JP5095366B2 - Positively chargeable toner for electrophotography - Google Patents
Positively chargeable toner for electrophotography Download PDFInfo
- Publication number
- JP5095366B2 JP5095366B2 JP2007305959A JP2007305959A JP5095366B2 JP 5095366 B2 JP5095366 B2 JP 5095366B2 JP 2007305959 A JP2007305959 A JP 2007305959A JP 2007305959 A JP2007305959 A JP 2007305959A JP 5095366 B2 JP5095366 B2 JP 5095366B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- average particle
- weight
- silica
- alumina
- 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.)
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- 239000002245 particle Substances 0.000 claims description 109
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- -1 polytetrafluoroethylene Polymers 0.000 claims description 64
- 239000000654 additive Substances 0.000 claims description 53
- 239000000377 silicon dioxide Substances 0.000 claims description 51
- 230000000996 additive effect Effects 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- 239000010419 fine particle Substances 0.000 claims description 34
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 31
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 14
- 229920001225 polyester resin Polymers 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 108091008695 photoreceptors Proteins 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000004645 polyester resin Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000001993 wax Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910020813 Sn-C Inorganic materials 0.000 description 3
- 229910020923 Sn-O Inorganic materials 0.000 description 3
- 229910018732 Sn—C Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- WBYCJULRJZHBGH-UHFFFAOYSA-N 3-dec-1-enylhexane-1,2,5,6-tetracarboxylic acid Chemical compound CCCCCCCCC=CC(C(CC(O)=O)C(O)=O)CC(CC(O)=O)C(O)=O WBYCJULRJZHBGH-UHFFFAOYSA-N 0.000 description 2
- UQGSHTCAJPRGCF-UHFFFAOYSA-N 3-hept-1-enyl-4-methylhexane-1,2,5,6-tetracarboxylic acid Chemical compound CCCCCC=CC(C(CC(O)=O)C(O)=O)C(C)C(CC(O)=O)C(O)=O UQGSHTCAJPRGCF-UHFFFAOYSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 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
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 2
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GWCHPNKHMFKKIQ-UHFFFAOYSA-N hexane-1,2,5-tricarboxylic acid Chemical compound OC(=O)C(C)CCC(C(O)=O)CC(O)=O GWCHPNKHMFKKIQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 2
- WDAISVDZHKFVQP-UHFFFAOYSA-N octane-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CCCCC(C(O)=O)CC(O)=O WDAISVDZHKFVQP-UHFFFAOYSA-N 0.000 description 2
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- PXRFIHSUMBQIOK-CVBJKYQLSA-L (z)-octadec-9-enoate;tin(2+) Chemical compound [Sn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O PXRFIHSUMBQIOK-CVBJKYQLSA-L 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- 229940084778 1,4-sorbitan Drugs 0.000 description 1
- URMOYRZATJTSJV-UHFFFAOYSA-N 2-(10-methylundec-1-enyl)butanedioic acid Chemical compound CC(C)CCCCCCCC=CC(C(O)=O)CC(O)=O URMOYRZATJTSJV-UHFFFAOYSA-N 0.000 description 1
- LIDLDSRSPKIEQI-UHFFFAOYSA-N 2-(10-methylundecyl)butanedioic acid Chemical compound CC(C)CCCCCCCCCC(C(O)=O)CC(O)=O LIDLDSRSPKIEQI-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
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- VGKYEIFFSOPYEW-UHFFFAOYSA-N 2-methyl-4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound Cc1cc(ccc1O)N=Nc1ccc(cc1)N=Nc1ccccc1 VGKYEIFFSOPYEW-UHFFFAOYSA-N 0.000 description 1
- XYHGSPUTABMVOC-UHFFFAOYSA-N 2-methylbutane-1,2,4-triol Chemical compound OCC(O)(C)CCO XYHGSPUTABMVOC-UHFFFAOYSA-N 0.000 description 1
- SZJXEIBPJWMWQR-UHFFFAOYSA-N 2-methylpropane-1,1,1-triol Chemical compound CC(C)C(O)(O)O SZJXEIBPJWMWQR-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- MFZOUWVHEQAVLP-UHFFFAOYSA-N 3-(10-methylundec-1-enyl)oxolane-2,5-dione Chemical compound CC(C)CCCCCCCC=CC1CC(=O)OC1=O MFZOUWVHEQAVLP-UHFFFAOYSA-N 0.000 description 1
- MAZRKDBLFYSUFV-UHFFFAOYSA-N 3-[(1-anilino-1,3-dioxobutan-2-yl)diazenyl]-2-hydroxy-5-nitrobenzenesulfonic acid chromium Chemical compound CC(=O)C(C(=O)NC1=CC=CC=C1)N=NC2=C(C(=CC(=C2)[N+](=O)[O-])S(=O)(=O)O)O.[Cr] MAZRKDBLFYSUFV-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 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
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
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Landscapes
- Developing Agents For Electrophotography (AREA)
Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられる電子写真用正帯電性トナーに関する。 The present invention relates to a positively chargeable toner for electrophotography used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
従来、トナーの流動性や帯電性を向上する目的で、外添剤についての検討が多く行われている。例えば、特許文献１では、感光体フィルミングを生じることなく、トナーの流動性及び帯電性を適正に保ち、トナー濃度を所定の値にコントロールでき、画像濃度の低下を防止することを目的に、平均粒径100〜1000nmのポリテトラフルオロエチレン及び平均粒径5〜300nmのシリカが外添され、前記シリカのうち、平均粒径20〜300nmのシリカがトナー母粒子100重量部に対して2.5重量部以上外添された二成分現像方式に用いられるトナーが開示されている。 Conventionally, many studies have been made on external additives for the purpose of improving toner fluidity and chargeability. For example, in Patent Document 1, without causing photoconductor filming, the toner fluidity and chargeability are appropriately maintained, the toner density can be controlled to a predetermined value, and the decrease in image density is prevented. Polytetrafluoroethylene having an average particle size of 100 to 1000 nm and silica having an average particle size of 5 to 300 nm are externally added. Among the silicas, silica having an average particle size of 20 to 300 nm is 2.5 wt. A toner for use in a two-component development system in which more than one part is externally added is disclosed.
また、感光体カブリが少なく、感光体の耐久性を高めることを目的に、トナー粒子の表面に１次粒子径0.05μm以上0.5μm未満であるポリテトラフルオロエチレン微粒子が添加されている、非磁性一成分現像方式に用いられる正帯電性トナーが開示されている(特許文献２参照)。
しかしながら、特許文献１のようにシリカを含有したトナー、なかでも、平均粒子径が小さいシリカを含有したトナーを感光体が新品である現像機に実装した場合、使用初期にカブリが発生し、その後、使用を継続するとカブリが解消する場合があることが判明した。この原因の詳細は不明であるが、新品の感光体の表面は平均粒子径の小さいシリカが付着し易く、シリカの付着によりカブリが生じたと推定される。 However, when a toner containing silica as in Patent Document 1, especially a toner containing silica having a small average particle diameter is mounted on a developing machine whose photoconductor is new, fog occurs at the initial stage of use, and thereafter It has been found that the fog may be resolved if the use is continued. Although the details of the cause are unknown, it is presumed that silica having a small average particle diameter is likely to adhere to the surface of a new photoreceptor, and fogging has occurred due to the adhesion of silica.
本発明の課題は、感光体使用初期のカブリが抑制される電子写真用正帯電性トナーを提供することにある。 An object of the present invention is to provide a positively chargeable toner for electrophotography in which fogging at the initial stage of use of a photoreceptor is suppressed.
本発明者らは、上記課題を解決する為に検討を重ねた結果、それぞれ特定の平均粒子径を有するシリカとポリテトラフルオロエチレンに加えて、シリカより平均粒子径の小さい疎水化処理されたアルミナを外添剤として特定量併用することにより、感光体使用初期のカブリが抑制されたトナーが得られることを見出し、本発明を完成するに至った。 As a result of repeated studies to solve the above problems, the present inventors have made a hydrophobized alumina having an average particle size smaller than silica in addition to silica and polytetrafluoroethylene each having a specific average particle size. It has been found that a toner in which fogging at the initial stage of use of the photoreceptor is suppressed can be obtained by using a specific amount of as an external additive, and the present invention has been completed.
即ち、本発明は、結着樹脂及び着色剤を含有するトナー母粒子に外添剤を外添してなる電子写真用トナーであって、前記結着樹脂がポリエステル系樹脂を含有してなり、前記外添剤として、平均粒子径5nm以上50nm未満の疎水化処理されたアルミナと、平均粒子径50〜300nmのシリカと、平均粒子径100〜1000nmのポリテトラフルオロエチレン微粒子とを外添してなり、平均粒子径50nm未満の外添剤中、前記疎水化処理されたアルミナの含有量が60重量％以上である、電子写真用正帯電性トナーに関する。 That is, the present invention is an electrophotographic toner obtained by externally adding an external additive to a toner base particle containing a binder resin and a colorant, wherein the binder resin contains a polyester resin, As the external additive, hydrophobized alumina having an average particle size of 5 nm or more and less than 50 nm, silica having an average particle size of 50 to 300 nm, and polytetrafluoroethylene fine particles having an average particle size of 100 to 1000 nm are externally added. The present invention relates to a positively chargeable toner for electrophotography, wherein the content of the hydrophobized alumina in the external additive having an average particle diameter of less than 50 nm is 60% by weight or more.
