JPH023174B2 - - Google Patents
Info
- Publication number
- JPH023174B2 JPH023174B2 JP59041314A JP4131484A JPH023174B2 JP H023174 B2 JPH023174 B2 JP H023174B2 JP 59041314 A JP59041314 A JP 59041314A JP 4131484 A JP4131484 A JP 4131484A JP H023174 B2 JPH023174 B2 JP H023174B2
- Authority
- JP
- Japan
- Prior art keywords
- monomers
- toner
- developer
- particle size
- average particle
- 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.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920002050 silicone resin Polymers 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 26
- 238000000034 method Methods 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 13
- 108091008695 photoreceptors Proteins 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 230000007423 decrease Effects 0.000 description 8
- 125000005233 alkylalcohol group Chemical group 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- KOXWOWPVSGRFCZ-YDFGWWAZSA-N (2e,4e)-3-methylhexa-2,4-diene Chemical compound C\C=C\C(\C)=C\C KOXWOWPVSGRFCZ-YDFGWWAZSA-N 0.000 description 1
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- KFSQJVOLYQRELE-HWKANZROSA-N (e)-2-ethylbut-2-enoic acid Chemical compound CC\C(=C/C)C(O)=O KFSQJVOLYQRELE-HWKANZROSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- CCGNWTMPKWFXAD-UHFFFAOYSA-N 1-ethenyl-3,4-dihydro-2h-pyridine Chemical compound C=CN1CCCC=C1 CCGNWTMPKWFXAD-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LMQFWQLDWMYEFX-UHFFFAOYSA-N 2-(4,6,6-trimethyl-5-bicyclo[3.1.1]heptanyl)pyridine Chemical compound CC1CCC(C2(C)C)CC12C1=CC=CC=N1 LMQFWQLDWMYEFX-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 1
- PHMRPWPDDRGGGF-UHFFFAOYSA-N 2-bromoprop-1-ene Chemical compound CC(Br)=C PHMRPWPDDRGGGF-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 description 1
- LCFYCLRCIJDYQD-UHFFFAOYSA-N 2-ethenyl-5-methylpyridine Chemical compound CC1=CC=C(C=C)N=C1 LCFYCLRCIJDYQD-UHFFFAOYSA-N 0.000 description 1
- VMWGBWNAHAUQIO-UHFFFAOYSA-N 2-ethenyl-6-methylpyridine Chemical compound CC1=CC=CC(C=C)=N1 VMWGBWNAHAUQIO-UHFFFAOYSA-N 0.000 description 1
- XNVAUNOSRHPXCY-UHFFFAOYSA-N 2-ethenylpyrrolidine Chemical compound C=CC1CCCN1 XNVAUNOSRHPXCY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- OZPOYKXYJOHGCW-UHFFFAOYSA-N 2-iodoethenylbenzene Chemical compound IC=CC1=CC=CC=C1 OZPOYKXYJOHGCW-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical compound CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AKDJZAVMDJYMIT-UHFFFAOYSA-N 4-but-3-enylpyridine Chemical compound C=CCCC1=CC=NC=C1 AKDJZAVMDJYMIT-UHFFFAOYSA-N 0.000 description 1
