JPH04328757A - Toner for developing electrostatic charge image - Google Patents
Toner for developing electrostatic charge imageInfo
- Publication number
- JPH04328757A JPH04328757A JP3124535A JP12453591A JPH04328757A JP H04328757 A JPH04328757 A JP H04328757A JP 3124535 A JP3124535 A JP 3124535A JP 12453591 A JP12453591 A JP 12453591A JP H04328757 A JPH04328757 A JP H04328757A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- weight
- particles
- silica
- melamine resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 239000004640 Melamine resin Substances 0.000 claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 125000005372 silanol group Chemical group 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000005291 magnetic effect Effects 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000003302 ferromagnetic material Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 239000012188 paraffin wax Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-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
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- MZUSCVCCMHDHDF-UHFFFAOYSA-N P(=O)(=O)[W] Chemical compound P(=O)(=O)[W] MZUSCVCCMHDHDF-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
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- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
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- 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
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、電子写真法、静電印刷
法、磁気記録法に用いられる静電荷像現像用トナーに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic printing, and magnetic recording.
【0002】0002
【従来の技術】従来、電子写真法としては米国特許第2
,297,691号明細書、特公昭42−23910号
公報(米国特許第3,666,363号明細書)、特公
昭43−24748号公報(米国特許第4,071,3
61号明細書)等、多数の方法が知られている。かかる
電子写真法は、一般には、光導電性物質を利用して種々
の手段により感光体上に電気的潜像を形成した後、該潜
像を現像粉(以下トナーと称す)を用いて現像し、必要
に応じて紙等の被転写材にトナー画像を転写した後、加
熱、加圧或いは溶剤蒸気等により定着して複写物を得る
ものである。又、トナー画像を転写する工程を有する場
合には、通常、感光体上の残余のトナーを除去する為の
クリーニング工程が設けられる。上記のうち電気的潜像
をトナーを用い可視化する現像方法としては、例えば、
米国特許第2,874,063号明細書に記載されてい
る磁気ブラシ法、同2,618,552号明細書に記載
されているカスケード現像法及び同2,221,776
号明細書に記載されている粉末雲法等がある。又、磁性
トナーを使用する方法としては、米国特許第3,909
,258号明細書に記載されている導電性トナーを使用
するマグネドライ法、トナー粒子の誘電分極を使用する
方法、トナーの撹乱による電荷移送の方法、又、特開昭
54−42141号公報及び特開昭55−18656号
公報の如き潜像に対してトナー粒子を飛翔させて現像す
る方法がある。これら各種の現像法に適用するトナーと
しては、従来、天然或いは合成の樹脂中に染料、顔料を
分散させた微粉末が使用されている。例えば、ポリスチ
レン等のバインダー樹脂中に着色剤を分散させたものを
1〜30μm程度に微粉砕した粒子がトナーとして用い
られている。磁性トナーとしては、マグネタイト等の磁
性体粒子を更に含有せしめたものが用いられている。又
、いわゆる二成分現像剤を用いる方式の場合には、これ
らのトナーを、通常、ガラスビーズ、鉄粉等のキャリア
粒子と混合して用いる。[Prior Art] Conventionally, as an electrophotographic method, US Pat.
, 297,691, Japanese Patent Publication No. 42-23910 (U.S. Patent No. 3,666,363), Japanese Patent Publication No. 43-24748 (U.S. Patent No. 4,071,3)
A number of methods are known, such as No. 61). Such electrophotography generally involves forming an electrical latent image on a photoreceptor by various means using a photoconductive substance, and then developing the latent image using developer powder (hereinafter referred to as toner). After the toner image is transferred to a transfer material such as paper as necessary, it is fixed by heating, pressure, solvent vapor, etc. to obtain a copy. Furthermore, when a process of transferring a toner image is included, a cleaning process is usually provided to remove residual toner on the photoreceptor. Among the above-mentioned developing methods for visualizing electrical latent images using toner, for example,
The magnetic brush method described in U.S. Pat. No. 2,874,063, the cascade development method described in U.S. Pat. No. 2,618,552, and U.S. Pat. No. 2,221,776.
There is a powder cloud method described in the specification of No. Further, as a method using magnetic toner, US Pat. No. 3,909
, 258, a method using dielectric polarization of toner particles, a method of charge transfer by toner disturbance, and JP-A-54-42141 and There is a method of developing a latent image by causing toner particles to fly against it, as disclosed in Japanese Patent Laid-Open No. 55-18656. As toners applied to these various developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as toner. As the magnetic toner, one further containing magnetic particles such as magnetite is used. In addition, in the case of a system using a so-called two-component developer, these toners are usually mixed with carrier particles such as glass beads and iron powder.
