JPH0287167A - Electrostatic image developing carrier and production thereof - Google Patents
Electrostatic image developing carrier and production thereofInfo
- Publication number
- JPH0287167A JPH0287167A JP63239180A JP23918088A JPH0287167A JP H0287167 A JPH0287167 A JP H0287167A JP 63239180 A JP63239180 A JP 63239180A JP 23918088 A JP23918088 A JP 23918088A JP H0287167 A JPH0287167 A JP H0287167A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- resin
- particles
- magnetic particles
- coating
- 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 11
- 239000002245 particle Substances 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000006249 magnetic particle Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000011161 development Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 36
- 238000000576 coating method Methods 0.000 abstract description 36
- 229910000859 α-Fe Inorganic materials 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 229910017518 Cu Zn Inorganic materials 0.000 description 13
- 229910017752 Cu-Zn Inorganic materials 0.000 description 13
- 229910017943 Cu—Zn Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011162 core material Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- -1 p-F decylstyrene Chemical compound 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920005792 styrene-acrylic resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910000809 Alumel Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-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
- DMADTXMQLFQQII-UHFFFAOYSA-N 1-decyl-4-ethenylbenzene Chemical compound CCCCCCCCCCC1=CC=C(C=C)C=C1 DMADTXMQLFQQII-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- LCNAQVGAHQVWIN-UHFFFAOYSA-N 1-ethenyl-4-hexylbenzene Chemical compound CCCCCCC1=CC=C(C=C)C=C1 LCNAQVGAHQVWIN-UHFFFAOYSA-N 0.000 description 1
- LUWBJDCKJAZYKZ-UHFFFAOYSA-N 1-ethenyl-4-nonylbenzene Chemical compound CCCCCCCCCC1=CC=C(C=C)C=C1 LUWBJDCKJAZYKZ-UHFFFAOYSA-N 0.000 description 1
- HLRQDIVVLOCZPH-UHFFFAOYSA-N 1-ethenyl-4-octylbenzene Chemical compound CCCCCCCCC1=CC=C(C=C)C=C1 HLRQDIVVLOCZPH-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZZAGLMPBQOKGGT-UHFFFAOYSA-N [4-[4-(4-prop-2-enoyloxybutoxy)benzoyl]oxyphenyl] 4-(4-prop-2-enoyloxybutoxy)benzoate Chemical compound C1=CC(OCCCCOC(=O)C=C)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCOC(=O)C=C)C=C1 ZZAGLMPBQOKGGT-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-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
- 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 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
- 238000004904 shortening Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIWGRJOAMMYDHR-UHFFFAOYSA-N trichloromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(Cl)(Cl)Cl ZIWGRJOAMMYDHR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1132—Macromolecular components of coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1131—Coating methods; Structure of coatings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
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、静電記録法、静電印刷法等に用
いられる静電像現像用キャリアに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a carrier for electrostatic image development used in electrophotography, electrostatic recording, electrostatic printing, and the like.
般に、電子写真法においては、光導電性材料よりなる感
光層を有する潜像担持体すなわち感光体に均一な静電荷
を与えた後、画像露光を行い、該感光体の表面に静電潜
像を形成し、この静電潜像を現像剤で現像してトナー画
像を形成する。形成したトナー画像は紙等の転写材に転
写し、加熱或は加圧などにより定着し複写画像を形成す
る。In general, in electrophotography, a uniform electrostatic charge is applied to a latent image carrier, i.e., a photoreceptor, which has a photosensitive layer made of a photoconductive material, and then image exposure is carried out to form an electrostatic latent on the surface of the photoreceptor. An image is formed, and this electrostatic latent image is developed with a developer to form a toner image. The formed toner image is transferred to a transfer material such as paper and fixed by heating or pressure to form a copy image.
静電潜像を現像する方法としては、湿式現像法と、乾式
現像法とが知られており、その内乾式現像法に用いられ
る現像剤としては、一般にトナー中に磁性体を含有する
磁性トナーのみよりなるl成分系現像剤と、磁性体を含
有しない非磁性トナーと磁性を有するキャリアとよりな
る2成分系現像剤とが知られている。Wet developing methods and dry developing methods are known as methods for developing electrostatic latent images. Of these, the developer used in the dry developing method is generally a magnetic toner containing a magnetic material in the toner. Two-component developers are known: a l-component developer consisting of only a magnetic substance, and a two-component developer consisting of a non-magnetic toner containing no magnetic material and a magnetic carrier.
後者の2成分系現像剤は、トナーとキャリアとを機械的
に撹拌することによってトナーを摩擦帯電させるので、
キャリアの特性、撹拌の条件等を選定することにより、
トナーの帯電極性及び帯電量を相当程度制御することが
可能であり、又トナーに付与することができる色彩の選
択範囲が広く、これらの点で前者の1成分系現像剤より
も優れている。The latter two-component developer triboelectrically charges the toner by mechanically stirring the toner and carrier.
By selecting carrier characteristics, stirring conditions, etc.
It is possible to control the charge polarity and charge amount of the toner to a considerable extent, and the range of colors that can be applied to the toner is wide, and in these respects it is superior to the former one-component developer.
2成分系現像剤に用いられるキャリアとしては、キャリ
アの耐久性、摩擦帯電性等の向上を図ることができるこ
とから、磁性体粒子の表面を樹脂でコーティングしたコ
ーティングキャリアが賞月されている。As a carrier used in a two-component developer, a coated carrier in which the surface of magnetic particles is coated with a resin has been praised because it can improve the durability, triboelectric charging properties, etc. of the carrier.
このようなコーティングキャリアとしては、コーティン
グ用樹脂を溶剤に溶解した塗布液を流動層中で磁性体粒
子の表面にスプレー塗布し、次いで乾燥して得られたス
プレーコーティングキャリアが最もよく用いられている
。The most commonly used coating carrier is a spray coating carrier obtained by spraying a coating solution in which a coating resin is dissolved in a solvent onto the surface of magnetic particles in a fluidized bed and then drying the coating solution. .
〔発明が解決しようとする問題点〕
しかしながら、前記スプレーコーティングの技術・にお
いては、溶剤を用いるためキャリア粒子が相互融合し、
その結果キャリアが大径化し所望の粒度分布のキャリア
の収率が大幅に減少する。又乾燥工程を必要とし、キャ
リアの製造に相当に長い時間を要し、生産性が低い問題
点がある。更に樹脂被覆率の増大、磁性粒子の小径化に
伴い、生産性は更に低下する。これに対して、時間短縮
による生産性向上手段として、■塗布液におけるコーテ
ィング用樹脂の濃度を高くし、或いは■スプレーノズル
の本数を多くすることが考えられる。[Problems to be Solved by the Invention] However, in the above-mentioned spray coating technology, since a solvent is used, the carrier particles may fuse with each other.
