JPH02287459A - Negatively chargeable magnetic developer - Google Patents
Negatively chargeable magnetic developerInfo
- Publication number
- JPH02287459A JPH02287459A JP1109521A JP10952189A JPH02287459A JP H02287459 A JPH02287459 A JP H02287459A JP 1109521 A JP1109521 A JP 1109521A JP 10952189 A JP10952189 A JP 10952189A JP H02287459 A JPH02287459 A JP H02287459A
- Authority
- JP
- Japan
- Prior art keywords
- developer
- powder
- silicic acid
- fine powder
- toner
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920002545 silicone oil Polymers 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 239000002966 varnish Substances 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 abstract description 78
- 239000002245 particle Substances 0.000 abstract description 22
- 241000519995 Stachys sylvatica Species 0.000 abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 52
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 51
- 238000000034 method Methods 0.000 description 43
- 238000012546 transfer Methods 0.000 description 22
- 238000011161 development Methods 0.000 description 21
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- -1 metal halide compound Chemical class 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 13
- 108091008695 photoreceptors Proteins 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 230000005684 electric field Effects 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000007580 dry-mixing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920006249 styrenic copolymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- 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
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-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
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- AHEAPQJDMSHYKL-UHFFFAOYSA-N 1H-indene 5-phenylpenta-2,4-dienenitrile Chemical compound C1=CC=C2CC=CC2=C1.N#CC=CC=CC1=CC=CC=C1 AHEAPQJDMSHYKL-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-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
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GBTKXRHCGMUSDA-UHFFFAOYSA-N [SiH3]OC(=O)CCC=C Chemical compound [SiH3]OC(=O)CCC=C GBTKXRHCGMUSDA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011324 bead Substances 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
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-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
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000006249 magnetic particle Substances 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
- 150000002688 maleic acid derivatives Chemical class 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
- 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
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZARXZEARBRXKMO-UHFFFAOYSA-N n,n-bis(ethenyl)aniline Chemical compound C=CN(C=C)C1=CC=CC=C1 ZARXZEARBRXKMO-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 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
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer 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
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 229910052905 tridymite Inorganic materials 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は電子写真、静電記録、静電印刷、磁気記録等に
於ける潜像を現像するための現像剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a developer for developing latent images in electrophotography, electrostatic recording, electrostatic printing, magnetic recording, and the like.
さらに詳しくは直接または間接電子写真現像方法に於い
て均一に負電荷に帯電し、正の静電荷像を可視化、また
は負の静電荷像を反転現像により可視化して、高品質な
画像を与える電子写真用現像剤に関する。More specifically, in direct or indirect electrophotographic development methods, electrons are uniformly charged to a negative charge to visualize a positive electrostatic charge image, or to visualize a negative electrostatic charge image by reversal development to produce high-quality images. It relates to a photographic developer.
従来電子写真法としては米国特許第２，２９７，６９１
号明細書等、多数の方法が知られているが、一般には光
導電性物質を利用し、種々の手段により感光体上に電気
的潜像を形成し、次いで該潜像を現像粉（以下トナーと
称す）を用いて現像し、必要に応じて紙等の転写材にト
ナー画像を転写した後、加熱、圧力あるいは溶剤蒸気な
どにより定着し複写物を得るものである。またトナー画
像を転写する工程を有する場合には、通常、感光体上の
残余のトナーを除去するための工程が設けられる。As a conventional electrophotographic method, U.S. Patent No. 2,297,691
Although a number of methods are known, such as those described in the specification of No. After the toner image is transferred to a transfer material such as paper as necessary, it is fixed by heat, pressure, solvent vapor, etc. to obtain a copy. Furthermore, when a process for transferring a toner image is included, a process for removing residual toner on the photoreceptor is usually provided.
電気的潜像をトナーを用いて可視化する現像方法は、例
えば米国特許第２，８７４，０６３号明細書に記載され
ている磁気ブラシ法、同２，６１８，５５２号明細書に
記載されているカスケード現像法及び同２．２２１，７
７６号明細書に記載されている粉末雲法、米国特許第３
，９０９，２５８号明細書に記載されている導電性の磁
性トナーを用いる方法などが知られている。Development methods for visualizing electrical latent images using toner include, for example, the magnetic brush method described in U.S. Pat. No. 2,874,063, and the magnetic brush method described in U.S. Pat. No. 2,618,552. Cascade development method and 2.221, 7
Powder cloud method described in US Pat. No. 76, U.S. Pat.
, 909,258, which uses conductive magnetic toner, is known.
これらの現像法に適用するトナーとしては、従来、天然
あるいは合成樹脂中に染料、顔料を分散させた微粉末が
使用されている。例えば、ポリスチレンなどの結着樹脂
中に着色剤を分散させたものをＩ〜３０μ程度に微粉砕
した粒子がトナーとして用いられている。磁性トナーと
してはマグネタイトなどの磁性体粒子を含有せしめたも
のが用いられている。いわゆる二成分現像剤を用いる方
式の場合には、トナーは通常ガラスピーズ、鉄粉などの
キャリアー粒子と混合されて用いられる。As toners applied to these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about I to 30 μm are used as a toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder.
また、最近、電子写真システムの用途が複写像を得る事
以外に、コンピューターの出力に用いられるプリンター
等に用いられるようになった。プリンタ用途の場合、発
光体（半導体レーザー等）が、画像信号に従ってオン−
オフ（ＯＮ−ＯＦＦ）され、その光が感光体上に投影さ
れる。この際、通常、印字率（１頁当りの印字面積の割
合）は３割以下であり、文字部分に対して露光を行う方
式（反転現像）が発光体寿命の点で優位である。Furthermore, recently, electrophotographic systems have been used not only for obtaining copied images but also for printers used for computer output. In the case of printer applications, a light emitter (semiconductor laser, etc.) is turned on according to an image signal.
The light is turned off (ON-OFF) and projected onto the photoreceptor. In this case, the printing rate (ratio of printing area per page) is usually 30% or less, and the method of exposing the character portion (reversal development) is advantageous in terms of the life of the light emitter.
また、反転現像は、同一原稿より、ポジ画像およびネガ
画像を出力する様な装置（例えば、マイクロフィルム出
力装置）に用いられ、さらに同一装置内で、２色以上の
現像を行う為に正規現像および反転現像を組み合わせて
いる装置等に使用されるようになった。In addition, reversal development is used in devices that output positive and negative images from the same document (for example, microfilm output devices), and regular development is used to develop two or more colors in the same device. It has come to be used in devices that combine reversal development and reversal development.
しかしながら、反転現像には次の様な問題点がある。通
常の現像（以下、正現像）における転写電界は、−次帯
電と同極性であり、画像担体（以下紙等）通過後、転写
電界が感光体上に印加されてもその影響は、イレース露
光（第１図中６）で消去される。However, reversal development has the following problems. The transfer electric field in normal development (hereinafter referred to as "normal development") has the same polarity as the -order charge, and even if the transfer electric field is applied onto the photoreceptor after passing through the image carrier (hereinafter referred to as paper, etc.), its influence will not be affected by erase exposure. It is erased at (6 in FIG. 1).
一方、反転現像における転写電界は、−次帯電と反対極
性であり、紙等通過後も、転写電界を印加すると感光体
上に反対極性の帯電が起り、イレース露光では消去でき
ず、画像に濃淡となってあられれる。これは「紙跡」と
称される現象である。On the other hand, the transfer electric field in reversal development has the opposite polarity to the negative charge, and even after passing through the paper etc., when the transfer electric field is applied, a charge of the opposite polarity occurs on the photoreceptor, which cannot be erased by erase exposure, and the density of the image changes. It will come to you. This is a phenomenon called "paper trail."
