JPH0473579B2 - - Google Patents
Info
- Publication number
- JPH0473579B2 JPH0473579B2 JP58066575A JP6657583A JPH0473579B2 JP H0473579 B2 JPH0473579 B2 JP H0473579B2 JP 58066575 A JP58066575 A JP 58066575A JP 6657583 A JP6657583 A JP 6657583A JP H0473579 B2 JPH0473579 B2 JP H0473579B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydrogen atom
- developer
- toner
- general formula
- 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.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 39
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- -1 silicon halide Chemical class 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 238000011161 development Methods 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 2
- 230000032258 transport Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 26
- 230000005291 magnetic effect Effects 0.000 description 25
- 239000000975 dye Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229910002016 Aerosil® 200 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OBHBXMOWIKWQNI-UHFFFAOYSA-N [3-(dimethylamino)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound CN(C)CC(O)COC(=O)C(C)=C OBHBXMOWIKWQNI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 2
- 229960000228 cetalkonium chloride Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 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
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000009191 jumping Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 2
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YQJPWWLJDNCSCN-UHFFFAOYSA-N 1,3-diphenyltetramethyldisiloxane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 YQJPWWLJDNCSCN-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- DEGZUQBZHACZKW-UHFFFAOYSA-N 2-(methylamino)ethyl 2-methylprop-2-enoate Chemical compound CNCCOC(=O)C(C)=C DEGZUQBZHACZKW-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- LDCWGVLBCJEQMT-UHFFFAOYSA-N 2-methyl-n-(2-methylprop-2-enyl)prop-2-en-1-amine Chemical compound CC(=C)CNCC(C)=C LDCWGVLBCJEQMT-UHFFFAOYSA-N 0.000 description 1
- PCUPXNDEQDWEMM-UHFFFAOYSA-N 3-(diethylamino)propyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C(C)=C PCUPXNDEQDWEMM-UHFFFAOYSA-N 0.000 description 1
- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- HDWNKEWYEDOKIZ-UHFFFAOYSA-N 5-(diethylamino)-2-methylidenepentanamide Chemical compound CCN(CC)CCCC(=C)C(N)=O HDWNKEWYEDOKIZ-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- LVGSUQNJVOIUIW-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-2-enamide Chemical compound CN(C)CCC=C(C)C(N)=O LVGSUQNJVOIUIW-UHFFFAOYSA-N 0.000 description 1
- NFKIMJJASFDDJG-UHFFFAOYSA-N 5-amino-N,N-diethyl-2-methylpent-2-enamide Chemical compound NCCC=C(C(=O)N(CC)CC)C NFKIMJJASFDDJG-UHFFFAOYSA-N 0.000 description 1
- ALXUOLQRSSGTMU-UHFFFAOYSA-N 6-(diethylamino)-2-methylhex-2-enamide Chemical compound CCN(CC)CCCC=C(C)C(N)=O ALXUOLQRSSGTMU-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- AGWGLQAQTSTART-UHFFFAOYSA-N [3-(dimethylamino)-2-hydroxypropyl] prop-2-enoate Chemical compound CN(C)CC(O)COC(=O)C=C AGWGLQAQTSTART-UHFFFAOYSA-N 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- FTWHFXMUJQRNBK-UHFFFAOYSA-N alpha-Methylen-gamma-aminobuttersaeure Natural products NCCC(=C)C(O)=O FTWHFXMUJQRNBK-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ABHNFDUSOVXXOA-UHFFFAOYSA-N benzyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CC1=CC=CC=C1 ABHNFDUSOVXXOA-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CAURZYXCQQWBJO-UHFFFAOYSA-N bromomethyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CBr CAURZYXCQQWBJO-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 1
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- IGFFTOVGRACDBL-UHFFFAOYSA-N dichloro-phenyl-prop-2-enylsilane Chemical compound C=CC[Si](Cl)(Cl)C1=CC=CC=C1 IGFFTOVGRACDBL-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 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
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CAPIMQICDAJXSB-UHFFFAOYSA-N trichloro(1-chloroethyl)silane Chemical compound CC(Cl)[Si](Cl)(Cl)Cl CAPIMQICDAJXSB-UHFFFAOYSA-N 0.000 description 1
- FLPXNJHYVOVLSD-UHFFFAOYSA-N trichloro(2-chloroethyl)silane Chemical compound ClCC[Si](Cl)(Cl)Cl FLPXNJHYVOVLSD-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- KHOQXNHADJBILQ-UHFFFAOYSA-N trimethyl(sulfanyl)silane Chemical compound C[Si](C)(C)S KHOQXNHADJBILQ-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G13/00—Electrographic processes using a charge pattern
- G03G13/06—Developing
- G03G13/08—Developing using a solid developer, e.g. powder developer
- G03G13/09—Developing using a solid developer, e.g. powder developer using magnetic brush
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Magnetic Brush Developing In Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
Description
本発明は、静電像を現像するための静電像現像
用現像剤及び該静電像現像用現像剤を使用する現
像方法に関する。
従来、電子写真・静電記録等における現像方法
としては、大別して乾式現像法と湿式現像法とが
ある。前者は、更に二成分系現像剤を用いる方法
と、一成分系現像剤を用いる方法として二分され
る。二成分系現像方法に属するものには、トナー
を搬送するキヤリヤーの種類により、鉄粉キヤリ
ヤーを用いるマグネツトブラシ法、ビーズ・キヤ
リヤーを用いるカスケード法、フアーを用いるフ
アーブラシ法等がある。
又、一成分系現像方法に属するものには、トナ
ー粒子を噴霧状態にして用いるパウダークラウド
法、トナー粒子を直接的に静電潜像面に接触させ
て現像する接触現像法（コンタクト現像、又はト
ナー現像ともいう）、トナー粒子を静電潜像面に
直接接触させず、トナー粒子を荷電して静電潜像
の有する電界により該潜像面に向けて飛行させる
ジヤンピング現像法、磁性の導電性トナーを静電
潜像面に接触させて現像するマグネドライ法等が
ある。二成分系現像方法では、必然的にキヤリヤ
ー粒子とトナー粒子との混合現像剤を用い、通常
現像過程の進行によりトナー粒子はキヤリヤー粒
子に比べ遥かに大量に消費させるから、両者の混
合比が変化し、もつて顕画像の濃度が変動し、
又、消費され難いキヤリヤー粒子の長時間使用に
よる劣化により画質が低下する等の問題点を本来
有している。
他方、一成分系の現像方法では、磁性トナーを
用いるマグネ・ドライ法及び磁性トナーを用いな
いコンタクト現像法は、トナーが被現像面の全
面、即ち画像部、非画像部に無差別に接触し、こ
れがために非画像部にまでもトナーが付着し易
い、所謂地カブリとなつて汚れが生じ易い問題が
あつた。（このカブリ汚れの点については二成分
系現像法においても同様に生じるという問題点で
あつた。）又、パウダー・クラウド法においても
パウダー状態のトナー粒子が非画像部に付着する
ことは避けられず、同じく地カブリが除去できな
い問題点を有している。
更に、一成分系現像方法に属する所謂ジヤンピ
ング現像法として、シート等の担持体にトナーを
均一に塗布した後、これを静電保持面に小間〓を
保つて対向させトナー担持体から静電像保持面に
トナーを静電像が有する電荷により吸引し付着さ
せて現像する方法が知られている。
（米国特許第2839400号明細書等）
この方法は、静電荷のない非画像部では、トナ
ーが吸引されないばかりか、トナーと非画像面と
が接触しないので、上述のカブリが出にくいとい
う長所を有している。又、キヤリヤー粒子を用い
ないので、上述した混合比の変動という事態もな
く、更にキヤリヤー粒子の劣化もない。
しかしながらこの方法は、トナー担持体シート
に予めトナーを付着させるため電界を与えている
が、均一になお且つ、薄く塗布することが困難で
塗布ムラが出易い。また、塗布されたトナー層
が、静電像と対向したとき、静電像への均一なト
ナーの離脱が困難である欠点を有している。
この点特開昭54−43027号公報、特開昭55−
18656号公報で提案される、磁性トナーと可動な
トナー担持体（スリーブローラー）と、該担持体
の内側に静止磁石を有する現像装置において、該
磁石の磁極に対向してスリーブローラーの外表面
に近接して磁性体材料のトナー厚規制部材を配置
し、スリーブローラーの外表面上に均一になお且
つ薄く塗布することのできる現像装置は、上記問
題点を除去したもので忠実性が高く画質の安定し
た静電像現像装置であると言える。
従来知られている現像剤を使用して繰り返し複
写を続けると、場合により、現像剤担持体上に担
持された現像剤層の均一性がそこなわれ、担持体
の円周方向にスジ上のコーテイング不良が発生し
たり、担持された現像剤の層の厚さが初期と比較
し部分的に極端に厚くなり、ハン点様のムラが発
生したり、サザ波様のコーテイング不良が発生す
る場合がある。前者は現像した際に画像に白筋と
して観察され、後者はハン点状あるいはサザ波状
の濃度ムラとなつて観察されたりする。この現象
は、通常の繰り返し複写ではほとんど発生しない
が、特に長期間超低温低湿の環境条件下での連続
使用で発生する場合があり好ましくない。
また、高温高湿においても、現像剤層の厚さが
変化し薄くなる場合が多く、しばしば画像濃度の
低下を引き起こし好ましくない場合があつた。
この点について検討を重ねた結果、その原因の
１つは電荷制御成分の安定性および信頼性にあ
り、これらの原因により該スリーブ上へのトナー
の付着及びスリーブからのトナーの転写が変化す
るためであることを見出した。
更に詳しく述べると、この様な現象は、環境条
件の変化によつて、現像剤担持体上に担持された
現像剤層において、摩擦帯電量の不均一部分が生