As a result, the diameter of the carrier increases, and the yield of carrier having a desired particle size distribution decreases significantly. Furthermore, it requires a drying process, takes a considerable amount of time to manufacture the carrier, and has the problem of low productivity. Furthermore, as the resin coverage increases and the diameter of the magnetic particles decreases, productivity further decreases. On the other hand, as a means of improving productivity by shortening the time, it is possible to (1) increase the concentration of the coating resin in the coating solution, or (2) increase the number of spray nozzles.
しかしながら、上記■の場合には、塗布液が磁性体粒子
に付着した際、高粘度のため滑らかに展延せず、ムラの
あるコーティングとなり、その結果キャリアの耐久性が
低下する。又、磁性体粒子同志が一度接触すると容易に
粘着、融合し、キャリアの収率が大幅に減少する。However, in the case of (2) above, when the coating liquid adheres to the magnetic particles, it does not spread smoothly due to its high viscosity, resulting in an uneven coating, resulting in a decrease in the durability of the carrier. Furthermore, once magnetic particles come into contact with each other, they easily adhere and fuse, resulting in a significant decrease in carrier yield.
又上記■の場合には、スプレーノズルの本数の増加にも
限度があるうえ、−度にスプレーされる塗布液量が多く
なると、磁性体粒子の融合率が高くなり、上記と同様の
問題点がある。一方、融合を防止するために、流動層中
にアジテータと称される剪断力を付与する機構を備える
技術もあるが、アジテータにより融合物を強制的に解砕
すると表面状態が粗く不均一となり、その結果キャリア
の耐久性か低下する。In addition, in the case of (2) above, there is a limit to the increase in the number of spray nozzles, and if the amount of coating liquid sprayed at a time increases, the fusion rate of the magnetic particles increases, resulting in the same problem as above. There is. On the other hand, in order to prevent fusion, some technologies include a mechanism called an agitator that applies shear force to the fluidized bed, but if the fused material is forcibly broken up by the agitator, the surface condition becomes rough and uneven. As a result, the durability of the carrier decreases.
更に、スプレーコートは、コーティング時間が長く、又
、溶剤の回収、焼却の必要があって、製造が容易でない
。Furthermore, spray coating requires a long coating time and requires recovery and incineration of the solvent, making it difficult to manufacture.
又、被覆層を形成する樹脂の溶剤溶解性が要求され、樹
脂の選択範囲が狭く、成膜性の良好な樹脂の選択に障害
となる。Further, the resin forming the coating layer is required to be soluble in a solvent, and the range of resin selection is narrow, which is an obstacle to selecting a resin with good film-forming properties.
又、溶剤を蒸発させる際に、キャリア表面上に細孔が発
生し、キャリア表面が均一とならない。Furthermore, when the solvent is evaporated, pores are generated on the carrier surface, making the carrier surface uneven.
又、融合しやすく、目的に合った粒径のキャリアを得る
ことが難しく、収率も悪い。In addition, it is easy to fuse, making it difficult to obtain a carrier with a particle size suitable for the purpose, and the yield is also poor.
又、スプレーされて飛散した原料の一部は層形成に使わ
れず、原料が無駄になると共に、このような未被覆材が
粉状となって、静電的にキャリア表面に付着して、現像
時に悪影響を与える。In addition, some of the sprayed and scattered raw material is not used for layer formation, and the raw material is wasted, and this uncoated material becomes powder and electrostatically adheres to the carrier surface, preventing development. sometimes have a negative impact.
これに対して、スプレーコーティングによらないコーチ
(ング技術が開発されている(特開昭54−35735
号、同55−118047号、同63−37358号、
同63−37359号、同63−37360号等参照)
。In response to this, a coaching technique that does not rely on spray coating has been developed (Japanese Patent Laid-Open No. 54-35735
No. 55-118047, No. 63-37358,
(See No. 63-37359, No. 63-37360, etc.)
.
これらに開示されるコーティングは、キャリア芯材とポ
リマー微粒子を機械的に混合し、キャリア芯材の表面を
ポリマー微粒子で静電的に包接させ被覆層を形成し、そ
の抜法ポリマー微粒子を熱で熔融して固着させるか、又
は、溶剤で溶解して固着させることでキャリア芯材の表
面に樹脂層を被覆する。The coating disclosed in these documents mechanically mixes a carrier core material and polymer particles, electrostatically encapsulates the surface of the carrier core material with the polymer particles to form a coating layer, and heats the extracted polymer particles. The resin layer is coated on the surface of the carrier core material by melting and fixing with a solvent or by melting and fixing with a solvent.
しかし、上記コーティング技術は、固定化に際して、芯
材上に包接させた樹脂を熔融させるので、樹脂粒子どう
しが接着したり、樹脂粒子を介して芯材どうじが接着融
合して、目的の粒径分布のキャリアを得るために収率が
悪化するという問題がある。However, the above coating technology melts the resin included on the core material during immobilization, so the resin particles may adhere to each other, or the core material may adhere and fuse together through the resin particles, resulting in the formation of the desired particles. There is a problem in that the yield deteriorates because carriers with a diameter distribution are obtained.
又、融点近傍或いは融点以上で芯材の表面を樹脂層で被
覆するので冷却工程に時間がかかり、更にはブロッキン
グした被覆キャリアをほぐし、単−粒子にする解砕工程
が必要となり、生産効率が著しく低下する。In addition, since the surface of the core material is coated with a resin layer near or above the melting point, the cooling process takes time, and furthermore, a crushing process is required to loosen the blocked coated carrier and make it into single particles, which reduces production efficiency. Significantly decreased.
更に得られたキャリアは部分的に樹脂被覆されたもので
あり、完全に樹脂被覆されたキャリに比べ、高温高温に
おける帯電安定性が悪いという問題がある。Furthermore, the obtained carrier is partially coated with resin, and there is a problem that charging stability at high temperatures is poorer than that of a carrier completely coated with resin.
更に樹脂の融点近傍或いはそれ以上で芯材に樹脂層を被
覆するので、樹脂の変質があり、又それを起こさせない
不活性雰囲気にする必要があり、生産装置が著しく複雑
なものになる。Furthermore, since the core material is coated with a resin layer at a temperature close to or above the melting point of the resin, the resin may deteriorate, and an inert atmosphere must be created to prevent this from occurring, making the production equipment extremely complicated.
一方、芯材上に包接させた樹脂を溶剤で溶解させる場合
には、上記したスプレーコートの場合と同様に、樹脂の
選択の幅が狭い。溶剤の回収、焼却、融合等の問題があ
る。On the other hand, when the resin included on the core material is dissolved with a solvent, the range of resin selection is narrow, as in the case of spray coating described above. There are problems with solvent recovery, incineration, fusion, etc.
