JPH0327054A - Electrophotographic carrier and binary developer - Google Patents
Electrophotographic carrier and binary developerInfo
- Publication number
- JPH0327054A JPH0327054A JP1160957A JP16095789A JPH0327054A JP H0327054 A JPH0327054 A JP H0327054A JP 1160957 A JP1160957 A JP 1160957A JP 16095789 A JP16095789 A JP 16095789A JP H0327054 A JPH0327054 A JP H0327054A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- toner
- copolymer
- coating
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000011162 core material Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 abstract description 35
- 239000011248 coating agent Substances 0.000 abstract description 25
- 238000000576 coating method Methods 0.000 abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 22
- 229920002554 vinyl polymer Polymers 0.000 description 21
- 239000000178 monomer Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- -1 bentyl methacrylate Chemical compound 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 239000000969 carrier Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229940090012 bentyl Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- 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
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- TXZUUQRMOIEKKQ-UHFFFAOYSA-N 2-[diethoxy(phenyl)silyl]oxy-n,n-dimethylethanamine Chemical compound CN(C)CCO[Si](OCC)(OCC)C1=CC=CC=C1 TXZUUQRMOIEKKQ-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino 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
- 239000000981 basic dye Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- ABHNFDUSOVXXOA-UHFFFAOYSA-N benzyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CC1=CC=CC=C1 ABHNFDUSOVXXOA-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 1
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000013078 crystal Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- IGFFTOVGRACDBL-UHFFFAOYSA-N dichloro-phenyl-prop-2-enylsilane Chemical compound C=CC[Si](Cl)(Cl)C1=CC=CC=C1 IGFFTOVGRACDBL-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SSROBHHOWHPCHF-UHFFFAOYSA-N n-octyl-n-(3-trimethoxysilylpropyl)octan-1-amine Chemical compound CCCCCCCCN(CCC[Si](OC)(OC)OC)CCCCCCCC SSROBHHOWHPCHF-UHFFFAOYSA-N 0.000 description 1
- ZFCBFSTWFATUJY-UHFFFAOYSA-N n-propyl-n-trimethoxysilylaniline Chemical compound CCCN([Si](OC)(OC)OC)C1=CC=CC=C1 ZFCBFSTWFATUJY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane 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
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CAPIMQICDAJXSB-UHFFFAOYSA-N trichloro(1-chloroethyl)silane Chemical compound CC(Cl)[Si](Cl)(Cl)Cl CAPIMQICDAJXSB-UHFFFAOYSA-N 0.000 description 1
- FLPXNJHYVOVLSD-UHFFFAOYSA-N trichloro(2-chloroethyl)silane Chemical compound ClCC[Si](Cl)(Cl)Cl FLPXNJHYVOVLSD-UHFFFAOYSA-N 0.000 description 1
- FWTXNEXEETXJTN-UHFFFAOYSA-N trimethoxy-(4-propylmorpholin-3-yl)silane Chemical compound CCCN1CCOCC1[Si](OC)(OC)OC FWTXNEXEETXJTN-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はトナーとともＣ静電荷像現像用現像剤を構成す
るキャリア及び二成分系現像剤に関する，
［従来の技術］
電子写真法として米国特許第２，２９７，８９１号明細
書、特公昭４２−２３９１０号公報及び特公昭４３−２
４７４８号公報等に種々の方法が記載されているが、こ
れらの方法は、いずれも光導電層に原稿に応じた光像を
照射することにより静電潜像を形威し、次いで該静電潜
像上にこれとは反対の極性を有するトナーと呼ばれる着
色微粉末を付着させて該静電潜像を現像し、必要に応じ
て紙等の転写材にトナー画像を転写した後、熱、圧力あ
るいは溶剤蒸気等により定着し複写物を得るものである
．該静電潜像を現像する工程は、潜像とは反対の極性に
帯電せしめたトナー粒子を静電引力により吸引せしめて
静電潜像上に付着させるものであるが（反転現像の場合
は、潜像の電荷と同極性の摩擦電荷を有するトナーを使
用）、一般にかかる静電潜像をトナーを用いて現像する
方法としては大別してトナーをキャリアと呼ばれる媒体
に少量分散させたいわゆる二成分系現像剤を用いる方法
と、キャリアを用いることなくトナー単独使用のいわゆ
る一成分系現像剤を用いる方法とがある．一般にかかる
二戒分系現像剤を構戒するキャリアは導電性キャリアと
絶縁性キャリアとに大別される．
導電性キャリアとしては通常酸化または未酸化の鉄粉が
用いられているが、この鉄粉キャリアを戒分とする現像
剤においてはトナーに対する摩擦帯電性が不安定であり
、また現像剤により形成される可視像にカブリが発生す
るという問題点がある．すなわち現像剤の使用に伴い、
鉄粉キャリア粒子の表面にトナー粒子が付着するためキ
ャリア粒子の電気抵抗が増大してバイアス電流が低下し
、しかも摩擦帯電性が不安定となり、この結果形成され
る可視像の画像濃度が低下しカブリが増大する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a carrier and a two-component developer that together with a toner constitute a developer for C electrostatic charge image development. Patent No. 2,297,891, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-2
Various methods are described in Japanese Patent No. 4748, etc., but in all of these methods, an electrostatic latent image is formed by irradiating the photoconductive layer with a light image corresponding to the original, and then the electrostatic latent image is formed. The electrostatic latent image is developed by attaching colored fine powder called toner having the opposite polarity onto the latent image, and if necessary, after transferring the toner image to a transfer material such as paper, heat, Copies are obtained by fixing using pressure or solvent vapor. In the process of developing the electrostatic latent image, toner particles charged to the opposite polarity to that of the latent image are attracted by electrostatic attraction and attached to the electrostatic latent image (in the case of reversal development, (using a toner with a triboelectric charge of the same polarity as the charge of the latent image).Generally speaking, methods for developing electrostatic latent images using toner can be roughly divided into so-called two-component methods in which a small amount of toner is dispersed in a medium called a carrier. There are two methods: one uses a developer, and the other uses a so-called one-component developer, which uses toner alone without using a carrier. In general, carriers used in such two-component type developers are broadly classified into conductive carriers and insulating carriers. Oxidized or unoxidized iron powder is usually used as a conductive carrier, but developers using this iron powder carrier have unstable triboelectric charging properties with respect to toner, and There is a problem that fog occurs in the visible image. In other words, with the use of developer,
As the toner particles adhere to the surface of the iron powder carrier particles, the electrical resistance of the carrier particles increases and the bias current decreases, and the triboelectric charging properties become unstable, resulting in a decrease in the image density of the visible image formed. and fog increases.