ずることによる。即ち、超低温低湿の環境条件下
では、担持体表面と現像剤との摩擦により発生す
る現像剤の摩擦帯電電荷が極端に大きい成分が発
生し、その電荷に帰因する鏡映力のため、担持体
近傍にその様な摩擦帯電電荷の極端に大きい成分
が蓄積しやすく、これが連続耐久などによつて、
現像剤層の上層部分の現像剤のコーテイングの均
一性や現像されやすさに影響を与え、現象とし
て、前記した白筋やハン点状のムラ、サザ波状の
コーテイング不良を生ずる。また高温高湿におけ
る現像剤層の厚さ減少も、現像剤と担持体との摩
擦帯電の不均一から発生するもので、担持体表面
近傍の現像剤の摩擦帯電量の不安定性によるもの
である。
従来、この様な乾式現像用トナーに用いられる
電荷制御剤としては、アミノ化合物、第４級アン
モニウム化合物及び有機染料特に塩基性染料とそ
の塩が知られており、ベンジルジメチル−ヘキサ
デシルアンモニウムクロライド、デシル−トリメ
チルアンモニウムクロライド、ニグロシン塩基、
ニグロシンヒドロクロライド、サフラニンγ及び
クリスタルバイオレツト等が使用されている。ニ
グロシン塩基及びニグロシンヒドロクロライドが
しばしば正電荷制御剤として用いられている。こ
れらは、通常熱可塑性樹脂に添加され、過熱溶融
分散し、これを微粉砕して、必要に応じて適当な
粒径に調整され使用される。
しかしながら、これらの電荷制御剤としての染
料は、構造が複雑で性質が一定していなく、安定
性に乏しい。また、熱混練時の分解、機械的衝
撃、摩擦、温湿度条件の変化、などにより分解又
は変質し荷電制御性が低下する現象を生ずる。
従つて、これらの染料を荷電制御剤として含有
したトナーを複写機に用い現像すると、複写回数
の増大に従い、染料が分解あるいは変質し、耐久
中にトナーの劣化を引き起こす。
又、これらの荷電制御剤としての染料は、熱可
塑性樹脂中に均一に分散する事が極めて困難であ
るため、粉砕して得られたトナー粒子間の摩擦帯
電量に差異を生じるという致命的欠点を有してい
る。このため、従来これらの染料の樹脂中への分
散をより均一に行うための種々の方法が行われて
いる。例えば、塩基性ニグロシン染料は、熱可塑
性樹脂との相溶性を向上させるために、高級脂肪
酸と造塩して用いられるが、しばしば未反応分の
脂肪酸あるいは、塩の分散生成物がトナー表面に
露出して、キヤリヤーあるいは、現像剤担持体を
汚染し、トナーの流動性低下やカブリ、画像濃度
の低下を引き起こす原因となつている。あるい
は、これらの染料の樹脂中への分散向上のため
に、予め染料粉末と樹脂粉末とを機械的粉砕混合
してから、熱溶融混練する方法もとられている
が、本来の分散不良性は回避する事ができず、未
だ実用上充分な荷電の均一さは得られていないの
が現実である。
又、荷電制御性の染料は親水性のものが多く、
これらの樹脂中への分散不良のために、溶融混練
後粉砕した際には、染料がトナー表面に露出す
る。高湿条件下での該トナーの使用の際には、こ
れら染料が親水性であるがために良質な画像が得
られないという欠点を有している。
この様に、従来の荷電制御性を有する染料をト
ナーに用いた際には、トナー粒子間において、あ
るいはトナーとキヤリヤー間、トナーとスリーブ
の如きトナー担持体間において、トナー粒子表面
に発生電荷量にバラツキを生じ、現像カブリ、ト
ナー飛散、キヤリヤー汚染等の障害が発生する。
またこれらは、複写枚数を多く重ねた際に特に顕
著な現象となつて現われ、実質上複写機には適さ
ない結果となる。
又、高湿条件下においては、トナー画像の転写
効率が著しく低下し、使用に耐えないものであ
る。又、常温常湿においてさえも該トナーを長期
保存した際には、用いた荷電制御性の染料の不安
定性のために、トナー凝集を起こし使用不可能に
なる場合が多い。
本発明者は、上記の如き従来の荷電性トナーに
まつわる種々の問題点を解決し、均一に強く帯電
し、静電荷像を可視化して高品質な画像を与える
事を目的として鋭意研究を行つた結果、後述の一
般式(1)、(2)、(3)、(4)又は(5)で示すエチレン性不飽
和アミノ化合物の少なくとも１種以上で処理され
たシリカ微粉体を現像剤に含有させれば優れた
種々の特性を示す静電像現像用現像剤が得られる
事を見出した。そしてさらに、この現像剤をスリ
ーブローラーの如き現像剤担持体を有する現像装
置に適用するのが非常に有効であることを見出し
た。
本発明の目的は、連続使用特性等の耐久性に優
れた静電像現像用現像剤及び現像方法を提供する
ことである。
本発明の他の目的は、高温高湿や低温低湿など
の環境変化に対しても安定である静電像現像用現
像剤及び現像方法を提供することである。
本発明は、少なくとも結着樹脂及び着色剤を有
するトナー、及びシリカ微粉体を有する静電像現
像用現像剤において、該シリカ微粉体は、ケイ素
ハロゲン化物の蒸気相酸化により生成されたシリ
カ微粉体を下記一般式(1)、(2)、(3)、(4)又は(5)
一般式(1)
〔式中R1は水素原子又はメチル基を示し、R2及
びR3は夫々水素原子、低級アルキル基、２−ヒ
ドロキシエチル、フエニル、ベンジル又はフエノ
キシエチル基を示し、ｐは１、２又は３を示し、
ｑは０又は１を示し、ｒは１を示し、ｐ＋ｑ＋ｒ
＝３を示す。〕
一般式(2)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、Ｙは−（CH2）ｍ−又は
The present invention relates to a developer for developing an electrostatic image and a developing method using the developer for developing an electrostatic image. Conventionally, developing methods for electrophotography, electrostatic recording, etc. are broadly classified into dry developing methods and wet developing methods. The former method is further divided into a method using a two-component developer and a method using a single-component developer. Two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner. Furthermore, the one-component development methods include the powder cloud method, in which toner particles are sprayed, and the contact development method, in which toner particles are brought into direct contact with the electrostatic latent image surface. (also referred to as toner development), jumping development method in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; magnetic conduction There is the MagneDry method, which develops by bringing a toner into contact with the electrostatic latent image surface. Two-component development methods inevitably use a developer mixture of carrier particles and toner particles, and as the development process progresses, the toner particles are consumed in far larger quantities than the carrier particles, so the mixing ratio of the two changes. However, the density of the microscope image changes,
Furthermore, there are inherent problems such as deterioration of image quality due to deterioration of carrier particles that are difficult to consume due to long-term use. On the other hand, in one-component developing methods, the Magne-Dry method using magnetic toner and the contact developing method that does not use magnetic toner, the toner comes into contact with the entire surface of the surface to be developed, that is, the image area and the non-image area, indiscriminately. This has caused a problem in that toner tends to adhere even to non-image areas, resulting in so-called background fog and dirt. (This fog stain problem also occurs in two-component development methods.) Also, in the powder cloud method, adhesion of powdered toner particles to non-image areas can be avoided. First, there is also the problem that background fog cannot be removed. Furthermore, in the so-called jumping development method, which belongs to the one-component development method, toner is uniformly applied to a carrier such as a sheet, and then the toner is placed facing an electrostatic holding surface with a distance between the toner carrier and the electrostatic image. A method is known in which toner is attracted and adhered to a holding surface by the electric charge of an electrostatic image, thereby developing the image. (U.S. Pat. No. 2,839,400, etc.) This method has the advantage that not only the toner is not attracted to the non-image area where there is no static charge, but also the toner and the non-image area do not come into contact, so the above-mentioned fogging is less likely to occur. have. Furthermore, since carrier particles are not used, there is no variation in the mixing ratio as described above, and there is no deterioration of the carrier particles. However, in this method, an electric field is applied in advance to adhere the toner to the toner carrier sheet, but it is difficult to apply the toner uniformly and thinly, and uneven application is likely to occur. Another drawback is that when the applied toner layer faces an electrostatic image, it is difficult to release the toner uniformly to the electrostatic image. In this regard, JP-A-54-43027, JP-A-55-
