction Methods 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 229910052757 nitrogen Inorganic materials 0.000 description 37
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 32
- 239000002904 solvent Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 238000009826 distribution Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000306 component Substances 0.000 description 25
- 239000011572 manganese Substances 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 239000003505 polymerization initiator Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 239000006229 carbon black Substances 0.000 description 16
- 235000019241 carbon black Nutrition 0.000 description 16
- 230000005291 magnetic effect Effects 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 10
- 238000011088 calibration curve Methods 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 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 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 125000005936 piperidyl group Chemical group 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- 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 5
- 238000003860 storage Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 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 description 3
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000004148 curcumin Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- PYXBAOCOBUVISP-UHFFFAOYSA-N 2-morpholin-4-yloctyl prop-2-enoate Chemical compound CCCCCCC(COC(=O)C=C)N1CCOCC1 PYXBAOCOBUVISP-UHFFFAOYSA-N 0.000 description 2
- REDVXIGDRDIWCE-UHFFFAOYSA-N 2-morpholin-4-ylpropyl prop-2-enoate Chemical compound C=CC(=O)OCC(C)N1CCOCC1 REDVXIGDRDIWCE-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
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- VMEZXMFPKOMWHR-UHFFFAOYSA-N (dimethylamino)methyl prop-2-enoate Chemical compound CN(C)COC(=O)C=C VMEZXMFPKOMWHR-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
- BJQFWAQRPATHTR-UHFFFAOYSA-N 1,2-dichloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1Cl BJQFWAQRPATHTR-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
- IMRIYYYRLGPJNM-UHFFFAOYSA-N 1-chloro-2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C(Cl)=CC1=CC=CC=C1 IMRIYYYRLGPJNM-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- DUDKKPVINWLFBI-UHFFFAOYSA-N 1-chlorobut-1-ene Chemical compound CCC=CCl DUDKKPVINWLFBI-UHFFFAOYSA-N 0.000 description 1
- DMADTXMQLFQQII-UHFFFAOYSA-N 1-decyl-4-ethenylbenzene Chemical compound CCCCCCCCCCC1=CC=C(C=C)C=C1 DMADTXMQLFQQII-UHFFFAOYSA-N 0.000 description 1
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-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
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- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- DEKYKRGSGMURRD-UHFFFAOYSA-N morpholin-4-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCN1CCOCC1 DEKYKRGSGMURRD-UHFFFAOYSA-N 0.000 description 1
- XWCUDBBUDRNSKP-UHFFFAOYSA-N n-(2-morpholin-4-ylethyl)prop-2-enamide Chemical compound C=CC(=O)NCCN1CCOCC1 XWCUDBBUDRNSKP-UHFFFAOYSA-N 0.000 description 1
- YYMRAHJYANNJQC-UHFFFAOYSA-N n-(morpholin-4-ylmethyl)prop-2-enamide Chemical compound C=CC(=O)NCN1CCOCC1 YYMRAHJYANNJQC-UHFFFAOYSA-N 0.000 description 1
- JLSGYVNIIASPIZ-UHFFFAOYSA-N n-methylmethanamine;propyl 2-methylprop-2-enoate Chemical compound CNC.CCCOC(=O)C(C)=C JLSGYVNIIASPIZ-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は電子写真法に用いられる電子写真用トナーの製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an electrophotographic toner used in electrophotography.
(従来の技術)
電子写真法においては、光導電層を帯電させた後、原図
に基づいた光像を照射し、光照射部分の静電荷を減少或
いは消滅させて静電潜像を形成し。(Prior Art) In electrophotography, after a photoconductive layer is charged, it is irradiated with a light image based on an original image to reduce or eliminate the electrostatic charge in the light-irradiated area to form an electrostatic latent image.
次いでこれを可視化するために現像剤を作用させる。乾
式現像剤は一般にトナーと呼ばれる微細な粉末とそれを
運搬するキャリアからなるf成分現像剤、磁性粉を含む
磁性トナーのみからなる一成分現像剤がある。前記トナ
ーの代表的なものは。Next, a developer is applied to visualize this. Dry developers generally include an f-component developer consisting of fine powder called toner and a carrier for transporting it, and a single-component developer consisting only of magnetic toner containing magnetic powder. What are the typical toners mentioned above?
染料、顔料などの着色材料及び/又は磁性粉と熱可塑性
樹脂などの結着材料との混合物である。It is a mixture of coloring materials such as dyes and pigments and/or magnetic powder and binding materials such as thermoplastic resins.
従来乾式トナーは、一般にカーボンブラック等の顔料を
熱可塑性樹脂中に溶融混練し、−様な分散体にした後、
適当な微粉砕装置によシ微細な粉末に粉砕する方法が行
われてきた。この方法により得られるトナーは数々の優
れた特性を有しているが、同時Kまた多くの欠点を有し
ている。例えば材料的に制限を受ける。すなわち溶融及
び粉砕という工程を要すため、適当な温度で流動化し。Conventional dry toners are generally made by melting and kneading a pigment such as carbon black into a thermoplastic resin to form a -like dispersion.
Grinding into fine powder using suitable pulverizing equipment has been practiced. Although the toner obtained by this method has a number of excellent properties, it also has a number of drawbacks. For example, there are limitations in terms of materials. In other words, since it requires a process of melting and pulverization, it must be fluidized at an appropriate temperature.
顔料などが均一に混合しうる状態となること、その混合
系が用いる粉砕装置によシ望みの粒径にかなりの速度で
処理できることが要求される。しかし、砕は易いものを
用いると、電子写真装置中でさらに粉砕され、生成した
微粉トナーは、装置の汚れ9画像のカプリといった欠点
を招来することになる。また、単に溶融し易いものを用
いると保存中或いは電子写真装置中でのトナーのブロッ
キング、光導電体表面へのフィルミングにつながる恐れ
もある。また、粉砕時に樹脂中に埋没していた顔料が表
面に現われることにより、摩擦帯電特性の微少な部分的
不均一を生ずることがあシ、これによって電子写真画像
が劣化し、さらには顔料の種類によっては耐湿性などに
も問題がでてくる。It is required that pigments and the like be mixed uniformly, and that the grinding equipment used in the mixing system be capable of processing the desired particle size at a considerable speed. However, if a material that is easily crushed is used, it will be further crushed in the electrophotographic apparatus, and the resulting fine powder toner will cause problems such as staining the apparatus and capping the image. Furthermore, if a material that is easily melted is used, there is a risk that toner may block during storage or in an electrophotographic apparatus, or may cause filming on the surface of the photoconductor. In addition, the pigment that was buried in the resin appears on the surface during crushing, which may cause minute local unevenness in triboelectric charging characteristics, which deteriorates the electrophotographic image, and furthermore, In some cases, there may be problems with moisture resistance.
さらに大きな欠点と考えられるのは、トナーの形と粒度
分布である。粉砕によって作られたトナーの形状は不定
形であり、トナー粒子間のからみ合い(凝集)を生じ易
く、トナー貯蔵時の安定性。What is considered to be an even bigger drawback is the shape and particle size distribution of the toner. The shape of the toner produced by pulverization is amorphous and tends to cause entanglement (agglomeration) between toner particles, which affects the stability of the toner during storage.
トナー供給時のディスペンス特性、さらには現像され良
画像の鮮鋭度への悪影響があり、また繰返し使用の場合
のクリーニング特性にも望ましくない要因として働く。This adversely affects the dispensing characteristics during toner supply and the sharpness of a good developed image, and also acts as an undesirable factor in the cleaning characteristics in the case of repeated use.
最大の欠点と考えられるのは、粉砕工程で望みの粒子サ
イズのものを望みの粒度分布の範囲内に入るように微粉
化することが極めて困峻であると ・いうことである。What is considered to be the biggest drawback is that it is extremely difficult to pulverize particles with the desired particle size into a desired particle size distribution during the pulverization process.
乾式電子写真現像剤として用いられるトナーの平均粒径
は一般KIOμm程度であるが、粉砕法では経済速度で
粉砕可能なように材料を選ぶと1μm以下のかなυの微
粒子のものも生じてしまう。また、そのようにしてさえ
数十Jtlpm或いはそれ以上の粗大粒子がわずかでは
あるが残存し製品に混入してくる。一般に得られる画質
、籍に解儂力、鮮鋭度、カブリなどはこれられずかな微
細粒子、粗大粒子の影響を強く受けて著しく低下してし
まう。The average particle size of toner used as a dry electrophotographic developer is generally about KIO μm, but in the pulverization method, if the material is selected so that it can be pulverized at an economical speed, fine particles of υ of 1 μm or less are produced. Further, even in such a case, a small amount of coarse particles of several tens of Jtlpm or more remain and are mixed into the product. Generally, the image quality obtained, including elucidation power, sharpness, fog, etc., is strongly affected by these small particles and coarse particles, and is significantly degraded.
こういった粉砕法の他に2例えば特公昭36−1023
1号公報及び特公昭43−10799号公報に見られる
ような重合法による乾式トナー製造法を提案されている
。前者はいわゆる水性懸濁重合法によるもので合成樹脂
単量体2重合開始剤。In addition to these pulverization methods, there are two other methods, such as the
Dry toner manufacturing methods using polymerization methods have been proposed as seen in Japanese Patent Publication No. 1 and Japanese Patent Publication No. 43-10799. The former is based on the so-called aqueous suspension polymerization method and uses a synthetic resin monomer dipolymerization initiator.
分散安定剤9着色材料等の混合物を水中に懸濁し重合し
てトナーを製造する工程と重合の過程又は重合終了後に
重合物を界面活性剤で処理することによシ静電荷を付与
する工程より成っている。後者はいわゆる乳化重合法に
よるもので、乳化剤(界面活性剤)9重合開始剤を含む
合成樹脂単量体の水性乳化液を重合させて得られるラテ
ックスに着色材料を加えてその乳化分散液を噴霧乾燥工
程で造粒し、トナーを製造するものである。これらのト
ナーに共通していることとして、いずれも形状が球形で
あシ、顔料をトナー内部に包含していること、工程中で
界面活性剤を用いていることなどが挙げられる。乳化重
合法では、単量体を水中に微細かつ安定に乳化するため
に界面活性剤の使用が必要で、これを乳化剤と称し用い
ている。Dispersion Stabilizer 9 A process of suspending a mixture of coloring materials, etc. in water and polymerizing it to produce a toner, and a process of imparting an electrostatic charge by treating the polymer with a surfactant during the polymerization process or after the completion of polymerization. It has become. The latter method is based on the so-called emulsion polymerization method, in which a coloring material is added to the latex obtained by polymerizing an aqueous emulsion of synthetic resin monomers containing an emulsifier (surfactant), 9 polymerization initiators, and the resulting emulsion dispersion is sprayed. It is granulated in the drying process to produce toner. What these toners have in common is that they are all spherical in shape, contain pigments inside the toner, and use surfactants in the process. In the emulsion polymerization method, it is necessary to use a surfactant to finely and stably emulsify monomers in water, and this is called an emulsifier.
また、懸濁重合法においては単量体の水中への微粒分散
安定化をはかシ2重合体が塊になるのを防止するために
分散安定剤を用いるが、これは大きく分けて二連シの方
法がある。In addition, in the suspension polymerization method, a dispersion stabilizer is used to stabilize the fine particle dispersion of the monomer in water and to prevent the dipolymer from forming agglomerates. There is a method.
そのひとつは、水溶性高分子を水中に溶解させる方式で
あり、水溶性高分子を比較的少食用いればよく操作も簡
単であるが、このような方法では微細かつ粒度分布の均
一な重合物を得ることはできないし、水溶性高分子が重
合体粒子表面に吸着又は、・クラフト化して重合体を汚
染する等の欠点がある。他は難溶性無機塩粉末をS濁さ
せて用いる方式であシャ難溶性無機塩粉末自身の分散を
よくすることにより、かなシ粒度分布の均一な重合物を
得ることができるが、単独で用いた場合には。One method is to dissolve water-soluble polymers in water, which is easy to operate and requires only a relatively small amount of water-soluble polymers. However, there are drawbacks such as the fact that the water-soluble polymer is adsorbed onto the surface of the polymer particles or becomes kraft, contaminating the polymer. The other method is to use a slightly soluble inorganic salt powder in a cloudy state, and by improving the dispersion of the slightly soluble inorganic salt powder itself, it is possible to obtain a polymer with a uniform particle size distribution. If there was.
その分散が不十分かつ不安定で、そのため界面活性剤を
併用してその分散の向上及び安定化を行っている。The dispersion is insufficient and unstable, so surfactants are used in combination to improve and stabilize the dispersion.
(発明が解決しようとする問題点)
しかし、上記のような界面活性剤の使用は決して望まし
いものではない。すなわち、界面活性剤を使用した場合
、界面活性という特性上これを完全に取除くことは他め
て困難で、かなシの手間と時間をかけて洗浄したとして
も重合粒子の表面に多少なりとも残存する。一方、乾式
の電子写真法に用いるトナーの電気特性は、はとんどそ
の表面の特性に依存しておシ、シ九がってトナー表面に
水溶性高分子とか界面活性剤が残存していると。(Problems to be Solved by the Invention) However, the use of surfactants as described above is by no means desirable. In other words, when a surfactant is used, it is difficult to completely remove it due to its surfactant properties, and even if you spend a lot of time and effort cleaning it, it will leave some residue on the surface of the polymer particles. remain. On the other hand, the electrical properties of toner used in dry electrophotography mostly depend on the properties of its surface, and depending on whether water-soluble polymers or surfactants remain on the toner surface. If there is.
たとえわずかであっても種々の問題を生じてくる。Even if it is only a small amount, it can cause various problems.
例えば界面活性剤自身の電気伝導度、湿度依存性が直接
トナーの電気特性に影響し、トナーの摩擦帯電特性を著
しく不安定にする。さらにトナー表面に界面活性剤が残
っていると、水分を吸収し易く高湿時での安定性が悪く
なる。また併用するキャリアや繰返し使用の場合の感光
体表面にトナーからの界面活性剤が転移付着して、感光
体の寿命を低下させ、電子写真特性を著しく不安定なも
のとしてしまう。For example, the electrical conductivity and humidity dependence of the surfactant itself directly affect the electrical properties of the toner, making the triboelectric charging properties of the toner extremely unstable. Furthermore, if the surfactant remains on the surface of the toner, it will easily absorb moisture and will have poor stability under high humidity conditions. Further, surfactant from the toner transfers and adheres to the carrier used in combination and the surface of the photoreceptor when used repeatedly, reducing the life of the photoreceptor and making the electrophotographic characteristics extremely unstable.
したがって2本発明は、前記の種々の欠点を解消し、界
面活性剤を使用することなく、写真特性の優れた電子写
真用トナーを製造しうる方法を提供することを目的とす
る。Therefore, it is an object of the present invention to provide a method that eliminates the various drawbacks mentioned above and can produce an electrophotographic toner with excellent photographic properties without using a surfactant.
(問題点を解決する丸めの手段)
本発明は、非水溶媒中で懸濁重合を行うことによって前
記の問題点を解決したものである。(Means for Solving the Problems) The present invention solves the above problems by carrying out suspension polymerization in a non-aqueous solvent.
すなわち2本発明は1重合性単量体を1着色剤及び/又
は磁性粉の存在下に、非水溶媒中で懸濁重合することを
特徴とする電子写真用トナーの製造方法に関する。That is, the present invention relates to a method for producing an electrophotographic toner, which comprises suspending and polymerizing monopolymerizable monomers in a non-aqueous solvent in the presence of a colorant and/or magnetic powder.
重合性単量体の非水溶媒中での懸濁重合は2重合性単量
体の非水溶媒中への分散を助ける分散安定剤を用いるこ
とが好ましい。本発明においては分散安定剤を用やなく
ても、非水溶媒中での懸濁重合は可能であるが2分散安
定剤を用いると1重合性単量体を広範囲に選択できると
ともに重合が安定化される。In suspension polymerization of a polymerizable monomer in a nonaqueous solvent, it is preferable to use a dispersion stabilizer that helps disperse the dipolymerizable monomer in the nonaqueous solvent. In the present invention, suspension polymerization in a non-aqueous solvent is possible without using a dispersion stabilizer, but using a two-dispersion stabilizer allows a wide selection of monopolymerizable monomers and stabilizes the polymerization. be converted into
重合性単量体の非水溶媒中での懸濁重合には。For suspension polymerization of polymerizable monomers in non-aqueous solvents.
連鎖移動剤を適宜存在させてもよい。また、帯電制御剤
、オフセット防止剤、i動性同上剤、クリー二/グ性向
上剤等のトナー特性向上剤も適宜存在させることができ
る。A chain transfer agent may be present as appropriate. In addition, toner property improvers such as charge control agents, anti-offset agents, i-dynamic agents, and cleaning/cleanability improvers may also be present as appropriate.
重合性単量体を非水溶媒中で懸濁重合させる方法として
は、予め重合開始剤2着色剤及び/又は磁性粉、必要に
応じてトナー特性向上剤を重合性単量体に溶解又は分散
させておき、この混合液を必要に応じて分散安定剤を予
め添加した非水溶媒中に添加し、攪拌しながら液の温度
を上げて重合せしめる方法1重合開始剤9着色剤及び/
又は磁性粉、必要に石じてその他の助剤を溶解又は分散
せしめた重合性単量体混合液を、必l!に応じて分散安
定剤を予め添加し所定の温度に保った非水溶媒中に攪拌
しながら所定の時間をかけて滴下し。As a method for suspension polymerizing a polymerizable monomer in a non-aqueous solvent, a polymerization initiator 2, a colorant and/or magnetic powder, and if necessary a toner property improver are dissolved or dispersed in the polymerizable monomer in advance. Method 1 Polymerization initiator 9 Coloring agent and/or
Or, be sure to use a polymerizable monomer mixture in which magnetic powder and other auxiliaries are dissolved or dispersed as necessary! Depending on the situation, a dispersion stabilizer was added in advance and added dropwise over a predetermined period of time into a non-aqueous solvent kept at a predetermined temperature while stirring.