- IDPBFZZIXIICIH-UHFFFAOYSA-N 4-ethenylpiperidine Chemical compound C=CC1CCNCC1 IDPBFZZIXIICIH-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- YAXPDWVRLUOOBJ-UHFFFAOYSA-N 4-ethylhex-3-en-3-ylbenzene Chemical compound CCC(CC)=C(CC)C1=CC=CC=C1 YAXPDWVRLUOOBJ-UHFFFAOYSA-N 0.000 description 1
- JJWKILYTXNFVIP-UHFFFAOYSA-N 6,7-dibromo-2,8,9,9-tetrachloro-4,5-diiodonon-2-ene Chemical compound ClC(C(C(C(C(C(I)C=C(C)Cl)I)Br)Br)Cl)Cl JJWKILYTXNFVIP-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 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
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical group ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- KNZIIQMSCLCSGZ-UHFFFAOYSA-N non-1-enylbenzene Chemical compound CCCCCCCC=CC1=CC=CC=C1 KNZIIQMSCLCSGZ-UHFFFAOYSA-N 0.000 description 1
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical compound CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Description
産業上の利用分野
本発明は、現像剤、特に現像剤の特性低下を防
止した電子写真二成分現像剤に関する。
従来技術
電子写真法あるいは静電記録法に適用される現
像方法として、トナーとキヤリヤからなる現像剤
を用い、トナーとキヤリヤ間の摩擦帯電によりト
ナーに電荷を付与し、このトナーにより静電潜像
を可視化する方法が知られている。感光体あるい
は静電記録体上の可視化されたトナー像は転写紙
に転写後、定着して複写物とし、一方転写後に感
光体あるいは静電記録体上の転写できなかつた残
留トナーが、次の複写工程に備える為にクリーニ
ングされる。この残留トナーのクリーニングは、
ブレード法、ブラシ法、ウエブ法等種々の方法に
より行われているが、数千回あるいは数万回と複
写工程を続けるうちにこれらのクリーニング法で
は除去しきれないトナーが徐々に感光体等の表面
に蓄積し、いわゆるクリーニング不良あるいはト
ナーフイルミングといつた不都合を生じる。この
ような現像を改善する為、例えば特公昭48−8141
号、同51−1130号、特開昭50−120631号、昭52−
84741号等で現像剤組成物に添加剤を混合する方
法が提案されている。即ち、特公昭48−8141号は
ポリテトラフルオロエチレン、弗化ポリビニリデ
ン等の表面エネルギーの低い有機重合体を、特公
昭51−1130号は摩擦帯電列が硫黄より小さい塗着
性のない重合体を、特開昭50−120631号は摩擦帯
電列が硫黄より小さい塗着性のない重合体とコロ
イド状シリカ等の研摩剤を、また特開昭52−
84741号はポリスチレン粒子を、それぞれ現像剤
中に添加し、付着能の低下あるいは研摩効果等に
より感光体等の表面へのクリーニング不良あるい
はトナーフイルミングを防止するものである。こ
れらの方法はクリーニング不良あるいはトナーフ
イルミングの防止という面ではある程度有用な方
法であるが、この様な添加剤を混合した現像剤は
混合しない現像剤に比較してトナーへの摩擦帯電
能が低下するという不具合を有する。つまり複写
枚数が1万〜2万枚から画像濃度の低下やカブリ
の増大が生じ、遂には複写できない現像が生じて
しまう。この現像は高温高湿の環境のとき特に顕
著に生じる。このとき感光体上にはトナーフイル
ミング現像は生じていないので、この現像は摩擦
帯電能の低下に寄因するものと考えられる。
一方、現像剤の寿命の延長をはかるため、各種
の方策が提案され、実施されて来た、その例を挙
げれば、特開昭47−13954号に開示されているア
クリル酸エステル、メタクリル酸エステル類とス
チレンの共重合体、特開昭47−17434号に開示さ
れているフツ化ポリマー、特開昭49−84249号に
開示されているパラキシレンポリマー、特開昭50
−2543号に開示されているシリコーン重合体等の
樹脂で、鉄粉、フエライト粉、マグネタイト粉、
ガラスビーズ等を被覆したキヤリヤを用いること
があり、これらの手段を施すことによつて、著し
い現像剤の長寿命化をはかることができる。しか
しまた一方ではトナーの帯電性を制御することに
よつても、現像剤寿命の延長をはかることがで
き、その例を挙げれば、特公昭49−12915号に開
示されているO,O′−ジヒドロキシアゾ染料の
クロム又はゴバルト錯体、特公昭42−1267号に開
示されているアジン系黒色染料である。またさら
に被覆キヤリヤと帯電制御剤含有トナーの組み合
せの例としては特開昭58−152256号に開示されて
