JPH03203744A - Magnetic toner - Google Patents
Magnetic tonerInfo
- Publication number
- JPH03203744A JPH03203744A JP1343254A JP34325489A JPH03203744A JP H03203744 A JPH03203744 A JP H03203744A JP 1343254 A JP1343254 A JP 1343254A JP 34325489 A JP34325489 A JP 34325489A JP H03203744 A JPH03203744 A JP H03203744A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- magnetic material
- group
- magnetic
- resin
- 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
- 239000000696 magnetic material Substances 0.000 claims abstract description 35
- -1 silane compound Chemical class 0.000 claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 27
- 229920001577 copolymer Polymers 0.000 description 23
- 239000011230 binding agent Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 125000003277 amino group Chemical group 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
- 239000011162 core material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- POZWNWYYFQVPGC-UHFFFAOYSA-N 3-methoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C(C)=C POZWNWYYFQVPGC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- 230000008901 benefit Effects 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 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
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005389 magnetism Effects 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical class [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
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 150000004756 silanes Chemical class 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
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電子写真、静電記録及び静電印刷等における
静電荷像を現像するための新規な磁性トナーに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel magnetic toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.
［従来の技術］
従来電子写真法としては米国特許第２，２９７，６９１
号明細書、特公昭４２−２３９１０号公報（米国特許第
３．６６６．３６３号明細書）及び特公昭４３−２４７
４８号公報（米国特許第４，０７１，３１ｉ１号明細書
）等に記載されているごとく、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、次いで該潜像をトナ
ーで現像して可視像とし、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、圧力等により定着し
、複写物を得るものである。[Prior art] As a conventional electrophotographic method, U.S. Patent No. 2,297,691
specification, Japanese Patent Publication No. 42-23910 (U.S. Patent No. 3.666.363) and Japanese Patent Publication No. 43-247
Although many methods are known, such as those described in U.S. Pat. An electrical latent image is formed thereon, and then the latent image is developed with toner to become a visible image. If necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heat, pressure, etc. , to obtain a copy.
静電荷像をトナーを用いて可視像化する現像方法も種々
知られている。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、同第２，６１８
，５５２号明細書に記載されているカスケード現像法及
び同第２，２２１，７７６号明細書に記載されているパ
ウダークラウド法、ファーブラシ現像法、液体現像法等
、多数の現像法が知られている。これらの現像法におい
て、特にトナー及びキャリヤーを主体とする現像剤を用
いる磁気ブラシ法、カスケード法、液体現像法等が広く
実用化されている。これらの方法はいずれも比較的安定
に良画像の得られる優れた方法であるが、反面キャリヤ
ーの劣化、トナーとキャリヤーの混合比の変動という２
成分系現像剤にまつわる共通の欠点を有する。Various developing methods are also known in which an electrostatic charge image is visualized using toner. For example, the magnetic brush method described in U.S. Pat. No. 2,874,063;
A large number of development methods are known, such as the cascade development method described in No. 2,221,776, the powder cloud method, the fur brush development method, and the liquid development method. ing. Among these developing methods, the magnetic brush method, cascade method, liquid developing method, etc., which use a developer mainly consisting of toner and carrier, are in particular widely put into practical use. All of these methods are excellent methods that can relatively stably obtain good images, but on the other hand, they suffer from two problems: deterioration of the carrier and fluctuations in the mixing ratio of toner and carrier.
It has common drawbacks associated with component-based developers.
係る欠点を回避するため、トナーのみよりなる１成分系
現像剤を用いる現像方法が各種提案されているが、中で
も磁性を有するトナー粒子より成る現像剤を用いる方法
に優れたものが多い。これらの１成分系現像方法は、現
像剤にキャリヤーを用いないのでキャリヤーとトナーの
混合比率の調整が不要であり、又、キャリヤーとトナー
を十分均一に混合するための攪拌操作を特に必要としな
いため現像装置全体を簡略且つコンパクトに構成できる
という利点を有する。更にキャリヤーの経時的劣化に基
づく、現像画質の低下といった不都合も生じない。In order to avoid such drawbacks, various development methods using one-component developers made only of toner have been proposed, among which many methods using developers made of magnetic toner particles are superior. These one-component developing methods do not use a carrier in the developer, so there is no need to adjust the mixing ratio of the carrier and toner, and there is no particular need for a stirring operation to mix the carrier and toner sufficiently and uniformly. Therefore, it has the advantage that the entire developing device can be constructed simply and compactly. Furthermore, problems such as deterioration in developed image quality due to deterioration of the carrier over time do not occur.
従来、これらトナーには現像される静電潜像の極性に応
じて予め正又は負の電荷が与えられる。Conventionally, these toners are previously given a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.
トナーに電荷を付与するためには、トナーの成分である
樹脂の摩擦帯電性のみを利用することも出来るが、この
方法ではトナーの帯電性が小さいので、現像によって得
られる画像はカブリ易く、不鮮明なものとなる。そこで
、所望の摩擦帯電性をトナーに付与するために、帯電性
を強化する染料、顔料等をはじめとする電荷制御剤を添
加することが行われている。In order to charge the toner, it is also possible to use only the triboelectricity of the resin that is a component of the toner, but with this method, the toner's chargeability is small, so the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectric charging properties to the toner, charge control agents such as dyes and pigments that enhance the charging properties are added.