また絶縁性キャリアとしては一般に鉄，ニッケル．フエ
ライト等の強磁性体より成るキャリア芯材の表面を絶縁
性樹脂により均一に被覆したキャリアが代表的なもので
ある。このキャリアを用いた現像剤においては、キャリ
ア表面にトナー粒子が融着することが導電性キャリアの
場合社比べて著しく少なく、耐久性に優れ、使用寿命が
長い点で特に高速の電子複写機に好適であるという利点
がある。Insulating carriers are generally iron and nickel. A typical example is a carrier in which the surface of a carrier core material made of a ferromagnetic material such as ferrite is uniformly coated with an insulating resin. Developers using this carrier have significantly fewer toner particles fused onto the carrier surface than those using conductive carriers, and are particularly suitable for high-speed electronic copying machines due to their excellent durability and long service life. It has the advantage of being suitable.
しかしながら、この絶縁性キャリアにおいては、キャリ
ア芯材の表面を被覆する被覆層が、十分な耐摩滅性およ
び芯材との強力な接着性を有すること（耐久性）、キャ
リア表面にトナーに−よる膜体が形戊されぬよう被覆層
が良好な固着防止特性を有すること（トナースベント特
性）、およびキャリアと共に用いられる特定のトナーと
の摩擦により所望の値ならびに極性の帯電状態が得られ
ること（帯電性）が要求される．すなわち、キャリアは
現像器内において、他のキャリア粒子およびトナー粒子
と摩擦されるが、キャリア被覆層の表面にトナーが付着
して被膜が形成されると帯電特性が不安定となる。However, in this insulating carrier, the coating layer covering the surface of the carrier core material must have sufficient abrasion resistance and strong adhesion to the core material (durability), and the coating layer that covers the surface of the carrier core material must have sufficient abrasion resistance and strong adhesion to the core material (durability). The coating layer must have good adhesion prevention properties (toner venting properties) so that the film body does not become deformed, and the desired charge value and polarity can be obtained by friction with the specific toner used with the carrier. (Chargeability) is required. That is, the carrier is rubbed against other carrier particles and toner particles in the developing device, but when toner adheres to the surface of the carrier coating layer and a film is formed, the charging characteristics become unstable.
従来、かかる問題点を解決する技術として、米国特許第
３，９２２，３８２号明細書において、臨界表面張力の
低い含フッ素ボリマーまたは含フッ素樹脂で被覆した被
覆キャリアが提案されているが、上記従来技術において
は含フッ素ボリマーのみで被覆したキャリアは成膜性が
悪く、部分的にしかキャリア表面を被覆できず、帯電特
性が不安定となってしまう傾向が極めて強い。Conventionally, as a technique for solving this problem, a coated carrier coated with a fluorine-containing polymer or fluorine-containing resin having a low critical surface tension has been proposed in U.S. Pat. No. 3,922,382. In terms of technology, carriers coated only with fluorine-containing polymers have poor film-forming properties, can only partially coat the carrier surface, and have a strong tendency to have unstable charging characteristics.
一方、スチレン・メタクリレート共重合体等のビニル系
樹脂でコートされたキャリアは、成膜性が良好で、キャ
リア芯材との接着性も強く、耐摩耗性に優れている．し
かしながら、このビニル系樹脂は、臨界表面張力が比較
的高いため、繰返しの使用に際してはやはりトナーのス
ベントが起こり易く、現像剤の寿命に若干問題がある．
また、正帯電性のトナーに対しては、帯電付与能力が低
いといつ間”題がある．さらに、その成膜性の良さのた
めに、キャリアが過剰に高抵抗化し易く、そのため、ト
ナーのチャージアップによりキャリアからのトナー離れ
が悪くなり易い。On the other hand, carriers coated with vinyl resins such as styrene/methacrylate copolymers have good film-forming properties, strong adhesion to the carrier core material, and excellent wear resistance. However, since this vinyl resin has a relatively high critical surface tension, toner tends to vent when used repeatedly, causing some problems in the lifespan of the developer.
In addition, positively chargeable toners often have problems if they have low charge imparting ability.Furthermore, due to their good film-forming properties, carriers tend to have an excessively high resistance, and as a result, toner Charge-up tends to make toner difficult to separate from the carrier.
また、特開昭５４−１１０８３９号公報（ ＵＳＰａｔ
ｅｎｔＮｏ．４２９７４２７）において含フッ素ポリマ
ーの成膜性を改良するため、成膜性の比較的良好なボリ
マーと混合して被覆したキャリアも提案されているが、
戒膜性がよくなれば必然的に高抵抗化し、前述の様なト
ナーのチャージアップ（よるキャリアからのトナー離れ
が悪くなる。Also, Japanese Patent Application Laid-Open No. 110839/1983 (US Pat
entNo. In order to improve the film-forming properties of fluorine-containing polymers, a carrier coated with a polymer mixed with relatively good film-forming properties has been proposed in 4297427).
If the film resistance improves, the resistance will inevitably increase, and the above-mentioned toner charge-up (due to toner separation from the carrier) will become worse.
さらに、この様にトナーがキャリアから離れづらくなっ
た状態で現像を長時間続けていると、上述のトナーによ
るキャリアのスベント化が一層促進されることとなり好
ましくない．
また、キャリアがあまりに高抵抗すぎる場合、画像濃度
の低下べ夕部中間調の再現性の劣化、或いは、感光体上
へキャリアが現像されてしまい感光体をキズつけたり、
画像上にキャリアが付着してしまうことがある。Furthermore, if development is continued for a long time in a state where the toner is difficult to separate from the carrier, the above-mentioned sventing of the carrier by the toner will be further promoted, which is undesirable. Furthermore, if the resistance of the carrier is too high, the image density may decrease, the reproducibility of halftones in the evening area may deteriorate, or the carrier may be developed onto the photoreceptor, causing damage to the photoreceptor.
Carrier may adhere to the image.
この様に、キャリア表面の抵抗をコントロールしつつコ
ート材の戒膜性をそこなわない様にすることは大変重要
でありながら困難なことなのである．この様な問題を解
決するために、従来から導電性微粒子をキャリアコート
樹脂中に分散させ、抵抗をコントロールする試みがなさ
れている．例えば、特公昭５３−６５３５号公報では、
０．１μ一以下の導電性微粒子を添加することが示され
ているし、他にも特開昭５４−７３４３号公報等多数出
願がなされている。In this way, it is extremely important, yet difficult, to control the resistance of the carrier surface without damaging the coating properties of the coating material. In order to solve these problems, attempts have been made to control the resistance by dispersing conductive fine particles in carrier coating resin. For example, in Japanese Patent Publication No. 53-6535,
It has been shown that conductive fine particles of 0.1 μm or less are added, and many other applications such as Japanese Patent Laid-Open No. 7343/1983 have been filed.