いる有機シリコン重合体被覆キヤリヤと特定の
O,O′−ジヒドロキシアゾ染料の2:1型クロ
ム錯塩を含むトナーがある。この組み合せは確か
に現像剤の帯電性の安定、長寿命化を可能にして
はいるが、上記の欠点、即ちクリーニング特性の
不良をまねがれえず、またさらに従来公知のクリ
ーニング助剤、即ち金属石ケン類、ポリオレフイ
ン粉末等を添加すると、帯電の安定、長寿命化に
悪影響を与えるという不都合を生じた。
発明の目的
本発明はこの様な事情に鑑みなされたものであ
つて、感光体あるいは静電記録体へのクリーニン
グ不良あるいはトナーフイルミングを防止し、画
像濃度の低下やカブリの増大を防止し、寿命の長
い電子写真二成分現像剤を提供することを目的と
する。
発明の構成
上記目的を達成するため、本発明者等は研究を
重ね、シリコン樹脂で表面を被覆したキヤリヤ
と、前記キヤリヤとの摩擦帯電により負に帯電す
るトナー粉末と、このトナー粉末の平均粒径より
も小さい平均粒径を有する微粉末とを混合してな
り、前記微粉末は、アクリル酸エステルモノマ
ー、メタクリル酸エステルモノマー、スチレン系
モノマー、含窒素付加重合性モノマー、重合性不
飽和カルボン酸モノマーから選択される1種類以
上のモノマーから得られる単独もしくは共重合体
からなり、0.05〜5μmの平均粒径を有することを
特徴とする電子写真二成分現像剤、さらに望まし
くは、トナー粉末がスチレン系樹脂中に着色剤と
帯電制御剤を含有してなり、前記帯電制御剤が
O,O′−ジヒドロキシアゾ染料のクロム錯塩で
あることを特徴とする電子写真二成分現像剤によ
つて本目的が達成されることを見出し、本発明を
完成した。
本発明に係る現像剤に用いられるトナーの平均
粒径より小さい微粉末は、アクリル酸エステルモ
ノマー、メタクリル酸エステルモノマー、スチレ
ン系モノマー、含窒素付加重合体モノマー、重合
性不飽和カルボン酸モノマーから選択される1種
類以上のモノマーから得られる単独もしくは共重
合体からなる。
この重合体を構成するモノマーの具体例として
はアクリル酸及びメタクリル酸の、アルキルアル
コール、ハロゲン化アルキルアルコール、アルコ
キシアルキルアルコール、アラルキルアルコー
ル、アルケニルアルコールの如きアルコールとの
エステル化物等が挙げられる。そして、上記アル
コールの具体例としてメチルアルコール、エチル
アルコール、プロピルアルコール、ブチルアルコ
ール、アミンアルコール、ヘキシルアルコール、
ヘプチルアルコール、オクチルアルコール、ノニ
ルアルコール、ドデシルアルコール、テトラデシ
ルアルコール、ヘキサデシルアルコールの如きア
ルキルアルコール;こられアルキルアルコールを
一部ハロゲン化したハロゲン化アルキルアルコー
ル;メトキシエチルアルコール、エトキシエチル
アルコール、エトキシエトキシエチルアルコー
ル、メトキシプロピルアルコール、エトキシプロ
ピルアルコールの如きアルコキシアルキルアルコ
ール;ベンジルアルコール、フエニルエチルアル
コール、フエニルプロピルアルコールの如きアラ
ルキルアルコール;アリルアルコール、クロトニ
ルアルコールの如きアルケニルアルコールが挙げ
られる。
これらのアクリル系モノマーは単独の重合体と
して用いても良く、また他の種類のモノマーを共
重合して用いても良い。この場合の他の種類のモ
ノマーの具体例としてはスチレン及びその誘導
体、例えばメチルスチレン、ジメチルスチレン、
トリメチルスチレン、エチルスチレン、ジエチル
スチレン、トリエチルスチレン、プロピルスチレ
ン、ブチルスチレン、ヘキシルスチレン、ヘプチ
ルスチレン、オクチルスチレンの如きアルキルス
チレン、フロロスチレン、クロロスチレン、ブロ
モスチレン、ジブロモスチレン、ヨードスチレン
の如きハロゲン化スチレン、更にニトロスチレ
ン、アセチルスチレン、メトキシスチレン等が挙
げられる。
また、付加重合性不飽和カルボン酸類、即ちα
−エチルアクリル酸、クロトン酸、α−メチルク
ロトン酸、α−エチルクロトン酸、イソクロトン
酸、チグリン酸、ウンゲリカ酸の如き付加重合性
不飽和脂肪族モノカルボン酸、又はマレイン酸、
フマル酸、イタコン酸、シトラコン酸、メサコン
酸、グルタコン酸、ジヒドロムコン酸の如き付加
重合性不飽和脂肪族ジカルボン酸が挙げられる。
また、これらカルボン酸の各種金属塩化したもの
も用いることができ、この金属塩化は重合終了後
に行うことができる。
また、前記付加重合性不飽和カルボン酸と前記
のアルキルアルコール、ハロゲン化アルキルアル
コール、アラルキルアルコール、アルケニルアル
コールの如きアルコールとのエステル化物等が挙
げられる。
また、前記付加重合性不飽和カルボン酸より誘
導されるアミド及びニトリル;エチレン、プロピ
レン、ブテン、イソブチレンの如き脂肪族モノオ
レフイン;1,3−ブタジエン、1,3−ペンタ
ジエン、2−メチル−1,3−ブタジエン、2,
3−ジメチル−1,3−ブタジエン、2,4−ヘ
キサジエン、3−メチル−2,4−ヘキサジエン
の如き共役ジエン系脂肪系ジオレフインが挙げら
れる。
更に酢酸ビニル類、ビニルエーテル類;ビニル
カルバゾール、ビニルピリジン、ビニルピロリド
ン等、2−ピニルピリジン、4−ビニルピリジ
ン、2−ビニル−6−メチルピリジン、2−ビニ
ル−5−メチルピリジン、4−ブテニルピリジ
ン、4−ペンチルピリジン、N−ビニルピペリジ
ン、4−ビニルピペリジン、N−ビニルジヒドロ
ピリジン、N−ビニルピロール、2−ビニルピロ
ール、N−ビニルピロリン、N−ビニルピロリジ
ン、2−ビニルピロリジン、N−ビニル2−ピロ
リドン、N−ビニル−2−ピペリドン、N−ビニ
ルカルバノールの含窒素ビニル化合物が挙げられ
る。
本発明で用いるトナー粉末の平均粒径より小さ