本発明は、前記各種問題点を解決し、樹脂被覆層を有す
るキャリアを作成するに当り、本発明の第1の目的は、
樹脂被覆層を構成する樹脂を広い範囲で選択でき、しか
も、樹脂被覆層を強固に固着できて、膜はがれが生じに
<<、耐久性があって経時的に安定した電荷付与性を有
する静電像現像用キャリアを提供することにある。The present invention solves the various problems mentioned above, and in producing a carrier having a resin coating layer, the first object of the present invention is to:
The resin constituting the resin coating layer can be selected from a wide range, and the resin coating layer can be firmly fixed, with no peeling, and is durable and has stable charge imparting properties over time. An object of the present invention is to provide a carrier for electrophotographic development.
本発明の第2の目的は、溶剤の回収等の処理を要せず、
簡単な手段により、短時間で製造することができ、しか
も、融合や細孔を生じに<<、目的の粒径分布のキャリ
アを高収率で得ることができる静電像現像用キャリアを
提供することにある。The second object of the present invention is to eliminate the need for treatment such as solvent recovery,
Provides a carrier for electrostatic image development that can be produced in a short time using simple means, and that can obtain a carrier with a desired particle size distribution at a high yield without causing coalescence or pores. It's about doing.
本発明の第3の目的は、コーティングに寄与しない未被
覆材の発生が少なく、従って、この未被覆材が遊離して
キャリア表面に静電的に付着することにより生じる障害
を防止できる静電像現像用キャリアを提供することにあ
る。A third object of the present invention is to reduce the occurrence of uncoated materials that do not contribute to coating, and thus to prevent problems caused by uncoated materials being released and electrostatically attached to the carrier surface. The purpose of the present invention is to provide a developing carrier.
本発明の第4の目的は、解砕工程が不必要で、短時間で
簡単な手段により、しかも高い収率で製造することがで
きる静電像現像用キャリアを提供することにある。A fourth object of the present invention is to provide a carrier for electrostatic image development that does not require a crushing step and can be produced in a short time, by simple means, and at a high yield.
本発明の第5の目的は、高温高湿においても安定した帯
電性能が得られ環境依存性のない静電像現像用キャリア
を提供することにある。A fifth object of the present invention is to provide a carrier for electrostatic image development that exhibits stable charging performance even at high temperatures and high humidity and is free from environmental dependence.
前記した本発明の目的は、重量平均粒径がlO〜200
μm磁性体粒子に重量平均粒径が前記磁性体粒子の1/
200未満の樹脂粒子を加えて均一混合物とし、品温を
50〜110℃の幅の中に設定した混合器中で、前記混
合物に繰返し衝撃力を与えて、前記磁性体粒子を前記樹
脂粒子の樹脂物質で被覆する静電像現像用キャリアの製
造方法及び該製造方法に拠った静電像現像用キャリアに
よって達成される。The object of the present invention described above is that the weight average particle size is 10 to 200
The weight average particle size of the μm magnetic particles is 1/1/1 of the magnetic particles.
Less than 200 resin particles were added to form a homogeneous mixture, and impact force was repeatedly applied to the mixture in a mixer whose temperature was set within a range of 50 to 110°C, so that the magnetic particles were mixed with the resin particles. This is achieved by a method for producing a carrier for electrostatic image development coated with a resin material and a carrier for electrostatic image development based on the production method.
尚本発明の態様においては、前記磁性体粒子の円形度が
0.7以上であることが好ましい。更に樹脂粒子はBE
T比表面積が40m2/g以上であることが好ましい。In the aspect of the present invention, it is preferable that the circularity of the magnetic particles is 0.7 or more. Furthermore, the resin particles are BE
It is preferable that the T specific surface area is 40 m2/g or more.
本発明の静電像現像用キャリアによれば、簡単な手段に
より短時間でしかも高い収率で製造することができ、か
つ耐久性が優れていて安定した摩擦帯電性が発揮される
。According to the carrier for electrostatic image development of the present invention, it can be produced by simple means in a short time and at a high yield, and exhibits excellent durability and stable triboelectric charging properties.
即ち、特定の粒径の磁性体粒子及び樹脂粒子を用い、乾
式コーティングによりキャリアが得られるため、■洗浄
、乾燥等の処理が不要となり、コーティングに要する時
間が大幅に短縮され、■融合率が小さく、その結果磁性
体粒子に対応した粒度分布のキャリアの収率が高い。又
■溶剤回収装置、溶剤燃焼装置等の処理設備が不要とな
り、生産コストを低減し、■樹脂粒子を用いた磁性体粒
子被覆効率が上がり、原料を効率的に利用することがで
き、■磁性体粒子の表面に樹脂粒子が付着して展延され
るため、耐剥離性、耐久性が優れ、安定した摩擦帯電性
が発揮され、■溶剤に難溶解の樹脂をも用いることが可
能となって、樹脂の選択範囲が格段に広くなり、種々の
特性を有するコーティングキャリアを得ることができる
。■被覆樹脂がキャリア表面を完全に被覆しているため
に高温高湿でも安定した摩擦帯電性が発揮され、環境依
存性のないコーティングキャリアを得ることができる。In other words, since the carrier can be obtained by dry coating using magnetic particles and resin particles of a specific particle size, processing such as washing and drying is not necessary, the time required for coating is significantly shortened, and ■ the fusion rate is reduced. As a result, the yield of carriers with a particle size distribution corresponding to the magnetic particles is high. In addition, it eliminates the need for processing equipment such as solvent recovery equipment and solvent combustion equipment, reducing production costs, increases the efficiency of coating magnetic particles with resin particles, and allows for efficient use of raw materials. Since the resin particles are attached and spread on the surface of the body particles, it has excellent peeling resistance and durability, and exhibits stable triboelectric charging properties, making it possible to use resins that are difficult to dissolve in solvents. As a result, the selection range of resins becomes much wider, and coated carriers having various properties can be obtained. ■Since the coating resin completely covers the surface of the carrier, stable triboelectric charging properties are exhibited even at high temperatures and high humidity, making it possible to obtain a coated carrier that is not dependent on the environment.
以下、本発明を具体的に説明する。 The present invention will be specifically explained below.
本発明の好ましい実施態様においては、重量平均粒径が
10〜200μm1円形度0.7以上の磁性体粒子と、
重量平均粒径が該磁性体粒子の1/200未満、BET
比表面積40a+”/g以上である樹脂粒子とを混合撹
拌して均一な混合状態とし、この混合物に衝撃力を繰返
して付与することにより、磁性体粒子の表面に樹脂粒子
を展延付着させてコーティングキャリアを作成する。In a preferred embodiment of the present invention, magnetic particles having a weight average particle diameter of 10 to 200 μm and a circularity of 0.7 or more;
Weight average particle size is less than 1/200 of the magnetic particles, BET
By mixing and stirring resin particles with a specific surface area of 40a+''/g or more to obtain a uniform mixed state, and repeatedly applying impact force to this mixture, the resin particles are spread and adhered to the surface of the magnetic particles. Create a coating carrier.