今日、当該技術分野で知られている電荷制御剤としては
、ニグロシン染料、アジン系染料（特公昭４２−１８２
７号公報）、モノアゾ染料の金属錯塩、サリチル酸、ナ
フトエ酸、ダイカルボン酸の金属錯塩、銅フタロシアニ
ン顔料などがある。これら染顔料から派生したものは、
優れた電荷制御特性を示す。Charge control agents known in the art today include nigrosine dyes, azine dyes (Japanese Patent Publication No. 42-182
7), metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid, and dicarboxylic acids, and copper phthalocyanine pigments. Those derived from these dyes and pigments are
Shows excellent charge control properties.
しかし、今後、オフィスにおける情報量の増加に伴う複
写枚数の増大、しかるに複写機の複写速度の高速化に伴
って、複写機の高信頼性が望まれる。そのためトナーは
更に安定化することが要求されている。However, in the future, as the amount of information in offices increases, the number of copies to be made will increase, and as the copying speed of copying machines increases, high reliability of copying machines will be desired. Therefore, toners are required to be further stabilized.
このような情況のもとで、トナーを更に安定化させる上
で電荷制御剤の分散性は重大な役割を持つ。ここで、染
顔料系の電荷制御剤は自己凝集力が強いため、現在用い
られている染・顔料系電荷制御剤は更に分散性を向上す
る必要がある。Under these circumstances, the dispersibility of the charge control agent plays an important role in further stabilizing the toner. Here, since dye/pigment type charge control agents have a strong self-cohesive force, it is necessary to further improve the dispersibility of the currently used dye/pigment type charge control agents.
又、最近、樹脂との相溶性を高める目的で、電荷制御剤
として、アミン基を含有するビニル系ポリマー、アミノ
基を含有する縮合系ポリマーなどのポリアミンなどが１
是案されているが、これらの電荷制御剤は、親水性のも
のが多く、特に、高湿下で摩擦帯電量が低下する。又、
高温条件下で摩擦帯電量が低下しないものは、低湿条件
下で、摩擦ＩＦ電量が異常に増加する。このような摩擦
ｆ電量が湿度により著しく変動する電荷制御剤を含有し
たトナーを用いると、温湿度の変化により画質が変化し
てしまい、常に良好な品質の画像を提供することが極め
て困難になる。Recently, polyamines such as vinyl polymers containing amine groups and condensation polymers containing amino groups have been used as charge control agents for the purpose of increasing compatibility with resins.
Although proposals have been made, many of these charge control agents are hydrophilic, and the amount of triboelectric charging decreases, especially under high humidity conditions. or,
If the amount of triboelectric charge does not decrease under high temperature conditions, the amount of triboelectric charge will abnormally increase under low humidity conditions. If a toner containing a charge control agent whose triboelectric charge varies significantly depending on humidity is used, the image quality will change due to changes in temperature and humidity, making it extremely difficult to consistently provide images of good quality. .
又、これらの磁性トナーには、トナー粘着剤中に磁性体
が相当量混入されているが、磁性体は一般にトナー結着
樹脂中への分散性が悪く、製造上バラツキのない均一な
トナーを得ることが困難であり、更に絶縁性磁性トナー
ではトナーの部分的な電気抵抗の低下の原因ともなり結
果として現像画質の低下や環境変動が大きくなるといっ
た不都合を生じる。In addition, these magnetic toners have a considerable amount of magnetic material mixed into the toner adhesive, but the magnetic material generally has poor dispersibility in the toner binder resin, making it difficult to produce a uniform toner with no variations in manufacturing. Furthermore, in the case of an insulating magnetic toner, it may cause a partial decrease in electric resistance of the toner, resulting in disadvantages such as a decrease in developed image quality and a large environmental fluctuation.
これらの問題を改良する目的で特開昭５４１２２１２９
号公報に開示されるようにシラン化合物による磁性体処
理が行なわれているが、今後の複写の高速化・更なる厳
しい環境下での使用において、トナーに含有するすべて
の物質の分散性を考慮するとまだ不十分である。In order to improve these problems, Japanese Patent Application Publication No. 54122129
As disclosed in the above publication, magnetic treatment with a silane compound is being carried out, but in the future when copying speeds are increased and the toner is used under harsher environments, the dispersibility of all substances contained in the toner must be considered. However, it is still insufficient.
従って、今後、複写の高速化に伴って、トナー帯電量の
温・湿度依存性及び画質の安定化により厳しい条件が要
求されると共に、電荷制御剤及び磁性体の樹脂との分散
性も考慮した上での帯電能の温・湿度依存性も厳しい条
件が要求され、このような理由から樹脂との更なる相溶
性及び分散性が良好な温・湿度依存性が少ない電荷制御
剤及び磁性体の開発が強く要請されている。Therefore, in the future, as copying speeds increase, strict conditions will be required to stabilize the temperature and humidity dependence of toner charge amount and image quality, and the dispersibility of charge control agents and magnetic materials with resin will also be required. Strict conditions are also required for the temperature and humidity dependence of the charging ability on the above, and for these reasons, charge control agents and magnetic materials that have better compatibility and dispersibility with resins and less temperature and humidity dependence are required. Development is strongly required.
［発明が解決しようとする課題］
本発明の目的は、かかる問題点を解決した磁性トナーを
提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a magnetic toner that solves these problems.