【0003】この様な乾式現像剤を使用する方法におい
て良好な画質の可視画像を形成する為には、現像剤が高
い流動性を有すること、トナー同士の凝集が発生しない
こと、更にトナーが均一な帯電性を有することが必要で
ある為、従来よりシリカ微粒子をトナー粉末に添加混合
することが行われている。しかし、シリカ微粒子はその
ままの状態では親水性である為に、これが添加された現
像剤は空気中の湿気により凝集を生じ、流動性が低下し
たり、甚だしい場合にはシリカの吸湿により現像剤の帯
電性能を低下させてしまうという問題がある。これに対
し、疎水化処理したシリカ微粒子を用いることが特開昭
46−5782号公報、特開昭48−47345号公報
、特開昭48−47346号公報等で提案されている。
疎水化処理は、具体的には、シリカ微粒子とシランカッ
プリング剤を反応させ、シリカ微粒子表面のシラノール
基を他の有機基で置換し疎水化するものであり、この際
のシランカップリング剤としては、例えば、ジメチルジ
クロルシラン、トリメチルアルコオキシシラン等が使用
されている。In order to form a visible image of good quality in such a method using a dry developer, it is necessary that the developer has high fluidity, that the toners do not aggregate with each other, and that the toner is uniform. Since it is necessary to have a good chargeability, fine silica particles have conventionally been added and mixed into toner powder. However, since fine silica particles are hydrophilic in their original state, the developer to which they are added will cause aggregation due to moisture in the air, resulting in a decrease in fluidity or, in extreme cases, due to moisture absorption by the silica. There is a problem that charging performance is deteriorated. In contrast, the use of hydrophobically treated silica fine particles has been proposed in JP-A-46-5782, JP-A-48-47345, JP-A-48-47346, and the like. Specifically, hydrophobization treatment involves reacting silica particles with a silane coupling agent to replace the silanol groups on the surface of the silica particles with other organic groups to make them hydrophobic. For example, dimethyldichlorosilane, trimethylalkoxysilane, etc. are used.
【0004】0004
【発明が解決しようとする課題】しかしながら、これら
のシリカ微粒子は一応疎水化処理されているとはいうも
のの、疎水化の程度が十分であるとはいい難く、高湿環
境下に放置された場合にはシリカの吸湿によりトナーの
帯電能が低下してしまうという問題がある。従って、本
発明の目的は、上記の如き問題点を解決した新規なトナ
ーを提供することにある。即ち、本発明の目的は、高温
高湿や低温低湿等の環境変化に対しても安定であり、常
に良好な特性を発揮することの出来る静電荷像現像用ト
ナーを提供することにある。又、本発明の他の目的は、
現像、定着及びクリーニング等のプロセスを含む電子写
真法において、長期に渡って多数の画像を形成した場合
においても、安定した画像を得ることの出来る耐久性に
優れたトナーを提供することにある。更に、本発明の他
の目的は、従来の荷電性トナーの有する種々の問題点を
同時に解決した、トナーが均一に強く帯電し、静電荷像
を可視化して、カブリやエッジ周辺へのトナーの飛び散
りのない高品質な画像を与えるトナーを提供することに
ある。[Problem to be Solved by the Invention] However, although these silica particles have been treated to make them hydrophobic, it is difficult to say that the degree of hydrophobization is sufficient, and if they are left in a high humidity environment. However, there is a problem in that the charging ability of the toner decreases due to moisture absorption of the silica. Therefore, an object of the present invention is to provide a new toner that solves the above-mentioned problems. That is, an object of the present invention is to provide a toner for developing electrostatic images that is stable against environmental changes such as high temperature and high humidity, low temperature and low humidity, and can always exhibit good characteristics. In addition, another object of the present invention is to
An object of the present invention is to provide a toner with excellent durability that can provide stable images even when a large number of images are formed over a long period of time in electrophotography including processes such as development, fixing, and cleaning. Furthermore, another object of the present invention is to solve various problems of conventional chargeable toners at the same time, to enable the toner to be uniformly and strongly charged, to visualize the electrostatic charge image, and to prevent fogging and toner dispersion around edges. The objective is to provide toner that provides high quality images without scattering.
【0005】[0005]
【課題を解決するための手段】上記の目的は、下記の本
発明により達成される。即ち、本発明は、バインダー樹
脂及び着色剤を少なくとも含有する静電荷像現像用トナ
ーにおいて、トナー粒子の表面近傍にシリカ微粒子を固
着させた後、メラミン系樹脂からなる微粒子を固着させ
たことを特徴とする静電荷像現像用トナーである。[Means for Solving the Problems] The above objects are achieved by the present invention as described below. That is, the present invention is characterized in that, in a toner for developing an electrostatic image containing at least a binder resin and a colorant, fine particles made of melamine resin are fixed after fine particles of silica are fixed near the surface of the toner particles. This is a toner for developing electrostatic images.
【0006】[0006]
【作用】本発明者は、上記の目的を同時に達成する為、
種々の添加剤を用い、その構成及び性能について様々の
角度から鋭意検討した結果、シリカ微粉末を予めトナー
表面近傍に固着させた後、メラミン系樹脂を固着させる
ことが極めて有効な手段であることを見い出し、本発明
を完成した。即ち、吸湿の原因となるシリカのシラノー
ル基をメラミン系樹脂で被覆することにより、高湿度環
境下においてもシリカが吸湿することがなく、本発明の
静電荷像現像用トナーは、いかなる環境下においても安
定した帯電能を有することが可能となる。又、被覆に用
いるメラミン系樹脂は、耐湿性、耐熱性、耐光性、耐摩
耗性及び電気的性質に優れた特性を有し、且つ無色透明
である為、本発明の静電荷像現像用トナーは、磁性トナ
ーのみならずカラートナーにも使用することが出来る。[Operation] In order to simultaneously achieve the above objectives, the present inventor has
As a result of using various additives and carefully examining their composition and performance from various angles, we found that it is an extremely effective method to first fix silica fine powder near the toner surface and then fix melamine resin. They discovered this and completed the present invention. That is, by coating the silica's silanol groups, which cause moisture absorption, with a melamine resin, the silica does not absorb moisture even in a high humidity environment, and the toner for developing electrostatic images of the present invention can be used under any environment. It also becomes possible to have stable charging ability. In addition, the melamine resin used for the coating has excellent moisture resistance, heat resistance, light resistance, abrasion resistance, and electrical properties, and is colorless and transparent, so it can be used in the toner for developing electrostatic images of the present invention. can be used not only for magnetic toners but also for color toners.