重合せしめる方法環が挙げられる。上記重合性単量体中
に着色剤及び/又は磁性粉等を溶解又は分散する際には
、普通の攪拌機を用りて比軟的高速で攪拌しても良いが
2重合開始前又は重合初期にホモミキサー等を使用して
高速剪断によシ攪拌するのが好ましい。Examples include methods for polymerization. When dissolving or dispersing the colorant and/or magnetic powder, etc. in the above polymerizable monomer, stirring may be carried out at relatively high speed using an ordinary stirrer, but before the start of bipolymerization or at the beginning of polymerization. It is preferable to use a homomixer or the like to stir the mixture by high-speed shearing.
懸濁重合は攪拌しつつ50〜200℃の温度で行うのが
好ましく、特に80〜150℃の温度で行うのが好まし
い、この懸濁重合は重合率が99重量−以上になるまで
進めるのが好ましく、特に99.9重量−以上になるま
で進めるのが好ましい。Suspension polymerization is preferably carried out with stirring at a temperature of 50 to 200°C, particularly preferably 80 to 150°C. This suspension polymerization is preferably carried out until the polymerization rate reaches 99% by weight or more. Preferably, it is particularly preferable to proceed until the weight reaches 99.9 weight or more.
重合率が低く、残存モノマーが多くなるとトナーの緒特
性が劣る傾向があシ、4?に保存安定性が劣る傾向がお
る。If the polymerization rate is low and the amount of residual monomer is large, the toner properties tend to be poor.4? storage stability tends to be poor.
また、S濁重合によって得られる重合体は、その重量平
均分子量が10000以上のものが好ましく9%に5o
ooo以上のものが好ましい。分子量が低すぎるとクリ
ーニング性及び保存安定性が低下し易くなる。In addition, the polymer obtained by S turbidity polymerization preferably has a weight average molecular weight of 10,000 or more.
ooo or more is preferable. If the molecular weight is too low, cleaning properties and storage stability tend to deteriorate.
また、得られた重合体は、ガラス転移点が30〜90℃
、特に50〜80℃であるのが好ましい。Furthermore, the obtained polymer has a glass transition point of 30 to 90°C.
, particularly preferably 50 to 80°C.
ガラス転移点が低すぎると、保存安定性が低下する傾向
があり、高すぎると、定着性が低下する傾向がある。ガ
ラス転移点の調整は、主に使用する重合性単量体の種類
と比率を選択することによシ行うことができる。If the glass transition point is too low, storage stability tends to decrease, and if it is too high, fixability tends to decrease. The glass transition point can be adjusted mainly by selecting the type and ratio of the polymerizable monomers used.
このような非水溶媒中の懸濁重合により得られる重合体
粒子の粒径分布の調整は重合性単量体と非水溶媒の比、
非水溶媒の穐類1分散安定剤の種類と量、攪拌効率等に
よって行われるが、1〜50μmになるようにgglす
るのが好ましく、特に5〜25μmのものが主成分とな
るように調整するのが最も好ましい。平均粒径としては
9〜15μmに調整するのが好ましい。The particle size distribution of polymer particles obtained by suspension polymerization in a non-aqueous solvent can be adjusted by adjusting the ratio of the polymerizable monomer to the non-aqueous solvent,
This is done depending on the type and amount of the non-aqueous solvent dispersion stabilizer, stirring efficiency, etc., but it is preferable to adjust the size to 1 to 50 μm, and in particular adjust it so that the main component is 5 to 25 μm. It is most preferable to do so. The average particle size is preferably adjusted to 9 to 15 μm.
次に、非水溶媒中の懸濁重合に使用される材料について
説明する。Next, materials used for suspension polymerization in a nonaqueous solvent will be explained.
トナーの結着橋脂原料である重合性単量体としては、以
下のものが挙げられる。Examples of the polymerizable monomer that is a raw material for the binding resin of the toner include the following.
(1) 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−エチルスチレン、
2.4−ジメチルスチレン、p−n−ブチルスチレ
ン、p−tert−ブチルスチレン、p−n−へキシル
スチレン、p−n−オクチルスチレン。(1) Styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene,
2.4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene.
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、n−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
クロルスチレン等のスチレン及びその誘導体。p-n-nonylstyrene, p-n-decylstyrene, p
-n-dodecylstyrene, n-methoxystyrene, p-
Styrene and derivatives thereof, such as phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.
(2) 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。(2) Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene.
(31塩化ビニル、塩化ビニリデン、臭化ビニル。(31 Vinyl chloride, vinylidene chloride, vinyl bromide.
弗化ビニルなどのハロゲン化ビニル類、酢酸ビニル、フ
ロピオン酸ビニル、ベンジェ酸ビニル、酪酸ビニルなど
のビニルエステル類。Vinyl halides such as vinyl fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate.
(4)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
ピル、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−クロルエテル、アクリル酸フェニ
ル、α−クロルアクリル酸メチル、メタクリル酸メチル
、メタクリル酸エチル、メタクリル酸プロピル、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#In−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、アクリロニトリル、メタクリロニ
トリル、アクリル酸2−ヒドロキシエチル、アクリル酸
2−ヒドロキシプロピル。(4) Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate,
2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , methacrylic #In-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, acrylonitrile, methacrylonitrile, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate.
メタクリル酸2−ヒドロキシエチル、メタクリル酸2−
ヒドロキシプロピル等のアクリル酸若しくはメタクリル
酸誘導体。2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate
Acrylic acid or methacrylic acid derivatives such as hydroxypropyl.
(5)ジメチルアミノメチルアクリレート、ジメチルア
ミノエチルアクリレート、ジメチルアミノプロピルアク
リレート、ジメチルアミノメチルメタクリレート、ジメ
チルアミノエチルメタクリレート、ジメチルアミンプロ
ピルメタクリレート等のジアルキルアミノアルキルアク
リレート及びジアルキルアミノアルキルメタクリレート
、アミノメチルアクリレート、アミノエチルアクリレー
ト。(5) Dialkylaminoalkyl acrylates such as dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, dimethylamine propyl methacrylate, dialkylaminoalkyl methacrylate, aminomethyl acrylate, aminoethyl Acrylate.
アミノメチルメタクリV−ト、アミノエチルメタクリレ
ート等のアミノアルキルアクリレート及びアミノアルキ
ルメタクリレート、モルホリノメチルアクリレート、モ
ルホリノエチルアクリレート。Aminoalkyl acrylates such as aminomethyl methacrylate, aminoethyl methacrylate, aminoalkyl methacrylates, morpholinomethyl acrylate, morpholinoethyl acrylate.
2−モルホリノプロピルアクリレート、3−モルホリノ
プロピルアクリレート、2−モルホリノプロピルアクリ
レート、4−モルホリノブチルアクリレート、3−モル
ホリノブチルアクリレート。2-morpholinopropyl acrylate, 3-morpholinopropyl acrylate, 2-morpholinopropyl acrylate, 4-morpholinobutyl acrylate, 3-morpholinobutyl acrylate.
2−モルホリノブチルアクリレート、2−モルホリノペ
ンチルアクリレート、2−モルホリノヘキシルアクリレ
ート、2−モルホリノオクチルアクリレート等のモルホ
リノアルキルアクリレート。Morpholinoalkyl acrylates such as 2-morpholinobutyl acrylate, 2-morpholinopentyl acrylate, 2-morpholinohexyl acrylate, and 2-morpholinooctyl acrylate.
これらと同様のモルホリノアルキルを有するメタクリレ
ート、上記に例示されるようなモルホリノアルキルアク
リレートにおいてモルホリノ基の代わシに、アジリジル
基、ピペラジル基又はピペリジル基が結合しているアジ
リジルアルキルアクリレート、ピペラジルアルキルアク
リレート及びビベリジルアルキルアクリレート、これら
と−様のアルキル基を有するアジリジルアルキルメタク
リレート、ピペラジルアルキルメタクリレート及びピペ
リジルアルキルメタクリレート、モルホリノメチルアク
リルアミド、モルホリノエチルアクリルアミド、3−モ
ルホリノプロピルアクリルアミド、2−モルホリノプロ
ピルアクリルアミド、4−モルホリノブチルアクリルア
ミド、3−モルホリノブチルアクリルアミド、2−モル
ホリノブチルアクリルアミド、2−モルホリノペンチル
アルキルアクリルアミド、2−モルホリノヘキシルアク
リルアミド、2−モルホリノオクチルアクリルアミド等
のモルホリノアルキルアクリルアミド。Methacrylates having morpholinoalkyl similar to these, aziridyl alkyl acrylates, piperadylalkyl acrylates in which an aziridyl group, piperazyl group or piperidyl group is bonded in place of the morpholino group in the morpholinoalkyl acrylates as exemplified above. and biveridyl alkyl acrylate, aziridyl alkyl methacrylate, piperadylalkyl methacrylate and piperidyl alkyl methacrylate having an alkyl group similar to these, morpholinomethyl acrylamide, morpholinoethyl acrylamide, 3-morpholinopropylacrylamide, 2-morpholinopropylacrylamide, Morpholinoalkylacrylamide such as 4-morpholinobutylacrylamide, 3-morpholinobutylacrylamide, 2-morpholinobutylacrylamide, 2-morpholinopentylalkylacrylamide, 2-morpholinohexylacrylamide, 2-morpholinooctylacrylamide.
これらと同様のモルホリノアルキル基を有するモルホリ
ノアルキルメタクリルアミド、上記に示されるようなモ
ルホリノアルキルアクリルアミドにオイて2モルホリノ
基の代わりにアジリジル基。Morpholinoalkyl methacrylamides having morpholinoalkyl groups similar to these, aziridyl groups instead of two morpholino groups in morpholinoalkylacrylamides as shown above.
ピペラジル基又はピペリジル基が結合しているアジリジ
ルアルキルアクリルアミド、ピペラジルアルキルアクリ
ルアミド及びピペリジルアルキルアクリルアミド、これ
らと同様のアルキル基を有するアジリジルアルキルメタ
クリルアミド、ピペラジルアルキルメタクリルアミド及
びピペリジルアルキルメタクリルアミド、モルホリノメ
チルチオアクリレート、モルホリノエチルチオアクリレ
ート、3−モルホリノプロピルチオアクリレート。Aziridyl alkyl acrylamide, piperazyl alkyl acrylamide and piperidyl alkyl acrylamide to which a piperazyl group or a piperidyl group is bonded, aziridyl alkyl methacrylamide having an alkyl group similar to these, piperadylalkyl methacrylamide and piperidyl alkyl methacrylamide, morpholino Methylthioacrylate, morpholinoethylthioacrylate, 3-morpholinopropylthioacrylate.
2−モルホリノプロピルチオアクリレート、4−モルホ
リノブチルチオアクリレート、3−モルホリノブチルチ
オアクリレート、2−モルホリノブチルチオアクリレー
ト、2−モルホリノペンチルチオアクリレート、2−モ
ルホリノヘキシルチオアクリレート、2−モルホリノオ
クチルアクリレート等のモルホリノアルキルチオアクリ
レート。Morpholinos such as 2-morpholinopropylthioacrylate, 4-morpholinobutylthioacrylate, 3-morpholinobutylthioacrylate, 2-morpholinobutylthioacrylate, 2-morpholinopentylthioacrylate, 2-morpholinohexylthioacrylate, 2-morpholinooctyl acrylate Alkylthioacrylate.
これらと同様のモルホリノアルキル基を有するモルホリ
ノアルキルチオメタクリレート、上記に例示されるよう
なモルホリノアルキルチオアクリレートにおいて1モル
ホリノ基の代わりにアジリジル基、ピペラジル基又はピ
ペリジル基が結合しているアジリジルアルキルチオアク
リレート、ピペラジルアルキルチオアクリレート及びピ
ペリジルアルキルチオアクリレート、これらと同様のア
ルキル基を有するアジリジルアルキルチオメタクリレー
ト、ピペラジルアルキルチオメタクリレート及びピペリ
ジルアルキルチオメタクリレート等のアミノ基含有付加
重合性単量体。Morpholinoalkylthiomethacrylates having a morpholinoalkyl group similar to these, aziridylalkylthioacrylates in which an aziridyl group, piperazyl group or piperidyl group is bonded instead of one morpholino group in the morpholinoalkylthioacrylates exemplified above, piperazyl Amino group-containing addition-polymerizable monomers such as alkylthioacrylates and piperidylalkylthioacrylates, aziridylalkylthiomethacrylates having alkyl groups similar to these, piperidylalkylthiomethacrylates, and piperidylalkylthiomethacrylates.
(6)アクリル酸、メタクリル酸、マレイン酸。(6) Acrylic acid, methacrylic acid, maleic acid.
7?−ル酸、イタコン酸等のカルボキシル基含有付加重
合性単量体及びそれらのナトリウム塩、カリウム塩、亜
鉛塩等の金属塩。7? carboxyl group-containing addition-polymerizable monomers such as acid and itaconic acid, and metal salts thereof such as sodium salts, potassium salts, and zinc salts.
(7) I)−スチレンスルホン酸、0−メチルスチ
レンスルホン酸9m−メチルスチレンスルホン酸。(7) I)-Styrenesulfonic acid, 0-methylstyrenesulfonic acid 9m-methylstyrenesulfonic acid.
クロルスチレンスルホン酸等のスチレンスルホン酸類、
アクリル酸メチルスルホン酸、アクリル酸エチルスルホ
ン酸、アクリル酸プロピルスルホン酸、メタクリル酸メ
チルスルホン酸、メタクリル酸エチルスルホン酸、メタ
クリル酸プロピルスルホン酸等のアクリル酸又はメタク
リル酸アルキルスルホン酸類及びそれらのナトリウム塩
、カリウム塩、亜鉛塩等の金属塩。Styrene sulfonic acids such as chlorstyrene sulfonic acid,
Acrylic or methacrylic alkylsulfonic acids such as methylsulfonic acrylate, ethylsulfonic acrylate, propylsulfonic acrylate, methylsulfonic methacrylate, ethylsulfonic methacrylate, propylsulfonic methacrylate, and their sodium salts , potassium salts, zinc salts, and other metal salts.
+81 ビニルメチルエーテル、ビニルエチルニーチ
ル、ビニルイノブチルエーテル等のビニルエーテル類。+81 Vinyl ethers such as vinyl methyl ether, vinyl ethyl nityl ether, vinyl inobutyl ether, etc.
(9) ビニルメチルケトン、ビニルへキシルケトン
、メチルイノプロペニルケトンなどのビニルケト7類。(9) Type 7 vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl inopropenyl ketone.
(10)N−ヒニルピロール、N−ビニルカルバゾール
、N−ビニルインドール、N−ビニルピロリドンなどの
N−ビニル化合物。(10) N-vinyl compounds such as N-hinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone.
(1i)ビニルナフタリン塩等。(1i) Vinylnaphthalene salt, etc.
これらの重合性単量体は1種若しくは2種以上組合せて
使用できる。これらの重合性単量体中でスチレン又はス
チレン誘導体を40〜100重量%使用すると、トナー
を電子写真複写装置で紙に複写した時に定着性が非常に
すぐれているので好ましい。These polymerizable monomers can be used alone or in combination of two or more. It is preferable to use styrene or a styrene derivative in an amount of 40 to 100% by weight among these polymerizable monomers because the toner has excellent fixing properties when copied onto paper using an electrophotographic copying device.
また9本発明の重合性単量体としては架橋剤となる重合
性の二重結合を2個以上有する化合物を一部用いること
もできる。例えばジビニルベンゼン、ジビニルナフタレ
ン及びそれらの誘導体のような芳香族ジビニル化合物、
エチレングリコールジメタクリレート、ジエチレングリ
コールジメタクリレート、トリエチレングリコールトリ
アクリレート、トリメチロールプロパントリアクリレー
ト等のジエチレン性カルボン酸エステル、N、N−シヒ
ニルアニリン、ジビニルエーテル、ジビニルスルファイ
トなどのジビニル化合物及び3個以上のビニル基を持つ
化合物等が単独で、又は混合物として使用できる。架橋
剤の使用量は重合性単量体総量に対して0〜20重量−
が好ましく、特に0〜5重量−が好ましい。Further, as the polymerizable monomer of the present invention, a compound having two or more polymerizable double bonds that can serve as a crosslinking agent can also be used in part. aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and their derivatives;
Diethylene carboxylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol triacrylate, and trimethylolpropane triacrylate, divinyl compounds such as N,N-cyhinylaniline, divinyl ether, and divinyl sulfite, and 3 or more vinyl Compounds having groups can be used alone or as a mixture. The amount of crosslinking agent used is 0 to 20% by weight based on the total amount of polymerizable monomers.
is preferable, and particularly preferably 0 to 5 weight.
本発明に用いる非水溶媒は、直鎖状または分岐状の脂肪
族炭化水素、脂環式炭化水素、芳香族炭化水素、ハロゲ
ン化炭化水素等の有機溶剤から。The nonaqueous solvent used in the present invention includes organic solvents such as linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons.
使用する重合性単量体が十分分散する程度に該単量体と
非相溶性のもの又は相溶性の低いものが適宜選択して使
用される。Those that are incompatible or have low compatibility with the polymerizable monomer used are appropriately selected and used to the extent that the monomer is sufficiently dispersed.
具体的には、ヘキサン、ヘプタン、オクタン。Specifically, hexane, heptane, and octane.
インオクタン、ノナン、デカン、イソデカン、ドデカン
、イルカン等の長鎖脂肪族炭化水素、インパラフィン系
の石油溶剤であるアイソパーE。Isopar E is a petroleum solvent based on long-chain aliphatic hydrocarbons such as inoctane, nonane, decane, isodecane, dodecane, and ilkane, and inparaffin.
アイソバ1− Q 、アイソパ+++ H,アイソパー
L(いずれもエクソン コーポレーション商品名)、シ
ェルシルア1(シェルオイルカンパニー商品名)。Isopa 1-Q, Isopa +++ H, Isopa L (all trade names of Exxon Corporation), and Shell Silua 1 (trade name of Shell Oil Company).
アムスコOM8.アムスコ460 (いずれもスピリッ
ツ社商品名)等が好ましい。これらは単独で又は2種以
上弁せて用いられる。Amsco OM8. Amsco 460 (all brand names of Spirits Inc.) and the like are preferred. These may be used alone or in combination of two or more.
