JPH02217863A - Electrophotographic developer composition - Google Patents
Electrophotographic developer compositionInfo
- Publication number
- JPH02217863A JPH02217863A JP1038399A JP3839989A JPH02217863A JP H02217863 A JPH02217863 A JP H02217863A JP 1038399 A JP1038399 A JP 1038399A JP 3839989 A JP3839989 A JP 3839989A JP H02217863 A JPH02217863 A JP H02217863A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- treated
- powder
- fine powder
- inorganic fine
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 71
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 19
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 70
- 239000000377 silicon dioxide Substances 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 9
- 239000007822 coupling agent Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 239000012320 chlorinating reagent Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000010445 mica Substances 0.000 abstract description 2
- 229910052618 mica group Inorganic materials 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- -1 -000 Chemical class 0.000 description 46
- 238000000034 method Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- DFYKHEXCUQCPEB-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C(C)=C DFYKHEXCUQCPEB-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004645 aluminates Chemical class 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子写真、静電記録等における電気的潜像や
電気信号を可視化する現像剤組成物に関し、特に、正帯
電性、現像性、転写性に優れた電子写真現像剤組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a developer composition for visualizing electrical latent images and electrical signals in electrophotography, electrostatic recording, etc. The present invention relates to an electrophotographic developer composition having excellent properties.
従来の技術
静電潜像を現像するための現像剤として、接触帯電、摩
擦帯電でトナーを帯電するタイプの一成分現像剤及び二
成分現脅剤が広く使用されているが、この様な現像剤に
おいて、接触帯電、摩擦帯電でトナーを帯電する場合、
トナー側、おるいは、キャリア、ブレード等の電荷付与
材料側に、電子供与性の物質や電子吸引性の物質を添加
し、帯電性制御を行なっている。従来トナーの帯電制御
を行なうためには、
（ｉ）トナー中、あるいは、トナー粒子表面に、染顔料
、界面活性剤、無機粉末等を混合又は付着させる。Prior Art As developers for developing electrostatic latent images, one-component developers and two-component developers that charge toner by contact charging or frictional charging are widely used. When charging toner with contact charging or frictional charging,
Chargeability is controlled by adding an electron-donating substance or an electron-attracting substance to the toner side, or to the charge-imparting material side such as a carrier or a blade. Conventionally, in order to control the charge of toner, (i) dyes and pigments, surfactants, inorganic powders, etc. are mixed or attached in the toner or on the surface of the toner particles.
に１）結着樹脂として、−０００、−ＣＭ 、−ＣＩ等
のハロゲン、’−８０２、−Ｎｌ２等の官能基を有する
樹脂状物を用いることが行なわれている。1) As a binder resin, a resin material having a halogen such as -000, -CM, or -CI, or a functional group such as '-802 or -Nl2 is used.
摩擦帯電現象は複雑であり、その機構は必ずしも明らか
でないが、一般に電子供与性物質は、正に帯電し、電子
吸引性物質は、負に帯電する。負帯電性トナーの場合に
は、粉体流動性改善のために、外添剤としてシリカ微粉
末等がしばしば用いられる。しかしながら、正帯電性ト
ナーに、これらシリカ微粉末などを添加すると、トナー
の帯電性を劣悪化させてしまう。そこで、例えば、特公
昭５３−２２４４７、特開昭５８−７９２５４、特開昭
５９−４５４５６、特開昭５９−１８９３５２号公報等
には、正帯電性のアミノ基や変性アミノ基を含む化合物
等でシリカ微粉末等の表面処理を行ない、帯電制御する
方法が提案されている。更に、本発明者等は、先にオニ
ウム塩構造を有する化合物で処理した無機微粉末を使用
することを提案した。Although the triboelectric charging phenomenon is complex and its mechanism is not necessarily clear, electron-donating substances are generally positively charged, and electron-withdrawing substances are negatively charged. In the case of negatively chargeable toner, fine silica powder or the like is often used as an external additive to improve powder fluidity. However, when these fine silica powders are added to a positively chargeable toner, the chargeability of the toner deteriorates. Therefore, for example, JP-A-53-22447, JP-A-58-79254, JP-A-59-45456, JP-A-59-189352, etc. disclose compounds containing positively chargeable amino groups or modified amino groups. A method has been proposed in which charging is controlled by surface treatment using fine silica powder or the like. Furthermore, the present inventors proposed the use of an inorganic fine powder that has been previously treated with a compound having an onium salt structure.
発明が解決しようとする課題
これらの方法は、確かにある範囲で有効ではあるが、繰
返しコピー時の経時安定性や、環境安定性、物理化学的
安定性に問題があり、正帯電性トナーの非電気特性的機
能と、電気特性に関する要求を共に満足させるものでは
ない。また、先に提案したオニウム塩構造を有する化合
物で処理したものを用いた場合には、かなり改善された
結果が得られるが、未だ充分でなく、実用上問題がおっ
た。即ち、粉体流動性を向上させるために添加量を増大
させると、Ｍ電の環境安定性が悪くなり、流動性の環境
依存性、経時不安定性等にも問題も生じるという結果に
なり、実用上未だ十分なものではなかった。Problems to be Solved by the Invention Although these methods are certainly effective to a certain extent, they have problems with stability over time during repeated copying, environmental stability, and physicochemical stability, and they have problems with positively chargeable toner. It does not satisfy both the non-electrical characteristic functions and the requirements regarding electrical characteristics. Furthermore, when a compound treated with the previously proposed compound having an onium salt structure is used, considerably improved results can be obtained, but the results are still insufficient and there are practical problems. In other words, if the amount added is increased in order to improve the powder fluidity, the environmental stability of M-den deteriorates, resulting in problems such as environmental dependence of fluidity and stability over time, making it impractical for practical use. It still wasn't good enough.
本発明は、従来技術における上記の問題点に鑑みてなさ
れたものであって、その目的は、粉体流動性と共に環境
安定性が改善された正帯電トナーとして使用される現像
剤組成物を提供することにある。The present invention has been made in view of the above-mentioned problems in the prior art, and its object is to provide a developer composition used as a positively charged toner that has improved powder flowability and environmental stability. It's about doing.
本発明の他の目的は、トナー帯電の立上りが早く、トナ
ーの帯Ｍｍ及び電荷分布の制御が可能であり、トナー帯
電性の物理化学的安定性及び経時安定性の優れた現像剤
組成物を提供することにある。Another object of the present invention is to provide a developer composition in which toner charge rises quickly, toner charge Mm and charge distribution can be controlled, and toner chargeability has excellent physicochemical stability and stability over time. It is about providing.
本発明の他の目的は、現像性、転写性の改善された、常
に良好な画質の形成を保証する現像剤組成物を提供する
ことにある。Another object of the present invention is to provide a developer composition that has improved developability and transferability and always ensures formation of good image quality.
本発明の更に他の目的は、カラーに使用できる無色もし
くは淡色の帯電制御剤を用いた現像剤組成物を提供する
ことにある。Still another object of the present invention is to provide a developer composition using a colorless or light-colored charge control agent that can be used for color.