【0007】[0007]
【好ましい実施態様】本発明の静電荷像現像用トナーに
用いるシリカ微粉末としては、BET法で測定した窒素
吸着による比表面積が、30m2/g以上(特に50〜
400m2/g)の範囲内のものが良好な結果を与える
。
又、シリカ微粉末のトナー中への添加量は、トナー10
0重量%に対して0.01〜2.0重量%、更に好まし
くは0.1〜1.5重量%の範囲で使用する。シリカ微
粉末の添加量が0.01重量%よりも少ない場合には、
トナーの帯電が不均一となり、いわゆる帯電ムラの原因
となる。一方、2.0重量%よりも多い場合には、トナ
ーに付着しきれずに遊離したシリカ微粉末が介在する様
になり、定着性悪化の原因となる。[Preferred Embodiment] The silica fine powder used in the electrostatic image developing toner of the present invention has a specific surface area due to nitrogen adsorption measured by the BET method of 30 m2/g or more (particularly 50 m2/g or more).
400 m2/g) gives good results. Also, the amount of silica fine powder added to the toner is 10
It is used in an amount of 0.01 to 2.0% by weight, more preferably 0.1 to 1.5% by weight relative to 0% by weight. When the amount of silica fine powder added is less than 0.01% by weight,
The charging of the toner becomes non-uniform, causing so-called charging unevenness. On the other hand, if the amount is more than 2.0% by weight, fine silica powder that is not fully adhered to the toner and becomes free will be present, causing deterioration in fixing performance.
【0008】シリカ微粉末をトナー表面近傍に固着させ
た後に、被覆されるメラミン系樹脂としては、1次粒径
が0.03〜2μm、好ましくは0.05〜1μmの範
囲内のものが良好な結果を与える。メラミン系樹脂の1
次粒径が0.03μm未満では、トナー間の結合防止作
用が期待できない。一方、1次粒径が2μmを越えると
、トナーに付着する粒子の個数が少なくなる為、トナー
粒子相互間の結合防止作用が低下し、好ましくない。
又、メラミン系樹脂の添加量は、トナー100重量%に
対して0.01〜2.0重量%、更に好ましくは0.1
〜1.5重量%の範囲内で使用するのがよい。メラミン
系樹脂の量が0.01重量%よりも少ない場合は、トナ
ーの疎水化を十分に果たすことが出来ず、一方、2.0
重量%を越えると、余剰の微粒状樹脂粉末が介在してし
まい、定着性低下という悪影響をもたらす。上記のシリ
カ微粒子及びメラミン系樹脂は、ヘンシェルミキサー等
による乾式混合により、トナー粒子の表面近傍に固着さ
せればよい。[0008] After the silica fine powder is fixed near the toner surface, the melamine resin to be coated has a primary particle size of 0.03 to 2 μm, preferably 0.05 to 1 μm. gives good results. Melamine resin 1
If the secondary particle size is less than 0.03 μm, the effect of preventing binding between toners cannot be expected. On the other hand, if the primary particle size exceeds 2 μm, the number of particles adhering to the toner decreases, and the effect of preventing the toner particles from bonding with each other decreases, which is not preferable. Further, the amount of the melamine resin added is 0.01 to 2.0% by weight, more preferably 0.1% by weight based on 100% by weight of the toner.
It is preferable to use it within the range of 1.5% by weight. If the amount of melamine resin is less than 0.01% by weight, the toner cannot be made sufficiently hydrophobic;
If the weight percentage is exceeded, excess fine particulate resin powder will be present, resulting in an adverse effect of deterioration of fixing performance. The silica fine particles and melamine resin described above may be fixed near the surface of the toner particles by dry mixing using a Henschel mixer or the like.
【0009】又、本発明に用いることの出来るバインダ
ー樹脂としては、例えば、ポリスチレン、ポリ−P−ク
ロルスチレン、ポリビニルトルエン、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;その他スチレン−アクリロニトリル共重合体、ス
チレン−ビニルメチルエーテル共重合体、スチレン−ブ
タジエン共重合体、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
素化パラフィン等を単独又は混合して使用することが出
来る。Binder resins that can be used in the present invention include, for example, styrenes such as polystyrene, poly-P-chlorostyrene, polyvinyltoluene, styrene-P-chlorostyrene copolymer, and styrene-vinyltoluene copolymer. Homopolymers and copolymers thereof; styrene and acrylic acid, such as styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, and styrene-n-butyl acrylate copolymer; Copolymers with esters; copolymers of styrene and methacrylic esters such as styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, styrene-n-butyl methacrylate copolymers; styrene and acrylic esters and methacrylic esters; other styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-butadiene copolymers, styrene-vinyl methyl ketone copolymers, styrene- Styrenic copolymers of styrene and other vinyl monomers such as acrylonitrile-indene copolymers and styrene-maleic ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyesters, polyamides, epoxy resins , polyvinyl butyral, polyacrylic acid, phenol resin, aliphatic or alicyclic hydrocarbon resin, petroleum resin, chlorinated paraffin, etc. can be used alone or in combination.