い平均粒径を有する微粉末は各種重合法を用いて
重合されたものを用いることができる。即ち、エ
マルジヨン重合、ソープフリーエマルジヨン重
合、サスペンジヨン重合等により粒子化された重
合体は勿論、上記各重合法又は溶液重合、バルク
重合等により得られた重合体を溶剤に溶解した後
スプレードライ法により造粒された微粉末や機械
的粉砕等の手法により得られる微粉末を用いるこ
とができる。前述の微粉末は無定形、球形、平板
状、顆粒状等の任意の形状のものを用いることが
できるが、特にほぼ球形のものが良い。
この微粉末は、現像剤中に混合される。
即ち、この微粉末とトナー粒子もしくはキヤリ
ヤー粒子をまず混合し、次いで現像剤中にこの混
合物を混合するか、あるいは現像剤中に微粉末を
直接混合する等の方法で混合される。
本発明に係る微粉末は1種類だけの使用に限定
されるものではなく、複数の種類を併用すること
ができる。又本発明に係る微粉末は他の添加剤と
併用することができる。
本発明に係る微粉末の平均粒径はトナー粉末の
平均粒径より小さい必要があるが、望ましくは
0.05〜5μm、より望ましくは0.1〜2μmの粒径を
有するものが好結果を与える。
本発明に係る微粉末の添加量はトナーに対し
0.01〜10重量%で用いることができるか、より望
ましくは0.05〜2.0重量%が好結果を与える。
本発明に係る現像剤に用いられるトナーはスチ
レン系樹脂中に着色剤を分散したものであり、こ
こにいうスチレン系樹脂とはスチレン系モノマー
を主成分として含む重合体又は共重合体を意味す
る。スチレン系モノマーの具体例としては、前記
のスチレンのほか、その誘導体が挙げられる。ス
チレンと共重合して用いることのできるモノマー
の具体例としては、前記のアクリル系モノマー、
即ちアクリル酸及びメタアクリル酸の各エステル
化物;前記の重合性不飽和カルボン酸類、そのエ
ステル化物及び、そのアミド及びニトリル;前記
の脂肪族モノオレフイン;前記の共役ジエン系脂
肪族ジオレフインが挙げられる。
更に塩化ビニル、臭化ビニル、ヨウ化ビニル、
1,2−ジクロルエチレン、1,2−ジブロムエ
チレン、1,2−ジヨードエチレン、塩化イソプ
ロペニル、臭化イソプロペニル、塩化アリル、臭
化アリル、塩化ビニリデン、弗化ビニル、弗化ビ
ニリデンの如きハロゲン化脂肪族オレフインが挙
げられる。
トナーには着色剤として各種の染料、顔料、カ
ーボンブラツクを含有させることができる。
帯電制御剤としては、銅フタロシアニンもしく
はその誘導体も用いられるが、特に有効なのは、
O,O′−ジヒドロキシアゾ染料の2:1型金属
錯塩、とくにクロム錯塩である。これは下記一般
式にて表わされる。
上式中、X,Y,Z,X′,Y′,及びZ′はそれ
ぞれ水素原子、アルキル基、アルコキシ基、ニト
ロ基、ハロゲン原子、カルボニル基、ヒドロキシ
ル基、スルホン基、スルホンアミド基等をあらわ
す。またさらにZはアミド結合を介して置換ある
いは非置換フエニル基に結合した原子団であつて
もよい。A
はH、アルカリ金属、脂肪族アンモ
ニウム、ピリジニウムカチオンをあらわす。
本発明に係る現像剤に用いられるキヤリヤとし
ては、鉄粉、フエライト粉、マグネタイト粉、ガ
ラスビーズなどから選択されるコアに、シリコン
樹脂を塗布して得られる。ここでシリコン樹脂と
しては、例えば(1)SiO2,CH3SiC3/2、
(CH3)2SiO、(CH3)3SiO1/2の構造単位を組み合
せてできる共重合体、(2)CH3SiO3/2、
(CH3)2SiO、C6H5SiO3/2、(C6H5)(CH3)SiO、
(C6H5)2SiOの構造単位を組み合せてできる共重
合体などで、硬化して三次元構造ポリマーとなる
ものである。さらにまたかかるポリマーを変性し
た、いわゆるアクリル変性シリコン樹脂、アルキ
ド変性シリコン樹脂、エポキシ性シリコン樹脂も
含まれる。キヤリヤ溶剤に溶かしたシリコン樹脂
をコアにスプレー塗布し、乾燥すれば得られる
が、そのときの乾燥は比較的高温で行なうか、乾
燥後電気炉に入れて硬化させるのが望ましい。
本発明の現像剤は感光体あるいは静電記録体に
形成された静電潜像を現像することができる。す
なわち、セレン、酸化亜鉛、硫化カドミウム、無
定形シリコン等の無機光導電材料、フタロシアニ
ン顔料、ビスアゾ顔料、等の有機光導電材料から
なる感光体に電子写真的に静電潜像を形成し、あ
るいはポリエチレンテレフタレートのような誘電
体を有する静電記録体に針状電極等により静電潜
像を形成し、磁気ブラシ法、カスケード法、タツ
チダウン法等の現像方法によつて、静電潜像に本
発明の現像剤を付着させトナー像を形成する。こ
のトナー像は紙等の転写材に転写後、定着して複
写物となり、感光体等の表面に残留するトナーは
クリーニングされる。クリーニング法としてはブ
レード法、ブラシ法、ウエブ法、ロール法等種々
の方法を用いることができる。
発明の効果
本発明の現像剤により得られる効果は以下のと
おりである。
1 クリーニング不良が防止できる。
感光体等に残留するトナーをクリーニングす
るとき、本発明の微粉末を添加した現像剤によ
ると、たとえ5万枚の複写を行なつたとしても
クリーニング不良が生じることはない。これに
対し従来知られている添加剤を用いた現像剤で
は、初期には十分なクリーニングがなし得るも
のの、徐々にクリーニング性能が低下し、2〜
3万枚を越えると感光体上に画像状にトナーが
残留し、次の複写物に残像あるいは帯状の黒い
筋等が発生してしまう。
2 現像剤寿命を長くできる。
現像剤の現像能力、特に摩擦帯電能は徐々に
低下するものであるが、特に従来の添加剤を用
いた現像剤ではこの低下が生じやすかつた。し
かし本発明に係る現像剤は現像能力の低下が生
じにくく、5万枚の複写を行なつても、特に影