課題を解決するための手段
本発明者等は検討の結果、無機微粉末を、置換又は非置
換アミノ基と、無機物質と結合しうる官能基とを有する
化合物によって表面処理した後、アンモニウム塩化剤で
処理することによって、表面に存在する置換又は非置換
アミノ基をアンモニウム塩に変換し、得られた表面処理
無機微粉末をでトナーに内添又は外添すると、上記の目
的が達成されることを見出し、本発明を完成するに至っ
た。Means for Solving the Problems As a result of studies, the present inventors surface-treated inorganic fine powder with a compound having a substituted or unsubstituted amino group and a functional group capable of bonding to an inorganic substance, and then treated the surface with an ammonium chloride agent. The above purpose can be achieved by converting the substituted or unsubstituted amino groups present on the surface into ammonium salts by treating with , and adding the resulting surface-treated inorganic fine powder internally or externally to the toner. They discovered this and completed the present invention.
したがって、本発明は、表面又は内部に無機微粉末を含
むトナー粒子を含有する電子写真現像剤組成物において
、該無機微粉末が、置換又は非置換アミノ基と、無機物
質と結合しうる官能基とを有する化合物によって表面処
理した後、アンモニウム塩化剤で処理したものでめるこ
とを特徴とする。Therefore, the present invention provides an electrophotographic developer composition containing toner particles containing inorganic fine powder on the surface or inside, in which the inorganic fine powder has a substituted or unsubstituted amino group and a functional group capable of bonding with an inorganic substance. After the surface is treated with a compound having the following, it is treated with an ammonium chloride agent.
本発明において使用される無機微粉末としては、シリカ
あるいはタルり、クレー、カオリン、ゼオライト、コー
ディエライト、ムライト、マイカ等のケイ素と他の金属
元素との混合酸化物類、シリコンカーバイド、シリコン
ナイトライド、シリコン、ボロンナイトライド、酸化ス
ズ、酸化亜鉛、酸化チタン、アルミナ、チタン酸バリウ
ム、チタン酸カリウム、炭酸カルシウム、ドロマイト、
硫酸バリウム、酸化セリウム、酸化クロム、酸化鉄、フ
ェライト類、酸化モリブデン、酸化ニッケル、酸化マグ
ネシウム、水酸化マグネシウム、酸化ジルコニウム、酸
化バナジウム、鉄、ニッケル、アルミニウム、金、銀、
銅、亜鉛、ヨウ化銅、カーボンブラック、グラファイト
、ダイヤモンド、アモルファスカーボン等、多くのもの
が利用できる。The inorganic fine powder used in the present invention includes mixed oxides of silicon and other metal elements such as silica or tar, clay, kaolin, zeolite, cordierite, mullite, and mica, silicon carbide, and siliconite. Ride, silicon, boron nitride, tin oxide, zinc oxide, titanium oxide, alumina, barium titanate, potassium titanate, calcium carbonate, dolomite,
Barium sulfate, cerium oxide, chromium oxide, iron oxide, ferrites, molybdenum oxide, nickel oxide, magnesium oxide, magnesium hydroxide, zirconium oxide, vanadium oxide, iron, nickel, aluminum, gold, silver,
Many materials are available, including copper, zinc, copper iodide, carbon black, graphite, diamond, and amorphous carbon.
これら無機微粉末の形状は、どのようなものでもよく、
例えば、球状、粒状、針状、繊維状、板状等任意の形状
のものが使用できる。These inorganic fine powders may have any shape,
For example, any shape such as spherical, granular, acicular, fibrous, or plate-like can be used.
また、粒径は、０．００１μｍ程度から、数μｓ程度、
好ましくは、約０．００５ ｔｕｎから約０．５μｓ程
度が使用目的によって適宜選択できる。In addition, the particle size ranges from about 0.001 μm to about several μs,
Preferably, about 0.005 tun to about 0.5 μs can be selected as appropriate depending on the purpose of use.
上記無機微粉末は、まず、置換又は非置換アミノ基と、
無機物質と結合しうる官能基とを有する化合物（以下、
アミノ化合物という）によって表面処理される。The above inorganic fine powder first contains a substituted or unsubstituted amino group,
A compound having a functional group capable of bonding to an inorganic substance (hereinafter referred to as
The surface is treated with an amino compound (called an amino compound).
本発明において使用するアミノ化合物は、置換又は非置
換アミノ基と共に、無機物質と結合しつる官能基を有す
る必要がある。The amino compound used in the present invention must have a substituted or unsubstituted amino group as well as a functional group that binds to an inorganic substance.
アミン化合物における置換又は非置換アミノ基は、次の
ものが例示される。−ＮＨ２、−ＮＨＲｌ、−ＮＲ２Ｒ
３（Ｒ１、Ｒ２及びＲ３は、それぞれ、メチル基、エチ
ル基等の脂肪族炭化水素基、フェニル基、トリル基、ベ
ンジル基等の芳香族炭化水素基を表わし、又はＲ２及び
Ｒ３は互いに結合してＮ原子と共に、ピリジン、ピペリ
ジン、キノリン、ビロール、ピロリドン、モルホリン、
イミダゾール等の複素環を形成する基を表わす。）
無機物質と結合しつる官能基としては、無機微粉末表面
の水酸基或いは吸着水層等と結合しうる官能基であれば
酸性基、塩基性基等何でもよいが、通常、無機物質と有
機物質を結合するカップリング剤類、即ち、シランカッ
プリング剤、チタネートカップリング剤、アルミネート
カップリング剤、ジルコネートカップリングＭ、クロム
コンプレックス系、その信金金属系カップリング剤等で
採用されている無機物質と反応しうる官能基が都合よく
使用できる。Examples of the substituted or unsubstituted amino group in the amine compound include the following. -NH2, -NHRl, -NR2R
3 (R1, R2 and R3 each represent an aliphatic hydrocarbon group such as a methyl group or an ethyl group, an aromatic hydrocarbon group such as a phenyl group, a tolyl group or a benzyl group, or R2 and R3 are bonded to each other. With the N atom, pyridine, piperidine, quinoline, virol, pyrrolidone, morpholine,
Represents a group forming a heterocycle such as imidazole. ) The functional group that binds to an inorganic substance may be any functional group such as an acidic group or a basic group as long as it can bind to a hydroxyl group on the surface of the inorganic fine powder or an adsorbed water layer, but usually, inorganic substances and organic substances Inorganic coupling agents used in coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling M, chromium complex type, and Shinkin metal type coupling agents, etc. Functional groups capable of reacting with the substance can be conveniently used.
カップリング剤の代表例であり、かつ本発明においても
各種観点から、シラン化合物が有利に用いられるので、
有機シラン化合物を例に、以下説明する。A silane compound is a typical example of a coupling agent, and is also advantageously used in the present invention from various viewpoints.
This will be explained below using an organic silane compound as an example.
シランカップリング剤は、一般に、無機物質と反応する
官能基Ｘ（−ＣＩなどハロゲン、メトキシ基、エトキシ
基等アルコキシ基等）と有機物質と反応する官能基（ア
ミノ基、塩素原子、エポキシ基、メルカプト基等）を含
む炭素鎖Ｙを有し、一般式
％式％
で表示されるが、本発明において最も有効な有機シラン
化合物の例としては、下記一般式で示されるシランカッ
プリング剤があげられる。Silane coupling agents generally have functional groups X that react with inorganic substances (halogens such as -CI, alkoxy groups such as methoxy groups, ethoxy groups, etc.) and functional groups that react with organic substances (amino groups, chlorine atoms, epoxy groups, etc.). The organic silane compound has a carbon chain Y containing a mercapto group, etc.) and is expressed by the general formula %. Examples of the most effective organic silane compounds in the present invention include silane coupling agents shown by the following general formula. It will be done.