In the developing device proposed in Japanese Patent No. 18656, which has magnetic toner, a movable toner carrier (sleeve roller), and a stationary magnet inside the carrier, a magnetic toner is placed on the outer surface of the sleeve roller opposite to the magnetic pole of the magnet. A developing device in which a toner thickness regulating member made of a magnetic material is placed in close proximity to the sleeve roller and is capable of uniformly and thinly coating the toner on the outer surface of the sleeve roller eliminates the above-mentioned problems and achieves high fidelity and image quality. It can be said that this is a stable electrostatic image developing device. When copying is continued repeatedly using a conventionally known developer, the uniformity of the developer layer carried on the developer carrier may be impaired, and streaks may appear in the circumferential direction of the carrier. When a coating defect occurs, or the thickness of the supported developer layer becomes extremely thick in some areas compared to the initial thickness, causing spots-like unevenness or a serpentine-like coating defect to occur. There is. The former is observed as white streaks on the image when developed, and the latter is observed as uneven density in the form of dots or serpentine waves. Although this phenomenon hardly occurs during normal repeated copying, it may occur particularly during continuous use under extremely low temperature and low humidity environmental conditions for a long period of time, which is undesirable. Further, even under high temperature and high humidity conditions, the thickness of the developer layer often changes and becomes thinner, which often leads to an undesirable decrease in image density. As a result of repeated studies on this point, we found that one of the causes is the stability and reliability of the charge control component, and these causes change the adhesion of toner onto the sleeve and the transfer of toner from the sleeve. I found that. More specifically, such a phenomenon is caused by the occurrence of non-uniform areas in the amount of triboelectric charge in the developer layer supported on the developer carrier due to changes in environmental conditions. In other words, under extremely low temperature and low humidity environmental conditions, components with extremely large triboelectric charges are generated due to friction between the surface of the carrier and the developer, and due to the mirroring force attributable to this charge, the developer is Extremely large components of such triboelectric charges tend to accumulate near the body, and due to continuous endurance, etc.
This affects the uniformity of the developer coating in the upper layer of the developer layer and the ease with which it is developed, and causes the aforementioned white streaks, patch-like unevenness, and serpentine coating defects. Furthermore, the decrease in the thickness of the developer layer at high temperatures and high humidity is also caused by uneven triboelectric charging between the developer and the carrier, and is due to instability in the amount of triboelectricity of the developer near the surface of the carrier. . Conventionally, known charge control agents used in such dry developing toners include amino compounds, quaternary ammonium compounds, and organic dyes, particularly basic dyes and their salts, including benzyldimethyl-hexadecyl ammonium chloride, Decyl-trimethylammonium chloride, nigrosine base,
Nigrosine hydrochloride, safranin γ, crystal violet, etc. are used. Nigrosine base and nigrosine hydrochloride are often used as positive charge control agents. These are usually added to a thermoplastic resin, melted and dispersed under heating, and then finely pulverized and adjusted to an appropriate particle size as necessary before use. However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability. Further, decomposition or deterioration occurs due to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc., resulting in a phenomenon in which charge controllability is deteriorated. Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, the dye decomposes or changes in quality as the number of copies increases, causing deterioration of the toner during durability. Furthermore, since it is extremely difficult to uniformly disperse these dyes as charge control agents in thermoplastic resins, this has the fatal drawback of causing a difference in the amount of triboelectric charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to more uniformly disperse these dyes into resins. For example, basic nigrosine dyes are used by forming salts with higher fatty acids to improve compatibility with thermoplastic resins, but unreacted fatty acids or salt dispersion products are often exposed on the toner surface. This contaminates the carrier or developer carrier, causing a decrease in toner fluidity, fog, and a decrease in image density. Alternatively, in order to improve the dispersion of these dyes into the resin, a method has been adopted in which the dye powder and the resin powder are mechanically pulverized and mixed in advance and then hot melt-kneaded, but the inherent poor dispersion is The reality is that this cannot be avoided, and that sufficient uniformity of charge has not yet been obtained for practical use. In addition, many charge control dyes are hydrophilic,
Due to poor dispersion in these resins, the dye is exposed on the toner surface when it is crushed after melt-kneading. When these toners are used under high humidity conditions, they have the disadvantage that good quality images cannot be obtained because these dyes are hydrophilic. In this way, when conventional dyes with charge control properties are used in toner, the amount of charge generated on the surface of toner particles is generated between toner particles, between toner and carrier, or between toner and toner carriers such as sleeves. This causes variations in the image quality and causes problems such as development fog, toner scattering, and carrier contamination.
Furthermore, these phenomena become particularly noticeable when a large number of copies are made, resulting in a result that is practically unsuitable for copying machines. Furthermore, under high humidity conditions, the toner image transfer efficiency is significantly reduced, making it unusable. Furthermore, when the toner is stored for a long period of time even at room temperature and humidity, the toner often aggregates and becomes unusable due to the instability of the charge control dye used. The inventor of the present invention has conducted extensive research with the aim of solving the various problems associated with conventional chargeable toners as described above, and creating a toner that is uniformly and strongly charged, visualizes the electrostatic charge image, and provides a high-quality image. As a result, the developer contains fine silica powder treated with at least one ethylenically unsaturated amino compound represented by the general formula (1), (2), (3), (4) or (5) described below. It has been found that a developer for electrostatic image development exhibiting various excellent properties can be obtained by doing so. Furthermore, it has been found that it is very effective to apply this developer to a developing device having a developer carrier such as a sleeve roller. An object of the present invention is to provide a developer for electrostatic image development and a developing method that have excellent durability such as continuous use characteristics. Another object of the present invention is to provide a developer and a developing method for electrostatic image development that are stable against environmental changes such as high temperature and high humidity, and low temperature and low humidity. The present invention provides a toner having at least a binder resin and a colorant, and a developer for electrostatic image development having a fine silica powder, wherein the fine silica powder is a fine silica powder produced by vapor phase oxidation of a silicon halide. The following general formula (1), (2), (3), (4) or (5) General formula (1) [In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each represent a hydrogen atom, a lower alkyl group, 2-hydroxyethyl, phenyl, benzyl, or a phenoxyethyl group, and p represents 1, 2, or 3. show,