紙跡対策としては、特開昭６０−２５６１７３号公報に
見られる様に紙等が通過した後、転写電流を下げる等の
手段があるが、この方法は、種々の部品（マイクロスイ
ッチ等）が必要であり、装置が煩雑化するとともに装置
原価が高（なる。また、転写電界を下げて感光体上に反
対極性の帯電が起らない範囲にする手段が考えられる。As a countermeasure against paper traces, there are measures such as lowering the transfer current after the paper has passed, as shown in Japanese Patent Application Laid-Open No. 60-256173. This makes the apparatus complicated and increases the cost of the apparatus.Also, it is conceivable to reduce the transfer electric field to a range in which charging of the opposite polarity does not occur on the photoreceptor.
しかしながら、この方法では転写効率を下げる為、転写
不良に伴なう画質低下が起る。反転現像法の他の併置と
しては、感光体と紙等とが反対極性に帯電されている為
、強電界により帯電させた場合に感光体と紙等とが、静
電的に吸着し、転写工程終了後も分離せず、次工程（ク
リーニング工程等）にまで、紙等が入り込み紙詰り等を
引起す。これは、「巻付」と称される現象である。巻付
対策としては、特開昭５６−６０４７０号公報に見られ
る様に感光体と紙等との密着を防ぐ手段がある。しかし
ながら、反転現像に於いて、この方法は必ずしも有効で
はない。すなわち、これは、反転現像の転写工程の分離
時における密着が、正現像方式に較べ強い為と考えられ
る。別の方法としては米国特許３，３５７，４００明細
書等に見られる様に、分離の補助手段として、分離帯電
またはベルト分離を具備する装置がある。これにより、
巻付現象に対しては効果があるものの、紙跡現象に対し
ては、効果はない。これは、分離帯電は、転写帯電に較
べて小さく、感光体上の電位にまで影響しない事による
。However, this method lowers the transfer efficiency, resulting in a reduction in image quality due to poor transfer. Another example of juxtaposition in the reversal development method is that the photoconductor and paper, etc. are charged with opposite polarities, so when charged with a strong electric field, the photoconductor and paper, etc. electrostatically attract each other, causing transfer. Even after the process is completed, the paper does not separate, and paper etc. enters the next process (cleaning process, etc.), causing paper jams. This is a phenomenon called "wrapping". As a countermeasure against wrapping, there is a means to prevent the photoreceptor from coming into close contact with paper, etc., as seen in Japanese Patent Laid-Open No. 56-60470. However, this method is not necessarily effective in reversal development. That is, this is considered to be because the close contact during separation in the transfer process of reversal development is stronger than that of normal development. Another method, as seen in U.S. Pat. No. 3,357,400, is an apparatus that includes separate charging or belt separation as an auxiliary means for separation. This results in
Although it is effective against the wrapping phenomenon, it is not effective against the paper trail phenomenon. This is because the separation charge is smaller than the transfer charge and does not affect the potential on the photoreceptor.
別の手段としては、転写電界を下げて静電吸着力を下げ
る手段があるが、この方法は、前述のように転写不良に
伴う画質低下が起こりやすい。また、転写電界を下げる
と、転写効率の低下が起こり、転写に不利なハガキ、Ｏ
ＨＰ用フィルム等の多様なニーズに答えられない。また
転写電界を下げると、画像の輪郭部分、線画部分の如き
、現像剤が集中しやすい部分（エッチ現像部分）で、転
写不良の一部である「転写なか抜け」が起る。これは、
エッチ現像部は通常部に較べ現像剤が多くのり、現像剤
凝集が起りやすく、転写電界に対する応答が下がる為と
考えられ、そのため、潜像に忠実である高品位な画像を
得るのが困難になるという問題点を有している。Another method is to reduce the electrostatic adsorption force by lowering the transfer electric field, but this method is likely to cause image quality deterioration due to poor transfer as described above. In addition, lowering the transfer electric field results in a decrease in transfer efficiency, which is detrimental to the transfer of postcards and O.
Unable to meet diverse needs for HP films, etc. Furthermore, when the transfer electric field is lowered, "transfer voids", which are part of transfer defects, occur in areas where developer tends to concentrate (etch development areas), such as image outlines and line drawing areas. this is,
This is thought to be due to the fact that more developer is deposited in the etch development area than in the normal area, and developer aggregation is more likely to occur, reducing the response to the transfer electric field.As a result, it is difficult to obtain high-quality images that are faithful to the latent image. It has the problem of becoming.
また乾式トナーを使用する方法において良好な画質の可
視画像を形成するためにはトナーが高い流動性を有し、
かつ均一な帯電性を有することが必要であり、そのため
に従来より、シリカ微粉体をトナーに含有させることが
行われている。しかしながらシリカ微粉体はそのままで
は親水性であるためにシリカ微粉体を含有するトナーは
空気中の湿気により凝集を生じて流動性が低下したり、
甚だしい場合にはシリカ微粉末の吸湿によりトナーの帯
電性能を低下させてしまう。In addition, in a method using dry toner, in order to form a visible image of good quality, the toner must have high fluidity.
It is also necessary to have uniform charging properties, and for this purpose, it has been conventionally practiced to include fine silica powder in the toner. However, since fine silica powder is hydrophilic as it is, toner containing fine silica powder may aggregate due to moisture in the air, resulting in decreased fluidity.
In severe cases, the silica fine powder absorbs moisture, which deteriorates the charging performance of the toner.
従ってこの欠点を克服する為に、ケイ酸微粉体の表面処
理による疎水化が提案されており、例えば特公昭５４−
１６２１９号公報、特開昭５５−１２００４１号公報、
特開昭５８−１８６７５１号公報等がある。これらに於
いて、種々のカップリング剤で、ケイ酸微粉体を表面処
理し、得られた疎水性ケイ酸微粉体を含有した現像剤を
提案している。また、更にケイ酸微粉体の一層の疎水化
と帯電性の制御を目的として、特開昭５８−６０７５４
号公報、特開昭５９−２０１０６３号公報に於いて、種
々のシリコーンオイルまたは、変性シリコーンオイルを
用いて表面処理を行ったケイ酸微粉体を添加した現像剤
を提案し、更に、特開昭５９−４５４５７号公報に於い
て、シランカップリング剤で処理され、かつシリコーン
オイルで処理したケイ酸微粉体を添加した現像剤を提案
している。Therefore, in order to overcome this drawback, it has been proposed to make silicic acid fine powder hydrophobic by surface treatment.
No. 16219, Japanese Patent Application Laid-open No. 120041/1983,
There are Japanese Patent Laid-Open No. 58-186751, etc. In these studies, developers have proposed a developer containing hydrophobic silicic acid fine powder obtained by surface-treating silicic acid fine powder with various coupling agents. In addition, for the purpose of further hydrophobicizing silicic acid fine powder and controlling the chargeability, Japanese Patent Application Laid-Open No. 58-60754
In JP-A No. 59-201063, a developer to which fine silicic acid powder was surface-treated using various silicone oils or modified silicone oils was proposed, and JP-A-59-201063 also proposed No. 59-45457 proposes a developer to which fine silicic acid powder treated with a silane coupling agent and silicone oil is added.
しかしながら、シリコーンオイルあるいはシリコ−ンオ
イルの様な高分子物質を処理剤として表面処理したケイ
酸微粉体を従来の一般的な乾式混合機にて、トナー表面
近傍に含有させた現像剤を用いて画出しを行った場合、
特に初期において画像部に白ポチが発生しやすいことが
判明した。However, fine silicic acid powder whose surface has been treated with silicone oil or a polymeric substance such as silicone oil is used in a conventional general dry mixer to form an image using a developer contained near the toner surface. If you make a withdrawal,
It has been found that white spots are likely to occur in the image area, especially in the early stages.
該白ポチの発生原因は分析より明らかにシリカダマが現
像されたことに起因する。Analysis clearly shows that the white spots are caused by the development of silica clumps.