ＸｍＳ！Ｚｎ
（Ｘ：塩素原子又はアルコキシ基
Ｚ：置換又は止置、換アミノ基を含む飽和炭化水素基又
は不飽和炭化水素基
ｍ、ｎ：１〜３の整数
なお上記式中、ｍ、ｎ≧２の場合、Ｘ及びＺはそのすべ
てが同一官能基である必要はない。また、ｎ≧２の場合
、２は少なくとも１つがアミノ基又は置換アミノ基を有
すればよい。）
本発明において、上記の一般式で示される有機シラン化
合物のうち、ざらに好ましいものは、２で示される基の
うちで、アミノ基以外の部分が飽和炭化水素基よりなる
ものでおる。XmS! Zn (X: chlorine atom or alkoxy group Z: substituted or unsubstituted, saturated hydrocarbon group or unsaturated hydrocarbon group containing substituted amino group m, n: integer from 1 to 3 In the above formula, m, n≧2 In this case, X and Z need not all be the same functional group. In addition, in the case of n≧2, at least one of 2 may have an amino group or a substituted amino group.) In the present invention, the above-mentioned Among the organic silane compounds represented by the general formula, most preferred are those in which the moiety other than the amino group is a saturated hydrocarbon group among the groups represented by 2.
本発明において使用できるアミノ化合物の具体例として
、次のものが例示されるが、特にＺが飽和炭化水素基、
非重合性の不飽和炭化水素基であるものが好ましい。Specific examples of amino compounds that can be used in the present invention include the following, but in particular, Z is a saturated hydrocarbon group,
A non-polymerizable unsaturated hydrocarbon group is preferred.
Ｔ−アミノプロピルトリエトキシシラン＋１２ ＮＣ３
Ｈ６ｓ；（ｏｃ ２１１５ ＞ ３γ−ジメチルアミノ
プロピルトリエトキシシラン（Ｃｔｆ ３ ） ２ ｆ
ｌｃ３ Ｎ ６５ｔ（ＱＣ２Ｎ ５ ） ３トフェニル
ーγ−アミノプロピルトリメトキシシラン
Ｃ６ｔｌ ５ ＮＨＣ３Ｈ６５ｔ（ＯＣＨ３＞ ３Ｎ−
フェニルアミノメチルトリメトキシシランＣ６Ｈ５ＮＨ
ＣＨ２５ｔ（ＯＣ１１３） ３ジメトキシメチル−２−
ピペリジノエチルシランβ−トリメトキシシリルエチル
−２−ビリジント（トリメトキシシリルプロピル）イミ
ダゾールＤ（Ｃ）ｆ２ ＞ ３５ｉ（ＯＣＨ３） ３Ｎ
−β−（アミノエチル）−γ−アミノブロビルトリメト
キシシラン
Ｈ２ＮＣ２Ｈ４ＮＨＣ３Ｈｓ ５ｉ（ＯＣＨ３） ３ト
β−（アミノエチル）−γ−アミノプロピルメチルジメ
トキシシラン
本発明において、前記の無機微粉末は、まず、上記アミ
ノ化合物により処理される。無機微粉末を処理する方法
としては、例えば、無機微粉末を、アミノ化合物の水溶
液あるいは有機溶剤溶液に浸漬、攪拌し、加熱して溶媒
を除去することにより処理したり、あるいは無機微粉末
を攪拌し、そこに、上記アミノ化合物又はその溶液を滴
下し、加熱、溶媒除去することにより処理する方法が採
用できる。又無機微粉末を、気相中で懸濁させておき、
アミノ化合物溶液を、スプレー又は気化して吹きつけ処
理することも可能である。T-aminopropyltriethoxysilane +12 NC3
H6s; (oc 2115 > 3γ-dimethylaminopropyltriethoxysilane (Ctf 3 ) 2 f
lc3 N 65t (QC2N 5 ) 3tophenyl-γ-aminopropyltrimethoxysilane C6tl 5 NHC3H65t (OCH3> 3N-
Phenylaminomethyltrimethoxysilane C6H5NH
CH25t(OC113) 3dimethoxymethyl-2-
Piperidinoethylsilane β-trimethoxysilylethyl-2-pyridinto(trimethoxysilylpropyl)imidazole D(C)f2 > 35i(OCH3) 3N
-β-(aminoethyl)-γ-aminobrobyltrimethoxysilane H2NC2H4NHC3Hs 5i(OCH3) 3-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane In the present invention, the inorganic fine powder is Treated with the above amino compound. Examples of methods for treating inorganic fine powder include immersing the inorganic fine powder in an aqueous solution of an amino compound or an organic solvent solution, stirring, and heating to remove the solvent, or stirring the inorganic fine powder. Then, a method can be adopted in which the above-mentioned amino compound or its solution is added dropwise thereto, followed by heating and removing the solvent. Further, inorganic fine powder is suspended in a gas phase,
It is also possible to spray or vaporize the amino compound solution.
上記の処理を行なうに際し、同時に他のカップリング剤
や表面処理剤その他の物質を併用処理したり、それらで
前処理又は後処理してもよい。When performing the above treatment, other coupling agents, surface treatment agents, and other substances may be used in combination, or pretreatment or posttreatment may be performed with them.
本発明において、アミン化合物で無機微粉末を処理する
に際し、最終的に熱処理を行なうことが望ましいが、極
度の高熱処理は、アミン化合物の分解や変質を誘発する
ので、２００℃以下が望ましい。アミン化合物の化学構
造にもよるが、一般には１００℃前後の処理温度が好ま
しい。In the present invention, when treating the inorganic fine powder with an amine compound, it is desirable to finally perform heat treatment, but extremely high heat treatment induces decomposition and alteration of the amine compound, so the temperature is preferably 200 ° C. or less. Although it depends on the chemical structure of the amine compound, a treatment temperature of around 100° C. is generally preferred.
本発明において、無機微粉末に対するアミン化合物の添
加量は、目的、用途あるいはアミノ化合物の構造により
異なる。通常、無機物表面に対して、本発明のアミン化
合物が、単分子層を形成する添加量以下で、十分効果を
発揮するが、必要に応じて、二層以上になるような添加
量で処理してもよい。In the present invention, the amount of the amine compound added to the inorganic fine powder varies depending on the purpose, use, or structure of the amino compound. Normally, the amine compound of the present invention exhibits a sufficient effect on the surface of an inorganic substance at an amount that is less than that which forms a monomolecular layer, but if necessary, it may be treated with an amount that forms two or more layers. You can.
本発明におけるアミノ化合物を用いて、無機微粉末の表
面処理を行なった場合、これら無機物質と結合しうる官
能基が、実際に無機微粉末表面の水酸基等と化学反応を
起こし、結合しているか否かは、検証を行なっていない
ので、明確ではないが、本発明におけるアミノ化合物で
、処理を行なった場合の効果は、非常に安定であるので
、アミノ化合物中の官能基と無機微粉末表面が仮りに反
応していない場合であっても、水素結合等の強い相互作
用の働きにより、アミノ化合物が無機微粉末表面に、強
固に担持、吸着されていると推測される。When the surface of inorganic fine powder is treated using the amino compound of the present invention, whether the functional groups that can bond with these inorganic substances actually cause a chemical reaction with the hydroxyl groups, etc. on the surface of the inorganic fine powder, and are bonded. It is not clear whether this is the case, as no verification has been conducted, but the effect of the treatment with the amino compound of the present invention is very stable, so the functional groups in the amino compound and the surface of the inorganic fine powder are Even if they do not react, it is presumed that the amino compound is strongly supported and adsorbed on the surface of the inorganic fine powder due to strong interactions such as hydrogen bonds.