【0010】又、本発明の静電荷像現像用トナーにおい
ては、必要に応じてトナーの帯電性を維持させる為に、
荷電制御剤を使用することも出来、従来公知の負或いは
正の荷電制御剤が用いられる。例えば、当該技術分野で
知られている荷電制御剤としては、以下のものが挙げら
れる。トナーを負荷電性に制御する荷電制御剤としては
、例えば、有機金属錯体、キレート化合物が良好であり
、モノアゾ金属錯体、アセチルアセトン金属錯体、芳香
族ハイドロキシカルボン酸、芳香族ダイカルボン酸系の
金属錯体がある。その他、芳香族ハイドロキシカルボン
酸、芳香族モノ及びポリカルボン酸及びその金属塩、無
水物、エステル類、又は、ビスフェノール等のフェノー
ル誘導体類等がある。In the toner for developing electrostatic images of the present invention, in order to maintain the chargeability of the toner, if necessary,
A charge control agent can also be used, and conventionally known negative or positive charge control agents can be used. For example, charge control agents known in the art include the following: As the charge control agent for controlling the negative chargeability of the toner, for example, organic metal complexes and chelate compounds are suitable, and monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes are suitable. There is. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids, their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.
【0011】又、トナーを正荷電性に制御する荷電制御
剤としては、例えば、ニグロシン及び脂肪酸金属塩等に
よる変性物、トリブチルベンジルアンモニウム−1−ヒ
ドロキシ−4−ナフトスルフォン酸塩、テトラブチルア
ンモニウム、テトラフルオロボレート等の四級アンモニ
ウム塩、及びこれらの類似体であるホスホニウム塩等の
オニウム塩及びこれらのレーキ顔料、又は、トリフェニ
ルメタン染料及びこれらのレーキ顔料等がある。(尚、
レーキ化剤としては、りんタングステン酸、りんモリブ
デン酸、りんタングステンモリブデン酸、タンニン酸、
ラウリン酸、没食子酸、フェリシアン化物、フェロシア
ン化物等が使用出来る。)その他、高級脂肪酸の金属塩
、アセチルアセトン金属錯体やジブチルスズオキサイド
、ジオクチルスズオキサイド、ジシクロヘキシルスズオ
キサイド等のジオルガノスズオキサイドやジブチルスズ
ボレート、ジオクチルスズボレート、ジシクロヘキシル
スズボレート等のジオルガノスズボレート等があり、こ
れらを単独で或いは2種類以上組み合わせて用いること
が出来る。これらの中でも、ニグロシン系、4級アンモ
ニウム塩の如き荷電制御剤が特に好ましく用いられる。Further, as the charge control agent for controlling the toner to be positively charged, for example, modified products of nigrosine and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium, Examples include quaternary ammonium salts such as tetrafluoroborate, onium salts such as phosphonium salts which are analogs thereof, and lake pigments thereof, triphenylmethane dyes and lake pigments thereof. (still,
As lake forming agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid,
Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc. can be used. ) In addition, there are metal salts of higher fatty acids, acetylacetone metal complexes, diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, and diorganotinborate such as dibutyltinborate, dioctyltinborate, dicyclohexyltinborate, etc. These can be used alone or in combination of two or more. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.
【0012】又、熱ロールによる定着時の離型性を改良
する目的で、低分子量ポリエチレン、低分子量ポリプロ
ピレン、マイクロクリスタリンワックス、カルナバワッ
クス、サゾールワックス、パラフィンワックス等のワッ
クス状物質を、バインダー樹脂100重量%に対し0.
5〜10重量%程度加えることも本発明の好ましい態様
の1つである。In addition, in order to improve the mold releasability during fixing with a hot roll, a waxy substance such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc. is added to the binder resin. 0.0% to 100% by weight.
Adding about 5 to 10% by weight is also one of the preferred embodiments of the present invention.
【0013】更に本発明の静電荷像現像用トナーを、二
成分系現像剤用に用いる場合にはキャリヤー粉と混合し
て用いられる。この場合、トナーとキャリヤー粉との混
合比は、トナー濃度として0.1〜50重量%、好まし
くは0.5〜10重量%、更に好ましくは3〜5重量%
の範囲である。この際に使用し得るキャリヤーとしては
、公知のものが全て使用可能であり、例えば、鉄粉、フ
ェライト粉、ニッケル粉の如き磁性を有する粉体、ガラ
スビーズ等、及びこれらの表面をフッ素系樹脂、ビニル
系樹脂或いはシリコン系樹脂等で処理したもの等が挙げ
られる。Furthermore, when the toner for developing electrostatic images of the present invention is used in a two-component developer, it is used in combination with a carrier powder. In this case, the mixing ratio of toner and carrier powder is 0.1 to 50% by weight, preferably 0.5 to 10% by weight, more preferably 3 to 5% by weight as toner concentration.
is within the range of All known carriers can be used at this time, such as magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, etc., and fluorine resin on the surface of these. , those treated with vinyl resin, silicone resin, or the like.