q represents 0 or 1, r represents 1, p+q+r
=3. ] General formula (2) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and Y is -(CH 2 )m- or
【式】を示し、ｍは１、２又は３
を示す。〕
一般式(3)
〔式中R4、R5、R6は夫々水素原子又は低級アル
キル基を示し、ｍは１、２又は３を示す。〕
一般式(4)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示す。〕
一般式(5)
〔式中R7は水素原子又は低級アルキル基を示し、
ｎは０、１、２又は３を示す。〕
で示されるエチレン性不飽和アミノ化合物の少な
くとも１種以上で処理されたシリカ微粉体である
ことを特徴とする静電像現像用現像剤に関する。
さらに、本発明は、静電像を表面に保持する静
電像保持体と、現像剤を表面に担持し現像部へ搬
送するための現像剤担持体とを現像部において一
定の間〓を設けて配置し、ケイ素ハロゲン化物の
蒸気相酸化により生成されたシリカ微粉体が下記
一般式(1)、(2)、(3)、(4)又は(5)
一般式(1)
〔式中R1は水素原子又はメチル基を示し、R2及
びR3は夫々水素原子、低級アルキル基、２−ヒ
ドロキシエチル、フエニル、ベンジル又はフエノ
キシエチル基を示し、ｐは１、２又は３を示し、
ｑは０又は１を示し、ｒは１を示し、ｐ＋ｑ＋ｒ
＝３を示す。〕
一般式(2)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、Ｙは−（CH2）ｍ−又は
[Formula] and m represents 1, 2 or 3. ] General formula (3) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and m represents 1, 2 or 3. ] General formula (4) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group. ] General formula (5) [In the formula, R 7 represents a hydrogen atom or a lower alkyl group,
n represents 0, 1, 2 or 3. ] The present invention relates to a developer for electrostatic image development, characterized in that it is a fine silica powder treated with at least one ethylenically unsaturated amino compound represented by the following. Furthermore, the present invention provides an electrostatic image holder that holds an electrostatic image on its surface and a developer carrier that carries developer on its surface and transports it to the developing section for a certain period of time in the developing section. The silica fine powder produced by vapor phase oxidation of silicon halide has the following general formula (1), (2), (3), (4) or (5) general formula (1) [In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each represent a hydrogen atom, a lower alkyl group, 2-hydroxyethyl, phenyl, benzyl, or a phenoxyethyl group, and p represents 1, 2, or 3. show,
q represents 0 or 1, r represents 1, p+q+r
=3. ] General formula (2) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and Y is -(CH 2 )m- or
【式】を示し、ｍは１、２又は３
を示す。〕
一般式(3)
〔式中R4、R5、R6は夫々水素原子又は低級アル
キル基を示し、ｍは１、２又は３を示す。〕
一般式(4)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示す。〕
一般式(5)
〔式中R7は水素原子又は低級アルキル基を示し、
ｎは０、１、２又は３を示す。〕
で示されるエチレン性不飽和アミノ化合物の少な
くとも１種以上で処理されたシリカ微粉体及びト
ナーを含有する現像剤を現像剤担持体上に担持さ
せ、該トナーを現像部において前記静電像保持体
に転移させて静電像を現像する現像方法に関す
る。
本発明において、一成分系磁性現像剤を用いる
現像工程について説明する。
実施例 １
第１図に本発明で用いる現像工程の１実施形態
が断面図で示される。同図において静電像保持体
１は矢印方向に動く。現像剤担持体である非磁性
円筒２は、現像部において静電像保持体表面と同
方向に進むように回転する。非磁性円筒２内部に
は、多極永久磁石３が回転しないように配されて
いる。現像剤容器４から送られる一成分系絶縁性
磁性現像剤６と非磁性円筒面上に塗布し、かつ円
筒面とトナー粒子との摩擦によつて、トナー粒子
に静電像電荷と逆極性の電荷を与える。さらに鉄
製のドクターブレード５を円筒表面に近接して
（間隔50μ〜500μ）、多極永久磁石３の一つの磁極
（図示ではＳ極）位置に対向して配置することに
より、現像剤層の厚さを薄く（30μ〜300μ）且つ
均一に規制する。この円筒２の回転速度を調節す
ることにより、現像剤層の表層速度及び好ましく
は内部速度が静電像保持面の速度と実質的に等
速、もしくはそれに近い速度となるようにする。
ドクターブレード５として鉄のかわりに永久磁石
を用いて対向磁極を形成してもよい。また、現像
部において現像剤担持体と静電像保持面との間で
交流バイアスを印加してもよい。この交流バイア
スはｆが200〜4000Hz、Vppが500〜3000Vであれ
ばよい。
以上の如く、この現像工程においては一成分磁
性現像剤を現像剤担持体上に安定に保持させる為
に、多極永久磁石３を内包する非磁性円筒２を用
いた。また、現像剤層を薄く均一に形成する為
に、円筒２表面に近接して磁性体薄板もしくは永
久磁石によるドクターブレード５を配置した。こ
の様に磁性体のドクターブレートを用いると、現
像剤担持体に内包された永久磁石の磁極との間に
対向磁極が形成され、ドクターブレードと現像剤
担持体間でトナー粒子鎖を強制的に立ち上がらせ
ることになり、現像剤担持体上の他の部分、例え
ば静電像面に相対する現像部分の現像剤層を薄く
規制するのに有利である。さらにその様な強制的
運動を現像剤に与えることにより現像剤層はより
均一になり、よつて非磁性体ドクターブレードで
は実現できなかつた薄く且つ均一なトナー層形成
が達せられる。しかもドクターブレードとスリー
ブとの間〓を広めに設定できるからトナー粒子の
破壊や凝集を防止する効果もある。現像部におけ
るトナー粒子の転移に際し、静電像の吸引作用あ
るいは交流バイアスの作用によつて静電像側にト
ナーは転移する。
本発明の現像剤に用いられるトナー用の結着樹
脂としては、従来電子写真用トナー結着樹脂とし
て知られる各種の材料樹脂が用いられる。
例えばポリスチレン、ポリスチレン・ブタジエ
ン共重合体、スチレン・アクリル共重合体等のス
チレン系共重合体、ポリエチレン、ポリエチレン
酢酸ビニル共重合体、ポリエチレンビニルアルコ
ール共重合体のようなエチレン系共重合体、フエ
ノール系樹脂、エポキシ系樹脂、アリルフタレー
ト樹脂、ポリアミド樹脂、ポリエステル樹脂、、
マレイン酸系樹脂等である。またいずれの樹脂も
その製造法等は特に制約されるものではない。こ
れは従来エマルジヨン重合等で製造した樹脂は不
純物が含まれ易く使いずらかつたものが本発明に
より容易に使用が可能になり、樹脂選択の範囲も
大きく広がる。これも本発明の大きな効果であ
る。
トナー中に含有させる磁性粉としては強磁性の
元素及びこれらを含む合金、化合物などであり、
マグネタイト、ヘマタイト、フエライトなどの
鉄、コバルト、ニツケル、マンガンなどの合金や
化合物、その他の強磁性合金など従来より磁性材
料として知られているものがある。通常使用する
磁性粉の大きさとしては平均粒径が0.05〜5μ好ま
しくは0.1〜1μが良い。この磁性粉は、トナー中
に10〜70重量％、好ましくは15〜35重量％含有さ
せるのがよい。この含有量であれば、前述の現像
方法において適切な磁気モーメントが働き、良好
な画像を作成することができ、定着性も優れてい
る。
トナーに用いる着色材料としては、従来公知の
カーボンブラツク、鉄黒などが使用でき、さら
に、従来公知の正荷電制御剤としての染料が、本
発明に用いられる処理されたシリカ微粉体との組
み合わせで使用する事ができる。
例えばベンジルジメチル−ヘキサデシルアンモ
ニウムクロライド、デシル−トリメチルアンモニ
ウムクロライド、ニグロシン塩基、ニグロシンヒ
ドロクロライド、サフラニンγ及びクリスタルバ
イオレツトなどの染料が挙げられる。
本発明で用いるケイ素ハロゲン化合物の蒸気相
酸化により生成されたシリカ微粉体とは、いわゆ
る乾式法シリカ、又はヒユームドシリカと称され
るものが好ましく、従来公知の技術によつて製造
されるものである。例えば四塩化ケイ素ガスの酸
水素焔中における熱分解酸化反応を利用する方法
で、基礎となる反応式は次の様なものである。
SiCl4＋2H2＋O2→SiO2＋4HCl
又、この製造工程において例えば、塩化アルミ
ニウム又は、塩化チタンなど他の金属ハロゲン化
合物をケイ素ハロゲン化合物と共に用いる事によ
つてシリカと他の金属酸化物の複合微粉体を得る
事も可能であり、本発明で用いるシリカ微粉体
は、それらも包含する。
本発明で用いるシリカ微粉体は、粒径が平均の
一次粒径として、0.001〜2μの範囲内である事が
好ましく、特に好ましくは、0.002〜0.2μの範囲
内のシリカ微粉体を使用するのがよい。
ケイ素ハロゲン化合物の蒸気相酸化により生成
されたシリカ微粉体の市販品としては、例えば、
以下の様な商品名のものがある。
AEROSIL 130
（日本アエロジル社） 200
300
380
TT600
MOX80
MOX170
COK84
Ca−Ｏ−SiL Ｍ−５
（CABOT Co.社） MS−７
MS−75
HS−５
EH−５
Wacker HDK Ｎ 20 Ｖ−15
（WACKER−CHEMIE GMBH社） N20E
T30
T40
Ｄ−Ｃ Fine Silica
（ダウコーニングCo.社）
Fransol
（Fransil社）
従来、トナーにこれらシリカ微粉体を添加する
例は公知である。しかしながら、このような物質
は安定性の点で必ずしも充分でなく、また正荷電
制御性を必要とするトナーではこのようなシリカ
を添加すると帯電性が変化してしまい不適当であ
つた。
本発明で用いられるエチレン性不飽和アミノ化
合物としては、エチレン性不飽和結合を有する下
記一般式(1)〜(5)で示す化合物が使用される。以下
一般式(1)〜(5)について説明する。
一般式(1)
〔式中R1は水素原子又はメチル基を示し、R2及
びR3は夫々水素原子、低級アルキル基、２−ヒ
ドロキシエチル、フエニル、ベンジル又はフエノ
キシエチル基を示し、ｐは１、２又は３を示し、
ｑは０又は１を示し、ｒは１を示し、ｐ＋ｑ＋ｒ
＝３を示す。〕
で表わされる上記アミンの誘導体又はそれらの第
４級アンモニウム塩。
上記化合物の好ましいものとしてはアリルアミ
ン、メタアリルアミン、メチルアリルアミン、ジ
メチルアリルアミン、トリメチルアリルアンモニ
ウムクロライド、２−ヒドロキシエチルアリルア
ミン、ジアリルアミン、ジメタアリルアミン、メ
チルジアリルアミン、ジメチルジアリルアンモニ
ウムクロライド、２−ヒドロキシエチルジアリル
アミン、ベンジルジアリルアミン等が例示でき
る。
一般式(2)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、Ｙは−（CH2）ｍ−又は
[Formula] and m represents 1, 2 or 3. ] General formula (3) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and m represents 1, 2 or 3. ] General formula (4) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group. ] General formula (5) [In the formula, R 7 represents a hydrogen atom or a lower alkyl group,