通常表面処理されたケイ酸微粉体は１次粒子径としては
ｌＯ〜２０μｍ程度であるが、トナーに乾式混合される
前の該ケイ酸微粉体の状態は１次粒子の凝集体（約５〜
１５０μ）や凝集体同志が更に凝集したダマ（約３０〜
３００μ）として存在する。Normally, the surface-treated fine silicic acid powder has a primary particle diameter of about 10 to 20 μm, but the state of the fine silicic acid powder before being dry mixed into the toner is an aggregate of primary particles (about 5 to 20 μm).
150μ) and clumps (approximately 30~
300μ).
また、シリカダマはトナー中に該シリカが０．６ｗｔ％
以上添加される場合に著しくなる。In addition, silica clumps contain 0.6 wt% of silica in the toner.
It becomes noticeable when more than 10% is added.
該ケイ酸微粉体は、トナーと共に乾式混合によって１次
粒子の凝集体及び凝集体の集合したダマを、はぐしなが
ら、現像剤表面近傍に強く付着しなければならない。し
かしながら、乾式混合の一般的方法としては、単なる添
加ないしヘンシェルミキサーやパーペンマイヤー等の混
合機による撹拌羽根等による周速数ｍ〜４０ ｍ ／
ｓ ｅ ｃ程度の混合が一般的である。The silicic acid fine powder must strongly adhere to the vicinity of the developer surface while removing aggregates of primary particles and lumps of aggregates by dry mixing with the toner. However, as a general method of dry mixing, simple addition or a mixing machine such as a Henschel mixer or Papenmeyer using a stirring blade or the like is used at a circumferential speed of several m to 40 m/min.
Mixing of about sec is common.
しかしながら、この方法では、中央部の回転軸部近傍と
撹拌羽根の先端とでは、周速の異なりが太き（また、回
転軸部には、羽根状のものがないため、撹拌力、分散力
が部分的に異なり、不均一な分散状態になり易い。従っ
て、この様な乾式混合では該ケイ酸微粉体の１次粒子の
凝集体や凝集体の集合したダマが、はぐれにり＜、その
ままの状態で現像剤中に残り易く、画像白ポチの原因と
なる。However, with this method, there is a large difference in circumferential speed between the vicinity of the rotating shaft in the center and the tip of the stirring blade (also, since there is no blade-shaped part in the rotating shaft, the stirring force and dispersion force Therefore, in such dry mixing, aggregates of the primary particles of the silicic acid fine powder and clumps of aggregates may become separated, resulting in a non-uniform dispersion state. It tends to remain in the developer in this state, causing white spots on the image.
またこれらのダマのほぐすほどのシェアを一般的混合機
で与えるとすでに分散しているケイ酸微粉体がトナー表
面に打ちこまれて固定され流動化剤としての用をなさな
（なる。Furthermore, if a general mixer is used to apply enough shear to loosen these clumps, the already dispersed silicic acid fine powder will be driven into the toner surface and fixed, rendering it useless as a fluidizing agent.
特にシリコーンオイルあるいはシリコーンオイルといっ
た高分子物質で表面処理されたケイ酸微粉体は強固に凝
集する傾向があり画像白ポチの発生傾向が顕著となる。In particular, silicic acid fine powder whose surface has been treated with silicone oil or a polymeric substance such as silicone oil has a tendency to strongly agglomerate, resulting in a marked tendency for white spots to occur in the image.
また、特開昭６０−１０７０３６号公報には嵩密度３０
ｍ ｇ ／ ｃ ｒｄ以下のシリカ微粉体をトナーに添
加する提案がなされているが、本発明者らが検討を行っ
た結果、反転現像における転写性の向上と画像白ポチの
防止の両立は困難であった。In addition, Japanese Patent Application Laid-Open No. 60-107036 discloses that the bulk density is 30.
A proposal has been made to add silica fine powder of m g/c rd or less to toner, but as a result of studies conducted by the present inventors, it has been found that it is difficult to simultaneously improve transferability in reversal development and prevent white spots on images. Met.
本発明の目的は上述の如き問題点を解決した負帯電性現
像剤の提供にある。An object of the present invention is to provide a negatively chargeable developer which solves the above-mentioned problems.
さらに本発明の目的は画出しの際にシリカダマによる画
像白ポチのない高品位な画像の得られる負帯電性現像剤
の提供にある。さらに本発明の目的は耐衝撃性に優れて
おり、凝集をおこさず流動性に優れて耐久性がある負帯
電性現像剤の提供にある。さらに本発明の目的は長期間
の保存でも初期の特性を維持する保存安定性に優れた負
帯電性現像剤の提供にある。A further object of the present invention is to provide a negatively chargeable developer capable of producing high-quality images without white spots due to silica lumps during image formation. A further object of the present invention is to provide a negatively chargeable developer which has excellent impact resistance, does not cause aggregation, has excellent fluidity, and is durable. A further object of the present invention is to provide a negatively chargeable developer that maintains its initial characteristics even during long-term storage and has excellent storage stability.
本発明は嵩密度が２５ｇ／ ｉ！以下でかつシリコーン
オイルで処理された疎水性乾式ケイ酸微粉体を含有する
ことを特徴とする負帯電性現像剤に関する。The bulk density of the present invention is 25 g/i! The present invention relates to a negatively chargeable developer characterized by containing hydrophobic dry silicic acid fine powder treated with silicone oil as described below.
また本発明に係るシリカは有機ケイ素化合物で処理され
た後シリコーンオイルで処理されていることが好ましい
。Furthermore, the silica according to the present invention is preferably treated with an organosilicon compound and then treated with silicone oil.
本発明者らは、鋭意研究した結果、シランカップリング
剤または及びシリコーンオイル処理された乾式法合成ケ
イ酸微粉体の１次粒子の凝集体及び凝集体同志が更に凝
集したダマの減少によって、該ケイ酸微粉体の嵩密度が
低下することを見出し、更に、嵩密度が２５ｇ／ｌ以下
の該ケイ酸微粉体を従来の一般的な乾式混合機にて、ト
ナー表面近傍に付与させたトナー現像剤では、現像剤中
の該ケイ酸微粉体の１次粒子の凝集体及び凝集体同志が
更に凝集したダマが見られず、しかも、該ケイ酸微粉体
が、トナー表面に均一に強く分散付着する事が見出した
。その結果、該トナーでは画像部にシリカダマによる白
ポチが発生することはない。As a result of intensive research, the present inventors have found that by reducing the aggregates of primary particles of dry-synthesized silicic acid fine powder treated with a silane coupling agent or silicone oil, and by reducing the lumps formed by further agglomerating the aggregates, It has been discovered that the bulk density of fine silicic acid powder decreases, and furthermore, the fine silicic acid powder having a bulk density of 25 g/l or less is applied to the vicinity of the toner surface using a conventional general dry mixer. In the developer, there were no aggregates of primary particles of the silicic acid fine powder in the developer, and no lumps formed by further agglomeration of the aggregates, and the silicic acid fine powder was uniformly and strongly dispersed and adhered to the toner surface. I found something to do. As a result, with this toner, white spots due to silica clumps do not occur in the image area.
本発明中シリコーンオイル処理された乾式合成法ケイ酸
微粉体の嵩密度とは、次の様にして求められる値である
。即ち、内径２．５２ｃｍ、高さ５，００ｃｍの容量１
００ｃｒｒｆの円筒容器を水平面上に静置し、容器の開
口部の約３ｃｍ上方から静かに試料を落して１５〜３０
ｓｅｃで容器内に充填させ、開口部の水平面より高く盛
り上がった過剰分を除去し、容器内の試料重量値から該
嵩密度を算出した値である。In the present invention, the bulk density of the dry-synthesized silicic acid fine powder treated with silicone oil is a value determined as follows. That is, a capacity 1 with an inner diameter of 2.52 cm and a height of 5,00 cm.