【0014】更に本発明の静電荷像現像用トナーは、磁
性材料を含有させ磁性トナーとすることも出来る。この
場合、含有される磁性材料は着色剤の役割も兼ねている
。トナー中に含める磁性材料としては、マグネタイト、
ヘマタイト、フェライト等の酸化鉄;鉄、コバルト、ニ
ッケルの様な金属、或いはこれらの金属とアルミニウム
、コバルト、銅、鉛、マグネシウム、スズ、亜鉛、アン
チモン、ベリリウム、ビスマス、カドミウム、カルシウ
ム、マンガン、セレン、チタン、タングステン、バナジ
ウム等の金属との合金及びその混合物等が挙げられる。
又、これらの強磁性体は、平均粒子が0.1〜2μm、
好ましくは0.1〜0.5μm程度のものが使用され、
トナー中に含有させる量としては、樹脂成分100重量
部に対し約20〜200重量部、特に好ましくは樹脂成
分100重量部に対し40〜150重量部程度がよい。
これらの強磁性体は10Kエルステッド印加での磁気特
性が、抗磁力が20〜150エルステッドであり、飽和
磁化が50〜200emu/g、残留磁化が2〜20e
mu/gのものが望ましい。Furthermore, the toner for developing electrostatic images of the present invention may contain a magnetic material to form a magnetic toner. In this case, the magnetic material contained also serves as a coloring agent. Magnetic materials included in the toner include magnetite,
Iron oxides such as hematite and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, and selenium. , alloys with metals such as titanium, tungsten, and vanadium, and mixtures thereof. In addition, these ferromagnetic materials have an average particle size of 0.1 to 2 μm,
Preferably, one with a diameter of about 0.1 to 0.5 μm is used,
The amount to be contained in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably about 40 to 150 parts by weight per 100 parts by weight of the resin component. These ferromagnetic materials have magnetic properties with a coercive force of 20 to 150 Oe, saturation magnetization of 50 to 200 emu/g, and residual magnetization of 2 to 20 e when 10 K Oe is applied.
mu/g is desirable.
【0015】又、本発明の静電荷像現像用トナーに使用
し得る着色剤としては、任意の適当な顔料又は染料が挙
げられる。トナー着色剤は周知であって、例えば、顔料
としては、カーボンブラック、アリニンブラック、アセ
チレンブラック、ナフトールイエロー、ハンザイエロー
、ローダミンレーキ、アリザリンレーキ、ベンガラ、フ
タロシアニンブルー及びインダンスレンブルー等がある
。これらの顔料は定着画像の光学濃度を維持するのに必
要にして且つ充分な量が用いられる。例えば、樹脂10
0重量部に対し0.1〜20重量部、好ましくは2〜1
0重量部程度添加する。又、同様の目的で更に染料が用
いられる。例えば、アゾ系染料、アントラキノン系染料
、キサンテン系染料、メチン系染料等が挙げられ、樹脂
100重量部に対し、0.1〜20重量部、好ましくは
0.3〜3重量部の添加量がよい。[0015] The colorant that can be used in the toner for developing electrostatic images of the present invention includes any suitable pigment or dye. Toner colorants are well known and include, for example, pigments such as carbon black, alinine black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red iron, phthalocyanine blue, and indanthrene blue. These pigments are used in amounts necessary and sufficient to maintain the optical density of the fixed image. For example, resin 10
0.1 to 20 parts by weight, preferably 2 to 1 parts by weight
Add about 0 parts by weight. Further, dyes are also used for the same purpose. Examples include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc., and the amount added is 0.1 to 20 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the resin. good.
【0016】更に、本発明の静電荷像現像用トナーは、
上記したシリカ微粒子及びメラミン系樹脂以外の添加剤
も必要に応じて使用することが出来る。他の添加剤とし
ては、例えば、テフロン、ステアリン酸亜鉛、ポリ弗化
ビニリデンの如き滑剤、中でもポリ弗化ビニリデンが好
ましい。或いは酸化セリウム、炭化ケイ素、チタン酸ス
トロンチウム等の研磨剤、中でもチタン酸ストロンチウ
ムが好ましい。或いは例えば、酸化チタン、酸化アルミ
ニウム等の流動性付与剤、中でも特に疎水性のものが好
ましい。その他、ケーキング防止剤、例えば、カーボン
ブラック、酸化亜鉛、酸化アンチモン、酸化スズ等の導
電性付与剤、或は逆極性の白色微粒子及び黒色微粒子を
、現像性向上剤として少量用いることも出来る。尚、こ
れらの添加剤は、シリカ微粒子と共に乾式混合によりト
ナー粒子表面近傍に固着させればよい。Furthermore, the toner for developing an electrostatic image of the present invention includes:
Additives other than the silica fine particles and melamine resin described above can also be used as necessary. Examples of other additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride, with polyvinylidene fluoride being preferred. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferred, with strontium titanate being preferred. Alternatively, for example, fluidity imparting agents such as titanium oxide and aluminum oxide, among which hydrophobic ones are particularly preferred. In addition, small amounts of anti-caking agents, such as conductivity imparting agents such as carbon black, zinc oxide, antimony oxide, and tin oxide, or white fine particles and black fine particles of opposite polarity, can also be used as developability improvers. Incidentally, these additives may be fixed near the surface of the toner particles by dry mixing together with the silica fine particles.
