JPH01140168A - Carrier for developer - Google Patents
Carrier for developerInfo
- Publication number
- JPH01140168A JPH01140168A JP62299497A JP29949787A JPH01140168A JP H01140168 A JPH01140168 A JP H01140168A JP 62299497 A JP62299497 A JP 62299497A JP 29949787 A JP29949787 A JP 29949787A JP H01140168 A JPH01140168 A JP H01140168A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- developer
- toner
- resin
- vinyl monomer
- 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
- 239000000178 monomer Substances 0.000 claims abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 15
- 239000011162 core material Substances 0.000 claims description 13
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007771 core particle Substances 0.000 abstract 2
- KMLPAHOXGCAUJO-UHFFFAOYSA-N 2-ethenylpyridine methyl 2-methylprop-2-enoate styrene Chemical compound C(C(=C)C)(=O)OC.C=CC1=CC=CC=C1.C(=C)C1=NC=CC=C1 KMLPAHOXGCAUJO-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920001897 terpolymer Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 40
- 229920005989 resin Polymers 0.000 description 40
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- -1 Vinyl phthalic acid imide Chemical class 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000007774 longterm Effects 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
- 229910052759 nickel Inorganic materials 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 description 2
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 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 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 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 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- JDCUKFVNOWJNBU-UHFFFAOYSA-N 2-ethenyl-1,3-thiazole Chemical compound C=CC1=NC=CS1 JDCUKFVNOWJNBU-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- MJKIORXNEJFOPX-UHFFFAOYSA-N 2-prop-1-en-2-ylpyridine Chemical compound CC(=C)C1=CC=CC=N1 MJKIORXNEJFOPX-UHFFFAOYSA-N 0.000 description 1
- SFOHETZMLXYFPZ-UHFFFAOYSA-N 2-prop-1-en-2-ylquinoline Chemical compound C1=CC=CC2=NC(C(=C)C)=CC=C21 SFOHETZMLXYFPZ-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- KPPONQWQFTVQMM-UHFFFAOYSA-N 3-ethenylpyrrolidine-2,5-dione Chemical compound C=CC1CC(=O)NC1=O KPPONQWQFTVQMM-UHFFFAOYSA-N 0.000 description 1
- WWDWPSQOAUMNDT-UHFFFAOYSA-N 3-prop-1-en-2-ylpyridine Chemical compound CC(=C)C1=CC=CN=C1 WWDWPSQOAUMNDT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- REEFSLKDEDEWAO-UHFFFAOYSA-N Chloraniformethan Chemical compound ClC1=CC=C(NC(NC=O)C(Cl)(Cl)Cl)C=C1Cl REEFSLKDEDEWAO-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- LTGPFZWZZNUIIK-LURJTMIESA-N Lysol Chemical compound NCCCC[C@H](N)CO LTGPFZWZZNUIIK-LURJTMIESA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 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
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- HBHZKFOUIUMKHV-UHFFFAOYSA-N chembl1982121 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HBHZKFOUIUMKHV-UHFFFAOYSA-N 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 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
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 244000266946 suren Species 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000008096 xylene 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1132—Macromolecular components of coatings
- G03G9/1133—Macromolecular components of coatings obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、静電潜像を現像する現像剤用キャリアに関し
、より詳細にはトナーへの帯電付与能力に優れていると
ともに、現像剤を汚染することのない現像剤用キャリア
に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a carrier for a developer that develops an electrostatic latent image, and more specifically, the present invention relates to a carrier for a developer that develops an electrostatic latent image. This invention relates to a developer carrier that does not cause contamination.
（従来技術及びその問題点）
二成分現像剤を用いる電子写真法においては、トナーと
磁性キャリアとを混合し、この二成分系混合物を、内部
に磁石を備えた現像スリーブ上に供給して、この混合物
からなる磁気ブラシを形成させ、静電潜像を有する電子
写真感光体にこの磁気ブラシを摺擦せしめることにより
、顕電性トナー像を感光体上に形成させる。トナーは磁
性キャリアとの摩擦により、感光体上の静電潜像の電荷
とは逆極性の電荷に帯電され、磁気ブラシ上のトナー粒
子がクーロン力により静電潜像上に付着して、静電潜像
の現像が行われる。このように、二成分現像剤において
は、キャリアとの摩擦により現像に必要な極性の電荷が
トナーに与えられるのであるが、一般にトナー成分であ
る樹脂とキャリアの摩擦帯電だけでは、充分な帯電特性
が得られないために、トナー中に染料および顔料等から
なる電荷制御剤を含有させ、帯電性能を向上させている
場合が少なくない。(Prior art and its problems) In electrophotography using a two-component developer, a toner and a magnetic carrier are mixed, and this two-component mixture is supplied onto a developing sleeve equipped with a magnet inside. A magnetic brush made of this mixture is formed and this magnetic brush is rubbed against an electrophotographic photoreceptor having an electrostatic latent image, thereby forming an electrostatic toner image on the photoreceptor. Due to friction with the magnetic carrier, the toner is charged with a charge of opposite polarity to that of the electrostatic latent image on the photoreceptor, and the toner particles on the magnetic brush adhere to the electrostatic latent image due to Coulomb force, causing the toner to become static. The electrolatent image is developed. In this way, in a two-component developer, the polar charge necessary for development is given to the toner by friction with the carrier, but generally the frictional charging between the resin and carrier, which are the toner components, does not provide sufficient charging characteristics. Therefore, in many cases, charge control agents such as dyes and pigments are included in toner to improve charging performance.