本発明の電子写真用正帯電性トナーは、感光体使用初期のカブリが抑制されるという優れた効果を奏するものである。 The positively chargeable toner for electrophotography of the present invention has an excellent effect that fog in the initial stage of use of the photoreceptor is suppressed.
本発明の電子写真用正帯電性トナーは、結着樹脂及び着色剤を含有するトナー母粒子に外添剤を外添するトナーであって、前記外添剤として、平均粒子径5nm以上50nm未満の疎水化処理されたアルミナと、平均粒子径50〜300nmのシリカと、平均粒子径100〜1000nmのポリテトラフルオロエチレン微粒子とを添加してなり、かつ、平均粒子径50nm未満の外添剤中、疎水化処理されたアルミナの含有量が特定量であることに１つの特徴を有する。 The positively chargeable toner for electrophotography of the present invention is a toner in which an external additive is externally added to a toner base particle containing a binder resin and a colorant, and the external additive has an average particle diameter of 5 nm or more and less than 50 nm. Of the hydrophobized alumina, silica having an average particle diameter of 50 to 300 nm, and polytetrafluoroethylene fine particles having an average particle diameter of 100 to 1000 nm, and in an external additive having an average particle diameter of less than 50 nm One feature is that the content of the hydrophobized alumina is a specific amount.
カブリは、トナーから遊離したシリカ等の微粒子が感光体表面に付着し、感光体の帯電性を低下させることにより発生するものである。とりわけ、未使用の感光体表面は平滑であることから、シリカ等の微粒子が付着しやすいために、カブリが発生しやすくなる。しかし、本発明においては、初期カブリの原因の一つである、感光体表面へのシリカ等の微粒子付着を防止できる。これは、一定の平均粒子径を有する、研磨性が高いアルミナ微粒子を使用することにより、感光体表面に微細な凹凸構造を形成させて、シリカ等の微粒子が感光体表面に付着しにくくなるためと考えられる。 Fog is generated when fine particles such as silica released from the toner adhere to the surface of the photoreceptor and lower the chargeability of the photoreceptor. In particular, since the unused photoreceptor surface is smooth, fine particles such as silica are likely to adhere, and thus fog is likely to occur. However, in the present invention, it is possible to prevent fine particles such as silica from adhering to the surface of the photoreceptor, which is one of the causes of initial fogging. This is because the use of alumina fine particles having a constant average particle diameter and high polishing properties makes it possible to form a fine uneven structure on the surface of the photoconductor, making it difficult for fine particles such as silica to adhere to the surface of the photoconductor. it is conceivable that.
また、本発明においては、正帯電性トナーの帯電性を長期に渡って良好に保つ観点から、平均粒子径50〜300nmのシリカと、平均粒子径100〜1000nmのポリテトラフルオロエチレン微粒子を併用する。これは、トナー母粒子から遊離しやすい大粒径の外添剤として、正帯電性のトナー母粒子に対して逆極性のポリテトラフルオロエチレン微粒子を添加することによりトナー母粒子からの大粒径外添剤の遊離を抑制することができ、その結果、トナー母粒子と前記ポリテトラフルオロエチレン微粒子の間で、帯電ブレード通過時や帯電ブレード通過前に摩擦帯電が発生し、トナー母粒子及びアルミナ粒子の帯電性が良好になるという優れた効果が奏されると推定される。また、かかる効果は、負帯電性のポリテトラフルオロエチレン微粒子と、疎水化処理されたアルミナ及びシリカとを併用することにより、ポリテトラフルオロエチレン微粒子を併用しない場合と比べて、より強固にアルミナ及びシリカがトナー母粒子に付着される点でも、初期カブリ抑制に寄与していると考えられる。さらに、アルミナの外添量が多くなると、長期使用時に上記効果が安定して発揮され、耐久性に優れることとなり、該アルミナが特定の疎水化処理剤により処理されたものである場合には、アルミナ表面に適正な帯電性が付与されるため、初期カブリ抑制がより安定して奏されるものと推定される。 In the present invention, silica having an average particle size of 50 to 300 nm and polytetrafluoroethylene fine particles having an average particle size of 100 to 1000 nm are used in combination from the viewpoint of maintaining good chargeability of the positively chargeable toner over a long period of time. . This is because, as an external additive having a large particle size that is easily released from the toner mother particles, polytetrafluoroethylene fine particles having a reverse polarity are added to the positively charged toner mother particles, thereby increasing the particle size from the toner mother particles. The release of the external additive can be suppressed, and as a result, frictional charging occurs between the toner base particles and the polytetrafluoroethylene fine particles when passing through the charging blade or before passing through the charging blade. It is presumed that an excellent effect of improving the chargeability of the particles is achieved. In addition, such an effect can be obtained by using negatively charged polytetrafluoroethylene fine particles together with hydrophobized alumina and silica in a stronger manner than when polytetrafluoroethylene fine particles are not used together. It is considered that silica is also attached to the toner base particles and contributes to suppression of initial fogging. Further, when the amount of external addition of alumina is increased, the above effect is stably exhibited during long-term use, and the durability is excellent.When the alumina is treated with a specific hydrophobizing agent, Since proper chargeability is imparted to the alumina surface, it is presumed that the initial fog suppression is more stably performed.
本発明における外添剤としては、平均粒子径5nm以上50nm未満の疎水化処理されたアルミナ(以下、外添剤Ａと記載することもある)と、平均粒子径50〜300nmのシリカ(以下、外添剤Ｂと記載することもある)と、平均粒子径100〜1000nmのポリテトラフルオロエチレン微粒子(以下、外添剤Ｃと記載することもある)を用いる。 Examples of the external additive in the present invention include hydrophobized alumina having an average particle size of 5 nm or more and less than 50 nm (hereinafter sometimes referred to as external additive A), and silica having an average particle size of 50 to 300 nm (hereinafter referred to as “external additive A”). External additive B) and polytetrafluoroethylene fine particles having an average particle size of 100 to 1000 nm (hereinafter sometimes referred to as external additive C) are used.
外添剤Ａのアルミナは疎水化処理が施されており、疎水化処理剤としては、ヘキサメチルジシラザン(HMDS)、ジメチルジクロロシラン(DMDS)、アミノシラン、オクチルシラン、シリコーンオイル等が挙げられる。なかでも、ポリテトラフルオロエチレン微粒子との帯電性の観点から、アミノシラン、オクチルシラン、シリコーンオイルが好ましく、適正な帯電性、及び流動性の観点から、アミノシランとシリコーンオイルを併用することが好ましい。また、正帯電性を呈することからもアミノシランとシリコーンオイルで処理疎水化処理することが好ましい。アミノシランとシリコーンオイルの処理量比(アミノシラン/シリコーンオイル)は、トナーの帯電性の観点から、1/10〜10/1が好ましく、1/5〜5/1がより好ましい。なお、疎水化処理の方法は特に限定されず、疎水化処理剤の処理量は、アルミナの表面積当たり1〜7mg/m2が好ましい。 The alumina of the external additive A is hydrophobized, and examples of the hydrophobizing agent include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), aminosilane, octylsilane, and silicone oil. Of these, aminosilane, octylsilane, and silicone oil are preferable from the viewpoint of chargeability with the polytetrafluoroethylene fine particles, and aminosilane and silicone oil are preferably used in combination from the viewpoint of appropriate chargeability and fluidity. Moreover, it is preferable to perform the hydrophobization treatment with aminosilane and silicone oil from the viewpoint of exhibiting positive chargeability. The treatment amount ratio of aminosilane to silicone oil (aminosilane / silicone oil) is preferably from 1/10 to 10/1, more preferably from 1/5 to 5/1, from the viewpoint of toner chargeability. The method for the hydrophobizing treatment is not particularly limited, and the treatment amount of the hydrophobizing agent is preferably 1 to 7 mg / m 2 per alumina surface area.