A cylindrical container of 00 crrf was placed on a horizontal surface, and a sample was gently dropped from about 3 cm above the opening of the container.
The bulk density is calculated from the weight of the sample in the container after filling the container with the sample in seconds, removing the excess that rose above the horizontal surface of the opening.
本発明中、嵩密度が２５ｇ／ ｉ！以下である及びシリ
コーンオイル処理された乾式合成ケイ酸微粉体を得る方
法としては、例えば、処理された該乾式法合成ケイ酸微
粉体を、衝撃式超微粉砕機コスモマイザ−（株式会社奈
良機械製作所製）で、該ケイ酸微粉体の１次粒子の凝集
体及び凝集体の集合したダマを解砕する方法がある。In the present invention, the bulk density is 25g/i! As a method for obtaining dry synthetic silicic acid fine powder treated with silicone oil as described below, for example, the treated dry synthetic silicic acid fine powder is passed through an impact type ultrafine grinder Costomizer (Nara Kikai Seisakusho Co., Ltd.). There is a method of crushing aggregates of primary particles of the silicic acid fine powder and clumps of aggregates.
本発明のシリコーンオイルで表面処理した乾式ケイ酸微
粉体の嵩密度とコスモマイザーでの解砕時間との関係の
一例を第１図に示す。An example of the relationship between the bulk density of the dry silicic acid fine powder surface-treated with the silicone oil of the present invention and the crushing time in a costomizer is shown in FIG.
また、複写画像等の高画質化の達成を目的として従来の
トナーよりも体積平均粒径が小さく、特殊な粒度分布を
有するトナーを使用する際に流動性改善のために多量の
シリカを添加することがあるが、その場合においても画
像部にシリカダマによる白ポチが発生することはなくま
た流動性改善の効果も大きい。Additionally, when using a toner with a special particle size distribution that has a smaller volume average particle diameter than conventional toners in order to achieve high quality copies, etc., a large amount of silica is added to improve fluidity. However, even in such cases, white spots due to silica lumps do not occur in the image area, and the effect of improving fluidity is significant.
例えば複写画像等の高画質化の達成を目的として５μｍ
以下の粒径を有する磁性トナー粒子が１７〜６０個数％
含有され６．３５〜１０．０８μｍの粒径を有する磁性
トナー粒子が５〜５０個数％含有され、１２．７μｍ以
上の粒径を有するトナー粒子が２．０体積％以下であり
、体積平均粒径が４．５〜９μｍである粒度分布を有す
るトナーに嵩密度が２５ｇ／ ｆ以下である該表面処理
された乾式ケイ酸微粉体を乾式混合することでシリカダ
マによる白ポチを防止するとともに優れた流動性を確保
することが可能である。For example, 5 μm for the purpose of achieving high image quality of copied images, etc.
17 to 60% by number of magnetic toner particles having the following particle size:
5 to 50% by number of magnetic toner particles having a particle size of 6.35 to 10.08 μm are contained, and 2.0% by volume or less of toner particles having a particle size of 12.7 μm or more; By dry mixing the surface-treated dry silicic acid fine powder with a bulk density of 25 g/f or less with a toner having a particle size distribution of 4.5 to 9 μm in diameter, it is possible to prevent white spots caused by silica clumps and to achieve excellent results. It is possible to ensure liquidity.
本発明における現像剤またはトナーの凝集度は下記のご
とく測定算出される。ホソカヮミクロン株式会社製のパ
ウダーテスタと、２０ｏメツシユのふるい、１００メツ
シユのふるい及び６ｏメツシユのふるいを順次重ねた三
段のふるいとを用いて測定した。測定手段としては、約
２ｇのトナーまたは現像剤からなる粉体を三段ふるいの
上段の６０メツシユのふるいの上にのせ、パウダーテス
タに２．５ｖの電圧を印加して、４０秒間三段ふるいを
振動させ、６０メツシユのふるいに残留した粉体重量ａ
ｇと、１００メツシユのふるいに残留した粉体の重Ｊｌ
ｂｇと、２００メツシユのふるいに残留した粉体型ｉｃ
ｇとから下式によって凝集度を算出する。The degree of aggregation of the developer or toner in the present invention is measured and calculated as follows. The measurement was carried out using a powder tester manufactured by Hosokawa Micron Co., Ltd. and a three-tiered sieve in which a 20 mesh sieve, a 100 mesh sieve, and a 6 mesh sieve were sequentially stacked. As a measuring method, approximately 2g of powder made of toner or developer was placed on a 60-mesh sieve on the upper stage of a three-stage sieve, a voltage of 2.5V was applied to the powder tester, and the powder was passed through the three-stage sieve for 40 seconds. The weight of the powder remaining on the 60-mesh sieve is
g, and the weight Jl of the powder remaining on the 100 mesh sieve.
bg and powder type IC remaining on the 200 mesh sieve.
The degree of agglomeration is calculated from g using the following formula.
また、嵩密度が２５ｇ／ Ｉ！以下の該表面処理した乾
式法合成微粉体を含有する現像剤では、現像剤中に、ケ
イ酸微粉体の１次粒子の凝集体や凝集体の集合したダマ
が極めて少ない為に、感光体として有機光導電性感光体
を用いても、該感光体表面を傷つけることが少ない。Also, the bulk density is 25g/I! In the following developer containing the surface-treated dry process synthetic fine powder, there are very few aggregates of primary particles of silicic acid fine powder or lumps of aggregates in the developer, so it cannot be used as a photoreceptor. Even when an organic photoconductive photoreceptor is used, the surface of the photoreceptor is less likely to be damaged.
本発明中、嵩密度が２５ｇ／ｆ以下で宜っシリコーンオ
イル処理された乾式法合成ケイ酸微粉体が使用されるが
、ここで言う乾式法とはケイ素ハロゲン化合物の蒸気相
酸化により生成するケイ酸微粉体の製造方法である。例
えば四塩化ケイ素ガスの酸素水素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。In the present invention, a dry-process synthesized silicic acid fine powder having a bulk density of 25 g/f or less and appropriately treated with silicone oil is used. This is a method for producing acid fine powder. For example, this method utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.
５ｉＣＩ！４＋２Ｈ２＋０２→ＳｉＯ２＋４ＨＣｆ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ってケイ酸と他の金属酸化
物の複合微粉体を得る事も可能であり、それらも包含す
る。5iCI! 4+2H2+02→SiO2+4HCfAlso,
In this manufacturing process, for example, aluminum chloride or
It is also possible to obtain a composite fine powder of silicic acid and other metal oxides by using another metal halide compound such as titanium chloride together with a silicon halide compound, and these are also included.
本発明に用いられるケイ素ハロゲン化合物の蒸気相酸化
により生成された市販のケイ酸微粉体としては、例えば
、以下の様な商品名で市販されているものがある。Commercially available fine silicic acid powders produced by vapor phase oxidation of silicon halogen compounds used in the present invention include, for example, those commercially available under the following trade names.
