JPH04184354A - Magnetic toner - Google Patents
Magnetic tonerInfo
- Publication number
- JPH04184354A JPH04184354A JP2312700A JP31270090A JPH04184354A JP H04184354 A JPH04184354 A JP H04184354A JP 2312700 A JP2312700 A JP 2312700A JP 31270090 A JP31270090 A JP 31270090A JP H04184354 A JPH04184354 A JP H04184354A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- magnetic
- magnetic material
- image
- particle size
- 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
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 78
- 239000000696 magnetic material Substances 0.000 claims description 76
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000012756 surface treatment agent Substances 0.000 claims description 3
- 230000005661 hydrophobic surface Effects 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000000057 synthetic resin Substances 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 16
- 238000004040 coloring Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 239000008119 colloidal silica Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 17
- 238000009826 distribution Methods 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- -1 acrylic ester Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000006247 magnetic powder Substances 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 210000005069 ears Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-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
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QJVOZXGJOGJKPT-UHFFFAOYSA-N albine Natural products C12CC(=O)C=CN2CC2CNC(CC=C)C1C2 QJVOZXGJOGJKPT-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- NCXTWAVJIHJVRV-UHFFFAOYSA-N ethane-1,2-diol;16-methylheptadecanoic acid;titanium Chemical compound [Ti].OCCO.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O NCXTWAVJIHJVRV-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical class [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- HTMIBDQKFHUPSX-UHFFFAOYSA-N methdilazine Chemical group C1N(C)CCC1CN1C2=CC=CC=C2SC2=CC=CC=C21 HTMIBDQKFHUPSX-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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer 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
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 229940114930 potassium stearate 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
- QDIGBJJRWUZARS-UHFFFAOYSA-M potassium;decanoate Chemical compound [K+].CCCCCCCCCC([O-])=O QDIGBJJRWUZARS-UHFFFAOYSA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は電子写真法、静電記録法などに用いられるトナ
ーに関し、特に絶縁性の磁性トナーに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a toner used in electrophotography, electrostatic recording, etc., and particularly relates to an insulating magnetic toner.
［従来の技術］
従来、電子写真法としては多数の方法が知られているが
、一般には光導電性物質を利用し、種々の手段により感
光体上に電気的潜像を形成し、ついで該潜像をトナーで
現像を行って可視像とし、必要に応じて、紙などの転写
材にトナー画像を転写した後、加熱、圧力などにより定
着し、複写物を得るものである。[Prior Art] Many methods have been known for electrophotography, but in general, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then the electrophotographic method is performed. The latent image is developed with toner to become a visible image, and if necessary, the toner image is transferred to a transfer material such as paper and then fixed by heat, pressure, etc. to obtain a copy.
近年、電子写真法を用いた機器は、従来の複写機以外に
プリンターやファクシミリなど多様になってきている。In recent years, devices using electrophotography have become diverse, including printers and facsimile machines in addition to conventional copying machines.
特に小型のプリンターやファクシミリでは、複写装置部
分を小さくする必要があるため、１成分トナーを用いた
現像装置を使う場合が多い。１成分現像方式は、２成分
方式のようにガラスや鉄粉などのキャリア粒子を用いな
いため、現像剤の重量が軽（、そのため装置自体も軽く
できる。さらに、２成分方式は２成分現像剤のキャリア
中のトナーの濃度を一定に保つ必要があるため、自動的
に濃度を検知し必要量のトナーを補給する装置が必要で
ある。よって、ここでも現像装置が太き（重（なる、１
成分方式の現像装置はこのような装置が必要とならない
ため、やはり小さ（軽（できる。このような１成分現像
方式に用いる１成分現像剤は、トナー中に磁性体を多量
に含有したものがほとんどである。Particularly in small printers and facsimile machines, it is necessary to make the copying device portion small, so a developing device using one-component toner is often used. Unlike the two-component method, the one-component development method does not use carrier particles such as glass or iron powder, so the weight of the developer is light (and therefore the device itself can also be lighter.Furthermore, the two-component method uses two-component developer Because it is necessary to maintain a constant concentration of toner in the carrier, a device that automatically detects the concentration and replenishes the required amount of toner is required. 1
Component type developing devices do not require such a device, so they are still small (and lightweight). Almost.
また、複写機においては、より高速、安定化の方向が常
に望まれている。とくに中速機、高速機などでは２成分
現像方式が主流である。これは、このようにある程度大
きな機械であると、現像装置の大台さや重さの問題より
高速での長期使用に対しての安定性が重要点になってく
るからである。一般に、２成分現像剤のトナーはカーボ
ンブラックなどにより着色し、他はほとんどポリマーか
らなっている。そのためトナー粒子は軽くまた静電気力
以外にキャリア粒子に付着する力がないため、特に高速
での現像ではトナーの飛散を招き、長期の使用でレンズ
や原稿ガラス、搬送部などの汚れを生じ画像の安定性を
損なうことがある。そこでトナー中に磁性体を含有させ
トナーを重くすると同時に磁性キャリア粒子に静電気力
以外に磁気力でも付着するようにし飛散を防ぐようにし
た現像剤が実用化されている。Furthermore, in copying machines, there is always a desire for faster and more stable copying machines. Particularly in medium-speed and high-speed machines, the two-component development method is the mainstream. This is because, in a machine of such a large size, stability for long-term use at high speed becomes more important than the problem of the size and weight of the developing device. Generally, the toner of a two-component developer is colored with carbon black or the like, and most of the other components are made of polymer. As a result, toner particles are light and have no force to adhere to carrier particles other than electrostatic force, which can cause toner scattering, especially during high-speed development, and cause stains on the lens, original glass, conveyance unit, etc. after long-term use, resulting in poor image quality. Stability may be impaired. Therefore, a developer has been put into practical use in which a magnetic substance is contained in the toner to make the toner heavier, and at the same time, the toner is attached to magnetic carrier particles by magnetic force in addition to electrostatic force to prevent scattering.
以上のように、磁性体を含有するトナーはますます重要
性を増している。As described above, toner containing magnetic material is becoming increasingly important.
一方、プリンターはおもにＬＥＤ、ＬＢＰプリンターが
主になりでおり、技術の方向としてより高解像度の方向
へ進んでいる。すなわち、従来２４０．３００ｄｐｉで
あったものが４００゜６００．８００ｄｐｉとできるよ
うになってきた。それにともなって現像方式も高濃度で
より高精細のものでなければならなくなってξた。On the other hand, printers are mainly LED and LBP printers, and technology is moving toward higher resolution. That is, what used to be 240.300 dpi can now be made to 400°600.800 dpi. Along with this, the development method had to be of higher density and higher definition.
また、中速の複写機は高機能化しており、そのためデジ
タル化の方向に進んでいる。この方向は、潜像をレーザ
ーで形成する方法が主であるため、やはり高解像度の方
向に進んでいる。ここでもやはり現像に対して高濃度で
しかも高精細というきびしい要求がある。In addition, medium-speed copying machines are becoming more sophisticated and are therefore moving toward digitalization. In this direction, the main method is to use a laser to form a latent image, so the trend is toward higher resolution. Here, too, there are strict demands for high density and high definition for development.
さらに、高速複写機は、高速化、安定化だけでなく、高
画質のプリンターから出力された画像をぶ稿として複写
する時高解像度に忠実に再現し、またアナログの写真原
稿を高階調に忠実に再現することが必要になってきてい
る。Furthermore, high-speed copying machines are not only faster and more stable, but also faithfully reproduce images output from high-quality printers in high resolution when copying them as manuscripts, and faithfully reproduce analog photo originals with high gradation. It has become necessary to reproduce this.
このように信号に忠実、原稿に忠実、すなわち、潜像に
忠実でしかも高濃度で現像をするトナーが必要になって
きている。In this way, there is a need for toner that is faithful to the signal, faithful to the original, that is, faithful to the latent image, and that can be developed at high density.
しかしながら、磁性体を含有するトナーを用いて以上の
ような高度な要求を満足することは難しい。However, it is difficult to satisfy the above-mentioned high requirements using toner containing a magnetic material.
たとえば、磁性トナーの着色力を上げて高濃度をだそう
として単に磁性体の含有量を上げれば、画像性が悪くな
り高解像度を満足することができなくなる。なぜなら、
磁性体を含有するトナーは磁場の影響を受けるためトナ
ーの搬送に磁界を利用するような１成分トナーでは、ト
ナー担持体上でトナー粒子が磁力線に沿って盛り上がり
穂を形成する。この時の穂の大きさはそのトナーのもつ
磁気力に関係している。磁性体を増すと穂も大きくなる
。このような穂はトナーが現像した後の潜像上でも凝集
力のため凝集塊として残る傾向であり、ａかい潜像を忠
実に再現することが難しくなってくる。For example, if the content of the magnetic material is simply increased in an attempt to increase the coloring power of the magnetic toner to achieve high density, the image quality will deteriorate and high resolution will not be satisfied. because,
Toner containing a magnetic substance is affected by a magnetic field. Therefore, in the case of a one-component toner that uses a magnetic field to transport toner, toner particles swell along magnetic lines of force on a toner carrier to form ears. The size of the ears at this time is related to the magnetic force of the toner. Increasing the amount of magnetic material also increases the size of the ears. Such spikes tend to remain as aggregates even on the latent image after the toner is developed due to the cohesive force, making it difficult to faithfully reproduce the amorphous latent image.
逆に高解像度を満足するために、磁性体の含有量を減ら
し磁気凝集力を小さくさせることも考えられるが、着色
力の減少の他に帯電量の増加にょる現像性の低下、トナ
ーの製造効率の低下などが生じる。ならばカーボンブラ
ックなどの着色剤の併用により改善することが考えられ
るが、さらに、特に環境依存性の悪化を招く場合があり
実用化はむずかしい。また、磁性体を含有するトナーを
用いた２成分現像方式の場合も同様なことが起こるため
、潜像に高度に忠実な現像を行うことが難しくなってい
る。On the other hand, in order to achieve high resolution, it is possible to reduce the content of magnetic material and reduce the magnetic cohesive force, but in addition to reducing the coloring power, there is also a decrease in developability due to an increase in the amount of charge, and a decrease in toner production. This may cause a decrease in efficiency. If this is the case, it may be possible to improve this by using a colorant such as carbon black in combination, but this may also lead to worsening of environmental dependence, making it difficult to put it into practical use. Furthermore, a similar problem occurs in the case of a two-component development method using toner containing a magnetic substance, making it difficult to perform development with high fidelity to the latent image.
そこで、磁気力を調整して高性能のトナーを得ることが
いくつか提案されている。Therefore, several proposals have been made to obtain high-performance toner by adjusting the magnetic force.
特開昭５８−９５７４８号公報に、飽和磁化が２５〜５
０ ｅ ｍ ｕ ／ ｇ 、保磁力が１５０〜３５０エ
ルステッドの磁性トナーが提案されている。これは、現
像性ならびに転写性ともに良好で、高品買のコピーが得
られるというものである。しかしながら、たとえばレー
ザーによる微細な潜像などを高精細に現像するためには
さらに磁化を小さくし磁気凝集力を減少させる方が好ま
しい、さらに、該提案では、トナーの帯電量が１５１μ
Ｃ／ｇ以上であることが必要であるとしているが、この
ように大きなＩＦ電量のトナーは静電的凝集力も大きく
、やはり高精細の画像を得ることは難しい、また、磁性
粒子の粒径の好ましい範囲として、０．３〜０．８μｍ
のものが使用できるとしているが着色力からはより細か
い方が好ましい。JP-A-58-95748 discloses that the saturation magnetization is 25 to 5.
Magnetic toners having a magnetic flux of 0 e mu/g and a coercive force of 150 to 350 Oe have been proposed. This means that both developability and transferability are good, and high-quality copies can be obtained. However, in order to develop a fine latent image using a laser with high precision, it is preferable to further reduce the magnetization and magnetic cohesive force.
C/g or more, but toner with such a large IF charge has a large electrostatic cohesive force, making it difficult to obtain high-definition images, and also due to the particle size of the magnetic particles. A preferred range is 0.3 to 0.8 μm
Although it is possible to use a finer one, it is preferable to use a finer one in terms of coloring power.