響の出やすい画像濃度0.7の原稿についても、
複写画像濃度の低下は殆んどない。更に高温高
湿の環境下でも影響を受けない。
3 感光体を傷つけにくく又トナーのフイルミン
グが生じない。
以下実施例及び比較例により本発明を更に具体
的に説明するが、本発明の範囲は以下の実施例に
より何ら制限されるものではない。なお各実施例
中、部は全て重量部を表わす。
実施例
スチレン−メタクリル酸ブチル共重合体 88部
O,O′−ジヒドロキシアゾ染料のクロム錯体
2部
カーボンブラツク 10部
の配合にて、混練、粉砕、分級後径粒12ミクロン
のトナーを得、このトナー100部に対して、ソー
プフリーエマルジヨン重合により得たメタクリル
酸メチル微粉末(粒径0.5ミクロン)を0.5部加え
てヘンシエルミルで混合し、本発明に係るトナー
を得た。
一方、メチルフエニルシロキサンを100ミクロ
ン鉄粉に流動床にて溶剤塗布し乾燥硬化させてキ
ヤリヤを得た。
このキヤリヤ100部に対して、トナー3部を十
分混合し、本発明に係る現像剤を得た。
比較例
微粉末を添加しないほかは実施例とまつたく同
様にして、対照現像剤を得た。
実 験
実施例及び比較例で得た現像剤を富士ゼロツク
ス製複写機FX4370に入れて、10万枚の実機走行
試験を行なつたところ、下記表のような結果が得
られ、本発明の現像剤の効果が明らかとなつた。
INDUSTRIAL APPLICATION FIELD The present invention relates to a developer, and particularly to an electrophotographic two-component developer that prevents deterioration of developer properties. Prior Art As a developing method applied to electrophotography or electrostatic recording, a developer consisting of toner and carrier is used, and the toner is charged by frictional charging between the toner and carrier, and this toner forms an electrostatic latent image. There are known methods to visualize this. The visualized toner image on the photoreceptor or electrostatic recording material is transferred to a transfer paper and fixed to form a copy, while the residual toner on the photoreceptor or electrostatic recording material that could not be transferred after transfer is transferred to the next step. It is cleaned in preparation for the copying process. To clean this residual toner,
Various cleaning methods are used to clean the photoreceptor, such as the blade method, brush method, and web method, but as the copying process continues thousands or tens of thousands of times, toner that cannot be removed by these cleaning methods gradually builds up on the photoreceptor, etc. It accumulates on the surface, causing problems such as poor cleaning or toner filming. In order to improve this kind of development, for example,
No. 51-1130, Japanese Unexamined Patent Publication No. 120631, 1973, 1972-
No. 84741 and the like propose a method of mixing additives into a developer composition. In other words, JP-B No. 48-8141 uses organic polymers with low surface energy such as polytetrafluoroethylene and polyvinylidene fluoride, and JP-Ko 51-1130 uses non-stick polymers with a triboelectric series smaller than that of sulfur. , JP-A-50-120631 discloses abrasives such as non-stick polymers and colloidal silica whose triboelectrification series is smaller than sulfur, and JP-A-52-120631.