しかしながら、これらの提案の方法における共通の課題
は、キャリアの表面抵抗を好ましい値にまで下げるため
に必要十分な量の導電性微粉を添加すると、コア材とコ
ート樹脂との密着性が低下し、前述したキャリアの耐久
性を損ねることになり、さらには、コート材をキャリア
表面にコートする工程においてすでに膜が形成されない
こともある。また、特に高湿下におけるトナーへの帯電
付与能力が低下してしまう、という別の問題も生ずる．
［発明が解決しようとする課題］
以上のような現状の問題点に鑑み、本発明の目的とする
ところは、以下の点を解決することにある．
本発明の第一の目的は、トナーのスペント化の少ない樹
脂コートキャリアを提供することにある．
本発明の第二の目的は、チャージアップしにくい樹脂コ
ートキャリアを提供することにある。However, a common problem with these proposed methods is that when a sufficient amount of conductive powder is added to reduce the surface resistance of the carrier to a desirable value, the adhesion between the core material and the coating resin decreases. This will impair the durability of the carrier as described above, and furthermore, a film may not be formed even in the process of coating the carrier surface with the coating material. In addition, another problem arises in that the ability to charge the toner decreases, especially under high humidity conditions. [Problems to be Solved by the Invention] In view of the current problems as described above, the purpose of the present invention is to solve the following points. The first object of the present invention is to provide a resin-coated carrier that causes less spent toner. A second object of the present invention is to provide a resin-coated carrier that is difficult to charge up.
本発明の第三の目的は、繰り返しの使用に際しても安定
した帯電特性を有する樹脂コートキャリアを提供するこ
とにある。A third object of the present invention is to provide a resin-coated carrier that has stable charging characteristics even when used repeatedly.
本発明の第四の目的は、耐摩耗性に優れた樹脂コートキ
ャリアを提供することにある。A fourth object of the present invention is to provide a resin-coated carrier with excellent abrasion resistance.
［課題を解決するための手段及び作用］本発明は、粒径
が１．０μ１以下の導電性微粒子が分散され、かつヒド
ロキシル価１〜１００を有するビニル系共重合体及びフ
ッ素樹脂を含む混合樹脂が、キャリア芯材に被覆されて
いることを特徴とする電子写真用キャリアおよび、該キ
ャリアと正帯電性トナーからなる現像剤に関するもので
ある．
本発明者らは鋭意研究した結果、ヒドロキシル基を含む
ビニル系樹脂は、キャリア芯材との結着性にすぐれてお
り、選択的にキャリア芯材に付着する傾向が強く、その
結果、他の混合物がキャリア被覆表面に露出される傾向
があるらしいことを見出した。本発明はこの特性を利用
したもので、正帯電性トナーに対して正帯電付与能力の
高いフッ素樹脂をキャリア被覆表面に積極的に露出させ
るとともに、表面が高抵抗になりすぎるのを防ぐための
導電性微粒子も同様社キＹリア表面にｆＪ ８ｉ的に露
出させることにより、耐久性に優れチャージアップを防
いだ正帯電付与能力の高いキャリアが得られる。[Means and effects for solving the problems] The present invention provides a mixed resin containing a vinyl copolymer and a fluororesin in which conductive fine particles having a particle size of 1.0 μ1 or less are dispersed and having a hydroxyl value of 1 to 100. The present invention relates to an electrophotographic carrier characterized in that it is coated with a carrier core material, and a developer comprising the carrier and a positively chargeable toner. As a result of intensive research by the present inventors, vinyl resins containing hydroxyl groups have excellent binding properties with carrier core materials, and have a strong tendency to selectively adhere to carrier core materials. It has been found that there appears to be a tendency for the mixture to be exposed on the carrier coated surface. The present invention takes advantage of this characteristic by actively exposing the fluororesin, which has a high ability to impart positive charge to positively chargeable toner, on the surface of the carrier coating, and also to prevent the surface from becoming too high in resistance. By exposing the conductive fine particles on the surface of the carrier in a similar manner, a carrier having excellent durability, preventing charge-up, and having a high ability to impart a positive charge can be obtained.
本発明に用いられるヒ，ドロキシル基を含むビニル系樹
脂とはヒドロキシル基を有するビニルモノマーと他のビ
ニルモノマーとの共重合体である。The vinyl resin containing a hydroxyl group used in the present invention is a copolymer of a vinyl monomer having a hydroxyl group and another vinyl monomer.
ヒドロキシル基を有するビニルモノマーとしてはアクリ
ル酸２−ヒドロキシエチル，アクリル酸２−ヒドロキシ
ブロビル，アクリル酸２−ヒドロキシブチル，アクリル
酸２−ヒドロキシー３−フェニルオキシプロビル，メタ
クリル酸２−ヒドロキシエチル，メタクリル酸２−ヒド
ロキシブロビル，メタクリル酸２−ヒドロキシブチル，
メタクリルｒｌ＆２−ヒドロキシ−３−フェニルオキシ
プロビル等がある。これらのモノマーは共重合体のヒド
ロキシル価が、１〜１００ （ＫＯＨｍｇ／ｇ） よ
り好ましくは５〜７０、さらに好ましくは１０〜Ｓｏ
（Ｋｏｕｍｇ／ｇ）になるように使用するのが良い。こ
の値が小さいとキャリア芯材と被覆層との結着性が不十
分となり、衝撃及び摩擦等により被覆が破壊されやすく
なり、さらに、本発明の主目的たる含フッ素樹脂のキャ
リア表面への露出効果が不充分で、キャリアの正帯電付
与能力が低下する．また、大きすぎると吸湿性が高まり
、高温高湿下におけるｆ電安定性がなくなる。Vinyl monomers having hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxybrobyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenyloxyprobyl acrylate, 2-hydroxyethyl methacrylate, and methacrylate. 2-hydroxybrobyl acid, 2-hydroxybutyl methacrylate,
Examples include methacryl RL & 2-hydroxy-3-phenyloxyprobyl. These monomers have a copolymer hydroxyl value of 1 to 100 (KOHmg/g), more preferably 5 to 70, and even more preferably 10 to So
(Koumg/g). If this value is small, the adhesion between the carrier core material and the coating layer will be insufficient, and the coating will be easily destroyed by impact, friction, etc., and furthermore, the exposure of the fluorine-containing resin to the carrier surface, which is the main objective of the present invention, will be reduced. The effect is insufficient, and the carrier's ability to impart positive charge decreases. On the other hand, if it is too large, the hygroscopicity will increase and the f-electrode stability will be lost under high temperature and high humidity conditions.
これらのヒドロキシル基を有するビニルモノマーと共重
合させる他のビニルモノマーとしては、スチレン．α−
メチルスチレン，ｐ−メチルスチレン， ｐ−ｔ−プチ
ルスチレン，ｐ−クロルスチレン等のスチレン誘導体；
メタクリル酸メチル．メタクリル酸エチル，メタクリル
酸プロビル．メタクリル酸ブチル，メタクリル酸ベンチ
ル，メタクリル酸ヘキシル，メタクリル酸ヘプチル，メ
タクリル酸オクチル，メタクリル酸ノニル．メタクリル
酸デシル．メタクリル酸ウンデシル，メタクリル酸ドデ
シル．メタクリル酸グリシジル，メタクリル酸メトキシ
エチル，メタクリル酸ブロボキシエチル．メタクリル酸
ブトキシエチル，メタクリル酸ベンジル，メタクリル酸
シクロヘキシル．アクリル酸メチル，アクリル酸エチル
，アクリル酸プロビル，アクリル酸ブチル．アクリル酸
ベンチル，アクリル酸ヘキシル，アクリル酸へブチル．
アクリル酸オクチル．アクリル酸ノニル，アクリル酸デ
シル．ビニルモノマーを挙げることができる。Other vinyl monomers to be copolymerized with these vinyl monomers having hydroxyl groups include styrene. α−
Styrene derivatives such as methylstyrene, p-methylstyrene, p-t-butylstyrene, p-chlorostyrene;
Methyl methacrylate. Ethyl methacrylate, probyl methacrylate. Butyl methacrylate, bentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. Decyl methacrylate. Undecyl methacrylate, dodecyl methacrylate. Glycidyl methacrylate, methoxyethyl methacrylate, broboxyethyl methacrylate. Butoxyethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate. Methyl acrylate, ethyl acrylate, probyl acrylate, butyl acrylate. Bentyl acrylate, hexyl acrylate, hebutyl acrylate.