また、さらに飽和磁化の小さいトナーとして特開昭５８
−８３８５８号公報に平均粒径が１００〜１０００人の
範囲にある金属微粉末を含有し体積抵抗が１０２〜１０
″、１０ ｅ ｍ ｕ ／ ｇ以上の飽和磁化を有する
磁性トナーが提案されている。In addition, as a toner with even lower saturation magnetization, JP-A-58
- Contains fine metal powder with an average particle size in the range of 100 to 1000 particles and has a volume resistivity of 102 to 10
'', a magnetic toner having a saturation magnetization of 10 emu/g or more has been proposed.
このようなトナーは、磁性粒子の粒径が小さいため着色
力が高く、またトナーの磁気力も小さい方向であるため
磁気凝集が少なくそのため高画質になる。しかしながら
、該磁性粒子の抵抗が小さいためトナーの体積抵抗も小
さく、とくに、高温高温環境下ではさらに体積抵抗が低
下しトナー帯電量の低下による画像性の悪化、転写性の
悪化が生じる。また、該金属微粉末のように非常に細か
い粒子は、トナー製造時の熱混練工程での酸化を受は易
く、さらに、微粉砕工程でも酸化を受ける可能性がある
ため管理が難しく、生産効率の低下が生じ、実用上問題
である。Such toner has high coloring power because the particle size of the magnetic particles is small, and since the magnetic force of the toner is also small, there is little magnetic aggregation, resulting in high image quality. However, since the resistance of the magnetic particles is low, the volume resistivity of the toner is also low, and particularly in high-temperature environments, the volume resistivity further decreases, resulting in deterioration of image quality and transferability due to a decrease in toner charge amount. In addition, extremely fine particles such as the fine metal powder are easily oxidized during the heat kneading process during toner production, and furthermore, they may be oxidized during the pulverization process, making it difficult to control and reducing production efficiency. This is a practical problem.
以上のように、小型化、軽量化、飛散などに非常に有効
である磁性体を含有するトナーにおいて、さらに、高解
像性、高階調性などを実現する潜像に忠実な現像をする
トナーはいまだ十分なものが得られていない。As mentioned above, in addition to toner containing a magnetic material that is very effective in reducing size, weight, and scattering, it is also a toner that develops faithfully to latent images that achieves high resolution and high gradation. Yes, we still haven't gotten enough.
［発明が解決しようとする！！題］
本発明の目的は、上記問題点を解決した磁性トナーを提
供することである。[Invention tries to solve! ! [Problem] An object of the present invention is to provide a magnetic toner that solves the above problems.
本発明の目的は、原稿に忠実、信号に忠実、すなわち潜
像に忠実な現像をする磁性トナーを提供することである
。An object of the present invention is to provide a magnetic toner that develops images faithfully to originals, faithfully to signals, that is, faithful to latent images.
また本発明の目的は、高解像性、高細線再現性である磁
性トナーを提供することである。Another object of the present invention is to provide a magnetic toner with high resolution and high fine line reproducibility.
さらに本発明の目的は、高＃調性、高画像濃度で、飛散
がなく、製造効率、孫コピーの良い磁性トナーを提供す
ることである。A further object of the present invention is to provide a magnetic toner with high #tonality, high image density, no scattering, good manufacturing efficiency, and good copyability.
さらに本発明の目的は、耐久安定性に優れた磁性トナー
を提供することである。A further object of the present invention is to provide a magnetic toner with excellent durability and stability.
［課題を解決するための手段及び作用コ本発明の特徴と
するところは、基本的には、磁場ＩＫＯｅにおけるσｓ
が１０〜４０ｅｍｕ／ｇ、水平方向フエレ径が０．０５
〜０．５μｍである金属酸化物で形成されている磁性体
を含有する磁性トナーにある。[Means and effects for solving the problem] The feature of the present invention is basically that σs in the magnetic field IKOe
is 10 to 40 emu/g, horizontal direction diameter is 0.05
A magnetic toner containing a magnetic material made of a metal oxide having a diameter of ~0.5 μm.
上記磁性トナーは、磁気力が搬送及び飛散防止のために
は十分であり、しかも高精細、高階調の現像のためには
十分率さな磁気凝集力、静電凝集力、着色力になるもの
である。The above-mentioned magnetic toner has sufficient magnetic force for transportation and scattering prevention, and has sufficient magnetic cohesive force, electrostatic cohesive force, and coloring force for high-definition and high-gradation development. It is.
磁性体を含有するトナーについて鋭意検討した結果、磁
気力が適当に小さな磁性体を必要量含有させることによ
り、大幅に性能を向上させることができることを見いだ
した。これは、磁性体を含有するトナーでは、画像性が
磁性体の性質により左右され、それはトナーの帯電量、
凝集力、着色力、真密度、搬送に影響を与えるためであ
る。As a result of intensive studies on toners containing magnetic substances, it has been found that performance can be significantly improved by containing a required amount of magnetic substances with an appropriately small magnetic force. This is because in the case of toner containing a magnetic material, the image quality is affected by the properties of the magnetic material, and this is due to the amount of charge on the toner,
This is because it affects cohesion, coloring power, true density, and conveyance.
本発明の磁性トナーにおいて、磁性体は磁場ＩＫＯｅに
おけるＯ８が重要である。実際の現像システムでは最大
ＩＫ６ｅの磁場しか関係してこない。σＳの範囲は、１
０〜４０ ｅ ｍ ｕ ／ ｇである。好ましくは２０
〜４０ ｅ ｍ ｕ ／ ｇが良い。In the magnetic toner of the present invention, O8 in the magnetic field IKOe is important as the magnetic material. In an actual development system, only a maximum magnetic field of IK6e is involved. The range of σS is 1
0-40 emu/g. Preferably 20
~40 emu/g is good.
磁気力の測定は、東夷工業社製のＶＳＭを用いた。磁場
ＩＫ６ｅにおけるａｓが１０ ｅ ｍ ｕ ／ ｇ未満
であると、トナーの飛散が問題となり、また搬送性も悪
く均一な良好な画像が得られない。To measure the magnetic force, a VSM manufactured by Toi Kogyo Co., Ltd. was used. If as in the magnetic field IK6e is less than 10 emu/g, toner scattering becomes a problem, and the conveyance property is also poor, making it impossible to obtain a uniform and good image.
Ｏ５が４０ ｍ ｕ ／ ｇより大きいと磁気凝集のた
め画像の悪い、すなわち、細線再現性、階調性等が悪く
なる場合がある。また、Ｈｃも画像性と関係が大ぎい。If O5 is greater than 40 mu/g, magnetic aggregation may result in poor images, that is, fine line reproducibility, gradation, etc. may deteriorate. Moreover, Hc also has a great relationship with image quality.
Ｈｃの範囲としては、５０〜２００６ｅである。理由は
明確ではないが、Ｈａが５０６ｅ未満であると、バック
グラウンドの汚れが生１じ問題となる。Ｈｃ＃＜２００
５ｅよりも大きいと搬送性が悪くなりコーティングが良
好でなくなり画像濃度ムラなど画質が悪化する。The range of Hc is 50 to 2006e. Although the reason is not clear, when Ha is less than 506e, background stains occur, which becomes a problem. Hc#<200
If it is larger than 5e, the conveyance property will be poor and the coating will not be good, resulting in poor image quality such as uneven image density.
磁性体の粒径はトナーの帯電量、着色力などに関係する
。磁性体の粒径は水平方向フェレ径で示す、測定は、透
過型電子顕微鏡により得られた、１万倍の磁性体の写真
を４倍に拡大し、４万倍の写真とした後、ランダムに２
５０個の磁性体を選び、その径を実測し平均粒径を求め
るものである。平均粒径は０．０５〜０．５μｍである
。好ましくは、０．０８〜０．４μｍ１ざらに好ましく
は、０．１〜０．４μｍである。さらに好ましくは、０
．２〜０．４μｍである。平均粒径０．０５μｍ未満で
あると帯電制菌が難しく、平均粒径０．５μｍよりも大
きいと着色力が不十分で細線再現性が問題となり、また
トナーの’ｉｔも不均一となるためバックグラウンドの
汚れなどが発生する。The particle size of the magnetic material is related to the amount of charge and coloring power of the toner. The particle size of the magnetic material is indicated by the Feret diameter in the horizontal direction.Measurements are made by enlarging a photograph of the magnetic material obtained by a transmission electron microscope 10,000 times to 4 times, making it a 40,000 times photograph, and then randomly to 2
Fifty magnetic substances are selected and their diameters are actually measured to determine the average particle size. The average particle size is 0.05-0.5 μm. The thickness is preferably 0.08 to 0.4 μm, more preferably 0.1 to 0.4 μm. More preferably, 0
．． It is 2 to 0.4 μm. If the average particle size is less than 0.05 μm, it will be difficult to control the charging bacteria, and if the average particle size is larger than 0.5 μm, the coloring power will be insufficient and fine line reproducibility will become a problem, and the toner's 'it' will also become non-uniform. Background stains, etc. occur.
磁性体の含有量は、３０〜６０ｗｔ％である。The content of the magnetic material is 30 to 60 wt%.
好ましくは、４０〜６０ｗｔ％、さらに好ましくは、４
０〜５５ｗｔ％である。さらに好ましくは、４０〜５０
ｗｔ％である。３０ｗｔ％未満であると、搬送性が不十
分となり画像濃度ムラなと生じ、飛散、バックグラウン
ドの汚れなども悪くなり問題となる。さらに、トナーの
製造効率の低下も起こり好ましくない、６０ｗｔ％より
も犬ぎいと、良好な画像が得られず細線再現性、階調性
などが不十分となる。Preferably 40 to 60 wt%, more preferably 4
It is 0 to 55 wt%. More preferably, 40 to 50
It is wt%. If it is less than 30 wt %, the conveyance property will be insufficient, resulting in uneven image density, and problems such as scattering and background stains will occur. Further, if the content is less than 60 wt %, which is undesirable because it also causes a decrease in toner production efficiency, good images cannot be obtained and fine line reproducibility, gradation, etc. become insufficient.
また、磁性体の含有量（ｗｔ％）は、トナーの重量平均
粒径が７μｍ以下である場合には、トナーの粒径と緊密
に関係する。トナーの重量平均粒径Ｄｔが７μｍ以下で
あると次式で導（ことが出来る。（ＷＴ＝−（１０／３
）Ｄｔ＋ （７２±３））、Ｌかし、（ＷＴ＞−（ｌ
Ｏ／３）Ｄｔ＋（７２±３））であると画像濃度の低下
、画質の低下が生じ、（ＷＴ＜−（１０／３）Ｄｔ＋
（７２±３））であるとバックグラウンドの汚れや画像
ムラを生じ、また、特に製造効率の低下が問題になる。Further, the content (wt%) of the magnetic material is closely related to the particle size of the toner when the weight average particle size of the toner is 7 μm or less. When the weight average particle diameter Dt of the toner is 7 μm or less, it can be derived from the following formula. (WT=-(10/3)
)Dt+ (72±3)), L, (WT>-(l
O/3)Dt+(72±3)), the image density and image quality will decrease, and (WT<-(10/3)Dt+
(72±3)) causes background stains and image unevenness, and in particular, a decrease in manufacturing efficiency becomes a problem.