即ち本発明の目的は、樹脂と磁性体及び電荷制御剤の分
散性が良好で、且つトナーとスリーブの如きトナー担持
体との間等の摩擦帯電量が温度、湿度の変化を受けずに
安定で、環境条件の変化に影響され難い安定した画像を
再現し得る磁性トナーの提供にある。That is, an object of the present invention is to ensure that the resin, magnetic material, and charge control agent have good dispersibility, and that the amount of triboelectric charge between the toner and a toner carrier such as a sleeve is stable without being affected by changes in temperature and humidity. Another object of the present invention is to provide a magnetic toner that can reproduce stable images that are not easily affected by changes in environmental conditions.
更に、本発明の目的は、正又は負の良好な摩擦帯電性を
有する磁性トナーの提供にある。A further object of the present invention is to provide a magnetic toner having good positive or negative triboelectric charging properties.
又、本発明の目的は、耐久性に優れカプリのない鮮明な
画像を得る磁性トナーの提供にある。Another object of the present invention is to provide a magnetic toner that has excellent durability and provides clear images without capri.
［課題を解決するための手段及び作用］本発明者は前記
の目的を達成する為、鋭意検討した結果、少なくとも一
般式（Ｉ）で表わされる重量平均分子量が２，０００〜
１，０００−．０００であるポリシラン化合物と一般式
（Ｉ１）で表わされるシラン化合物で処理された磁性体
と
一般式（Ｉ）
（式中、Ｒ１，Ｒ２，Ｒ３及びＲ４は、アルキル、アリ
ール、ｆＷ ｊｈアルキル、置換アリール、及びアルコ
キシから成る群から選ばれ、いずれも同してあっても或
は異なってもよい。ｎとｍはポリマー中の総千ツマ−に
対するそれぞれの千ツマー数の割合を示すモル比であり
、ｎ＋ｍ＝１となり、Ｏｗｎ≦１．０≦ｍ＜１である。[Means and effects for solving the problem] In order to achieve the above-mentioned object, the inventors of the present invention made extensive studies and found that the weight average molecular weight represented by the general formula (I) is at least 2,000 to 2,000.
1,000-. 000 and a magnetic material treated with a silane compound represented by general formula (I1) and general formula (I) (wherein R1, R2, R3 and R4 are alkyl, aryl, fW jh alkyl, substituted selected from the group consisting of aryl and alkoxy, both of which may be the same or different; n and m are molar ratios indicating the proportion of each 1,000-mer number to the total 1,000-mers in the polymer; Yes, n+m=1, and Own≦1.0≦m<1.
）
−形成（ＩＩ）
５ｉＸ３
（式中、Ｒは末端ビニル基を有する有機官能基であり、
Ｘは、水酸基又は加水分解して水酸基となる基である。) -Formation (II) 5iX3 (wherein R is an organic functional group having a terminal vinyl group,
X is a hydroxyl group or a group that is hydrolyzed to become a hydroxyl group.
） を含有する磁性トナーにより本発明は達成される。) The present invention is achieved by a magnetic toner containing the following.
即ち、本発明は重合度の異なるポリシラン化合物とシラ
ン化合物で処理された磁性体を含有することで、より結
着樹脂との相溶性に優れ、良好な分散性を有し、正又は
負の良好な摩擦帯電性を有した磁性トナーに関する。That is, the present invention contains a polysilane compound with a different degree of polymerization and a magnetic material treated with a silane compound, so that it has better compatibility with the binder resin, has good dispersibility, and has good positive or negative polarity. The present invention relates to a magnetic toner having triboelectric charging properties.
ポリシランは主鎖のσ−結合の軌道準位が高く、共役に
よってσ電子が非局在化（フィジカル・レビュー８３０
５８７１ ＰＰ （Ｉ９８４）） Ｌ／て半導体的な特
性を示す。又、Ｓｉ主鎖が長くなる、つまり分子量が大
ぎくなるとイオン化ポテンシャルが小さくなる。（ジャ
ーナル・オブ・アメリカン・ケミカル・ソサエティー、
９２．５１９ ＰＰ （Ｉ！＋７０））これにより、
ポリシランの分子量を調節し、低分子量ポリシランは負
帯電性トナーの電荷制御剤として、又高分子量ポリシラ
ンは、正帯電性トナーの電荷制御剤として用いることが
可能であると考えられる。又、局在したπ−軌道を有す
る側鎖基は、主鎖のσ−軌道と相互作用を及ぼし、結果
的にイオン化ポテンシャルを小せしめるため、側鎖基と
してフェニル基など置換したポリシリコンで高分子量の
ものは正の電荷制御剤として有用であると考えられる。Polysilane has a high orbital level of the σ-bond in the main chain, and σ electrons are delocalized due to conjugation (Physical Review 830
5871 PP (I984)) Shows semiconductor-like characteristics. Furthermore, as the Si main chain becomes longer, that is, the molecular weight becomes larger, the ionization potential becomes smaller. (Journal of the American Chemical Society,
92.519 PP (I!+70)) This gives us
It is considered that by adjusting the molecular weight of the polysilane, a low molecular weight polysilane can be used as a charge control agent for negatively chargeable toners, and a high molecular weight polysilane can be used as a charge control agent for positively chargeable toners. In addition, side chain groups with localized π-orbitals interact with the σ-orbitals of the main chain, resulting in a decrease in ionization potential. Those of molecular weight are considered useful as positive charge control agents.