アルミナは、平均粒子径が5nm以上である場合には感光体表面の適度な研磨性が得られ、感光体の表面の凹凸形状を適正に保つことができる。また、50nm未満である場合は、感光体表面の研磨性が過度になり過ぎず、感光体磨耗が生じにくく、感光体の寿命を長くすることができる。従って、これらの観点から、外添剤Ａの平均粒子径は、5nm以上50nm未満であり、好ましくは5〜30nmであり、より好ましくは5〜20nmである。本明細書において、アルミナ等の外添剤の平均粒子径とは、外添する際の個々の外添剤の粒径のことであり、平均粒子径の異なる２種以上を混合して用いる場合は、混合する前のそれぞれの平均粒子径を意味する。平均粒子径の測定は、後述の実施例に記載の方法により測定される。 When the average particle size of alumina is 5 nm or more, moderate polishing properties of the surface of the photoreceptor can be obtained, and the uneven shape of the surface of the photoreceptor can be appropriately maintained. On the other hand, when the thickness is less than 50 nm, the surface of the photoconductor is not excessively polished, the photoconductor is hardly worn, and the life of the photoconductor can be extended. Therefore, from these viewpoints, the average particle diameter of the external additive A is 5 nm or more and less than 50 nm, preferably 5 to 30 nm, and more preferably 5 to 20 nm. In this specification, the average particle diameter of an external additive such as alumina is the particle diameter of each external additive at the time of external addition. When two or more kinds having different average particle diameters are mixed and used Means the average particle diameter before mixing. The average particle diameter is measured by the method described in Examples described later.
外添剤Ｂの平均粒子径は、シリカ埋没防止によるトナーの耐久性向上及び流動性付与の観点から、50〜300nmであり、好ましくは50〜200nmであり、より好ましくは50〜100nmである。 The average particle diameter of the external additive B is 50 to 300 nm, preferably 50 to 200 nm, and more preferably 50 to 100 nm, from the viewpoint of improving the durability of the toner by preventing silica embedding and imparting fluidity.
シリカは公知の方法で製造されたものを用いることできるが、シリカの分散性の観点から、乾式法、高温加水分解法により製造されたものが好ましい。また、無水シリカのほか、ケイ酸アルミニウム、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸マグネシウム、ケイ酸亜鉛などを含有するものであってもよいが、SiO2を80重量％以上含むものが好ましく、85重量％以上含むものがより好ましい。 Although what was manufactured by the well-known method can be used for a silica, what was manufactured by the dry process and the high temperature hydrolysis method from a dispersible viewpoint of a silica is preferable. In addition to anhydrous silica, it may contain aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate, etc., but preferably contains SiO 2 at 80% by weight or more, Those containing 85% by weight or more are more preferable.
また、シリカは、ポリテトラフルオロエチレン微粒子との帯電による相互作用の観点から、疎水化処理された疎水性シリカであるのが好ましい。疎水化の方法は特に限定されず、疎水化処理剤としては、アルミナの疎水化処理に用いられる処理剤と同様の処理剤を使用することができる。これらの処理剤のなかでは、トナーの適正な帯電性、及び流動性の観点から、アミノシランとシリコーンオイルを併用することが好ましく、前記処理剤により疎水化処理されたシリカは正帯電性を呈し、負帯電性のポリテトラフルオロエチレン微粒子と併用することにより、より安定したトナーの帯電性向上効果を奏する。疎水化処理剤の処理量は、シリカの表面積当たり1〜7mg/m2が好ましい。 Further, the silica is preferably a hydrophobic silica that has been subjected to a hydrophobization treatment from the viewpoint of interaction with the polytetrafluoroethylene fine particles due to charging. The method of hydrophobizing is not particularly limited, and as the hydrophobizing agent, a treating agent similar to the treating agent used for the hydrophobizing treatment of alumina can be used. Among these treatment agents, aminosilane and silicone oil are preferably used in combination from the viewpoint of proper chargeability and fluidity of the toner, and silica hydrophobized with the treatment agent exhibits positive chargeability, By using in combination with negatively charged polytetrafluoroethylene fine particles, a more stable toner charging effect can be obtained. The treatment amount of the hydrophobizing agent is preferably 1 to 7 mg / m 2 per silica surface area.
外添剤Ｃの平均粒子径は、100〜1000nmであり、好ましくは100〜800nmであり、より好ましくは150〜600nmである。平均粒子径が100nm以上であると、連続印字時にトナー母粒子に外添された該微粒子がトナー中に埋め込まれ難いと考えられ、効果の発現が持続しやすく、1000nm以下であると、トナーから遊離した粒子が適度に存在し、本発明の効果を発現し易い。ここで、外添剤Ｃ、即ち、ポリテトラフルオロエチレン微粒子の平均粒子径は、電子顕微鏡写真から測定した１次粒子の粒子径を数平均して算出したものである。 The average particle diameter of the external additive C is 100 to 1000 nm, preferably 100 to 800 nm, and more preferably 150 to 600 nm. When the average particle size is 100 nm or more, it is considered that the fine particles externally added to the toner base particles during continuous printing are difficult to be embedded in the toner, and the effect is easily maintained. The liberated particles are present moderately and the effects of the present invention are easily exhibited. Here, the average particle diameter of the external additive C, that is, the polytetrafluoroethylene fine particles is calculated by averaging the particle diameters of the primary particles measured from the electron micrograph.
このようなポリテトラフルオロエチレン微粒子としては、より具体的には乳化重合により製造された球形に近い形状のもの等が挙げられる。これらは市販されており、例えば「KTL-500F」(喜多村社製、平均粒子径500nm)、「ルブロン L2」(ダイキン工業社製、平均粒子径300nm)、「ルブロン L5」(ダイキン工業社製、平均粒子径200nm)、「フルオン ルブリカント L170J」(旭アイシーアイフロロポリマーズ社製、平均粒子径100nm)、「フルオン ルブリカント L172J」(旭アイシーアイフロロポリマーズ社製、平均粒子径100nm)、「MP-1100」(三井・デュポンフロロケミカル社製、平均粒子径200nm)、「MP-1200」(三井・デュポンフロロケミカル社製、平均粒子径300nm)、「TLP-10F-1」(三井・デュポンフロロケミカル社製、平均粒子径200nm)等が挙げられる。 More specific examples of such polytetrafluoroethylene fine particles include those having a shape close to a sphere produced by emulsion polymerization. These are commercially available, for example, `` KTL-500F '' (manufactured by Kitamura, average particle size 500 nm), `` Lublon L2 '' (manufactured by Daikin Industries, average particle size 300 nm), `` Lublon L5 '' (manufactured by Daikin Industries, (Average particle size 200 nm), `` Fullon Lubricant L170J '' (Asahi ICC Fluoropolymers, average particle size 100 nm), `` Fullon Lubricant L172J '' (Asahi ICC Fluoropolymers, average particle size 100 nm), `` MP-1100 (Mitsui / DuPont Fluorochemicals, average particle size 200 nm), MP-1200 (Mitsui / DuPont Fluorochemicals, average particle size 300 nm), TLP-10F-1 (Mitsui / DuPont Fluorochemicals) And an average particle diameter of 200 nm).
外添剤Ａの外添量は、感光体表面の研磨性、トナーの耐久性の観点から、トナー母粒子100重量部に対して、0.1〜5.0重量部が好ましく、1.0〜4.0重量部がより好ましく、2.0〜3.0重量部がさらに好ましい。 The external addition amount of the external additive A is preferably 0.1 to 5.0 parts by weight, more preferably 1.0 to 4.0 parts by weight with respect to 100 parts by weight of the toner base particles, from the viewpoint of the abrasiveness of the photoreceptor surface and the durability of the toner. Preferably, 2.0 to 3.0 parts by weight are more preferable.
外添剤Ｂの外添量は、トナーの流動性適正化の観点から、トナー母粒子100重量部に対して、0.1〜5.0重量部が好ましく、0.3〜4.0重量部がより好ましく、0.5〜3.0重量部がさらに好ましい。 The external addition amount of the external additive B is preferably 0.1 to 5.0 parts by weight, more preferably 0.3 to 4.0 parts by weight, and more preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the toner base particles from the viewpoint of optimizing the fluidity of the toner. Part by weight is more preferred.
外添剤Ｃの外添量は、トナー母粒子100重量部に対して、0.01〜1.5重量部であることが好ましく、0.05〜1.0重量部であることがより好ましい。添加量が、上記範囲より多いと、トナーの流動性・搬送性の適正量より小さくなり、画像濃度が低くなる傾向があり、この範囲より少ないと、トナーの流動性・搬送性の適正量より大きくなり、画像上及び感光体上のカブリが多くなる傾向がある。 The amount of external additive C added is preferably 0.01 to 1.5 parts by weight, more preferably 0.05 to 1.0 parts by weight, based on 100 parts by weight of toner base particles. If the added amount is larger than the above range, the toner tends to be smaller than the appropriate amount of fluidity / conveyance and the image density tends to be low. There is a tendency that fog is increased on the image and the photosensitive member.