しかしながら、電荷制御剤をトナー中に内添する場合、
キャリアとの摩擦帯電に直接支配されるトナー表面に電
荷制御剤を均一に露出させるためには、樹脂中での分散
状態を一定にするとともに多量の電荷制御剤を添加する
必要がある。このようにして得られたトナーを、長期に
わたって使用する場合、初期には良好な現像特性を示す
が、現像操作を進めてい（につれて劣化が起こってくる
。However, when a charge control agent is internally added to a toner,
In order to uniformly expose the charge control agent on the toner surface, which is directly controlled by frictional charging with the carrier, it is necessary to keep the dispersion state in the resin constant and to add a large amount of the charge control agent. When the toner thus obtained is used for a long period of time, it initially exhibits good development characteristics, but as the development operation progresses, deterioration occurs.
その原因は、染願料は多（の場合結着樹脂との相溶性が
または濡れ性が良くない為である。すなわち、現像器内
での撹拌操作によって、電荷制御剤が脱落し、染料およ
び顔料のみからなる微粒子が発生する。これら電荷制御
性微粒子は、本来フェライト等のキャリアとの摩擦電荷
が強く発生し易い物質であるので、キャリアに強く吸着
する傾向を有し、その結果、トナーとキャリア間の摩擦
電荷の値が低下したり、極性が不安定になったり、現れ
る。また、近年、現像用トナーはカラー画像を得る為に
、赤色、青色等の有彩色トナーが使用されることが多く
なってきた。この所謂カラートナーｂ定着用樹脂として
光透過率の小さい樹脂、例えばスチレン系樹脂、エポキ
シ樹脂、ポリエステル樹脂等を使用した場合、分光反射
特性が悪く、鮮明な定着画像が得られない。このために
光透過率の大きい樹脂、例えばＭＭＡ、ＥＡ、ＰＦＭＡ
等のアクリル系樹脂を使用して鮮明な色調を有する定着
画像を得ようとしている。しかしながら、これらＭＭＡ
、ＥＡ、ＰＦＭＡ等のアクリル系樹脂は、摩擦帯電系列
上、正帯電側に位置しているため、負帯電性トナーとし
て使用する場合、負の電荷制御剤をかなりの量添加して
も、従来のキャリアとの摩擦では十分な負の電荷が得ら
れず、カブリ等が発生して鮮明な画像が得られない。こ
のようにトナー中に電荷制御剤を内添して、現像に必要
なトナー帯電量を維持するには、未だ解決すべき問題点
を有している。The reason for this is that the dye charge has poor compatibility or wettability with the binder resin. In other words, the charge control agent falls off due to the stirring operation in the developing device, and the dye and Fine particles consisting only of pigments are generated.These charge control fine particles are substances that tend to generate strong frictional charges with carriers such as ferrite, so they tend to strongly adsorb to carriers, and as a result, toner and The value of frictional charge between carriers may decrease, or the polarity may become unstable.In recent years, chromatic toners such as red and blue have been used for developing toners in order to obtain color images. If a resin with low light transmittance, such as styrene resin, epoxy resin, or polyester resin, is used as the so-called color toner B fixing resin, the spectral reflection characteristics will be poor, making it difficult to obtain a clear fixed image. For this reason, resins with high light transmittance, such as MMA, EA, and PFMA,
Attempts are being made to obtain fixed images with clear color tones using acrylic resins such as. However, these MMA
Acrylic resins such as , EA, and PFMA are located on the positive charging side in the triboelectric charging system, so when used as a negatively charging toner, even if a considerable amount of negative charge control agent is added, Due to friction with the carrier, sufficient negative charge cannot be obtained, causing fogging and the like, making it impossible to obtain a clear image. In this way, there are still problems to be solved in order to maintain the toner charge amount necessary for development by internally adding a charge control agent to the toner.
そこで、トナーへの電荷付与特性の同上をトナーの添加
剤のみにより達成するのではなく、キャアリ側からトナ
ーへ積極的に負電荷を付与するために特開昭６１−１４
５５６３号公報等に有機スズ化合物からなる電荷付与剤
をキャリアの表面に存在させることが記載されている。Therefore, instead of achieving the same charge imparting characteristics to the toner only by using toner additives, in order to actively impart a negative charge to the toner from the carrier side, Japanese Patent Laid-Open No. 61-14
No. 5563 and the like describes that a charge imparting agent made of an organic tin compound is present on the surface of a carrier.
（発明が解決しようとする問題点）
しかしながら、上記公報に記載された有機スズ化合物は
、バインダー樹脂と共にキャリア芯材上に被覆しており
、電荷付与に有効に働かせるにはこの有機スズ化合物を
キャリア表面に均一存在させなければならず、被覆時に
表面上に有機スズ化合物を均一に露出させることはかな
り難しい。また、電荷付与材とバインダー樹脂との相溶
性が良いことも必要であり、相溶性が悪い場合は長期間
撹拌操作が継続されると電荷付与材の脱落により現像剤
の汚染を引き起こし、ひいては帯電量の低下とともにカ
ブリが発生する。(Problems to be Solved by the Invention) However, the organic tin compound described in the above publication is coated on the carrier core material together with a binder resin, and in order to effectively provide charge, the organic tin compound is coated on the carrier core material. It must be uniformly present on the surface, and it is quite difficult to uniformly expose the organotin compound on the surface during coating. It is also necessary that the charge-imparting material and the binder resin have good compatibility; if the compatibility is poor, if the stirring operation is continued for a long period of time, the charge-imparting material will fall off and cause contamination of the developer, which may lead to charging. Fog occurs as the amount decreases.
本発明の目的は、上記問題点を解決したキャリア、即ち
、長期にわたる攪拌操作においても安定した電荷付与効
果と耐久性を合わせ持った現像剤ない優れた画像を得る
現像剤用キャリアを提供することにある。An object of the present invention is to provide a carrier that solves the above-mentioned problems, that is, a carrier for a developer that has both a stable charge imparting effect and durability even during long-term stirring operations, and that produces excellent images without a developer. It is in.