Octyl acrylate. Nonyl acrylate, decyl acrylate. Mention may be made of vinyl monomers.
これらの他のビニルモノマーのうち、１分子中に１個の
ビニル基を有するビニルモノマーでは、スチレン，スチ
レン誘導体，メタクリル酸エステル．アクリル酸エステ
ル等が好ましく、特にアルキル基に１〜５個の炭素原子
を有するメタクリル酸あるいはアクリル酸のアルキルエ
ステルが好ましい。Among these other vinyl monomers, vinyl monomers having one vinyl group in one molecule include styrene, styrene derivatives, methacrylic acid esters. Acrylic acid esters are preferred, and alkyl esters of methacrylic acid or acrylic acid having 1 to 5 carbon atoms in the alkyl group are particularly preferred.
これらのビニルモノマーのうち、ヒドロキシル基を有す
るビニルモノマーは、共重合体のヒドロキシル価が１〜
１００ （ＫＯＨ一ｇ／ｇ）になるように使用される。Among these vinyl monomers, vinyl monomers having a hydroxyl group have a copolymer with a hydroxyl value of 1 to 1.
100 (1 g/g of KOH).
これらのビニルモノマーは懸濁重合法．乳化重合法，溶
液重合法の如き方法で共重合される。また、この共重合
体はメラミンアルデヒド架橋あるいはイソシアネート架
橋されていてもよい．なお、本発明において、ヒドロキ
シル価は、ＪＩＳ−ＫＯＯ７０に基づいて測定した値を
いう。These vinyl monomers are produced using suspension polymerization. It is copolymerized using methods such as emulsion polymerization and solution polymerization. Further, this copolymer may be crosslinked with melamine aldehyde or isocyanate. In addition, in this invention, a hydroxyl number refers to the value measured based on JIS-KOO70.
一方、ヒドロキシル基を含むビニル系樹脂と混合される
含フッ素樹脂としては、ボリ弗化ビニル、ボリ弗化ビニ
リデン、ポリトリフルオロエチレン、ポリトリフルオル
クロルエチレンの如きハローフルオロボリマー ポリテ
トラフルオロエチレン、ポリバーフルオルプロピレン、
弗化ビニリデンとアクリル単量体との共重合体、弗化ビ
ニリデンとトリフルオルクロルエチレンとの共重合体、
テトラフルオロエチレンとへキサフルオロブロビレンと
の共重合体、弗化ビニルと弗化ビニリデンとの共重合体
、弗化ビニリデンとテトラフルオロエチレンとの共重合
体、弗化ビニリデンとへキサフルオロプロピレンとの共
重合体、テトラフルオロエチレンと弗化ビニリデン及び
非弗素化単量体のターボリマーのようなフルオロターボ
リマー等が好ましく用いられる。On the other hand, examples of the fluororesin to be mixed with the vinyl resin containing hydroxyl groups include polyvinyl fluoride, polyvinylidene fluoride, halofluorobolymers such as polytrifluoroethylene and polytrifluorochloroethylene, polytetrafluoroethylene, Polyvar fluoropropylene,
Copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and trifluorochloroethylene,
A copolymer of tetrafluoroethylene and hexafluoropropylene, a copolymer of vinyl fluoride and vinylidene fluoride, a copolymer of vinylidene fluoride and tetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, A copolymer of tetrafluoroethylene, vinylidene fluoride, and a fluoroturbopolymer such as a nonfluorinated monomer is preferably used.
これらの含フッ素樹脂とヒドロキシル基を有するビニル
系樹脂との混合比率は、ヒドロキシル基を有するビニル
系樹脂の前述の特徴的効果のために、幅広い範囲で適用
可能である。具体的Ｃは、含フッ素樹脂とヒドロキシル
基を有するビニル系樹脂の比率（Ｉｉ量比）は、３：９
７乃至９５：５、より好ましくは５：９５乃至９０：１
０、さらに好ましくは８０：２０乃至２０：８０が良い
．含フッ素樹脂の含有量が３重量％未満では、含フッ素
樹脂の添加効果が不充分になる傾向があり、一方、含フ
ッ素樹脂の含有量が９５重量％を越える場合では、ヒド
ロキシル基を有するビニル系樹脂の存在量が少なくなる
ために、コア材に対する樹脂被覆層の密着性が低下する
傾向がある。The mixing ratio of these fluororesins and the vinyl resin having a hydroxyl group can be applied within a wide range due to the above-mentioned characteristic effects of the vinyl resin having a hydroxyl group. Specifically, in C, the ratio of the fluororesin to the vinyl resin having a hydroxyl group (Ii quantitative ratio) is 3:9.
7 to 95:5, more preferably 5:95 to 90:1
0, more preferably 80:20 to 20:80. If the content of the fluororesin is less than 3% by weight, the effect of adding the fluororesin tends to be insufficient. On the other hand, if the content of the fluororesin exceeds 95% by weight, vinyl having hydroxyl groups Since the amount of the system resin decreases, the adhesion of the resin coating layer to the core material tends to decrease.
上記被覆樹脂の処理量は、被覆材の成膜性や耐久性から
、一般に総量でキャリア芯材に対し０．１〜３０重量％
（好ましくは０．５〜２０重量％）が良い。被覆量が０
．１重量％未満では、塗布による効果の発現が不充分な
傾向にあり、３０重量％を超える場合は、均一な膜厚の
被覆層を形成することが困難になる。The amount of the above-mentioned coating resin to be treated is generally 0.1 to 30% by weight based on the carrier core material in total, considering the film formability and durability of the coating material.
(preferably 0.5 to 20% by weight). Coverage amount is 0
．． If it is less than 1% by weight, the effects of coating tend to be insufficient, and if it exceeds 30% by weight, it becomes difficult to form a coating layer with a uniform thickness.
これらの被覆樹脂に添加する導電性微粒子としては、１
０Ω・ｃｍ以下、好ましくは１Ω・ｃｍ以下の体積抵抗
率を有する適当な無機物の微粒子状材料が使用される。As the conductive fine particles added to these coating resins, 1
A suitable inorganic particulate material having a volume resistivity of less than 0 Ω·cm, preferably less than 1 Ω·cm is used.