n represents 0, 1, 2 or 3. ] A developer containing a toner and a silica fine powder treated with at least one ethylenically unsaturated amino compound represented by the above is supported on a developer carrier, and the toner is used in the developing section to hold the electrostatic image. The present invention relates to a developing method for developing an electrostatic image by transferring it to a body. In the present invention, a developing process using a one-component magnetic developer will be described. Example 1 FIG. 1 shows a cross-sectional view of one embodiment of the developing process used in the present invention. In the figure, the electrostatic image holder 1 moves in the direction of the arrow. The non-magnetic cylinder 2, which is a developer carrier, rotates in the developing section so as to move in the same direction as the surface of the electrostatic image carrier. A multipolar permanent magnet 3 is arranged inside the nonmagnetic cylinder 2 so as not to rotate. The one-component insulating magnetic developer 6 sent from the developer container 4 is coated on the non-magnetic cylindrical surface, and the friction between the cylindrical surface and the toner particles causes the toner particles to have a polarity opposite to that of the electrostatic image charge. Gives a charge. Furthermore, by arranging the iron doctor blade 5 close to the cylindrical surface (with an interval of 50 μm to 500 μm) and facing one magnetic pole (S pole in the figure) of the multipolar permanent magnet 3, the thickness of the developer layer can be increased. Control the thickness to be thin (30μ to 300μ) and uniform. By adjusting the rotational speed of the cylinder 2, the surface speed and preferably the internal speed of the developer layer are made to be substantially equal to or close to the speed of the electrostatic image holding surface.
Instead of iron, a permanent magnet may be used as the doctor blade 5 to form opposing magnetic poles. Further, an alternating current bias may be applied between the developer carrier and the electrostatic image holding surface in the developing section. This AC bias may have f of 200 to 4000 Hz and Vpp of 500 to 3000 V. As described above, in this developing step, the non-magnetic cylinder 2 containing the multipolar permanent magnet 3 was used in order to stably hold the one-component magnetic developer on the developer carrier. In addition, in order to form a thin and uniform developer layer, a doctor blade 5 made of a magnetic thin plate or a permanent magnet was placed close to the surface of the cylinder 2. When a magnetic doctor blade is used in this way, opposing magnetic poles are formed between the magnetic poles of the permanent magnet contained in the developer carrier, and the toner particle chains are forced between the doctor blade and the developer carrier. This is advantageous in controlling the thickness of the developer layer in other parts of the developer carrier, for example, in the development part facing the electrostatic image surface. Further, by imparting such forced movement to the developer, the developer layer becomes more uniform, thereby achieving a thin and uniform toner layer formation that could not be achieved with a non-magnetic doctor blade. Moreover, since the distance between the doctor blade and the sleeve can be set wide, it is also effective in preventing the destruction and aggregation of toner particles. When the toner particles are transferred in the developing section, the toner is transferred to the electrostatic image side due to the attraction action of the electrostatic image or the action of an alternating current bias. As the binder resin for toner used in the developer of the present invention, various resin materials conventionally known as toner binder resins for electrophotography are used. For example, styrene copolymers such as polystyrene, polystyrene/butadiene copolymer, styrene/acrylic copolymer, ethylene copolymers such as polyethylene, polyethylene vinyl acetate copolymer, polyethylene vinyl alcohol copolymer, and phenolic copolymers. Resin, epoxy resin, allyl phthalate resin, polyamide resin, polyester resin,
Maleic acid resin, etc. Furthermore, there are no particular restrictions on the manufacturing method of any of the resins. This is because conventionally, resins produced by emulsion polymerization or the like tend to contain impurities and are difficult to use, but the present invention allows them to be used easily, and the range of resin selection is greatly expanded. This is also a great effect of the present invention. The magnetic powder to be contained in the toner includes ferromagnetic elements and alloys and compounds containing them.
There are conventionally known magnetic materials such as alloys and compounds of iron such as magnetite, hematite, and ferrite, cobalt, nickel, and manganese, and other ferromagnetic alloys. Generally used magnetic powder has an average particle size of 0.05 to 5μ, preferably 0.1 to 1μ. This magnetic powder is preferably contained in the toner in an amount of 10 to 70% by weight, preferably 15 to 35% by weight. With this content, an appropriate magnetic moment is activated in the above-mentioned developing method, a good image can be created, and the fixing property is also excellent. As the coloring material used in the toner, conventionally known carbon black, iron black, etc. can be used.Furthermore, a conventionally known dye as a positive charge control agent can be used in combination with the treated silica fine powder used in the present invention. It can be used. Examples include dyes such as benzyldimethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, nigrosine base, nigrosine hydrochloride, safranin gamma and crystal violet. The silica fine powder produced by vapor phase oxidation of a silicon halogen compound used in the present invention is preferably what is called dry process silica or fumed silica, and is produced by a conventionally known technique. For example, this method utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows. SiCl 4 +2H 2 +O 2 →SiO 2 +4HCl Also, in this manufacturing process, for example, by using other metal halide compounds such as aluminum chloride or titanium chloride together with silicon halide, a composite fine powder of silica and other metal oxides can be produced. It is also possible to obtain silica particles, and the silica fine powder used in the present invention includes these types. The fine silica powder used in the present invention preferably has a particle size in the range of 0.001 to 2μ, particularly preferably 0.002 to 0.2μ, as an average primary particle size. Good. Commercial products of silica fine powder produced by vapor phase oxidation of silicon halogen compounds include, for example,