磁性体粒子と樹脂粒子との混合重量比は、磁性体粒子1
00重量部に対して樹脂粒子を0.1〜10重量部、好
ましくは0.5〜4重量部を使用する。The mixing weight ratio of magnetic particles and resin particles is: magnetic particles 1
The resin particles are used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 4 parts by weight.
磁性体粒子と樹脂粒子との混合物に加える衝撃力は、磁
性体粒子が粉砕されない程度の大きさであればよく、例
えばトナーの製造において粉砕時に通常必要とされる機
械的エネルギーの115〜l/lO程度の大きさの衝撃
力であればよい。The impact force applied to the mixture of magnetic particles and resin particles may be large enough not to crush the magnetic particles, for example, 115 to 1/2 of the mechanical energy normally required for crushing in toner production. An impact force of approximately 100 liters is sufficient.
磁性体粒子に規定する重量平均粒径lO〜200μmに
おいて、その下限未満のときは、得られるコーティング
キャリアが小径となり、感光体へのキャリア付着が生じ
やすく、その結果画質が劣化する。If the weight average particle diameter is less than the lower limit of the range of 10 to 200 μm specified for magnetic particles, the coating carrier obtained will have a small diameter, and the carrier will easily adhere to the photoreceptor, resulting in deterioration of image quality.
一方上限を超えるときには、得られるコーティングキャ
リアが比表面積の小さい大径となり、トナーに適正摩擦
帯電を与えるには、トナー濃度の厳密な制御が必要にな
り、トナー濃度コントロールシステムが高価となる。ま
たコーティングキャリアを現像剤担持体上に均一にしか
も高い密度で担持させることが困難となり、その結果キ
ャリアに付着して現像空間に搬送されるトナー量が不安
定となって現像性、画質の劣化を招来する。On the other hand, when the upper limit is exceeded, the resulting coating carrier has a large diameter with a small specific surface area, and in order to impart appropriate triboelectric charging to the toner, strict control of the toner concentration is required, making the toner concentration control system expensive. In addition, it becomes difficult to support the coating carrier uniformly and at a high density on the developer carrier, and as a result, the amount of toner that adheres to the carrier and is transported to the development space becomes unstable, resulting in deterioration of developability and image quality. invite.
磁性体粒子の材料としては、磁場によってその方向に強
く磁化する物質、例えば鉄、フェライト、マグネタイト
をはじめとする鉄、ニッケル、コバルト等の強磁性を示
す金属或いはこれらの金属を含む合金又は化合物等を用
いることが好ましい。Materials for the magnetic particles include substances that are strongly magnetized in the direction of magnetic fields, such as iron, ferrite, magnetite, and other ferromagnetic metals such as iron, nickel, and cobalt, or alloys or compounds containing these metals. It is preferable to use
尚、フェライトとは、ここでは鉄を含有する磁性酸化物
を総称しており、MO−Fe、03の化学式で示される
フェライトであり、上記化学式において、Mは2価の金
属を表し、具体的には、ニッケル、銅、亜鉛、マンガン
、マグネシウム、リチウム等を表す。In addition, ferrite here is a general term for magnetic oxides containing iron, and is a ferrite represented by the chemical formula MO-Fe, 03. In the above chemical formula, M represents a divalent metal, and the specific represents nickel, copper, zinc, manganese, magnesium, lithium, etc.
磁性体粒子は、その円形度が、0.7以上であることが
好ましい。このような円形度の高い磁性体粒子を用いる
ときには、得られるコーティングキャリアも円形度か高
くなり、キャリアの流動性が上る。その結果適正な量の
トナーを現像空間に安定に搬送することが可能となって
一層優れた現像性が発揮される。It is preferable that the magnetic particles have a circularity of 0.7 or more. When such highly circular magnetic particles are used, the obtained coated carrier also has a high circularity and the fluidity of the carrier increases. As a result, it becomes possible to stably convey an appropriate amount of toner to the developing space, and more excellent developing performance is exhibited.
ここで、円形度とは、次式で定義されるものをいう。Here, the circularity is defined by the following formula.
円形度=
二の円形度は、例えば画像解析装置(日本アビオニクス
製)を用いて測定することができる。Circularity = The circularity of 2 can be measured using, for example, an image analysis device (manufactured by Nippon Avionics).
樹脂粒子の重量平均粒径は、磁性体粒子を基準にして、
相対的にそのl/200未満、好ましくはl/400以
下であるが、実用的には0.001−1pm、好ましく
は0.01〜0.15.u m、 B E T比表面積
40m”/g以上の樹脂粒子を用いる。樹脂粒子の重量
平均粒径が1.0μmを超え、或いはBET比表面積が
40m2/Hに及ばぬときには、磁性体粒子表面での樹
脂粒子の展延が難しく、乾式コーティング処理が困難と
なる。又、0.01μm未満或いはBET比表面積が6
QOm”/gを超えると分散性が悪くなり、均一なコー
ティングが達成できないことがあり、収率も低下するこ
とがある。The weight average particle diameter of the resin particles is based on the magnetic particles,
It is relatively less than 1/200, preferably less than 1/400, but practically 0.001-1 pm, preferably 0.01-0.15. Use resin particles with a BET specific surface area of 40 m"/g or more. When the weight average particle diameter of the resin particles exceeds 1.0 μm or the BET specific surface area does not reach 40 m2/H, the surface of the magnetic particles It is difficult to spread the resin particles, making dry coating processing difficult.Also, if the resin particles are less than 0.01 μm or the BET specific surface area is 6.
If it exceeds QOm''/g, the dispersibility deteriorates, uniform coating may not be achieved, and the yield may also decrease.
樹脂粒子の材料としては、特に限定されず、種々の樹脂
を用いることができ己。即ち、本発明においては非溶剤
系の乾式コーティングが可能であり、溶剤に難溶性の樹
脂も用いることができ、樹脂の選択範囲が相当に広くな
る。具体的には、例えばスチレン系樹脂、アクリル系樹
脂、スチレン−アクリル系樹脂、ビニル系樹脂、エチレ
ン系樹脂、ロジン変成樹脂、ポリアミド樹脂、ポリエス
テル樹脂、シリコーン樹脂、弗素系樹脂等の樹脂を用い
ることができる。これらの樹脂は組合せて用いてもよい
。The material for the resin particles is not particularly limited, and various resins can be used. That is, in the present invention, non-solvent dry coating is possible, resins that are poorly soluble in solvents can also be used, and the range of resin selection is considerably widened. Specifically, resins such as styrene resin, acrylic resin, styrene-acrylic resin, vinyl resin, ethylene resin, rosin modified resin, polyamide resin, polyester resin, silicone resin, fluorine resin, etc. may be used. Can be done. These resins may be used in combination.
これらのうち特にスチレン−アクリル系樹脂、アクリル
系樹脂を好ましく用いることができる。Among these, styrene-acrylic resins and acrylic resins can be particularly preferably used.