具体的には、カーボンブラック粉末、グラファイト粉末
、Ｃｕ． Ｚｎ， Ｓｎ．＾２、Ｔｉ， Ｓｂ等の単独
あるいは合金あるいは酸化物等が使用される．粒径は、
本発明の目的であるキャリア被覆膜の表面へ露出させる
ことかう、１．０ｔｔｍ以下、好ましくは０．５μｍ以
下、より好ましくは０．１μｍ以下である．コート樹脂
に対する導電性微粉末の添加量は、樹脂に対して０．１
ｗｔ％〜２０ｗｔ％、好ましくは０．２ ｗｔ％〜１
０ｗｔ％である， ０．１ ａｔ％未満では本発明の効
果が顕著でなく、２０ｗｔ％を超えると本発明の特徴の
ひとつであるコート膜の戒膜性が十分良好なものではな
くなる．
本発明に用いられるキャリア芯材としては、鉄粉、フエ
ライト等の一般のものが使用され、その粒径は、ｌ（１
〜ｌ０００７ｚｍ、好ましくは２０〜２００μｍが適当
である．
上記のキャリア芯材の表面を前述の導電性微粒子の添加
された樹脂で被覆する方法としては、該樹脂を溶剤中に
溶解もしくは懸濁せしめ、さらに、導電性微粒子粉末を
添加し、分散機にて充分分散させ、スプレー等の一般的
な方法で塗布させることができる．
本発明のキャリアと組合せて二戒分系現像剤に用いられ
るトナーの結着樹脂としては、ボリスチレン、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量体：ス
チレンーブロビレン共重合体、スチレンービニルトルエ
ン共重合体、スチレンービニルナフタリン共重合体、ス
チレンーアクリル酸メチル共重合体、スチレンーアクリ
ル酸エチル共重合体、スチレンーアクリル酸ブチル共重
合体、スチレンーアクゾル酸オクチル共重合体、スチレ
ンーメタクリル酸メチル共重合体、スチレンーメタクリ
ル酸エチル共重合体、スチレンーメタクリル酸ブチル共
重合体、スチレンーアクリルーアミノアクリル系共重合
体、スチレンーアミノアクリル系共重合体、スチレンー
アクリロニトリル共重合体、スチレンービニルメチルエ
ーテル共重合体、スチレンービニルエチルエーテル共重
合体、スチレンービニルメチルケトン共重合体、スチレ
ンープタジエン共重合体、スチレンーイソブレン共重合
体、スチレンーアクリロニトリルーインデン共重合体、
スチレンーマレイン酸共重合体、スチレンーマレイン酸
エステル共重合体などのスチレン系共重合体；ボリメチ
ルメタクリレート、ポリブチルメタクリレート、ポリ酢
酸ビニル、ポリエチレン、ボリブロピレン、ポリエステ
ル、ポリウレタン、ボリアミド、エボキシ樹脂、ポリビ
ニルブチラール、ポリアクリル酸樹脂、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、パラフィンワックスなどが、単独或いは
必要に応じて２種以上組合せて使用できる．
上記トナーにおいては、任意の適当な顔料や染料が着色
剤として使用可能であるゆ例えば、力一ボンブラック．
鉄黒，フタロシアニンブルー，群青．キナクリドン，ベ
ンジジンイエローなどの染料または顔料が用いられる．
また、正荷電制御剤として、・アミノ化合物，第４級ア
ンモニウム化合物および有機染料，特に塩基性染料とそ
の塩，ペンジルジメチルーヘキサデシルアンモニウムク
ロライド．デシルートリメチルアンモニウムクロライド
．ニグロシン塩基，ニグロシンヒドロクロライド，サフ
ラニンγ及びクリスタルバイオレット．等を添加しても
良い．本発明のキャリアとの組み合せにおいて、正荷電
性を有するトナーが良好な摩擦電荷を付与される点で好
ましい．
上記したトナーの構成は、一般に行われている混合一粉
砕法によるトナーに用いてもよく、またマイクロカプセ
ルトナーの壁材または芯材、あるいはその両方に用いる
ことも可能である。本発明において、トナーとは、コロ
イダルシリカが外添されている着色樹脂粒子を意味する
場合もあるし、着色樹脂粒子そのものを意味する場合も
ある．
尚、本発明において正荷電性シリカとは、ブローオフ法
で測定した時に、鉄粉キャリアまたはステンレス製キャ
リアに対しプラスのトリボ電荷を有するものをいう．
シリカ徹粉体の処理に用いる、側鎖に窒素原子を有する
シリコンオイルとしては、少なくとも下記式で表わされ
る部分構造を具備するシリコンオイルが使用できる。Specifically, carbon black powder, graphite powder, Cu. Zn, Sn. ^2, Ti, Sb, etc. alone, alloys, or oxides are used. The particle size is
The thickness to be exposed to the surface of the carrier coating film, which is the object of the present invention, is 1.0 ttm or less, preferably 0.5 μm or less, more preferably 0.1 μm or less. The amount of conductive fine powder added to the coat resin is 0.1 to the resin.
wt% to 20 wt%, preferably 0.2 wt% to 1
If it is less than 0 wt% or 0.1 at%, the effect of the present invention will not be significant, and if it exceeds 20 wt%, the coating properties of the coating film, which is one of the characteristics of the present invention, will not be sufficiently good. As the carrier core material used in the present invention, general materials such as iron powder and ferrite are used, and the particle size thereof is l(1
-10007zm, preferably 20-200μm is suitable. In order to coat the surface of the carrier core material with the resin to which the conductive fine particles have been added, the resin is dissolved or suspended in a solvent, the conductive fine particles are further added, and the resin is placed in a dispersion machine. It can be sufficiently dispersed and applied by a general method such as spraying. The binder resin of the toner used in the two-component developer in combination with the carrier of the present invention includes monomers of styrene and its substituted products such as polystyrene and polyvinyltoluene; styrene-brobylene copolymer; Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl axolate copolymer , styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-acrylic-aminoacrylic copolymer, styrene-aminoacrylic copolymer, styrene- Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene- acrylonitrile-indene copolymer,
Styrenic copolymers such as styrene-maleic acid copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl Butyral, polyacrylic acid resin, terpene resin,
Phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin waxes, etc. can be used alone or in combination of two or more as necessary. Any suitable pigment or dye can be used as a colorant in the above toner, such as Rikibon Black.
Iron black, phthalocyanine blue, ultramarine. Dyes or pigments such as quinacridone and benzidine yellow are used. In addition, as positive charge control agents, amino compounds, quaternary ammonium compounds, organic dyes, especially basic dyes and their salts, penzyldimethyl-hexadecyl ammonium chloride. Desyltrimethylammonium chloride. Nigrosine base, nigrosine hydrochloride, safranin gamma and crystal violet. etc. may be added. In combination with the carrier of the present invention, positively charged toners are preferred because they provide good triboelectric charge. The above-described toner structure may be used for a toner produced by the commonly used mixing and pulverizing method, and may also be used for the wall material, the core material, or both of the microcapsule toner. In the present invention, toner may mean colored resin particles to which colloidal silica is externally added, or may mean colored resin particles themselves. In the present invention, positively charged silica refers to silica that has a positive triboelectric charge relative to an iron powder carrier or a stainless steel carrier when measured by a blow-off method. As the silicone oil having a nitrogen atom in the side chain used in the treatment of the silica powder, a silicone oil having at least a partial structure represented by the following formula can be used.