その他2重合性単量体と相溶性の高い有機溶剤を適当量
混入すると9重合性単量体の分散性がさらに良好になる
場合がある。混入する場合は非水溶媒中0〜30重量−
が好ましく、特に0〜15重量−が好ましい。具体的に
は、トルエン、キシレン、メタノール、エタノール、ブ
タノール、酢酸エチル、酢酸ブチル、セロソルブアセテ
ート。If an appropriate amount of an organic solvent having high compatibility with other dipolymerizable monomers is mixed, the dispersibility of the heponepolymerizable monomer may be further improved. If mixed, 0 to 30% by weight in a non-aqueous solvent.
is preferable, and 0 to 15 weight is particularly preferable. Specifically, toluene, xylene, methanol, ethanol, butanol, ethyl acetate, butyl acetate, and cellosolve acetate.
ブチルセロソルブ等が好ましいものとして挙げられる。Preferred examples include butyl cellosolve.
重合性単量体と非水溶媒との割合は、前者/後者の重量
比で60/40〜10/90であるのが好ましい。この
割合が大きすぎると、I!!濁重合しにくくなシ、小さ
すぎると、収率が低下する傾向がある。The ratio of the polymerizable monomer to the nonaqueous solvent is preferably 60/40 to 10/90 in weight ratio of the former/latter. If this ratio is too large, I! ! If it is too small, the yield tends to decrease because it is difficult to undergo turbid polymerization.
次に9分散安定剤について説明する。Next, 9 dispersion stabilizer will be explained.
分散安定剤は非水溶媒に可溶でかつトナーの結着樹脂と
非相溶性のものが選択して使用され、その配合割合は2
分散安定剤の種類によって異なシー概に言えず限定され
るものではないが、一般には全トナー成分に対して1〜
20重量%が好ましく、特に2〜15重量−が好ましい
。なお9本発明において全トナー成分とは9着色剤及び
/又は磁性粉9分散安定剤、結着樹脂成分である重合性
単量体並びに各種トナー特性向上剤の総量を言う。A dispersion stabilizer that is soluble in a non-aqueous solvent and incompatible with the binder resin of the toner is selected and used, and the blending ratio is 2.
Although the dispersion stabilizer varies depending on the type of dispersion stabilizer and is not limited to general terms, it is generally used in amounts of 1 to 1 to 1 for all toner components.
20% by weight is preferred, particularly 2-15% by weight. In the present invention, the total toner component refers to the total amount of colorant and/or magnetic powder, dispersion stabilizer, polymerizable monomer as a binder resin component, and various toner property improvers.
分散安定剤が少なすぎると分散が不安定となる傾向があ
り、20重量憾を越えるとトナーが軟化し耐ブロッキン
グ性が低下する傾向がある。If the amount of dispersion stabilizer is too small, the dispersion tends to become unstable, and if it exceeds 20% by weight, the toner tends to become soft and the blocking resistance tends to decrease.
分散安定剤としては、各種ゴム、ブチル化メラミン樹脂
等のアミノプラスト樹脂、ゴムグラフト樹脂、アルキド
樹脂、ポリブタジェン、長鎖の炭素鎖をもつアクリル酸
エステル及び/又はメタク′ リル酸エステルを必須成
分とする重合体等が用いられる。Dispersion stabilizers include various rubbers, aminoplast resins such as butylated melamine resins, rubber graft resins, alkyd resins, polybutadiene, and acrylic esters and/or methacrylic esters having long carbon chains as essential components. Polymers and the like are used.
これらの分散安定剤は、得られるトナーに一部取シとま
れる為、トナーの緒特性に影響を与える。These dispersion stabilizers are partially absorbed into the resulting toner and therefore affect the toner properties.
以下に本発明において好ましい分散安定剤について説明
する。Preferred dispersion stabilizers in the present invention will be explained below.
ゴムは、内部凝集力が大きく、定着性を損うことなく耐
オフセット性を向上させる効果があるので好ましい。ま
た、ゴムが不飽和結合を含有する場合はゴムに重合性単
量体がグラフトした形となってトナー中に存在するので
好ましい。ゴムとしては、天然ゴム(標準マレ−シアゴ
ム、略して8MRで規格された各グレード等)、スチレ
ン−ブタジェンゴム、アクリロニトリルブタジェンゴム
、ブチルゴム、クロロブJ#〆レンゴム、ブタジェンゴ
ム、インプレンゴム、エチレンプロピレンゴム、ウレタ
ンゴム、シリコーンゴム、アクリルゴム等の合成ゴム、
再生ゴム等が挙げられる。Rubber is preferable because it has a large internal cohesive force and is effective in improving offset resistance without impairing fixing properties. Further, when the rubber contains an unsaturated bond, it is preferable because the polymerizable monomer is grafted onto the rubber and is present in the toner. Rubbers include natural rubber (standard Malaysian rubber, abbreviated as various grades standardized by 8MR, etc.), styrene-butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, chlorobutene rubber, butadiene rubber, imprene rubber, ethylene propylene rubber, Synthetic rubber such as urethane rubber, silicone rubber, acrylic rubber,
Examples include recycled rubber.
ポリブタジェンは9通常1.4−付加及び/又は1.2
−付加によって得られるものであり、1.4−付加の場
合にはシス形構造及び/又はトランス形構造をとる。耐
オフセット性を向上させることに重点をおく場合には、
共重合性のよい1,4−付加でシス形構造を多く有する
ポリブタジェンが好ましい。また、ポリブタジェンの分
子量については。Polybutadiene has 9 usually 1,4-addition and/or 1,2
-It is obtained by addition, and in the case of 1.4-addition, it takes a cis structure and/or a trans structure. When focusing on improving offset resistance,
Polybutadiene, which has a high copolymerizability and has a large number of cis-type structures due to 1,4-addition, is preferred. Also, regarding the molecular weight of polybutadiene.
特に制限はないが、取り扱い上(主として溶媒への溶は
易さ等)の観点から10,000以内が好ましい。ま九
2分散安定性の面からは分子ill、000以上が好ま
しい。このポリブタジェンは、トナー成分を分散させる
と共に、残存する不飽和結合基によってトナーの結着樹
脂と重合する。従って。Although there is no particular limit, it is preferably within 10,000 from the viewpoint of handling (mainly ease of dissolution in a solvent, etc.). From the viewpoint of dispersion stability, the molecular weight is preferably 000 or more. This polybutadiene disperses the toner components and polymerizes with the binder resin of the toner through the remaining unsaturated bond groups. Therefore.
ポリブタジェンに重合性単量体がグラフトした形となり
トナー中に存在するようになるため、ポリブタジェンが
一種の分子内可塑剤的に作用し、定着性が向上する。ま
た、ポリブタジェンの量9分子量及び不飽和結合基の量
を増減することにより架橋密度を増減できるため、耐オ
フセット性をも同時に向上させることができる。Since the polymerizable monomer is grafted onto the polybutadiene and is present in the toner, the polybutadiene acts as a kind of intramolecular plasticizer and improves fixing properties. Further, by increasing or decreasing the molecular weight of polybutadiene and the amount of unsaturated bond groups, the crosslinking density can be increased or decreased, so that offset resistance can also be improved at the same time.
長鎖の炭素鎖をもつアクリル酸エステル及び/又はメタ
クリル酸エステルを必須成分とする重合体は、トナーの
諸物件のバランスが良好であるため好ましい。A polymer containing as an essential component an acrylic ester and/or a methacrylic ester having a long carbon chain is preferable because the toner has a good balance of various properties.
上記重合体としては、炭素数8以上のアルキル基を有す
るアクリル酸アルキルエステル及び/又はメタクリル酸
アルキルエステルを必須成分とする重合体がより好まし
く、炭素数12〜17のアルキル基を有するアクリル酸
アルキルエステル及び/又はメタクリル酸アルキルエス
テルを必須成分とする重合体が特に好ましい。核必須成
分のアルキル基の炭素数が少なすぎると非水溶媒中にお
いて重合性単量体及びその共重合体を充分安定に分散す
ることが困難となる。The above polymer is more preferably a polymer containing an alkyl acrylate ester and/or alkyl methacrylate having an alkyl group having 8 or more carbon atoms as an essential component, and an alkyl acrylate having an alkyl group having 12 to 17 carbon atoms. Particularly preferred are polymers containing esters and/or methacrylic acid alkyl esters as essential components. If the number of carbon atoms in the alkyl group, which is an essential core component, is too small, it will be difficult to sufficiently stably disperse the polymerizable monomer and its copolymer in a nonaqueous solvent.
具体的には、2−エチルへキシルアクリレート。Specifically, 2-ethylhexyl acrylate.
2−エチルへキシルメタクリレート、ラウリルメタクリ
レート、ラウリルアクリレート、ステアリルメタクリレ
ート、ステアリルアクリレート等が挙げられるが、特に
ラウリルメタクリレートを必須成分とするとトナーの諸
物件のバランスが良いので好ましい。Examples include 2-ethylhexyl methacrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, and stearyl acrylate, and it is particularly preferable to use lauryl methacrylate as an essential component because the toner has a good balance of various properties.
これらを必須成分とする重合体としては、上記単量体の
単独重合体、2種以上の上記単量体よシなる共重合体、
上記単量体とその他の単量体との共重合体が挙げられる
。その他の単量体を共重合させる場合、必須成分となる
上記単量体は70重量%以上共重合させるのが好まし込
。必須成分となる上記単量体が少なすぎると分散安定剤
としての作用が低下する傾向がある。Polymers containing these as essential components include homopolymers of the above monomers, copolymers of two or more of the above monomers,
Examples include copolymers of the above monomers and other monomers. When copolymerizing other monomers, it is preferable to copolymerize 70% by weight or more of the above monomers, which are essential components. If the amount of the above-mentioned monomers, which are essential components, is too small, the effect as a dispersion stabilizer tends to decrease.
その他の単量体としては、先に結着樹脂原料である重合
性単量体として例示し九ものく但し、必須成分となる単
量体として挙げたものを除く)等の1種又は2種以上を
用いることができる。Examples of other monomers include one or two of the nine listed above as polymerizable monomers that are raw materials for the binder resin, but excluding those listed as monomers that are essential components. The above can be used.
この分散安定剤は、正帯電性トナーを製造する場合には
、その他の単量体として、結着樹脂原料である重合性単
量体として例示したもののうち。When producing a positively chargeable toner, this dispersion stabilizer may be used as other monomers among those exemplified as polymerizable monomers that are raw materials for the binder resin.
(5)に示したようなアミノ基含有付加重合性単量体を
分散安定剤中好ましくは1〜30重量%共重合するのが
好ましい。この分散安定剤を用いると正帯電制御剤を使
用しないですむか又は帯電制御剤を通常の半分以下の量
使用すればよい。従って。It is preferable to copolymerize the amino group-containing addition polymerizable monomer shown in (5) in the dispersion stabilizer in an amount of preferably 1 to 30% by weight. When this dispersion stabilizer is used, it is not necessary to use a positive charge control agent, or it is sufficient to use a charge control agent in an amount less than half of the usual amount. Therefore.
正帯電制御剤を使用することによる欠点が解消若しくは
軽減され、耐湿性、耐ブロッキング性及び帯電安定性に
優れた長寿命のトナーを得ることができる。また、帯電
制御剤を使用しない場合には。The disadvantages caused by using a positive charge control agent are eliminated or reduced, and a long-life toner with excellent moisture resistance, anti-blocking properties, and charge stability can be obtained. Also, if a charge control agent is not used.
トナーを任意に着色できるので、カラートナー化するこ
とも可能である。Since the toner can be colored arbitrarily, it is also possible to make it into a colored toner.
ま九、負帯電性トナーを製造する場合には、その他の単
量体として結着樹脂原料である重合性単量体として例示
し九もののうち、(6)及び(7)に示したようなカル
ボキシル基及び/又はスルホン基を有する重合性単量体
及び/又はそれらの金属塩を。(9) When producing a negatively chargeable toner, other monomers such as those shown in (6) and (7) among the nine examples of polymerizable monomers that are raw materials for the binder resin may be used. Polymerizable monomers having carboxyl groups and/or sulfone groups and/or metal salts thereof.
分散安定剤中好ましくは1〜30重量%共重合するのが
好ましい。この分散安定剤を用いると負帯電制御剤を使
用しないで済むか又は帯電制御剤を通常の半分以下の量
使用すればよい。従って前記正帯電性トナーを製造する
場合と同様の効果が得られる。Preferably, 1 to 30% by weight of the dispersion stabilizer is copolymerized. When this dispersion stabilizer is used, it is not necessary to use a negative charge control agent, or it is sufficient to use a charge control agent in an amount less than half of the usual amount. Therefore, the same effects as in the case of producing the positively chargeable toner can be obtained.
また、前記長鎖の炭素鎖をもつアクリル酸エステル及び
/又はメタクリル酸エステルを必須成分とする重合体く
、結着樹脂原料である重合性単量体と反応性の不飽和結
合基を導入した重合体を分散安定剤として用いるとさら
に好ましい。なぜならば9分散安定剤に重合性単量体が
グラフトした形となってトナー粒子中及び周囲にとシこ
まれるため2分散安定剤が一攬の分子内可塑剤的に作用
しトナーの定着性が向上するとともに、架橋密度を調整
することによって耐オフセット性も向上できるためであ
る。In addition, in the polymer containing the long carbon chain acrylic ester and/or methacrylic ester as an essential component, an unsaturated bonding group reactive with the polymerizable monomer that is the raw material for the binder resin is introduced. It is further preferred to use a polymer as a dispersion stabilizer. This is because the polymerizable monomer is grafted onto the dispersion stabilizer No. 9 and is infiltrated into and around the toner particles, so the dispersion stabilizer No. 2 acts like an intramolecular plasticizer and improves the fixing properties of the toner. This is because offset resistance can also be improved by adjusting the crosslinking density.
結着樹脂原料である重合性単量体と重合架橋しうる不飽
和結合基は2例えば分散安定剤の成分としてグリシジル
メタクリレート及び/又はグリシジルアクリレートを好
ましくは1〜30モルチ共重合させておき、このオキシ
ラン環と反応するカルボキシル基含有重合性単量体をグ
リシジルメタクリレート及び/又はグリシジルアクリレ
ートとほぼ当量付加させる方法、カルボキシル基含有重
合性単量体を好ましくは1〜30モル慢分散安定剤の成
分として共重合させてからグリシジルメタクリレート及
び/又はグリシジルアクリレートをほぼ当量付加反応さ
せる方法等により導入することができる。The number of unsaturated bond groups that can be polymerized and crosslinked with the polymerizable monomer, which is a raw material for the binder resin, is 2. For example, as a component of a dispersion stabilizer, glycidyl methacrylate and/or glycidyl acrylate are preferably copolymerized in an amount of 1 to 30 mol. A method in which a carboxyl group-containing polymerizable monomer that reacts with an oxirane ring is added to glycidyl methacrylate and/or glycidyl acrylate in an approximately equivalent amount, and the carboxyl group-containing polymerizable monomer is preferably used as a component of a 1 to 30 mol chronic dispersion stabilizer. It can be introduced by a method of copolymerizing and then subjecting glycidyl methacrylate and/or glycidyl acrylate to an approximately equivalent addition reaction.
カルボキシル基含有重合性単量体としては、メタクリル
酸、アクリル酸、マレイン酸、フマル酸。Examples of carboxyl group-containing polymerizable monomers include methacrylic acid, acrylic acid, maleic acid, and fumaric acid.
イタコン酸等が挙げられる。その他、水酸基若しくはア
ミノ基とインシアネート含有重合性単量体との付加反応
等を用いることもでき2分散安定剤に重合架橋しうる不
飽和結合基を導入する方法に制限はない。なお、前記正
帯電性トナー及び負帯電性トナーを製造する場合にも1
分散安定剤に不飽和結合基を導入することが好ましく、
この場合。Examples include itaconic acid. In addition, an addition reaction between a hydroxyl group or an amino group and an incyanate-containing polymerizable monomer may be used, and there is no restriction on the method of introducing an unsaturated bonding group capable of polymerization and crosslinking into the two-dispersion stabilizer. Note that 1 is also used when producing the positively chargeable toner and negatively chargeable toner.
It is preferable to introduce an unsaturated bond group into the dispersion stabilizer,
in this case.
トナーの定着性及び耐オフセット性の向上に加えて帯電
安定性もさらに向上する。In addition to improving toner fixing properties and anti-offset properties, charging stability is further improved.
なお、この分散安定剤は、溶液重合、塊状重合。This dispersion stabilizer can be used for solution polymerization and bulk polymerization.
乳化重合、水性lI!!l濁重合、非水溶媒懸濁重合等
公知の重合方法によシ、公知の重合開始剤を用いて製造
される。前記重合方法のうち2本発明においては非水溶
媒懸濁重合が特に好ましい。これらの重合体は1重量平
均分子量が1,000〜100,000に調整されるの
が好ましいが、これに限定されるものではない。Emulsion polymerization, aqueous lI! ! It is produced by a known polymerization method such as suspension polymerization or non-aqueous solvent suspension polymerization using a known polymerization initiator. Among the above polymerization methods, non-aqueous suspension polymerization is particularly preferred in the present invention. These polymers preferably have a weight average molecular weight of 1,000 to 100,000, but are not limited thereto.
本発明における非水溶媒中での懸濁重合に用いる重合開
始剤としては、過酸化ベンゾイル、過安息香酸tert
−ブチル等の過酸化物、アゾビスイソブチロニトリル、
アゾビスインブチルバレロニトリル等のアゾ系化合物等
の油溶性の重合開始剤を全重合性単量体に対して好まし
くは0.1〜20重量慢、 @に好ましくは0.1〜1
0重量慢重量子使用なお重合開始剤の種類と量及び重合
反応時の温度を適宜選択することによ、9)ナーの結着
樹脂の分子量を114整することができる。In the present invention, the polymerization initiators used for suspension polymerization in a non-aqueous solvent include benzoyl peroxide, perbenzoic acid tert.