（問題点を解決する手段及び作用）
本発明によれば、芯物質上に含窒素複素環ビニル単量体
、芳香族ビニル単量体及びアルキルアクリレートまたは
メタクリレートを含有する多元重合体を被覆した現像剤
用キャリアを使用することにより上記問題点を解決し、
本発明の目的が達成される。(Means and Effects for Solving the Problems) According to the present invention, a developing device in which a core material is coated with a multicomponent polymer containing a nitrogen-containing heterocyclic vinyl monomer, an aromatic vinyl monomer, and an alkyl acrylate or methacrylate. The above problems are solved by using a carrier for the drug,
The objectives of the invention are achieved.
以下、本発明の詳細な説明する
本発明は含窒素複素環ビニル単量体、ビニル単量体及び
アクリレート又はメタクリレートの王者の多元共重合体
をキャリア芯村上に被覆することが本発明の特徴である
。この多元重合体はキャリア芯材に有効−に被覆するこ
とが出来るとともに、キャリア芯材との接着性が良好で
そして優れた負電荷付与効果を有しいるため、長期にわ
たる攪拌操作においても良好な電荷付与特性と耐久性及
び非凝集性を示し、得られる画像特性が長期間安定した
現像剤を提供することが可能となった。The present invention will be described in detail below.The present invention is characterized in that a carrier core Murakami is coated with a multi-component copolymer of nitrogen-containing heterocyclic vinyl monomer, vinyl monomer, and acrylate or methacrylate. be. This multi-component polymer can be effectively coated on the carrier core material, has good adhesion to the carrier core material, and has an excellent negative charge imparting effect, so it can be used effectively even during long-term stirring operations. It has become possible to provide a developer that exhibits charge-imparting properties, durability, and non-aggregation properties, and whose image properties are stable over a long period of time.
本発明に使用される、含窒素複素環ビニル単量体として
は、含窒素複素環化合物の１個の水素原子がエチレン系
不飽和基で１換された構造のそれ自体公知の単量体、特
に一般式
式中、Ｒ１は水素原子または炭素数４以下（以下低級と
呼ぶ）のアルキル基であり、Ｙは含窒素複素環基である
、
の単量体をあげることがてき。As the nitrogen-containing heterocyclic vinyl monomer used in the present invention, a monomer known per se having a structure in which one hydrogen atom of a nitrogen-containing heterocyclic compound is substituted with an ethylenically unsaturated group; In particular, in the general formula, R1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms (hereinafter referred to as lower), and Y is a nitrogen-containing heterocyclic group.
本発明の目的を特に有用な単量体は、一般式式中、Ｒ２
は前述した意味を有し、
Ｒ２は低級アルキル基であり、７はゼ
ロまたは１の数である、
で表されるビニルピリジン系単量体、例えば４ビニル−
ピリジン（４−ＶＰ） 、２−ビニルピリジン（２−Ｖ
Ｐ） 、３−ビニルピリジン、２−イソプロペニルピリ
ジン、３−イソプロペニルピリジン、２−メチル−５−
ビニルピリジン（ＭＶＰ）、５−エチル−２−ビニルピ
リジン（ＥＶＰ）等である。Particularly useful monomers for the purpose of the present invention are those of the general formula R2
has the above-mentioned meaning, R2 is a lower alkyl group, and 7 is a number of zero or 1.
Pyridine (4-VP), 2-vinylpyridine (2-V
P), 3-vinylpyridine, 2-isopropenylpyridine, 3-isopropenylpyridine, 2-methyl-5-
Vinylpyridine (MVP), 5-ethyl-2-vinylpyridine (EVP), and the like.
これらのビニルピリジン系単量体の他に、２−ビニルキ
ノリン、２−イソプロペニルキノリン、２−ビニルチア
ゾール、ビニルカルバゾール、ビニルコハク酸イミド、
ビニルフタル酸イミド、ビニル−ε−カプロラクタム、
ビニルピロリドン等を用いることができる。この中でも
、２−ビニルピリジン（２−ＶＰ）が特に好ましい。In addition to these vinylpyridine monomers, 2-vinylquinoline, 2-isopropenylquinoline, 2-vinylthiazole, vinylcarbazole, vinylsuccinimide,
Vinyl phthalic acid imide, vinyl-ε-caprolactam,
Vinylpyrrolidone and the like can be used. Among these, 2-vinylpyridine (2-VP) is particularly preferred.
前記多元共重合体を構成゛するビニル芳香族単量体とし
ては、芳香族炭化水素の１個の核水素原子がエチレン系
不飽和基で置換された構造のそれ自体公知の単量体、特
に一般式
式中、Ｒ，、Ｒｇ及びｎは前述した意
味を有する、
の単量体、例えばスチレン（ＳＴ）、α−メチルスチレ
ン、ビニルトルエン等をあげることができ、これらの内
でもスチレンが好適である。The vinyl aromatic monomer constituting the multi-component copolymer may be a monomer known per se having a structure in which one nuclear hydrogen atom of an aromatic hydrocarbon is substituted with an ethylenically unsaturated group, particularly monomers known per se. In the general formula, R,, Rg and n have the above-mentioned meanings. Examples of such monomers include styrene (ST), α-methylstyrene, vinyltoluene, etc. Among these, styrene is preferred. It is.
更に、アルキルアクリレート又はメタクリレートとして
は、下記式
式中、Ｒ８は前述した意味を存し、
Ｒ４は炭素数１２以下のアルキル基
である
の単量体、例えばメチルアクリレート（ＭＡ）、エチル
アクリレート、２−エチルへキシルアクリレート（２−
ＥＨＡ） 、メチルメタクリレート（ＭＭＡ） 、エチ
ルメタクリレート、２−エチルへキシルアクリレート等
を挙げることができる。Further, as the alkyl acrylate or methacrylate, monomers such as methyl acrylate (MA), ethyl acrylate, 2 -ethylhexyl acrylate (2-
EHA), methyl methacrylate (MMA), ethyl methacrylate, 2-ethylhexyl acrylate, and the like.