In No. 84741, polystyrene particles are added to each developer to prevent poor cleaning or toner filming on the surface of a photoreceptor etc. due to a reduction in adhesion ability or a polishing effect. Although these methods are somewhat useful in preventing poor cleaning or toner filming, developers mixed with such additives have a lower ability to triboelectrically charge toner than developers without such additives. There is a problem with this. In other words, when the number of copies is 10,000 to 20,000, image density decreases and fog increases, and finally, development occurs that makes it impossible to copy. This development occurs particularly markedly in a high temperature and high humidity environment. At this time, toner film development did not occur on the photoreceptor, so this development is considered to be due to a decrease in triboelectric charging ability. On the other hand, in order to extend the life of the developer, various measures have been proposed and implemented. and styrene copolymers, fluorinated polymers disclosed in JP-A-47-17434, para-xylene polymers disclosed in JP-A-49-84249, JP-A-50
-Resins such as silicone polymers disclosed in No. 2543, including iron powder, ferrite powder, magnetite powder,
A carrier coated with glass beads or the like may be used, and by implementing these measures, the life of the developer can be significantly extended. However, on the other hand, it is also possible to extend the life of the developer by controlling the chargeability of the toner. For example, O, O′- It is a chromium or gobalt complex of dihydroxyazo dye, and is an azine-based black dye disclosed in Japanese Patent Publication No. 1267-1983. A further example of a combination of a coated carrier and a toner containing a charge control agent is a 2:1 type combination of an organosilicon polymer coated carrier and a specific O,O'-dihydroxyazo dye disclosed in JP-A-58-152256. There are toners that contain chromium complex salts. Although this combination certainly makes it possible to stabilize the chargeability and extend the lifespan of the developer, it cannot imitate the above-mentioned drawbacks, that is, the poor cleaning properties, and furthermore, Addition of metal soaps, polyolefin powder, etc. has the disadvantage of adversely affecting charging stability and longevity. Purpose of the Invention The present invention has been made in view of the above circumstances, and aims to prevent poor cleaning or toner filming on a photoconductor or electrostatic recording medium, prevent a decrease in image density and an increase in fog, The purpose of the present invention is to provide an electrophotographic two-component developer with a long life. Structure of the Invention In order to achieve the above object, the inventors of the present invention have conducted repeated research on a carrier whose surface is coated with a silicone resin, a toner powder that is negatively charged due to frictional electrification with the carrier, and an average particle size of this toner powder. and a fine powder having an average particle size smaller than the particle diameter, and the fine powder includes an acrylic acid ester monomer, a methacrylic acid ester monomer, a styrene monomer, a nitrogen-containing addition polymerizable monomer, and a polymerizable unsaturated carboxylic acid. An electrophotographic two-component developer comprising a single or copolymer obtained from one or more monomers selected from monomers and having an average particle size of 0.05 to 5 μm, more preferably, the toner powder is styrene. The present object is achieved by an electrophotographic two-component developer containing a coloring agent and a charge control agent in a system resin, wherein the charge control agent is a chromium complex salt of an O,O'-dihydroxyazo dye. The inventors have discovered that the following can be achieved, and have completed the present invention. The fine powder smaller than the average particle size of the toner used in the developer according to the present invention is selected from acrylic acid ester monomers, methacrylic acid ester monomers, styrene monomers, nitrogen-containing addition polymer monomers, and polymerizable unsaturated carboxylic acid monomers. It consists of a homopolymer or a copolymer obtained from one or more types of monomers. Specific examples of monomers constituting this polymer include esters of acrylic acid and methacrylic acid with alcohols such as alkyl alcohols, halogenated alkyl alcohols, alkoxyalkyl alcohols, aralkyl alcohols, and alkenyl alcohols. Specific examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amine alcohol, hexyl alcohol,
Alkyl alcohols such as heptyl alcohol, octyl alcohol, nonyl alcohol, dodecyl alcohol, tetradecyl alcohol, and hexadecyl alcohol; halogenated alkyl alcohols that partially halogenate these alkyl alcohols; methoxyethyl alcohol, ethoxyethyl alcohol, ethoxyethoxyethyl Alcohol, alkoxyalkyl alcohols such as methoxypropyl alcohol and ethoxypropyl alcohol; aralkyl alcohols such as benzyl alcohol, phenylethyl alcohol and phenylpropyl alcohol; and alkenyl alcohols such as allyl alcohol and crotonyl alcohol. These acrylic monomers may be used as a single polymer, or may be copolymerized with other types of monomers. Specific examples of other types of monomers in this case include styrene and its derivatives, such as methylstyrene, dimethylstyrene,
Alkylstyrenes such as trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene , and further include nitrostyrene, acetylstyrene, methoxystyrene, and the like. Additionally, addition polymerizable unsaturated carboxylic acids, namely α
- addition-polymerizable unsaturated aliphatic monocarboxylic acids such as ethyl acrylic acid, crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, tiglic acid, ungellic acid, or maleic acid,
Examples include addition-polymerizable unsaturated aliphatic dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and dihydromuconic acid.