ＡＥＲＯ３ＩＬ （アエロジル） １３０（日本
アエロジル社） ２００ｘ５０
Ｔ６００
０Ｘ８０
０Ｘ１７０
０Ｋ８４
Ｃａ −０−ＳｉＬ （Ｃａ−０−ジル）Ｍ−５（Ｃ
ＡＢＯＴＯ（キャボット） Ｃｏ、社） ＭＳ−
７Ｓ−５
Ｈ５
Ｗａｃｋｅｒ ＨＤＫ Ｎ ２０
Ｖ−１５（ＷＡＣＫＥＲ−ＣＨＥＭＩＥ （ヴア゛ン
カー Ｎ−２０Ｅケミ）ＧＭＢＨ社’）
Ｔ−３０Ｄ−ＣＦｉｎｅ ＳｉＩ！ｉｃａ
（ファイン シリカ）（ダウコーニングＣｏ、社）
Ｆｒａｎｓｏ ｌ （フランゾル）
（Ｆｒａｎｓｉ ｌ （フランシル）社）また、本発
明中、乾式法合成ケイ酸微粉体は、シリコーンオイルで
表面処理され、これらの処理剤と反応あるいは物理吸着
状態で使用される。またシリコーンオイルで処理する前
に有機ケイ素化合物で処理しであることが好ましい。AERO3IL (Aerosil) 130 (Japan Aerosil Co., Ltd.) 200x50 T600 0X80 0X170 0K84 Ca -0-SiL (Ca-0-SiL) M-5 (C
ABOTO Co., Ltd.) MS-
7S-5 H5 Wacker HDK N 20
V-15 (WACKER-CHEMIE (WACKER-CHEMIE) GMBH')
T-30D-CFine SiI! ica
(Fine Silica) (Dow Corning Co., Ltd.) Fransol (Fransol) In the present invention, the dry method synthesized silicic acid fine powder is surface-treated with silicone oil, and these treatment agents It is used in reaction with or physically adsorbed. It is also preferable to treat with an organosilicon compound before treating with silicone oil.
本発明中、有機ケイ素化合物は例えばヘキサメチルジシ
ラザン、ビニルトリエトキシシラン、ビニルトリメトキ
シシラン、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
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、ジフェニルジェトキシシラン
、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、ｌ、３−ジフェニルテトラメチル
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。In the present invention, organosilicon compounds include, for example, hexamethyldisilazane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl Phenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α
-Chlorethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane,
Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilylacrylate, vinylmethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyljethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, l, 3- Examples include diphenyltetramethyldisiloxane, and dimethylpolysiloxane which has 2 to 12 siloxane units per molecule and contains one Si-bonded hydroxyl group in each unit located at the end.
本発明中で用いられるシリコーンオイルとしては一般に
次の式により示される。The silicone oil used in the present invention is generally represented by the following formula.
Ｒ：炭素数１〜３のアルキル基
Ｒ′： アルキル、ハロゲン変性アルキル、フェニル
、変性フェニル等のシリコンオイ
ル変性基
Ｒ′： 炭素数１〜３のアルキル基又はアルコキシ基
で表わされ、例えば、ジメチルシリコンオイル、アルキ
ル変性シリコンオイル、γ−メチルスチレン変性シリコ
ンオイル、クロルフェニルシリコンオイル、フッ素変性
シリコンオイル等が挙げられるが、上記に限定される物
ではない。R: Alkyl group having 1 to 3 carbon atoms R': Alkyl, halogen-modified alkyl, phenyl, silicone oil modified group such as modified phenyl R': Represented by an alkyl group or alkoxy group having 1 to 3 carbon atoms, for example, Examples include dimethyl silicone oil, alkyl-modified silicone oil, γ-methylstyrene-modified silicone oil, chlorphenyl silicone oil, fluorine-modified silicone oil, but are not limited to the above.
上記シリコンオイルは２５℃に於ける粘度が５〜１００
０センチストークスの物が好ましい。The above silicone oil has a viscosity of 5 to 100 at 25℃.
0 centistoke is preferred.
本発明中、これらの有機ケイ素化合物及びシリコーンオ
イルは１種あるいは２種以上の混合物で用いられる。In the present invention, these organosilicon compounds and silicone oils may be used alone or in a mixture of two or more.
本発明中に於いて、嵩密度が２５ｇ／ｌ以下で宜つこれ
らのシリコーンオイル処理された、乾式法合成ケイ酸微
粉体の適用量は、トナー１００重量部に対して、該ケイ
酸微粉体０．０１〜８重量部、好ましくは０．１〜５重
量部使用するのが良い。In the present invention, the amount of the silicone oil-treated, dry-processed synthetic silicic acid fine powder having a bulk density of 25 g/l or less is as follows: 100 parts by weight of the toner. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight.
本発明の現像剤に使用される結着樹脂としては、オイル
塗布する装置を有する加熱加圧ローラ定着装置を使用す
る場合には、下記トナー用結着樹脂の使用が可能である
。As the binder resin used in the developer of the present invention, the following binder resins for toner can be used when a heating and pressure roller fixing device having an oil coating device is used.
例えば、ポリスチレン、ポリ−ｐ−クロルスチレン、ポ
リビニルトルエンなどのスチレン及びその置換体の単重
合体；スチレン−ｐ−クロルスチレン共重合体、スチレ
ン−ビニルトルエン共重合体、スチレン−ビニルナフタ
リン共重合体、スチレン−アクリル酸エステル共重合体
、スチレン−メタクリル酸エステル共重合体、スチレン
−α−クロルメタクリル酸メチル共重合体、スチレン−
アクリロニトリル共重合体、スチレン−ビニルメチルエ
ーテル共重合体、スチレン−ビニルエチルエーテル共重
合体、スチレン−ビニルメチルケトン共重合体、スチレ
ン−ブタジェン共重合体、スチレンイソプレン共重合体
、スチレン−アクリロニトリル−インデン共重合体など
のスチレン系共重合体；ポリ塩化ビニル、フェノール樹
脂、天然変性フェノール樹脂、天然樹脂変性マレイン酸
樹脂、アクリル樹脂、メタクリル樹脂、ポリ酢酸ビニー
ル、シリコーン樹脂、ポリエステル樹脂、ポリウレタン
、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、キシレ
ン樹脂、ポリビニルブチラール、テルペン樹脂、クマロ
ンインデン樹脂、石油系樹脂などが使用できる。For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers , styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-
Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene isoprene copolymer, styrene-acrylonitrile-indene Styrenic copolymers such as copolymers; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin , furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron indene resin, petroleum resin, etc. can be used.
オイルを殆ど塗布しない加熱加圧ローラ定着方式におい
ては、現像剤像支持体部材上に現像剤像の一部がローラ
に転移するいわゆるオフセット現象、および現像剤像支
持部材に対する現像剤の密着性が重要な問題である。よ
り少ない熱エネルギーで定着する現像剤は、通常保存中
もしくは現像器中でブロッキングもしくはケーキングし
易い性質があるので、同時にこれらの問題も考慮しなけ
ればならない。これらの現象には現像剤中の結着樹脂の
物性が最も大きく関与しているが、本発明者らの研究に
よれば、現像剤中の磁性体の含有量を減らすと、定着時
に現像剤像支持部材に対する現像剤の密着性は良（なる
が、オフセットが起こり易くなり、またブロッキングも
しくはケーキングも生じ易くなる。それゆえ、本発明に
おいてオイルを殆ど塗布しない加熱加圧ローラ定着方式
を用いる時には、結着樹脂の選択がより重要である。好
ましい結着物質としては、架橋されたスチレン系共重合
体もしくは架橋されたポリエステルがある。In the heating and pressure roller fixing method, in which almost no oil is applied, there is a so-called offset phenomenon in which a part of the developer image on the developer image support member is transferred to the roller, and the adhesion of the developer to the developer image support member is reduced. This is an important issue. Developers that require less thermal energy to fix tend to be prone to blocking or caking during storage or in a developing device, so these issues must also be taken into consideration. The physical properties of the binder resin in the developer are most responsible for these phenomena, but according to the research of the present inventors, reducing the content of magnetic material in the developer increases the The adhesion of the developer to the image supporting member is good (although offset is likely to occur, and blocking or caking is also likely to occur. Therefore, in the present invention, when using a heated pressure roller fixing method that does not apply much oil, The selection of the binder resin is more important. Preferred binder materials include crosslinked styrenic copolymers and crosslinked polyesters.