【0017】本発明の静電荷像現像用トナーを作製する
には、先ず、バインダー樹脂、着色剤としての顔料又は
染料、必要に応じて荷電制御剤、磁性体その他の添加剤
等をヘンシェルミキサー、ボールミル等の混合機により
充分前混合してから加熱ロール、ニーダー、エクストル
ーダーの如き熱混練機を用いて溶融、混和及び練肉して
、樹脂類を互いに相溶せしめた中に、顔料、染料、磁性
体等を分散又は溶融せしめ、冷却固化後、粉砕及び分級
を行ってトナーを得る。次に、この様にして形成したト
ナーに、更に、シリカ微粒子、メラミン系樹脂及びその
他の添加剤をヘンシェルミキサー等の混合機により充分
混合し、本発明に係る静電荷像現像用トナーを得ること
が出来る。To prepare the toner for developing electrostatic images of the present invention, first, a binder resin, a pigment or dye as a coloring agent, a charge control agent, a magnetic substance and other additives as required, etc. are mixed in a Henschel mixer, Pigments and dyes are mixed thoroughly using a mixer such as a ball mill, then melted, kneaded, and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins compatible with each other. , a magnetic material or the like is dispersed or melted, cooled and solidified, and then pulverized and classified to obtain a toner. Next, fine silica particles, melamine resin, and other additives are thoroughly mixed with the toner thus formed using a mixer such as a Henschel mixer to obtain the toner for developing electrostatic images according to the present invention. I can do it.
【0018】[0018]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれら実施例に何ら限定されるもので
はない。実施例1スチレン−メタクリル酸−n−ブチル
共重合体 100重量%マグネ
タイト
85重量%アセチルアセトンのクロム錯体
2
重量%低分子ポリプロピレン
3重量%上記材料をヘンシェルミキサーによって前混
合を行った後、130℃で、2軸混練押出機によって溶
融混練を行った。次に、この混練物を放冷後、カッター
ミルで粗粉砕した後、ジェット気流を用いた微粉砕機を
用いて粉砕し、更に風力分級機を用いて分級して、体積
平均粒径が8.5μmの黒色微粉体(トナー)を得た。
この様にして得た上記の磁性トナー100重量%に対し
、シリカ微粒子0.4重量%をヘンシェルミキサーによ
り乾式混合させた後、更に、一次粒径0.3μmのメラ
ミン系樹脂を0.5重量%を加え、乾式混合させて本発
明の静電荷像現像用トナーとした。このトナーを、α−
Si感光体を用いたキャノン(株)製複写機NP665
0を用いて評価したところ、表1に示した様に、常温常
湿度環境下(23℃、65%)、低温低湿度環境下(1
5℃、10%)、高温高湿度環境下(32℃、85%)
のいずれの環境下においても終始高い反射画像濃度を保
ち、カブリもなく、画像周辺へのトナーの飛散がない、
且つ、解像度の高い良好な画像が得られた。又、定着性
についても全く問題のないレベルであった。尚、定着性
については、低温低湿度環境下(15℃、10%)に、
上記の評価機を一晩放置し、評価機及びその内部の定着
器を完全に低温低湿度環境になじんだ状態とした後、連
続200枚の複写画像を行い、その複写画像の200枚
目を定着性の評価に用いた。即ち、定着性の評価は、こ
の200枚目の画像をシルボン紙で往復10回、約10
0gの荷重で擦り、画像のはがれを反射濃度の低下率(
%)で評価し、表1に示した。EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way. Example 1 Styrene-n-butyl methacrylate copolymer 100% by weight magnetite
Chromium complex of 85% by weight acetylacetone
2
Weight% low molecular weight polypropylene
3% by weight of the above materials were premixed using a Henschel mixer, and then melt-kneaded at 130°C using a twin-screw kneading extruder. Next, after cooling this kneaded material, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a volume average particle size of 8. A black fine powder (toner) of .5 μm was obtained. To 100% by weight of the magnetic toner thus obtained, 0.4% by weight of silica fine particles was dry mixed using a Henschel mixer, and then 0.5% by weight of melamine resin with a primary particle size of 0.3 μm was added. % and dry mixed to obtain the toner for developing electrostatic images of the present invention. This toner is
Canon Co., Ltd. copier NP665 using a Si photoreceptor
As shown in Table 1, the results were evaluated using 0.
5℃, 10%), high temperature and high humidity environment (32℃, 85%)
Maintains high reflective image density from beginning to end under any environment, no fogging, and no toner scattering around the image.
Moreover, good images with high resolution were obtained. Furthermore, the fixing properties were at a level with no problems at all. Regarding fixing properties, under a low temperature and low humidity environment (15°C, 10%),
After leaving the above evaluation machine overnight to allow the evaluation machine and its internal fixing device to become completely accustomed to the low-temperature, low-humidity environment, 200 copies were made in succession, and the 200th copy was made. It was used to evaluate fixability. In other words, to evaluate the fixability, the image on the 200th sheet was moved back and forth 10 times with Silbon paper, about 10 times.