Furthermore, various metal salts of these carboxylic acids can also be used, and this metal salt formation can be carried out after the completion of polymerization. Also included are esterification products of the addition-polymerizable unsaturated carboxylic acid and alcohols such as the alkyl alcohols, halogenated alkyl alcohols, aralkyl alcohols, and alkenyl alcohols. Also, amides and nitrites derived from the addition-polymerizable unsaturated carboxylic acids; aliphatic monoolefins such as ethylene, propylene, butene, and isobutylene; 1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-butadiene, 2,
Examples include conjugated diene-based aliphatic diolefins such as 3-dimethyl-1,3-butadiene, 2,4-hexadiene, and 3-methyl-2,4-hexadiene. Furthermore, vinyl acetates, vinyl ethers; vinylcarbazole, vinylpyridine, vinylpyrrolidone, etc., 2-pinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, 2-vinyl-5-methylpyridine, 4-butenylpyridine, -Pentylpyridine, N-vinylpiperidine, 4-vinylpiperidine, N-vinyldihydropyridine, N-vinylpyrrole, 2-vinylpyrrole, N-vinylpyrrole, N-vinylpyrrolidine, 2-vinylpyrrolidine, N-vinyl 2-pyrrolidone , N-vinyl-2-piperidone, and N-vinylcarbanol. The fine powder having an average particle size smaller than the average particle size of the toner powder used in the present invention can be obtained by polymerization using various polymerization methods. That is, not only polymers made into particles by emulsion polymerization, soap-free emulsion polymerization, suspension polymerization, etc., but also polymers obtained by each of the above polymerization methods, solution polymerization, bulk polymerization, etc. are dissolved in a solvent and then spray-dried. A fine powder granulated by a method or a fine powder obtained by a method such as mechanical pulverization can be used. The above-mentioned fine powder can be in any shape such as amorphous, spherical, flat, granular, etc., but it is particularly preferable to use a substantially spherical powder. This fine powder is mixed into the developer. That is, this fine powder is first mixed with toner particles or carrier particles, and then this mixture is mixed into a developer, or the fine powder is mixed directly into a developer. The fine powder according to the present invention is not limited to the use of only one type, but a plurality of types can be used in combination. Further, the fine powder according to the present invention can be used in combination with other additives. The average particle size of the fine powder according to the present invention needs to be smaller than the average particle size of the toner powder, but preferably
A particle size of 0.05 to 5 μm, more preferably 0.1 to 2 μm gives good results. The amount of fine powder added according to the present invention is
0.01 to 10% by weight can be used, more preferably 0.05 to 2.0% by weight gives good results. The toner used in the developer of the present invention has a colorant dispersed in a styrene resin, and the styrene resin herein refers to a polymer or copolymer containing a styrene monomer as a main component. . Specific examples of the styrene monomer include the above-mentioned styrene and its derivatives. Specific examples of monomers that can be copolymerized with styrene include the above-mentioned acrylic monomers,
Namely, esterified products of acrylic acid and methacrylic acid; the above-mentioned polymerizable unsaturated carboxylic acids, their esterified products, amides and nitriles thereof; the above-mentioned aliphatic monoolefins; and the above-mentioned conjugated diene-based aliphatic diolefins. Furthermore, vinyl chloride, vinyl bromide, vinyl iodide,
1,2-dichloroethylene, 1,2-dibromoethylene, 1,2-diiodoethylene, isopropenyl chloride, isopropenyl bromide, allyl chloride, allyl bromide, vinylidene chloride, vinyl fluoride, vinylidene fluoride Examples include halogenated aliphatic olefins such as. The toner can contain various dyes, pigments, and carbon black as colorants. Copper phthalocyanine or its derivatives are also used as charge control agents, but particularly effective are
2:1 type metal complexes of O,O'-dihydroxyazo dyes, especially chromium complexes. This is expressed by the following general formula. In the above formula, X, Y, Z, X', Y', and Z' each represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, a carbonyl group, a hydroxyl group, a sulfone group, a sulfonamide group, etc. express. Furthermore, Z may be an atomic group bonded to a substituted or unsubstituted phenyl group via an amide bond. A represents H, an alkali metal, an aliphatic ammonium, or a pyridinium cation. The carrier used in the developer according to the present invention is obtained by coating a core selected from iron powder, ferrite powder, magnetite powder, glass beads, etc. with silicone resin. Here, as the silicon resin, for example, (1) SiO 2 , CH 3 SiC 3/2 ,
A copolymer made by combining the structural units of (CH 3 ) 2 SiO and (CH 3 ) 3 SiO 1/2 , (2) CH 3 SiO 3/2 ,
( CH3 ) 2SiO , C6H5SiO3 / 2 , ( C6H5 )( CH3 )SiO,
It is a copolymer made by combining structural units of (C 6 H 5 ) 2 SiO, and it hardens into a three-dimensional structural polymer. Furthermore, so-called acrylic-modified silicone resins, alkyd-modified silicone resins, and epoxy silicone resins that are modified from such polymers are also included. It can be obtained by spraying a silicone resin dissolved in a carrier solvent onto the core and drying it, but it is preferable to dry at a relatively high temperature or to harden it in an electric furnace after drying. The developer of the present invention can develop an electrostatic latent image formed on a photoreceptor or an electrostatic recording medium. That is, an electrostatic latent image is electrophotographically formed on a photoreceptor made of an inorganic photoconductive material such as selenium, zinc oxide, cadmium sulfide, or amorphous silicon, or an organic photoconductive material such as a phthalocyanine pigment or a bisazo pigment; An electrostatic latent image is formed on an electrostatic recording medium having a dielectric material such as polyethylene terephthalate using a needle-like electrode, and a book is printed on the electrostatic latent image using a developing method such as a magnetic brush method, a cascade method, or a touch-down method. A toner image is formed by adhering the developer of the invention. After this toner image is transferred to a transfer material such as paper, it is fixed and becomes a copy, and the toner remaining on the surface of the photoreceptor etc. is cleaned. As the cleaning method, various methods such as a blade method, a brush method, a web method, and a roll method can be used. Effects of the Invention The effects obtained by the developer of the invention are as follows. 