又、本発明の電荷制御剤は、現在用いられている電荷制
御剤に比べ高分子量であるため樹脂との相溶性も良く、
分散も均一であるために、良好な電荷制御が望める。又
、主鎖が疎水性のため高湿下でも帯電性は失われず、良
好な電荷制御が行なえると考えられる。In addition, the charge control agent of the present invention has a higher molecular weight than currently used charge control agents, and therefore has good compatibility with resins.
Since the dispersion is also uniform, good charge control can be expected. Furthermore, since the main chain is hydrophobic, the chargeability is not lost even under high humidity, and it is thought that good charge control can be performed.
正又は負の電荷制御剤として用いる場合の境界は分子量
、側鎖基と考慮する必要があり、一義的には決められな
いが、負の電荷制御剤とじては、重量平均分子量が２０
，０００以下のものが好ましく、正の電荷制御剤として
は、重量平均分子量が２０．０００以上のものが好まし
い。The boundary when used as a positive or negative charge control agent needs to be taken into consideration with molecular weight and side chain groups, and cannot be determined unambiguously, but for a negative charge control agent, the weight average molecular weight is 20.
,000 or less, and as a positive charge control agent, one having a weight average molecular weight of 20,000 or more is preferable.
重量平均分子量が、２，０００より小なるものは、結着
樹脂との相溶性が不十分であり、又重量平均分子量が１
，０００，０００より大なるものは、トナー作製時の混
練過程において混合性が悪く、偏析や凝集が起こり、帯
電性能の低下を生じる。If the weight average molecular weight is less than 2,000, the compatibility with the binder resin is insufficient, and if the weight average molecular weight is less than 1.
,000,000 has poor mixing properties during the kneading process during toner production, causing segregation and agglomeration, resulting in a decrease in charging performance.
中でも好ましくは結着樹脂の重量平均分子量よりも低い
重量平均分子量を有するポリシラン化合物を用いること
である。Among these, it is preferable to use a polysilane compound having a weight average molecular weight lower than that of the binder resin.
本発明における一般式（Ｉ）で表される上述のポリシラ
ン化合物の具体例として以下のものが挙げられる。Specific examples of the above-mentioned polysilane compound represented by general formula (I) in the present invention include the following.
Ｈ３
し２Ｈ８
ＣＩ（３
しｉ３
上記構造式中のＸとＹはいずれも単量体の重合１位を示
す。そしてｎは、Ｘ／ （Ｘ＋Ｙ） 、まで、ｍはＹ／
（Ｘ＋Ｙ）の計算式によりそれぞれ攬められる。H3 2H8 CI(3 shii3 In the above structural formula, both X and Y indicate the 1st polymerization position of the monomer. Then, n is X/ (X+Y), m is Y/
They are each captured using the calculation formula (X+Y).
上記ポリシラン化合物は多くの公知方法で製造でき、単
独又は２種以上の併用で用いられるが、ｌ・要に応じて
、従来公知の電荷制御剤を本発明の電荷制御剤と組み合
わせて使用することもできる。The above-mentioned polysilane compound can be produced by many known methods and used alone or in combination of two or more types. However, if necessary, a conventionally known charge control agent may be used in combination with the charge control agent of the present invention. You can also do it.
これら電荷制御剤を結着樹脂及び磁性体を必須成分とす
るトナー中に配合することにより、未発」のトナーが得
られる。By blending these charge control agents into a toner containing a binder resin and a magnetic material as essential components, an "unexploited" toner can be obtained.
本発明に用いる前記−形成（ＩＩ）で表わされる前窓の
シラン化合物は同一分子中に異なる二種以上の官能基を
有し、その一方は無機物質と化学結合する反応基であり
、他方は有機物質と化学結合する反応基であり、特に末
端ビニル基を有していることが重要である。The front window silane compound represented by the above-mentioned -formation (II) used in the present invention has two or more different functional groups in the same molecule, one of which is a reactive group that chemically bonds with an inorganic substance, and the other is a reactive group that chemically bonds with an inorganic substance. It is a reactive group that chemically bonds with an organic substance, and it is especially important that it has a terminal vinyl group.
本発明の如く一般式（ｌりで表わされる特定の７ラン化
合物で処理された磁性体を用いた磁性トナーは未処理の
磁性体或は他のシランカップリング剤で処理された磁性
体を用いた磁性トナーに比べて、前述の本発明の目的を
充分に達成することができ、極めて好ましいものであっ
た。特にトナーの帯電特性の安定性、耐湿性、転写性な
どに優れており、絶縁磁性トナーとして最適であった。As in the present invention, a magnetic toner using a magnetic material treated with a specific 7-ranium compound represented by the general formula The toner was extremely preferable as it was able to fully achieve the above-mentioned object of the present invention compared to the magnetic toner previously described.In particular, the toner has excellent stability in charging characteristics, moisture resistance, transferability, etc. It was ideal as a magnetic toner.
本発明に用いる前記−形成Ｒ５１Ｘ、で表わされる末端
ビニル基を有する特定のシラン化合物に於て、Ｘは水酸
基又は加水分解して水酸基となる基であるが具体的には
例えば、アルコキシ基、アシルオキシ基、クロル原子な
どである。In the specific silane compound having a terminal vinyl group represented by -formation R51X used in the present invention, X is a hydroxyl group or a group that becomes a hydroxyl group when hydrolyzed. groups, chlorine atoms, etc.