これらのアルキルアクリレートまたはメタクリレートは
単独でも、或いは２種以上の組合せで使用し得るが、特
にメチルメタクリレートが好ましい。These alkyl acrylates or methacrylates may be used alone or in combination of two or more, but methyl methacrylate is particularly preferred.
本発明においては、前述した３種類の単量体の量比が、
ビニル単量体を２乃至８０重量％、芳香族ビニル単量体
を５乃至８０重量％、及びアルキルアクリレートまたは
メタクリレート単量体を５乃至８５重量％を含有する多
元重合体として使用することが好ましい。即ち、含窒素
複素環単量体の量が上記範囲よりも少ない場合は、帯電
特性の持続性や安定性が得られない、一方この量が上記
範囲よりも覆い場合は、やはり現像剤としてのの流動性
が悪くなる。また、ビニル芳香族単量体が上記範囲より
も少ない場合は、やはり現像剤としての流動性が悪くな
り、上記範囲よりも覆いときは帯電特性の持続性と安定
性が低下する。更にアルキルアクリレート又はメタクリ
レートの量が少ない場合は、帯電特性の安定性や持続性
が低下し、多い場合は現像剤としての流動性が悪くなる
。In the present invention, the quantitative ratio of the three types of monomers mentioned above is
Preferably, it is used as a multipolymer containing 2 to 80% by weight of vinyl monomers, 5 to 80% by weight of aromatic vinyl monomers, and 5 to 85% by weight of alkyl acrylate or methacrylate monomers. . That is, if the amount of the nitrogen-containing heterocyclic monomer is less than the above range, sustainability and stability of charging characteristics cannot be obtained.On the other hand, if this amount exceeds the above range, it will not work as a developer. liquidity becomes worse. Furthermore, if the amount of the vinyl aromatic monomer is less than the above range, the fluidity as a developer will be poor, and the sustainability and stability of charging characteristics will be lower than the above range when covered. Furthermore, if the amount of alkyl acrylate or methacrylate is small, the stability and sustainability of charging characteristics will be reduced, and if it is large, the fluidity of the developer will be poor.
本発明に用いる多元共重合体は、キャリア芯材との接着
性等を考慮して、５，０００乃至１００，０００重量平
均分子量特に２０．０００乃至８０．０００重量平均分
子量を有するることが好ましい。The multicomponent copolymer used in the present invention preferably has a weight average molecular weight of 5,000 to 100,000, particularly a weight average molecular weight of 20.000 to 80.000, taking into account adhesiveness with the carrier core material. .
上記多元共重合体は公知の製造方法によって製造される
が、一つの製造例として下記にしめす。The above-mentioned multi-component copolymer is produced by a known production method, and one production example is shown below.
冷却管付きのステンレス製重合槽（１００１＞に脱イオ
ン水４２ｋｇ、ポリビニルアルコール、オレイン酸カリ
、Ｔｒｉ ｔｏｎＸ−１００（ローム・アンド・ハース
社製非イオン活性剤）をそれぞれ５６０ｇ加え、窒素置
換したのち、２−ＶＰ、ＳＴ、ＭＭＡが重量比で１５：
６０：２５のモノマー混合物２８ｋｇ中の２量、ベンゾ
イルパーオキサイド１４０ｇ加えて７０℃で９０分重合
させた。42 kg of deionized water, polyvinyl alcohol, potassium oleate, and 560 g each of Tri ton , 2-VP, ST, MMA in a weight ratio of 15:
Two amounts of 28 kg of a 60:25 monomer mixture and 140 g of benzoyl peroxide were added and polymerized at 70° C. for 90 minutes.
次に反応槽の温度を９０〜９５℃に上げて残る１４ ｋ
ｔｒのモノマー混合物と２８０ｇのベンゾイルパーオキ
サイドを４時間にわたって加え、２時間の熟成の後冷却
した。得られた共重合体エマルジョンは食塩２８０ｇ、
硫酸バンド５６０ｇの混合水浴中で析出させ充分に水洗
した後、乾燥して多元重合体を生成した。Next, raise the temperature of the reactor to 90-95℃ and the remaining 14k
tr monomer mixture and 280 g of benzoyl peroxide were added over 4 hours, aged for 2 hours, and then cooled. The obtained copolymer emulsion contained 280 g of common salt,
It was precipitated in a mixed water bath containing 560 g of sulfuric acid band, thoroughly washed with water, and then dried to produce a multi-component polymer.