なお、本発明にあけるアミン化合物で無機微粉末を処理
すると、通常、親水性表面を有する無機微粉末は、処理
前に比べ疎水化される場合が多い。Note that when an inorganic fine powder is treated with the amine compound of the present invention, the inorganic fine powder that usually has a hydrophilic surface is often made more hydrophobic than before the treatment.
処理された無機微粉末は、次いで、アンモニウム塩化剤
によって処理される。使用することができるアンモニウ
ム塩化剤としては、例えば、塩酸、硫酸などの酸類、ア
ルキルハライド、ジアルキル１ｉＡＷ１等のアルキル化
剤等が都合よく用いられる。The treated inorganic fine powder is then treated with an ammonium chloride agent. As the ammonium chlorinating agent that can be used, for example, acids such as hydrochloric acid and sulfuric acid, alkylating agents such as alkyl halides and dialkyl 1iAW1, etc. are conveniently used.
アルキル化剤としては、例えば、メチルクロライド、メ
チルブロマイド、ベンジルクロライド、長鎖アルキルク
ロライド、エピクロルヒドリン、ジメチル硫酸、ジエチ
ル硫酸、エチレンオキサイド等があげられる。また、モ
ノクロル酢酸ナトリウム等のベタイン化剤を用いること
もできる。更にまた、上記のアルキル化剤等でアンモニ
ウム塩化処理を施した後に、イオン交換反応を利用して
対イオン置換を行ない、所望の構造、物性制御を行なう
こともできる。Examples of the alkylating agent include methyl chloride, methyl bromide, benzyl chloride, long-chain alkyl chloride, epichlorohydrin, dimethyl sulfate, diethyl sulfate, and ethylene oxide. Moreover, a betainizing agent such as sodium monochloroacetate can also be used. Furthermore, after ammonium salt treatment with the above-mentioned alkylating agent or the like, counter ion substitution can be performed using an ion exchange reaction to control the desired structure and physical properties.
このようにして、Ｃｌ−１Ｂｒ”、Ｆ−等のハロゲンア
ニオン、ＣＨ３５０４−１ＣＨ３＋Ｓ０３等の硫酸、ス
ルホン酸系アニオン又はカルボン酸系アニオン、８「４
−等の硼酸系アニオン等、各種対アニオンを有するアン
モニウム塩を得ることができる。In this way, halogen anions such as Cl-1Br", F-, sulfuric acid such as CH3504-1CH3+S03, sulfonic acid anions or carboxylic acid anions, 8"4
It is possible to obtain ammonium salts having various counter anions such as boric acid anions such as -.
アンモニウム塩化剤による処理は、アミノ化合物で表面
処理した無機微粉末を水或いは有機溶剤中に分散させ、
前記アンモニウム塩化剤を添加し、密封容器中で、通常
的５０℃〜約１３０℃で数時間反応させた後、濾過、洗
浄、乾燥、更に必要に応じて粉砕を行なう。勿論、処理
物によっては、常温、低温での反応も可能であり、また
、加圧が必要な場合もある。簡単に処理を行なう場合に
は、前記のアミノ化合物処理と同様に、アミノ化合物処
理無機微粉末中に、アンモニウム塩化剤溶液を滴下し、
ｉ！痒、混合、加熱処理を行なったり、アミノ化合物処
理無機微粉末を気相中に懸濁させた状態で、アンモニウ
ム塩化剤溶液をスプレーし、処理を行なってもよい。Treatment with an ammonium chloride agent involves dispersing inorganic fine powder whose surface has been treated with an amino compound in water or an organic solvent.
The ammonium chloride agent is added and reacted in a sealed container at typically 50° C. to about 130° C. for several hours, followed by filtration, washing, drying and, if necessary, pulverization. Of course, depending on the material to be treated, the reaction may be carried out at room temperature or low temperature, and pressurization may be necessary in some cases. If the treatment is to be carried out simply, an ammonium chloride solution is added dropwise to the amino compound-treated inorganic fine powder in the same way as the amino compound treatment described above.
i! The treatment may be carried out by carrying out itch, mixing, or heat treatment, or by spraying an ammonium chloride solution while the amino compound-treated inorganic fine powder is suspended in a gas phase.
この処理により、無機微粉末表面に付着したアミン化合
物の置換又は非置換アミノ基が、アンモニウム塩化され
る。Through this treatment, substituted or unsubstituted amino groups of the amine compound attached to the surface of the inorganic fine powder are converted to ammonium salt.
このように処理された本発明における表面処理した無機
微粉末は、トナー粒子内部に内添して用いる場合は、約
０．１容量％乃至約３０容量％好ましくは、約１容但％
乃至約２０奮量％の添加量で用いるのがよい。When the surface-treated inorganic fine powder of the present invention is used as an internal addition inside the toner particles, the amount of the surface-treated inorganic fine powder of the present invention is about 0.1% by volume to about 30% by volume, preferably about 1% by volume.
It is preferable to use it in an amount of about 20% to about 20%.
トナー粒子表面に外添して用いる場合は、約０．０１重
量％から約２０重量％、好ましくは約０．１重量％から
約１０重量％程度の添加量で用いるのがよい。外添後、
機械力処理、熱処理、化学処理等の手段で、トナー粒子
表面に固着させたり、埋め込んでもよい。When externally added to the surface of toner particles, it is preferably used in an amount of about 0.01% to about 20% by weight, preferably about 0.1% to about 10% by weight. After external addition,
It may be fixed to or embedded in the surface of the toner particles by mechanical treatment, heat treatment, chemical treatment, or the like.
本発明における表面処理した無機微粉末が、トナー粒子
と同程度、あるいは更に、トナー粒子より大きな粒度を
有する場合は、用途に応じて適宜、添加量を決めればよ
い。When the surface-treated inorganic fine powder in the present invention has a particle size comparable to, or even larger than, the toner particles, the amount to be added may be determined as appropriate depending on the application.
本発明における表面処理した無機微粉末は、前述の如く
トナーの正帯電性及び導電性の制御に極めて顕著な効果
を示すので、正帯電性トナーの正帯電性制御剤として、
トナー内部及び／又は外部に添加して用いるのが非常に
有効である。The surface-treated inorganic fine powder of the present invention has an extremely remarkable effect on controlling the positive chargeability and conductivity of toner as described above, and therefore, it can be used as a positive chargeability control agent for positively chargeable toner.
It is very effective to add it inside and/or outside the toner.
本発明における表面処理した無機微粉末は、もちろん、
特に、外添して用いる場合、トナーの耐ブロツキング性
改善、粉体流動性改善、クリーニング性改善等にも極め
て効果がある。The surface-treated inorganic fine powder in the present invention is, of course,
In particular, when used externally, it is extremely effective in improving toner blocking resistance, powder fluidity, and cleaning properties.
本発明の現像剤組成物におけるトナーの結着樹脂として
は、従来公知のもの、例えば、スチレン−アクリル系共
重合体、スチレン−ブタジェン共重合体、ポリエステル
、ポリアミド、エポキシ、ポリカーボネート、ポリウレ
タン、シリコーン、フッ素系樹脂、ポリエチレン、ポリ
プロピレン、エチレン−酢酸ビニル共重合体、ポリオレ
フィン系重合体などが使用できる。これらの樹脂は、熱
定着用、圧力定着用のどちらのものでもよい。Examples of the binder resin for the toner in the developer composition of the present invention include conventionally known ones, such as styrene-acrylic copolymer, styrene-butadiene copolymer, polyester, polyamide, epoxy, polycarbonate, polyurethane, silicone, Fluororesins, polyethylene, polypropylene, ethylene-vinyl acetate copolymers, polyolefin polymers, etc. can be used. These resins may be used for heat fixing or pressure fixing.