- peroxides such as butyl, azobisisobutyronitrile,
An oil-soluble polymerization initiator such as an azo compound such as azobisin butylvaleronitrile is preferably used in an amount of 0.1 to 20% by weight, preferably 0.1 to 1% by weight, based on all polymerizable monomers.
By appropriately selecting the type and amount of the polymerization initiator and the temperature during the polymerization reaction, it is possible to adjust the molecular weight of the binder resin of 9) to 114.
連鎖移動剤としては、t−ドデシルメルカプタン等のア
ルキルメルカプタン、ジイソプロピルキサントゲン等の
低級アルキルキサントゲン類、四塩化炭素、四臭化炭素
等があり9重合性単量体に対して0〜2重量−使用され
るのが好ましい。Examples of chain transfer agents include alkyl mercaptans such as t-dodecyl mercaptan, lower alkyl xanthogens such as diisopropyl xanthogen, carbon tetrachloride, carbon tetrabromide, etc., and are used in amounts of 0 to 2 by weight based on the polymerizable monomer. Preferably.
本発明に好ましく用いられる着色剤としては。Colorants preferably used in the present invention include:
顔料又は染料を挙げることができ9例えば種々のカーボ
ンブラック、ニグロシン染料(C,1,N150415
)、アニリンブルー(C,L魔50405)。Pigments or dyes such as various carbon blacks, nigrosine dyes (C,1,N150415
), Aniline Blue (C, L 50405).
カルコオイルブルー(C,LNaazoec Blu
e 3 )sクロームイエ”−(C,LNa1409
0 )、 ウルトラマリンブルー (C,LNa77
103 )、デュポンオイルレット’(C,L&261
os)、オリエントオイルレッドナ330 (C,1,
N1160505 )t キノリンイエロー(C,L魔
47005)、メチレンブルークロライド(C,I、N
CL52015 )、 フタロシアニンブルー(C,
L嵐74160)、マラカイトグリーンオクサレー)
(C,L&42000 )。Calco oil blue (C, LNaazoec Blu
e 3 ) s chrome ye”-(C, LNa1409
0), Ultramarine Blue (C, LNa77
103), DuPont Oillet' (C, L & 261
os), Orient Oil Redna 330 (C, 1,
N1160505)t Quinoline yellow (C, L 47005), methylene blue chloride (C, I, N
CL52015), Phthalocyanine Blue (C,
L Arashi 74160), malachite green oxalay)
(C,L&42000).
ランプブラック(C,L磁77266)、 ローズベ
ンガル(C0LNa45435 )、オイルブラック。Lamp black (C, L magnetic 77266), rose bengal (C0LNa45435), oil black.
アゾオイルブラックなどを単独で或いはそれらを混合し
て用いることができる。これら着色剤は任意の量を用い
ることができるが、必要な濃度を得るためと経済的な理
由のために、全トナー成分中に好ましくは1〜30重量
%、特に好ましくは5〜15重量−になるような割合で
使用される。Azo oil black and the like can be used alone or in combination. These colorants can be used in any amount, but in order to obtain the required concentration and for economic reasons, they are preferably 1 to 30% by weight, particularly preferably 5 to 15% by weight, in the total toner components. used in proportions such that
顔料或いは染料としては2重合反応系中もしくは本発明
のトナー中への分散性を増加させる目的 ゛で種々の処
理を施したものを使用してもよい。前記処理としては9
例えばニグロシン染料、(C,LNllL50415)
をステアリン酸、マレイン酸の如き有機酸を用いての処
理がある。The pigment or dye may be subjected to various treatments for the purpose of increasing its dispersibility in the double polymerization reaction system or in the toner of the present invention. The above processing is 9
For example, nigrosine dye, (C, LNllL50415)
There is a treatment using organic acids such as stearic acid and maleic acid.
これら着色剤の中で2本発明のトナーに特に好ましいの
は種々のカーボンブラック、例えばファ−ネスブラック
、チャンネルブラック、サーマルブラック、アセチレン
ブラック、ランプブラックなどである。さらに前記カー
ボンブラックは表面処理を施されていてもよい。表面処
理としては。Among these colorants, two particularly preferred for the toner of the present invention are various carbon blacks such as furnace black, channel black, thermal black, acetylene black, lamp black, and the like. Furthermore, the carbon black may be surface-treated. As for surface treatment.
例えば酸素、オゾン及び硝酸など種々の酸化剤を用いて
の酸化処理、ジブチルフタレート、ジオクチルフタレー
トなどの有機酸エステルによる表面吸着処理などがある
。Examples include oxidation treatment using various oxidizing agents such as oxygen, ozone, and nitric acid, and surface adsorption treatment with organic acid esters such as dibutyl phthalate and dioctyl phthalate.
磁性粉は磁性トナーを製造する場合に使用され。Magnetic powder is used when manufacturing magnetic toner.
これは1着色剤を兼ねることができる。好ましい磁性粉
としては9例えばマグネタイト或いはフェライトの如き
鉄或いはニッケル、コバルトなどの強磁性を示す元素の
酸化物若しくは化合物がある。This can also serve as a coloring agent. Preferred magnetic powders include oxides or compounds of iron such as magnetite or ferrite, or ferromagnetic elements such as nickel and cobalt.
これら磁性粉は粒径が0.01〜3μmの粉末状のもの
が好ましく、また磁性粉の表面が樹脂、チタンカップリ
ング剤、シランカップリング剤或いは高級脂肪酸金属塩
などで処理されていてもよい。これら磁性粉は全トナー
成分中に対して好ましくは20〜80重1*、特に好ま
しくは35〜70重量%になるように使用されるのが好
ましい。これ以下の量で2着色剤として使用してもよい
し2着色剤と併用してもよい。These magnetic powders are preferably in powder form with a particle size of 0.01 to 3 μm, and the surface of the magnetic powder may be treated with a resin, a titanium coupling agent, a silane coupling agent, a higher fatty acid metal salt, etc. . These magnetic powders are preferably used in an amount of 20 to 80% by weight 1*, particularly preferably 35 to 70% by weight, based on the total toner components. It may be used as a second coloring agent or in combination with a second coloring agent in an amount less than this amount.
オフセット防止剤は必要に応じ使用される。オフセット
防止剤は重合時に種々の形態で系中に存在せしめ製品と
してのトナーに含有せしめることができる。又は、オフ
セット防止剤が存在しない本発明のトナーに後から添加
することもできる。An offset inhibitor is used as necessary. The anti-offset agent is present in the system in various forms during polymerization and can be incorporated into the toner product. Alternatively, the anti-offset agent can be added later to the toner of the present invention in which no anti-offset agent is present.
前記のオフセット防止剤として種々の天然ワックス、例
えばカルナウバワックス、硬化とマシ[しくけ低分子量
オレフィン重合体などが本発明に用いられるが、好まし
くは低分子量オレフィン重合体が用いられる。この低分
子量オレフィン重合体としては、オレフィンの重合体、
オレフィンとオレフィン以外の単量体の共重合体で低分
子量のものが使用される。ここで、オレフィンとしては
エチレン、プロピレン、ブテン−1等があシ、オレフィ
ン以外の単量体としては、アクリル酸エステル、メタク
リル酸エステルなどがある。この低分子量オレフィン重
合体としては1例えば、%開昭55−153944号公
報に記載されているポリアルキレン、特開昭50−93
647号公報に記載されている低分子量オレフィン共重
合体を使用することができる。Various natural waxes such as carnauba wax, hardening and improving low molecular weight olefin polymers can be used as the anti-offset agent in the present invention, and low molecular weight olefin polymers are preferably used. This low molecular weight olefin polymer includes an olefin polymer,
A low molecular weight copolymer of an olefin and a monomer other than olefin is used. Here, olefins include ethylene, propylene, butene-1, etc., and monomers other than olefins include acrylic esters, methacrylic esters, etc. Examples of the low molecular weight olefin polymer include polyalkylene described in % 153944, Japanese Patent Application Laid-open No. 50-93.
The low molecular weight olefin copolymers described in Japanese Patent No. 647 can be used.
本発明に用いる低分子量オレフィン重合体の分子量は通
常の高分子化合物で言う低分子量の概念に含まれるもの
であればよいが、一般には重量平均分子量(Mw)で1
,000〜45,000.好ましくは2,000−へ0
00のものである。The molecular weight of the low molecular weight olefin polymer used in the present invention may be within the concept of low molecular weight in ordinary polymer compounds, but generally the weight average molecular weight (Mw) is 1.
,000~45,000. Preferably 2,000-0
00.
本発明に用いることのできる低分子量ポリオレフィン重
合体は軟化点が100〜180℃、特に130〜160
℃を有するものが好ましい。The low molecular weight polyolefin polymer that can be used in the present invention has a softening point of 100 to 180°C, particularly 130 to 160°C.
℃ is preferred.
本発明に用いることのできる低分子量オレフィン重合体
の量は特に限界はないが、好ましくはトナー総量に対し
て0〜30重量−の範囲であり。There is no particular limit to the amount of the low molecular weight olefin polymer that can be used in the present invention, but it is preferably in the range of 0 to 30% by weight based on the total amount of toner.
特に好ましくは1〜10重量−使用される。低分子量オ
レフィン重合体が少なすぎるとこれを添加することによ
るオフセット防止効果が発現せず。Particularly preferably from 1 to 10% by weight are used. If the amount of the low molecular weight olefin polymer is too small, the anti-offset effect due to its addition will not be exhibited.
多すぎると重合反応中にゲル化などを起こすことがある
。If the amount is too large, gelation may occur during the polymerization reaction.
さらに、流動性向上剤、り17−ユング性向上剤などを
必要に応じて用いることができる。これらは1重合反応
系中に存在せしめ製品トナー中に存在させることもでき
るが、好ましくは製品トナーに後に外添処理される。こ
れらの含有量としては本発明のトナーに対して各々0〜
3重量%が好ましい。流動性向上剤には、シラン、チタ
ン、アルミニウム、カルシウム、マグネシウム及びマグ
ネシウムの酸化物又は前記酸化物をチタンカップリング
剤若しくはシランカップリング剤で疎水化処理したもの
があシ、クリーニング性向上剤には。Furthermore, a fluidity improver, a 17-Jung property improver, etc. can be used as necessary. These can be present in the polymerization reaction system and then present in the product toner, but preferably they are externally added to the product toner afterwards. The content of each of these is 0 to 0 for the toner of the present invention.
3% by weight is preferred. Fluidity improvers include silane, titanium, aluminum, calcium, magnesium, and magnesium oxides, or those obtained by hydrophobizing the oxides with a titanium coupling agent or a silane coupling agent. teeth.
ステアリン醗亜鉛、ステアリン酸リチウム及びラウリル
酸マグネシウムの如き高級脂肪酸の金属塩或いはペンタ
エリスリトールベンゾエートの如き芳香族酸エステルが
ある。These include metal salts of higher fatty acids such as zinc stearate, lithium stearate and magnesium laurate, or aromatic acid esters such as pentaerythritol benzoate.
本発明において、帯電量及び帯電極性をより所望の値に
調整するために本発明のトナーに帯電制御剤を用いるこ
ともできる。In the present invention, a charge control agent can also be used in the toner of the present invention in order to adjust the charge amount and charge polarity to more desired values.
本発明に好ましく用いられる帯電制御剤としては、酒精
可溶ニグロシン染料、脂肪酸変性ニグロシン染料、カル
ボキシル基含有樹脂変性二グロシン染料等のニグロシン
染料、スピロンブラックTRH,スビロンブラックTP
H(保土谷化学工業■製)などのアゾ染料、p−フルオ
ロ安息香酸。As the charge control agent preferably used in the present invention, nigrosine dyes such as alcohol soluble nigrosine dyes, fatty acid-modified nigrosine dyes, carboxyl group-containing resin-modified nigrosine dyes, Spiron black TRH, Subiron black TP
Azo dyes such as H (manufactured by Hodogaya Chemical Industry ■), p-fluorobenzoic acid.
p−ニトロ安息香酸、2.4−ジ−t−ブチルサリチル
酸などの芳香族酸誘導体、ジブチル−スズオキシド、ジ
オクチル−スズオキシドなどのスズ化合物などを挙げる
ことができる。これらは1重合性単量体に対して0〜5
重量%使用されるのが好ましい。Examples include aromatic acid derivatives such as p-nitrobenzoic acid and 2,4-di-t-butylsalicylic acid, and tin compounds such as dibutyl-tin oxide and dioctyl-tin oxide. These are 0 to 5 per polymerizable monomer.
Preferably, % by weight is used.
非水溶媒中での懸濁重合が完了した後、遠心分離機で脱
溶媒し、′t!i燥及び必要に応じて分級して。After suspension polymerization in a non-aqueous solvent is completed, the solvent is removed using a centrifuge and 't! i Dry and classify if necessary.
トナー粒子を得ることができる。Toner particles can be obtained.
本発明によシ得られるトナーを二成分現像剤として使用
する場合には、偏平状、海綿状、コイン状1球状、真球
状等9種々の形状の酸化鉄粉、マンガン、コバルト、ニ
ッケル、 亜鉛、 1m、マグネシウム、鉛、ストロン
チウム、バリウム、リチウム等のフェライト、テフロン
樹脂、アクリル樹脂。When the toner obtained according to the present invention is used as a two-component developer, iron oxide powder, manganese, cobalt, nickel, zinc, etc. in nine different shapes such as flat, cavernous, coin-shaped, spherical, etc. , 1m, ferrite such as magnesium, lead, strontium, barium, lithium, Teflon resin, acrylic resin.
ポリエステル樹脂、シリコン樹脂、メラミン樹脂。Polyester resin, silicone resin, melamine resin.
ブタジェン樹脂、ブチラール樹脂等を表層にコーティン
グ処理した酸化鉄粉、フェライト、種々の樹脂と磁性粉
との混線物からなる粒子等のキャリアと組み合わせて使
用することができる。It can be used in combination with a carrier such as iron oxide powder whose surface layer is coated with butadiene resin, butyral resin, etc., ferrite, or particles made of a mixture of various resins and magnetic powder.
二成分現像剤のトナー濃度は、一般にキャリアの比表面
積に依存し、使用するキャリアが不定形又は細粒径であ
るときは3〜10重量−に1球形又は粗粒径であるとき
は1〜5重を−にされるのが好ましい。The toner concentration of a two-component developer generally depends on the specific surface area of the carrier, and when the carrier used is amorphous or has a fine particle size, it is 3 to 10% by weight, and when the carrier is spherical or has a coarse particle size, it is 1 to 10% by weight. It is preferable that the quintuple is set to -.
本発明によシ得られるトナーは種々の現像プロセス、例
えば米国特許第2.618,552号に記載されている
カスケード現像法、米国特許第2.874065号に記
載されている磁気ブラシ法。The toners obtained according to the present invention can be used in various development processes, such as the cascade development method described in U.S. Pat. No. 2,618,552, and the magnetic brush method described in U.S. Pat. No. 2,874,065.
米国特許第2.221,776号に記載されているパウ
ダー・クラウド法、米国特許第3,166.432号に
記載のタッチダウン現像法、特開昭55−18656号
公報に記載されている所謂ジャンピング法、キャリアと
して粉砕法によって製造された磁性トナーを用いる所謂
マイクロトーニング法及び磁性トナー同志の摩擦帯電に
よって必要なトナー電荷を得る所謂バイポーラ・マグネ
チック法などに用いることができる。The powder cloud method described in U.S. Patent No. 2,221,776, the touchdown development method described in U.S. Pat. It can be used in a jumping method, a so-called microtoning method using magnetic toner produced by a pulverization method as a carrier, and a so-called bipolar magnetic method in which a necessary toner charge is obtained by frictional charging of magnetic toners.
また1本発明によシ得られるトナーは種々の定着法1例
えば所・謂オイルレス及びオイル塗布ヒートロール法、
フラッシュ法、オーブン法、圧力定着法などに用いるこ
とができる。Furthermore, the toner obtained according to the present invention can be fixed using various fixing methods, such as so-called oil-less and oil-coated heat roll methods,
It can be used in flash method, oven method, pressure fixing method, etc.
さらに1本発明のトナーは種々のクリーニング方法2例
えば、所11Iファーブラシ法、ブレード法などに用い
ることができる。Furthermore, the toner of the present invention can be used in various cleaning methods, such as the fur brush method and the blade method.
(作用)
本発明におhては、懸濁溶媒として非水溶媒を用いるた
め、界面活性剤を使用する必要がなくなる。その結果9
重合粒子の表面における界面活性剤の残留による問題点
はすべて解消され、耐湿性及び諸々の写真特性に優れた
トナーが得られる。(Function) In the present invention, since a non-aqueous solvent is used as the suspending solvent, there is no need to use a surfactant. Result 9
All problems caused by residual surfactant on the surface of polymer particles are eliminated, and a toner with excellent moisture resistance and various photographic properties can be obtained.
また1重合に用いる分散安定剤の徨類を選択することに
より、耐オフセット性及び/又は定着性に優れたトナー
が得られる。Furthermore, by selecting the type of dispersion stabilizer used in monopolymerization, a toner with excellent anti-offset properties and/or fixing properties can be obtained.
(実施例)
次に1本発明の実施例を示すが2本発明はこれに限定さ
れるものではない。以下、慢は重量%を意味する。(Example) Next, an example of the present invention will be shown, but the present invention is not limited thereto. Hereinafter, "arrogant" means % by weight.
実施例1
(1) 分散安定剤の合成
攪拌装置、窒素導入口、M下ロート、@変針及びコンデ
ンサを装着した4っ072スコにアイツバ−G(エクン
ンコーポレーション商品名、インパラフィン)xooo
gを仕込み、窒素気流下で120℃に保温、攪拌した。Example 1 (1) Synthesis of dispersion stabilizer A 4072 Sco was equipped with a stirring device, nitrogen inlet, M lower funnel, @ variable needle, and a condenser, and Aitzva-G (trade name of Ekun Corporation, Imparaffin) xooo
g was charged and stirred while keeping the temperature at 120° C. under a nitrogen stream.