There are product names such as the following. AEROSIL 130 (Japan Aerosil Co., Ltd.) 200 300 380 TT600 MOX80 MOX170 COK84 Ca-O-SiL M-5 (CABOT Co.) MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 V-15 (WACKER- CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Fransol (Fransil) Examples of adding these fine silica powders to toner are known. However, such substances do not necessarily have sufficient stability, and addition of such silica to toners requiring positive charge controllability changes the chargeability, making them unsuitable. As the ethylenically unsaturated amino compound used in the present invention, compounds represented by the following general formulas (1) to (5) having an ethylenically unsaturated bond are used. General formulas (1) to (5) will be explained below. General formula (1) [In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each represent a hydrogen atom, a lower alkyl group, 2-hydroxyethyl, phenyl, benzyl, or a phenoxyethyl group, and p represents 1, 2, or 3. show,
q represents 0 or 1, r represents 1, p+q+r
=3. ] Derivatives of the above amines represented by these or quaternary ammonium salts thereof. Preferred examples of the above compounds include allylamine, metaallylamine, methylallylamine, dimethylallylamine, trimethylallylammonium chloride, 2-hydroxyethylallylamine, diallylamine, dimethallylamine, methyldiallylamine, dimethyldiallylammonium chloride, 2-hydroxyethyldiallylamine, benzyl Examples include diallylamine. General formula (2) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and Y is -(CH 2 )m- or
【式】を示し、ｍは１、２又は３
を示す。〕
で表わされるアクリル酸又はメタアクリル酸のア
ミノアルキルエステル及びそれらの第４級アンモ
ニウム塩。
上記化合物の好ましいものとしては２−アミノ
エチルアクリレート、２−アミノエチルメタアク
リレート、２−メチルアミノエチルアクリレー
ト、２−メチルアミノエチルメタアクリレート、
２−ジメチルアミノエチルアクリレート、２−ジ
メチルアミノエチルメタアクリレート、３−ジメ
チルアミノ−２−ヒドロキシプロピルアクリレー
ト、３−ジメチルアミノ−２−ヒドロキシプロピ
ルメタアクリレート等が例示できる。
一般式(3)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、ｍは１、２又は３を示す。〕
で表わされるアクリル酸又はメタアクリル酸のア
ミノアルキルアミド及びそれらの第４級アンモニ
ウム塩。
上記化合物の好ましいものとしては、ジメチル
アミノエチルアクリルアミド、ジメチルアミノエ
チルメタアクリルアミド、ジエチルアミノエチル
アクリルアミド、ジエチルアミノエチルメタアク
リルアミド、ジメチルアミノプロピルアクリルア
ミド、ジメチルアミノプロピルメタアクリルアミ
ド、ジエチルアミノプロピルアクリルアミド、ジ
エチルアミノプロピルメタアクリルアミド等が例
示できる。
一般式(4)
〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示す。〕
で表わされるアルキルアミノアクリルイミド及び
アルキルアミノメタアクリルイミド並びにそれら
の第４級アンモニウム塩。
上記化合物の好ましいものとしては、例えばジ
メチルアミナクリルイミド、ジメチルアミンメタ
アクリルイミド、ジエチルアミンアクリルイミ
ド、ジエチルアミンメタアクリルイミド等が例示
できる。
一般式(5)
〔式中R7は水素原子又は低級アルキル基を示し
及びｎは０、１、２又は３を示す。〕
で表わされるビニルイミダゾール誘導体。
上記化合物の好ましいものとしては、Ｎ−ビニ
ルイミダゾール、２−メチル−Ｎ−ビニルイミダ
ゾール、２−ビニルイミダゾール等が例示でき
る。
エチレン性不飽和アミノ化合物中好ましいもの
としては、アリルアミン、ジメチルアミノエチル
メタアクリレート、ジエチルアミノエチルメタア
クリレート、３−ジメチルアミノ−２−ヒドロキ
シプロピルメタアクリレート、ジメチルアミノエ
チルアクリルアミド及びＮ−ビニルイミダゾール
が、特に好ましいものとしてはアリルアミン、ジ
メチルアミノエチルメタアクリレート及びジエチ
ルアミノエチルメタアクリレートが例示できる。
上記エチレン性不飽和アミノ化合物は単独で又
は２種以上併用して使用できる。
前記したシリカ微粉体をエチレン性不飽和アミ
ノ化合物で処理する方法としては、従来公知の方
法が用いられる。例えば、該エチレン性不飽和ア
ミノ化合物を適当な溶剤に溶解し、シリカ微粉体
を投入し混合する方法、あるいはシリカ微粉体を
懸濁せしめたエチレン性不飽和アミン溶液をスプ
レードライする方法、シリカ微粉体表面でグラフ
ト化する方法など種々の方法が用いられる。
エチレン性不飽和アミノ化合物のシリカ微粉体
に対する好ましい処理量としては0.01〜20重量％
である。
また、上記エチレン性不飽和アミノ化合物に加
え、シランカツプリング剤や他の有機ケイ素化合
物の併用も好ましい。
その様な有機ケイ素化合物の例は、ヘキサメチ
ルジシラザン、トリメチルシラン、トリメチルク
ロルシラン、トリメチルエトキシシラン、ジメチ
ルジクロルシラン、メチルトリクロルシラン、ア
リルジメチルクロルシラン、アリルフエニルジク
ロルシラン、ベンジルジメチルクロルシラン、ブ
ロムメチルジメチルクロルシラン、α−クロルエ
チルトリクロルシラン、β−クロルエチルトリク
ロルシラン、クロルメチルジメチルクロルシラ
ン、トリオルガノシリルメルカプタン、トリメチ
ルシリルメルカプタン、トリオルガノシリルアク
リレート、ビニルジメチルアセトキシシラン、ジ
メチルエトキシシラン、ジメチルジメトキシシラ
ン、ジフエニルジエトキシシラン、ヘキサメチル
ジシロキサン、１，３−ジビニルテトラメチルジ
シロキサン、１，３−ジフエニルテトラメチルジ
シロキサン、および１分子当り２から12個のシロ
キサン単位を有し末端に位置する単位にそれぞれ
１個宛のSiに結合した水酸基を含有するジメチル
ポリシロキサン等がある。これらの１種あるいは
２種以上の混合物で用いられる。
また、これらの処理されたシリカ微粉体の適用
量は現像剤重量に対して、0.01〜20重量％のとき
に効果を発揮し、特に好ましくは0.1〜３重量％
添加した際に優れた安定性を有する正しい帯電性
を示す。添加形態について好ましい態様を述べれ
ば、現像剤重量に対して0.01〜３重量％の処理さ
れたシリカ微粉体がトナー粒子表面に付着してい
る状態にあるのが良い。
本発明においては、前述の如く特定のエチレン
性不飽和アミノ化合物で処理されたシリカ微粉体
と混合されているトナーは、後述の実施例で示す
ように磁性キヤリヤーと混合して、二成分系現像
剤とし、磁気ブラシ法を用いる二成分系現像方法
に用いることもできる。
この様にして構成された本発明の現像剤は、用
いられる現像剤が荷電制御成分として前記したと
ころのシリカ微粉体を含有するため、現像剤担持
体上に担持された現像剤層に付与される摩擦帯電
量が均一化され、超低温低湿の耐久において生じ
やすい過剰の電荷のみを適当な飽和値までシリカ
微粉体を介してリークし、その結果安定な現像剤
層を形成する。高温高湿においては、安定なコー
テイング状態を与えるに必要な摩擦帯電量を保持
しやすく、濃度低下などを生じやすい。
また、他の特徴は、安定な現像剤層の形成が容
易なため、従来、十分には理解できなかつた現像
カブリや、潜像のエツヂ周辺へのトナーの飛び散
りがなく、高い画像濃度が得られ、ハーフトーン
の再現性がよい事である。
以上、第１図に示す現像装置を参照しながら本
発明の基本的な構成と特色について述べたが以下
の実施例２〜５に基づいてさらに本発明の現像剤
及び現像方法について説明する。以下の実施例中
の部数は重量部である。
実施例 ２
スチレン−ブタジエン共重合体（70：30） 100部
カーボンブラツク ３部
ニグロシン ４部
上記材料をブレンダーでよく混合した後150℃
に熱した２本ロールで混練した。混合物を自然放
冷後、カツターミルで粗粉砕した後、ジエツト気
流を用いた微粉砕機を用いて粉砕し、さらに風力
分級機を用いて分級して粒径５〜20μの微粉体
（トナー）を得た。
次にシリカ微粉体アエロジル200（日本アエロジ
ル社製）を70℃に加熱した密閉型ヘンシエルミキ
サー中に入れ、シリカに対して5.0重量％の処理
量となる様にトルエンで希釈したメチルジアリル
アミンを滴下しながら高速で攪拌した。得られた
微粉体を120℃にて乾燥した。
該処理シリカ微粉体0.6重量％と上記トナー
99.4重量％をヘンシエルミキサーで混合したもの
10部に、粒径100〜200μの鉄粉キヤリヤー100部
加え混合して二成分系現像剤を得た。処理シリカ
微粉体をトナー粒子表面に有するトナーの摩擦帯
電量は＋20.0μc／ｇと高い正摩擦帯電性を有して
いた。
次いでOPC感光体上に従来公知の電子写真法
により、負の静電荷像を形成し、これを上記の現
像剤を用いた磁気ブラシ法で粉体現像してトナー
画像を作り、普通紙に転写し加熱定着させた。得
られた転写画像は濃度が1.38と十分高く、カブリ
も全くなく、画像周辺のトナー飛び散りがなく解
像力の高い良好な画像が得られた。
上記現像剤を用いて連続して転写画像を作成
し、耐久性を調べたが100000枚後の転写画像も初
期の画像を比較して、全く、そん色のない画像で
あつた。
また、環境条件を35℃、80％RHにしたとこ
ろ、画頭脳度は1.30と常温常湿とほとんど変化の
ない値であり、カブリや飛び散りもなく鮮明な画
像が得られ、耐久性も100000枚までほとんど変化
なかつた。次に10℃、10％RHの低温低湿におい
て転写画像を得たところ、画像濃度は1.40と高く
ベタ黒も極めて滑らかに現像、転写され飛び散り
や中抜けのない優秀な画像であつた。この環境条
件で耐久試験を行つたところ、連続、及び間けつ
でコピーしたが、やはり100000枚まで濃度変動は
±0.2と実用上充分であつた。
またこの現像剤を35℃、90％RHの環境で１ケ
月間保存した後に画像を得たが、画像濃度は1.28
と保存前とほとんど変らず、画質も良好であつ
た。
比較例 １
アエロジル200をメチルジアリルアミンで処理
しない他は実施例２と同様に現像剤を得、現像、
転写を行つたが、反転した画像が得られたのみで
あり、摩擦帯電量は−3.0μc／ｇを負の帯電性を
示した。
実施例 ３
メチルジアリルアミンの代りに２−メチルアミ
ノエチルアクリレートを用いた他は実施例２と同
様に行つたところ、画像濃度は1.31と高く、カブ
リ、飛び散り、転写ぬけなどがなく、解像力も高
い潜像に忠実な画像が得られた。
100000枚の耐久試験でも初期の画像と比較して
全くそん色のない画像が得られた。この現像剤を
35℃、90％RHの環境で１ケ月間保存した後に画
像を得たが、画像濃度は1.25と保存前とほとんど
変らず画質も良好であつた。また35℃、85％RH
の環境で画出しを行つたが、初期から極めて良好
な画像が得られ、100000枚後の画像も良好であつ
た。転写効率も90％と優れていた。
実施例 ４
実施例２においてメチルジアリルアミンの代り
にジエチルアミノプロピルメタアクリレートをシ
リカに対して５重量％となる様に処理した他は実
施例２と同様に行つたところ、得られた現像剤は
低温低湿、高温高湿、常温常湿の各環境において
画質、耐久性ともに優れた特性を示した。
実施例 ５
実施例２においてメチルジアリルアミンの代り
に２−メチル−Ｎ−ビニルイミダゾールをシリカ
に対して３重量％となる様に処理した他は実施例
２と同様に行つたところ、得られた現像剤は低温
低湿、高温高湿、常温常湿の各環境において画
質、耐久性ともに優れた特性を示した。[Formula] and m represents 1, 2 or 3. ] Aminoalkyl esters of acrylic acid or methacrylic acid and quaternary ammonium salts thereof. Preferred examples of the above compounds include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-methylaminoethyl acrylate, 2-methylaminoethyl methacrylate,
Examples include 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylamino-2-hydroxypropyl acrylate, and 3-dimethylamino-2-hydroxypropyl methacrylate. General formula (3) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and m represents 1, 2 or 3. ] Aminoalkylamides of acrylic acid or methacrylic acid and quaternary ammonium salts thereof. Preferred examples of the above compounds include dimethylaminoethyl acrylamide, dimethylaminoethylmethacrylamide, diethylaminoethyl acrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylacrylamide, diethylaminopropylmethacrylamide, etc. can. General formula (4) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group. ] Alkylaminoacrylimide and alkylaminomethacrylimide represented by these and their quaternary ammonium salts. Preferred examples of the above compounds include dimethylamine acrylimide, dimethylamine methacrylimide, diethylamine acrylimide, diethylamine methacrylimide, and the like. General formula (5) [In the formula, R 7 represents a hydrogen atom or a lower alkyl