また、その他の添加剤として、カーボンブラック、含金
属染料、ニグロシン、第４級アンモニウム塩等の帯電制
御剤、シアン、マゼンタ、イエローその他の有彩色の染
料及び顔料、マグネタイト、γ−へマタイト、フェライ
ト等の磁性体、酸化スズ、ヨウ化銅等の導電性制御剤、
補強剤、離型剤等、従来周知のものも使用も可能である
。Other additives include carbon black, metal-containing dyes, nigrosine, charge control agents such as quaternary ammonium salts, cyan, magenta, yellow and other chromatic dyes and pigments, magnetite, γ-hematite, and ferrite. magnetic substances such as, conductivity control agents such as tin oxide, copper iodide, etc.
Conventionally known reinforcing agents, mold release agents, etc. can also be used.
また、本発明における表面処理した無機微粉末をトナー
の外添剤として使用する場合、即ち、（１）バインダー
樹脂中に、類似構造の低級アミン塩、第４級アンモニウ
ム塩、ピリジニウム塩等のアンモニウム塩類が内添され
ているか、又は（ｉｉ）バインダー樹脂自体の分子鎖末
端もしくは側鎖にアンモニウム塩構造を有する様なトナ
ーと組合せ用いた場合には、正帯電制御側の効果が最も
顕著である。In addition, when the surface-treated inorganic fine powder of the present invention is used as an external additive for toner, (1) ammonium salts such as lower amine salts, quaternary ammonium salts, pyridinium salts, etc. having similar structures may be added to the binder resin. When used in combination with a toner in which salts are internally added or (ii) the binder resin itself has an ammonium salt structure at the end or side chain of its molecular chain, the positive charge control effect is most remarkable. .
更に、外添剤として、シリカ、カーボン、アルミナ、酸
化チタン、酸化亜鉛、樹脂微粉、酸化スズ等、従来公知
のものも併用することができる。Furthermore, conventionally known external additives such as silica, carbon, alumina, titanium oxide, zinc oxide, fine resin powder, and tin oxide can also be used.
本発明の現像剤組成物におけるトナーの製造方法として
は、混線粉砕法、スプレィドライ法、直接型合法等任意
のものが使用できる。外添剤ブレンド法も従来公知の任
意の方法が採用できる。As a method for producing the toner in the developer composition of the present invention, any method can be used, such as a cross-wire pulverization method, a spray dry method, or a direct method. As for the external additive blending method, any conventionally known method can be adopted.
トナー粒度としては、コールタ−カウンター法で測定し
た平均粒度ｄ５０が１〜２０ｇａ＋が好ましく、より好
ましくは、５−〜１５μｓ程度である。As for the toner particle size, the average particle size d50 measured by Coulter Counter method is preferably 1 to 20 ga+, more preferably about 5 to 15 μs.
また、トナーは、キャリアを用いる二成分税像法及び、
キャリアを用いない一成分説像法のいずれの方法で使用
してもよい。Further, the toner can be prepared using a two-component tax imaging method using a carrier;
Any one-component imaging method that does not use a carrier may be used.
また、カラー像形成用のトナーとして用いてもよい。It may also be used as a toner for forming color images.
また、本発明における表面処理した無機微粉末自体をキ
ャリアとして用いたり、あるいは、キャリア材料又は帯
電ブレード／ロール材料中に添加混合し、トナーの帯電
性を制御することも可能である。Further, it is also possible to use the surface-treated inorganic fine powder itself as a carrier, or to add and mix it into a carrier material or charging blade/roll material to control the charging property of the toner.
作用
トナー帯電性の環境安定性は、基本的にアンモニウム塩
構造によって達成される。ところで、アンモニウム塩構
造を有する化合物（以下、アンモニウム化合物という）
で直接無機微粉末を処理すると、アンモニウム化合物の
自己凝集力が強いために、アンモニウム化合物と無機物
間の反応と同時、或いはそれよりも早くアンモニウム化
合物自体の凝集、結晶化が進行し、無機微粉末表面をア
ンモニウム塩化合物で均一に処理することが困難である
。The environmental stability of the functional toner chargeability is essentially achieved by the ammonium salt structure. By the way, compounds with an ammonium salt structure (hereinafter referred to as ammonium compounds)
When directly treating inorganic fine powder with It is difficult to uniformly treat the surface with ammonium salt compounds.
しかしながら、本発明においては、無機微粉末を先ずア
ミン化合物で処理し、次いでアンモニウム塩化するから
、アンモニウム化合物が無機物表面に均一に分布した状
態になるものと考えられる。However, in the present invention, since the inorganic fine powder is first treated with an amine compound and then converted into an ammonium salt, it is thought that the ammonium compound is uniformly distributed on the surface of the inorganic substance.
その結果、本発明においては、表面処理無機微粉末の添
加による効果が十分に発揮され、トナーの粉体流動性を
向上させる等の目的で、表面処理無機微粉末を多量に添
加した場合でも、トナーの帯電性が損なわれず、帯電の
安定性と、粉体流動性、耐ブロッキング性、クリーニン
グ性等の非電気的機能の両者の要求が、初めて両立して
満足されることになると考えられる。As a result, in the present invention, the effect of adding the surface-treated inorganic fine powder is fully exhibited, and even when a large amount of the surface-treated inorganic fine powder is added for the purpose of improving the powder fluidity of the toner, etc. It is thought that for the first time, the requirements for charging stability and non-electrical functions such as powder fluidity, anti-blocking properties, and cleaning properties can be simultaneously satisfied without impairing the charging properties of the toner.
実施例
次に本発明を実施例及び比較例によって説明する。なお
、実施例及び比較例中、常温常湿は２２℃、５５％Ｒ，
Ｈ，、低温低湿は１０℃、１５％Ｒ，Ｈ，、高温高湿は
２８℃、８５％Ｒ，Ｈ，を意味する。EXAMPLES Next, the present invention will be explained by examples and comparative examples. In addition, in the examples and comparative examples, normal temperature and normal humidity are 22°C, 55% R,
H, low temperature and low humidity means 10°C, 15% R,H, high temperature and high humidity means 28°C and 85% R,H.
実施例１
部分疎水化シリカ微粉末（ｆ？−８１２、日本アエロジ
ル社製）を気相中に懸濁させ、下記構造の置換アミノシ
ラン溶液を、置換アミノシラン／シリカ＝１５／１００
（重量比））となるようにスプレーし、乾燥し、約
１２０℃で熱処理して、表面処理シリカ（ａ）を得た。Example 1 Partially hydrophobized silica fine powder (f?-812, manufactured by Nippon Aerosil Co., Ltd.) was suspended in a gas phase, and a substituted aminosilane solution having the following structure was mixed with substituted aminosilane/silica = 15/100.
(weight ratio)), dried, and heat-treated at about 120° C. to obtain surface-treated silica (a).