（式中、Ｒ，は水素、アルキル基、アリール基又はアル
コキシ基を示し、Ｒ２はアルキレン基又はフエニレン基
を示し、Ｒ，及びＲ４は水素、アルキル基、又はアリー
ル基を示し、Ｒ，は含窒素複素環基を示す）上記アルキ
ル基、アリール基、アルキレン基、フェニレン基は窒素
原子を有するオルガノ基を有していても良いし、また帯
電性を損ねない範囲で、ハロゲン等の置換基を有してい
ても良い．又、本発明で用いる含窒素シランカツブリン
グ剤は、一般に下記式で示される構造を有する。(In the formula, R represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R2 represents an alkylene group or a phenylene group, R, and R4 represent hydrogen, an alkyl group, or an aryl group, and R represents a The above alkyl group, aryl group, alkylene group, and phenylene group (representing a nitrogen heterocyclic group) may have an organo group having a nitrogen atom, or may have a substituent such as a halogen to the extent that the chargeability is not impaired. You may have one. Further, the nitrogen-containing silane cobbling agent used in the present invention generally has a structure represented by the following formula.
Ｒ．−Ｓｔ−Ｙｎ
（Ｒは、アルコキシ基またはハロゲンを示し、Ｙはアミ
ノ基又は窒素原子を少なくとも１つ以上有するオルガノ
基を示し、ｍおよびｎは１〜３の整数であってｍ＋ｎ鱈
４である．）
窒素原子を少なくとも１つ以上有するオルガノ基として
は、有機基を置換基として有するア主ノ基または含窒素
複素環基または含窒素複素環基を有する基が例示される
．含窒素複素環基としては、不飽和複素環基または飽和
複素環基があり、それぞれ公知のものが通用可能である
。不飽和複素環基としては、例えば下記のものが例示さ
れる。R. -St-Yn (R represents an alkoxy group or halogen, Y represents an amino group or an organo group having at least one nitrogen atom, m and n are integers of 1 to 3, and m+n is 4) .) Examples of the organo group having at least one nitrogen atom include a main group having an organic group as a substituent, a nitrogen-containing heterocyclic group, or a group having a nitrogen-containing heterocyclic group. Examples of the nitrogen-containing heterocyclic group include unsaturated heterocyclic groups and saturated heterocyclic groups, and publicly known ones can be used. Examples of the unsaturated heterocyclic group include the following.
飽和複素環基としては、例えば下記のものが例示される
。Examples of the saturated heterocyclic group include the following.
本発明に使用される複素環基としては、安定性を考慮す
ると五員環または六員環のものが良い．そのような処理
剤の例としてはア主ノブロビルトリメトキシシラン，ア
ミノブロビルトリエトキシシラン，ジメチルアミノブロ
ビルトリメトキシシラン，ジエチルアミノブロビルトリ
メトキシシラン．ジブロピルア主ノブロビルトリメトキ
シシラン，ジブチルアミノブロビルトリメトキシシラン
，モノブチルア主ノブロビルトリメトキシシラン．ジオ
クチルアミノプロビルトリメトキシシラン，ジブチルア
主ノブロビルジメトキシシラン，ジブチルアよノブロビ
ルモノメトキシシラン．ジメチルアミノフェニルトリエ
トキシシラン．トリメトキシシリルーγ−プロビルフェ
ニルアミン，トリメトキシシリルーＹ−プロビルベンジ
ルアミン等があり、さらに含窒素複素環基としては前述
の構造のものが使用でき、そのような化合物の例として
は、トリメトキシシリルーγ−ブロビルビベリジン．ト
リメトキシシリルーγ−ブロピルモルホリン，トリメト
キシシリルーγ−ブロビルイ主ダゾール等がある。The heterocyclic group used in the present invention is preferably a five-membered or six-membered ring in terms of stability. Examples of such treatment agents include nobrobyltrimethoxysilane, aminobrobyltriethoxysilane, dimethylaminobrobyltrimethoxysilane, and diethylaminobrobyltrimethoxysilane. Dibropyrua-based nobrobil trimethoxysilane, dibutylaminobrobyl trimethoxysilane, monobutylar-based nobrobil trimethoxysilane. Dioctylaminopropyltrimethoxysilane, dibutyl-nobrobil dimethoxysilane, dibutyl-nobrovir monomethoxysilane. Dimethylaminophenyltriethoxysilane. There are trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-Y-propylbenzylamine, etc. Furthermore, as the nitrogen-containing heterocyclic group, those having the above structure can be used, and examples of such compounds are , trimethoxysilyl-γ-brobylbiberidine. Examples include trimethoxysilyl-γ-propylmorpholine, trimethoxysilyl-γ-brobyl-dazole, and the like.
これらの処理された正荷電性シリカ微粉体の通用量は、
正荷電性トナー１００ ［［量部に対して、０．０１〜
８重量部のときに効果を発揮し、特に好ましくは０．１
〜Ｓｌｉ量部添加した時に優れた安定性を有する正の帯
電性を示す．添加形態については好ましい態様を述べれ
ば、正荷電性トナー１００重量部に対して、０．１〜３
重量部の処理されたシリ力微粉体がトナー粒子表面に付
着している状態にあるのが良い．
又、本発明に用いられるシリカ微粉体は、必要に応じて
シランカップリング剤、疎水化の目的で有機ケイ素化合
物などの処理剤で処理されていても良く、シリカ微粉体
と反応あるいは物理吸着する上記処理剤で処理される．
そのような処理剤としては、例えばヘキサメチルジシラ
ザン、トリメチルシラン、トリメチルクロルシラン、ト
リメチルエトキシシラン、ジメチルジクロルシラン、メ
チルトリクロルシラン、アリルジメチルクロルシラン、
アリルフェニルジクロルシラン、ベンジルジメチルクロ
ルシラン、プロムメチルジメチルクロルシラン、α−ク
ロルエチルトリクロルシラン、β−クロルエチルトリク
ロルシラン、クロルメチルジメチルクロルシラン、トリ
オルガノシリルメルカブタン、トリメチルシリルメルカ
ブタン、トリオルガノシリルアクリレート、ビニルジメ
チルアセトキシシラン、ジメチルエトキシシラン、ジメ
チルジメトキシシラン、ジフエニルジエトキシシラン、
ヘキサメチルジシロキサン、１．３−ジビニルテトラメ
チルジシロキサン、！．３−ジフェニルテトラメチルジ
シロキサン、および１分子当り２から１２個のシロキサ
ン単位を有し、末端に位置する単位にそれぞれ１個宛の
Ｓｉに結合した水酸基を含有するジメチルポリシロキサ
ン等がある．これら１ｆ！ｌＩあるいは２種以上の混合
物で用いられる。The typical amount of these treated positively charged silica fine powders is:
Positively charged toner 100 [[0.01 to 100 parts]
The effect is exhibited when the amount is 8 parts by weight, particularly preferably 0.1
-Exhibits positive chargeability with excellent stability when a certain amount of Sl is added. A preferred form of addition is 0.1 to 3 parts by weight per 100 parts by weight of positively charged toner.