本発明における一般式（Ｉりで表わされる上述のシラン
化合物の具体例として以下のものが挙げられる。Specific examples of the above-mentioned silane compound represented by the general formula (I) in the present invention include the following.
Ｃ）Ｉ２−ＣＨＳｆ （ＯＣＣＨ３）３１
ＣＬ−Ｃ）ＩＳｉ （ＱＣ）１３） ３Ｃ）Ｉ２−ＣＨ
５ｉ （ＯＣＬＣＨ３）ｓＣＨ２＝ＣＨ５ｉＣｊ’。C) I2-CHSf (OCCH3)31 CL-C) ISi (QC)13) 3C) I2-CH
5i (OCLCH3)sCH2=CH5iCj'.
ＣＨ２−Ｃ）ｌｓｉ（ＱＣ）１２ｃＨ２０Ｇ）＋３）
。CH2-C)lsi(QC)12cH20G)+3)
.
ｐ ＣＨ２−ＣＨ５ｉ （ＯＨ） 。p CH2-CH5i (OH).
などが市販されており、単独又は２種以上の併用で用い
られるが、いずれも本発明に好ましく使用できる。These are commercially available and can be used alone or in combination of two or more, and any of them can be preferably used in the present invention.
本発明に用いられる磁性体としてはマグネタイト、マグ
ネタイト、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及びその混合物等が挙げられる。Magnetic materials used in the present invention include iron oxides such as magnetite, magnetite, and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Beryllium, bismuth, cadmium, calcium,
Examples include alloys with metals such as manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.
これらの磁性体は平均粒径が０．１〜２μ程度、特に０
．１〜１．０μのものが望ましく、これらの磁性体を前
述の特定のシラン化合物の溶液或は更に表面性や色調を
改良する目的で樹脂や染料を加えた溶液で処理し、この
処理された磁性体を用いて他は従来法に従って磁性トナ
ーを製造すればよい。These magnetic materials have an average particle size of about 0.1 to 2μ, especially 0.
．． 1 to 1.0 μm is desirable, and these magnetic materials are treated with a solution of the specific silane compound mentioned above, or a solution containing resin or dye for the purpose of improving surface properties and color tone. A magnetic toner may be manufactured by using a magnetic material and other conventional methods.
又、シラン化合物或はその溶液を磁性体を攪拌しながら
スプレーなどで吹きつけて処理する方法もある。There is also a method of spraying a silane compound or its solution onto a magnetic material while stirring it.
処理された磁性体のトナー中に含有させる量としては樹
脂成分１００重量部に対し約２０〜２００重量部、特に
好ましくは樹脂成分１００重量部に対し４０〜１５０重
量部である。The amount of the treated magnetic material contained in the toner is approximately 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably 40 to 150 parts by weight per 100 parts by weight of the resin component.
磁性体の添加量が２０重量部未満のトナーでは、トナー
の磁性が弱く、トナーが現像スリーブより離脱して、カ
ブリのある画像が得られる。又、磁性体の添加量が２０
０重量部を越える場合には、トナーの磁力が必要以上に
強くなり、トナーが現像スリーブより離脱しにくく、画
像濃度が低下する。When the amount of the magnetic substance added is less than 20 parts by weight, the toner has weak magnetism, and the toner separates from the developing sleeve, resulting in a foggy image. Also, the amount of magnetic material added is 20
If the amount exceeds 0 parts by weight, the magnetic force of the toner becomes stronger than necessary, making it difficult for the toner to separate from the developing sleeve, resulting in a decrease in image density.
トナーの結着樹脂としては、ポリスチレン、ポリ−ｐ−
クロロスチレン、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−クロロスチレ
ン共重合体、スチレン−プロピレン共重合体、スチレン
−ビニルトルエン共重合体、スチレン−ビニルナフタレ
ン共重合体、スチレン−アクリル酸メチル共重合体、ス
チレン−アクリル酸エチル共重合体、スチレン−アクリ
ル酸ブチル共重合体、スチレン−アクリル酸オクチル共
重合体、スチレン−アクリル酸２−エチルヘキシル共重
合体等のスチレン−アクリル共重合体、スチレン−メタ
クリル酸メチル共重合体、スチレン−メタクリル酸エチ
ル共重合体、スチレン−メタクリル酸ブチル共重合体、
スチレン−α−クロルメタクリル酸メチル共重合体、ス
チレンーアクリロ二トリル共重合体、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、スチレン−マレイン酸共重合体、スチレン−マ
レイン酸エステル共重合体などのスチレン系共重合体；
ポリメチルメタクリレート、ポリブチルメタクリレート
、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポ
リプロピレン、ポリエステル、ポリウレタン、ポリアミ
ド、エポキシ樹脂、ポリビニルブチラール、シリコーン
樹脂、ポリアクリル酸樹脂、ロジン、変性ロジン、テル
ペン樹脂、フェノール樹脂、脂肪族又は脂環族炭化水素
樹脂、芳香族系石油樹脂、塩素化パラフィン、パラフィ
ンワックスなどが挙げられ、単独或は混合して使用でき
る。As the binder resin of the toner, polystyrene, poly-p-
Monopolymers of styrene and its substituted products such as chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-2-ethylhexyl acrylate copolymer, etc. Acrylic copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate 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 - Styrenic copolymers such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer;
Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, silicone resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin , aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., which can be used alone or in combination.