外添剤Ａとシリカ（外添剤Ｂを含む）の重量比(外添剤Ａ/シリカ)は、初期カブリ抑制の観点から、0.4〜6であることが好ましく、0.5〜5であることがより好ましい。さらにシリカは、外添剤Ｂ以外の平均粒子径が50nm未満及び300nm超のシリカの含有量が少ないことが好ましく、外添剤Ａと外添剤Ｂの重量比(外添剤Ａ/外添剤Ｂ)は、初期カブリ抑制の観点から、0.5〜5であることが好ましく、1〜3であることがより好ましい。また、トナーの耐久性の観点から、2〜3であることが好ましい。 The weight ratio of external additive A to silica (including external additive B) (external additive A / silica) is preferably 0.4 to 6, and preferably 0.5 to 5 from the viewpoint of suppressing initial fogging. More preferred. Further, the silica preferably has a small content of silica having an average particle size other than external additive B of less than 50 nm and more than 300 nm, and the weight ratio of external additive A to external additive B (external additive A / external additive). Agent B) is preferably 0.5 to 5 and more preferably 1 to 3 from the viewpoint of suppression of initial fogging. Further, from the viewpoint of toner durability, it is preferably 2 to 3.
また、外添剤Ａと外添剤Ｃの重量比(外添剤Ａ/外添剤Ｃ)は、トナーの初期カブリ抑制の観点から1〜10であることが好ましく、2〜8であることがより好ましく、3〜6であることがさらに好ましい。また、トナーの耐久性の観点から5〜8が好ましい。 The weight ratio of the external additive A to the external additive C (external additive A / external additive C) is preferably 1 to 10 and preferably 2 to 8 from the viewpoint of suppressing initial fogging of the toner. Is more preferable, and 3 to 6 is even more preferable. Further, from the viewpoint of toner durability, 5 to 8 is preferable.
なお、本発明においては、本発明の効果を損なわない範囲で、平均粒子径5nm以上50nm未満の疎水化処理されたアルミナと、平均粒子径50〜300nmのシリカと、平均粒子径100〜1000nmのポリテトラフルオロエチレン微粒子以外の外添剤を使用してもよい。前記アルミナ、シリカ及びポリテトラフルオロエチレン微粒子の外添剤中の総含有量は、60重量％以上であることが好ましく、80重量％以上であることがより好ましく、実質的に100重量％であることがさらに好ましい。また、トナーの初期カブリ抑制の観点から、前記アルミナの含有量は、平均粒子径が50nm未満である外添剤中、60重量％以上であり、60〜100重量％が好ましく、80〜100重量％がより好ましい。さらに、平均粒子径が50nm未満のシリカは、トナーの初期カブリの抑制の観点から少ないことが好ましい。具体的には、平均粒子径が50nm未満のシリカと平均粒子径5nm以上50nm未満の疎水化処理されたアルミナの重量比(シリカ／アルミナ)が１未満であることが好ましく、0.5以下がより好ましく、0、即ち、50nm未満のシリカを実質的に含有しないことがさらに好ましい。 In the present invention, within a range not impairing the effects of the present invention, hydrophobized alumina having an average particle diameter of 5 nm or more and less than 50 nm, silica having an average particle diameter of 50 to 300 nm, and an average particle diameter of 100 to 1000 nm External additives other than polytetrafluoroethylene fine particles may be used. The total content of the alumina, silica and polytetrafluoroethylene fine particles in the external additive is preferably 60% by weight or more, more preferably 80% by weight or more, and substantially 100% by weight. More preferably. Further, from the viewpoint of suppressing initial fogging of the toner, the content of the alumina is 60% by weight or more, preferably 60 to 100% by weight, preferably 80 to 100% by weight in the external additive having an average particle diameter of less than 50 nm. % Is more preferable. Further, the amount of silica having an average particle diameter of less than 50 nm is preferably small from the viewpoint of suppressing initial fogging of the toner. Specifically, the weight ratio (silica / alumina) of silica having an average particle diameter of less than 50 nm and hydrophobized alumina having an average particle diameter of 5 nm or more and less than 50 nm is preferably less than 1, more preferably 0.5 or less. , 0, i.e., substantially no silica of less than 50 nm.
本発明におけるトナー母粒子は結着樹脂及び着色剤を含有し、低温定着性の観点から、本発明は、前記結着樹脂がポリエステル系樹脂を含有することにも１つの特徴を有する。 The toner base particles in the present invention contain a binder resin and a colorant. From the viewpoint of low-temperature fixability, the present invention also has one feature in that the binder resin contains a polyester resin.
ポリエステル系樹脂は、2価以上のアルコールからなるアルコール成分と、2価以上のカルボン酸化合物からなるカルボン酸成分を縮重合させて得られる。 The polyester resin is obtained by polycondensing an alcohol component composed of a divalent or higher alcohol and a carboxylic acid component composed of a divalent or higher carboxylic acid compound.
2価以上のアルコールとしては、式(I)： As the dihydric or higher alcohol, the formula (I):
(式中、Ｒ1Ｏはオキシアルキレン基であり、Ｒ1はエチレン及び／又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの付加モル数を示し、それぞれ正の数であり、ｘとｙの和の平均値は1〜16が好ましく、1〜8がより好ましく、1.5〜4がさらに好ましい)
で表されるビスフェノールＡのアルキレンオキサイド付加物が含有されていることが好ましい。かかるビスフェノールＡのアルキレンオキサイド付加物の含有量は、アルコール成分中、50モル％以上が好ましく、60モル％以上がより好ましく、80モル％以上がさらに好ましい。
(In the formula, R 1 O is an oxyalkylene group, R 1 is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, (The average value of the sum is preferably 1-16, more preferably 1-8, and even more preferably 1.5-4)
It is preferable that the alkylene oxide addition product of bisphenol A represented by these is contained. The content of the alkylene oxide adduct of bisphenol A is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 80 mol% or more in the alcohol component.
式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物としては、ポリオキシプロピレン(2.2)−2,2−ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(3.3)−2,2−ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン(2.0)−2,2−ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.0)−ポリオキシエチレン(2.0)−2,2−ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(6)−2,2−ビス(4-ヒドロキシフェニル)プロパン等のビスフェノールＡのアルキレン(炭素数2〜3)オキサイド(平均付加モル数1〜16)付加物等が挙げられる。 Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis. (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4- Alkylene (carbon number 2-3) oxide (average number of moles added 1-16) adducts of bisphenol A such as hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, etc. Is mentioned.
式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物以外のアルコール成分としては、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、1,2−プロピレングリコール、1,3−プロピレングリコール、1,4−ブタンジオール、ネオペンチルグリコール、1,4−ブテンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール等のジオール類、ビスフェノールＡ、水素添加ビスフェノールＡ等、その他の二価のアルコールが挙げられる。 Examples of alcohol components other than the alkylene oxide adduct of bisphenol A represented by the formula (I) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Other dihydric alcohols such as diols such as butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, etc. .
また、2価以上のカルボン酸化合物としては、例えば、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、フタル酸、イソフタル酸、テレフタル酸、シクロヘキサンジカルボン酸、コハク酸、アジピン酸、セバチン酸、アゼライン酸、マロン酸等が挙げられ、更にn-ブチルコハク酸、n-ブテニルコハク酸、イソブチルコハク酸、イソブテニルコハク酸、n-オクチルコハク酸、n-オクテニルコハク酸、n-ドデシルコハク酸、n-ドデセニルコハク酸、イソドデシルコハク酸、イソドデセニルコハク酸等の炭素数1〜20のアルキル基又は炭素数2〜20のアルケニル基で置換されたコハク酸が挙げられる。上記のような酸、これらの酸の無水物、及び酸のアルキルエステルを、本明細書では総称してカルボン酸化合物と呼ぶ。 Examples of the divalent or higher carboxylic acid compound include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, and sebacic acid. , Azelaic acid, malonic acid, and the like. -Succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid and the like. Such acids, anhydrides of these acids, and alkyl esters of these acids are collectively referred to herein as carboxylic acid compounds.
また、ポリエステルは、トナーの定着性とトナー製造時の粉砕性の観点から、アルコール成分及び／又はカルボン酸成分として3価以上のモノマーを用いて得られた架橋ポリエステルであることが好ましい。3価以上のモノマーの含有量は、アルコール成分及びカルボン酸成分の総量中、2〜50モル％が好ましく、10〜30モル％がより好ましい。 The polyester is preferably a cross-linked polyester obtained using a trivalent or higher monomer as an alcohol component and / or a carboxylic acid component from the viewpoint of toner fixing properties and pulverization properties during toner production. The content of the trivalent or higher monomer is preferably 2 to 50 mol%, more preferably 10 to 30 mol%, based on the total amount of the alcohol component and the carboxylic acid component.
3価以上のアルコールとしては、ソルビトール、1,2,3,6−ヘキサンテトロール、1,4−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、1,2,4−ブタントリオール、1,2,5−ペンタントリオール、グリセロール、2-メチルプロパントリオール、2-メチル−1,2,4−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、1,3,5−トリヒドロキシベンゼン、その他の三価以上のアルコールを挙げることができる。 Trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1, 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, other trivalent compounds The above alcohol can be mentioned.