It is preferable that the weight part of the treated silicate fine powder is attached to the surface of the toner particles. Furthermore, the silica fine powder used in the present invention may be treated with a treatment agent such as a silane coupling agent or an organosilicon compound for the purpose of hydrophobization, if necessary, to react with or physically adsorb to the silica fine powder. Treated with the above processing agent.
Examples of such treatment agents include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenyldichlorosilane, benzyldimethylchlorosilane, prommethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercabutane, trimethylsilylmercabutane, triorganosilyl Acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane,! ．． Examples include 3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane, which has 2 to 12 siloxane units per molecule and each unit located at the end contains one hydroxyl group bonded to Si. These 1f! It is used as lI or as a mixture of two or more types.
本発明のキャリアとトナー（及びシリカ微粉体）との混
合方法は、一般に行なわれている混合方法が適用できる
が、トナー濃度は、現像剤（キャリア＋トナー）１００
重量部中に、トナー０．５〜２０重量部（更に好ましく
は、１〜１０重量部）を含むことが好ましい。A commonly used mixing method can be used to mix the carrier and toner (and silica fine powder) of the present invention, but the toner concentration is 100% of the developer (carrier + toner).
It is preferable that the toner contains 0.5 to 20 parts by weight (more preferably 1 to 10 parts by weight) in the parts by weight.
以下、実施例にて詳述する。以下の実施例で示すｒ部」
は、重量部である．
［実施例］
及亘里ユ
キャリア芯材として、平均粒径６９μｍの球状フエライ
ト粒子を用意した。This will be explained in detail in Examples below. "r part" shown in the following examples.
is parts by weight. [Example] Spherical ferrite particles with an average particle size of 69 μm were prepared as the core material of Oiwatari Ucarrier.
上記共重合体（合計ｌＯ部）をアセトンとメチルエチル
ケトンの混合溶剤（混合重量比＝１ ＋ １）９０部に
溶解してｌＯ％濃度の溶液を調製した。この溶液１００
部に導電性カーボンブラック（平均粒径＝ ０． ０２
ｐｍ，比電気抵抗＝０．ｌ２Ω−ｃｍ）を０．１部添加
し、ポールミルボットで２４ｈｒ分散して被覆溶液を調
製した。The above copolymer (10 parts in total) was dissolved in 90 parts of a mixed solvent of acetone and methyl ethyl ketone (mixed weight ratio = 1 + 1) to prepare a solution with a 10% concentration. This solution 100
conductive carbon black (average particle size = 0.02
pm, specific electrical resistance = 0. A coating solution was prepared by adding 0.1 part of 12Ω-cm) and dispersing it for 24 hours using a Pall Mill Bot.
調製した被覆溶液を塗布機（スビラコーター岡田精工社
製）で前記フエライト粒子に塗布した。溶剤を除去後に
、温度９０℃で１時間乾燥して、樹脂コーティングキャ
リアＡ１を生成した。The prepared coating solution was applied to the ferrite particles using a coating machine (Subira Coater manufactured by Okada Seiko Co., Ltd.). After removing the solvent, it was dried at a temperature of 90° C. for 1 hour to produce a resin coated carrier A1.
被覆前後の重量変化から換算して、フエライト粒子には
、約０．８重量％の共重合体が被覆されていた。The ferrite particles were coated with about 0.8% by weight of the copolymer, calculated from the weight change before and after coating.
一方、
上記組成物を混合し、溶融混練し、粉砕し、分級して、
体積平均粒径１ ２ｇｍのシアン樹脂微粒子を生成した
。シアン樹脂粒子１００部とアミノ変性シリコーンオイ
ルで処理された正帯電性疎水性コロイダルシリ力０．８
重量％とをヘンシェルミキサーで混合してシアントナー
を調製した。On the other hand, the above composition is mixed, melt-kneaded, pulverized, and classified,
Cyan resin fine particles having a volume average particle diameter of 12 gm were produced. Positively charged hydrophobic colloidal silicone treated with 100 parts of cyan resin particles and amino-modified silicone oil with a strength of 0.8
% by weight using a Henschel mixer to prepare a cyan toner.
前記トナーと前記キャリアＡ，とを７：９３の重量比率
でＶ−ブレンダーを用いて混合して二成分系現像剤を得
た。The toner and carrier A were mixed at a weight ratio of 7:93 using a V-blender to obtain a two-component developer.
キヤノン社製複写機ＮＰ−４８３５に、得られた二成分
系現像剤を適用し、種々の環境で画像形成テスト（画像
出し）を行ったところ、画像反射濃度は常温常湿（２３
℃，６０％ＲＨ）下でｌ．２５、低温低湿（１５℃，
ｉｏ％ＲＨ）下で１．２７、高温高温（３５℃，９０％
ＲＨ）下で１．３０とそれぞれ高く、カブリのない鮮や
かな画像が得られた。When the obtained two-component developer was applied to a Canon Co., Ltd. copier NP-4835 and an image formation test (image production) was performed in various environments, the image reflection density was
℃, 60% RH). 25. Low temperature and low humidity (15℃,
io%RH) under 1.27, high temperature (35℃, 90%
RH) and a high value of 1.30, a clear image without fogging was obtained.
さらに、上記現像剤をＮＰ−４８３５の現像器に投入し
、画像出しを行なわないで、スリーブのみを回転させる
外部空回転器により常温常温環境下で４時間空回転耐久
を行ないチャージアップおよびキャリア劣化のシュミレ
ート耐久とした。この空回転後の現像剤の入った現像器
でＮＰ−４８３５による画像出しを行なったところ、初
期とほとんど変わらぬ高画質の濃度１．２０の画像が得
られ、この事実より、実質上のチャージアップが防止で
き、がっ、キャリアのトナースベント等の実質的な劣化
もないことが判明した。Furthermore, the above developer was put into the developing device of NP-4835, and an external idle rotator that rotates only the sleeve without image formation was used to run idle for 4 hours at room temperature to prevent charge-up and carrier deterioration. The durability was simulated. When an image was produced using NP-4835 using the developing device containing the developer after idling, a high-quality image with a density of 1.20, which was almost the same as the initial image, was obtained. It was found that it was possible to prevent the toner from blowing up, and there was no substantial deterioration such as toner venting of the carrier.