又特に圧力定着に適したトナーを与えるために好適な結
着樹脂として限定して挙げると下記のものが゛単独或は
混合して使用できる。In order to provide a toner particularly suitable for pressure fixing, the following binder resins may be used alone or in combination.
ポリオレフィン（低分子量ポリエチレン、低分子量ポリ
プロピレン、酸化ポリエチレン、ポリ４フツ化エチレン
など）、エポキシ樹脂、ポリエステル樹脂、スチレン−
ブタジェン共重合体（モノマー比：５〜３０：９５〜７
０）、オレフィン共重合体（エチレン−アクリル酸共重
合体、エチレン−アクリル酸エステル共重合体、エチレ
ン−メタクリル酸共重合体、エチレン−メタクリル酸エ
ステル共重合体、エチレン酢酸ビニル共重合体、アイオ
ノマー樹脂）、ポリビニルピロリドン、メチルビニルエ
ーテル−無水マレイン酸共重合体、マレイン酸変性フェ
ノール樹脂、フェノール変性テルペン樹脂。Polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene, polytetrafluoroethylene, etc.), epoxy resins, polyester resins, styrene
Butadiene copolymer (monomer ratio: 5-30:95-7
0), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.
特に、前述の特定のシラン化合物との組合せの効果が顕
著なトナー用結着樹脂は、スチレン系樹脂、ポリ塩化ビ
ニル、ポリエチレン、ポリ酢酸ビニル、ポリプロピレン
、ポリエステル樹脂、アクリル系樹脂、シリコーン樹脂
、エポキシ樹脂、キシレン樹脂、マレイン酸変性フェノ
ール樹脂、メチルビニルエーテル−無水マレイン酸共重
合体などであった。In particular, toner binder resins that are particularly effective in combination with the specific silane compounds mentioned above include styrene resins, polyvinyl chloride, polyethylene, polyvinyl acetate, polypropylene, polyester resins, acrylic resins, silicone resins, and epoxy resins. resin, xylene resin, maleic acid-modified phenol resin, methyl vinyl ether-maleic anhydride copolymer, etc.
又、本発明のトナーには、必要に応じて上記以外の添加
剤を混合しても良い。添加剤としては、例えばテフロン
、ステアリン酸亜鉛の如き滑剤二酸化セリウム、炭化ケ
イ素等の研磨材；例えばコロイダルシリカ、酸化チタン
、酸化アルミニウム等の流動性付与剤−ケーキング防止
剤；例えばカーボンブラック、酸化スズ等の導電性付与
剤；低分子量ポリエチレンなどの定着助剤等がある。Furthermore, additives other than those mentioned above may be mixed into the toner of the present invention, if necessary. Examples of additives include lubricants such as Teflon and zinc stearate; abrasives such as cerium dioxide and silicon carbide; flow agents such as colloidal silica, titanium oxide, and aluminum oxide; and anti-caking agents such as carbon black and tin oxide. and fixing aids such as low molecular weight polyethylene.
特に、アルキルクロロシラン、アルキルアミノシラン、
アルキルアルコキシシラン或はシリコーンオイル等で処
理された疎水性シリカがトナーに外添されることが好ま
しい。In particular, alkylchlorosilane, alkylaminosilane,
It is preferable that hydrophobic silica treated with alkyl alkoxysilane or silicone oil is externally added to the toner.
以上の如く本発明のポリシラン化合物と特定のシラン化
合物で処理された磁性体を磁性トナーに用いると磁性体
、電荷制御剤の結着樹脂への分散性及び密着性が極めて
良好になり、且つトナーの耐湿性、流動性、耐衝撃性も
著しく改善され、更にトナーの帯電特性の安定化も改善
され、トナー特性及び耐久性の良好な磁性トナーが得ら
れる。As described above, when a magnetic material treated with the polysilane compound of the present invention and a specific silane compound is used in a magnetic toner, the dispersibility and adhesion of the magnetic material and charge control agent to the binder resin are extremely good, and the toner is The moisture resistance, fluidity, and impact resistance of the toner are also significantly improved, and the stabilization of the charging characteristics of the toner is also improved, so that a magnetic toner with good toner characteristics and durability can be obtained.
本発明に係る磁性トナーを作製するには前記本発明に係
るポリシラン化合物電荷制御剤及び処理された磁性体を
、上記結着樹脂及び添加剤等をボールミルその他の混合
機により充分混合してから加熱ロール、ニーダ−、エク
ストルーダー等の熱混練機を用いて溶融及び混練して樹
脂類を互いに相溶せしめた中に顔料又は染料を分散又は
溶解せしめ、冷却固化後、粉砕及び分級して平均粒径５
〜２０μのトナーを得ることが出来る。或は結着樹脂溶
液中に材料を分散した後、噴露乾燥することにより得る
方法、或は、結着樹脂を構成すべき単量体に所定材料を
混合して乳化懸濁液とした後に重合させてトナーを得る
重合法トナー製造法、或はコア材とシェル材からなるい
わゆるマイクロカプセルトナーのコア部及び／又はシェ
ル部に含有させる方法等の方法が応用できる。To produce the magnetic toner according to the present invention, the polysilane compound charge control agent according to the present invention and the treated magnetic material are thoroughly mixed with the binder resin and additives in a ball mill or other mixer, and then heated. Pigments or dyes are dispersed or dissolved in the resin by melting and kneading using a heat kneader such as a roll, kneader, or extruder, and the resins are made to be compatible with each other. After being cooled and solidified, it is crushed and classified to obtain average particles. Diameter 5
~20μ toner can be obtained. Alternatively, after dispersing the material in a binder resin solution and then spray drying it, or by mixing a specified material with the monomers that should constitute the binder resin to form an emulsified suspension. Methods such as a polymerization toner production method in which a toner is obtained by polymerization, or a method in which the toner is incorporated into the core and/or shell of a so-called microcapsule toner consisting of a core material and a shell material can be applied.