スチレン系共重合体のスチレンモノマーに対するコモノ
マーとしては、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、アクリル酸ド
デシル、アクリル酸オクチル、アクリル酸−２−エチル
ヘキシル、アクリル酸フェニル、メタクリル酸、メタク
リル酸メチル、メタクリル酸エチル、メタクリル酸ブチ
ル、メタクリル酸オクチル、アクリロニトリル、メタク
リニトリル、アクリルアミドなどのような二重結合を有
するモノカルボン酸もしくはその置換体；例えば、マレ
イン酸、マレイン酸ブチル、マレイン酸メチル、マレイ
ン酸ジメチルなどのような二重結合を有するジカルボン
酸及びその置換体；例えば塩化ビニル、酢酸ビニル、安
息香酸ビニルなどのようなビニルエステル類；例えばエ
チレン、プロピレン、ブチレンなどのようなエチレン系
オレフィン類；例えばビニルメチルケトン、ビニルヘキ
シルケトンなどのようなビニルケトン類；例えばビニル
メチルエーテル、ビニルエチルエーテル、ビニルイソブ
チルエーテルなどのようなビニルエーテル類；等のビニ
ル単量体が単独もしくは２つ以上用いられる。Examples of comonomers for the styrene monomer in the styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and methacrylate. acids, monocarboxylic acids having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrinitrile, acrylamide, etc., or substituted products thereof; for example, maleic acid, butyl maleate, Dicarboxylic acids with double bonds and substituted products thereof such as methyl maleate, dimethyl maleate, etc.; vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate, etc.; e.g. ethylene, propylene, butylene, etc. vinyl monomers such as ethylene olefins; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; More than one is used.
ここで架橋剤としては主として２個以上の重合可能な二
重結合を有する化合物が用いられ、例えば、ジビニルベ
ンゼン、ジビニルナフタレンなどのような芳香族ジビニ
ル化合物；例えばエチレングリコールジアクリレート、
エチレングリコールジアクリレート、ｌ、３−ブタジオ
ールジメタクリレートなどのような二重結合を２個有す
るカルボン酸エステル；ジビニルアニリン、ジビニルエ
ーテル、ジビニルスルフィド、ジビニルスルホンなどの
ジビニル化合物；及び３個以上のビニル基を有する化合
物；が単独もしくは混合物として用いられる。As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate,
Carboxylic acid esters having two double bonds such as ethylene glycol diacrylate and l,3-butadiol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and three or more vinyl Compounds having groups can be used alone or as a mixture.
また、加圧定着方式を用いる場合には、圧力定着現像剤
用結着樹脂の使用が可能であり、例えばポリエチレン、
ポリプロピレン、ポリメチレン、ポリウレタンエラスト
マー、エチレン−エチルアクリレート共重合体、エチレ
ン−酢酸ビニル共重合体、アイオノマー樹脂、スチレン
−ブタジェン共重合体、スチレン−イソプレン共重合体
、線状飽和ポリエステル、パラフィンなどがある。In addition, when using a pressure fixing method, it is possible to use a binder resin for pressure fixing developer, such as polyethylene,
Examples include polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ionomer resin, styrene-butadiene copolymer, styrene-isoprene copolymer, linear saturated polyester, and paraffin.
また、本発明の現像剤には負荷電制御剤をトナーに配合
（内添）、またはトナー粒子と混合（外添）して用いる
ことが好ましい。Further, in the developer of the present invention, it is preferable to use a negative charge control agent by blending it into the toner (internal addition) or mixing it with toner particles (external addition).
たとえば、モノアゾ染料の金属錯塩；サリチル酸、アル
キルサリチル酸、ジアルキルサリチル酸またはナフトエ
酸の金属錯塩等の負荷電制御剤が用いられる。For example, a negative charge control agent such as a metal complex salt of a monoazo dye; a metal complex salt of salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, or naphthoic acid is used.
また上述した負荷電制御剤（結着樹脂としての作用を有
しないもの）は、微粒子状として用いることが好ましい
。この場合、この荷電制御剤の個数平均粒径は、具体的
には、４μｍ以下（更には３μｍ以下）が好ましい。Further, it is preferable to use the above-mentioned negative charge control agent (one that does not act as a binder resin) in the form of fine particles. In this case, the number average particle diameter of the charge control agent is specifically preferably 4 μm or less (more preferably 3 μm or less).
現像剤に内添する際、このような負荷電制御剤は、結着
樹脂１００重量部に対して０．１〜２０重量部（更には
０．２〜１０重量部）用いることが好ましい。When internally added to the developer, such a negative charge control agent is preferably used in an amount of 0.1 to 20 parts by weight (more preferably 0.2 to 10 parts by weight) based on 100 parts by weight of the binder resin.
本発明中の現像剤は、必要に応じて種々の添加剤を内添
あるいは外添混合しても良い。Various additives may be added internally or externally to the developer according to the present invention, if necessary.
着色剤としては従来より知られている染料、顔料が使用
可能であり、通常、結着樹脂１００重量部に対して０．
５〜２０重量部使用しても良い。他の添加剤としては、
例えばステアリン酸亜鉛の如き滑剤、あるいは酸化セリ
ウム、炭化ケイ素の如き研磨剤あるいは例えば樹脂微粒
子、酸化アルミニウムの如き流動性付与剤、ケーキング
防止剤、あるいは例えばカーボンブラック、酸化スズ等
の導電性付与剤がある。As the coloring agent, conventionally known dyes and pigments can be used, and usually 0.00 parts by weight per 100 parts by weight of the binder resin.
5 to 20 parts by weight may be used. Other additives include
For example, a lubricant such as zinc stearate, an abrasive such as cerium oxide or silicon carbide, a fluidity imparting agent such as fine resin particles, aluminum oxide, an anti-caking agent, or a conductivity imparting agent such as carbon black or tin oxide. be.
また、熱ロール定着時の離型性を良くする目的で低分子
量ポリエチレン、低分子量ポリプロピレン、マイクロク
リスタリンワックス、カルナバワックス、サゾールワッ
クス、パラフィンワックス等のワックス状物質を０．５
〜５ｗｔ％程度現像剤中に加えることも本発明の好まし
い形部の１つである。In addition, in order to improve mold releasability during hot roll fixing, waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc.
Adding about 5 wt % to the developer is also one of the preferred features of the present invention.
さらに、本発明中の現像剤は、着色剤の役割を兼ねても
良いが、磁性材料を含有する場合特に効果が顕著である
。そこに使われる磁性材料としては、マグネタイト、γ
−酸化鉄、フェライト、鉄過剰型フェライト等の酸化鉄
；鉄、コバルト、ニッケルのような金属或はこれらの金
属とアルミニウム、コバルト、銅、鉛、マグネシウム、
スズ、亜鉛、アンチモン、ベリリウム、ビスマス、カド
ミウム、カルシウム、マンガン、セレン、チタン、タン
グステン、バナジウムのような金属との合金およびその
混合物等が挙げられる。Further, the developer in the present invention may also serve as a colorant, but the effect is particularly significant when it contains a magnetic material. Magnetic materials used there include magnetite, γ
- Iron oxides such as iron oxides, ferrites, and iron-rich ferrites; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium,
Examples include alloys with metals such as tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.
これらの磁性体は平均粒径が０．１−１μｍ１好ましく
はＯ０１〜０゜５μｍ程度のものが望ましく、現像剤中
に含有させる量としては樹脂成分１００重量部に対し３
０〜１２０重量部、好ましくは樹脂成分１００重量部に
対し４０〜１１０重量部である。These magnetic substances preferably have an average particle size of about 0.1-1 μm, preferably about 0.01 to 0.5 μm, and are contained in the developer in an amount of 3 to 100 parts by weight of the resin component.
The amount is 0 to 120 parts by weight, preferably 40 to 110 parts by weight per 100 parts by weight of the resin component.