磁性体の嵩密度を大きくすることで、磁気力が適当に小
さな磁性体を含有する磁性トナーの耐久安定性を著しく
向上させることができる。磁性トナーの耐久安定性には
、トナー中における磁性体の分散が大きく関わることが
知られている０Ｍｉ性体のトナー粒子中における分散性
を高める手段として、従来より磁性体の形状・粒度・粒
度分布・比表面積・吸油量等の規定が知られている。こ
れらの手段のうち、本発明における磁気力の小さな磁性
体のトナー粒子中における分散性を高め、磁性トナーの
耐久安定性を向上させるには１Ｍｉ性体の嵩密度を０．
３５ｇ／ｃｍ’以上、より好ましく ｌｔ ０ 、５
ｇ ／ ｃ ｍ ’以上と規定することが、特に有効で
ある。磁性体の嵩密度が、０．３５ｇ／ｃｍ’よりも小
さいときには、トナー粒度による磁性体の分散が不均一
になり、繰り返し使用によフて磁性体を多く含有するト
ナー粒子が現像されることなく偏析する事でトナー全体
としての現像性を阻害し、濃度低下を招くような場合が
多い。By increasing the bulk density of the magnetic material, the durability and stability of a magnetic toner containing a magnetic material with an appropriately small magnetic force can be significantly improved. It is known that the dispersion of the magnetic material in the toner has a large effect on the durability stability of magnetic toner.As a means of increasing the dispersibility of the 0Mi material in the toner particles, the shape, particle size, and particle size of the magnetic material have been conventionally improved. Regulations for distribution, specific surface area, oil absorption, etc. are known. Among these means, in order to improve the dispersibility of the magnetic material with a small magnetic force in the toner particles in the present invention and to improve the durability stability of the magnetic toner, the bulk density of the 1Mi magnetic material is set to 0.
35 g/cm' or more, more preferably lt 0, 5
It is particularly effective to specify g/cm' or more. When the bulk density of the magnetic material is smaller than 0.35 g/cm', the dispersion of the magnetic material depending on the toner particle size becomes uneven, and toner particles containing a large amount of magnetic material may be developed by repeated use. In many cases, the toner's segregation inhibits the developability of the toner as a whole, leading to a decrease in density.
トナーの帯電量も適正でないと良好な画像が得られない
、トナーの畢電量は、ブローオフ測定法により求めた。A good image cannot be obtained unless the toner charge amount is appropriate.The toner charge amount was determined by a blow-off measurement method.
測定機は、東芝ケミカル社製のものを用いた。A measuring device manufactured by Toshiba Chemical Co., Ltd. was used.
キャリアは、ＥＦＶ２００／３００ （日本鉄粉社製）
を用い、トナー濃度２ｗｔ％で測定した。The carrier is EFV200/300 (manufactured by Nippon Tetsuko Co., Ltd.)
The measurement was performed using a toner concentration of 2 wt%.
混合時間は約２分とした。このときの測定値の絶対値が
５〜５０μｃ／ｇが良い。好ましくは、５〜４０μｃ
／ ｇ 、さらに好ましくは５〜３０μｃ ／ ｇであ
る。５μｃ／ｇ未満であると、画像の鮮鋭さが悪くなり
、バックグラウンドの汚れを生じる。さらに、高温高温
環境下では、画像濃度の低下などが問題となってくる。The mixing time was about 2 minutes. The absolute value of the measured value at this time is preferably 5 to 50 μc/g. Preferably 5-40μc
/g, more preferably 5 to 30μc/g. If it is less than 5 μc/g, the sharpness of the image will deteriorate and background stains will occur. Furthermore, in high-temperature environments, a reduction in image density becomes a problem.
５０μｃ ／ ｇより大きいと、静電凝集力が大きくな
り画質が低下し細線再現性などが不十分となる。特に、
低温低湿環境下ではトナー担持体との鏡映力が必要以上
に大きくなるため、画像濃度の低下などが生じる。When it is larger than 50 μc/g, electrostatic cohesive force becomes large, image quality deteriorates, and fine line reproducibility becomes insufficient. especially,
In a low-temperature, low-humidity environment, the mirroring force with the toner carrier becomes larger than necessary, resulting in a decrease in image density.
本発明のトナーの粒径は、コールタ−カウンター社製Ｔ
Ａ−ｎ型機により測定した。アパーチャーとして１００
μｍのものを用い、粒度は体積分布から求めた重量基準
の平均径、変化係数は重量分布の標準偏差を重量平均径
で割ったものに１００を掛けだした。The particle size of the toner of the present invention is T
It was measured using an A-n type machine. 100 as aperture
Particles of μm were used, the particle size was the weight-based average diameter determined from the volume distribution, and the coefficient of change was the standard deviation of the weight distribution divided by the weight average diameter, multiplied by 100.
トナーの結着樹脂としては、ポリスチレン、ポリｐ−ク
ロルスチレン、ポリビニルトルエン、スチレン−ｐクロ
ルスチレン共重合体、スチレンビニルトルエン共重合体
等のスチレン及びその置換体の単独重合体及びそれらの
共重合体；スチレン−アクリル酸メチル共重合体、スチ
レン−アクリル酸エチル共重合体、スチレン−アクリル
酸ｎ−ブチル共重合体等のスチレンとアクリル酸エステ
ルとの共重合体：スチレン−メタクリル酸メチル共重合
体、スチレン−メタクリル酸エチル共重合体、スチレン
−メタクリル酸ｎ−ブチル共重合体等のスチレンとメタ
クリル酸エステルとの共重合体；スチレンとアクリル酸
エステル及びメタクリル酸エステルとの多元共重合体；
その化スチレンーアクリロニトリル共重合体、スチレン
−ビニルメチルエーテル共重合体、スチレン−ブタジェ
ン共重合体、スチレン−ビニルメチルケトン共重合体、
スチレン−アクリロニトリル−インデン共重合体、スチ
レン−マレイン酸エステル共重合体等のスチレンと他の
ビニル系モノマーとのスチレン系共重合体：ポリメチル
メタクリレート、ポリブチルメタクリレート、ポリ酢酸
ビニル、ポリエステル、ポリアミド、エポキシ樹脂、ポ
リビニルブチラール、ポリアクリル酸、フェノール樹脂
、脂肪族又は脂環族炭化水素樹脂、石油樹脂、塩素化パ
ラフィン、等が単独又は混合して使用出来る。As the binder resin for the toner, homopolymers of styrene and its substituted products, such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, and styrene-vinyltoluene copolymer, and copolymers thereof are used. Copolymer: Copolymer of styrene and acrylic ester such as styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-n-butyl acrylate copolymer: Styrene-methyl methacrylate copolymer Copolymers of styrene and methacrylic esters such as styrene-ethyl methacrylate copolymer, styrene-n-butyl methacrylate copolymer; multi-component copolymers of styrene and acrylic esters and methacrylic esters;
Styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-vinyl methyl ketone copolymer,
Styrenic copolymers of styrene and other vinyl monomers, such as styrene-acrylonitrile-indene copolymers and styrene-maleic acid ester copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyester, polyamide, Epoxy resin, polyvinyl butyral, polyacrylic acid, phenol resin, aliphatic or alicyclic hydrocarbon resin, petroleum resin, chlorinated paraffin, etc. can be used alone or in combination.
特に圧力定着方式に供せられるトナー用の結着樹脂とし
て、低分子量ポリエチレン、低分子量ポリプロピレン、
エチレン−酢酸ビニル共重合体、エチレン−アクリル酸
エステル共重合体、高級脂肪酸、ポリアミド樹脂、ポリ
エステル樹脂等が単独又は混合して使用出来る。In particular, low molecular weight polyethylene, low molecular weight polypropylene,
Ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, higher fatty acids, polyamide resins, polyester resins, etc. can be used alone or in combination.
用いる重合体、共重合体、或はポリマーブレンドは、ス
チレンに代表されるビニル芳香族系又はアクリル系の千
ツマ−を４０重量％以上の量で含有すると、より望まし
い結果が得られる。More desirable results can be obtained if the polymer, copolymer, or polymer blend used contains 40% by weight or more of a vinyl aromatic or acrylic compound represented by styrene.
トナーには、任意の適当な顔料や染料が着色剤として使
用できる０例えば、カーボンブラック、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
公知の染顔料がある。Any suitable pigment or dye can be used as a colorant in the toner, including known dyes and pigments such as carbon black, phthalocyanine blue, ultramarine blue, quinacridone, and benzidine yellow.
本発明の磁性トナーの磁性体として、表面を疎水化処理
された磁性体を用いることにより、トナーの帯電性を安
定化させ、樹脂中への磁性体の分散を良好なものとし、
環境安定性、耐久性の向上が図れる。By using a magnetic material whose surface has been hydrophobized as the magnetic material of the magnetic toner of the present invention, the charging property of the toner is stabilized and the magnetic material is well dispersed in the resin.
Environmental stability and durability can be improved.
本発明に用いられる疎水化処理剤としは、一般に用いら
れるカップリング剤なら何でもよいが、好ましくはシラ
ン系カップリング剤及びチタン系カップリング剤等であ
る。以下に本発明に用いられる疎水化処理剤の１例を挙
げる。The hydrophobizing agent used in the present invention may be any commonly used coupling agent, but silane coupling agents, titanium coupling agents, etc. are preferable. An example of the hydrophobizing agent used in the present invention is listed below.
シラン系カップリング剤としては下記化合物を挙げるこ
とができるが、本発明においてはこれに限るものではな
い。Examples of the silane coupling agent include the following compounds, but the present invention is not limited thereto.
例えばメチルトリメトキシシラン、ビニルトリメトキシ
シラン、ビニルトリメトキシシラン、ビニルトリス（２
−メトキシエトキシ）シラン、γ−メタクリロキシプロ
ピルトリメトキシシラン、γ−アミノプロピルトリメト
キシシラン、Ｎ−β−（アミノエチル）−γ−アミノプ
ロピルトリメトキシシラン、γ−メルカプトプロピルト
リメトキシシラン、β−（３，４−エポキシシクロヘキ
シル）エチルトリメトキシシラン、γ−グリシドキシプ
ロピルトリメトキシシラン、などがある。For example, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(2
-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like.
チタン系カップリング剤としては下記化合物を挙げるこ
とができるが、本発明においてはこれに限るものではな
い。Examples of the titanium-based coupling agent include the following compounds, but the present invention is not limited thereto.
例えば、イソブロビルトリイソステアロイルチタネート
、イソプロピルトリドデシルベンゼンスルフォニルチタ
ネート、イソプロピルトリス（ジオクチルパイロフォス
フェート）チタネート、テトライソプロピルビス（ジオ
クチルフォスファイト）チタネート、テトラオクチルビ
ス（ジトリデシル）オスファイト）チタネート、イソプ
ロピルトリオクタノイルチタネート
タクリルイソステアロイルチタネート、イソプロピルイ
ソステアロイルジアクリルチタネート、イソプロピルト
リ（ジオクチルフォスフェート）チタネート、イソプロ
ピルトリクシルフェニルチタネート、イソプロピルトリ
（Ｎ−アミノエチル−アミノエチル）チタネート、ジク
ミルフェニルオキシアセテートチタネート、ジイソステ
アロイルエチレンチタネート、ビス（ジオクチルパイロ
フォスフェート）エチレンチタネート、ビス（ジオクチ
ルパイロフォスフェート）オキシアセテートチタネート
、テトラ（２．２−ジアリルオキシメチル−１−ブチル
）ビス（ジ−トリデシル）フォスファイトチタネートな
どがある。For example, isobrobyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl) osphite) titanate, isopropyl triota Noyl titanate tacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, Diisostearoyl ethylene titanate, bis(dioctyl pyrophosphate) ethylene titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl) phosphite titanate and so on.
本発明において、磁性体に本発明に用いられる処理剤を
疎水化処理する方法としては、従来公知の方法が用いら
れる。その例としては、シラン系カップリング剤または
チタン系カップリング剤をトルエンまたはキシレン等の
溶媒に溶解し、その中に磁性体を徐々に加えつつ、混合
撹拌し、ついで溶媒をろ過等により除去することで磁性
体表面に疎水性の処理剤膜を形成する。In the present invention, conventionally known methods are used to hydrophobize the magnetic material with the treatment agent used in the present invention. For example, a silane coupling agent or a titanium coupling agent is dissolved in a solvent such as toluene or xylene, a magnetic substance is gradually added thereto, and the mixture is stirred, and then the solvent is removed by filtration or the like. This forms a hydrophobic treatment agent film on the surface of the magnetic material.
また、乾式でのミキサーによる混合で磁性体表面に吸着
させる方法や、トナー製造時に磁性体とそれら処理剤と
を混合して混線により磁性体表面に付着させる方法でも
よい。Alternatively, a method in which the magnetic material is adsorbed to the surface of the magnetic material by mixing with a dry mixer, or a method in which the magnetic material and the processing agent are mixed during toner production and the material is adhered to the surface of the magnetic material by crosstalk may be used.