［実施例］
以下、本発明を実施例により、更に具体的に説明するが
、本発明はこれらの実施例により何ら限定されるもので
はない。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
尚、以下の配合における「部」は全て重量部である。In addition, all "parts" in the following formulations are parts by weight.
実施例１〜２．比較例１〜２ 以下の方法で磁性体を処理した。Examples 1-2. Comparative examples 1-2 The magnetic material was treated in the following manner.
処理方法（Ｉ）
γ−メタクリルオキシプロピルメトキシシラン（商品名
、Ｚ−６０３０、ダウ・コーニング社製）５部を酢酸で
ｐＨ４，０に調整した水１０００部に添加して良く攪拌
した。Treatment method (I) 5 parts of γ-methacryloxypropylmethoxysilane (trade name, Z-6030, manufactured by Dow Corning) were added to 1000 parts of water adjusted to pH 4.0 with acetic acid and stirred well.
次いでマグネタイト微粒子（商品名、ＥＰＴ−１０００
、戸田工業製）５００部を加え攪拌を３０分続け、２４
時間放置後マグネタイトをｔ１取し、メチルアルコール
で洗浄後乾燥して本発明の特定のシラン化合物で処理さ
れた磁性体を得た。この磁性体を磁性体Ａとする。Next, magnetite fine particles (trade name, EPT-1000
, manufactured by Toda Kogyo) and continued stirring for 30 minutes.
After standing for a period of time, the magnetite was collected at t1, washed with methyl alcohol, and dried to obtain a magnetic material treated with the specific silane compound of the present invention. This magnetic material is referred to as magnetic material A.
次に、別の処理方法（２）を示す。Next, another processing method (2) will be shown.
を１時間混合攪拌後ポリエステル樹脂の５％メチルエチ
ルケトン溶液５００部及びメチルエチルケトンパーオキ
シド０．１部を注加して攪拌を１時間続け２４時間放置
した。この分散液から固形分を濾過乾燥して本発明の特
定のシラン化合物及びポリエステル樹脂で処理した磁性
粉体の塊状物を得た。After mixing and stirring for 1 hour, 500 parts of a 5% solution of polyester resin in methyl ethyl ketone and 0.1 part of methyl ethyl ketone peroxide were added, stirring was continued for 1 hour, and the mixture was left for 24 hours. The solid content was filtered and dried from this dispersion to obtain a lump of magnetic powder treated with the specific silane compound and polyester resin of the present invention.
これを粉砕して処理された磁性体を得た。この磁性体を
磁性体Ｂとする。This was crushed to obtain a treated magnetic material. This magnetic material will be referred to as magnetic material B.
次に上記の磁性体Ａ、Ｂを用いて下記の如くして磁性ト
ナーを作った。Next, a magnetic toner was prepared using the above magnetic materials A and B in the following manner.
実施例１
上記の各処方量を十分にヘンシェルミキサーに・より予
備混合を行ない、３木ロールミルで少なくとも２回以上
溶融混練し、冷却後ハンマーミルを用いて約１〜２１ｎ
ｍ程度に粉砕して、次いでエアージェット方式による微
粉砕機で４０μｍ以下の粒径に微粉砕した。更に得られ
た微粉砕物を分級して、１〜２０μｍを選択して負帯電
性磁性トナーを得た。Example 1 The above prescription amounts were sufficiently premixed using a Henschel mixer, melted and kneaded at least twice using a Miki roll mill, and after cooling were mixed using a hammer mill to give approximately 1 to 21 nm.
The mixture was ground to a particle size of 40 μm or less using an air jet type pulverizer. Further, the obtained finely pulverized product was classified to select a size of 1 to 20 μm to obtain a negatively charged magnetic toner.
このトナー１００部に対し、流動性付与剤としてシリコ
ーンオイル処理した疎水性シリカ０．８部をヘンシェル
ミキサーで混合外添した。To 100 parts of this toner, 0.8 parts of hydrophobic silica treated with silicone oil was mixed and externally added as a fluidity imparting agent using a Henschel mixer.
このトナーを市販のキャノン製複写機（商品名ＮＰ−８
５８０）を１００枚／分機に改造した機械に適用し画像
テストを行なったところ、高画像濃度（Ｉ，３８）で７
００，０００枚耐久後もカブリのない良好な画像が得ら
れた。Apply this toner to a commercially available Canon copier (product name NP-8).
580) was applied to a machine modified to produce 100 sheets per minute, and an image test was performed.
Good images without fogging were obtained even after 00,000 sheets of durability.
又、低温低湿下において、チャージアップによる画像濃
度低下や、高温高温下においてカブリのない良好な画像
が得られた。In addition, good images were obtained with no reduction in image density due to charge-up under low temperature and low humidity conditions, and without fogging under high temperature conditions.