一本発明において、キャリア芯材に樹脂被覆する方法と
しては、流動床コーティング法等の樹脂物質の混合物を
適当な溶媒に溶解し、得られる溶液中にキャリア芯物質
を浸漬するか或いはキャリア芯物質に樹脂溶液を吹きつ
け、しかる後に脱溶媒、乾燥、高温焼付する方法等の従
来より使用されている方法が適用できる。本発明に使用
されるキャリア芯物質としては種々のものが使用され、
磁性体、例えば、酸化鉄、還元鉄、銅、ケイ素鋼、フェ
ライト、ニッケル、コバルト等と、マンガン、亜鉛、ア
ルミニウム等との合金、例えば、鉄・ニッケル合金、鉄
・コバルト合金、鉄・アルミニウム合金などの磁性体等
の従来より使用されているものが使用できる。また、前
記多元共重合体を溶解する有機溶媒としては、例えばメ
タノール、エタノール等の低級アルコールやｎ−ヘキサ
ン、オクタン、シクロヘキサン等の脂肪族系炭化水素、
ジクロロエタン、四塩化炭素、クロロベンゼン等のハロ
ゲン化炭化水素、ジメチルエーテル、ジエチルエーテル
、テトラヒドロフラン、エチレングリコールジメチルエ
ーテル、エチレングリコ−ジエチルエーテル等のエーテ
ル類、アセトン、メチルエチルケトン、シクロヘキサノ
ン等のケトン類、酢酸エチル、酢酸メチル等のエステル
類等を一種或いは２種以上混合して使用することができ
る。In the present invention, the carrier core material is coated with resin by dissolving a mixture of resin materials in an appropriate solvent, such as by fluidized bed coating method, and by immersing the carrier core material in the resulting solution. Conventionally used methods can be applied, such as spraying a resin solution onto the resin, followed by desolvation, drying, and high-temperature baking. Various carrier core materials are used in the present invention,
Alloys of magnetic materials, such as iron oxide, reduced iron, copper, silicon steel, ferrite, nickel, cobalt, etc., and manganese, zinc, aluminum, etc., such as iron-nickel alloys, iron-cobalt alloys, iron-aluminum alloys It is possible to use conventionally used magnetic materials such as . Examples of the organic solvent for dissolving the multi-component copolymer include lower alcohols such as methanol and ethanol; aliphatic hydrocarbons such as n-hexane, octane, and cyclohexane;
Halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, and chlorobenzene, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, and methyl acetate. These esters can be used alone or in combination of two or more.
被覆層の厚みは好適に選択できるが、樹脂溶液を５乃至
４０％より好ましくは１０乃至３０％の範囲に調整して
被覆層すると作業性が良い。本発明のキャリアは、任意
のトナーと二成分現像剤を構成することができる。Although the thickness of the coating layer can be suitably selected, workability is improved if the coating layer is prepared by adjusting the resin solution to a range of 5 to 40%, preferably 10 to 30%. The carrier of the present invention can constitute a two-component developer with any toner.
上記トナーは、少な（とも着色剤と結着樹脂とを含有し
ており、現像方式や定着方式等に適合した種々のものが
使用できる。The above-mentioned toner contains a small amount of colorant and a binder resin, and various toners suitable for the developing method, fixing method, etc. can be used.
上記着色剤としては、従来トナーに使用されている種々
のものが使用でき、例えば、カーボンブランク、ハンザ
イエロー、ベンジジンイエロー、スレンイエロー、キノ
リンイエロー、パーマネントオレンジ、ピラゾロンオレ
ンジ、パルカンオレンジ、ウォッチヤングレッド、パー
マネントレッド、ブリリアントカーミン６Ｂ、ピラゾロ
ンレッド、リソールレッド、ローダミンＢレーキ、レー
キレッドＣ，ローズベンガル、アニリンブルー、ウルト
ラマリンブルー、フタロシアニンブルー、フタロシアニ
ングリーン、等の種々の顔料や種々の染料等が例示され
る。これら着色剤は、一種又は二種以上混合して用いら
れ、十分な画像濃度が得られる量、例えば、１〜３０重
量％、好ましくは、２〜２０重量％用いられる。また、
上記トナーが磁性トナーであるときは、上記着色剤とと
もに、磁性体が使用される。例えば、フェライト、マグ
ネタイトをはじめとする鉄、コバルト、ニッケル、マン
ガン等の強磁性をしめす金属またはその合金が例示でき
る。これちの磁性体は、平均粒径０．１〜１μｍ程度の
大きさを有しており一種または二種以上混合して、通常
２０〜７５重量％、好ましくは、４０〜７５重量％用い
られる。上記結着剤としては、スチレン系共重合体、ア
クリル系共重合体、スチレン−アクリル共重合体、ポリ
エチレン、塩素化ポリエチレン、ポリプロピレン、アイ
オノマー等のオレフィン系重合体、ポリ塩化ビニル、ポ
リエステル、ポリアミド、ポリウレタン、エポキシ樹脂
、ジアリルフタレート樹脂、シリコーン樹脂、ケトン樹
脂、ポリビニルブチラール樹脂、フェノール樹脂、ロジ
ン変性フェノール樹脂、キシレン樹脂、ロジン変性マレ
イン酸樹脂、ロジンエステル、石油樹脂等、各種重合体
が例示される。As the above-mentioned coloring agent, various types conventionally used in toners can be used, such as carbon blank, Hansa yellow, benzidine yellow, suren yellow, quinoline yellow, permanent orange, pyrazolone orange, Palkan orange, and Watch Young Red. , Permanent Red, Brilliant Carmine 6B, Pyrazolone Red, Lysol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Phthalocyanine Blue, Phthalocyanine Green, etc., and various pigments and various dyes are exemplified. be done. These colorants may be used alone or in a mixture of two or more, and used in an amount that provides sufficient image density, for example, 1 to 30% by weight, preferably 2 to 20% by weight. Also,
When the toner is a magnetic toner, a magnetic material is used together with the colorant. For example, ferromagnetic metals such as iron, cobalt, nickel, manganese, etc., including ferrite and magnetite, or alloys thereof can be used. These magnetic substances have an average particle size of about 0.1 to 1 μm, and are used singly or in combination of two or more in an amount of usually 20 to 75% by weight, preferably 40 to 75% by weight. Examples of the binder include styrene copolymers, acrylic copolymers, styrene-acrylic copolymers, polyethylene, chlorinated polyethylene, polypropylene, olefin polymers such as ionomers, polyvinyl chloride, polyester, polyamide, Examples of various polymers include polyurethane, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, phenol resin, rosin-modified phenol resin, xylene resin, rosin-modified maleic acid resin, rosin ester, petroleum resin, etc. .