このスチレン−アクリル系樹脂は、スチレン系単量体と
アクリル系単量体とが共重合されて得られる樹脂である
。スチレン系単量体の具体例としては、例えばスチレン
、0−メチルスチレン、l−メチルスチレン、p−メチ
ルスチレン、α−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−ブチルスチレン、p
−t−ブチルスチレン、p−へキシルスチレン、p−オ
クチルスチレン、p−ノニルスチレン、p−デシルスチ
レン、p−Fデシルスチレン、p−メトキシスチレン、
p−フェニルスチレン、p−クロルスチレン、3.4−
ジクロルスチレン等を挙ケることができ、これらの単量
体は単独で用いてもよいし、複数のものを組合せて用い
てもよい。This styrene-acrylic resin is a resin obtained by copolymerizing a styrene monomer and an acrylic monomer. Specific examples of styrene monomers include styrene, 0-methylstyrene, l-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-butylstyrene. , p
-t-butylstyrene, p-hexylstyrene, p-octylstyrene, p-nonylstyrene, p-decylstyrene, p-F decylstyrene, p-methoxystyrene,
p-phenylstyrene, p-chlorostyrene, 3.4-
Examples include dichlorostyrene, and these monomers may be used alone or in combination.
アクリル系単量体の具体例としては、例えばアクリル酸
、アクリル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、アクリル酸イソブチル、アクリル酸プロピル、ア
クリル酸オクチル、アクリル酸ドデシル、アクリル酸ラ
ウリル、アクリル酸2−エチルヘキシル、アクリル酸ス
テアリル、アクリル酸2−クロルエチル、アクリル酸フ
ェニル、σクロルアクリル酸メチル等のアクリル酸もし
くはそのエステル類;メタクリル酸、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸プロピル、メタ
クリル酸ブチル、メタクリル酸イソブチル、メタクリル
酸オクチル、メタクリル酸ドデシル、メタクリル酸ラウ
リル、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、メタクリル酸ジメ
チルアミノエチル、メタクリル酸ジエチルアミノエチル
等のメタクリル酸もしくはエステル類;その他を挙げる
ことができ、これらの単量体は単独で用いてもよいし、
複数のものを組合せて用いてもよい。Specific examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, dodecyl acrylate, lauryl acrylate, and diacrylic acid. - Acrylic acid or its esters such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, σmethyl chloroacrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylic acid or esters such as isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; others These monomers may be used alone or
A combination of a plurality of them may be used.
前記スチレン−アクリル系樹脂を得る場合において、ス
チレン系単量体と、アクリル系単量体の組成比は、重量
比で9:l−1:9であることが好ましい。スチレン成
分はコーテイング膜を硬くし、アクリル成分はコーテイ
ング膜を強靭なものとする。又、これらの組成比を適宜
変更することにより、コーティングキャリアとトナーと
の摩擦帯電におけるトナーの帯電量を相当程度制御する
ことができる。When obtaining the styrene-acrylic resin, the composition ratio of the styrene monomer and the acrylic monomer is preferably 9:1-1:9 by weight. The styrene component makes the coating film hard, and the acrylic component makes the coating tough. In addition, by appropriately changing these composition ratios, the amount of charge of the toner during frictional charging between the coating carrier and the toner can be controlled to a considerable extent.
キャリアの重量平均粒径は磁性体粒子に対応した適正な
範囲内にあることが好ましい。即ち、キャリアの重量平
均粒径が過小のときには、感光体へのキャリア付着が生
じやすくなって画質が劣化する。一方重量平均粒径が過
大のときには、比表面積が小さくなるため、トナーを適
正に摩擦帯電させることが困難となり、又キャリアを現
像剤担持体上に均一にしかも高い密度で担持させること
が困Mとなり、現像性が悪化する。The weight average particle diameter of the carrier is preferably within an appropriate range corresponding to the magnetic particles. That is, when the weight average particle diameter of the carrier is too small, the carrier tends to adhere to the photoreceptor, resulting in deterioration of image quality. On the other hand, when the weight average particle size is too large, the specific surface area becomes small, making it difficult to triboelectrically charge the toner appropriately, and also making it difficult to support the carrier uniformly and at a high density on the developer carrier. As a result, developability deteriorates.
又、特性の揃ったキャリアとするためには、キャリアの
粒度分布は狭いことが好ましい。Further, in order to obtain a carrier with uniform properties, it is preferable that the particle size distribution of the carrier is narrow.
尚、磁性体粒子の重量平均粒径(〒W)は、[マイクロ
トラック−Type 7981−OXJ (リーズ・
アンド・ノースラップ(LEEDS & N0RTII
RUP)社製、樹脂粒子の重量平均粒径(7w)は「コ
ールタ・mode IN4シリーズ」((株)コールタ
−社製)を用いて測定されたものである。The weight average particle diameter (〒W) of the magnetic particles is [Microtrac-Type 7981-OXJ (Leeds)
and Northrup (LEEDS & N0RTII
The weight average particle diameter (7w) of the resin particles was measured using "Coulter mode IN4 series" (manufactured by Coulter Co., Ltd.).
本発明の静電像現像用キャリアは、例えば以下のような
方法により製造することができる。The electrostatic image developing carrier of the present invention can be produced, for example, by the following method.
即ち、重量平均粒径がlO〜200μIの磁性体粒子と
重量平均粒径が当該磁性体粒子の1/200未満、かつ
BET比表面積が40m”1g以上である樹脂粒子とを
、例えば通常の撹拌装置等により混合撹拌して均一に混
合し、得られた混合物を樹脂の物性によって品温を50
〜110℃の幅の中に設定した、例えば高速撹拌型混合
器などに移し、前記混合物に10〜60分間、好ましく
は15−’30分間衝撃力を繰返し付与することにより
、磁性体粒子の表面に樹脂粒子を展延付着させてコーテ
ィングキャリアを得る。That is, magnetic particles having a weight average particle diameter of 10 to 200 μI and resin particles having a weight average particle diameter of less than 1/200 of the magnetic particles and a BET specific surface area of 40 m''1 g or more are mixed, for example, with normal stirring. Mix uniformly by stirring using a device, etc., and adjust the temperature of the resulting mixture to 50% depending on the physical properties of the resin.
The surface of the magnetic particles is transferred to, for example, a high-speed stirring type mixer set within a temperature range of ~110°C, and the mixture is repeatedly subjected to impact force for 10 to 60 minutes, preferably 15 to 30 minutes. A coating carrier is obtained by spreading and adhering resin particles to the coating carrier.
この際品温が高すぎると、樹脂粒子の粘着性が高くなり
、その結果樹脂粒子粉末の粒子同志が凝集し塊状化する
現象が生じ、又磁性体粒子同志が樹脂粒子により結合さ
れて融合するようになり、磁性体粒子の表面に樹脂粒子
を均一に付着させることが困難となる。At this time, if the product temperature is too high, the adhesiveness of the resin particles will increase, resulting in a phenomenon in which the particles of the resin particle powder agglomerate and become lumps, and magnetic particles may be bonded together and fused by the resin particles. This makes it difficult to uniformly adhere the resin particles to the surface of the magnetic particles.