Rubbing with a load of 0g, the peeling of the image is measured by the rate of decrease in reflection density (
%) and shown in Table 1.
【0019】実施例2ポリエステル樹脂
100重量%マグネタイト
85重量%モノアゾ系鉄錯体
2重量%低分子ポリプ
ロピレン
3重量%以上の材
料を用い、実施例1と同様の方法によりトナー化し、本
発明の静電荷像現像用トナーを得た。得られたトナーに
ついての画像評価を実施例1と同様の方法で行い、結果
を表1に示した。Example 2 Polyester resin
100% magnetite
85% by weight monoazo iron complex
2% by weight low molecular weight polypropylene
A toner was prepared in the same manner as in Example 1 using 3% by weight or more of the material to obtain an electrostatic image developing toner of the present invention. Image evaluation of the obtained toner was performed in the same manner as in Example 1, and the results are shown in Table 1.
【0020】実施例3マグネタイトの代わりにカーボン
ブラック5重量%加えた以外は実施例1と同様の方法で
本発明の静電荷像現像用トナーを得た。このトナー8重
量%に対し、フッ素系樹脂で表面を被覆した粒径約80
μmのフェライトキャリア100重量%を混合して二成
分系現像剤とした。又、補充剤としてはトナーのみを用
いた。得られたトナーについての画像評価を実施例1と
同様の方法で行い、結果を表1に示した。Example 3 An electrostatic image developing toner of the present invention was obtained in the same manner as in Example 1, except that 5% by weight of carbon black was added instead of magnetite. For 8% by weight of this toner, the particle size of particles coated with fluororesin is approximately 80%.
A two-component developer was prepared by mixing 100% by weight of a μm ferrite carrier. Further, only toner was used as a replenisher. Image evaluation of the obtained toner was performed in the same manner as in Example 1, and the results are shown in Table 1.
【0021】実施例4実施例1において、アセチルアセ
トンのクロム錯体の代わりニグロシンを5重量%添加し
、シリカ微粒子を0.6重量%、及びメラミン系樹脂を
、0.7重量%(トナー基準)添加する以外は実施例1
と同様にして本発明の静電荷像現像用トナーを得た。
画像評価については、前記のキャノン(株)製複写機N
P6650を改造し、反転現像機構を備えた機械により
評価したところ、良好な画像を得ることが出来た。その
詳細な評価結果は、表1に示した。Example 4 In Example 1, 5% by weight of nigrosine was added instead of the chromium complex of acetylacetone, 0.6% by weight of silica particles, and 0.7% by weight of melamine resin (based on toner). Example 1 except that
In the same manner as above, an electrostatic image developing toner of the present invention was obtained. For image evaluation, use the above-mentioned Canon Co., Ltd. copier N.
When P6650 was modified and evaluated using a machine equipped with a reversal development mechanism, good images could be obtained. The detailed evaluation results are shown in Table 1.
【0022】実施例5実施例1において、バインダー樹
脂をスチレン−アクリル酸−n−ブチル共重合体に、及
びアセチルアセトンのクロム錯体の代わりにニグロシン
2重量%とする以外は、実施例1と同様の方法で本発明
の静電荷像現像用トナーを得た。画像評価については、
キャノン(株)製複写機NP3825を用いて行ない、
良好な結果を得ることが出来た。その詳細な結果は、表
1に示した。Example 5 The same procedure as in Example 1 was carried out, except that the binder resin was changed to styrene-n-butyl acrylate copolymer, and 2% by weight of nigrosine was used instead of the chromium complex of acetylacetone. An electrostatic image developing toner of the present invention was obtained by the method. For image evaluation,
Performed using a copier NP3825 manufactured by Canon Co., Ltd.
Good results were obtained. The detailed results are shown in Table 1.
【0023】比較例1実施例1において、シリカ微粒子
を添加しない以外は実施例1と同様にして比較用のトナ
ーを得た。このトナーを実施例1と同様の方法で評価し
たところ、表1に示した様にいずれの環境においても画
質が悪く、又、画像濃度も低く、特に低温低湿環境下に
おいて帯電ムラの発生が確認出来た。Comparative Example 1 A comparative toner was obtained in the same manner as in Example 1 except that fine silica particles were not added. When this toner was evaluated using the same method as in Example 1, as shown in Table 1, the image quality was poor in all environments, and the image density was also low, and uneven charging was observed, especially in low temperature and low humidity environments. done.
【0024】比較例2実施例1において、シリカ微粒子
を2.5重量%添加する以外は、実施例1と同様にして
比較用のトナーを得た。得られたトナーには遊離したシ
リカが多量に存在していた。又、画像評価の結果は表1
に示した通り画像濃度は低めであり、特に、定着性の評
価において濃度低下率が55%と悪くなっていた。Comparative Example 2 A comparative toner was obtained in the same manner as in Example 1 except that 2.5% by weight of silica fine particles were added. The obtained toner contained a large amount of free silica. In addition, the results of image evaluation are shown in Table 1.
As shown in , the image density was low, and in particular, the density reduction rate was 55% in the fixability evaluation.