別に、ラウリルメタクリレ−)10009に7ゾビスイ
ソブチロニトリル25廖を溶解させた液を上記フラスコ
に2時間かけて均一に滴下し2発熱に注意しつつ6時間
120℃に保温した後、冷却した。重合率は99.9チ
以上であシ、固型分50′sのポリラウリルメタクリレ
ート溶液からなる分散安定剤溶液が得られた。Separately, a solution prepared by dissolving 25 volumes of 7zobisisobutyronitrile in lauryl methacrylate (methacrylate) 10009 was uniformly dropped into the flask over 2 hours, and the temperature was kept at 120°C for 6 hours while being careful not to generate heat. Cooled. A dispersion stabilizer solution consisting of a polylauryl methacrylate solution with a polymerization rate of 99.9% or more and a solid content of 50's was obtained.
(2) 懸濁重合液の製造工程
攪拌装置、窒素導入口、11下ロート、温度計及ヒコン
テンサを装着した4つロフラスコにアイソパーE(エク
ンンコーポレーション商品名、イソパラフィン)100
09及び前記分散安定剤溶液140gを仕込み、窒素気
流下で90℃に保温し。(2) Production process of suspension polymerization solution A 4-bottle flask equipped with a stirrer, nitrogen inlet, 11 lower funnel, thermometer, and Hikontensa was charged with 100 ml of Isopar E (trade name of Ekun Corporation, isoparaffin).
09 and 140 g of the above dispersion stabilizer solution were charged and kept at 90° C. under a nitrogen stream.
攪拌した。別に2重合性単量体としてスチレン630g
及びブチルメタクリレート2709.着色剤としてカー
ボンブラックφ44(三菱化成工業■製、ファーネスブ
ラック系カーボンブラック)65g、帯電制御剤として
スビロンブラックTRH(保土谷化学工業■製ニグロシ
ン染料の商品名)15g、低分子量ポリプロピレン(商
品名ビスコールs s OP、三洋化成工業■製)20
s*重合開始剤としてアゾビスインブチロニ)IJル1
89をホモミキサーで3000camで30分間混合分
散させた液を前記フラスコに2時間かけて均一に滴下し
9発熱に注意しつつ6時間保温した後、冷却して懸濁重
合液を得た。このときの重合率は99.9−以上であっ
た。また9重合体の分子量は高速液体クロマトグラフィ
により標準ポリスチレンによる検量線を用いて測定した
ところ2重量平均分子量(以後Mwとする) 7200
0.数平均分子量(以後Mnとする)30000であっ
た。Stirred. Separately, 630g of styrene as a dipolymerizable monomer
and butyl methacrylate 2709. As a coloring agent, 65 g of carbon black φ44 (manufactured by Mitsubishi Kasei Corporation, furnace black type carbon black), 15 g of Subiron Black TRH (trade name of nigrosine dye, manufactured by Hodogaya Chemical Industries, Ltd.) as a charge control agent, low molecular weight polypropylene (trade name) Viscole s s OP, manufactured by Sanyo Chemical Industries ■) 20
s*As a polymerization initiator, azobisin butyroni) IJ 1
89 was mixed and dispersed in a homomixer at 3000 cam for 30 minutes, and the mixture was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while being careful not to generate heat, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 or more. The molecular weight of the 9-polymer was measured by high-performance liquid chromatography using a standard polystyrene calibration curve, and the weight average molecular weight (hereinafter referred to as Mw) was 7200.
0. The number average molecular weight (hereinafter referred to as Mn) was 30,000.
(3)乾燥工程 前記a濁重合液を遠心分離機で脱溶媒した後。(3) Drying process After removing the solvent from the cloudy polymer solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得た。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ粒
径分布1〜50μm、平均粒径13μmであった。さら
に示差走査熱量計でガラス転移点(以下Tgとする)を
測定したところ76℃であった。It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Further, the glass transition point (hereinafter referred to as Tg) was measured with a differential scanning calorimeter and was found to be 76°C.
(4) tf価
このトナーはさらに市販の絶縁性キャリアを用いた普通
紙複写機(小西六写真工業■製、商品名U−Bix 1
600)を用いて電子写真特性を試験した。(トナー濃
度5%)。ただしトナーには流動性向上剤として疎水性
向上剤として疎水性シリカ(日本アエロジル■製R−9
72)及びステアリン酸亜鉛をそれぞれ上記トナーに対
して0.6%及び0.11の外添処理を施した。試験結
果を第1表に示す。(4) TF value This toner can be used in a plain paper copying machine using a commercially available insulating carrier (manufactured by Konishiroku Photo Industry ■, product name: U-Bix 1).
600) was used to test the electrophotographic properties. (toner concentration 5%). However, the toner contains hydrophobic silica (R-9 manufactured by Nippon Aerosil ■) as a fluidity improver and a hydrophobicity improver.
72) and zinc stearate were externally added to the above toner at a concentration of 0.6% and 0.11%, respectively. The test results are shown in Table 1.
実施例2
(1)懸濁重合液の製造工程
実施例1と同様のフラスコにアイソパーE10009及
び前記実施例1の(1)で得られた分散安定剤溶液14
09を仕込み、窒素気流下で90℃に保温し、攪拌する
。別に9重合性単量体としてスチレン720g、ブチル
アクリレート180g、カーボンブラックφ44 65
9.スビロンブラックTRH159,ビスコール550
P209、重合開始剤としてパーブチル0(日本油脂■
製、t−ブチルパーオキサイド(2−エチルヘキサノエ
ート)の商品名)189をホモミキサーで300 Or
、p、mで30分間混合分散させた液を上記フラスコに
2時間かけて均一に滴下し2発熱に注意しつつ6時間保
温し九のち冷却して懸濁重合液を得た。このときの重合
率は99.9慢以上であシ。Example 2 (1) Manufacturing process of suspension polymerization solution Isopar E10009 and the dispersion stabilizer solution 14 obtained in (1) of Example 1 were placed in the same flask as in Example 1.
09 was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include 720 g of styrene, 180 g of butyl acrylate, and carbon black φ44 65
9. Subiron black TRH159, Viscole 550
P209, Perbutyl 0 (NOF ■) as a polymerization initiator
Co., Ltd., trade name of t-butyl peroxide (2-ethylhexanoate)) 189 in a homomixer at 300 or
, p, and m for 30 minutes, the mixture was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time should be 99.9 or higher.
実施例1と同様に求め比重合体の分子量はMwが850
00、Mnが38000であった。The molecular weight of the specific polymer was determined in the same manner as in Example 1, and the Mw was 850.
00, and Mn was 38,000.
(2)乾燥工程
上記M満貫合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したところ粒径分布1〜50μm、平
均粒径12μmであった。さらに示差走査熱量計でTg
を測定したところ72℃であった。(2) Drying process The above M-filled solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 12 μm. Furthermore, Tg was measured using a differential scanning calorimeter.
When measured, it was 72°C.
(3)評価
このトナーを実施例1と同様にして電子写真特性を評価
した。試験結果を第1表に示す。(3) Evaluation The electrophotographic properties of this toner were evaluated in the same manner as in Example 1. The test results are shown in Table 1.
比較例1(水性W!A濁重合によるトナーめ製造)スチ
レン70g、ブチルメタクリレート309゜グラフト化
カーボン(グラフトカーボンGP−E−2.カーボンブ
ラック/ポリマー成分/スチレンモノマー=30/30
/40.菱有工業■製)159及び過酸化ベンゾイル2
gをホモミキサーで十分混合し、リン酸三カルシウムの
1%水溶液500gを加え、ホモミキサーでさらに30
00r、p、mで30分間分散した。Comparative Example 1 (Production of toner by aqueous W!A turbidity polymerization) Styrene 70g, butyl methacrylate 309° grafted carbon (grafted carbon GP-E-2. Carbon black/polymer component/styrene monomer = 30/30
/40. Ryoyu Kogyo ■) 159 and benzoyl peroxide 2
Mix well with a homomixer, add 500g of a 1% aqueous solution of tricalcium phosphate, and mix with a homomixer for another 30g.
Dispersion was carried out for 30 minutes at 00r, p, m.
この分散液をフラスコに移し、90’ICで7時間@濁
重合した。重合率は約99%であった。この重合体を脱
水し、pH2以下の塩酸水溶液で洗浄後乾燥し、トナー
を得た。このトナーの樹脂のMwは97000.Mnは
5ooooであった。This dispersion was transferred to a flask and subjected to turbid polymerization at 90'IC for 7 hours. The polymerization rate was about 99%. This polymer was dehydrated, washed with an aqueous hydrochloric acid solution having a pH of 2 or less, and then dried to obtain a toner. The Mw of the resin in this toner is 97,000. Mn was 5oooo.
比較例2(乳化重合後、スプレー乾燥することによるト
ナーの製造)
31#)、X、テンレスビーカーにグラフト化カーボン
GP−E−21009に重合性単量体としてスチレン4
009.アクリル酸ブチル120g及び連鎖移動剤とし
てt−ドデシルメルカプタン0.6gをホモミキサーに
て300 Or−90mで30分間混合分散させた。Comparative Example 2 (Production of toner by spray drying after emulsion polymerization) 31#),
009. 120 g of butyl acrylate and 0.6 g of t-dodecyl mercaptan as a chain transfer agent were mixed and dispersed in a homomixer at 300 m or 90 m for 30 minutes.
次いで、このカーボン分散液にイオン交換水13009
に乳化剤としてアニオン界面活性剤であるドデシルベン
ゼンスルホン酸ナトリウム129、ノニオン界面活性剤
であるノニボールPE−68(三洋化成工業■オキシプ
ロピレンーオキシエチレンプロツクボリマーの商品名)
3g、ノイゲンEA170(第一工業製薬■製ポリオキ
シエチレングリコールノニルフェニルエーテルノ商品名
)3G及び重合開始剤として過硫酸アンモニウム129
を溶解した水溶液を加え、ホモミキサーでさらに300
0 c、p、mで30分間乳化し、黒色プレエマルジョ
ンヲ得り。Next, ion exchange water 13009 was added to this carbon dispersion.
Sodium dodecylbenzenesulfonate 129, an anionic surfactant, and Noniball PE-68, a nonionic surfactant, are used as emulsifiers (trade name of Sanyo Chemical Industries' Oxypropylene-Oxyethylene Block Polymer).
3g, Neugen EA170 (trade name of polyoxyethylene glycol nonyl phenyl ether manufactured by Daiichi Kogyo Seiyaku ■) 3G and ammonium persulfate 129 as a polymerization initiator.
Add an aqueous solution of
Emulsify at 0 C, P, M for 30 minutes to obtain a black pre-emulsion.
次いで、攪拌装置、窒素導入口、温度計及びコンデンサ
を装着した3I!の4つロセパラプルフラスコに黒色プ
レエマルジョンを移し、窒素気流下でフラスコの温度を
70℃で5時間重合させたのち、冷却して、乳化重合液
を得た。このときの重合率は99.9%以上であった。Next, 3I! was equipped with a stirrer, nitrogen inlet, thermometer and condenser. The black pre-emulsion was transferred to a four-piece parallel flask, and the flask was polymerized at a temperature of 70° C. for 5 hours under a nitrogen stream, and then cooled to obtain an emulsion polymerization liquid. The polymerization rate at this time was 99.9% or more.
また9重合体の分子量はゲルクロマトグラフィによシ標
準ポリスチレンによる検量線を用いて測定したところM
wは86000、Mnは30000であった。このよう
にして得られ丸孔化重合液を110℃の温度でスプレー
乾燥してトナーを得た。The molecular weight of the 9-polymer was determined by gel chromatography using a standard polystyrene calibration curve.
w was 86,000, and Mn was 30,000. The thus obtained round-hole polymerization liquid was spray-dried at a temperature of 110° C. to obtain a toner.
比較例3(粉砕法)
トルエンを溶媒とする溶液重合でスチレン/ブチルメタ
クリレート=70/30(重量比)2分子量1 Mw
70000及びMn 30000の重合体を作シ、減圧
脱溶剤を行いトルエンを堆り除いて白色固体を作った。Comparative Example 3 (pulverization method) Styrene/butyl methacrylate = 70/30 (weight ratio) 2 molecular weight 1 Mw by solution polymerization using toluene as a solvent
Polymers of 70,000 and Mn of 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to form a white solid.
この重合体9009にカーボンブラック65g。65g of carbon black was added to this polymer 9009.
スピロンブラックT几H15g及び低分子量ポリプロピ
レン(ビスコール550P)20Gを二本ロールで混練
し、ジェットミルで粉砕してトナーを得た。15 g of Spiron Black T Bottle H and 20 G of low molecular weight polypropylene (Viscol 550P) were kneaded with two rolls and pulverized with a jet mill to obtain a toner.
比較例1〜3で得られたトナーの粒子径、平均粒径、5
〜25μmの粒子の収率、主要樹脂成分のガラス転移点
及び実施例1〜2と同様に試験した電子写真特性を第1
表に示す。Particle size and average particle size of toners obtained in Comparative Examples 1 to 3, 5
The yield of ~25 μm particles, the glass transition temperature of the main resin component, and the electrophotographic properties tested in the same manner as in Examples 1 and 2 were determined in the first
Shown in the table.
なお、実施例1〜2及び比較例1〜3における電子写真
特性の評価は次のようにして行った。The electrophotographic properties of Examples 1 and 2 and Comparative Examples 1 and 3 were evaluated as follows.
(a) 解像度:電子写真学会テストチャートNl1
1を用い、それぞれの作成した現像剤を
使用して普通紙に複写した。複写され
た画像が細部まで像が読みとれるか比
較し、評価した。(a) Resolution: Electrophotography Society Test Chart Nl1
1, and each prepared developer was used to make copies on plain paper. The copied images were compared and evaluated to see if they could be read in detail.
(bl 画像濃度:解像度と同様にして複写した紙の
黒色部の濃度を濃度計で測定し判定
した。(bl Image density: In the same manner as the resolution, the density of the black part of the copied paper was measured with a densitometer and determined.
(C) 階調性:解像度と同様にして、テストチャー
ト中央部の11段階にわかれた濃淡
部を用いて評価した。(C) Gradation: Evaluated in the same way as the resolution using the 11-level gray area in the center of the test chart.
(d) クリーニング性:それぞれ作成した現像剤を
複写機を用い温度30℃、湿度80
1Ri(の条件で連続複写を行い、クリーニング不良が
発生するまでのコピー
枚数で評価した。(d) Cleanability: Each of the prepared developers was continuously copied using a copying machine at a temperature of 30° C. and a humidity of 80.1 Ri, and the number of copies until cleaning failure occurred was evaluated.
(e) 耐ブロッキング性:実施例1〜2.比較例1
〜3で作成したトナーを50℃、湿
度95チの条件で72時間放置し、ト
ナーがブロッキングしたかどうかを判
定し。(e) Blocking resistance: Examples 1-2. Comparative example 1
The toner prepared in steps 3 to 3 was left for 72 hours at 50° C. and humidity of 95° C., and it was determined whether the toner was blocked.
◎:非常に優れている O:優れている △:やや劣る ×:劣る として評価した。◎: Very good O: Excellent △: Slightly inferior ×: Inferior It was evaluated as
(f) 帯電安定性:それぞれ作成した現像剤を複写
機で攪拌し、一定時間毎に帯電量を
測定し、帯電量変化で判定し。(f) Charge stability: The prepared developers were stirred in a copying machine, the amount of charge was measured at regular intervals, and the change in the amount of charge was determined.
0:非常に優れている ○:優れている △:やや劣る X:劣る として評価した。0: Very good ○: Excellent △: Slightly inferior X: Inferior It was evaluated as
実施例3
(1)懸濁重合液の製造工程
攪拌装置、窒素導入口1滴下ロート、温度計及びコンデ
ンサを4つロフラスコにアイソパーE10009及び天
然ゴム(SM几−5)のアイソパーH溶液(固形分30
%)aaagを仕込み。Example 3 (1) Production process of suspension polymerization solution A stirrer, 1 nitrogen inlet, dropping funnel, thermometer, and 4 condensers were placed in a flask. 30
%) prepare aaag.
窒素気流下で90℃に保温し、攪拌した。別に。The mixture was kept at 90° C. under a nitrogen stream and stirred. Especially.
重合性単量体としてスチレン574g及びブチルメタク
リレート2469.着色剤としてカーボンブラックナ4
4 659.帯電制御剤としてスピロンブラックTRH
159及び重合開始剤としてアゾビスインブチロニトリ
ル189をホモミキサー+300 Or、p、mで30
分間混合分散させた液を上記フラスコに2時間かけて均
一に滴下し2発熱に注意しつつ6時間保温した後、冷却
して懸濁重合液を得た。このときの重合率は99.91
以上であつ九。また9重合体の分子量(ゲル分を除いた
場&)は高速液体クロマトグラフィによシ標準ポリスチ
レンによる検量線を用いて測定したところ、Mwは72
000.Mnは30000であった。Styrene 574g and butyl methacrylate 2469g as polymerizable monomers. Carbon blackener 4 as a coloring agent
4 659. Spiron black TRH as a charge control agent
159 and azobisinbutyronitrile 189 as a polymerization initiator in a homomixer + 300 Or, p, m for 30
The mixed and dispersed solution was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. The polymerization rate at this time was 99.91
That's all for now. In addition, the molecular weight (excluding gel content) of the 9-polymer was measured by high-performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 72.
000. Mn was 30,000.
(2)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得た。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ1
粒径分布1〜50μm、平均粒径13μmであった。さ
らに示差走査熱量計でTgを測定したところ、65℃で
あった。It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.
実施例4
(1)懸濁重合液の製造工程
実施例3と同様のフラスコにアイソパーE100091
)’スチレンーブタジェンコム(II8几P(インター
ナショナル インステイテユート オプ シンセテイツ
クラバー プロデューサーズ、インコーボレイテイド)
により付与された品種番号1002番〕のアイソパーG
溶液(固型分zss)zoogを仕込み、窒素気流下で
90℃に保温し、攪拌する。別に9重合性単量体として
スチレン6969.ブチルアクリレート1749、 カ
ーボンブラック◆44 asg、スピロンブラックT
RH159及びノく−ブチル0189をホモミキサーで
300 Or、p−mで30分間混合分散させた液を上
記フラスコに2時間かけて均一に滴下し2発熱に注意し
つつ6時間保温したのち冷却して懸濁重合液を得た。こ
のときの重合率は99.9%以上であシ、実施例1と同
様に求めた重合体の分子量(ゲル分を除いた場合)はM
wが65000.Mnが32000であった。Example 4 (1) Production process of suspension polymerization solution Isopar E100091 was placed in the same flask as in Example 3.