以下、本発明を実施例によって具体的に説明するが、本
発明がこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
(トナーの製造)
ポリエステル樹脂; 100重量部、カーポンプラッり
;10重量部及び低分子量ポリプロピレン;3!!量部
をボールミルを用いて混合し、混練、粉砕、分級し、平
均粒径11μmのトナーを得た。(Manufacture of toner) Polyester resin; 100 parts by weight, Carpon Platter; 10 parts by weight, and low molecular weight polypropylene; 3! ! Amounts of the mixture were mixed using a ball mill, kneaded, pulverized, and classified to obtain a toner having an average particle size of 11 μm.
(現像剤の調合)
トナー粒子の含有率が下記各キャリア粒径に対応して適
正になるように、各実施例及び比較例で作成したキャリ
アと上記トナー粒子とを混合し、静電潜像現像剤を調合
した。(Preparation of developer) The carrier prepared in each example and comparative example and the above toner particles were mixed so that the content of toner particles was appropriate for each carrier particle size below, and the electrostatic latent image was formed. A developer was prepared.
(キャリアの作成)
実施例1
Cu−Zn系フェライトキャリア
(重量平均粒径rw80μm) 5000重
量部メチルメタクリレート/ブチルメタクリレート(重
量組成比8/2)共重合体(rvo、06μm)100
重量部
上記材料を高速撹拌型混合器で15分間混合し、オーダ
ードミクスチャを作成した。その後前記混合器に温水を
循環させ、品温を70℃とし、主撹拌羽根を回転させ1
5分間コーティングを行いコーティングキャリアを得た
。(Preparation of carrier) Example 1 Cu-Zn-based ferrite carrier (weight average particle diameter rw 80 μm) 5000 parts by weight Methyl methacrylate/butyl methacrylate (weight composition ratio 8/2) copolymer (rvo, 06 μm) 100
Part by Weight The above materials were mixed for 15 minutes using a high-speed stirring type mixer to prepare an ordered mixture. After that, warm water was circulated through the mixer to bring the product temperature to 70°C, and the main stirring blade was rotated for 1 hour.
Coating was carried out for 5 minutes to obtain a coated carrier.
尚、統記する実施例、比較例において、抜出して記載し
た条件のみ実施例1と異り、他は同一条件としてコーテ
ィングキャリアを得た。In addition, in the examples and comparative examples to be summarized, coated carriers were obtained under the same conditions as in Example 1 except for the conditions that are extracted and described.
実施例2
Cu−Zn系フェライトキャリア
(rv100μm) 5000重
量部* MMA/HMA(8/2)(rvo、06μm
) 75重量部(註)*メチルメタクリレー
ト/ブチルメタクリレート(8/ 2)共重合体
実施例3
鉄粉キャリア
(rv100p+a) 5000
重量部MMA/HMA(8/2XrwO,06μm)実
施例4
Mg −Cu −Zn系フェライトキャリア(rw45
μm)
MMA/HMA(8/2)(rwO,06,u m)実
施例5
Cu−Zn系フェライトキャリア
(rw80μm)
60重量部
5000重量部
125重量部
5000重量部
MMA/HMA(8/20FvO010μIl)
too重量部実施例6
Mg −Cu −Zn系フェライトキャリア(rv45
μm) 5000重量部MMA/
HMA(8/2XrwO,IO,u m) 1
25重量部実施例7
Cu−Zn系フェライトキャリア
(rw25μm) 5000重
量部MMA/HMA(8/2)(rwO,06μm)
175重量部実施例8
Cu−Zn系フェライトキャリア
(rw80μm) 5000重
量部MMA/ * 5t(6/4)(7wO,075t
t m) 100重量部(註)*スチレン
実施例9
Cu−Zn系フェライトキャリア
(rw80μm) 500
0重量部シリコーン微粒子(rvO,1μm)
100重量部実施例1O
Cu−Zn系フェライトキャリア
(rw80μm) 500
0重量部四弗化エチレン樹脂微粒子
(rwo、2μm) 15
0重量部実施例11
Cu−Zn系フェライトキャリア
(rw80μm) 5000重
量部トリクロルメチルメタクリレート微粒子(rwo、
08μm) 125重量部
比較例(1)
Cu−Zn系フェライトキャリア
(rw100μm) 500
0重量部MMA重量部(25/75)(rvO,5μ!
l) 75重量部比較例(2)
実施例1と同一組成、温度を120°O1:up比較例
(3)
Mg −Cu −Zn系フェライトキャリア(rw44
μm) 5000重量部!i1
MA(rwO,4,u m)
150重量部比較例(4)
Cu−Zn系フエライトキャリア
(rv80.u m) 500
0重量部MMA/HMA(8/2XrwO,06,u
m) 100重量部前記の実施例、比較例で得
たコーティングキャリアに係る諸事項を表1に示す。Example 2 Cu-Zn ferrite carrier (rv 100 μm) 5000 parts by weight* MMA/HMA (8/2) (rvo, 06 μm
) 75 parts by weight (Note) * Methyl methacrylate/butyl methacrylate (8/2) copolymer Example 3 Iron powder carrier (rv100p+a) 5000
Weight part MMA/HMA (8/2XrwO, 06μm) Example 4 Mg-Cu-Zn ferrite carrier (rw45
MMA/HMA (8/2) (rwO, 06, um) Example 5 Cu-Zn ferrite carrier (rw80μm) 60 parts by weight 5000 parts by weight 125 parts by weight 5000 parts by weight MMA/HMA (8/20FvO010μIl)
Too weight part Example 6 Mg-Cu-Zn based ferrite carrier (rv45
μm) 5000 parts by weight MMA/
HMA (8/2XrwO,IO,um) 1
25 parts by weight Example 7 Cu-Zn ferrite carrier (rw 25 μm) 5000 parts by weight MMA/HMA (8/2) (rwO, 06 μm)
175 parts by weight Example 8 Cu-Zn ferrite carrier (rw 80 μm) 5000 parts by weight MMA/ * 5t (6/4) (7wO, 075t
t m) 100 parts by weight (Note) *Styrene Example 9 Cu-Zn ferrite carrier (rw 80 μm) 500
0 parts by weight silicone fine particles (rvO, 1 μm)
100 parts by weight Example 1O Cu-Zn ferrite carrier (rw 80 μm) 500
0 parts by weight Tetrafluoroethylene resin fine particles (rwo, 2 μm) 15
0 parts by weight Example 11 Cu-Zn ferrite carrier (rw 80 μm) 5000 parts by weight Trichloromethyl methacrylate fine particles (rwo,
08 μm) 125 parts by weight Comparative example (1) Cu-Zn ferrite carrier (rw100 μm) 500
0 parts by weight MMA parts by weight (25/75) (rvO, 5μ!
l) 75 parts by weight Comparative example (2) Same composition as Example 1, temperature 120° O1:up Comparative example (3) Mg-Cu-Zn based ferrite carrier (rw44
μm) 5000 parts by weight! i1
MA(rwO,4,um)
150 parts by weight Comparative example (4) Cu-Zn ferrite carrier (rv80.um) 500
0 parts by weight MMA/HMA (8/2XrwO,06,u
m) 100 parts by weight Table 1 shows various matters related to the coated carriers obtained in the above Examples and Comparative Examples.