及血員ユ
実施例１の混合樹脂（混合比＝１ ： １）に代えて、
スチレンーメタクリル酸２−ヒドロキシメチルーメタク
リル酸メチルーメタクリル酸エチル（モノマー組成重量
比＝５７： ２０： １３： １０，ヒドロキシル価＝
４０） ３．５部とメチルエーテル化メラミンホルムア
ルデヒド樹脂１．５部とフフ化ビニリデンーテトラフル
オロエチレン共重合体（モノマー組成重量比＋−７５：
２５）５部とをメチルエチルケトン溶液Ｃ溶解し１０％
濃度の溶液を調製した．この溶液１００部に導電性Ｚｎ
Ｏ粉末（平均粒径−０ ． １ｕｍ）を０．２部添加し
、実施例１と同様の方法で被覆液を作成し、その後コー
ティングキャリアを得々．一方、
上記組成分を混合し、溶融混練し、粉砕，分級工程を経
て、体積平均粒径１１μ箇の黒色微粒子を得た．この徴
゛粒子に実施例１で用いた正帯電性疎水性コロイダルシ
リカｏ．ｓ ３１量％とをヘンシェルミキサーで混合し
てトナーを調製した．
前記トナーと前記キャリアとを２：９８の重量比率でＶ
−ブレンダーを用いて混合して、二成分系現像剤を得た
。In place of the mixed resin of Example 1 (mixing ratio = 1:1),
Styrene - 2-hydroxymethyl methacrylate - methyl methacrylate - ethyl methacrylate (monomer composition weight ratio = 57: 20: 13: 10, hydroxyl value =
40) 3.5 parts of methyl etherified melamine formaldehyde resin and vinylidene fluoride-tetrafluoroethylene copolymer (monomer composition weight ratio +-75:
25) Dissolve 5 parts of methyl ethyl ketone solution C to 10%
A solution of the same concentration was prepared. Conductive Zn was added to 100 parts of this solution.
A coating solution was prepared in the same manner as in Example 1 by adding 0.2 parts of O powder (average particle size -0.1 um), and then a coated carrier was prepared. On the other hand, the above components were mixed, melt-kneaded, crushed, and classified to obtain black fine particles with a volume average particle diameter of 11 μm. The positively charged hydrophobic colloidal silica used in Example 1 was added to these characteristic particles. A toner was prepared by mixing 31% by weight of C.s with a Henschel mixer. The toner and the carrier are mixed in a weight ratio of 2:98.
- A two-component developer was obtained by mixing using a blender.
この現像剤をキヤノン製複写機ＮＰ−５０００をボジト
ナー現像用に改造した機械に適用し、実施例１と同様の
評価をしたところ、各環境とも、高濃度、高画質の画像
が得られた．さらに、実施例１と同様に、この現像器の
みを４時間空回転した後も、初期とほとんど変わらぬ高
画質の画像が得られた．
［発明の効果］
本発明は、ヒドロキシル基を含むビニル系樹脂は、キャ
リア芯材との結着性にすぐれており、選択的にキャリア
芯材に付着する傾向が強く、その結果、他の混合物がキ
ャリア被覆表面に露出される傾向があるという特性を利
用したもので、正帯電性トナー社対して正帯電付与能力
の高いフッ素樹脂をキャリア被覆表面に積極的に露出さ
せるとともＣ１表面が高抵抗になりすぎるのを防ぐため
の導電性微粒子も同様にキャリア表面に積極的に露出さ
せることにより、耐久性に優れチャージアップを防いだ
正帯電付与能力の高いキャリアである。When this developer was applied to a Canon NP-5000 copier that had been modified for use in black toner development and evaluated in the same manner as in Example 1, images of high density and high quality were obtained in each environment. Furthermore, as in Example 1, even after idling only this developing device for 4 hours, a high-quality image that was almost the same as the initial image was obtained. [Effects of the Invention] The present invention provides that vinyl resins containing hydroxyl groups have excellent binding properties with carrier core materials, have a strong tendency to selectively adhere to carrier core materials, and as a result, can be mixed with other mixtures. This takes advantage of the characteristic that C1 tends to be exposed on the surface of the carrier coating. Conductive fine particles to prevent excessive resistance are likewise actively exposed on the carrier surface, resulting in a carrier with excellent durability and high ability to impart positive charge that prevents charge-up.
Claims (2)
、かつヒドロキシル価１〜１００を有するビニル系共重
合体及びフッ素樹脂を含む混合樹脂が、キャリア芯材に
被覆されていることを特徴とする電子写真用キャリア。(1) The carrier core material is coated with a mixed resin containing a vinyl copolymer and a fluororesin having a hydroxyl value of 1 to 100 and in which conductive fine particles with a particle size of 1.0 μm or less are dispersed. Characteristic carrier for electrophotography.
リアとを含有していることを特徴とする二成分系現像剤
。(2) A two-component developer comprising a positively chargeable toner and the carrier according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1160957A JP2854327B2 (en) | 1989-06-26 | 1989-06-26 | Electrophotographic carrier and two-component developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1160957A JP2854327B2 (en) | 1989-06-26 | 1989-06-26 | Electrophotographic carrier and two-component developer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0327054A true JPH0327054A (en) | 1991-02-05 |
| JP2854327B2 JP2854327B2 (en) | 1999-02-03 |
Family
ID=15725846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1160957A Expired - Fee Related JP2854327B2 (en) | 1989-06-26 | 1989-06-26 | Electrophotographic carrier and two-component developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2854327B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05134463A (en) * | 1991-04-26 | 1993-05-28 | Canon Inc | Electrophotographic carrier, two-component developer, production of electrophotographic toner and imge forming method |
| JPH0926675A (en) * | 1995-07-13 | 1997-01-28 | Fuji Xerox Co Ltd | Photographic carrier and its production and electrostatic charge imparting member |
| JP2003502896A (en) * | 1999-06-10 | 2003-01-21 | レイセオン・カンパニー | Transistor amplifier with reduced parasitic oscillation |
| JP2008219507A (en) * | 2007-03-05 | 2008-09-18 | Mitsubishi Electric Corp | Low noise amplifier |
| JP2009109771A (en) * | 2007-10-30 | 2009-05-21 | Ricoh Co Ltd | Carrier of electrophotographic toner, manufacturing method thereof, electrophotographic developer, and image forming method |
-
1989
- 1989-06-26 JP JP1160957A patent/JP2854327B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05134463A (en) * | 1991-04-26 | 1993-05-28 | Canon Inc | Electrophotographic carrier, two-component developer, production of electrophotographic toner and imge forming method |
| JPH0926675A (en) * | 1995-07-13 | 1997-01-28 | Fuji Xerox Co Ltd | Photographic carrier and its production and electrostatic charge imparting member |
| JP2003502896A (en) * | 1999-06-10 | 2003-01-21 | レイセオン・カンパニー | Transistor amplifier with reduced parasitic oscillation |
| JP2008219507A (en) * | 2007-03-05 | 2008-09-18 | Mitsubishi Electric Corp | Low noise amplifier |
| JP2009109771A (en) * | 2007-10-30 | 2009-05-21 | Ricoh Co Ltd | Carrier of electrophotographic toner, manufacturing method thereof, electrophotographic developer, and image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2854327B2 (en) | 1999-02-03 |
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