3価以上のカルボン酸化合物としては、1,2,4−ベンゼントリカルボン酸、2,5,7−ナフタレントリカルボン酸、1,2,4−ナフタレントリカルボン酸、1,2,4−ブタントリカルボン酸、1,2,5−ヘキサントリカルボン酸、1,3−ジカルボキシル−2-メチル-2-メチレンカルボキシプロパン、テトラ(メチレンカルボキシル)メタン、1,2,7,8−オクタンテトラカルボン酸、エンポール三量体酸、その他の三価以上のカルボン酸化合物を挙げることができる。 Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer Examples thereof include body acid and other trivalent or higher carboxylic acid compounds.
また、多価カルボン酸化合物として、式(II)： Further, as the polyvalent carboxylic acid compound, the formula (II):
(式中、Ｘは炭素数3以上の側鎖を1個以上有する炭素数5〜30のアルキレン基又はアルケニレン基である)
で表されるテトラカルボン酸も挙げられる。具体的には次の(1)〜(12)に示すもの等が挙げられる。
(1) 4−ネオペンチリデニル−1,2,6,7−ヘプタンテトラカルボン酸
(2) 4−ネオペンチル−1,2,6,7−ヘプテン(4)−テトラカルボン酸
(3) 3−メチル−4−ヘプテニル−1,2,5,6−ヘキサンテトラカルボン酸
(4) 3−メチル−3−ヘプチル−5−メチル−1,2,6,7−ヘプテン(4)−テトラカルボン酸
(5) 3−ノニル−4−メチリデニル−1,2,5,6−ヘキサンテトラカルボン酸
(6) 3−デシリデニル−1,2,5,6−ヘキサンテトラカルボン酸
(7) 3−ノニル−1,2,6,7−ヘプテン(4)−テトラカルボン酸
(8) 3−デセニル−1,2,5,6−ヘキサンテトラカルボン酸
(9) 3−ブチル−3−エチレニル−1,2,5,6−ヘキサンテトラカルボン酸
(10)3−メチル−4−ブチリデニル−1,2,6,7−ヘプタンテトラカルボン酸
(11)3−メチル−4−ブチル−1,2,6,7−ヘプテン(4)−テトラカルボン酸
(12)3−メチル−5−オクチル−1,2,6,7−ヘプテン(4)−テトラカルボン酸
(In the formula, X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having one or more side chains having 3 or more carbon atoms)
The tetracarboxylic acid represented by these is also mentioned. Specific examples include the following (1) to (12).
(1) 4-Neopentylidenyl-1,2,6,7-heptanetetracarboxylic acid
(2) 4-Neopentyl-1,2,6,7-heptene (4) -tetracarboxylic acid
(3) 3-Methyl-4-heptenyl-1,2,5,6-hexanetetracarboxylic acid
(4) 3-Methyl-3-heptyl-5-methyl-1,2,6,7-heptene (4) -tetracarboxylic acid
(5) 3-Nonyl-4-methylidenyl-1,2,5,6-hexanetetracarboxylic acid
(6) 3-decylidenyl-1,2,5,6-hexanetetracarboxylic acid
(7) 3-Nonyl-1,2,6,7-heptene (4) -tetracarboxylic acid
(8) 3-decenyl-1,2,5,6-hexanetetracarboxylic acid
(9) 3-Butyl-3-ethylenyl-1,2,5,6-hexanetetracarboxylic acid
(10) 3-Methyl-4-butylidenyl-1,2,6,7-heptanetetracarboxylic acid
(11) 3-Methyl-4-butyl-1,2,6,7-heptene (4) -tetracarboxylic acid
(12) 3-Methyl-5-octyl-1,2,6,7-heptene (4) -tetracarboxylic acid
アルコール成分とカルボン酸成分との縮重合は、例えば、不活性ガス雰囲気中にて、さらには減圧下、180〜250℃の温度で行うことができるが、本発明の効果がより顕著に奏される観点から、エステル化触媒の存在下で行うことが好ましい。エステル化触媒としては、ジブチル錫オキシド、チタン化合物、Ｓｎ-Ｃ結合を有していない錫(II)化合物等が挙げられ、これらはそれぞれ単独で又は両者を併用して用いられる。これらのなかでは、本発明の効果がより顕著に奏される観点から、Ｓｎ-Ｃ結合を有していない錫(II)化合物が好ましい。 The condensation polymerization of the alcohol component and the carboxylic acid component can be performed, for example, in an inert gas atmosphere and further under reduced pressure at a temperature of 180 to 250 ° C., but the effect of the present invention is more remarkably exhibited. From the viewpoint of the production, it is preferably carried out in the presence of an esterification catalyst. Examples of esterification catalysts include dibutyltin oxide, titanium compounds, tin (II) compounds having no Sn—C bond, and the like. These may be used alone or in combination. Among these, a tin (II) compound having no Sn—C bond is preferable from the viewpoint of more remarkable effects of the present invention.
Ｓｎ-Ｃ結合を有していない錫(II)化合物としては、Ｓｎ-Ｏ結合を有する錫(II)化合物、Ｓｎ-Ｘ(Ｘはハロゲン原子を示す)結合を有する錫(II)化合物等が好ましく、Ｓｎ-Ｏ結合を有する錫(II)化合物がより好ましい。 Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferably, a tin (II) compound having a Sn—O bond is more preferable.
Ｓｎ-Ｏ結合を有する錫(II)化合物としては、シュウ酸錫(II)、酢酸錫(II)、オクタン酸錫(II)、2-エチルヘキサン酸錫(II)、ラウリル酸錫(II)、ステアリン酸錫(II)、オレイン酸錫(II)等の炭素数2〜28のカルボン酸基を有するカルボン酸錫(II)；オクチロキシ錫(II)、ラウロキシ錫(II)、ステアロキシ錫(II)、オレイロキシ錫(II)等の炭素数2〜28のアルコキシ基を有するアルコキシ錫(II)；酸化錫(II)；硫酸錫(II)等が、Ｓｎ-Ｘ(Ｘはハロゲン原子を示す)結合を有する錫(II)化合物としては、塩化錫(II)、臭化錫(II)等のハロゲン化錫(II)等が挙げられ、これらの中では、帯電立ち上がり効果及び触媒能の点から、(Ｒ1ＣＯＯ)2Ｓｎ(ここでＲ1は炭素数5〜19のアルキル基又はアルケニル基を示す)で表される脂肪酸錫(II)、(Ｒ2Ｏ)2Ｓｎ(ここでＲ２は炭素数6〜20のアルキル基又はアルケニル基を示す)で表されるアルコキシ錫(II)及びＳｎＯで表される酸化錫(II)が好ましく、(Ｒ1ＣＯＯ)2Ｓｎで表される脂肪酸錫(II)及び酸化錫(II)がより好ましく、オクタン酸錫(II)、2-エチルヘキサン酸錫(II)、ステアリン酸錫(II)及び酸化錫(II)がさらに好ましい。 Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, from the standpoint of charge rising effect and catalytic ability , (R 1 COO) 2 Sn (wherein R 1 represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 2 O) 2 Sn (where R 2 Is C 6-20 alk An alkoxytin (II) represented by SnO or a tin (II) oxide represented by SnO, and a fatty acid tin (II) and tin oxide represented by (R 1 COO) 2 Sn (II) is more preferred, and tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferred.
錫(II)化合物の存在量は、アルコール成分とカルボン酸成分の総量100重量部に対して、0.01〜1.0重量部が好ましく、0.1〜0.7重量部がより好ましい。 The abundance of the tin (II) compound is preferably 0.01 to 1.0 part by weight, more preferably 0.1 to 0.7 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.
かくして得られるポリエステル系樹脂のうち、芳香族カルボン酸化合物以外のカルボン酸化合物と、多価アルコールの縮重合により得られたポリエステル系樹脂が、芳香族カルボン酸化合物を用いて得られたポリエステル系樹脂と比較して酸強度が低く、解離定数(ｐＫａ)が小さいため、本発明の結着樹脂として好ましく用いられる。 Of the polyester resins thus obtained, a polyester resin obtained by condensation polymerization of a carboxylic acid compound other than an aromatic carboxylic acid compound and a polyhydric alcohol is obtained using an aromatic carboxylic acid compound. Since the acid strength is low and the dissociation constant (pKa) is small, the binder resin of the present invention is preferably used.
かかる芳香族ポリカルボン酸化合物以外のカルボン酸化合物としては、上記で例示したカルボン酸化合物のうち、マレイン酸、フマル酸、炭素数1〜20のアルキル基又は炭素数2〜20のアルケニル基で置換されたコハク酸等のジカルボン酸、1,2,4−ブタントリカルボン酸、1,2,5−ヘキサントリカルボン酸等のトリカルボン酸、並びに1,2,7,8−オクタンテトラカルボン酸や式(II)のテトラカルボン酸等が挙げられる。 As the carboxylic acid compound other than the aromatic polycarboxylic acid compound, among the carboxylic acid compounds exemplified above, maleic acid, fumaric acid, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms is substituted. Dicarboxylic acids such as succinic acid, 1,2,4-butanetricarboxylic acid, tricarboxylic acids such as 1,2,5-hexanetricarboxylic acid, and 1,2,7,8-octanetetracarboxylic acid and the formula (II ) Tetracarboxylic acid and the like.