疎水化処理剤の磁性体に対する処理量としては、０．０
１〜１ ０ｗｔ％であり、好ましくは０、０５〜８ｗｔ
％であり、更に好ましくは、０、１〜５ｗｔ％である。The amount of hydrophobizing agent applied to the magnetic material is 0.0
1 to 10 wt%, preferably 0.05 to 8 wt%
%, more preferably 0.1 to 5 wt%.
本発明の磁性トナーを得るには、樹脂に磁性体、着色剤
などを加えて混練したのち、粉砕して分級する粉砕方法
の他、重合性単量体、重合開始剤、磁性体、着色剤など
を溶媒中で懸濁又は乳化させる重合法が好ましく用いら
れる。In order to obtain the magnetic toner of the present invention, in addition to a pulverization method in which a magnetic material, a coloring agent, etc. are added to a resin, the mixture is kneaded, and then pulverized and classified, a polymerizable monomer, a polymerization initiator, a magnetic material, and a coloring agent are added. A polymerization method in which the components are suspended or emulsified in a solvent is preferably used.
本発明者が鋭意検討した結果、磁場ＩＫ６ｅにおける飽
和磁化の強さが１０〜４ ０ ｅ ｍ ｕ ／ ｇの磁
気力の弱い磁性粉を用いることで磁気凝集力を押さえ、
重合時における分散性を向上させ、かつトナー化に際し
て現像時における磁気凝集力を弱めることで画像上に尾
びきや飛び散りのない鮮明なトナー像が得られると考え
られる．また、水平方向フェレ径が０．０５〜０．５μ
ｍである磁性粉が適度に含有されることで重合性単量体
、磁性粉などの着色剤、その他の組成物の粘度が増粘さ
れるために各重合組成物の分散性が良好となり所望の粒
径の粒度の均一な重合トナーが得られるためにトナーの
摩擦帯電が安定化すると考えられる。As a result of intensive studies by the present inventor, the magnetic cohesive force can be suppressed by using magnetic powder with a weak magnetic force with a saturation magnetization strength of 10 to 40 e mu / g in a magnetic field IK6e,
It is thought that by improving the dispersibility during polymerization and weakening the magnetic cohesive force during development during toner formation, a clear toner image without tailing or scattering can be obtained. In addition, the horizontal direction Feret diameter is 0.05 to 0.5μ
By appropriately containing the magnetic powder (m), the viscosity of the polymerizable monomer, coloring agent such as magnetic powder, and other compositions is increased, so that the dispersibility of each polymer composition is improved and desired. It is thought that triboelectric charging of the toner is stabilized because a polymerized toner having a uniform particle size of .
重合法による場合に使用される単量体は、上記の結着樹
脂の各々の単量体など公知の重合性単量体である。The monomers used in the case of the polymerization method are known polymerizable monomers such as the monomers of each of the above-mentioned binder resins.
重合開始剤としては、いずれか適当な重合開始剤、たと
えば、２．２゛−アゾビス−（２．４−ジメチルバレロ
ニトリル）、２，２° −アゾビスイソブチロニトリル
、１．１゛−アゾビス（シクロヘキサン−１−カルボニ
トリル）、２．２°−アゾビス−４−メトキシ−２．４
−ジメチルバレロニトリル、その他のアゾビスイソブチ
ロニトリル（ＡＩＢＮ）の如きアゾ系またはジアゾ系重
合開始剤；ベンゾイルパーオキサイド、メチルエチルケ
トンパーオキサイド、イソプロピルパーオキシカーボネ
ート、キュメンハイドロパーオキサイド、２．４−ジク
ロリルベンゾイルパーオキサイド、ラウロイルパーオキ
サイドの如き過酸化物系重合開始剤が挙げられる．これ
ら重合開始剤は、一般には、重合性単量体の重量の約０
．５〜５％の開始剤で十分である。As the polymerization initiator, any suitable polymerization initiator such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'- Azobis(cyclohexane-1-carbonitrile), 2.2°-azobis-4-methoxy-2.4
- Azo or diazo polymerization initiators such as dimethylvaleronitrile and other azobisisobutyronitrile (AIBN); benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichloro Examples include peroxide-based polymerization initiators such as lylbenzoyl peroxide and lauroyl peroxide. These polymerization initiators generally contain about 0% of the weight of the polymerizable monomer.
．． 5-5% initiator is sufficient.
一方、必要に応じて添加される荷電制御剤としては、一
般公知のものが用いられる。On the other hand, a generally known charge control agent may be used as the charge control agent added as necessary.
例えば、ニグロシン、炭素数２〜１６のアルキル基を含
むアジン系染料、モノアゾ染料の金属錯塩、サリチル酸
の金属錯塩、ジアルキルサリチル酸の金属錯塩等が用い
られる。For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms, metal complex salts of monoazo dyes, metal complex salts of salicylic acid, metal complex salts of dialkyl salicylic acid, etc. are used.
重合粒子の安定化のために界面活性剤を使用することが
できる。例えば、アニオン性活性剤としてはバルミチン
酸カリウム、ステアリン酸カリウム、カプリン酸カリウ
ム、オレイン酸カリウム、ドデシルスルホン酸ナトリウ
ム、ラウリル酸ナトリウム、ロジン酸ナトリウム、アル
キルナトリウムスルホコハク酸エステル等がある。カチ
オン性活性剤としては長鎖４級アミン塩等がある。非イ
オン活性剤としてはリシルイン酸、ラウリン酸、リシル
イン酸、カプロン酸のエチレンオキサイド縮合物、オレ
イルアルコール、セチルアルコール、ラウリンアルコー
ル等のエチレンオキサイド縮合物がある。Surfactants can be used to stabilize the polymerized particles. For example, anionic active agents include potassium valmitate, potassium stearate, potassium caprate, potassium oleate, sodium dodecylsulfonate, sodium laurate, sodium rosinate, alkyl sodium sulfosuccinate, and the like. Examples of cationic activators include long chain quaternary amine salts. Examples of nonionic surfactants include ethylene oxide condensates of lysyllic acid, lauric acid, lysyllic acid, and caproic acid, and ethylene oxide condensates of oleyl alcohol, cetyl alcohol, and lauric alcohol.
以上の界面活性剤は単独または組合せて用いることがで
きる。界面活性剤濃度は一般に臨界ミセル濃度（ＣＭＣ
）以下が良好であるが、エマルジョン粒子径の増大や粒
子の安定化を目的としてＣＭＣ以上添加してもよい。The above surfactants can be used alone or in combination. The surfactant concentration is generally determined by the critical micelle concentration (CMC).
) or less is preferable, but it may be added in an amount greater than CMC for the purpose of increasing the emulsion particle size or stabilizing the particles.
重合法により本発明のトナーを得るには、以下のような
方法がとられる。The following method is used to obtain the toner of the present invention by the polymerization method.
重合性単量体中に本発明の磁性粉を、２０〜５０ｗｔ％
含有させ、更にワックス、重合開始剤等の添加荊を加え
、超音波分散機、ホモジナイザー等によって均一に熔解
または分散せしめた単量体系を、懸濁安定剤を含有する
水相（すなわち連続相）中に通常の攪拌機またはホモミ
キサー、ホモジナイザー等により分散せしめる。好まし
くは、単量体液滴が所望のトナー粒子のサイズ、−般に
３０μｍ以下の大きさを有するように攪拌速度、時間を
調整し、その後は分散安定剤の作用によりほぼその状態
が維持されるよう、攪拌を粒子の沈降が防止される程度
に行えば良い。重合温′度は４０℃以上、−船釣には５
０〜９０℃の温度に設定して行えば良い。反応終了後、
生成したトナー粒子を洗浄、ろ過により回収し乾燥する
。懸濁重合法においては通常上ツマー１００重量部に対
して水３００〜３０００重量部を分散媒として使用する
。20 to 50 wt% of the magnetic powder of the present invention in the polymerizable monomer
The monomer system containing additives such as wax and a polymerization initiator, and then uniformly melted or dispersed using an ultrasonic disperser, homogenizer, etc., is added to an aqueous phase (i.e., a continuous phase) containing a suspension stabilizer. The mixture is dispersed using a conventional stirrer, homomixer, homogenizer, etc. Preferably, the stirring speed and time are adjusted so that the monomer droplets have the desired toner particle size, generally 30 μm or less, and thereafter this state is maintained approximately by the action of a dispersion stabilizer. It is sufficient to perform stirring to such an extent that sedimentation of the particles is prevented. Polymerization temperature is 40℃ or higher, -5 for boat fishing.
The temperature may be set at 0 to 90°C. After the reaction is complete,
The generated toner particles are collected by washing, filtration, and dried. In the suspension polymerization method, 300 to 3000 parts by weight of water is usually used as a dispersion medium based on 100 parts by weight of the upper part of the polymer.
このようにして得られた重合トナーに対し流動性改質剤
をトナー粒子と混合して用いても良い。A fluidity modifier may be mixed with the toner particles and used for the polymerized toner thus obtained.
流動性改質剤としては、コロイダルシリカ、脂肪酸金属
塩等がある。また、増量の目的で炭酸カルシウム、微粉
末状シリカ等の充填剤を０．５〜２０重量％の範囲内で
トナー中に配合しても良い。Examples of fluidity modifiers include colloidal silica and fatty acid metal salts. Further, for the purpose of increasing the amount, fillers such as calcium carbonate and finely powdered silica may be added to the toner in an amount of 0.5 to 20% by weight.
磁性体としては、鉄、亜鉛、コバルト、ニッケル、銅、
マグネシウム、マンガン、アルミニウム、珪素などの元
素を含む金属酸化物などがある。Magnetic materials include iron, zinc, cobalt, nickel, copper,
These include metal oxides containing elements such as magnesium, manganese, aluminum, and silicon.
本発明の磁性体の製法は、従来知られている方法でよい
。１例としてこのような磁性体の中からスピネル型酸化
鉄の合成例について記述する。The magnetic material of the present invention may be manufactured by any conventionally known method. As an example, an example of the synthesis of spinel type iron oxide from among such magnetic materials will be described.
（合成例）
反応器として、内容積１８０Ｉｌの気泡酸化型反応塔を
用いた。工業用硫酸鉄を水に溶解し、第一鉄濃度１３５
ｇ／Ａの溶液４０ｊ２を用意する。別に、苛性ソーダ濃
度１８３ ｇ／Ｊ２（７）溶液、４０１を用意し、これ
に上記硫酸鉄溶液を攪拌しながら加え中和を行い、残留
苛性ソーダが５ｇ／λとなるようにした。これに工業用
水酸化亜鉛溶液ｐ）（１１，３、亜鉛濃度４０ｇ／ｊ２
のものを５０４２加え、第一鉄濃度４０ ｇ／ｉの反応
液を準備した。(Synthesis Example) A bubble oxidation type reaction tower with an internal volume of 180 Il was used as a reactor. Dissolve industrial iron sulfate in water to obtain a ferrous iron concentration of 135
A solution 40j2 of g/A is prepared. Separately, a caustic soda solution 401 having a concentration of 183 g/J2(7) was prepared, and the above-mentioned iron sulfate solution was added to it while stirring to neutralize it so that the residual caustic soda was 5 g/λ. To this, industrial zinc hydroxide solution p) (11,3, zinc concentration 40g/j2
A reaction solution with a ferrous iron concentration of 40 g/i was prepared.
上記反応液の温度８０℃を維持しながら酸化用空気を１
０４２７ｍ１ｎの割合で吹き込み、酸化反応を行った。While maintaining the temperature of the above reaction solution at 80°C, 1 liter of oxidizing air was added.
The oxidation reaction was carried out by blowing at a rate of 0,427 ml.
反応は約７時間で終了した。The reaction was completed in about 7 hours.
ついで、このスラリーを洗浄乾燥して、スピネル型酸化
鉄を得た。This slurry was then washed and dried to obtain spinel type iron oxide.
得られた磁性体は、水平方向フェレ径０．２７μｍ、Ｂ
ＥＴ８．８ｍ２／ｇ、ａｓ３０．３ｅｍｕ／ｇ、Ｈｃ１
７４６ｅ、 σｒ５．ｌｅｍｕ／ｇであった。The obtained magnetic material had a horizontal Feret diameter of 0.27 μm, B
ET8.8m2/g, as30.3emu/g, Hc1
746e, σr5. lemu/g.