group, and n represents 0, 1, 2 or 3. ] Vinylimidazole derivative represented by. Preferred examples of the above compounds include N-vinylimidazole, 2-methyl-N-vinylimidazole, and 2-vinylimidazole. Among the ethylenically unsaturated amino compounds, allylamine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 3-dimethylamino-2-hydroxypropyl methacrylate, dimethylaminoethyl acrylamide and N-vinylimidazole are particularly preferred. Examples include allylamine, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. The above ethylenically unsaturated amino compounds can be used alone or in combination of two or more. A conventionally known method can be used to treat the fine silica powder described above with an ethylenically unsaturated amino compound. For example, a method in which the ethylenically unsaturated amino compound is dissolved in a suitable solvent and fine silica powder is added and mixed; a method in which an ethylenically unsaturated amine solution in which fine silica powder is suspended is spray-dried; Various methods are used, including methods of grafting on the body surface. The preferable amount of ethylenically unsaturated amino compound to be treated with silica fine powder is 0.01 to 20% by weight.
It is. In addition to the ethylenically unsaturated amino compound described above, it is also preferable to use a silane coupling agent or other organosilicon compound in combination. Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl phenyldichlorosilane, benzyldimethylchlorosilane. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and having 2 to 12 siloxane units per molecule. Examples include dimethylpolysiloxane, which contains one Si-bonded hydroxyl group in each unit located at the end. These can be used alone or in a mixture of two or more. In addition, the applied amount of these treated silica fine powders is effective when it is 0.01 to 20% by weight, particularly preferably 0.1 to 3% by weight, based on the weight of the developer.
Shows correct charging properties with excellent stability when added. Regarding the preferred form of addition, it is preferable that 0.01 to 3% by weight of treated silica fine powder based on the weight of the developer be attached to the surface of the toner particles. In the present invention, the toner mixed with silica fine powder treated with a specific ethylenically unsaturated amino compound as described above is mixed with a magnetic carrier as shown in the examples below, and developed into a two-component system. It can also be used as a two-component developing method using a magnetic brush method. In the developer of the present invention constructed in this way, since the developer used contains the above-mentioned fine silica powder as a charge control component, it is not applied to the developer layer supported on the developer carrier. The amount of frictional electrification caused by the developer is made uniform, and only the excess charge that is likely to occur during durability at ultra-low temperature and low humidity is leaked through the fine silica powder to an appropriate saturation value, resulting in the formation of a stable developer layer. At high temperatures and high humidity, it is easy to maintain the amount of triboelectric charge required to provide a stable coating, and a decrease in concentration is likely to occur. Another feature is that it is easy to form a stable developer layer, so there is no development fog or toner scattering around the edges of the latent image, which has not been fully understood in the past, and high image density can be achieved. and the reproducibility of halftones is good. The basic structure and features of the present invention have been described above with reference to the developing device shown in FIG. 1, and the developer and developing method of the present invention will be further explained based on Examples 2 to 5 below. Parts in the following examples are parts by weight. Example 2 Styrene-butadiene copolymer (70:30) 100 parts Carbon black 3 parts Nigrosine 4 parts The above materials were thoroughly mixed in a blender and then heated to 150°C.
The mixture was kneaded using two heated rolls. After allowing the mixture to cool naturally, it is coarsely pulverized using a cutter mill, then pulverized using a pulverizer using a jet air flow, and further classified using an air classifier to obtain fine powder (toner) with a particle size of 5 to 20μ. Obtained. Next, silica fine powder Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) was placed in a closed Henschel mixer heated to 70°C, and methyldiallylamine diluted with toluene was added dropwise to give a treatment amount of 5.0% by weight based on the silica. while stirring at high speed. The obtained fine powder was dried at 120°C. 0.6% by weight of the treated silica fine powder and the above toner
99.4% by weight mixed in a Henschel mixer
To 10 parts, 100 parts of iron powder carrier having a particle size of 100 to 200 μm was added and mixed to obtain a two-component developer. The toner having the treated silica fine powder on the surface of the toner particles had a high positive triboelectric chargeability of +20.0 μc/g. Next, a negative electrostatic image is formed on the OPC photoconductor using a conventionally known electrophotographic method, and this is powder developed using the magnetic brush method using the above developer to create a toner image, which is transferred to plain paper. The film was then heat-fixed. The resulting transferred image had a sufficiently high density of 1.38, had no fogging, and had no toner scattering around the image, resulting in a good image with high resolution. Transfer images were continuously created using the above developer and their durability was examined, but the transferred images after 100,000 sheets were compared with the initial images and were found to have no color at all. In addition, when the environmental conditions were set to 35℃ and 80% RH, the screen surface area was 1.30, a value that was almost unchanged from normal temperature and humidity, and clear images were obtained without fogging or scattering, and the durability was 100,000 sheets. There was almost no change until then. Next, when a transferred image was obtained at a low temperature and low humidity of 10° C. and 10% RH, the image density was as high as 1.40, and solid black was developed and transferred extremely smoothly, resulting in an excellent image with no scattering or voids. When a durability test was conducted under these environmental conditions, the density fluctuation was ±0.2 up to 100,000 copies, which was sufficient for practical use, even though copies were made continuously and intermittently. An image was obtained after storing this developer in an environment of 35°C and 90% RH for one month, but the image density was 1.28.