上記重合体のうち、アクリル系重合体、スチレン−アク
リル共重合体またはポリエステルを主成分とする物が好
ましい。これらの重合体は、重量平均分子量３０００〜
１０００００、特に、５０００〜７５０００の範囲にあ
るものが好ましい。Among the above polymers, those whose main component is an acrylic polymer, a styrene-acrylic copolymer, or a polyester are preferred. These polymers have a weight average molecular weight of 3000~
100,000, particularly preferably in the range of 5,000 to 75,000.
なお、トナーが熱定着性トナーであるとき、上記重合体
は、軟化点５０〜１６０℃、好ましくは、１２０〜１６
０℃を有するものが好ましい。また、トナーが圧力定着
性トナーであるときは、ポリエチレン、ポリプロピレン
等のオレフィン系ポリマー、ポリアミド等の容易に塑性
変形する重合体が用いられる。また、本発明においては
、キャリアが帯電付与能力に優れているため、電荷制御
剤をトナー中に含有しなくてもよいが、より効果的に帯
電付与を行うために含有させる場合は、現像器内の汚染
や、カラートナーの色調を粗悪にしない程度の少量の範
囲で使用すればよい。電荷制御剤としては、例えば、ナ
フテン酸、オクチル酸等の脂肪酸や樹脂酸のコバルト、
鉛、亜鉛、セリウム、カルシウム、ニッケル等の金属塩
である金属石鹸等が例示される。Note that when the toner is a heat fixable toner, the above polymer has a softening point of 50 to 160°C, preferably 120 to 16°C.
Those having a temperature of 0°C are preferred. Further, when the toner is a pressure fixable toner, an olefin polymer such as polyethylene or polypropylene, or a polymer that is easily plastically deformed such as polyamide is used. In addition, in the present invention, since the carrier has excellent charge imparting ability, it is not necessary to include a charge control agent in the toner, but if it is included in order to impart charge more effectively, it is necessary to It is sufficient to use a small amount that does not cause contamination within the toner or deteriorate the color tone of the color toner. Examples of charge control agents include fatty acids such as naphthenic acid and octylic acid, cobalt resin acids,
Examples include metal soaps that are metal salts of lead, zinc, cerium, calcium, nickel, and the like.
本発明に使用されるトナーを製造するには、前記バイン
ダー樹脂中に着色剤を含有させ、必要に応じて各種添加
剤を含有させて、ボールミル等により混合し、混練、粉
砕、分級の各工程を経て本発明のに用いられるトナーを
えることができる。In order to produce the toner used in the present invention, the binder resin contains a coloring agent, and if necessary, various additives are added to the binder resin, and the mixture is mixed using a ball mill or the like, followed by kneading, pulverization, and classification steps. The toner used in the present invention can be obtained through this process.
なお、上記以外の製造方法、例えば、スプレードライ法
、界面重合法、懸濁重合法あるいは溶液重合法等の方法
によっても得ることができる。また、トナーの粒径は５
乃至３０μｍ特に好ましくは７乃至１３μｍのものが使
用される。またコロイダルシリカのような流動化剤、酸
化セリウム、チタン酸ストロンチウム、炭化硅素などの
研磨剤、ステアリン酸亜鉛、弗化ビニリデン等の滑剤に
より表面処理をおこなってもよい。Note that it can also be obtained by a manufacturing method other than the above, such as a spray drying method, an interfacial polymerization method, a suspension polymerization method, or a solution polymerization method. Also, the particle size of the toner is 5
A thickness of 7 to 13 μm is used, particularly preferably 7 to 13 μm. Further, surface treatment may be performed using a fluidizing agent such as colloidal silica, an abrasive agent such as cerium oxide, strontium titanate, or silicon carbide, or a lubricant such as zinc stearate or vinylidene fluoride.
現像剤は、上記本発明のキャリアとトナーを混合するこ
とにより得られるが、トナー濃度を３乃至４．５％に調
整して使用される。The developer is obtained by mixing the above-mentioned carrier of the present invention and toner, and is used with the toner concentration adjusted to 3 to 4.5%.
以下に実施例および比較例により本発明を説明する。The present invention will be explained below with reference to Examples and Comparative Examples.
（実施例１）
キャリア芯材として平均粒径１５０μｍのフエライ）
（ＳＦＣ−１５０、日本鉄粉製）を前述した製造例によ
り作成した２−ビニルピリジンとスチレン及びメチルメ
タクリレートとからなる共重合体（共重合比１５：６０
：２５）をメタノールに溶解させ溶−ｆｊ、ｔ７４度２
０％の樹脂溶液で流動床コーティング法により被覆した
。すなわち、上記フェライトを浮遊させ、流動床コーテ
ィング装置に入れ、該装置の下部より空気を供給して上
記フェライトを流動状態とし、前記樹脂溶液を上記装置
の上方より噴霧し、８０℃で乾燥して溶削を揮散させ１
００℃で乾燥して本発明のキャリアを得た。(Example 1) Ferrite with an average particle size of 150 μm as a carrier core material)
(SFC-150, manufactured by Nippon Steel Powder Co., Ltd.) is a copolymer of 2-vinylpyridine, styrene, and methyl methacrylate (copolymerization ratio 15:60) prepared according to the production example described above.
:25) in methanol and dissolved at -fj,t74 degrees 2
Coated with 0% resin solution by fluidized bed coating method. That is, the ferrite is suspended, placed in a fluidized bed coating device, air is supplied from the bottom of the device to make the ferrite fluidized, the resin solution is sprayed from above the device, and dried at 80°C. Vaporize the melting 1
The carrier of the present invention was obtained by drying at 00°C.
また、結着樹脂としてスチレン−アクリル共重合体１０
重量部、着色剤としてカーボンブラック（プリンテック
スし、デクサ社製商品名）８．５重量部、低分子量ポリ
プロピレン（ビスコール５５０Ｐ、三洋化成社製商品名
）２．５重量部を用いて常法により粒径５〜２０μｍの
粉体黒トナーを作成した。そして、上記本発明のキャリ
アとトナーを混合し、トナー濃度４．５％の現像剤を得
た。In addition, styrene-acrylic copolymer 10 was used as a binder resin.