得られた表面処理シリカ（ａ）に、更にメチルクロライ
ドを、表面処理シリカに存在するジメチルアミノ基と当
モル口演下し、加熱加圧し、乾燥処理することにより、
表面処理シリカ（ｂ）を得た。The obtained surface-treated silica (a) is further mixed with methyl chloride in equivalent molar proportions to the dimethylamino groups present in the surface-treated silica, heated and pressurized, and dried.
Surface-treated silica (b) was obtained.
得られた表面処理シリカ（ｂ）の表面における置換アミ
ノシランは下記のごとく変性されたものと推測される。It is presumed that the substituted aminosilane on the surface of the obtained surface-treated silica (b) was modified as described below.
スチレン−ｎ−ブチルメタクリ ９０重量部レート
共重合体
（Ｔｌ；１＝６５℃、韮＝３５，０００）カーボンブラ
ック（ｐＨ＝８） ７重量部ニグロシン変
性物 ３重量部上記成分を溶融混線、
粉砕、分級し、平均粒度ｄ ５Ｏ−１２ｕ１のトナーを
得た。Styrene-n-butyl methacrylate 90 parts by weight Rate copolymer (Tl; 1 = 65°C, weight = 35,000) Carbon black (pH = 8) 7 parts by weight Nigrosine modified product 3 parts by weight The above components were melted and mixed.
It was crushed and classified to obtain a toner having an average particle size of d5O-12u1.
このトナーに、前記表面処理シリカ（ｂ）を０，４重量
％外添混合し、更にフッ化ビニリデン／テトラフルオロ
エチレン系共重合体とメチルメタクリレート−スチレン
共重合体を混合した樹脂で被覆した平均粒径５０即のフ
ェライトキャリアと、キャリア／トナー−１００／７の
重量比で混合して現像剤をＩＩ製した。得られた現像剤
について、ブローオフトライボ測定装置とチャージスペ
クトログラフ測定装置で帯電性を評価した。その結果を
第１表に示す。To this toner, 0.4% by weight of the surface-treated silica (b) was externally added and further coated with a resin mixture of vinylidene fluoride/tetrafluoroethylene copolymer and methyl methacrylate-styrene copolymer. A developer II was prepared by mixing a ferrite carrier having a particle size of 50 and a carrier/toner weight ratio of 100/7. The charging properties of the obtained developer were evaluated using a blow-off tribometer and a charge spectrograph measurement device. The results are shown in Table 1.
第１表
上記の結果から明らかなように、上記現像剤は極めて良
好な帯電性を示し、トナー粉体の流動性も、パウダーテ
スターでの粉体圧縮率が約２７％〜約３０％と極めて良
好であった。As is clear from the above results in Table 1, the above developer exhibits extremely good charging properties, and the fluidity of the toner powder is also extremely high, with a powder compressibility of about 27% to about 30% using a powder tester. It was good.
この現像剤を、〜複写機（ＦＸ−２７００改造機：二成
分現像剤が実装でき、定着ロールをシリコーンロールに
改造したもの）に供給し、３０００枚の複写テストを行
なったところ、極めて鮮明な画質の画像が安定して得ら
れた。This developer was supplied to a copying machine (a modified FX-2700 machine that could be equipped with a two-component developer and the fixing roll was modified to a silicone roll) and a 3,000-sheet copying test was performed. Stable quality images were obtained.
比較例１
実施例１におけるトナーに外添剤を添加することなく、
そのまま実施例１と同一のキャリアと混合して現像剤を
調製した。実施例１と同様な方法で帯電性を評価したと
ころ、常温常湿時；＋１９μＣ／（１、高温高湿時：千
１０μＣ／ｇ、低温低湿時：＋２１μＣ／ｇであり、帯
電の環境依存が大きく、かつ、帯電の立ち上がりが遅か
った。また、粉体圧縮率は、常温常湿で約４３％であっ
て、粉体流動性カ悪り、複写ａ （ＦＸ−２７００改造
１１１ ＞ テ（７）１０００枚（７）プリントテスト
中、しばしばトナーのディスペンス不良と濃度むらが発
生した。Comparative Example 1 Without adding any external additive to the toner in Example 1,
A developer was prepared by mixing the same carrier as in Example 1 as it was. When the charging property was evaluated in the same manner as in Example 1, it was found that at room temperature and humidity: +19 μC/(1, at high temperature and high humidity: 1,000 μC/g, at low temperature and low humidity: +21 μC/g, and the environmental dependence of charging was In addition, the powder compressibility was about 43% at normal temperature and humidity, and the powder flowability was poor. ) 1000 sheets (7) During the print test, poor toner dispensing and uneven density often occurred.
比較例２
実施例１におけるトナーに、部分疎水化シリカ微粉末（
Ｒ−８１２、日本アエロジル社製）を何等処理すること
なく、そのまま０．４重量％外添し、更に実施例１と同
一のキャリアと混合して現像剤をｗ４製した。得られた
現像剤は、常温常湿で一４μＣ／（７の帯電量を示し、
極性が反転し、かつ電荷分布が非常に広く、実用に耐え
得るレベルではなかった。Comparative Example 2 Partially hydrophobized silica fine powder (
R-812 (manufactured by Nippon Aerosil Co., Ltd.) was externally added in an amount of 0.4% by weight without any treatment, and further mixed with the same carrier as in Example 1 to prepare a developer w4. The obtained developer showed a charge amount of -4μC/(7) at room temperature and humidity,
The polarity was reversed and the charge distribution was extremely wide, which was not at a level that could withstand practical use.
比較例３
実施例１におけるトナーに、実施例１における表面処理
シリカ（ａ）を０．４重量％外添し、更に実施例１と同
一のキャリアと同様に混合して現像剤を！Ｊｉ製した。Comparative Example 3 To the toner in Example 1, 0.4% by weight of the surface-treated silica (a) in Example 1 was externally added, and the same carrier as in Example 1 was further mixed in the same manner as in Example 1 to form a developer! Made by Ji.
得られた現像剤の帯電性を評価したところ、常温常湿時
：＋１５μＣ／ｇ、高温高湿時：＋４μＣ／ｇ、低温低
湿時：＋１６μＣ／ｇであり、帯電の環境依存が大きく
、特に高温高湿時、約１０％の逆極性トナーが観察され
た。When the chargeability of the obtained developer was evaluated, it was +15 μC/g at normal temperature and humidity, +4 μC/g at high temperature and high humidity, and +16 μC/g at low temperature and low humidity. At high humidity, about 10% of reverse polarity toner was observed.
比較例４
部分疎水化シリカ微粉末（Ｒ−８１２、日本アエロジル
社製）を気相中に懸濁し、下記アンモニウム塩構造を有
するシラン溶液をシラン／シリカ−１５／１００となる
ようにスプレーし、乾燥し、約１００℃で２時間熱処理
して、表面処理シリカ（Ｃ）を得た
実施例１におけるトナーに、上記表面処理シリカ（Ｃ）
を０．４重量％外添混合し、実施例１と同一のキャリア
と同様に混合して現像剤を１１製した。Comparative Example 4 Partially hydrophobized silica fine powder (R-812, manufactured by Nippon Aerosil Co., Ltd.) was suspended in a gas phase, and a silane solution having the following ammonium salt structure was sprayed so that the ratio of silane/silica was 15/100. The surface-treated silica (C) was added to the toner in Example 1, which was dried and heat-treated at about 100° C. for 2 hours to obtain the surface-treated silica (C).
0.4% by weight was externally added and mixed in the same manner as in Example 1 to prepare developer No. 11.