本発明中の現像剤の作製は、ビニル系、非ビニル系の熱
可塑性樹脂、必要に応じて、磁性粉、着色剤としての顔
料または染、料、荷電制御剤、その他の添加剤等をボー
ルミルの如き混合機により充分混合してから加熱ロール
、ニーグー、エクストルーダーの如き熱混練機を用いて
溶融、混練して樹脂類を互いに相溶せしめた中に、磁性
粉、着色剤、正荷電制御剤、その他の添加剤を分散又は
溶解せしめ、冷却固化後粉砕及び分級をおこなった後、
嵩密度が２５ｇ／ｆ以下でシリコーンオイル処理された
乾式法合成ケイ酸微粉体、及び必要に応じて、その他の
外添剤等を外添混合され、本発明に係るところの負帯電
性トナーを得ることが出来る。The developer in the present invention is produced by ball milling vinyl or non-vinyl thermoplastic resin, magnetic powder, pigment or dye as a coloring agent, charge control agent, other additives, etc. The magnetic powder, coloring agent, and positive charge control are mixed thoroughly using a mixer such as a mixer, and then melted and kneaded using a heat kneader such as a heated roll, niegoo, or extruder to make the resins mutually soluble. After dispersing or dissolving the additives and other additives, cooling and solidifying, pulverizing and classifying,
A negatively chargeable toner according to the present invention is prepared by mixing dry-process synthetic silicic acid fine powder with a bulk density of 25 g/f or less and treated with silicone oil, and other external additives as necessary. You can get it.
本発明のトナーを使用する場合の感光体としては、硫化
カドミウム、セレン、酸化亜鉛、有機光導電体（ｏｐｃ
）、アモルファスシリコン（α−５ｉ）などが用いられ
る。When using the toner of the present invention, photoreceptors include cadmium sulfide, selenium, zinc oxide, and organic photoconductors (OPC).
), amorphous silicon (α-5i), etc. are used.
また、本発明の現像剤を使用した場合、感光体上の残現
像剤等のクリーニング方法としてはプレードクリーニン
グ方式、ファーブラシクリーニング方式、磁気ブラシク
リーニング方式等が用いられるが、本発明においては、
本発明の現像剤及び感光体との優れた組み合せを考慮し
た場合、ブレードクリーニング方式が好ましい。また、
クリーニング工程に至る直前において必要に応じて現像
剤クリーニングを容易にするために除電工程等を設けて
も良い。Further, when the developer of the present invention is used, a blade cleaning method, a fur brush cleaning method, a magnetic brush cleaning method, etc. are used as a method for cleaning residual developer etc. on the photoreceptor, but in the present invention,
In consideration of the excellent combination of the developer of the present invention and the photoreceptor, the blade cleaning method is preferred. Also,
Immediately before the cleaning process, a static elimination process or the like may be provided as necessary to facilitate cleaning of the developer.
以下実施例にもとづいて、具体的に本発明の方法につい
て説明する。しかしながら、これによって本発明の実施
の態様がなんら限定されるものではない。実施例中の部
数はすべて重量部である。The method of the present invention will be specifically described below based on Examples. However, this does not limit the embodiments of the present invention in any way. All parts in the examples are parts by weight.
〔実施例１〕
・スチレン／アクリル酸ブチル／ジビニルベンゼン共重
合体 １００部（共重合重量比８０／１９．５１０．５
．重量平均分子量３２万）・マグネタイト（平均粒径０
．２μｍ） １００部・アゾ
染料のクロム錯体
１部・低分子量エチレン−プロピレン共重合体
４部上記材料をブレンダーでよ（混合
した後、１５０℃に設定した２軸混練押出機にて混練し
た。得られた混練物を冷却し、カッターミルにて粗粉砕
した後、ジェット気流を用いた微粉砕機を用いて微粉砕
し、得られた微粉砕粉を固定壁型風力分級機で分級して
分級粉を生成した。さらに、得られた分級粉をコアンダ
効果を利用した多分割分級装置（日鉄鉱業社製エルボジ
ェット分級機）で超微粉及び粗粉を同時に厳密に分級除
去して≦５μｍの磁性トナー粒子が４８個数％、１２．
７０μｍ以上の磁性トナー粒子がＯ体積％、６．３５〜
１０．０８μｍの磁性トナー粒子が３０個数％、体積平
均径が６．５μｍの黒色微粉体（負帯電性絶縁性磁性ト
ナー）を得た。[Example 1] - Styrene/butyl acrylate/divinylbenzene copolymer 100 parts (copolymerization weight ratio 80/19.510.5
．． Weight average molecular weight 320,000)・Magnetite (average particle size 0
．． 2μm) 100 parts Chromium complex of azo dye
1 part/Low molecular weight ethylene-propylene copolymer
4 parts The above materials were mixed in a blender (after mixing, kneaded in a twin-screw kneading extruder set at 150°C. The obtained kneaded product was cooled, coarsely pulverized in a cutter mill, and then kneaded using a jet stream. The resulting finely pulverized powder was classified using a fixed-wall wind classifier to produce classified powder.Furthermore, the obtained classified powder was subjected to multi-part classification using the Coanda effect. Ultra-fine powder and coarse powder were simultaneously strictly classified and removed using a device (Elbowjet classifier manufactured by Nippon Steel Mining Co., Ltd.), and magnetic toner particles with a size of ≦5 μm were 48% by number.12.
Magnetic toner particles of 70 μm or more are O volume %, 6.35 ~
A black fine powder (negatively charged insulating magnetic toner) containing 30% by number of magnetic toner particles of 10.08 μm and a volume average diameter of 6.5 μm was obtained.
一方、ケイ酸微粉体として乾式法で合成されたケイ酸微
粉体（商品名、アエロジル＠２００．比表面積および２
００ｄ／ｇ、アエロジル社製）を７０℃に加熱した密閉
型ヘンシェルミキサー中に入れ、該ケイ酸微粉体に対し
て１０重量％の処理量となる様にアルコールで希釈した
ヘキサメチルシラザンを噴霧しながら高速で撹拌した。On the other hand, silicic acid fine powder synthesized by dry method as silicic acid fine powder (trade name, Aerosil@200. Specific surface area and 2
00d/g, manufactured by Aerosil) was placed in a closed Henschel mixer heated to 70°C, and hexamethylsilazane diluted with alcohol was sprayed to give a treatment amount of 10% by weight to the silicic acid fine powder. while stirring at high speed.
その後温度を１２０℃にて乾燥を行い、再び温度を７０
℃とした後さらに２０重量％の処理量となる様にアルコ
ールで希釈したジメチルポリシロキサン（２５℃におけ
る粘度８０ｃｅｓ）を噴霧しながら高速で撹拌し温度を
３００℃まであげ２時間熱処理を行い、ヘキサメチルジ
シラザン及びシリコーンオイルで処理された負帯電性疎
水性ケイ酸微粉体（Ｉ）を得た。After that, drying was carried out at a temperature of 120°C, and the temperature was again reduced to 70°C.
℃, and then stirred at high speed while spraying dimethylpolysiloxane (viscosity 80 ces at 25℃) diluted with alcohol to give a treatment amount of 20% by weight.The temperature was raised to 300℃ and heat treated for 2 hours. A negatively charged hydrophobic silicic acid fine powder (I) treated with methyldisilazane and silicone oil was obtained.
該ケイ酸微粉体（Ｉ）の嵩密度は３８ｇ／ｆであった。The bulk density of the silicic acid fine powder (I) was 38 g/f.
次に該ケイ酸微粉体（Ｉ）をコスモマイザーで解砕し、
嵩密度が表１に示す値であるケイ酸微粉体（■〜■）を
得た。このうち嵩密度が１８ｇ／ｆであるケイ酸微粉体
（ＩＩ）２．０部を前述の磁性トナー１００部とともに
ヘンシェルミキサーで混合し負帯電性現像剤Ａを得た。Next, the silicic acid fine powder (I) is crushed with a costomizer,
Fine silicic acid powders (■ to ■) having bulk densities shown in Table 1 were obtained. Of these, 2.0 parts of silicic acid fine powder (II) having a bulk density of 18 g/f was mixed with 100 parts of the aforementioned magnetic toner in a Henschel mixer to obtain a negatively chargeable developer A.