1. Poor cleaning can be prevented. When cleaning the toner remaining on the photoreceptor, etc., the developer containing the fine powder of the present invention will not cause cleaning defects even if 50,000 copies are made. On the other hand, with developers using conventionally known additives, although sufficient cleaning can be achieved initially, the cleaning performance gradually decreases and
If the number of copies exceeds 30,000, toner remains in the form of an image on the photoreceptor, resulting in afterimages or band-like black streaks on the next copy. 2. The life of the developer can be extended. The developing ability of a developer, particularly the triboelectric charging ability, gradually decreases, and this decrease is particularly likely to occur in developers using conventional additives. However, the developer according to the present invention is less likely to cause a decrease in developing ability, and even after 50,000 copies are made, even for originals with an image density of 0.7, which is particularly susceptible to such effects,
There is almost no decrease in the density of the copied image. Furthermore, it is not affected by high temperature and high humidity environments. 3. The photoreceptor is not easily damaged and toner filming does not occur. The present invention will be explained in more detail below using Examples and Comparative Examples, but the scope of the present invention is not limited in any way by the Examples below. In each example, all parts represent parts by weight. Example Styrene-butyl methacrylate copolymer 88 parts O,O'-dihydroxyazo dye chromium complex
By mixing 2 parts with 10 parts of carbon black, a toner with a particle diameter of 12 microns was obtained after kneading, pulverization, and classification.For 100 parts of this toner, methyl methacrylate fine powder obtained by soap-free emulsion polymerization (particle size 0.5 micron) was added and mixed in a Henschel mill to obtain a toner according to the present invention. On the other hand, methylphenylsiloxane was applied to 100 micron iron powder using a solvent in a fluidized bed and dried and hardened to obtain a carrier. 3 parts of toner were sufficiently mixed with 100 parts of this carrier to obtain a developer according to the present invention. Comparative Example A control developer was obtained in the same manner as in the example except that no fine powder was added. Experiment When the developers obtained in the Examples and Comparative Examples were put into a Fuji Xerox copying machine FX4370 and an actual running test was conducted on 100,000 copies, the results shown in the table below were obtained, indicating that the developer of the present invention The effectiveness of the drug has become clear.
【表】
枚数。
[Table] Number of sheets.
Claims (1)
前記キヤリヤとの摩擦帯電により負に帯電するト
ナー粉末と、このトナー粉末の平均粒径よりも小
さい平均粒径を有する微粉末とを混合してなり、
前記微粉末は、アクリル酸エステルモノマー、メ
タクリル酸エステルモノマー、スチレン系モノマ
ー、含窒素付加重合性モノマー、重合性不飽和カ
ルボン酸モノマーから選択される1種類以上のモ
ノマーから得られる単独もしくは共重合体からな
り、0.05〜5μmの平均粒径を有することを特徴と
する電子写真二成分現像剤。 2 トナー粉末がスチレン系樹脂中に着色剤と帯
電制御剤を含有してなり、前記帯電制御剤がO,
O′−ジヒドロキシアゾ染料のクロム錯塩である
ことを特徴とする特許詳求の範囲第1項に記載の
電子写真二成分現像剤。[Claims] 1. A carrier whose surface is coated with silicone resin;
A toner powder that is negatively charged due to frictional charging with the carrier and a fine powder having an average particle size smaller than the average particle size of the toner powder are mixed,
The fine powder is a single or copolymer obtained from one or more monomers selected from acrylic acid ester monomers, methacrylic acid ester monomers, styrene monomers, nitrogen-containing addition polymerizable monomers, and polymerizable unsaturated carboxylic acid monomers. 1. An electrophotographic two-component developer characterized by having an average particle size of 0.05 to 5 μm. 2. The toner powder contains a colorant and a charge control agent in a styrene resin, and the charge control agent contains O,
The electrophotographic two-component developer according to item 1 of the claims, characterized in that it is a chromium complex salt of O'-dihydroxyazo dye.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59041314A JPS60186864A (en) | 1984-03-06 | 1984-03-06 | Developer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59041314A JPS60186864A (en) | 1984-03-06 | 1984-03-06 | Developer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60186864A JPS60186864A (en) | 1985-09-24 |
JPH023174B2 true JPH023174B2 (en) | 1990-01-22 |
Family
ID=12605044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59041314A Granted JPS60186864A (en) | 1984-03-06 | 1984-03-06 | Developer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60186864A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2775209B2 (en) * | 1992-04-17 | 1998-07-16 | セイコーインスツルメンツ株式会社 | DC motor |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63284564A (en) * | 1987-05-15 | 1988-11-21 | Konica Corp | Developer for negative charge latent image |
JP3767846B2 (en) | 1999-05-28 | 2006-04-19 | 株式会社リコー | Toner for developing electrostatic image and image forming method |
JP4189923B2 (en) | 2004-06-25 | 2008-12-03 | 株式会社リコー | Image forming method, image forming apparatus using the same, and process cartridge |
-
1984
- 1984-03-06 JP JP59041314A patent/JPS60186864A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2775209B2 (en) * | 1992-04-17 | 1998-07-16 | セイコーインスツルメンツ株式会社 | DC motor |
Also Published As
Publication number | Publication date |
---|---|
JPS60186864A (en) | 1985-09-24 |
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