尚、条件、特性の測定法は下記の通りである。The conditions and methods for measuring characteristics are as follows.
1、品 温
芯材に樹脂粒子を付着してなる粒子が、衝撃力を付与さ
れて流動する粒子集団中に、温度測定プローブを挿入し
て、該プローブに粒子をランダムに接触させて得られる
、粒子の近似的な表面温度の平均値をいう。温度測定プ
ローブは、熱電対、測温抵抗体等からなり、その起電力
、抵抗値等を電気的に測定することにより、温度を測定
することができる。熱電対としては、例えば、クロメル
−アルメル熱電対が挙げられる。1. Product Particles obtained by inserting a temperature measurement probe into a particle group in which resin particles are attached to a thermocore material and flowing under an impact force, and randomly bringing the particles into contact with the probe. The approximate average surface temperature of The temperature measurement probe is composed of a thermocouple, a resistance temperature detector, etc., and can measure temperature by electrically measuring its electromotive force, resistance value, etc. Examples of thermocouples include chromel-alumel thermocouples.
本発明における品温の測定は、長さlOc+a、直径6
.4+++mのステンレス(SUS304)製カバー付
きのクロメル−アルメル熱電対(林電工(株)製)を用
い、その端部を5cm挿入して行う。In the present invention, the temperature of the product is measured by length lOc+a, diameter 6
.. A chromel-alumel thermocouple (manufactured by Hayashi Denko Co., Ltd.) with a 4+++m stainless steel (SUS304) cover is used, and its end is inserted 5 cm.
2、白粉量の測定方法
コーティングキャリア20gと15mffのメタノール
と、を20+s12のサンプル管に入れ、ウェーブロー
タ(回転数46rpm)で10分間撹拌し、その上澄液
を光電比色計(波長522ns)専用セルに入れその透
過率を測定して求めた。2. Method for measuring white powder amount 20 g of coating carrier and 15 mff of methanol were placed in a 20+S12 sample tube, stirred for 10 minutes with a wave rotor (rotation speed 46 rpm), and the supernatant liquid was measured with a photoelectric colorimeter (wavelength 522 ns). The transmittance was determined by placing it in a dedicated cell and measuring its transmittance.
3 、 (Fe”)の測定方法
0.001%酢酸水溶液9IIIQに0.2%、2.2
−ジピリジルのエタノール呈色試薬1Il12と界面活
性剤を加えた溶液とコーティングキャリアIgとを20
諷aのサンプル瓶に入れ、ウェーブロータ(回転数46
rpw+)で2分間撹拌を行う。その上澄液を光電比色
計(波長522nm)の専用セルに入れ、その透過率を
測定する。その透過率Tから吸光度(log〒)を計算
、それに検量線7アクタを乗じて求められる。3. Measuring method for (Fe”) 0.2% in 0.001% acetic acid aqueous solution 9IIIQ, 2.2
- A solution containing dipyridyl ethanol coloring reagent 1Il12 and a surfactant and coating carrier Ig at 20%
Put it in a sample bottle and turn it into a wave rotor (rotation speed 46).
rpw+) for 2 minutes. The supernatant liquid is put into a special cell of a photoelectric colorimeter (wavelength: 522 nm), and its transmittance is measured. The absorbance (log〒) is calculated from the transmittance T, and is obtained by multiplying it by the calibration curve 7 actors.
(F e ” ” ) −1og T X検量線7アク
タ4、樹脂粒子の粒径はコールタ−社モデルN−4を用
いて行った。(F e "") -1og T
5、BET比表面積
測定はマイクロメリティックスフ0−ソープ■2300
形(高滓製作所製)を用いて行った。5. BET specific surface area measurement using Micromeritics F0-Soap ■2300
This was done using a mold (manufactured by Takasu Seisakusho).
6、融合率は1.Okgのコーティングキャリアを所定
の篩を用いてふるった後、メツシュを通過したコーティ
ングキャリアの量から算出して求めた。6. The fusion rate is 1. It was calculated from the amount of coated carrier that passed through the mesh after sifting Okg of coated carrier using a predetermined sieve.
100μmキャリアには80メツシユ、80μmキャリ
アには100メツシユ、45μmキャリアは200メツ
シユ、(トナーの摩擦帯電性の評価)
上記現像剤のそれぞれを用いて、高温高湿環境条件下及
び低温低湿環境条件下におけるトナーの摩擦帯電量を測
定した。80 meshes for 100 μm carrier, 100 meshes for 80 μm carrier, 200 meshes for 45 μm carrier (Evaluation of triboelectricity of toner) Using each of the above developers, under high temperature, high humidity environmental conditions and low temperature, low humidity environmental conditions. The amount of triboelectric charge of the toner was measured.
ただし、磁性体粒子の重量平均粒径が60.umを超え
るキャリアを組合せた現像剤については公知のブローオ
フ法によりトナーの摩擦帯電量を測定し、磁性体粒子の
重量平均粒径が60μm以下であるキャリアを組合せた
現像剤については実際に現像プロセスを遂行してトナー
の摩擦帯電性を測定した。結果を表2に示す。However, the weight average particle diameter of the magnetic particles is 60. For developers that are combined with a carrier that exceeds um, the amount of triboelectric charge of the toner is measured by a known blow-off method, and for a developer that is combined with a carrier that has magnetic particles with a weight average particle size of 60 μm or less, the amount of triboelectric charge of the toner is measured by the actual development process. The triboelectric charging properties of the toner were measured. The results are shown in Table 2.
(実写テストl)
上記現像剤実施例1〜9、比較例(2)〜(4)をそれ
ぞれ用いて、接触型現像器を備えた電子写真複写機「υ
−Bix5500J(コニカ族)により複写画像を形成
する実写テストを行い、下記の項目について、夫々評価
した。結果を表3に示す。(Actual photocopying test 1) Using the above developer Examples 1 to 9 and Comparative Examples (2) to (4), an electrophotographic copying machine "υ" equipped with a contact type developer was used.
- A photocopying test was conducted in which a copy image was formed using Bix5500J (Konica Group), and the following items were evaluated. The results are shown in Table 3.