ポリエステル系樹脂の軟化点は、トナーの定着性、保存性及び耐久性の観点から、120〜160℃が好ましく、120〜150℃がより好ましい。本明細書において、軟化点は、後述の実施例に記載の方法により測定される。 The softening point of the polyester resin is preferably 120 to 160 ° C., more preferably 120 to 150 ° C., from the viewpoint of toner fixability, storage stability and durability. In the present specification, the softening point is measured by the method described in Examples described later.
ポリエステル系樹脂のガラス転移点は、トナーの定着性、保存性及び耐久性の観点から、45〜75℃が好ましく、50〜70℃がより好ましい。また、トナーの帯電性の観点から、酸価は、5〜80mgKOH/gが好ましく、5〜60mgKOH/gがより好ましく、5〜50mgKOH/gがさらに好ましい。本明細書において、ガラス転移点及び酸価は、後述の実施例に記載の方法により測定される。 The glass transition point of the polyester resin is preferably 45 to 75 ° C., more preferably 50 to 70 ° C., from the viewpoint of toner fixability, storage stability and durability. Further, from the viewpoint of chargeability of the toner, the acid value is preferably 5 to 80 mgKOH / g, more preferably 5 to 60 mgKOH / g, and further preferably 5 to 50 mgKOH / g. In this specification, a glass transition point and an acid value are measured by the method as described in the below-mentioned Example.
なお、本発明において、ポリエステル系樹脂とは、ポリエステルユニットを有する樹脂をいう。ポリエステルユニットとはポリエステル構造を有する部位を指し、ポリエステル系樹脂には、ポリエステルのみならず、実質的にその特性を損なわない程度に変性されたポリエステルも含まれるが、本発明においては、ポリエステル系樹脂はポリエステルであることが好ましい。変性されたポリエステルとしては、例えば、特開平１１−１３３６６８号公報、特開平１０−２３９９０３号公報、特開平８−２０６３６号公報等に記載の方法によりフェノール、ウレタン、エポキシ等によりグラフト化やブロック化したポリエステルや、ポリエステルユニットを含む2種以上の樹脂ユニットを有する複合樹脂が挙げられる。 In the present invention, the polyester resin means a resin having a polyester unit. The polyester unit refers to a portion having a polyester structure, and the polyester resin includes not only polyester but also polyester modified to such an extent that the properties are not substantially impaired. Is preferably polyester. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more types of resin units including a polyester unit.
ポリエステル系樹脂以外の結着樹脂としては、例えば、スチレン−アクリル樹脂等のビニル系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン等の他の樹脂が併用されていてもよいが、ポリエステル系樹脂の含有量は、結着樹脂中、70重量％以上が好ましく、80重量％以上がより好ましく、90重量％以上がさらに好ましく、実質的に100重量％であることがさらに好ましい。 As the binder resin other than the polyester resin, for example, a vinyl resin such as a styrene-acrylic resin, other resins such as an epoxy resin, a polycarbonate, and a polyurethane may be used in combination. In the binder resin, 70% by weight or more is preferable, 80% by weight or more is more preferable, 90% by weight or more is further preferable, and substantially 100% by weight is further preferable.
着色剤としては、トナー用着色剤として用いられている染料、顔料等を使用することができ、カーボンブラック；鉄黒等の無機顔料；Ｃ．Ｉ．ピグメント・イエロー１、同３、同７４、同９７、同９８等のアセト酢酸アリールアミド系モノアゾ黄色顔料；Ｃ．Ｉ．ピグメント・イエロー１２、同１３、同１４、同１７等のアセト酢酸アリールアミド系ジスアゾ黄色顔料；Ｃ．Ｉ．ソルベント・イエロー１９、同７７、同７９、Ｃ．Ｉ．ディスパース・イエロー１６４等の黄色染料；Ｃ．Ｉ．ピグメント・レッド４８、同４９：１、同５３：１、同５７、同５７：１、同８１、同１２２、同５等の赤色もしくは紅色顔料；Ｃ．Ｉ．ソルベント・レッド４９、同５２、同５８、同８等の赤色系染料；Ｃ．Ｉ．ピグメント・ブルー１５：３等の銅フタロシアニン及びその誘導体の青色系染顔料；Ｃ．Ｉ．ピグメント・グリーン７、同３６(フタロシアニン・グリーン)等の緑色顔料等が挙げられ、これらは単独で又は２種以上を混合して用いることができ、本発明のトナーは、黒トナー、カラートナー、フルカラートナーのいずれであってもよい。着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、3〜10重量部がより好ましい。 As the colorant, dyes and pigments used as toner colorants can be used. Carbon black; inorganic pigments such as iron black; I. Acetoacetic acid arylamide monoazo yellow pigments such as CI Pigment Yellow 1, 3, 74, 97, 98; I. C.I. Pigment Yellow 12, 13, 13, 17, etc. acetoacetic acid arylamide disazo yellow pigments; I. Solvent Yellow 19, 77, 79, C.I. I. Yellow dyes such as disperse yellow 164; I. Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5 and the like; C.I. I. Red dyes such as Solvent Red 49, 52, 58, 8; I. Blue dyes and pigments of copper phthalocyanine and its derivatives such as CI Pigment Blue 15: 3; I. Pigment Green 7 and 36 (phthalocyanine green), and the like. These may be used alone or in admixture of two or more. The toner of the present invention includes black toner, color toner, Any of full-color toners may be used. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明においては、結着樹脂、着色剤以外に、荷電制御剤、離型剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、磁性体等の添加剤をトナー母粒子に配合してもよい。 In the present invention, in addition to the binder resin and the colorant, a charge control agent, a release agent, a conductivity adjusting agent, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a magnetic substance, etc. These additives may be added to the toner base particles.
荷電制御剤としては、従来電子写真用に用いられる事が知られている全ての正帯電性の荷電制御剤から、1種又は2種類以上が用いられる。具体的には、ニグロシン系染料、例えば「ボントロンN-07」、「ボントロンN-09」、「ボントロンN-04」(以上オリエント化学社製)等、アミンを側鎖に含有するトリフェニルメタン系染料、例えば「COPY BLUE PR」(ヘキスト社製)、四級アンモニウム塩、例えば「TP-415」(保土谷化学社製)、「COPY CHARGE PSY 」(ヘキスト社製)、「ボントロンP-51」(オリエント化学社製)、セチルトリメチルアンモニウムブロミド等、ポリアミン樹脂、例えば「ボントロンP-52」(オリエント化学社製)等、その他を挙げることができる。荷電制御剤は結着樹脂100重量部に対し、好ましくは0.1〜8.0重量部、より好ましくは0.2〜5.0重量部含有される。 As the charge control agent, one or more of all positively chargeable charge control agents conventionally known to be used for electrophotography are used. Specifically, nigrosine dyes such as “Bontron N-07”, “Bontron N-09”, “Bontron N-04” (manufactured by Orient Chemical Co., Ltd.), etc., a triphenylmethane type containing an amine in the side chain Dyes such as `` COPY BLUE PR '' (manufactured by Hoechst), quaternary ammonium salts such as `` TP-415 '' (manufactured by Hodogaya Chemical), `` COPY CHARGE PSY '' (manufactured by Hoechst), `` Bontron P-51 '' (Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide and the like, polyamine resins such as “Bontron P-52” (Orient Chemical Co., Ltd.) and the like. The charge control agent is preferably contained in an amount of 0.1 to 8.0 parts by weight, more preferably 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the binder resin.
離型剤としては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、カルナウバワックス、モンタンワックス、サゾールワックス及びそれらの脱酸ワックス等のエステル系ワックス、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられる。これらのなかでは、トナーの離型性及び安定性の観点から、脂肪族炭化水素系ワックス及びエステル系ワックスが好ましく、これらは単独で又は2種以上を混合して含有されていても良い。離型剤の含有量は、結着樹脂100重量部に対して、0.1〜20重量部が好ましく、0.5〜10重量部がより好ましい。 As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples include ester waxes such as montan wax, sasol wax and their deoxidized wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. Of these, aliphatic hydrocarbon waxes and ester waxes are preferred from the viewpoint of toner releasability and stability, and these may be contained alone or in admixture of two or more. The content of the release agent is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明の電子写真用正帯電性トナーは、特に限定されることはなく、従来公知の方法を用いて製造することができ、例えば混練・粉砕し、分級する方法、並びに重合性単量体、重合開始剤、着色剤及び荷電制御剤等を成分とする重合性組成物を水性分散媒中に懸濁して重合することにより直接的にトナー母粒子を製造する方法等により製造することができる。得られたトナー母粒子に、外添剤として、少なくとも前記の特定平均粒子径を有するアルミナ、シリカ及びポリテトラフルオロエチレン微粒子を添加することにより本発明のトナーが得られる。 The positively chargeable toner for electrophotography of the present invention is not particularly limited and can be produced using a conventionally known method. For example, a kneading / pulverizing and classification method, a polymerizable monomer, It can be produced by a method of directly producing toner mother particles by suspending a polymerizable composition comprising a polymerization initiator, a colorant, a charge control agent and the like in an aqueous dispersion medium and polymerizing. The toner of the present invention can be obtained by adding at least alumina, silica and polytetrafluoroethylene fine particles having the specific average particle diameter as external additives to the obtained toner base particles.