By a conventional method using 8.5 parts by weight of carbon black (Printex, trade name manufactured by Dexa Corporation) and 2.5 parts by weight of low molecular weight polypropylene (Viscol 550P, trade name manufactured by Sanyo Chemical Co., Ltd.) as a coloring agent. A powder black toner having a particle size of 5 to 20 μm was prepared. Then, the carrier of the present invention and toner were mixed to obtain a developer having a toner concentration of 4.5%.
上記得られた現像剤を混合撹拌機ユニバーサルボールミ
ルＵＢ３１（ヤマト機器化学社製）で１時間混合撹拌し
て摩擦帯電させ、トナー帯電量の変化を測定した。その
結果、帯電の立ち上がりが早く、撹拌後１０分以内に−
１３，６μｃ／ｇの適正帯電量まで達し、そき後を変動
が少なく一定の帯電量を維持していた。また、この現像
剤を復写機（三田工業社製、ＤＣ−１２０５）にて画像
出しを行い、更に５ｏｏｏｏ枚の耐刷複写テストを行い
画像特性について評価した。その結果、画像濃度も十分
な高濃度をしめし、カプリの発生もなく鮮明の画像が初
期から５００００枚まで続いた。耐刷終了後の現像剤は
、被覆樹脂の剥離等による微細粒子の発生もなかった。The developer obtained above was mixed and stirred for 1 hour using a mixing stirrer Universal Ball Mill UB31 (manufactured by Yamato Kiki Kagaku Co., Ltd.) to triboelectrically charge the developer, and the change in the toner charge amount was measured. As a result, charging starts quickly, and within 10 minutes after stirring, -
The appropriate charge amount of 13.6 μc/g was reached, and thereafter a constant charge amount was maintained with little fluctuation. Further, an image was produced using this developer using a copying machine (manufactured by Sanda Kogyo Co., Ltd., DC-1205), and further a printing durability test of 500 sheets was conducted to evaluate the image characteristics. As a result, the image density was sufficiently high, and clear images continued from the initial stage up to 50,000 copies without any occurrence of capri. After the end of printing, no fine particles were generated in the developer due to peeling off of the coating resin.
（実施例２）
実施例１において被覆樹脂を２−ビニルピリジンとスチ
レン及び２−エチルへキシルアクリレート（共重合比１
５：５５：３０）の共重合体とした以外は同様の操作に
より、樹脂被覆キャリアを得た。また、結着樹脂として
メタクリル酸メチルとアクリル酸エチルの共重合体１０
０重量部、着色剤としてオイルブルー２Ｎ（オリエント
化学社製商品名）２重量部、低分子量ポリ、プロピレン
（ビスコール５５０Ｐ （三洋化成社製商品名）２゜５
重量部、電荷制御剤としてサリチル酸亜鉛ボントロンＥ
−８４（オリエント化学社製商品名）０゜５重量部使用
し、実施例１と同様にして青色トナーを得、前記樹脂被
覆キャリアと混合してトナー濃度４．５％の現像剤を作
成した。(Example 2) In Example 1, the coating resin was 2-vinylpyridine, styrene, and 2-ethylhexyl acrylate (copolymerization ratio 1
A resin-coated carrier was obtained by the same operation except that a copolymer of 5:55:30) was used. In addition, a copolymer of methyl methacrylate and ethyl acrylate 10 is used as a binder resin.
0 parts by weight, 2 parts by weight of Oil Blue 2N (trade name manufactured by Orient Chemical Co., Ltd.) as a coloring agent, 2 parts by weight of low molecular weight poly, propylene (Viscol 550P (trade name manufactured by Sanyo Chemical Co., Ltd.) 2゜5
Parts by weight, Zinc salicylate Bontron E as charge control agent
-84 (trade name manufactured by Orient Chemical Co., Ltd.) 0.5 parts by weight was used to obtain a blue toner in the same manner as in Example 1, and mixed with the resin-coated carrier to prepare a developer with a toner concentration of 4.5%. .
次に、実施例１と同様の試験を行ったところ、帯電立ち
上がりは早く１０分後には−１２，３μｃ／ｇ迄達し、
その後も帯電量は大きな変動を示さなかった。また、耐
刷複写テストにおいても、鮮明な青色画像が初期から耐
刷終了まで得ることができた。また、耐刷後の現像剤を
観察したところ微細粒子の発生がなく被覆樹脂の剥離は
見られなかった。Next, when a test similar to that in Example 1 was conducted, charging started quickly and reached -12.3 μc/g after 10 minutes.
Even after that, the amount of charge did not show large fluctuations. Also, in the printing durability copying test, a clear blue image could be obtained from the initial stage to the end of the printing durability. Further, when the developer was observed after printing, no fine particles were generated and no peeling of the coating resin was observed.
（実施例３）
被覆樹脂として２−ビニルピリジンとスチレン及びメチ
ルメタアクリレートの共重合比が（３０：２０：５０）
である共重合体を使用し、他は実施例１と同様の操作及
び試験を行った。その結果、帯電立ち上がりが早く１分
間の混合撹拌によりトナー帯電量−１３，０μｃ／ｇに
達した。その後撹拌操作を継続して行ったが帯電量は安
定に推移した。更に、耐刷複写試験に置いてもカブリの
発生のない良好な画像が１枚目から得られ耐刷終了まで
画像に変化はなかった。また、耐刷後の現像剤を観察し
たところ微細粒子等の汚染物質の発生もな（耐刷前の状
態と殆ど変わらなかった。(Example 3) The copolymerization ratio of 2-vinylpyridine, styrene, and methyl methacrylate as the coating resin was (30:20:50)
The same operations and tests as in Example 1 were carried out except that a copolymer having the following properties was used. As a result, charging started quickly and the toner charge amount reached -13.0 μc/g after 1 minute of mixing and stirring. After that, the stirring operation was continued, but the amount of charge remained stable. Furthermore, even in the durability copying test, a good image without fogging was obtained from the first sheet, and there was no change in the image until the end of the durability printing. Furthermore, when the developer was observed after the printing cycle, there was no generation of contaminants such as fine particles (the condition was almost the same as before the printing cycle).