The image quality was also good, almost unchanged from before the storage. Comparative Example 1 A developer was obtained in the same manner as in Example 2 except that Aerosil 200 was not treated with methyldiallylamine, and developed and
Although transfer was performed, only an inverted image was obtained, and the triboelectric charge amount was -3.0 μc/g, indicating negative chargeability. Example 3 The same procedure as in Example 2 was carried out except that 2-methylaminoethyl acrylate was used instead of methyldiallylamine. The image density was as high as 1.31, there was no fogging, scattering, or transfer omission, and the resolution was high. An image faithful to the statue was obtained. Even in a durability test of 100,000 sheets, images with no color contrast were obtained compared to the initial images. This developer
Images were obtained after being stored in an environment of 35°C and 90% RH for one month, and the image density was 1.25, which was almost unchanged from before storage and the image quality was good. Also 35℃, 85%RH
When printing images under the following conditions, very good images were obtained from the beginning, and the images after 100,000 prints were also good. The transfer efficiency was also excellent at 90%. Example 4 The same procedure as in Example 2 was carried out except that diethylaminopropyl methacrylate was used in place of methyldiallylamine at a concentration of 5% by weight based on the silica. It exhibited excellent image quality and durability in both high temperature, high humidity, and room temperature and humidity environments. Example 5 The same procedure as in Example 2 was carried out except that 2-methyl-N-vinylimidazole was used in place of methyldiallylamine in an amount of 3% by weight based on the silica. The agent showed excellent image quality and durability in each environment: low temperature and low humidity, high temperature and high humidity, and room temperature and normal humidity.
第１図は本発明に適用できる現像工程の一実施
形態を示す断面図である。
１……静電像保持体、２……非磁性円筒（現像
剤担持体）、５……ドクターブレード、６……絶
縁性磁性現像剤。
FIG. 1 is a sectional view showing an embodiment of a developing process applicable to the present invention. 1... Electrostatic image holder, 2... Non-magnetic cylinder (developer carrier), 5... Doctor blade, 6... Insulating magnetic developer.
Claims (1)
ー、及びシリカ微粉体を有する静電像現像用現像
剤において、 該シリカ微粉体は、ケイ素ハロゲン化物の蒸気
相酸化により生成されたシリカ微粉体を下記一般
式(1)，(2)，(3)，(4)又は(5) 一般式(1) 〔式中R1は水素原子又はメチル基を示し、R2及
びR3は夫々水素原子、低級アルキル基、２−ヒ
ドロキシエチル、フエニル、ベンジル又はフエノ
キシエチル基を示し、ｐは１、２又は３を示し、
ｑは０又は１を示し、ｒは１を示し、ｐ＋ｑ＋ｒ
＝３を示す。〕 一般式(2) 〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、Ｙは−（CH2）ｍ−又は
【式】を示し、ｍは１、２又は３ を示す。〕 一般式(3) 〔式中R4、R5、R6は夫々水素原子又は低級アル
キル基を示し、ｍは１、２又は３を示す。〕 一般式(4) 〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示す。〕 一般式(5) 〔式中R7は水素原子又は低級アルキル基を示し、
ｎは０、１、２又は３を示す。〕 で示されるエチレン性不飽和アミノ化合物の少な
くとも１種以上で処理されたシリカ微粉体である
ことを特徴とする静電像現像用現像剤。 ２ 静電像を保持する静電像保持体と、現像剤を
表面に担持し現像部へ搬送するための現像剤担持
体とを現像部において一定の間〓を設けて配置
し、ケイ素ハロゲン化物の蒸気相酸化により生成
されたシリカ微粉体が下記一般式(1)，(2)，(3)，(4)
又は(5) 一般式(1) 〔式中R1は水素原子又はメチル基を示し、R2及
びR3は夫々水素原子、低級アルキル基、２−ヒ
ドロキシエチル、フエニル、ベンジル又はフエノ
キシエチル基を示し、ｐは１、２又は３を示し、
ｑは０又は１を示し、ｒは１を示し、ｐ＋ｑ＋ｒ
＝３を示す。〕 一般式(2) 〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示し、Ｙは−（CH2）ｍ−又は
【式】を示し、ｍは１、２又は３ を示す。〕 一般式(3) 〔式中R4、R5、R6は夫々水素原子又は低級アル
キル基を示し、ｍは１、２又は３を示す。〕 一般式(4) 〔式中R4、R5及びR6は夫々水素原子又は低級ア
ルキル基を示す。〕 一般式(5) 〔式中R7は水素原子又は低級アルキル基を示し、
及びｎは０、１、２又は３を示す。〕 で示されるエチレン性不飽和アミノ化合物の少な
くとも１種以上で処理されたシリカ微粉体及びト
ナーを含有する現像剤を現像剤担持体に担持さ
せ、該トナーを現像部において前記静電像保持体
に転移させて静電像を現像することを特徴とする
現像方法。[Scope of Claims] 1. A toner having at least a binder resin and a colorant, and a developer for electrostatic image development having fine silica powder, wherein the fine silica powder is produced by vapor phase oxidation of silicon halide. Silica fine powder is expressed by the following general formula (1), (2), (3), (4) or (5) general formula (1) [In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each represent a hydrogen atom, a lower alkyl group, 2-hydroxyethyl, phenyl, benzyl, or a phenoxyethyl group, and p represents 1, 2, or 3. show,
q represents 0 or 1, r represents 1, p+q+r
=3. ] General formula (2) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, Y represents -(CH 2 )m- or [Formula], and m represents 1, 2 or 3. ] General formula (3) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and m represents 1, 2 or 3. ] General formula (4) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group. ] General formula (5) [In the formula, R 7 represents a hydrogen atom or a lower alkyl group,
n represents 0, 1, 2 or 3. ] A developer for electrostatic image development, comprising fine silica powder treated with at least one ethylenically unsaturated amino compound represented by the following. 2. An electrostatic image holder that holds an electrostatic image and a developer carrier that carries developer on its surface and transports it to the developing section are arranged with a certain distance between them in the developing section, and silicon halide The silica fine powder produced by vapor phase oxidation has the following general formulas (1), (2), (3), (4).
or (5) general formula (1) [In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each represent a hydrogen atom, a lower alkyl group, 2-hydroxyethyl, phenyl, benzyl, or a phenoxyethyl group, and p represents 1, 2, or 3. show,
q represents 0 or 1, r represents 1, p+q+r
=3. ] General formula (2) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, Y represents -(CH 2 )m- or [Formula], and m represents 1, 2 or 3. ] General formula (3) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group, and m represents 1, 2 or 3. ] General formula (4) [In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom or a lower alkyl group. ] General formula (5) [In the formula, R 7 represents a hydrogen atom or a lower alkyl group,
and n represents 0, 1, 2 or 3. ] A developer containing a toner and a silica fine powder treated with at least one ethylenically unsaturated amino compound represented by the above is supported on a developer carrier, and the toner is transferred to the electrostatic image carrier in a developing section. A developing method characterized by developing an electrostatic image by transferring it to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066575A JPS59192263A (en) | 1983-04-15 | 1983-04-15 | Development method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066575A JPS59192263A (en) | 1983-04-15 | 1983-04-15 | Development method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59192263A JPS59192263A (en) | 1984-10-31 |
| JPH0473579B2 true JPH0473579B2 (en) | 1992-11-24 |
Family
ID=13319885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58066575A Granted JPS59192263A (en) | 1983-04-15 | 1983-04-15 | Development method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59192263A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160151A (en) * | 1983-03-04 | 1984-09-10 | Canon Inc | Developer |
-
1983
- 1983-04-15 JP JP58066575A patent/JPS59192263A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160151A (en) * | 1983-03-04 | 1984-09-10 | Canon Inc | Developer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59192263A (en) | 1984-10-31 |
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