但し、現像条件の中ドラム−スリーブ間距離、ドクタブ
レードースリーブ間距離は各キャリア粒径によって適正
条件に設定した。However, the distance between the drum and the sleeve and the distance between the doctor blade and the sleeve in the development conditions were set to appropriate conditions depending on the particle size of each carrier.
又、上記実施例to、ttは有機感光体及び接触型現像
器を備えた電子写真複写機rU−Bix1550J (
コニカ族)により、実写テストを行い評価を行った。In addition, the above Examples to and tt are an electrophotographic copying machine rU-Bix1550J (
A live-action test was conducted and evaluated by the Konica family.
以上の実施例の結果からも理解されるように、本発明の
実施例!−11によれば、簡単な手段により短時間でし
かも高い収率でキャリアを得ることができ、また実写テ
ストにおいては耐久性が優れていて安定した摩擦帯電性
が発揮され、キャリア付着を伴わず適正トナー濃度を維
持し、現象性に優れている良好な画質の画像を形成する
ことかでき lこ 。As can be understood from the results of the above examples, this is an example of the present invention! According to No. 11, carriers can be obtained in a short time and with a high yield using simple means, and in live-action tests, it has excellent durability and stable triboelectric charging properties, and does not cause carrier adhesion. It is possible to maintain appropriate toner density and form images of good quality with excellent phenomenon properties.
又、キャリア表面を完全に樹脂被覆しているために環境
依存性がなく、均一な強靭な被覆層が得られていて、高
温・高湿、低温・低湿を含め安定した性能を得ることが
できる。In addition, since the carrier surface is completely coated with resin, there is no environmental dependence, and a uniform and strong coating layer is obtained, allowing stable performance at high temperatures, high humidity, and low temperatures and low humidity. .
又、コーティングキャリア作成時間も短く、被覆率が変
っても、混合比率を変えるだけでコーティング時間が長
くなることはない。Furthermore, the time required to prepare the coating carrier is short, and even if the coverage changes, the coating time will not become longer just by changing the mixing ratio.
Claims (3)
重量平均粒径が前記磁性体粒子の1/200未満の樹脂
粒子を加えて均一混合物とし、品温を50〜110℃の
幅の中に設定した混合器中で、前記混合物に繰返し衝撃
力を与えて、前記磁性体粒子を前記樹脂粒子の樹脂物質
で被覆した静電像現像用キャリア。(1) Add resin particles with a weight average particle size of less than 1/200 of the magnetic particles to magnetic particles with a weight average particle size of 10 to 200 μm to form a homogeneous mixture, and adjust the product temperature to a range of 50 to 110°C. A carrier for electrostatic image development, wherein the magnetic particles are coated with the resin material of the resin particles by repeatedly applying impact force to the mixture in a mixer set in the mixer.
を特徴とする請求項1に記載の静電像現像用キャリア。(2) The carrier for electrostatic image development according to claim 1, wherein the magnetic particles have a circularity of 0.7 or more.
、重量平均粒径が前記磁性体粒子の1/200未満の樹
脂粒子を加えて均一混合物とし、品温を50〜110℃
の幅の中に設定した混合器中で、前記混合物に繰返し衝
撃力を与えて、前記磁性体粒子を前記樹脂粒子の樹脂物
質で被覆する静電像現像用キャリアの製造方法。(3) Add resin particles with a weight average particle size of less than 1/200 of the magnetic particles to magnetic particles with a weight average particle size of 10 to 200 μm to form a uniform mixture, and keep the product temperature at 50 to 110°C.
A method for producing a carrier for electrostatic image development, comprising repeatedly applying an impact force to the mixture in a mixer set within a width of 10 to 10, to coat the magnetic particles with the resin material of the resin particles.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63239180A JP2709943B2 (en) | 1988-09-22 | 1988-09-22 | Electrostatic image developing carrier and method of manufacturing the same |
DE68919313T DE68919313T2 (en) | 1988-09-22 | 1989-09-13 | Carrier particles for developing processes for electrostatic images and manufacturing processes. |
EP19890116985 EP0360146B1 (en) | 1988-09-22 | 1989-09-13 | Carrier for electrostatic image development and method of preparing it |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63239180A JP2709943B2 (en) | 1988-09-22 | 1988-09-22 | Electrostatic image developing carrier and method of manufacturing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0287167A true JPH0287167A (en) | 1990-03-28 |
JP2709943B2 JP2709943B2 (en) | 1998-02-04 |
Family
ID=17040914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63239180A Expired - Lifetime JP2709943B2 (en) | 1988-09-22 | 1988-09-22 | Electrostatic image developing carrier and method of manufacturing the same |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0360146B1 (en) |
JP (1) | JP2709943B2 (en) |
DE (1) | DE68919313T2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5017258A (en) * | 1986-06-20 | 1991-05-21 | Shell Oil Company | Pipe rehabilitation using epoxy resin composition |
US5182181A (en) * | 1990-03-20 | 1993-01-26 | Konica Corporation | Resin coated carriers for electrostatic image development and the method of preparing the same |
US8399171B2 (en) | 2009-06-02 | 2013-03-19 | Sharp Kabushiki Kaisha | Method of manufacturing resin-layer coated carrier, resin-layer coated carrier, developer, developing device, and image forming apparatus |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE795370A (en) * | 1972-02-14 | 1973-05-29 | Ibm | PROCESS FOR THE MANUFACTURING OF BEARING MATERIALS USABLE IN AN ELECTROPHOTOGRAPHIC REPRODUCTION APPARATUS |
CA1140784A (en) * | 1979-06-04 | 1983-02-08 | Xerox Corporation | Conductive powder coated electrostatographic carriers |
JPS6337359A (en) * | 1986-08-01 | 1988-02-18 | Minolta Camera Co Ltd | Production of carrier for electrostatic latent image development |
-
1988
- 1988-09-22 JP JP63239180A patent/JP2709943B2/en not_active Expired - Lifetime
-
1989
- 1989-09-13 EP EP19890116985 patent/EP0360146B1/en not_active Expired - Lifetime
- 1989-09-13 DE DE68919313T patent/DE68919313T2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5017258A (en) * | 1986-06-20 | 1991-05-21 | Shell Oil Company | Pipe rehabilitation using epoxy resin composition |
US5182181A (en) * | 1990-03-20 | 1993-01-26 | Konica Corporation | Resin coated carriers for electrostatic image development and the method of preparing the same |
US8399171B2 (en) | 2009-06-02 | 2013-03-19 | Sharp Kabushiki Kaisha | Method of manufacturing resin-layer coated carrier, resin-layer coated carrier, developer, developing device, and image forming apparatus |
Also Published As
Publication number | Publication date |
---|---|
EP0360146A3 (en) | 1990-06-20 |
EP0360146A2 (en) | 1990-03-28 |
DE68919313T2 (en) | 1995-04-06 |
JP2709943B2 (en) | 1998-02-04 |
DE68919313D1 (en) | 1994-12-15 |
EP0360146B1 (en) | 1994-11-09 |
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