実施例２
実施例１の磁性体Ａを磁性体Ｂにする以外実施例１と同
様に行なった結果、同様な結果が得られた。Example 2 The same procedure as in Example 1 was performed except that magnetic material A in Example 1 was replaced with magnetic material B, and the same results were obtained.
比較例１
実施例１の磁性体Ａを未処理のマグネタイトにする以外
実施例１と同様に行なった結果、５００．０００枚耐久
後の画像濃度が１．２０と低下した。Comparative Example 1 The same procedure as in Example 1 was carried out except that the magnetic material A in Example 1 was replaced with untreated magnetite. As a result, the image density after running for 500,000 sheets decreased to 1.20.
現像器を調べると、スリーブ上にトナー付着が観察され
た。Upon inspection of the developer, toner adhesion was observed on the sleeve.
実施例３
実施例の処理方法（Ｉ）と同様にして、シラン化合物処
理剤をビニルトリエトキシシランを用いて磁性体を処理
した磁性体を用いる他は実施例１と同様に行なったとこ
ろ、７００，０００枚耐久後も画像濃度は１．３５と高
く、良好な結果が得られた。Example 3 The same procedure as in Example 1 was conducted except that a magnetic material treated with vinyltriethoxysilane as a silane compound treatment agent was used in the same manner as in the treatment method (I) of Example 1. Even after running on ,000 sheets, the image density was as high as 1.35, and good results were obtained.
実施例４
上記客処方量で実施例１と同様にトナーを作製し、得ら
れたトナーは正帯電性磁性トナーであった。Example 4 A toner was produced in the same manner as in Example 1 using the above-mentioned amount prescribed by the customer, and the obtained toner was a positively charged magnetic toner.
７０枚／分に改造した市販のキャノン製複写機（商品名
ＮＰ−５５４０）にこの磁性トナーを適用し、実施例１
と同様に行なったところ、５００，０００枚耐久後も１
．３７と高い画像濃度でカブリのない鮮明な画像が得ら
れた。又、環境変動することもなく、良好な画像が得ら
れた。This magnetic toner was applied to a commercially available Canon copying machine (product name NP-5540) modified to produce 70 sheets per minute, and Example 1 was obtained.
When I did the same thing, even after 500,000 sheets, 1
．． A clear image without fog was obtained with a high image density of 37. In addition, good images were obtained without any environmental changes.
比較例２
実施例４において、ポリシラン化合物をニグロシン染料
４部にする以外は実施例４と同様にトナーを作製した。Comparative Example 2 A toner was produced in the same manner as in Example 4, except that the polysilane compound was changed to 4 parts of nigrosine dye.
得られたトナーは正帯電性トナーであり、実施例４と同
様に行なったところ、高温高温環境下においてカブリの
ある画像が得られた。The obtained toner was a positively chargeable toner, and when it was carried out in the same manner as in Example 4, a foggy image was obtained in a high temperature environment.
［発明の効果］
以上説明した通り、本発明のトナーは、高温高湿下であ
っても優れた現像性を示し、高品質の画像を長期間安定
して供給することができる。[Effects of the Invention] As described above, the toner of the present invention exhibits excellent developability even under high temperature and high humidity conditions, and can stably supply high-quality images over a long period of time.
Claims (1)
が２，０００〜１，０００，０００であるポリシラン化
合物と一般式（II）で表わされるシラン化合物で処理さ
れた磁性体とを含有することを特徴とする磁性トナー。 一般式（ I ） ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３及びＲ＿４は、アルキ
ル、アリール、置換アルキル、置換アリール、及びアル
コキシから成る群から選ばれ、いずれも同じであっても
或は異なってもよい。ｎとｍはポリマー中の総モノマー
に対するそれぞれのモノマー数の割合を示すモル比であ
り、ｎ＋ｍ＝１となり、０＜ｎ≦１、０≦ｍ＜１である
。） 一般式（II） ＲＳｉＸ＿３ （式中、Ｒは末端ビニル基を有する有機官能基であり、
Ｘは、水酸基又は加水分解して水酸基となる基である。 ）[Scope of Claims] A magnetic material treated with at least a polysilane compound represented by general formula (I) having a weight average molecular weight of 2,000 to 1,000,000 and a silane compound represented by general formula (II); A magnetic toner characterized by containing. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. n and m are molar ratios indicating the proportion of the number of each monomer to the total monomers in the polymer, n+m=1, 0<n≦1, 0≦m<1 ) General formula (II) RSiX_3 (wherein, R is an organic functional group having a terminal vinyl group,
X is a hydroxyl group or a group that is hydrolyzed to become a hydroxyl group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1343254A JPH03203744A (en) | 1989-12-29 | 1989-12-29 | Magnetic toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1343254A JPH03203744A (en) | 1989-12-29 | 1989-12-29 | Magnetic toner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03203744A true JPH03203744A (en) | 1991-09-05 |
Family
ID=18360109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1343254A Pending JPH03203744A (en) | 1989-12-29 | 1989-12-29 | Magnetic toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03203744A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012018206A (en) * | 2010-07-06 | 2012-01-26 | Canon Inc | Magnetic toner |
-
1989
- 1989-12-29 JP JP1343254A patent/JPH03203744A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012018206A (en) * | 2010-07-06 | 2012-01-26 | Canon Inc | Magnetic toner |
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