本発明では、前記アルミナ、シリカ及びポリテトラフルオロエチレン微粒子を同時にトナー母粒子に添加してもよいが、トナーの帯電安定性の観点から、アルミナを外添した後に、シリカ及びポリテトラフルオロエチレン微粒子を外添する方法により製造されるトナーが好ましい。なお、ポリテトラフルオロエチレン微粒子の添加はシリカと同時に添加、又はシリカよりも後に添加することが好ましい。 In the present invention, the alumina, silica and polytetrafluoroethylene fine particles may be simultaneously added to the toner base particles. However, from the viewpoint of charging stability of the toner, after adding alumina externally, the silica and polytetrafluoroethylene fine particles are added. A toner produced by the method of externally adding is preferably used. In addition, it is preferable to add polytetrafluoroethylene fine particles simultaneously with silica, or after silica.
トナー母粒子と外添剤を混合する際に用いられる混合機としては、ヘンシェルミキサー、スーパーミキサー等の高速攪拌機、Ｖ型ブレンダー等の乾式混合に用いる攪拌装置が好ましい。また、攪拌装置を用いる際には、外添剤を十分にトナー母粒子に付着させるために、攪拌具の周速を上げたり、攪拌時間を長くしたりすることが好ましい。 As the mixer used for mixing the toner base particles and the external additive, a high-speed stirrer such as a Henschel mixer or a super mixer, or a stirrer used for dry mixing such as a V-type blender is preferable. In addition, when using a stirrer, it is preferable to increase the peripheral speed of the stirrer or lengthen the stirring time in order to allow the external additive to sufficiently adhere to the toner base particles.
かくして外添剤が添加されるが、さらに必要に応じて、流動性向上剤、クリーニング性向上剤などを添加することができる。 In this way, the external additive is added, but if necessary, a fluidity improver, a cleaning property improver, etc. can be added.
なお、遊離外添剤等の除去のため、トナー母粒子に外添剤を表面処理した後は、篩工程を施してもよい。 In order to remove free external additives and the like, after the external additives are surface-treated on the toner base particles, a sieving step may be performed.
流動性向上剤としては、例えば、酸化チタン、チタン酸バリウム、チタン酸マグネシウム、チタン酸カルシウム、チタン酸ストロンチウム、酸化亜鉛、ケイ砂、クレー、雲母、ケイ灰石、ケイソウ土、酸化クロム、酸化セリウム、ベンガラ、三酸化アンチモン、酸化マグネシウム、酸化ジルコニウム、硫酸バリウム、炭酸バリウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素などを挙げることができる。 Examples of the fluidity improver include titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, and cerium oxide. , Bengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
クリーニング性向上剤としては、ステアリン酸亜鉛に代表される高級脂肪酸の金属塩等を併用してもよい。 As the cleaning property improver, a metal salt of a higher fatty acid represented by zinc stearate may be used in combination.
本発明のトナーの体積中位粒径(Ｄ50)は、現像ローラーへの付着性改善の観点から、3〜10μmが好ましく、4〜9μmがより好ましく、5〜9μmがさらに好ましい。なお、本明細書において、体積中位粒径(Ｄ50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になる粒径を意味する。 The volume median particle size (D 50 ) of the toner of the present invention is preferably from 3 to 10 μm, more preferably from 4 to 9 μm, and even more preferably from 5 to 9 μm, from the viewpoint of improving adhesion to the developing roller. In the present specification, the volume-median particle size (D 50 ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.
本発明の電子写真用正帯電性トナーは、規制ブレード等と現像ローラーとの間隙を通過させることによって、トナーの帯電を行う、非磁性１成分現像方式に好適に用いられ、なかでも正帯電型有機感光体を使用した非磁性１成分現像方式に用いることにより、本発明の効果がより顕著になる。 The positively chargeable toner for electrophotography of the present invention is suitably used for a non-magnetic one-component development system in which a toner is charged by passing through a gap between a regulating blade or the like and a developing roller. The effect of the present invention becomes more prominent when used in a non-magnetic one-component development system using an organic photoreceptor.
〔樹脂の軟化点〕
フローテスター(島津製作所、CFT-500D)を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出する。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出する温度を軟化点とする。
[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min. While applying a load of 1.96 MPa with a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . Plot the plunger drop amount of the flow tester against the temperature, and let the softening point be the temperature at which half of the sample flows out.
〔樹脂のガラス転移点〕
示差走査熱量計(セイコー電子工業社製、DSC210)を用いて、試料0.01〜0.02gをアルミパンに計量し、200℃まで昇温し、その温度から降温速度10℃／分で0℃まで冷却したサンプルを昇温速度10℃／分で昇温し、吸熱の最高ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度とする。
[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and cool from that temperature to 0 ° C at a rate of 10 ° C / min. The sample is heated at a heating rate of 10 ° C / min, and the temperature is the intersection of the base line extension below the maximum endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex. .
〔樹脂の酸価〕
JIS K0070の方法に基づき測定する。但し、測定溶媒のみJIS K0070の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒(アセトン：トルエン＝1:1(容量比))に変更した。
[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
〔トナーの体積中位粒径(Ｄ50)〕
本明細書において、トナーの体積中位粒径(Ｄ50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になるトナーの粒径を意味する。
測定機：コールターマルチサイザーII(ベックマンコールター社製)
アパチャー径：100μm
解析ソフト：コールターマルチサイザーアキュコンプ バージョン 1.19(ベックマンコールター社製)
電解液：アイソトンII(ベックマンコールター社製)
分散液：エマルゲン109Ｐ(花王社製、ポリオキシエチレンラウリルエーテル、HLB：13.6)5重量％電解液
分散条件：分散液5mLに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mLを添加し、さらに、超音波分散機にて1分間分散させる。
測定条件：前記電解液100mLに、3万個のトナー粒子の粒径を20秒間で測定できる濃度となるように、前記分散液を加え、3万個の粒子を測定し、その粒度分布から体積中位粒径(Ｄ50)を求める。
[Volume-median particle size of toner (D 50 )]
In this specification, the volume-median particle size (D 50 ) of the toner means the particle size of the toner in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% by weight Electrolyte dispersion condition: 10 mg of measurement sample was added to 5 mL of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Thereafter, 25 mL of an electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: The dispersion is added to 100 mL of the electrolytic solution so that the particle size of 30,000 toner particles can be measured in 20 seconds, and 30,000 particles are measured. Determine the median particle size (D 50 ).
〔アルミナ及びシリカの平均粒子径〕
本明細書において、アルミナ及びシリカの平均粒子径とは一次粒子の個数平均粒径を意味し、下記式より求める。
個数平均粒径(nm)＝6/(ρ×比表面積(m2/g))×1000
式中、ρはアルミナの比重(3.99)又はシリカの比重(2.2)であり、比表面積は疎水化処理前の原体の、窒素吸着法により求められたBET比表面積である。
なお、上記式は、粒径Rの球と仮定して、
BET比表面積＝S×(1/m)
m(粒子の重さ)＝4/3×π×(R/2)3×比重
S(表面積)＝4π(R/2)2
から得られる式である。
[Average particle diameter of alumina and silica]
In this specification, the average particle diameter of alumina and silica means the number average particle diameter of primary particles, and is obtained from the following formula.
Number average particle diameter (nm) = 6 / (ρ × specific surface area (m 2 / g)) × 1000
In the formula, ρ is the specific gravity of alumina (3.99) or the specific gravity of silica (2.2), and the specific surface area is the BET specific surface area determined by the nitrogen adsorption method of the raw material before hydrophobization treatment.
Note that the above equation assumes a sphere with a particle size R,
BET specific surface area = S x (1 / m)
m (weight of particle) = 4/3 x π x (R / 2) 3 x specific gravity
S (surface area) = 4π (R / 2) 2
Is an expression obtained from
〔ポリテトラフルオロエチレン微粒子の平均粒子径〕
ポリテトラフルオロエチレン微粒子の平均粒子径とは、ポリテトラフルオロエチレン微粒子の一次粒子の個数平均粒径のことであり、下記方法に従って求める。
個数平均粒径は、走査型電子顕微鏡にて撮影倍率5000〜50000倍の適切な倍率で、粒径(長径と短径の平均値)を100個の一次粒子について測定し、それらの平均値をポリテトラフルオロエチレン微粒子の平均粒子径とする。
[Average particle diameter of polytetrafluoroethylene fine particles]
The average particle size of the polytetrafluoroethylene fine particles is the number average particle size of primary particles of the polytetrafluoroethylene fine particles, and is determined according to the following method.