)' Styrene-Butagencom (II8P (International Institute of Synthetics Clubber Producers, Inc.)
Isopar G of product number 1002 given by
A solution (solid content: zss) is charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include styrene 6969. Butyl acrylate 1749, carbon black ◆44 asg, Spiron black T
A solution obtained by mixing and dispersing RH159 and Noku-butyl 0189 at 300 Orr and pm for 30 minutes using a homomixer was added dropwise uniformly to the above flask over 2 hours, and kept warm for 6 hours while being careful not to generate heat, and then cooled. A suspension polymerization solution was obtained. The polymerization rate at this time was 99.9% or more, and the molecular weight of the polymer (excluding gel content) determined in the same manner as in Example 1 was M
w is 65000. Mn was 32,000.
(2)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したところ9粒径分布1〜50μm、
平均粒径14.5μmであった。さらに示差走査熱量計
でTgを測定したところ70℃であった。(2) Drying process The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.
実施例5
(1)懸濁重合液の製造
攪拌装置、窒素導入口9滴下ロート、温度計及びコンデ
ンサを装着した四つロフラスコにアイソパーE 100
0s及びポリオイル130(日本ゼオン■製ポリブタジ
ェン)xoogを仕込み、窒素気流下で90℃に保温し
、攪拌する。別に9重合性単量体としてスチレン574
g及びブチルメタクリレート2469.着色剤としてカ
ーボンブラックナ44 659.帯電制御剤としてスビ
ロンブラックT几H159及び重合開始剤としてアゾビ
スイソブチロニトリル18gをホモミキサーでa o
o o r、p、mで30分間混合し9分散させた液を
上記フラスコに2時間かけて均一に滴下し。Example 5 (1) Production of suspension polymerization solution Isopar E 100 was placed in a four-lobe flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser.
0s and Polyoil 130 (polybutadiene manufactured by Zeon Corporation) Separately 9 Styrene 574 as a polymerizable monomer
g and butyl methacrylate 2469. Carbon blackener 44 659 as a coloring agent. Subiron Black T H159 as a charge control agent and 18 g of azobisisobutyronitrile as a polymerization initiator were mixed in a homomixer.
Mix at o o r, p, m for 30 minutes and disperse the resulting liquid dropwise uniformly into the above flask over 2 hours.
発熱に注意しつつ、6時間保温した後、冷却して懸濁重
合液を得た。このときの重合率は、99.9−以上であ
った。また9重合体の分子量(ゲル分を除いた場合)は
、高速液体クロマトグラフィーにより標準ポリスチレン
による検量線を用いて測定したところ、Mwは7200
G、Mnは30000であった。The mixture was kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 or more. The molecular weight of the 9-polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 7200.
G and Mn were 30,000.
(2)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得た。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ9
粒径分布1〜50μm、平均粒径13μmであった。更
に、示差走査熱量計でTgを測定し九ところ、65℃で
あった。It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 9.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Further, Tg was measured using a differential scanning calorimeter and found to be 65°C.
実施例6
(1) 懸濁重合液の製造工程
実施例5と同様のフラスコにアイソパーE10009及
びポリオイル160(日本ゼオン■製ポリブタジェンの
商品名)50gを仕込み、窒素気流下に90℃に保温し
、攪拌する。別に9重合性単量体としてスチレン696
9及びブチルアクリレート1749. カーボンブラッ
クφ4465g、スビロンブラックT几H1s g 及
ヒバーブチル018gをホモミキサーでa o o o
r−p−mで30分間混合し9分散させた液を上記
フラスコに2時間かけて均一に滴下し1発熱に注意しつ
つ。Example 6 (1) Manufacturing process of suspension polymerization solution 50 g of Isopar E10009 and Polyoil 160 (trade name of polybutadiene manufactured by Nippon Zeon ■) were charged into a flask similar to that in Example 5, and kept at 90°C under a nitrogen stream. Stir. Separately, styrene 696 is used as a polymerizable monomer.
9 and butyl acrylate 1749. Carbon black φ4465g, Subiron Black T 几H1sg and Hibarbutyl 018g were mixed in a homomixer.
The dispersed liquid was mixed for 30 minutes at rpm and uniformly dropped into the flask over 2 hours, being careful not to generate heat.
6時間保温した後、冷却して懸濁重合液を得た。After keeping the temperature for 6 hours, it was cooled to obtain a suspension polymerization liquid.
このときの重合率は、99.9%以上であシ、実施例1
と同様に求めた重合体の分子量(ゲル分を除いた場合)
はMwが65000.Mnが32000であった。The polymerization rate at this time was 99.9% or more, Example 1
Molecular weight of the polymer determined in the same manner as (excluding gel content)
has Mw of 65000. Mn was 32,000.
(2)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
し、トナーを得た。得られたトナーをコールタ−カウン
ターで粒子径を測定したところ。(2) Drying process The suspension polymerization solution was subjected to centrifugal desolvation and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter.
粒径分布1〜50μm、平均粒径14.5μmであつた
。更に、示差走査熱量計でガラス転移点を測定したとこ
ろ、70℃であった。The particle size distribution was 1 to 50 μm, and the average particle size was 14.5 μm. Further, the glass transition point was measured using a differential scanning calorimeter and was found to be 70°C.
実施例7
(1)分散安定剤の製造
攪拌装置、窒素導入口1滴下ロート、温度計及びコンデ
ンサを装着した四つロフラスコにアイソパーu7oog
を仕込み、窒素気流下で120℃に保温し、攪拌し九。Example 7 (1) Production of dispersion stabilizer Isopar u7oog was placed in a four-loaf flask equipped with a stirring device, a dropping funnel with one nitrogen inlet, a thermometer, and a condenser.
9. Prepare the mixture, keep it warm at 120℃ under a nitrogen stream, and stir.9.
別に、ラウリルメタクリレ−)8689.グリシジルメ
タクリレート24g。Separately, lauryl methacrylate) 8689. 24g of glycidyl methacrylate.
ブチルメタクリレート85g及び過酸化ベンゾイル(重
合開始剤)259を溶解させた混合液を上記フラスコに
2時間かけて均一に滴下し九後。A mixture of 85 g of butyl methacrylate and 259 g of benzoyl peroxide (polymerization initiator) was uniformly dropped into the flask over 2 hours.
140℃まで昇温し、4時間保温した。保温後。The temperature was raised to 140°C and kept at this temperature for 4 hours. After keeping warm.
50℃まで降温し、グリシジル基とメタクリル酸の反応
触媒としてカチオンM!−100(日本油脂■製4級ア
ンモニウム塩の商品名)&59とアイソパーH150g
を添加した。50℃で1時間保温し、カチオンMs −
100の溶解を確認した後。The temperature was lowered to 50°C, and cation M! was used as a reaction catalyst between glycidyl groups and methacrylic acid. -100 (trade name of quaternary ammonium salt made by NOF ■) &59 and Isopar H 150g
was added. Incubate at 50°C for 1 hour to convert the cation Ms −
After confirming the dissolution of 100.
メタクリル酸239及びアイソパーH1509を1時間
かけて滴下する。滴下中に10分につき15℃の割合で
昇温し、140℃で7〜8時間保温した。酸価が45以
下になれば終点として冷却した。これによシ、不揮発分
S OS、酸価4.2の赤褐色の分散安定剤溶液を得た
。Methacrylic acid 239 and Isopar H1509 are added dropwise over 1 hour. During the dropping, the temperature was increased at a rate of 15°C per 10 minutes, and the temperature was kept at 140°C for 7 to 8 hours. When the acid value became 45 or less, cooling was performed as the end point. As a result, a reddish-brown dispersion stabilizer solution with a non-volatile content of SOS and an acid value of 4.2 was obtained.
(2)懸濁重合液の製造
攪拌装置、窒素導入口1滴下ロート、温度計及びコンデ
ンサを装着した四つロフラスコにアイソパーE100O
s及び(1)で得られた分散安定剤200gを仕込み、
窒素気流下に90℃に保温し。(2) Production of suspension polymerization solution Isopar E100O
s and 200 g of the dispersion stabilizer obtained in (1) were charged,
Insulated at 90°C under nitrogen flow.
攪拌した。別に9重合性単量体としてスチレン574g
及びブチルメタクリレート2469.着色剤としてカー
ボンブラックφ44 ssg、帯電制御剤としてスビ
ロンブラックTRH159及び重合開始剤としてアゾビ
スインブチロニトリル189をホモミキサーで300
Or、p、mで30分間混合し9分散させた液を上記フ
ラスコに2時間かけて均一に滴下し9発熱に注意しつつ
、6時間保温した後、冷却して!!!濁重濁液合液た。Stirred. Separately, 574g of styrene as a polymerizable monomer
and butyl methacrylate 2469. Carbon black φ44 ssg as a coloring agent, Subiron black TRH159 as a charge control agent, and azobisin butyronitrile 189 as a polymerization initiator were mixed in a homomixer at 300 ml.
Mix with Or, p, and m for 30 minutes and disperse the 9 liquid dropwise uniformly over 2 hours into the above flask. 9 Keep warm for 6 hours while being careful not to generate heat, then cool! ! ! The turbid and heavy turbid liquid was mixed.
このときの重合率は、99.9−以上であった。また9
重合体の分子量(ゲル分を除いた場合)は、高速液体ク
ロマトグラフィーによシ標準ポリスチレンによる検量線
を用いて測定したところ、Mw72000゜Mn 30
000であった。The polymerization rate at this time was 99.9 or more. Also 9
The molecular weight of the polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and found to be Mw 72000°Mn 30
It was 000.
(3)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得九。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ1
粒径分布1〜50μm、平均粒径13μmであった。更
に、示差走査熱量計でTgを測定したところ、65℃で
あった。Dry in a dryer at 40°C to obtain toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.
実施例8
(1) 懸濁重合液の製造工程
実施例7と同様のフラスコにアイソパーE10009及
び実施例7の(1)で゛得られた分散安定剤100gを
仕込み、窒素気流下に90℃に保温し、攪拌する。別に
、重合性単量体としてスチレン696g及びブチルアク
リレート1749.カーボンプラックナ44 659.
スビロンブラックTRH159及びパーブチル0 18
9をホそミキサーでs o ’o o r−p−mで3
0分間混合し2分散させた液を上記フラスコに2時間か
けて均一に滴下し1発熱に注意しつつ、6時間保温した
後、冷却して懸濁重合液を得た。このときの重合率は。Example 8 (1) Manufacturing process of suspension polymerization solution Isopar E10009 and 100 g of the dispersion stabilizer obtained in Example 7 (1) were charged into a flask similar to that in Example 7, and heated to 90°C under a nitrogen stream. Keep warm and stir. Separately, 696 g of styrene and 1749 g of butyl acrylate were used as polymerizable monomers. Carbon Plakna 44 659.
Subiron Black TRH159 and Perbutyl 0 18
9 with a hoso mixer so 'o o r-p-m 3
The dispersion solution obtained by mixing for 0 minutes was uniformly dropped into the above flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. What is the polymerization rate at this time?
99.9%以上であり、実施例1と同様に求めた重合体
の分子量(ゲル分を除いた場合)はMw65000、M
n30000であった。99.9% or more, and the molecular weight of the polymer determined in the same manner as in Example 1 (excluding gel content) was Mw65000, M
It was n30,000.
(2)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
し、トナーを得た。得られたトナーをコールタ−カウン
ターで粒子径を測定したところ。(2) Drying process The suspension polymerization solution was subjected to centrifugal desolvation and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter.
粒径分布1〜50μm、平均粒径14.5μmであった
。更に、示差走査熱量計でガラス転移点を測定したとこ
ろ、70℃であった。The particle size distribution was 1 to 50 μm, and the average particle size was 14.5 μm. Further, the glass transition point was measured using a differential scanning calorimeter and was found to be 70°C.
比較例4(粉砕法)
トルエンを溶媒とする溶液重合でスチレン/ブチルメタ
クリレート−70/30(重量比)2分子量Mw 70
000及びMn 30000の重合体を作り、減圧脱溶
剤を行い、トルエンを取り除いて白色固体を作った。Comparative Example 4 (pulverization method) Styrene/butyl methacrylate-70/30 (weight ratio) 2 molecular weight Mw 70 by solution polymerization using toluene as a solvent
Polymers of 000 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid.
この重合体920gにカーポンブラックナ4465g及
びスビロンブラックT几H159を二本ロールで混練し
、ジェットミルで粉砕し2分級してトナーを得た。920 g of this polymer was kneaded with 4465 g of Carpon Blackna and Subiron Black T Bottle H159 using two rolls, and the mixture was pulverized using a jet mill and classified into two to obtain a toner.
得られたトナーをコールタ−カウンターで粒子径を測定
したところ2粒径分布1〜50μm、平均粒径12μm
であった。さらに、示差走査熱量計でTgを測定したと
ころ、73℃であった。When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 12 μm.
Met. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.
実施例3〜8及び比較例4における電子写真特性の評価
は、実施例1〜2及び比較例1〜3と同様に行い、さら
に定着性及び耐オフセット性を下記(g)に示す方法で
評価した。The evaluation of electrophotographic properties in Examples 3 to 8 and Comparative Example 4 was performed in the same manner as in Examples 1 to 2 and Comparative Examples 1 to 3, and the fixing properties and offset resistance were further evaluated by the method shown in (g) below. did.
(g) 定着特性:普通紙複写機のヒートロール温度
制御装置を切夛、外部からヒートロ
ール温度を制御できるようにしてIX
l 1nch黒ベタを各温度で定着させた。(g) Fixing characteristics: The heat roll temperature control device of the plain paper copying machine was cut off so that the heat roll temperature could be controlled from the outside, and IX 1 1nch black solid was fixed at each temperature.
そのときに目視でオフセット(コール ド、ホットとも)の有無を判定した。At that time, visually check the offset (call) The presence or absence of hot and cold was determined.
なお、220℃以上にヒートロール温 度を保つことができなかったので、試 験は220℃迄とした。In addition, the heat roll temperature should not exceed 220℃. I couldn't keep my temperature up, so I tried The temperature was up to 220°C.
実施例3〜8及び比較例40絆価結果を表2に実施例9
(1)分散安定剤の製造
攪拌装置、窒素導入口2滴下ロート、温度計及びコンデ
ンサを装着した4つロフラスコにアイソパーH7009
を仕込み、窒素気流下で120℃に保温し、攪拌した。Examples 3 to 8 and comparative example 40 bond value results are shown in Table 2. Example 9 (1) Production of dispersion stabilizer Isopar H7009 was placed in a four-bottle flask equipped with a stirring device, a dropping funnel with two nitrogen inlets, a thermometer, and a condenser.
was charged, kept at 120°C under a nitrogen stream, and stirred.
別に2クリルメタクリレ−)8539.グリシジルメタ
クリレート24g。Separately 2 acrylic methacrylate) 8539. 24g of glycidyl methacrylate.
ジメチルアミンエチルメタクリレート1009及び重合
開始剤としてベンゾイルパーオキサイド259を溶解さ
せた混合液を上記フラスコに2時間かけて均一に滴下し
た後、140℃まで昇温し4時間保温する。保温後50
℃まで降温し、カチオン隔−100s、sgとアイツバ
−Hxsogを添加した。50℃で1時間保温攪拌し、
カチオンM!−100の溶解を確認後、メタクリル酸2
39、アイソパーH1509を1時間かけて滴下し九。A mixture of dimethylamine ethyl methacrylate 1009 and benzoyl peroxide 259 as a polymerization initiator was uniformly dropped into the above flask over 2 hours, and then the temperature was raised to 140° C. and kept for 4 hours. After keeping warm 50
The temperature was lowered to °C, and cation spacing -100s, sg and Aituba-Hxsog were added. Stir at 50°C for 1 hour,
Cation M! -After confirming the dissolution of 100, methacrylic acid 2
39. Drop Isopar H1509 over 1 hour.9.
滴下中に10分につき15℃の割合で昇温し140℃で
7〜8時間保温した。酸価が4.5以下になった所を終
点として冷却した。During the dropping, the temperature was increased at a rate of 15°C per 10 minutes and kept at 140°C for 7 to 8 hours. Cooling was carried out with the end point being the point where the acid value became 4.5 or less.
これによシネ稀発分50%、酸価4.2の赤かつ色の分
散安定剤溶液を得た。This gave a red colored dispersion stabilizer solution with a cine rare fraction of 50% and an acid value of 4.2.
(2) II!!濁重合液の製造工程攪拌装置、窒素
導入口9滴下ロート、温度計及びコンデンサを装着した
4つロフラスコにアイソパーH10009及び(1)で
得られた分散安定剤2009を仕込み窒素気流下で90
℃に保温し。(2) II! ! Production process of cloudy polymerization liquid Isopar H10009 and the dispersion stabilizer 2009 obtained in (1) were charged into a four-bottle flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser, and the mixture was heated to 90°C under a nitrogen stream.
Keep warm at ℃.
攪拌する。別に9重合性単量体としてスチレン5749
及びブチルメタクリレート2469.着色剤としてカー
ボンブラックナ44 sog及び重合開始剤としてア
ゾビスインブチロニトリルxsgをホモミキサーで30
0 Or、I)0mで30分間混合分散させた液を上記
フラスコに2時間かけて均一に滴下し9発熱に注意しつ
つ6時間保温した後、冷却して懸濁重合液を得た。この
ときの重合率は99.91以上であった。″!九2重合
体の分子量(ゲル分を除いた場合)は高速液体クロマト
グラフィにより標準ポリスチレンによる検量線を用いて
測定したところ、Mwは72000.Mnは30000
であった。Stir. Separately, 9 styrene 5749 as a polymerizable monomer
and butyl methacrylate 2469. Carbon blackener 44 sog as a coloring agent and azobisin butyronitrile xsg as a polymerization initiator were mixed in a homomixer at 30
0 Or, I) The solution mixed and dispersed at 0 m for 30 minutes was uniformly dropped into the above flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. The polymerization rate at this time was 99.91 or more. ``!The molecular weight of the 92 polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 72,000.Mn was 30,000.