磁性体を含有するトナーの製法としては従来しられた方
法でよい。The toner containing the magnetic material may be produced by any conventional method.
［実施例］
以下本発明を実施例により具体的に説明するが、これは
本発明をなんら限定するものではない。なお以下の配合
における％はすべて重量％である。[Examples] The present invention will be specifically explained below using Examples, but these are not intended to limit the present invention in any way. Note that all percentages in the following formulations are percentages by weight.
実施例１〜４並びに比較例１〜２に用いた磁性体を表−
１に示す。The magnetic materials used in Examples 1 to 4 and Comparative Examples 1 to 2 are shown in the table below.
Shown in 1.
夾」１辻１
を粉体混合し、これを１４０℃に設定した２本ロールミ
ルで約２５分間熱混練し、冷却後、粗粉砕、微粉砕（ジ
ェットミル）した。さらに、アルビネ社製ジグザグ分級
器により、微粉、粗粉をカットし、トナー組成物を得た
。得られたトナーの粒度は、重量平均径８．１μｍ、変
化係数３３％であった。これに負帯電性コロイダルシリ
カを１．０％外添し現像剤とした。このトナーの帯電量
は、−１５μｃ／ｇであった。The mixture was powder-mixed and heat-kneaded for about 25 minutes in a two-roll mill set at 140°C, and after cooling, it was coarsely pulverized and then finely pulverized (jet mill). Further, fine powder and coarse powder were cut using a zigzag classifier manufactured by Albine Co., Ltd. to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 8.1 μm and a variation coefficient of 33%. 1.0% of negatively charged colloidal silica was externally added to this to prepare a developer. The charge amount of this toner was -15 μc/g.
これを、キャノン製レーザービームプリンターＬＢＰ−
ＳＸを改造し、３００ｄｐｉから６００ｄｐｉへ高微細
潜像化した機械で評価した。This is the Canon laser beam printer LBP-
Evaluation was performed using a machine that modified the SX and increased the fineness of latent images from 300 dpi to 600 dpi.
その結果、潜像を忠実に現像するため、細線再現性が非
常に優れていることがわかった。また、網点も非常に良
（再現し、階調性が非常に良かった。さらに、ベタ黒画
像の画像濃度も１．３以上あり、しかも濃度ムラがな（
均一であった。As a result, it was found that the thin line reproducibility was extremely excellent because the latent image was developed faithfully. In addition, the halftone dots were very good (reproduced and the gradation was very good. Furthermore, the image density of the solid black image was over 1.3, and there was no density unevenness (
It was uniform.
工較■ユ
実施例１の磁性体１を磁性体４とした以外は実施例１と
同様にトナーを作製した。得られたトナーの粒度は、重
量平均径８．３μｍ、変化係数３５％であった。A toner was produced in the same manner as in Example 1, except that Magnetic Material 4 was used instead of Magnetic Material 1 in Example 1. The particle size of the obtained toner was a weight average diameter of 8.3 μm and a variation coefficient of 35%.
これを実施例１と同様に評価した。This was evaluated in the same manner as in Example 1.
その結果、特に細線再現性は、潜像に忠実だとはいえず
、また、階調性も十分とはいえなかった。As a result, the fine line reproducibility in particular could not be said to be faithful to the latent image, and the tonality could not be said to be sufficient.
実施例１と同様にトナー化した。得られたトナーの粒度
は、重量平均径８．５μｍ、変化係数３１％であった。A toner was prepared in the same manner as in Example 1. The particle size of the obtained toner was a weight average diameter of 8.5 μm and a variation coefficient of 31%.
また、流動性付与剤として正帯電性コロイダルシリカを
１．０％外添した。このトナーの帯電量は、＋１９μｃ
／ｇであった。これを、キャノン製デジタル複写機ＮＰ
−９３３０を３００ｄｐｉから６００ｄｐｉとした機械
で評価した。Further, 1.0% of positively charged colloidal silica was externally added as a fluidity imparting agent. The amount of charge of this toner is +19μc
/g. This is a Canon digital copier NP.
-9330 was evaluated using a machine that changed the resolution from 300 dpi to 600 dpi.
その結果、細線再現性、階調性、画像濃度とも非常に良
く、長期間の画像出しでも安定していた。特に、環境安
定性も良好であった。As a result, fine line reproducibility, gradation, and image density were all very good, and the image was stable even over a long period of time. In particular, the environmental stability was also good.
Ｌ校±１
実施例２の磁性体Ｎｏ、１を磁性体ＮＯ６５とした以外
は実施例２と同様にトナーを作製した。得られたトナー
の粒度は、重量平均径８．７μｍ、変化係数３０％であ
った。L calibration ±1 A toner was produced in the same manner as in Example 2 except that magnetic material No. 1 in Example 2 was replaced with magnetic material No. 65. The particle size of the obtained toner was a weight average diameter of 8.7 μm and a variation coefficient of 30%.
これを実施例１と同様に評価した。This was evaluated in the same manner as in Example 1.
その結果、特に細線再現性は、潜像に忠実だとはいえず
、また、階調性も十分とはいえなかった。As a result, the fine line reproducibility in particular could not be said to be faithful to the latent image, and the tonality could not be said to be sufficient.
実施例１と同様にトナー化した。トナー化の際、粉砕効
率が良好であった。得られたトナーの粒度は、重量平均
径１２．２μｍ、変化係数３２％であった。負帯電性コ
ロイダルシリカを０．８％、酸化セリウム３．５％を外
添した。A toner was prepared in the same manner as in Example 1. The pulverization efficiency was good during toner production. The particle size of the obtained toner was a weight average diameter of 12.2 μm and a variation coefficient of 32%. 0.8% of negatively charged colloidal silica and 3.5% of cerium oxide were externally added.
このトナーの帯電量は、−７μｃ／ｇであった。The charge amount of this toner was -7 μc/g.
これを、キャノン製複写機ＮＰ−８５８０改造機を用い
て評価した。得られた画像は、画像濃度が高く、しかも
、細線再現性、階調性が良好であった。また、高温高温
、低温低湿などの厳しい環境下でも安定な画像が得られ
た。特に、高速機にもかかわらず飛散が非常に少なかっ
た。また、コピー画像を原稿として用い複写する孫コピ
ー性も優れていた。This was evaluated using a modified Canon NP-8580 copier. The obtained image had high image density, and also had good fine line reproducibility and gradation. Furthermore, stable images were obtained even under harsh environments such as high temperatures, high temperatures, and low temperatures and low humidity. In particular, despite the high speed of the aircraft, there was very little scattering. Furthermore, the ability to make copies using a copied image as a manuscript was also excellent.
を粉体混合し、これを１１０℃に設定した３本ロールミ
ルで約４０分間熱混練し、冷却後、粗粉砕、微粉砕（ジ
ェットミル）した、さらに、アルピネ社製ジグザグ分級
器により、微粉、粗粉をカットし、トナー組成物を得た
。得られたトナーの粒度は、重量平均径７．７μｍ、変
化係数３６％であった。これに負帯電性コロイダルシリ
カを０．９％外添しさらにフェライトコートキャリアと
５％となるようにＶ型混合機で混合し現像剤とした。こ
のトナーの帯電量は、−２０μｃ／ｇであった。The mixture was mixed into powder, heat-kneaded for about 40 minutes in a three-roll mill set at 110°C, and after cooling, coarsely pulverized and finely pulverized (jet mill). The coarse powder was cut to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 7.7 μm and a variation coefficient of 36%. Negatively chargeable colloidal silica was externally added in an amount of 0.9% to this, and further mixed with a ferrite coated carrier to a concentration of 5% using a V-type mixer to prepare a developer. The charge amount of this toner was -20 μc/g.
これを、キャノン製デジタルカラー複写機ＣＬＣ−５０
０改造機にいれ、評価した。This is a Canon digital color copier CLC-50.
I put it in a modified machine and evaluated it.
その結果、長時間の現像でも飛散がなく、非常に良好な
画像が得られた。特に、文字画像の細線再現性が良く、
シャープであった。また、ベタ黒画像も均一で画像濃度
も十分であった。As a result, very good images were obtained with no scattering even during long-term development. In particular, fine line reproducibility of character images is good,
It was sharp. Furthermore, the solid black image was uniform and the image density was sufficient.
実施例５〜８並びに比較例３〜４に用いた磁性体を表−
２に示す。これらの実施例はＤｔ≦７の場合である。The magnetic materials used in Examples 5 to 8 and Comparative Examples 3 to 4 are shown in the table below.
Shown in 2. These examples are for the case where Dt≦7.
叉Ｊ１糺二
を粉体混合し、これを１４０℃に設定した２本ロールミ
ルで約３０分間熱混練し、冷却後、粗粉砕、微粉砕（ジ
ェットミル）した。さらに、エルボウジエツト分級器に
より、微粉、粗粉をカットし、トナー組成物を得た。得
られたトナーの粒度は、重量平均径６．５μｍ、変化係
数２９％であった。これをＷＴ＝−（１０／３）Ｄｔ＋
（７２±３）に代入すると、ＷＴ＝−５０，３±３と
なり、本実施例の磁性体含有量５１．５％はこの式を満
たす、これに負帯電性コロイダルシリカを１．２％外添
し現像剤とした。このトナーの帯電量は、−１１μｃ／
ｇであった。Powder-mixed J1 Koji was heated and kneaded for about 30 minutes in a two-roll mill set at 140°C, and after cooling, it was coarsely pulverized and finely pulverized (jet mill). Furthermore, fine powder and coarse powder were cut using an elbow jet classifier to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 6.5 μm and a variation coefficient of 29%. This is WT=-(10/3)Dt+
(72±3), WT=-50,3±3, and the magnetic material content of this example, 51.5%, satisfies this formula. It was used as an additive developer. The charge amount of this toner is -11μc/
It was g.
これを、キャノン製レーザービームプリンターＬＢＰ−
３Ｘを改造し、３００ｄｐｉから８００ｄｐｉへ高微細
潜像化した機械で評価した。This is the Canon laser beam printer LBP-
The evaluation was performed using a machine that modified the 3X and increased the fineness of latent images from 300 dpi to 800 dpi.
その結果、潜像を忠実に現像するため、細線再現性が非
常に優れていることがわかった。また、網点も非常に良
く再現し、階調性が非常に良かった。さらに、ベタ黒画
像の画像濃度も１．４以上あり、しかも濃度ムラがな（
均一であった。As a result, it was found that the thin line reproducibility was extremely excellent because the latent image was developed faithfully. In addition, the halftone dots were reproduced very well, and the gradation was very good. Furthermore, the image density of solid black images is 1.4 or more, and there is no density unevenness (
It was uniform.
Ｌ較■ユ
実施例５の磁性体Ｎｏ、６を磁性体Ｎｏ、９とした以外
は実施例１と同様にトナーを作製した。得られたトナー
の粒度は、重量平均径６．７μｍ、変化係数３１％であ
った。Comparison L A toner was produced in the same manner as in Example 1 except that magnetic material No. 6 in Example 5 was changed to magnetic material No. 9. The particle size of the obtained toner was a weight average diameter of 6.7 μm and a variation coefficient of 31%.
これを実施例５と同様に評価した。This was evaluated in the same manner as in Example 5.
その結果、特に細線再現性は、潜像に忠実だとはいえず
、また、階調性も十分とはいえなかった。As a result, the fine line reproducibility in particular could not be said to be faithful to the latent image, and the tonality could not be said to be sufficient.
実施例５と同様にトナー化した。得られたトナーの粒度
は、重量平均径６．１μｍ、変化係数３２％であった。A toner was prepared in the same manner as in Example 5. The particle size of the obtained toner was a weight average diameter of 6.1 μm and a variation coefficient of 32%.