（比較例１）
被覆樹脂としてスチレンと２−ビニルピリジンから成る
共重合体を使用し、他は実施例１と同様にして現像剤を
得、同様の試験を行った。(Comparative Example 1) A developer was obtained in the same manner as in Example 1 except that a copolymer of styrene and 2-vinylpyridine was used as the coating resin, and the same tests were conducted.
その結果、３分間混合撹拌しても帯電量は一１０μｃ／
ｇまでしか上がらず帯電立ち上がりが遅く帯電量も低い
ものとなった。また、耐刷複写試験においても初期から
カブリが発生し、べた画像の縁には滲みがみられ粗悪な
画像となった。さらに１００００枚を過ぎた頃から定着
不良も発生した。耐刷後の現像剤は被覆樹脂の剥離によ
る微細粒子がみられた。As a result, even after mixing and stirring for 3 minutes, the amount of charge was -10μc/
The charge rise was slow and the amount of charge was low. In addition, fogging occurred from the initial stage in the durability copying test, and blurring was observed at the edges of the solid image, resulting in a poor-quality image. Furthermore, after 10,000 sheets were printed, fixing failures occurred. After printing, fine particles were observed in the developer due to peeling of the coating resin.
（比較例２）
被覆樹脂としてメチルメタアクリレートと２−ビニルピ
リジンとの共重合体を使用し、他は実施例１と同様にし
て現像剤を得、同様の試験を行った。(Comparative Example 2) A developer was obtained in the same manner as in Example 1 except that a copolymer of methyl methacrylate and 2-vinylpyridine was used as the coating resin, and the same tests were conducted.
その結果、帯電量の立ち上がりが遅く、１０分間撹して
も一９μｃ／ｇ迄しか上昇せずその後も４１続して撹拌
操作を行ったが帯電量は上昇しなかった。また、耐刷複
写試験においては、カプリの発生とべた部の画像の滲み
が見られたｅｉＢｔ刷後の現像剤の観察をおこなったと
ころ、現像剤の汚染は殆ど無かった。As a result, the charge amount was slow to rise, and even after 10 minutes of stirring, the charge amount increased only to 19 μc/g, and even after 41 consecutive stirring operations, the charge amount did not increase. Furthermore, in the durability copying test, the developer was observed after the eiBt printing, in which the occurrence of capri and blurring of the image in the solid area, was observed, and it was found that there was almost no contamination of the developer.
上記実施例及び比較例より、本発明の多元共重合体によ
り被覆されたキャリアは、良好な帯電付与特性と耐久性
を合わせ持ったものであることがわかる。From the above Examples and Comparative Examples, it can be seen that the carrier coated with the multi-component copolymer of the present invention has both good charge imparting properties and durability.
（発明の効果）
本発明によれば、実施例からも明らかなように黒色のト
ナーはもちろん、結着樹脂に負帯電しにくいアクリル系
樹脂を使用したカラートナー等に対しても良好な帯電付
与効果を与えるとともに、長期の撹拌操作にも樹脂の剥
離がないキャリア芯物質への密着性に優れた樹脂被覆キ
ャリアが提供される。(Effects of the Invention) According to the present invention, as is clear from the examples, good charging can be imparted not only to black toner but also to color toners etc. whose binder resin uses an acrylic resin that is difficult to be negatively charged. Provided is a resin-coated carrier that not only provides a good effect but also has excellent adhesion to a carrier core material without peeling of the resin even during long-term stirring operations.
Claims (4)
ビニル単量体及びアルキルアクリレートまたはメタクリ
レートを含有する多元重合体を被覆したことを特徴とす
る現像剤用キャリア。(1) A developer carrier characterized in that a core material is coated with a multicomponent polymer containing a nitrogen-containing heterocyclic vinyl monomer, an aromatic vinyl monomer, and an alkyl acrylate or methacrylate.
ることを特徴とする特許請求の範囲第１項記載の現像剤
用キャリア。(2) The developer carrier according to claim 1, wherein the nitrogen-containing heterocyclic vinyl monomer is vinylpyridine.
とする特許請求の範囲第１項記載の現像剤用キャリア。(3) The developer carrier according to claim 1, wherein the aromatic vinyl monomer is styrene.
／メチルメタクリレート共重合体であることを特徴とす
る特許請求の範囲第１項記載の現像剤用キャリア。(4) The developer carrier according to claim 1, wherein the multi-component polymer is a 2-vinylpyridine/styrene/methyl methacrylate copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62299497A JPH01140168A (en) | 1987-11-26 | 1987-11-26 | Carrier for developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62299497A JPH01140168A (en) | 1987-11-26 | 1987-11-26 | Carrier for developer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01140168A true JPH01140168A (en) | 1989-06-01 |
Family
ID=17873341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62299497A Pending JPH01140168A (en) | 1987-11-26 | 1987-11-26 | Carrier for developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01140168A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354638A (en) * | 1989-12-11 | 1994-10-11 | Tdk Corporation | Magnetic carrier for use in electrophotographic development |
-
1987
- 1987-11-26 JP JP62299497A patent/JPH01140168A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354638A (en) * | 1989-12-11 | 1994-10-11 | Tdk Corporation | Magnetic carrier for use in electrophotographic development |
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