Met.
(3)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得た。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ1
粒径分布1〜50μm、平均粒径13μmであった。さ
らに示差走査熱量計でTgを測定したところ、65℃で
あった。It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.
実施例1O
(1)分散安定剤の製造
攪拌装置、a索導入口2滴下ロート、温度計及びコンデ
ンサを装着した4つロフラスコにアイソパーH7009
を仕込み、窒素気流下で120℃に保温し、攪拌した。Example 1O (1) Production of dispersion stabilizer Isopar H7009 was placed in a four-loop flask equipped with a stirrer, two dropping funnels, a thermometer and a condenser.
was charged, kept at 120°C under a nitrogen stream, and stirred.
別にラウリルメタクリレートssag、 グリシジルメ
タクリレート24g。Separately, lauryl methacrylate ssag, glycidyl methacrylate 24g.
モルホリノエチルメタクリレート100g及び重合開始
剤ベンゾイルパーオキサイド259を溶解させた混合液
を上記フラスコに2時間かけて均−VC滴下した後、1
40℃まで昇温し4時間保温した。保温後50℃まで降
温し、カチオン隔−1008,5gとアイソパーHis
ogを添加した。50℃で1時間保温攪拌し、カチオン
f4−100の溶解を確認後、メタクリル酸23g、ア
イソパーH150gを1時間かけて滴下した。滴下中に
10分につき15℃の割合で昇温し170℃で7〜8時
間保温した。酸価が45以下になった所で終点として冷
却した。A mixture of 100 g of morpholinoethyl methacrylate and 259 g of benzoyl peroxide as a polymerization initiator was uniformly added dropwise to the flask over 2 hours, and then 1
The temperature was raised to 40°C and kept for 4 hours. After incubation, the temperature was lowered to 50°C, and the cation spacing was -1008.5g and the isopar His
og was added. After stirring at 50° C. for 1 hour and confirming the dissolution of cation f4-100, 23 g of methacrylic acid and 150 g of Isopar H were added dropwise over 1 hour. During the dropping, the temperature was increased at a rate of 15°C per 10 minutes and kept at 170°C for 7 to 8 hours. When the acid value became 45 or less, cooling was performed as the end point.
これによシネ稀発分50俤、酸価40の赤かつ色の分散
安定剤溶液を得た。As a result, a red and colored dispersion stabilizer solution with a cine-reduced content of 50 yen and an acid value of 40 was obtained.
(2)懸濁重合液の製造工程
実施例9と同様のフラスコにアイソパーE10009お
よび(1)で得られた分散安定剤3009を仕込み窒素
気流下で90℃に保温し、攪拌する。別に1重合性単量
体としてスチレン616 g。(2) Manufacturing process of suspension polymerization solution Isopar E10009 and the dispersion stabilizer 3009 obtained in (1) are charged into a flask similar to that in Example 9, kept at 90° C. under a nitrogen stream, and stirred. Separately, 616 g of styrene was used as a single polymerizable monomer.
ブチルアクリレ−)1549.カーボンブラックφ44
sog及びバーブチル018gをホモミキサーで3
00 Or、p、mで30分間混合分散させた液を上記
フラスコに2時間かけて均一に滴下し。Butyl acrylate) 1549. Carbon black φ44
3. Sog and barbutyl 018g in a homomixer
The liquid mixed and dispersed at 00 Or, p, and m for 30 minutes was uniformly dropped into the flask over 2 hours.
発熱に注意しつつ6時間保温したのち冷却して懸濁重合
液を得た。このときの重合率は99.9%以上であり2
重合体の分子量(ゲル分を除いた場合)はMwが650
00.Mnが32000であう九。The mixture was kept warm for 6 hours while being careful not to generate heat, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9% or more and 2
The molecular weight of the polymer (excluding gel content) is Mw 650.
00. Nine with Mn of 32,000.
(3)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したところ9粒径分布1〜50μm、
平均粒径14.5μmであった。さらに示差走査熱量計
でTgを測定したところ70℃であった。(3) Drying step The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.
実施例11
(1)懸濁重合液の製造工程
実施例9と同様のフラスコにアイソパーEiooog及
び前記実施例9の(1)で得られた分散安定剤2009
を仕込み窒素気流下で90℃に保温し、攪拌し九。別に
2重合性単量体としてスチレン7199.ブチルアクリ
レート1809.7タロシアニンプル一10g及びバー
ブチル018優をホモミキサーでa o o o r、
p−mで30分間混合分散させ九液を上記フラスコに2
時間かけて均一に滴下し9発熱に注意しつつ6時間保温
し九〇ち冷却して懸濁重合液を得九。このときの重合率
は99.9 S以上であシ2重合体の分子1(ゲル分を
除いた場合)はMwが63000.Mnが31000で
6つ九。Example 11 (1) Production process of suspension polymerization solution Isopar Eiooog and the dispersion stabilizer 2009 obtained in (1) of Example 9 were placed in the same flask as in Example 9.
9. Prepare and keep warm at 90°C under nitrogen stream, stir. Separately, styrene 7199 is used as a dipolymerizable monomer. 10 g of butyl acrylate 1809.7 talocyanine puri and barbutyl 018 were mixed in a homomixer,
Mix and disperse at pm for 30 minutes and transfer the 9 liquids to the above flask.
Drop it evenly over a period of time and keep it warm for 6 hours while being careful not to generate heat, then cool to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 S or more, and the Mw of molecule 1 of the dipolymer (excluding gel content) was 63,000. Mn is 31000, 6 nine.
(2)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したところ2粒径分布1〜50μm、
平均粒径14.3μmであった。さらに示差走査熱量計
でTgを測定し九とζろ71℃であった。(2) Drying process The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, there were two particle size distributions: 1 to 50 μm;
The average particle size was 14.3 μm. Further, the Tg was measured using a differential scanning calorimeter and was found to be 71°C.
比較例5
トルエンを溶媒とする溶液重合でジメチルアミノエチル
メタクリレート/スチレン/ブチルメタクリレート−1
/69/30 (重量比)1分子量Mw70000及び
Mn3000 Gの重合体を作り。Comparative Example 5 Dimethylaminoethyl methacrylate/styrene/butyl methacrylate-1 was produced by solution polymerization using toluene as a solvent.
/69/30 (weight ratio) 1 A polymer with a molecular weight of 70,000 Mw and 3,000 G of Mn was prepared.
減圧脱溶剤を行い、トルエンを取り除いて白色固体を作
った。The solvent was removed under reduced pressure to remove toluene and a white solid was produced.
この重合体9209にカーボンブラック809を二本ロ
ールで混練し、ジェットミルで粉砕し。Carbon black 809 was kneaded with this polymer 9209 using two rolls, and the mixture was pulverized using a jet mill.
分級してトナーを得た。The toner was obtained by classification.
得られ九トナーをコールタ−カウンターで粒子径を測定
したところ9粒径分布1〜50μm、平均粒径12μm
であり九。さらに、示差走査熱量計でTgを測定したと
ころ、73℃であった。The particle size of the obtained nine toners was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 12 μm.
And nine. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.
比較例6
比較例5でジメチルアミノエチルメタクリレート/スチ
レン/ブチルメタクリレートの重量比を1/69/30
から30/69/1に変え丸抱は全く同様にしてトナー
を作製した。Comparative Example 6 In Comparative Example 5, the weight ratio of dimethylaminoethyl methacrylate/styrene/butyl methacrylate was 1/69/30.
A toner was prepared in exactly the same manner except that the toner was changed from 30/69/1 to 30/69/1.
重合体の分子量Mwは70000.Mnは30000で
あった。また、得られたトナーは粒径分布1〜59μm
、平均粒径12 μmであり、Tgは71℃であった。The molecular weight Mw of the polymer is 70,000. Mn was 30,000. In addition, the obtained toner has a particle size distribution of 1 to 59 μm.
, the average particle size was 12 μm, and the Tg was 71°C.
比較例7
トルエンを溶媒とする溶液重合でスチレン/ブチルメタ
クリレート−70/30(重量比)1分子量Mw700
00及びMn30000の重合体を作シ、減圧脱溶剤を
行い、トルエンを取り除いて白色固体を作った。この重
合体8709にカーボンブラックφ44 aogおよ
びオイルブラック80(オリエント化学工業■製ニゲa
シン染料の商品名)50gを加え2本ロールで混練し、
ジェットミルで粉砕し9分級してトナーを得た。Comparative Example 7 Styrene/butyl methacrylate-70/30 (weight ratio) 1 molecular weight Mw 700 by solution polymerization using toluene as a solvent
Polymers of 00 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid. This polymer 8709 was mixed with carbon black φ44 aog and oil black 80 (nigea manufactured by Orient Chemical Industry ■).
Add 50g of Shin dye (product name) and knead with two rolls.
It was pulverized with a jet mill and classified into 9 parts to obtain a toner.
得られたトナーは粒径分布1〜50μm、平均粒径12
μmであシ、Tgは71’Cであった。The obtained toner had a particle size distribution of 1 to 50 μm and an average particle size of 12
It was measured in μm and Tg was 71'C.
実施例12
(11分散安定剤の製造
攪拌装置、窒素導入口2滴下ロート、温度計およびコン
デンサを装着し九4つロフラスコにアイソパー8700
9を仕込み、窒素気流下で120℃に保温し、攪拌した
。別にラウリルメタクリレート8539.メタクリル酸
23g、p−スチレンスルホン酸100g及び重合開始
剤としてベンゾイルパーオキサイド259を溶解させた
混合液を上記フラスコに2時間かけて均一に滴下した後
。Example 12 (11 Production of dispersion stabilizer) A 94-hole flask was equipped with an Isopar 8700 stirrer, two nitrogen inlets, a dropping funnel, a thermometer, and a condenser.
9 was charged, the temperature was kept at 120°C under a nitrogen stream, and the mixture was stirred. Separately lauryl methacrylate 8539. A mixture of 23 g of methacrylic acid, 100 g of p-styrenesulfonic acid, and 259 g of benzoyl peroxide as a polymerization initiator was uniformly dropped into the flask over 2 hours.
140’Cまで昇温し4時間保温した。保温後50℃ま
で降温し、カチオンFdx−100a5gとアイソパー
H150gを添加した。50℃で1時間保温攪拌し、カ
チオンMx−100の溶液を確認後。The temperature was raised to 140'C and kept at this temperature for 4 hours. After keeping warm, the temperature was lowered to 50° C., and 5 g of cation Fdx-100a and 150 g of Isopar H were added. After stirring at 50° C. for 1 hour and confirming the solution of cation Mx-100.
グリシジルメタクリレート24g、アイソパーH150
9を1時間かけて滴下した。滴下中に10分につき15
℃の割合で昇温し140℃で8時間保温後冷却した。Glycidyl methacrylate 24g, Isopar H150
9 was added dropwise over 1 hour. 15 per 10 minutes during dripping
The temperature was raised at a rate of 140° C., kept at 140° C. for 8 hours, and then cooled.
これにより不稀発分50%の赤かつ色の分散安定剤溶液
を得九。As a result, a red and colored dispersion stabilizer solution containing 50% non-rare fraction was obtained.
(21!温室合液の製造工程
攪拌装置、窒素導入口1滴下ロート、温度計及びコンデ
ンサを装着した4つロフラスコにアイソパーE1000
1i1及び(1)で得られた分散安定剤2 ’009を
仕込み窒素気流下で90℃に保温し。(21! Production process of greenhouse mixture
1i1 and the dispersion stabilizer 2'009 obtained in (1) were charged and kept at 90°C under a nitrogen stream.
攪拌した。別に1重合性単量体としてスチレン574g
及びブチルメタクリレート2469.着色剤としてカー
ボンブラックナ44 sog及び重合開始剤としてア
ゾビスイソブチロニトリル189をホモミキサーで30
0 Or、p、mで30分間混合分散させた液を上記フ
ラスコに2時間かけて滴下し2発熱に注意しつつ6時間
保温した後。Stirred. Separately, 574 g of styrene as a single polymerizable monomer
and butyl methacrylate 2469. Carbon blackener 44 sog as a coloring agent and azobisisobutyronitrile 189 as a polymerization initiator were mixed in a homomixer at 30°C.
A solution mixed and dispersed for 30 minutes at 0 Or, p, and m was added dropwise to the above flask over 2 hours, and the mixture was kept warm for 6 hours while being careful not to generate heat.
冷却して懸濁重合液を得た。このときの重合率は99.
9−以上であった。i九2重合体の分子量(ゲル分を除
いた場合)は高速クロヤトグラフィによシ標準ポリスチ
レンによる検量線を用いて測定し九ところ、Mwは72
000.Mnは30000であった。It was cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.
It was 9- or more. The molecular weight of the i92 polymer (excluding gel content) was measured by high-speed chromatography using a standard polystyrene calibration curve, and the Mw was 72.
000. Mn was 30,000.
(3)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、トナーを得た。得られたトナ
ーをコールタ−カウンターで粒子径を測定したところ9
粒径分布1〜50μm、平均粒径13μmであった。さ
らに示差走査熱量計でTgを測定したところ、65℃で
あった。It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 9.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.
実施例13
(1)分散安定剤の製造
攪拌装置、窒素導入口、@下ロート、温度計およびコン
デンサを装着した4つロフラスコにアイソパーH700
sを仕込み、窒素気流下で120℃に保温し、攪拌した
。別にラウリルメタクリレ−)8539.メタクリル#
1123g及び重合開始剤ベンゾイルパーオキサイド2
59を溶解させた混合液を上記フラスコに2時間かけて
均一に滴下した後、140℃まで昇温し4時間保温した
。Example 13 (1) Production of dispersion stabilizer Isopar H700 was placed in a four-bottle flask equipped with a stirring device, nitrogen inlet, @ lower funnel, thermometer and condenser.
s was charged, kept at 120°C under a nitrogen stream, and stirred. Separately lauryl methacrylate) 8539. Methacrylic #
1123g and polymerization initiator benzoyl peroxide 2
A mixed solution in which 59 was dissolved was uniformly dropped into the flask over 2 hours, and then the temperature was raised to 140° C. and kept at that temperature for 4 hours.
保温後50℃まで降温し、カチオンbh−100asg
とアイソパーHisogを添加した。50℃で1時間保
温攪拌し、カチオンMl−100の溶解を確認後、グリ
シジルメタクリレート249゜アイソパーH150gを
1時間かけて滴下した。After insulating, the temperature was lowered to 50℃, and the cation bh-100asg
and Isopar Hisog were added. After stirring at 50° C. for 1 hour and confirming the dissolution of the cation Ml-100, 150 g of glycidyl methacrylate 249° Isopar H was added dropwise over 1 hour.
滴下中に10分につき15℃の割合で昇温し140℃で
8時間保温後冷却した。During the dropping, the temperature was increased at a rate of 15°C per 10 minutes, kept at 140°C for 8 hours, and then cooled.
これにより不稀発分SOWの赤かつ色の分散安定剤溶液
を得九。As a result, a red and colored dispersion stabilizer solution of SOW was obtained.
(2)懸濁重合液の製造工程
実施例12と同様のフラスコにアイソパーE10009
および(1)で得られた分散安定剤3009を仕込み窒
素気流下で90℃に保温し、攪拌する。別に1重合性単
量体としてスチレン6169゜ブチルアクリレート15
49. カーボンブラックナ44 aog及びバーブ
チル0189をホモミキサーで300 Or、p−mで
30分間混合分散させ九液を上記フラスコに2時間かけ
て滴下し2発熱に注意しつつ6時間保温したのち冷却し
て懸濁重合液を得た。このときの重合率は99.9 S
以上であシ1重合体の分子量(ゲル分を除いた場合)は
Mwが65000.Mnが32000であった。(2) Production process of suspension polymerization solution Isopar E10009 was added to the same flask as in Example 12.
Then, the dispersion stabilizer 3009 obtained in (1) is charged, kept at 90° C. under a nitrogen stream, and stirred. Separately, one polymerizable monomer is styrene 6169°butyl acrylate 15
49. Carbon Blackna 44 AOG and Barbutyl 0189 were mixed and dispersed in a homomixer at 300 Orr and pm for 30 minutes, and the liquid was added dropwise into the above flask over 2 hours. A suspension polymerization solution was obtained. The polymerization rate at this time was 99.9 S
The molecular weight (excluding gel content) of the above-mentioned ASI 1 polymer is Mw of 65,000. Mn was 32,000.
(3)乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したとζろ9粒径分布1〜50μm、
平均粒径14.5μmであった。さらに示差走査熱量計
でTgを測定したところ70℃であった。(3) Drying step The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.
実施例14
(1)@満貫合液の製造工程
実施例12と同様のフラスコにアイソパーExooog
及び実施例12の(1)で得られた分散安定剤200g
を仕込み窒素気流下で90℃に保温し、攪拌した。別に
9重合性単量体としてスチレン7199. ブチルアク
リレ−)1809. フタロシアニンブルー10 g及
Uハ=7’fko 18 gをホモミキサーで300O
r−p−fflで30分間混合分散させた液を上記フラ
スコに2時間かけて滴下し9発熱に注意しつつ6時間保
温したのち冷却して懸濁重合液を得た。このときの重合
率は99.9チ以上であり1重合体の分子量(ゲル分を
除いた場合)はMwが63000.Mnが31000で
あった。Example 14 (1) @Manufacturing process of liquid
and 200 g of the dispersion stabilizer obtained in Example 12 (1)
was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include styrene 7199. Butyl acrylate) 1809. Phthalocyanine blue 10 g and Uha = 7'fko 18 g in a homomixer at 300O
A liquid mixed and dispersed for 30 minutes using r-p-ffl was added dropwise to the flask over 2 hours, kept warm for 6 hours while being careful to avoid heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 inches or more, and the molecular weight of one polymer (excluding gel content) was 63,000. Mn was 31,000.