また、流動性付与剤として正帯電性コロイダルシリカを
１．３％外添した。このトナーの帯電量は、＋１５μｃ
／ｇであった。これを、キャノン製デジタル複写機ＮＰ
−９３３０を３００ｄｐｉから８００ｄｐｉとした機械
で評価した。Further, 1.3% of positively charged colloidal silica was externally added as a fluidity imparting agent. The amount of charge of this toner is +15μc
/g. This is a Canon digital copier NP.
-9330 was evaluated on a machine with a resolution of 300 dpi to 800 dpi.
その結果、細線再現性、階調性、画像濃度とも非常に良
く、感光体上の転写前のトナー像は非常に潜像に忠実で
あった。また、環境特性も良好であった。As a result, fine line reproducibility, gradation, and image density were all very good, and the toner image before transfer on the photoreceptor was very faithful to the latent image. Furthermore, the environmental characteristics were also good.
比１訓Ａ
実施例６の磁性体Ｎ０１６を磁性体Ｎｏ、１０とした以
外は実施例６と同様にトナーを作製した。得られたトナ
ーの粒度は、重量平均径６．０ｕｍ、変化係数３１％で
あった。Ratio 1 Lesson A A toner was produced in the same manner as in Example 6 except that magnetic material No. 10 was changed from magnetic material No. 16 in Example 6. The particle size of the obtained toner was a weight average diameter of 6.0 um and a variation coefficient of 31%.
これを実施例５と同様に評価した。This was evaluated in the same manner as in Example 5.
その結果、特に細線再現性は、潜像に忠実だとはいえず
、また、階調性も十分とはいえなかった。As a result, the fine line reproducibility in particular could not be said to be faithful to the latent image, and the tonality could not be said to be sufficient.
実施例５と同様にトナー化した。トナー“化の際、粉砕
効率が良好であった。得られたトナーの粒度は、重量平
均径５．ＯｌＬｍ、変化係数２８％であった。負帯電性
コロイダルシリカを１．５％、酸化セリウム４．５％を
外添した。このトナーの帯電量は、−１３μｃ／ｇであ
った。A toner was prepared in the same manner as in Example 5. When producing the toner, the pulverization efficiency was good. The particle size of the obtained toner was a weight average diameter of 5.01 Lm and a variation coefficient of 28%. 1.5% of negatively charged colloidal silica and cerium oxide. 4.5% was added externally.The charge amount of this toner was -13 μc/g.
これを、キャノン製複写機ＮＰ−８５８０改造機を用い
て評価した。得られた画像は、画像濃度が高（、しかも
、細線再現性、階調性が非常に良好であった。また、高
温高温、低温低湿などの厳しい環境下でも安定な画像が
得られた。特に、高速機にもかかわらず飛散が非常に少
なかった。This was evaluated using a modified Canon NP-8580 copier. The obtained image had high image density (and very good fine line reproducibility and gradation). Also, a stable image was obtained even under harsh environments such as high temperature, low temperature and low humidity. In particular, despite the high speed of the aircraft, there was very little scattering.
また、コピー画像を原稿として用い複写する孫コピー性
も特に優れていた。Furthermore, the ability to make copies using a copy image as a manuscript was also particularly excellent.
を粉体混合し、これを１００℃に設定した３本ロールミ
ルで約５０分間熱混練し、冷却後、粗粉砕、微粉砕（ジ
ェットミル）した。さらに、エルボウジエツト分級器に
より、微粉、粗粉をカットし、トナー組成物を得た。得
られたトナーの粒度は、重量平均径６．５μｍ、変化係
数３４％であった。これに負帯電性コロイダルシリカを
１．０％外添しさらにフェライトコートキャリアと３％
となるように■型混合機で混合し現像剤とした。このト
ナーの帯電量は、−１８μｃ／ｇであった。The mixture was mixed into powders, heated and kneaded for about 50 minutes in a three-roll mill set at 100°C, and after cooling, coarsely pulverized and finely pulverized (jet mill). Furthermore, fine powder and coarse powder were cut using an elbow jet classifier to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 6.5 μm and a variation coefficient of 34%. To this, 1.0% of negatively charged colloidal silica was externally added, and further 3% of ferrite coated carrier was added.
The mixture was mixed in a ■ type mixer to obtain a developer. The charge amount of this toner was -18 μc/g.
これを、キャノン製デジタルカラー複写機ＣＬＣ−５０
０改造様にいれ、評価した。その結果、長時間の現像で
も飛散がなく、非常に良好な画像が得られた０文字画像
の細線再現性が特に良く、シャープであった。また、ベ
タ黒画像も均一で画像濃度も十分であった。This is a Canon digital color copier CLC-50.
I put it in 0 mods and evaluated it. As a result, there was no scattering even during long-term development, and a very good image was obtained.The thin line reproducibility of the 0 character image was particularly good and sharp. Furthermore, the solid black image was uniform and the image density was sufficient.
実施例９〜１２並びに比較例５〜９に用いた磁性体を表
−３に示す。これらの実施例は磁性体を疎水化処理した
場合である。Table 3 shows the magnetic materials used in Examples 9 to 12 and Comparative Examples 5 to 9. These Examples are cases where the magnetic material was subjected to hydrophobization treatment.
失」１糺旦
まず、前言己磁性体Ｎｏ、１１ １００ｇに対し、γ−
メタクリロキシプロピルトリメトキシシラン１ｇをトル
エン１００ｍρに溶解した溶液を加え、約３時間撹拌し
、ろ過乾燥してチタン系カップリング剤による疎水化処
理された磁性体を得た。First, for 100 g of self-magnetic material No. 11, γ-
A solution of 1 g of methacryloxypropyltrimethoxysilane dissolved in 100 mρ of toluene was added, stirred for about 3 hours, filtered and dried to obtain a magnetic material that had been hydrophobized with a titanium coupling agent.
前記処方量を粉体混合し、これを１４０℃に設定した２
本ロールミルで約３０分間熱混練し、冷却後、粗粉砕、
微粉砕（ジェットミル）した、さらに、エルボウジエツ
ト分級器により、微粉、粗粉をカットし、トナー組成物
を得た。得られたトナーの粒度は、重量平均径８．５μ
ｍ、変化係数３０％であった。これに負帯電性コロイダ
ルシリカを０．８％外添し現像剤とした。このトナーの
帯電量は、−１５μｃ／ｇであった。The prescribed amount was mixed into powder and the temperature was set at 140°C.
Heat kneaded in this roll mill for about 30 minutes, cooled, coarsely crushed,
The powder was finely pulverized (jet mill), and fine powder and coarse powder were cut using an elbow jet classifier to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 8.5μ.
m, and the coefficient of change was 30%. 0.8% of negatively charged colloidal silica was externally added to this to prepare a developer. The charge amount of this toner was -15 μc/g.
これを、キャノン製レーザービームプリンターＬＢＰ−
ＳＸを改造し、３００ｄｐｉから６００ｄｐｉへ高微細
潜像化した機械で評価した。This is the Canon laser beam printer LBP-
Evaluation was performed using a machine that modified the SX and increased the fineness of latent images from 300 dpi to 600 dpi.
その結果、潜像を忠実に現像するため、細線再現性が非
常に優れていることがわかった。また、網点も非常に良
く再現し、階調性が非常に良かった。さらに、ベタ黒画
像の画像濃度も１．４以上あり、しかも濃度ムラがなく
均一であった。また、低温低湿、高温高温ともにガサツ
キやカブリ等のない高画質な画像が得られた。As a result, it was found that the thin line reproducibility was extremely excellent because the latent image was developed faithfully. In addition, the halftone dots were reproduced very well, and the gradation was very good. Furthermore, the image density of the solid black image was 1.4 or more, and was uniform with no density unevenness. In addition, high-quality images without roughness or fogging were obtained both at low temperatures and low humidity, and at high and high temperatures.
工数■１
実施例９の磁性体Ｎｏ、１１を実施例９と同様に疎水化
処理した磁性体Ｎｏ、１４を用いる以外は実施例９と同
様にトナーを作製した。得られたトナーの粒度は、重量
平均径８．６μｍ、変化係数３３％であった。これを実
施例９と同様に評価した。Man-hours (1) A toner was produced in the same manner as in Example 9, except that magnetic material No. 14, obtained by subjecting magnetic material No. 11 of Example 9 to hydrophobization treatment in the same manner as in Example 9, was used. The particle size of the obtained toner was a weight average diameter of 8.6 μm and a variation coefficient of 33%. This was evaluated in the same manner as in Example 9.
その結果、特に細線再現性は、潜像に忠実だとはいえず
、また、階調性も十分とはいえなかった。As a result, the fine line reproducibility in particular could not be said to be faithful to the latent image, and the tonality could not be said to be sufficient.
比１０引旦
実施例９の磁性体Ｎｏ、１１の表面処理をしないで用い
る以外は実施例１１と同様にトナーを作製した。得られ
たトナーの粒度は重量平均径８．３μｍ、変化係数３４
％であった。これを実施例９と同様に評価した。A toner was produced in the same manner as in Example 11, except that magnetic materials No. 9 and 11 were used without surface treatment. The particle size of the obtained toner was a weight average diameter of 8.3 μm and a variation coefficient of 34.
%Met. This was evaluated in the same manner as in Example 9.
その結果、潜像忠実性には優れており、階調性も良好で
あったが、低温低湿下において、初期は画像濃度も高（
、良好な結果を示したが多数枚の複写で次第に濃度が低
下した。As a result, the latent image fidelity was excellent and the gradation was also good, but the image density was initially high at low temperature and low humidity (
, showed good results, but the density gradually decreased after copying a large number of sheets.
磁性体Ｎｏ、１１の表面処理剤をイソプロピルトリオク
タノイルチタネート１．４ｇに変える以外は実施例９と
同様に磁性体の表面処理およびトターの作製を行なった
。得られたトナーの粒度は、重量平均径８．１ｕｍ、変
化係数３２％であった。また、流動性付与剤として正帯
電性コロイダルシリカを０．８％外添した。このトナー
の帯電量は、＋１４．３μｃ／ｇであった。The surface treatment of the magnetic material and the preparation of the toter were carried out in the same manner as in Example 9, except that the surface treatment agent for magnetic material No. 11 was changed to 1.4 g of isopropyltrioctanoyl titanate. The particle size of the obtained toner was a weight average diameter of 8.1 um and a variation coefficient of 32%. Additionally, 0.8% of positively charged colloidal silica was externally added as a fluidity imparting agent. The charge amount of this toner was +14.3 μc/g.
これを、キャノン製デジタル複写機ＮＰ−９３３０を３
００ ｄ ｐ ｉ カら６ｏＯｄｐｉとした機械で評価
した。This is done using Canon's digital copier NP-9330.
The evaluation was made using a machine that changed the speed from 00 dpi to 60 dpi.
その結果、細線再現性、階調性、゛画像濃度とも非常に
良好で、非常に潜像に忠実であった。また、環境特性も
良好であった。As a result, fine line reproducibility, gradation, and image density were all very good, and the latent image was very faithful. Furthermore, the environmental characteristics were also good.
Ｌ艶丞ｌ
実施例１０の疎水化表面処理した磁性体Ｎ０１１１を実
施例１０と同様に疎水化表面処理した磁性体Ｎｏ、１５
を用いる以外は実施例１０と同様にトナーを作製した。Magnetic material No. 15 whose surface was hydrophobized in the same manner as in Example 10 from the magnetic material No. 111 which was subjected to the hydrophobization surface treatment of Example 10
A toner was produced in the same manner as in Example 10 except that the following was used.
得られたトナーの粒度は、重量平均径８．１μｍ、変化
係数３３％であった。これを実施例９と同様に評価した
。The particle size of the obtained toner was a weight average diameter of 8.1 μm and a variation coefficient of 33%. This was evaluated in the same manner as in Example 9.
その結果、高い画像濃度を示したが、特に細線再現性は
、潜像に忠実だとはいえず、また、階調性も十分とはい
えなかった。As a result, although a high image density was exhibited, the reproducibility of fine lines in particular was not faithful to the latent image, and the gradation was not sufficient.