現像剤Ａを市販のレーザービームプリンターであるＬＢ
Ｐ−８ＩＩ （キャノン製）を用いて初期面出を行った
ところ画像濃度が１．３４カブリのない解像力の高い鮮
明な画像が得られ、画像部に白ポチは全く見られなかっ
た。以下結果は表２に示す。LB, a commercially available laser beam printer, uses developer A.
When initial plane exposure was performed using P-8II (manufactured by Canon), a clear image with an image density of 1.34 and no fog and high resolution was obtained, and no white spots were observed in the image area. The results are shown in Table 2 below.
〔実施例２〕
実施例１においてケイ酸微粉体（ＩＩ）のかわりに嵩密
度が２３ｇ／ｆであるケイ酸微粉体（ＩＩＩ）を用いる
以外は同様に行ったところ画線部にわずかに白ポチが見
られたものの肉眼ではわかりにくく実用１全（問題はな
かった。[Example 2] The same procedure as in Example 1 was performed except that silicic acid fine powder (III) having a bulk density of 23 g/f was used instead of silicic acid fine powder (II), and a slight whiteness was observed in the image area. Although there were some spots, it was difficult to see with the naked eye, and it was difficult to see with the naked eye (there were no problems).
〔実施例３〕
実施例１においてへキサメチルジシラザンのかわりにト
リエトキシデシルシランを用いる以外は同様にして処理
、ケイ酸微粉体を作成しこのケイ酸微粉体をコスモマイ
ザーを用いて解砕し嵩密度２０ｇ／ｌのケイ酸微粉体（
ＩＶ）を得た。このケイ酸微粉体（ＩＶ）を用いて実施
例１と同様に行ったところ同様に画像白ポチのない良好
な結果が得られた。[Example 3] A fine silicic acid powder was prepared in the same manner as in Example 1 except that triethoxydecylsilane was used instead of hexamethyldisilazane, and the fine silicic acid powder was crushed using a costomizer. Fine silicic acid powder with a bulk density of 20 g/l (
IV) was obtained. When the same procedure as in Example 1 was carried out using this silicic acid fine powder (IV), good results were obtained with no white spots on the image.
比較例１
実施例１において表１の未解砕のケイ酸微粉体（Ｉ）を
ケイ酸微粉体（ｎ）のかわりに用いる以外は同様に行っ
たところ初期画像部にシリカダマによる３０−１００μ
ｍ程度の白ポチが生じ特にベタ黒では目立ったが数十枚
の面出に肉眼ではわからなくなった。Comparative Example 1 The same procedure as in Example 1 was carried out except that the uncrushed silicic acid fine powder (I) shown in Table 1 was used instead of the silicic acid fine powder (n). As a result, 30-100 μm of silica agglomerates were formed in the initial image area.
A white spot of about 100 yen was generated, which was noticeable especially on solid black, but it was no longer noticeable to the naked eye due to the appearance of several dozen sheets.
比較例２
実施例１においてへキサメチルジシラザンのみで処理し
たケイ酸微粉体をコスモマイザーで解砕して嵩密度１８
ｇ／ｊ７のケイ酸微粉体（Ｖ）を得た。このケイ酸微粉
体（Ｖ）を用いて実施例１と同様に行ったところ画像白
ポチは良好であったが転写中抜けが発生した。Comparative Example 2 The silicic acid fine powder treated only with hexamethyldisilazane in Example 1 was crushed with a costomizer to give a bulk density of 18
A fine silicic acid powder (V) of g/j7 was obtained. When this silicic acid fine powder (V) was used in the same manner as in Example 1, the white spots in the image were good, but voids in the transfer occurred.
また実施例、 比較例の結果を表２に示す。Also examples, Table 2 shows the results of the comparative example.
４、4,
添付図面第１図は、 シリカの解砕時間と嵩密度の 関係を示すグラフに関する図である。 ＄１つ コスεマイ？ｆｑ先肇−ｉ１ Figure 1 of the attached drawings shows Silica crushing time and bulk density It is a figure regarding the graph which shows a relationship. $1 Cos ε my? fq destination-i1
Claims (1)
またはワニスで処理された疎水性乾式シリカを含有する
ことを特徴とする負帯電性現像剤。(1) A negatively chargeable developer characterized by containing hydrophobic dry silica having a bulk density of 25 g/l or less and treated with silicone oil or varnish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1109521A JPH02287459A (en) | 1989-04-28 | 1989-04-28 | Negatively chargeable magnetic developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1109521A JPH02287459A (en) | 1989-04-28 | 1989-04-28 | Negatively chargeable magnetic developer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02287459A true JPH02287459A (en) | 1990-11-27 |
Family
ID=14512367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1109521A Pending JPH02287459A (en) | 1989-04-28 | 1989-04-28 | Negatively chargeable magnetic developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02287459A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561019A (en) * | 1994-04-22 | 1996-10-01 | Matsushita Electric Industrial Co., Ltd. | Magnetic toner |
| JPH0959533A (en) * | 1995-08-21 | 1997-03-04 | Nippon Aerojiru Kk | Fine powder of surface-modified metal oxide and its production |
| US5702858A (en) * | 1994-04-22 | 1997-12-30 | Matsushita Electric Industrial Co., Ltd. | Toner |
| US6077640A (en) * | 1998-05-11 | 2000-06-20 | Nippon Aerosil Co., Ltd. | Fine powder of hydrophobic metal oxide, method for producing it, and toner composition for electrophotography |
| US7083888B2 (en) * | 2000-09-07 | 2006-08-01 | Shin-Etsu Chemical Co., Ltd. | External additive for electrostatically charged image developing toner |
| JP2007191355A (en) * | 2006-01-19 | 2007-08-02 | Nippon Aerosil Co Ltd | Surface-hydrophobized silica powder by dry method |
| JP2009263152A (en) * | 2008-04-23 | 2009-11-12 | Nippon Shokubai Co Ltd | Particle and its manufacturing method |
-
1989
- 1989-04-28 JP JP1109521A patent/JPH02287459A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561019A (en) * | 1994-04-22 | 1996-10-01 | Matsushita Electric Industrial Co., Ltd. | Magnetic toner |
| US5702858A (en) * | 1994-04-22 | 1997-12-30 | Matsushita Electric Industrial Co., Ltd. | Toner |
| JPH0959533A (en) * | 1995-08-21 | 1997-03-04 | Nippon Aerojiru Kk | Fine powder of surface-modified metal oxide and its production |
| EP0860478A1 (en) | 1995-08-21 | 1998-08-26 | Nippon Aerosil Co., Ltd. | Surface-modified metal oxide fine particles and process for producing the same |
| US5843525A (en) * | 1995-08-21 | 1998-12-01 | Nippon Aersoil Co., Ltd. | Surface-modified metal oxide fine particles and process for producing the same |
| US6077640A (en) * | 1998-05-11 | 2000-06-20 | Nippon Aerosil Co., Ltd. | Fine powder of hydrophobic metal oxide, method for producing it, and toner composition for electrophotography |
| US7083888B2 (en) * | 2000-09-07 | 2006-08-01 | Shin-Etsu Chemical Co., Ltd. | External additive for electrostatically charged image developing toner |
| JP2007191355A (en) * | 2006-01-19 | 2007-08-02 | Nippon Aerosil Co Ltd | Surface-hydrophobized silica powder by dry method |
| JP2009263152A (en) * | 2008-04-23 | 2009-11-12 | Nippon Shokubai Co Ltd | Particle and its manufacturing method |
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