得られた現像剤の帯電性を評価したところ、常温常湿時
：＋７μＣ／ｇ、高温高湿時：＋３μＣ／ｇ、低温低湿
時：＋５μＣ／Ｑで必り、帯電性が低く、かつ、逆極性
トナー量が約５％から約１５％程度観察された。また、
粉体圧縮率は、常温常湿で２９％であり、良好であった
が、帯電性が劣り、実用レベルには達しなかった。When the chargeability of the obtained developer was evaluated, it was found that the chargeability was low at room temperature and humidity: +7 μC/g, at high temperature and high humidity: +3 μC/g, and at low temperature and low humidity: +5 μC/Q. The amount of polar toner was observed to be about 5% to about 15%. Also,
The powder compressibility was 29% at room temperature and humidity, which was good, but the charging property was poor and did not reach a practical level.
上記表面処理シリカ（Ｃ）と実施例１の表面処理シリカ
（ｂ）とを顕微鏡及び偏光顕微鏡で観察して比較したと
ころ、表面処理シリカ（Ｃ）には、シランの凝集物と考
えられる１０＃Ｉ程度の凝集体が散見されたが、表面処
理シワ力（ｂ）には、凝集体は観察されなかった。When the surface-treated silica (C) and the surface-treated silica (b) of Example 1 were observed and compared using a microscope and a polarizing microscope, it was found that the surface-treated silica (C) contained 10#, which is considered to be an aggregate of silane. Aggregates of grade I were observed here and there, but no aggregates were observed in surface treatment wrinkle strength (b).
実施例２
実施例１のアミノ化合物の代わりに、β−トリメトキシ
シリルエチル−２−ピリジンを用い、部分疎水化シリカ
微粉末（Ｒ−９７２、日本アエロジル社製）にシラン／
シリカ＝５ ／１００ （重量比）となるようにスプ
レーし、実施例１と同様に処理した。Example 2 β-trimethoxysilylethyl-2-pyridine was used instead of the amino compound of Example 1, and silane/
Silica was sprayed at a ratio of 5/100 (weight ratio) and treated in the same manner as in Example 1.
処理されたシリカに、更にジメチル硫酸を、シリカに存
在するピリジン基と当量になるように溶液状態で添加し
、加熱処理し、更に乾燥して、表面処理シリカを得た。Dimethyl sulfate was further added in a solution state to the treated silica in an amount equivalent to the pyridine groups present in the silica, followed by heat treatment and further drying to obtain surface treated silica.
スチレン−ｎ−ブチルメタクリ
レート共重合体
Ｃ丁Ｑ＝６５℃、 ＨＷ＝４３，０００）銅フタロシア
ニン顔料
４級アンモニウム塩（ボントロン
Ｐ−５１、オリエント化学社製）
上記成分を溶ａ混練、粉砕、分級し、平均粒度ｄ５０−
１３１ＩＭのシアントナーを得た。Styrene-n-butyl methacrylate copolymer C-Q = 65°C, HW = 43,000) Copper phthalocyanine pigment quaternary ammonium salt (Bontron P-51, manufactured by Orient Chemical Co., Ltd.) The above components were melt-kneaded, pulverized, and classified. and the average particle size d50-
A cyan toner of 131IM was obtained.
このトナーに、上記表面処理シリカを０．８重量％、酸
化錫微粉末（平均粒径的０．２１１Ｉｆｔ）を１．０重
量％外添混合し、更にパークロロアクリレート−メチル
メタクリレート−スチレン共重合体で被覆した平均粒径
５０即のフェライトキャリアと、キャリア／トナー＝１
００／８の重量比で混合して現像剤を調製した。得られ
た現像剤について、実施例１と同様にチャージスペクト
ログラフ法及びブローオフ法で帯電性を評価したところ
、常温常湿時：＋１６ μｃ／ａ 、高温高湿時： ＋
１４ μｃ／ａ 、低温低湿３重量部
３重量部
９４重量部
時：す１６μＣＩＱで、極めて安定であり、電荷分布も
非常にシャープであった。帯電の立上がり、経時安定性
も同様に良好であった。また、粉体圧縮率も３２％であ
り、良好な粉体流動性を有することが確認された。To this toner, 0.8% by weight of the above-mentioned surface-treated silica and 1.0% by weight of fine tin oxide powder (average particle size: 0.211 Ift) were added, and further, perchloroacrylate-methyl methacrylate-styrene copolymer was added. A ferrite carrier with an average particle size of 50 and carrier/toner = 1
A developer was prepared by mixing at a weight ratio of 00/8. The charging properties of the obtained developer were evaluated using the charge spectrograph method and the blow-off method in the same manner as in Example 1. At normal temperature and normal humidity: +16 μc/a, at high temperature and high humidity: +
14 μc/a, 3 parts by weight, 3 parts by weight, 94 parts by weight at low temperature and low humidity: 16 μC/a, extremely stable, and the charge distribution was also very sharp. Charging rise and stability over time were similarly good. Furthermore, the powder compressibility was 32%, and it was confirmed that the powder had good fluidity.
この現像剤を、複写機（、ＦＸ−２７００改造機）に供
給し、５０００枚の複写テストを行なったところ、極め
て鮮明なシアン画像が常に安定して得られた。When this developer was supplied to a copying machine (a modified FX-2700 machine) and a copying test of 5,000 sheets was performed, extremely clear cyan images were always stably obtained.
実施例３
実施例２のトナーに実施例２の表面処理シリカ１．０重
量部を外添混合して、−成分現像剤を調整した。この現
像剤を複写機（ＦＸ−２７００）のカラー現像ユニット
（非磁性−成分現像装置）に供給し、３０００枚の複写
テストを行なったところ、常に鮮明なシアン画像が得ら
れた。、複写テスト時の帯電性をチャージスペクトログ
ラフ法で評価したところ、常温常湿時：＋６μＣ／ｇ、
高温高湿時：＋５μＣ／（７、低温低湿時：＋７μＣ／
ｇで、極めて安定でめり、かつ電荷分布も非常にシャー
プであった。Example 3 1.0 parts by weight of the surface-treated silica of Example 2 was externally added to the toner of Example 2 to prepare a -component developer. When this developer was supplied to a color developing unit (non-magnetic component developing device) of a copying machine (FX-2700) and a 3,000 copy test was conducted, clear cyan images were always obtained. When the chargeability during the copying test was evaluated using the charge spectrograph method, at room temperature and normal humidity: +6 μC/g,
At high temperature and high humidity: +5μC/(7, at low temperature and low humidity: +7μC/
g, it was extremely stable and sharp, and the charge distribution was also very sharp.
実施例４
実施例１の表面処理シリカ（ａ）を、更に塩化ベンジル
溶液でアンモニウム塩化処理を施し、表面処理シリカを
作成した。Example 4 The surface-treated silica (a) of Example 1 was further subjected to ammonium chloride treatment using a benzyl chloride solution to produce surface-treated silica.
スチレン−ブタジェン ９５重量部（ＴＰ
６２℃、）ｆＷ＝５３．０００）マゼンタ染料（ローダ
ミン系） ５重量部上記成分を溶融混線、粉砕、
分級し、平均粒度ｄ５０−９Ｎ１のマゼンタトナーを得
た。Styrene-butadiene 95 parts by weight (TP
62°C, ) fW = 53.000) Magenta dye (rhodamine type) 5 parts by weight The above components were melted, mixed, pulverized,
It was classified to obtain a magenta toner having an average particle size of d50-9N1.