実施例９と同様にトナー化した。トナー化の際、粉砕効
率が良好であった。得られたトナーの粒度は、重量平均
径７．７μｍ、変化係数２６％であった。負帯電性コロ
イダルシリカを０．８％外添した。このトナーの帯電量
は、−１２，４μｃ／ｇであった。A toner was prepared in the same manner as in Example 9. The pulverization efficiency was good during toner production. The particle size of the obtained toner was a weight average diameter of 7.7 μm and a variation coefficient of 26%. 0.8% of negatively charged colloidal silica was externally added. The charge amount of this toner was -12.4 μc/g.
これを、キャノン製複写機ＮＰ−８５８０改造機を用い
て評価した。得られた画像は、画像濃度が高（、しかも
、ガサツキがなく、細線再現性、階調性が非常に良好で
あった。また、高温高温、低温低湿などの厳しい環境下
でも安定な画像が得られた。特に、高速機にもかかわら
ず飛散が非常に少なく、画像濃度の変動がなく、耐久安
定性に優れていた。また、コピー画像を原稿として用い
複写する孫コピー性も特に優れていた。This was evaluated using a modified Canon NP-8580 copier. The images obtained had high image density (in addition, there was no roughness, and the fine line reproducibility and gradation were very good. In addition, the images were stable even under harsh environments such as high temperatures, low temperatures, and low humidity. In particular, despite being a high-speed machine, there was very little scattering, there was no fluctuation in image density, and it had excellent durability and stability.It also had particularly excellent copying properties when copying images using copy images as originals. Ta.
磁性体Ｎｏ、１３の表面処理剤をビス（ジオクチルパイ
ロフォスフェート）エチレンチタネート１．８ｇに変え
て処理した磁性体を用いた。A magnetic material treated by changing the surface treatment agent of magnetic material No. 13 to 1.8 g of bis(dioctylpyrophosphate) ethylene titanate was used.
これらを粉体混合し、これを１００℃に設定した３本ロ
ールミルで約３０分間熱混練し、冷却後、粗粉砕、微粉
砕（ジェットミル）した。さらに、エルボウジエツト分
級器により、微粉、粗粉をカットし、トナー組成物を得
た。得られたトナーの粒度は、重量平均径７．９μｍ、
変化係数３２％であった。これに負帯電性コロイダルシ
リカを０．５％外添し、さらにフェライトコートキャリ
アとトナー濃度が５％となるようにターブラーミキサー
で混合し現像剤とした。このトナーの帯電量は、−２８
μｃ／ｇであった。These were mixed into powders, and this was heat-kneaded for about 30 minutes in a three-roll mill set at 100°C, and after cooling, it was coarsely pulverized and finely pulverized (jet mill). Furthermore, fine powder and coarse powder were cut using an elbow jet classifier to obtain a toner composition. The particle size of the obtained toner was a weight average diameter of 7.9 μm,
The coefficient of change was 32%. Negatively chargeable colloidal silica was externally added in an amount of 0.5%, and the mixture was further mixed with a ferrite-coated carrier using a turbulence mixer so that the toner concentration was 5% to obtain a developer. The charge amount of this toner is -28
It was μc/g.
これを、キャノン製デジタルカラー複写機ＣＬＣ−５０
０改造機にいれ、評価した。その結果、長時間の現像で
も飛散、カブリがな（、画像ムラのない非常に良好な画
像が得られた。特に低温低湿下においてガサツキもなく
、文字画像の細線再現性が特に良く、シャープであった
。また、ベタ黒画像も均一で画像濃度も十分であった。This is a Canon digital color copier CLC-50.
I put it in a modified machine and evaluated it. As a result, very good images were obtained with no scattering or fogging (and no image unevenness) even during long-term development.There was no roughness, especially under low temperature and low humidity, and the fine line reproducibility of character images was particularly good, and the images were sharp. Also, the solid black image was uniform and the image density was sufficient.
さらに、高温高湿下においてもトナーが飛散することな
く、良好な画像も得られた。Furthermore, good images were obtained without toner scattering even under high temperature and high humidity conditions.
実施例９と同様にしてトナーを作製した。得られたトナ
ーの粒度は、重量平均径８．０μｍ、変化係数２９％で
あった。これを実施例９と同様に評価した。A toner was produced in the same manner as in Example 9. The particle size of the obtained toner was a weight average diameter of 8.0 μm and a variation coefficient of 29%. This was evaluated in the same manner as in Example 9.
その結果、環境安定性は良好であり、高い画像濃度を示
したが、特に細線再現性は、潜像に忠実だとはいえず、
また、階調性も十分とはいえなかった。As a result, the environmental stability was good and the image density was high, but the fine line reproducibility in particular could not be said to be faithful to the latent image.
Furthermore, the gradation was not sufficient.
実施例９と同様にしてトナーを作製した。得られたトナ
ーの粒度は、重量平均径８．７μｍ、変化係数３８％で
あった。このトナーは、実施例９に比べ、粉砕性が若干
悪かった。A toner was produced in the same manner as in Example 9. The particle size of the obtained toner was a weight average diameter of 8.7 μm and a variation coefficient of 38%. This toner had slightly worse crushability than Example 9.
これを実施例９と同様に評価したところ、現像スリーブ
上のトナーの搬送性が悪く、画像上にガサツキや濃度ム
ラが見られた。When this was evaluated in the same manner as in Example 9, the conveyance of the toner on the developing sleeve was poor, and roughness and density unevenness were observed on the image.
実施例１３〜１６並θに比較例１０〜１２に用いた磁性
体を表−４に示す、これらの実施例は磁性体の嵩密度を
限定した場合である。Table 4 shows the magnetic materials used in Examples 13 to 16 and Comparative Examples 10 to 12, and these examples are cases in which the bulk density of the magnetic materials is limited.
夫１」ＬＬｌ
上記材料を混合した後、１４０℃に設定した２軸押し出
し式混線機にて溶融混練し、冷却後、気流式粉砕機を用
いて微粉砕し、更に風力分級をおこない、重量平均粒径
８．５μｍのトナーを得た。これに疎水化されたコロイ
ダルシリカ０．８ｗｔ％を外添し現像剤とした。この現
像剤の帯電量は、＋１８μｃ／ｇであった。Husband 1'' LLl After mixing the above materials, melt-knead them in a twin-screw extruder mixer set at 140°C, cool them, finely grind them in an air-flow grinder, further perform air classification, and then A toner with a particle size of 8.5 μm was obtained. 0.8 wt % of hydrophobized colloidal silica was externally added to this to prepare a developer. The amount of charge of this developer was +18 μc/g.
この現像剤５００ｇを市販の複写機ＮＰ−４８３５に適
用し、連続１０，０００枚の複写を行った後に、画像濃
度・細線再現性・階調再現性の評価を行った。この結果
、表−５に示すように、優れた性能を確認した。500 g of this developer was applied to a commercially available copying machine NP-4835, and after 10,000 copies were continuously made, image density, fine line reproducibility, and gradation reproducibility were evaluated. As a result, as shown in Table 5, excellent performance was confirmed.
１１五ユＡ
実施例１３と同じ材料を用い、微粉砕及び風力分級の条
件を変更して、重量平均粒径５．７μｍのトナーを得た
。このトナーにアミノ変性シリコーンオイルで処理され
たコロイダルシリカ１．０ｗｔ％を外添し現像剤とした
。この現像剤の帯電量は、＋２９μｃ／ｇであった。115U A A toner having a weight average particle size of 5.7 μm was obtained by using the same materials as in Example 13 and changing the conditions of pulverization and air classification. 1.0 wt % of colloidal silica treated with amino-modified silicone oil was externally added to this toner to prepare a developer. The amount of charge of this developer was +29 μc/g.
この現像剤を、実施例１３と同様にして評価したところ
、表−５に示すように極めて優れた画像性を有する画像
が得られた。This developer was evaluated in the same manner as in Example 13, and as shown in Table 5, images with extremely excellent image properties were obtained.
工数五土工
磁性体Ｎｏ、１９を用いる以外は実施例１４と同様にし
て重量平均粒径５．８μｍ、帯電量＋３２μｃ／ｇの現
像剤を得た。この現像剤を、実施例１３と同様にして評
価したところ、表−５に示すように、画像濃度の低下が
みられ、鮮鋭さに欠けた画像となった。A developer having a weight average particle diameter of 5.8 μm and a charge amount of +32 μc/g was obtained in the same manner as in Example 14 except that Godoko magnetic material No. 19 was used. When this developer was evaluated in the same manner as in Example 13, as shown in Table 5, a decrease in image density was observed, resulting in an image lacking in sharpness.
（Ｍｉ性体Ｎｏ、１７ ５３．３ｗｔ％上記材
料を用い、実施例１４と同様にトナー化し、疎水性コロ
イダルシリカ０．８ｗｔ％を外添し、重量平均粒径６．
３μｍの現像剤を得た。(Mi material No. 17 53.3 wt% The above material was made into a toner in the same manner as in Example 14, 0.8 wt% of hydrophobic colloidal silica was externally added, and the weight average particle size was 6.
A developer with a thickness of 3 μm was obtained.
この現像剤の帯電量は、−２５μｃ／ｇであった。The charge amount of this developer was -25 μc/g.
この現像剤を、アモルファスシリコン感光体を具備する
市販の複写機ＮＰ−６６５０を、感光体のダーク電位が
＋３５０Ｖとなるように改造して評価をおこなったとこ
ろ、表−５に示すように良好な画像を得た。This developer was evaluated by modifying a commercially available copying machine NP-6650 equipped with an amorphous silicon photoreceptor so that the dark potential of the photoreceptor was +350V. As shown in Table 5, good results were obtained. Got the image.
Ｌ較■ユニ
磁性体Ｎｏ、’２０を用いる以外は実施例１５と同様に
して重量平均粒径６．１μｍ、帯電量＋５４μｃ／ｇの
現像剤を得た。この現像剤を、実施例１５と同様にして
評価したところ、表−５に示すように、画像濃度が薄く
、しかも濃度むらがあり階調再現性・細線再現性に劣る
画像となった。複写機の現像器を観察したところ、トナ
ー担持スリーブ上のトナーコートが、著しく不均一にな
っていた。Comparison L: A developer having a weight average particle size of 6.1 μm and a charge amount of +54 μc/g was obtained in the same manner as in Example 15 except that Unimagnetic material No. '20 was used. When this developer was evaluated in the same manner as in Example 15, as shown in Table 5, the image density was low, the density was uneven, and the gradation reproducibility and fine line reproducibility were poor. When the developing unit of the copying machine was observed, the toner coating on the toner carrying sleeve was found to be extremely non-uniform.
上記材料を用い、実施例１３と同様にトナー化し、疎水
性コロイダルシリカ０．３ｗｔ％を外添し、重量平均粒
径１２．３μｍの現像剤を得た。Using the above materials, a toner was prepared in the same manner as in Example 13, and 0.3 wt% of hydrophobic colloidal silica was externally added to obtain a developer having a weight average particle size of 12.3 μm.
この現像剤の帯電量は、＋１５μｃ ／ ｇであった。The amount of charge of this developer was +15 μc/g.
この現像剤を、市販のデジタル複写機ＮＰ−９３３０を
６００ｄｐｉに改造したマシンに適用し、実施例１３と
同様に評価したところ、表−５に示したように、安定し
て高解像度の良好なトナー画像を得た。This developer was applied to a commercially available digital copying machine NP-9330 modified to 600 dpi, and evaluated in the same manner as in Example 13. As shown in Table 5, it was found to be stable and have good high resolution. A toner image was obtained.
Ｌ校！ユニ
磁性体Ｎｏ、１８の比率を２７．４ｗｔ％とした以外は
実施例１６と同様にして、重量平均粒径１２．５μｍの
現像剤を得た。この現像剤の帯電量は、＋１６μｃ／ｇ
であった。L school! A developer having a weight average particle size of 12.5 μm was obtained in the same manner as in Example 16 except that the ratio of unimagnetic material No. 18 was 27.4 wt%. The amount of charge of this developer is +16μc/g
Met.
この現像剤を、実施例１６と同様にして評価したところ
、表−５に示すように、実施例１６と比較してバックグ
ラウンド汚れが顕著で、ラインのとぎれがちな解像性に
も劣った画像となった。When this developer was evaluated in the same manner as in Example 16, as shown in Table 5, compared to Example 16, background stains were noticeable and the resolution was poor, with lines tending to be broken. It became an image.