The number average particle size is measured with a scanning electron microscope at an appropriate magnification of 5000 to 50000 times, and the particle size (average value of major axis and minor axis) is measured for 100 primary particles. The average particle size of the polytetrafluoroethylene fine particles is used.
樹脂製造例１
ポリオキシプロピレン(2.2)−2，2−ビス(4−ヒドロキシフェニル)プロパン3500g、イソドデセニル無水コハク酸50g、フマル酸1110g、ハイドロキノン2.5g及び、ジブチル錫オキシド5gを、４口フラスコに入れ、温度計、ステンレス製攪拌棒、流下式コンデンサー、及び窒素導入管を取り付けマントルヒーター中で210℃の温度で攪拌した。重合度は、ＡＳＴＭ Ｅ２８−６７に準拠した軟化点測定より追跡を行い、軟化点が115℃に達したときに反応を終了した。得られた樹脂のガラス転移温度(Ｔｇ)はピーク１本で60℃であり、酸価は、6mgKOH/gであった。これを樹脂ａとする。
Resin production example 1
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (3500 g), isododecenyl succinic anhydride (50 g), fumaric acid (1110 g), hydroquinone (2.5 g) and dibutyltin oxide (5 g) were placed in a four-necked flask and a thermometer. A stainless stir bar, a flow-down condenser, and a nitrogen introduction tube were attached, and the mixture was stirred in a mantle heater at a temperature of 210 ° C. The degree of polymerization was tracked by measuring the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 115 ° C. The glass transition temperature (Tg) of the obtained resin was 60 ° C. with one peak, and the acid value was 6 mgKOH / g. This is resin a.
実施例１〜６及び比較例１〜７（実施例２は参考例である）
ポリエステル樹脂ａ 100重量部
カーボンブラック(REGAL-330R、キャボット社製) 4重量部
ニグロシン染料(ボントロンN-04、オリエント化学社製) 4重量部
低分子量ポリプロピレンワックス(ハイワックスNP-055、三井石油化学社製) 2重量部
上記組成を予備混合し、100℃に加熱した２軸ルーダーで混練した後冷却し、冷却物を機械式粉砕機で2mmのメッシュをパスする程度まで粗粉砕し、次いで風力式粉砕・分級機にて粉砕分級して、体積中位粒径(Ｄ50)で8μmになる様にトナー母粒子を調製した。
Examples 1-6 and Comparative Examples 1-7 (Example 2 is a reference example)
Polyester resin a 100 parts by weight Carbon black (REGAL-330R, manufactured by Cabot) 4 parts by weight Nigrosine dye (Bontron N-04, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight Low molecular weight polypropylene wax (High Wax NP-055, Mitsui Petrochemical) 2 parts by weight) Pre-mixed the above composition, kneaded with a twin-screw rudder heated to 100 ° C, cooled, and coarsely pulverized the cooled product to a level that passes a 2 mm mesh with a mechanical pulverizer, then wind power The toner base particles were prepared so as to have a volume median particle size (D 50 ) of 8 μm.
得られたトナー母粒子100重量部に、表１に示す種類及び量の外添剤を添加しヘンシェルミキサーで混合して、実施例１〜６及び比較例１〜７の正帯電性トナーを得た。トナーの体積中位粒径(Ｄ50)は8μmであった。なお、外添剤の添加は、１段目でアルミナを添加し攪拌した後、２段目でシリカ及びポリテトラフルオロエチレン微粒子を添加して攪拌を行なうことにより実施した。 External additives of the types and amounts shown in Table 1 were added to 100 parts by weight of the obtained toner base particles and mixed with a Henschel mixer to obtain positively chargeable toners of Examples 1 to 6 and Comparative Examples 1 to 7. It was. The volume median particle size (D 50 ) of the toner was 8 μm. The external additive was added by adding alumina in the first stage and stirring, and then adding silica and polytetrafluoroethylene fine particles in the second stage and stirring.
試験例１〔初期カブリ〕
未使用の感光体が搭載された東芝製普通紙ファクシミリ「TF-5500」に各実施例及び各比較例のトナーを実装して、白ベタ画像を印字し、その途中で電源を切った。感光体表面のトナーをメンディングテープに付着させ、画像濃度測定器「SPM-50」(Gretag社製)にて着色濃度を測定し、トナーを付着させる前のテープの着色濃度との差を求め、以下の評価基準に従って初期カブリを評価した。結果を表１に示す。
Test Example 1 [Initial fog]
The toner of each of the examples and comparative examples was mounted on a plain paper facsimile “TF-5500” manufactured by Toshiba on which an unused photoconductor was mounted, and a solid white image was printed. The toner on the surface of the photoconductor is attached to the mending tape, the color density is measured with an image density measuring instrument “SPM-50” (Gretag), and the difference from the color density of the tape before the toner is applied is determined. The initial fog was evaluated according to the following evaluation criteria. The results are shown in Table 1.
〔初期カブリの評価基準〕
Ａ：着色濃度の差が0.12未満
Ｂ：着色濃度の差が0.12以上、0.13未満
Ｃ：着色濃度の差が0.13以上、0.15未満
Ｄ：着色濃度の差が0.15以上
[Evaluation criteria for initial fog]
A: Color density difference is less than 0.12 B: Color density difference is 0.12 or more and less than 0.13 C: Color density difference is 0.13 or more and less than 0.15 D: Color density difference is 0.15 or more
試験例２〔耐久性〕
東芝製普通紙ファクシミリ「TF-5500」に各実施例及び各比較例のトナーを実装し、印字率5％の画像を10000枚連続印刷した。その際、1000枚印刷毎にベタ画像を印刷し、得られた画像を目視で観察し、以下の評価基準に従って、耐久性としてベタ追従性を評価した。結果を表１に示す。
Test Example 2 [Durability]
The toner of each Example and each Comparative Example was mounted on a Toshiba plain paper facsimile “TF-5500”, and 10,000 images with a printing rate of 5% were continuously printed. At that time, a solid image was printed every 1000 sheets printed, the obtained image was visually observed, and solid followability was evaluated as durability according to the following evaluation criteria. The results are shown in Table 1.
〔耐久性の評価基準〕
Ａ：10000枚印刷後も、ベタ追従性が良好
Ｂ：5000枚印刷以降で、ベタ追従性が低下
Ｃ：5000枚印刷前に、ベタ追従性が低下
[Durability Evaluation Criteria]
A: Solid followability is good even after printing 10,000 sheets. B: Solid followability decreases after printing 5000 sheets. C: Solid followability decreases before printing 5000 sheets.
比較例１〜７のトナーと対比して、実施例１〜６のトナーは初期カブリが抑制されていることが分かる。なかでも、アルミナ／シリカの重量比が１以上の実施例１及び３〜６では耐久性にも優れていることが分かる。一方、平均粒子径が50nm未満の外添剤中アルミナの含有量が50重量％又は0重量％である比較例１〜４のトナーでは、初期カブリが発生しており、一定量以上のアルミナが必要であることがわかる。また、アルミナとシリカのみしか外添されていない比較例５〜７のトナーでも、初期カブリが発生している。このことから、感光体表面研磨効果によると推定されるアルミナの初期カブリ抑制効果を発揮させるには、ポリテトラフルオロエチレン微粒子が存在することが必要であることが示唆される。 In contrast to the toners of Comparative Examples 1 to 7, it can be seen that the toners of Examples 1 to 6 have suppressed initial fogging. Especially, it turns out that it is excellent also in durability in Example 1 and 3-6 in which the weight ratio of alumina / silica is 1 or more. On the other hand, in the toners of Comparative Examples 1 to 4 in which the content of alumina in the external additive having an average particle size of less than 50 nm is 50% by weight or 0% by weight, initial fog occurs, and a certain amount or more of alumina is present. It turns out that it is necessary. In addition, initial fogging also occurred in the toners of Comparative Examples 5 to 7 in which only alumina and silica were externally added. This suggests that the presence of polytetrafluoroethylene fine particles is necessary to exert the initial fog suppression effect of alumina presumed to be due to the photoreceptor surface polishing effect.
本発明の電子写真用正帯電性トナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に好適に用いられる。
The positively chargeable toner for electrophotography of the present invention is suitably used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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| JP5926942B2 (en) * | 2011-12-09 | 2016-05-25 | サカタインクス株式会社 | Nonmagnetic electrostatic charge image developing toner manufacturing method |
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| JP7052804B2 (en) * | 2017-09-28 | 2022-04-12 | 日本ゼオン株式会社 | Toner for static charge image development |
| JP2020079856A (en) * | 2018-11-13 | 2020-05-28 | コニカミノルタ株式会社 | Toner for electrostatic charge image development and developer |
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