このトナーに、上記表面処理シリカを０．５重量％、ポ
リメチルメタクリレート微粉末（平均粒径約０．３１ｔ
ｍ）を０．５型口％外添混合し、更に実施例２と同様の
フェライトキャリアと、キャリア／トナー−１００／６
の重量比で混合して現像剤を調製した。得られた現像剤
について、実施例１と同様にチャージスペクトログラフ
法及びブローオフ法で帯電性を評価したところ、常温常
湿時：す２３μＣ／ｇ、高温高湿時：＋１９μｃ／ｇ
、低温低湿時：＋５μＣ／Ｑで、極めて安定であり、電
荷分布も非常にシャープであった。帯電の立上がり、経
時安定性も非常に良好であった。To this toner, 0.5% by weight of the above-mentioned surface-treated silica and polymethyl methacrylate fine powder (average particle size of about 0.31t) were added.
m) was externally added at 0.5% by type, and further the same ferrite carrier as in Example 2 and carrier/toner-100/6 were mixed.
A developer was prepared by mixing in a weight ratio of . The charging properties of the obtained developer were evaluated using the charge spectrograph method and the blow-off method in the same manner as in Example 1. At normal temperature and normal humidity: 23 μC/g, at high temperature and high humidity: +19 μc/g
, at low temperature and low humidity: +5 μC/Q, extremely stable, and the charge distribution was also very sharp. The charging rise and stability over time were also very good.
この現像剤を、複写機（ＦＸ−２７００改造機）に供給
し、実施例１と同様の方法で５０００枚の複写テストを
行なったところ、良好な画質のマゼンタ画像が常に安定
して得られた。When this developer was supplied to a copying machine (a modified FX-2700 machine) and a 5000 copy test was conducted in the same manner as in Example 1, magenta images of good quality were always stably obtained. .
実施例５
部分疎水化シリカ微粉末（Ｒ−９７２、日本アエロジル
社製）をγ−アミノプロピルトリエトキシシランを用い
てシラン／シリカ＝５ ／１００ （ＩＩ比）となる
ように処理し、更に塩酸でアンモニウム塩化処理を施し
、表面処理シリカを得た。Example 5 Partially hydrophobized silica fine powder (R-972, manufactured by Nippon Aerosil Co., Ltd.) was treated with γ-aminopropyltriethoxysilane so that the silane/silica ratio was 5/100 (II ratio), and then treated with hydrochloric acid. Ammonium chloride treatment was performed to obtain surface-treated silica.
スチレン−ブチルメタクリレート ４７重量部共重合
体（丁９＝６５℃、Ｈｗ＝２８Ｃｔ、 ０００）７
Ｆｅ２Ｏ２５０重量部
４級アンモニウム塩（ボントロン １．５重量部Ｐ−５
１、オリエント化学社製）
ポリプロピレンワックス １．５重量部上記
成分を溶融混線、粉砕、分級し、平均粒度ｄ５０−１２
ｍの磁性トナーを得た。Styrene-butyl methacrylate 47 parts by weight copolymer (9=65°C, Hw=28Ct, 000) 7
Fe2O250 parts by weight Quaternary ammonium salt (Bontron 1.5 parts by weight P-5
1. (manufactured by Orient Chemical Co., Ltd.) Polypropylene wax 1.5 parts by weight The above components were melt mixed, crushed, and classified to obtain an average particle size of d50-12.
A magnetic toner of m was obtained.
この磁性トナーを、複写機（ＦＸ−２７００、富士ゼロ
ックスＵ製）の磁性−成分現像装置に供給し、３０００
枚の複写テストを行なったところ、極めて良好な画質の
セピア色画像が常に安定して得られた。This magnetic toner was supplied to a magnetic component developing device of a copying machine (FX-2700, manufactured by Fuji Xerox U), and
When we conducted a copying test on several sheets, we were able to consistently obtain sepia-colored images of extremely good quality.
複写テスト時における現像ロール上のトナーの帯電量を
チャージスペクトログラフ法で評価したところ、＋５μ
Ｃ／Ｑから＋７μＣ／ｇまでの範囲でおり、極めて安定
な帯電性を示した。When the charge amount of the toner on the developing roll during a copying test was evaluated using the charge spectrograph method, it was found to be +5μ.
The chargeability ranged from C/Q to +7 μC/g, indicating extremely stable charging properties.
発明の効果
本発明の現像剤組成物は、無機微粉末の表面処理を、前
記のアミン化合物で処理した後、アンモニウム塩化剤を
用いてアンモニウム塩化するから、トナー帯電の立止り
が早く、トナーの帯電量及び電荷分布の制御を容易に行
なうことができ、特に正帯電性及び導電性の制御に有効
である。そして、トナー帯電性の環境安定性、物理化学
的安定性及び経時安定性の点で優れたものである。Effects of the Invention In the developer composition of the present invention, the surface of the inorganic fine powder is treated with the above-mentioned amine compound, and then the ammonium chloride is converted into ammonium chloride using an ammonium chloride agent. The amount of charge and charge distribution can be easily controlled, and it is particularly effective in controlling positive chargeability and conductivity. Furthermore, the toner is excellent in terms of environmental stability, physicochemical stability, and stability over time of toner chargeability.
また、本発明の現像剤組成物は、トナーの帯電性と、粉
体流動性、耐ブロッキング性、クリーニング性等の非電
気的機能との両者の要求を満足するものであり、したが
って、良好な画質の画像を与えることができる。Furthermore, the developer composition of the present invention satisfies the requirements for both toner chargeability and non-electrical functions such as powder fluidity, anti-blocking property, and cleaning property, and therefore has good properties. It can provide high quality images.
更に、本発明における前記アミノ化合物は無色又は淡色
であるから、本発明の瑛像剤組成物は、カラー画像の形
成に有利に用いることができる。Furthermore, since the amino compound in the present invention is colorless or light-colored, the photographic image agent composition of the present invention can be advantageously used for forming color images.
Claims (2)
有する電子写真現像剤組成物において、該無機微粉末が
、置換又は非置換アミノ基と、無機物質と結合しうる官
能基とを有する化合物によつて表面処理した後、アンモ
ニウム塩化剤で処理したものであることを特徴とする電
子写真現像剤組成物。(1) In an electrophotographic developer composition containing toner particles containing inorganic fine powder on the surface or inside, the inorganic fine powder has a substituted or unsubstituted amino group and a functional group capable of bonding to an inorganic substance. An electrophotographic developer composition, characterized in that the composition is surface-treated with a compound and then treated with an ammonium chloride.
とする特許請求の範囲第１項に記載の電子写真現像剤組
成物。(2) The electrophotographic developer composition according to claim 1, wherein the compound is an organosilicon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038399A JPH02217863A (en) | 1989-02-20 | 1989-02-20 | Electrophotographic developer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038399A JPH02217863A (en) | 1989-02-20 | 1989-02-20 | Electrophotographic developer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02217863A true JPH02217863A (en) | 1990-08-30 |
Family
ID=12524217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1038399A Pending JPH02217863A (en) | 1989-02-20 | 1989-02-20 | Electrophotographic developer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02217863A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722838B2 (en) * | 2006-10-13 | 2014-05-13 | Evonik Degussa Gmbh | Surface-modified, structurally modified fumed silicas |
-
1989
- 1989-02-20 JP JP1038399A patent/JPH02217863A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722838B2 (en) * | 2006-10-13 | 2014-05-13 | Evonik Degussa Gmbh | Surface-modified, structurally modified fumed silicas |
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