（以下余白）
以下の実施例１７〜１９並びに比較例１３〜１４は重合
法によって作製した場合である。(Left below) Examples 17 to 19 and Comparative Examples 13 to 14 below were produced by a polymerization method.
上記処方量で均一に溶解または分散させた重合性単量体
組成物を水中に懸濁安定剤を分散させた分散媒中にて懸
濁重合することにより磁性重合トナーを得た。A magnetic polymerized toner was obtained by suspension polymerizing the polymerizable monomer composition uniformly dissolved or dispersed in the above prescribed amount in a dispersion medium containing a suspension stabilizer dispersed in water.
得られたトナーの粒径をコールタ−カウンター社製コー
ルタ−カウンターＴＡ−２粒度分布計により、１００μ
ｍアパーチャーを用いて測定したところ、重量平均粒径
８．１μｍで、個数分布で５．０４μｍ以下が７％、重
量分布で１２．７μｍ以上が０％を有する粒度分布のシ
ャープなトナーが得られた。The particle size of the obtained toner was measured using a Coulter Counter TA-2 particle size distribution meter manufactured by Coulter Counter Co., Ltd. to 100 μm.
When measured using m aperture, a toner with a sharp particle size distribution was obtained, with a weight average particle size of 8.1 μm, a number distribution of 7% of particles of 5.04 μm or less, and a weight distribution of 0% of particles of 12.7 μm or more. Ta.
得られたトナーをキャノン製レーザービームプリンター
（ＬＢＰ−ＳＸ）を３００ ｄ ｐ ｉ カら６００ｄ
ｐｉに改造した機械で評価した。The obtained toner was transferred to a Canon laser beam printer (LBP-SX) from 300 dpi to 600 dpi.
Evaluation was performed using a machine modified to a pi.
その結果、細線再現性に優れ、画像も帯電ムラ等による
画像ムラを生じず、尾びき、画像の回りの飛び散り等も
ない鮮明な画像が得られた。また、ベタ黒部における画
像濃度も１．４以上もあった。As a result, a clear image with excellent fine line reproducibility, no image unevenness caused by uneven charging, etc., and no tailing or scattering around the image was obtained. Furthermore, the image density in solid black areas was also 1.4 or higher.
実施例１７と同様にして磁性重合トナーを得た。得られ
た重合トナーの重量平均粒径は、７．６μｍであり、個
数分布で５．０４μｍ以下が１１％、重量分布で１２．
７μｍ以上が０％であった。A magnetic polymerized toner was obtained in the same manner as in Example 17. The weight average particle diameter of the obtained polymerized toner was 7.6 μm, 11% of particles were 5.04 μm or less in number distribution, and 12.5 μm in weight distribution.
7 μm or more was 0%.
このトナーを、キャノン製デジタル複写機ＮＰ−９３３
０を３００ｄｐｉから６００ｄｐｉに改造した機械で評
価した。Use this toner on a Canon digital copier NP-933.
0 was evaluated using a machine modified from 300 dpi to 600 dpi.
その結果、実施例１７と同様に良好な結果が得られた。As a result, similar to Example 17, good results were obtained.
特に、濃度ムラのない均一な画像が得られた。In particular, uniform images with no density unevenness were obtained.
上記磁性体Ｎｏ、２３のシランカップリング剤処理方法
について以下に示す。The method for treating the magnetic material No. 23 with a silane coupling agent will be described below.
の割合で混合し、７０℃に加熱しながら超音波分散機（
１０ＫＨｚ、２００Ｗ）にて３０分間分散、処理し、前
記シランカップリング剤処理磁性粉のスチレンスラリー
を得た。Mix at the ratio of
10 KHz, 200 W) for 30 minutes to obtain a styrene slurry of the silane coupling agent-treated magnetic powder.
実施例１と同様にして磁性重合トナーを得た。得られた
重合トナーの重量平均粒径は、６．６μｍであり、個数
分布で４．００μｍ以下が７％、重量分布で１０．０８
μｍ以上が０％であった。これに負帯電性コロイダルシ
リカを１．０％外添した。A magnetic polymerized toner was obtained in the same manner as in Example 1. The weight average particle size of the obtained polymerized toner was 6.6 μm, 7% of particles were 4.00 μm or less in number distribution, and 10.08 in weight distribution.
The value of µm or more was 0%. To this, 1.0% of negatively charged colloidal silica was externally added.
得られたトナーを実施例１７と同様にキャノン製レーザ
ービームプリンター（ＬＢＰ−８Ｘ）を３００ｄｐｉか
ら６００ｄｐｉに改造した機械で評価した。The obtained toner was evaluated in the same manner as in Example 17 using a Canon laser beam printer (LBP-8X) modified from 300 dpi to 600 dpi.
その結果、細線再現性に優れ、画像も帯電ムラ等による
画像ムラを生じず、尾びき、画像の回りの飛び散り等も
ない鮮明な画像が得られた。特に、ハーフトーン部にお
いて階調再現性が良好であった。また、ベタ黒部におけ
る画像濃度も１．５以上もあった。As a result, a clear image with excellent fine line reproducibility, no image unevenness caused by uneven charging, etc., and no tailing or scattering around the image was obtained. In particular, the gradation reproducibility was good in the halftone part. Furthermore, the image density in solid black areas was also 1.5 or higher.
また、複数枚の複写においても画像は安定して均一画像
が得られた。Further, even when a plurality of copies were made, a stable and uniform image was obtained.
実施例１７と同様にして重合トナーを得た。A polymerized toner was obtained in the same manner as in Example 17.
粒度は、重量平均粒径８．３μｍで、個数分布で５．０
４μｍ以下が９％、重量分布で１２．７μｍ以上が０．
５％であった。The particle size is a weight average particle size of 8.3 μm and a number distribution of 5.0.
9% is 4 μm or less, and 0.0% is 12.7 μm or more in weight distribution.
It was 5%.
これを実施例１７と同様に評価したところ、画像の回り
にトナーの凝集による尾びきや飛び散りがあり、潜像に
忠実だとは言えず、更に画像濃度も１．２５と低かった
。When this was evaluated in the same manner as in Example 17, there was tailing and scattering around the image due to toner aggregation, and it could not be said that the latent image was faithful, and furthermore, the image density was low at 1.25.
実施例１７と同様にして重合トナーを得た。A polymerized toner was obtained in the same manner as in Example 17.
粒度は、重量平均粒径８．１μｍで、個数分布で５．０
４ｕｍ以下が８％、重量分布で１２．７μｍ以上が１．
５％であった。The particle size is a weight average particle size of 8.1 μm and a number distribution of 5.0.
8% is 4um or less, and 1.8% is 12.7μm or more in weight distribution.
It was 5%.
これを実施例１７と同様に評価した結果、カバーリング
パワーが低くなり画像濃度が低下し、さらに階調の再現
性が悪かった。This was evaluated in the same manner as in Example 17, and as a result, the covering power was low, the image density was low, and the gradation reproducibility was poor.
［発明の効果］
本発明によれば、磁気力が適当に小さい磁性体を適当量
含有させることで、細線再現性が向上し、潜像あるいは
信号に高忠実な現像による画質が得られる。[Effects of the Invention] According to the present invention, by containing an appropriate amount of a magnetic material having an appropriately small magnetic force, fine line reproducibility is improved and image quality can be obtained by development with high fidelity to a latent image or signal.
更に、磁性体を疎水化表面処理又は嵩密度を大台くする
ことで、耐久安定性の向上を図ることができる。Furthermore, durability and stability can be improved by subjecting the magnetic material to a hydrophobic surface treatment or by increasing the bulk density.
Claims (7)
ｇ、水平方向フェレ径が０．０５〜０．５μｍである金
属酸化物で形成されている磁性体を含有することを特徴
とする磁性トナー。(1) σs in a magnetic field of 1 K■e is 10 to 40 emu/
g. A magnetic toner comprising a magnetic material made of a metal oxide and having a horizontal Feret diameter of 0.05 to 0.5 μm.
あることを特徴とする請求項（１）に記載の磁性トナー
。(2) The magnetic toner according to claim 1, wherein the magnetic substance content in the toner is 30 to 60 wt%.
ーの粒径をＤｔ（μｍ）としたとき、 ＷＴ＝−（１０／３）Ｄｔ＋（７２±３） Ｄｔ≦７ を満足することを特徴とする請求項（１）に記載の磁性
トナー。(3) When the magnetic substance content (wt%) in the toner is WT and the particle size of the toner is Dt (μm), WT=-(10/3)Dt+(72±3) Dt≦7 is satisfied. The magnetic toner according to claim 1, characterized in that:
ることを特徴とする請求項（１）乃至（３）のいずれか
に記載の磁性トナー。(4) The magnetic toner according to any one of claims (1) to (3), wherein the magnetic material has a bulk density of 0.35 g/cm^3 or more.
開始剤及び磁性体より重合される重合トナーであること
を特徴とする請求項（１）乃至（４）のいずれかに記載
の磁性トナー。(5) The magnetic toner according to any one of claims (1) to (4), wherein the magnetic toner is a polymerized toner polymerized from at least a synthetic resin monomer, a polymerization initiator, and a magnetic material. .
する請求項（１）乃至（５）のいずれかに記載の磁性ト
ナー。(6) The magnetic toner according to any one of claims (1) to (5), wherein the magnetic material has been subjected to a hydrophobic surface treatment.
又はチタン系カップリング剤よりなることを特徴とする
請求項（６）に記載の磁性トナー。(7) The magnetic toner according to claim (6), wherein the surface treatment agent for the magnetic material is a silane coupling agent or a titanium coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2312700A JPH04184354A (en) | 1990-11-20 | 1990-11-20 | Magnetic toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2312700A JPH04184354A (en) | 1990-11-20 | 1990-11-20 | Magnetic toner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04184354A true JPH04184354A (en) | 1992-07-01 |
Family
ID=18032380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2312700A Pending JPH04184354A (en) | 1990-11-20 | 1990-11-20 | Magnetic toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04184354A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578375A (en) * | 1993-09-30 | 1996-11-26 | Toda Kogyo Corporation | Granular magnetite particles and process for producing the same |
| JP2002123037A (en) * | 2000-07-28 | 2002-04-26 | Canon Inc | Dry toner, image forming method and process cartridge |
| EP1207433A2 (en) † | 2000-11-20 | 2002-05-22 | Ricoh Company, Ltd. | Toner for developing latent electrostatic images, and image forming method and device |
| JP2009151342A (en) * | 1999-02-22 | 2009-07-09 | Canon Inc | Toner, image forming method and apparatus unit |
| US7678524B2 (en) | 2005-05-19 | 2010-03-16 | Canon Kabushiki Kaisha | Magnetic toner |
| WO2021200746A1 (en) * | 2020-03-31 | 2021-10-07 | パウダーテック株式会社 | Ferrite powder, ferrite resin composition, resin molded body, electronic component, electronic equipment, or electronic equipment housing |
-
1990
- 1990-11-20 JP JP2312700A patent/JPH04184354A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578375A (en) * | 1993-09-30 | 1996-11-26 | Toda Kogyo Corporation | Granular magnetite particles and process for producing the same |
| JP2009151342A (en) * | 1999-02-22 | 2009-07-09 | Canon Inc | Toner, image forming method and apparatus unit |
| JP2002123037A (en) * | 2000-07-28 | 2002-04-26 | Canon Inc | Dry toner, image forming method and process cartridge |
| EP1207433A2 (en) † | 2000-11-20 | 2002-05-22 | Ricoh Company, Ltd. | Toner for developing latent electrostatic images, and image forming method and device |
| EP1207433B2 (en) † | 2000-11-20 | 2013-06-12 | Ricoh Company, Ltd. | Toner for developing latent electrostatic images, and image forming method and device |
| US7678524B2 (en) | 2005-05-19 | 2010-03-16 | Canon Kabushiki Kaisha | Magnetic toner |
| WO2021200746A1 (en) * | 2020-03-31 | 2021-10-07 | パウダーテック株式会社 | Ferrite powder, ferrite resin composition, resin molded body, electronic component, electronic equipment, or electronic equipment housing |
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