【0025】比較例3実施例1において、メラミン系樹
脂を添加しなかった以外は実施例1と同様にして比較用
のトナーを得た。又、その画像評価を実施例1と同様に
行なったところ、その結果は表1に示した通りであり、
特に、高温高湿度下においての画像濃度の低さが顕著で
あった。Comparative Example 3 A comparative toner was obtained in the same manner as in Example 1 except that the melamine resin was not added. In addition, the image evaluation was performed in the same manner as in Example 1, and the results were as shown in Table 1.
In particular, the image density was noticeably low under high temperature and high humidity conditions.
【0026】比較例4実施例1において、添加するメラ
ミン系樹脂を2.5重量%にする以外は、実施例1と同
様の方法で比較用のトナーを得た。又、その画像評価を
同様に行なったところ、得られたトナー中には遊離微粒
状の樹脂粉末が多量に存在し、この為に定着性が悪くな
ってしまった。Comparative Example 4 A comparative toner was obtained in the same manner as in Example 1 except that the amount of melamine resin added was 2.5% by weight. Further, when the image was evaluated in the same manner, it was found that a large amount of free fine resin powder was present in the obtained toner, which resulted in poor fixing performance.
【表1】
表1トナーの評価結果[Table 1]
Table 1 Toner evaluation results
【表1】
表1の続き[Table 1]
Continuation of Table 1
【0027】[0027]
【発明の効果】上記の様に本発明の静電荷像現像用トナ
ーは、これまでのトナーに関連した問題が著しく改善さ
れ、特に、高湿度環境下におけるシリカの吸湿に起因す
るトナーの帯電性の低下の問題に対し極めて有効なもの
である。即ち、シリカ微粒子の上に、耐湿性に優れたメ
ラミン系樹脂を固着させることにより、帯電性が良好な
状態で、トナーの耐湿性及び流動性を高めることが出来
る。つまり、本発明の静電荷像現像用トナーは、トナー
の均一な帯電性をシリカを添加することにより達成し、
一方、メラミン系樹脂は、トナーの流動性を高め、更に
、添加されたシリカの吸湿によって生じる環境変動によ
る帯電能の不安定化防止を達成する。この様な機能分離
の達成により、本発明の静電荷像現像用トナーによれば
いかなる環境下においても、安定した高品質の複写画像
を得ることが出来る。Effects of the Invention As described above, the electrostatic image developing toner of the present invention has significantly improved the problems associated with conventional toners. This is extremely effective in solving the problem of decrease in That is, by fixing a melamine resin having excellent moisture resistance on the silica fine particles, it is possible to improve the moisture resistance and fluidity of the toner while maintaining good chargeability. In other words, the toner for developing an electrostatic image of the present invention achieves uniform chargeability of the toner by adding silica,
On the other hand, the melamine resin improves the fluidity of the toner and further prevents the charging ability from becoming unstable due to environmental changes caused by moisture absorption of the added silica. By achieving such functional separation, the electrostatic image developing toner of the present invention allows stable and high-quality copied images to be obtained under any environment.
Claims (3)
も含有する静電荷像現像用トナーにおいて、トナー粒子
の表面近傍にシリカ微粒子を固着させた後、メラミン系
樹脂からなる微粒子を固着させたことを特徴とする静電
荷像現像用トナー。1. A toner for developing an electrostatic image containing at least a binder resin and a colorant, characterized in that silica particles are fixed near the surface of the toner particles, and then fine particles made of a melamine resin are fixed. Toner for developing electrostatic images.
.0重量%(トナー基準)である請求項1に記載の静電
荷像現像用トナー。Claim 2: The amount of silica fine particles added is 0.01 to 2.
.. The toner for developing an electrostatic image according to claim 1, wherein the content is 0% by weight (based on the toner).
量が、0.01〜2.0重量%(トナー基準)である請
求項1に記載の静電荷像現像用トナー。3. The toner for developing electrostatic images according to claim 1, wherein the amount of the fine particles made of melamine resin is 0.01 to 2.0% by weight (based on the toner).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3124535A JPH04328757A (en) | 1991-04-30 | 1991-04-30 | Toner for developing electrostatic charge image |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3124535A JPH04328757A (en) | 1991-04-30 | 1991-04-30 | Toner for developing electrostatic charge image |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04328757A true JPH04328757A (en) | 1992-11-17 |
Family
ID=14887880
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3124535A Pending JPH04328757A (en) | 1991-04-30 | 1991-04-30 | Toner for developing electrostatic charge image |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04328757A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878498B2 (en) | 2002-11-12 | 2005-04-12 | Fuji Xerox Co., Ltd. | Electrostatic latent image developing toner, its production method, developer, image-forming device and image-forming method |
JP2015132681A (en) * | 2014-01-10 | 2015-07-23 | 京セラドキュメントソリューションズ株式会社 | Two-component developer, and manufacturing method of two-component developer |
-
1991
- 1991-04-30 JP JP3124535A patent/JPH04328757A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878498B2 (en) | 2002-11-12 | 2005-04-12 | Fuji Xerox Co., Ltd. | Electrostatic latent image developing toner, its production method, developer, image-forming device and image-forming method |
JP2015132681A (en) * | 2014-01-10 | 2015-07-23 | 京セラドキュメントソリューションズ株式会社 | Two-component developer, and manufacturing method of two-component developer |
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