(2) 乾燥工程
上記懸濁重合液を遠心脱溶媒し、乾燥機で40℃で乾燥
しトナーを得た。得られたトナーをコールタ−カウンタ
ーで粒子径を測定したところ9粒径分布1〜50μm、
平均粒径14.3μmであった。さらに示差走査熱量計
でTgを測定したところ71℃であった。(2) Drying process The above suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.3 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 71°C.
比較例8
トルエンを溶媒とする溶液重合でp−スチレンスルホン
酸/スチレン/ブチルメタクリレート=1/69/30
(重量比)9分子量Mw 70000及びMn 30
000の重合体を作シ、減圧脱溶剤を行い、トルエンを
取り除いて白色固体を作った。Comparative Example 8 Solution polymerization using toluene as a solvent p-styrene sulfonic acid/styrene/butyl methacrylate = 1/69/30
(Weight ratio) 9 Molecular weight Mw 70000 and Mn 30
000 polymer was prepared, the solvent was removed under reduced pressure, and toluene was removed to produce a white solid.
この重合体9209にカーボンブラック809を二本ロ
ールで混練し、ジェットミルで粉砕し。Carbon black 809 was kneaded with this polymer 9209 using two rolls, and the mixture was pulverized using a jet mill.
分級してトナーを得た。The toner was obtained by classification.
得られ九トナーをコールタ−カウンターで粒子径を測定
したところ9粒径分布1〜50μm、平均粒径12μm
であった。さらに、示差走査熱量計でTgを測定し九と
ころ、73℃であった。The particle size of the obtained nine toners was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 12 μm.
Met. Furthermore, Tg was measured with a differential scanning calorimeter and found to be 73°C.
比較例9
JIL例8でp−スチレンスルホン酸/スチレン/ブチ
ルメタクリレートの重量比を1/69/30から30/
69/1に変えた他は全く同様にしてトナーを作製した
。粒径分布は1〜50μm、平均粒径IL5μm、 ’
l’gは81℃であり九。またMwは72000.Mn
は3000Gであつ九。Comparative Example 9 In JIL Example 8, the weight ratio of p-styrene sulfonic acid/styrene/butyl methacrylate was changed from 1/69/30 to 30/
A toner was produced in exactly the same manner except that 69/1 was used. Particle size distribution is 1-50 μm, average particle size IL5 μm, '
l'g is 81℃ and 9. Also, Mw is 72000. Mn
is 3000G and nine.
実施例9〜14及び比較例5〜9の評価得られた各トナ
ー5重量%及び酸化鉄粉(日本鉄粉■製、商品名EFV
20G/300)95重量%を混合し現像剤を作製した
。この現像剤のブローオフ帯電量を測定し9表3に結果
を示した。Examples 9 to 14 and Comparative Examples 5 to 9 were evaluated using 5% by weight of each toner and iron oxide powder (manufactured by Nippon Iron Powder ■, trade name EFV).
A developer was prepared by mixing 95% by weight of 20G/300). The amount of blow-off charge of this developer was measured and the results are shown in Table 3.
現像剤の実機複写試験は、実施例9〜11及び比較例5
〜7についてはシャープ■製複写機8F−755型を用
い、実施例12〜14及び比較例8〜9についてはコピ
ア■裏複写機NC−3000型を用いて行った。The actual machine copying test of the developer was conducted in Examples 9 to 11 and Comparative Example 5.
Examples 12 to 14 and Comparative Examples 8 to 9 were carried out using a copying machine model 8F-755 manufactured by Sharp ■, and Copier ■ reverse copying machine model NC-3000 for Examples 12 to 14 and comparative examples 8 to 9.
電子写真特性の評価は、実施例1〜2及び比較例1〜3
と同様に行った。表3に評価結果を示す。Evaluation of electrophotographic properties was carried out in Examples 1 to 2 and Comparative Examples 1 to 3.
I did the same thing. Table 3 shows the evaluation results.
実施例15
(1) l!!濁重濁液合液造工程
攪拌装置、窒素導入口9滴下ロート、温度計及びコンデ
ンサを装着した4つロフラスコにアイソパーE 100
09及び天然ゴム(SM几−5)のアイソパーH溶液(
固型分3os)aaagを仕込み、窒素気流下で90℃
に保温し、攪拌した。Example 15 (1) l! ! Isopar E 100 in a 4-bottle flask equipped with a stirring device, a nitrogen inlet with 9 dropping funnels, a thermometer, and a condenser.
09 and natural rubber (SM 几-5) Isopar H solution (
Prepare solid content 3os) aaag and heat at 90℃ under nitrogen stream.
The mixture was kept warm and stirred.
別に9重合性単量体としてスチレン574g及びプール
メタクリレート2469.磁性粉としてMG−WF (
三井金属鉱業■製、−1グネタイト)11659、帯電
制御剤としてスピロンブラックTRH(保土谷化学工業
■製) 15 lie低分子量ポリプロピVン(ビスコ
ール660 F、三洋化成工業■製)zog及び重合開
始剤としてアゾビスインブチロニトリル189をホモミ
キサーでa o o o r、p、mで30分間混合分
散させた液を上記フラスコに2時間かけて均一に滴下し
9発熱に注意しつつ6時間保温し九後、冷却して懸濁重
合液を得意。このときの重合率は99.91以上であつ
九。また2重合体の分子量(ゲル分を除いた場合)は高
速液体クロマトグラフィによシ標準ポリスチレンによる
検量線を用いて測定したところ。Separately, 574 g of styrene and 2469 g of pool methacrylate were used as polymerizable monomers. MG-WF (
Mitsui Kinzoku Kogyo ■, -1 Gnetite) 11659, Spiron black TRH (Hodogaya Chemical Industry ■) as a charge control agent, low molecular weight polypropylene (Viscol 660 F, Sanyo Chemical Industries ■) zog and polymerization initiation A solution prepared by mixing and dispersing azobisinbutyronitrile 189 as an agent for 30 minutes at a o o o r, p, m using a homomixer was added dropwise uniformly into the above flask over 2 hours. After keeping it warm for 90 minutes, cool it and make a suspension polymerization liquid. The polymerization rate at this time was 99.91 or more. The molecular weight of the dipolymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve.
Mwは72000.Mnは30000であった。Mw is 72000. Mn was 30,000.
(2)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、磁性トナーを得た。得られ良
磁性トナーをコールタ−カウンターで粒子径を測定した
ところ2粒径分布1〜50μm、平均粒径13μmであ
った。さらに示差走査熱量計でTgを測定したところ、
65℃であった。It was dried in a dryer at 40°C to obtain a magnetic toner. The particle size of the obtained good magnetic toner was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.
(3)評価
この磁性トナーは普通紙複写機(小西六写真工業■製、
U−Bix 1200)を用いて電子写真特性を試験
した。ただしトナーには流動性向上剤として疎水性シリ
カ(日本アエロジル■製R−972)及びステアリン酸
亜鉛をそれぞれ上記トナーに対して0.6チ及び0.1
優の外添処理を施した。(3) Evaluation This magnetic toner is used for plain paper copying machines (manufactured by Konishiroku Photo Industry),
Electrophotographic properties were tested using U-Bix 1200). However, the toner contains hydrophobic silica (R-972 manufactured by Nippon Aerosil ■) and zinc stearate as fluidity improvers at 0.6 and 0.1%, respectively, for the above toner.
Excellent external additive treatment was applied.
実施例16
(1)懸濁重合液の製造
攪拌装置、窒素導入口9滴下ロート、温度計及びコンデ
/すを装着した四つロフラスコにアイソパーE 100
09及びポリオイル130(日本ゼオン@製ポリブタジ
ェン)1009を仕込み、窒素気流下で90℃に保温し
、攪拌する。別に9重合性単量体としてスチレン574
静及びブチルメタクリレ−)2469.磁性粉としてM
G−WFitasg、帯電制御剤としてスピロンブラッ
クTRH(保土谷化学工業■製) 159e低分子量ポ
リプロビレ/(ビスコール660P)209及び重合開
始剤としてアゾビスインブチロニトリル189をホモミ
キサーでa o o o r−p−mで30分間混合し
9分散させた液を上記フラスコに2時間かけて均一に滴
下し9発熱に注意しつつ、6時間保温した後、冷却して
懸濁重合液を得た。このときの重合率は、99.9−以
上であった。また2重合体の分子量(ゲル分を除いた場
合)は、高速液体クロマトグラフィーによシ標準ポリス
チレンによる検量線を用いて測定したところ、Mwは7
2000、Mnはaooooであった。Example 16 (1) Production of suspension polymerization solution Isopar E 100 was placed in a four-lobe flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser.
09 and polyoil 130 (polybutadiene manufactured by Nippon Zeon@) 1009 were charged, kept at 90° C. under a nitrogen stream, and stirred. Separately 9 Styrene 574 as a polymerizable monomer
static and butyl methacrylate) 2469. M as magnetic powder
G-WFitasg, Spiron black TRH (manufactured by Hodogaya Chemical Industry ■) 159e low molecular weight polypropylene/(Viscol 660P) 209 as a charge control agent, and azobisin butyronitrile 189 as a polymerization initiator were mixed in a homomixer. The dispersion solution was mixed for 30 minutes at rpm and was uniformly dropped into the above flask over 2 hours. After keeping the temperature for 6 hours while paying attention to heat generation, the suspension was cooled to obtain a suspension polymerization solution. . The polymerization rate at this time was 99.9 or more. The molecular weight of the dipolymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 7.
2000, Mn was aooooo.
(2)乾燥工程 上記懸濁重合液を遠心分離機で脱溶媒した後。(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、磁性トナーを得た。得られた
磁性トナーをコールタ−カウンターで粒子径を測定した
ところ9粒径分布1〜50μm、平均粒径13μmであ
った。更に、示差走査熱量計でTgを測定したところ、
65℃であった。It was dried in a dryer at 40°C to obtain a magnetic toner. When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.
実施例17
攪拌装置、窒素導入口、M下ロート、温度計及びコンデ
ンサを装着した四つロフラスコにアイソパーE100o
g及び実施例7の(1)で得られた分散安定剤2009
を仕込み、窒素気流下に90℃に保温し、攪拌した。別
に9重合性単量体としてスチレン5749及びブチルメ
タクリレート2469、磁性粉としてMG−WF 11
659.帯電制御剤としてスビロンブラックTRH15
G、 低分子量ポリプロピレン(ビスコール660P)
209及び重合開始剤としてアゾビスイソブチロニトリ
ル18gをホモミキサーで3000cpmで30分間混
合し2分散させた液を上記フラスコに2時間かけて均一
に滴下し2発熱に注意しつつ、6時間保温した後、冷却
して懸濁重合液を得た。このときの重合率は、99.9
−以上であった。また。Example 17 Isopar E100o was placed in a four-lobe flask equipped with a stirrer, nitrogen inlet, M lower funnel, thermometer and condenser.
g and dispersion stabilizer 2009 obtained in Example 7 (1)
was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers were styrene 5749 and butyl methacrylate 2469, and magnetic powder was MG-WF 11.
659. Subiron Black TRH15 as a charge control agent
G, low molecular weight polypropylene (Viscol 660P)
209 and 18 g of azobisisobutyronitrile as a polymerization initiator were mixed for 30 minutes at 3,000 cpm using a homomixer, and the dispersed liquid was uniformly dropped into the above flask over 2 hours.2 While being careful of heat generation, the mixture was kept warm for 6 hours. After that, it was cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9
-That's all. Also.
重合体の分子量(ゲル分を除いた場合)は、高速液体ク
ロマトグラフィーによシ標準ポリスチレンによる検量線
を用いて測定したところ、 Mw72000、Mn30
000であった。The molecular weight of the polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and found to be Mw72000, Mn30.
It was 000.
上記懸濁重合液を遠心分離機で脱溶媒した後。After removing the solvent from the suspension polymerization solution using a centrifuge.
乾燥機で40℃で乾燥し、磁性トナーを得た。得られた
磁性トナーをコールタ−カウンターで粒子径を測定した
ところ1粒径分布1〜50μm、平均粒径13μmであ
った。更に、示差走査熱量計でTgを測定したところ、
65℃であった。It was dried in a dryer at 40°C to obtain a magnetic toner. When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.
比較例10
トルエンを溶媒とする溶液重合でスチレン/ブチルメタ
クリレート−70/30(重量比)9分子量Mw700
00及びMn30000の重合体を作り、減圧脱溶剤を
行い、トルエンを取り除いて白色固体を作った。Comparative Example 10 Styrene/butyl methacrylate - 70/30 (weight ratio) 9 molecular weight Mw 700 by solution polymerization using toluene as a solvent
Polymers of 00 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid.
この重合体920gに磁性粉としてMG−WF1165
g、低分子量ポリプロピレン(ビスコール660P)2
09及びスビロンブラックTRH159を二本ロールで
混練し、ジェットミルで粉砕し2分級して磁性トナーを
得た。MG-WF1165 was added to 920 g of this polymer as magnetic powder.
g, low molecular weight polypropylene (Viscol 660P) 2
09 and Subiron Black TRH159 were kneaded with two rolls, pulverized with a jet mill, and classified into two to obtain a magnetic toner.
得られた磁性トナーをコールタ−カウンターで粒子径を
測定したところ9粒径分布1〜50μm。When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
平均粒径12μmであった。さらに、示差走査熱量計で
Tgを測定したところ、73℃であった。The average particle size was 12 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.
実施例16.17及び比較例1Oの電子写真特性の評価
には、実施例15と同様の装置を用いて行った。なお、
実施例16〜18及び比較例10の電子写真特性の評価
試験は、実施例3〜8及び比較例4と同様罠行った。試
験結果を表4に示す。The electrophotographic properties of Examples 16 and 17 and Comparative Example 1O were evaluated using the same apparatus as in Example 15. In addition,
Evaluation tests for electrophotographic properties of Examples 16 to 18 and Comparative Example 10 were conducted in the same manner as Examples 3 to 8 and Comparative Example 4. The test results are shown in Table 4.
表4 評価 (発明の効果) 本発明により、非水溶媒懸濁重合法を利用して。Table 4 Evaluation (Effect of the invention) According to the present invention, a non-aqueous suspension polymerization method is utilized.
特に高湿度下における解像度1画像濃度及び階調性が優
れると共に、特にクリーニング性、帯電安定性及び耐ブ
ロッキング性に優れた乾式現像に適した電子写真用トナ
ーを得ることができる。In particular, it is possible to obtain an electrophotographic toner which is suitable for dry development and has excellent single-resolution image density and gradation properties under high humidity, as well as particularly excellent cleaning properties, charging stability, and blocking resistance.
さらに9分散安定剤を選択することKよシ、定着性及び
/又は耐オフセット性に優れたトナーを得ることができ
る。Furthermore, by selecting the dispersion stabilizer 9, it is possible to obtain a toner with excellent fixing properties and/or offset resistance.
Claims (1)
に、非水溶媒中で懸濁重合することを特徴とする電子写
真用トナーの製造方法。 2、さらに分散安定剤を用いる特許請求の範囲第1項記
載の電子写真用トナーの製造方法。 3、分散安定剤が、ゴムである特許請求の範囲第2項記
載の電子写真用トナーの製造方法。 4、分散安定剤が、ポリブタジエンである特許請求の範
囲第2項記載の電子写真用トナーの製造方法。 5、分散安定剤が、長鎖の炭素鎖をもつアクリル酸エス
テル及び/又はメタクリル酸エステルを必須成分とする
重合体である特許請求の範囲第2項記載の電子写真用ト
ナーの製造方法。 6、長鎖の炭素鎖が炭素数8以上のアルキル基である特
許請求の範囲第5項記載の電子写真用トナーの製造方法
。 7、重合体が、アミノ基含有付加重合性単量体を共重合
成分として有するものである特許請求の範囲第5項又は
第6項記載の電子写真用トナーの製造方法。 8、重合体が、カルボキシル基及び/又はスルホン基を
有する重合性単量体及び/又はそれらの金属塩を共重合
成分として有するものである特許請求の範囲第5項又は
第6項記載の電子写真用トナーの製造方法。 9、重合体が、さらに重合性単量体と反応性の不飽和結
合基を有するものである特許請求の範囲第5項、第6項
、第7項又は第8項記載の電子写真用トナーの製造方法
。[Claims] 1. A method for producing an electrophotographic toner, which comprises suspending and polymerizing a polymerizable monomer in a non-aqueous solvent in the presence of a colorant and/or magnetic powder. 2. The method for producing an electrophotographic toner according to claim 1, further comprising a dispersion stabilizer. 3. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is rubber. 4. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is polybutadiene. 5. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is a polymer containing as an essential component an acrylic ester and/or a methacrylic ester having a long carbon chain. 6. The method for producing an electrophotographic toner according to claim 5, wherein the long carbon chain is an alkyl group having 8 or more carbon atoms. 7. The method for producing an electrophotographic toner according to claim 5 or 6, wherein the polymer has an amino group-containing addition polymerizable monomer as a copolymerizable component. 8. The electron according to claim 5 or 6, wherein the polymer has a polymerizable monomer having a carboxyl group and/or a sulfone group and/or a metal salt thereof as a copolymerization component. Method of manufacturing photographic toner. 9. The electrophotographic toner according to claim 5, 6, 7, or 8, wherein the polymer further has an unsaturated bond group reactive with the polymerizable monomer. manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62157045A JPH0812469B2 (en) | 1987-06-24 | 1987-06-24 | Method of manufacturing toner for electrophotography |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62157045A JPH0812469B2 (en) | 1987-06-24 | 1987-06-24 | Method of manufacturing toner for electrophotography |
Publications (3)
Publication Number | Publication Date |
---|---|
JPH01962A true JPH01962A (en) | 1989-01-05 |
JPS64962A JPS64962A (en) | 1989-01-05 |
JPH0812469B2 JPH0812469B2 (en) | 1996-02-07 |
Family
ID=15640992
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62157045A Expired - Lifetime JPH0812469B2 (en) | 1987-06-24 | 1987-06-24 | Method of manufacturing toner for electrophotography |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0812469B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01183663A (en) * | 1988-01-14 | 1989-07-21 | Canon Inc | Electrophotographic sensitive body |
-
1987
- 1987-06-24 JP JP62157045A patent/JPH0812469B2/en not_active Expired - Lifetime
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