JP5467677B2 - Toner for electrophotography - Google Patents
Toner for electrophotography Download PDFInfo
- Publication number
- JP5467677B2 JP5467677B2 JP2009139144A JP2009139144A JP5467677B2 JP 5467677 B2 JP5467677 B2 JP 5467677B2 JP 2009139144 A JP2009139144 A JP 2009139144A JP 2009139144 A JP2009139144 A JP 2009139144A JP 5467677 B2 JP5467677 B2 JP 5467677B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- toner
- binder resin
- softening point
- acid
- 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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- -1 carboxylic acid compound Chemical class 0.000 claims description 52
- 229920000728 polyester Polymers 0.000 claims description 43
- 239000011230 binding agent Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims 9
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 229920005989 resin Polymers 0.000 description 50
- 239000011347 resin Substances 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000010936 titanium Substances 0.000 description 26
- 238000003860 storage Methods 0.000 description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 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 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000032050 esterification Effects 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 238000012643 polycondensation polymerization Methods 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 6
- 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
- 239000003086 colorant Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 6
- 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 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000377 silicon dioxide 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
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910020923 Sn-O Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HCZHHEIFKROPDY-UHFFFAOYSA-N kynurenic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC(=O)C2=C1 HCZHHEIFKROPDY-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-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
- 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 2
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229910020813 Sn-C Inorganic materials 0.000 description 2
- 229910018732 Sn—C Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative 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
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- QCIYAEYRVFUFAP-UHFFFAOYSA-N hexane-2,3-diol Chemical compound CCCC(O)C(C)O QCIYAEYRVFUFAP-UHFFFAOYSA-N 0.000 description 2
- TXGJTWACJNYNOJ-UHFFFAOYSA-N hexane-2,4-diol Chemical compound CCC(O)CC(C)O TXGJTWACJNYNOJ-UHFFFAOYSA-N 0.000 description 2
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-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
- 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-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
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 2
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 2
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-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
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- 229940015975 1,2-hexanediol Drugs 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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- QWPXQVDMKQUGJX-UHFFFAOYSA-N 2-(6-methylhept-1-enyl)butanedioic acid Chemical compound CC(C)CCCC=CC(C(O)=O)CC(O)=O QWPXQVDMKQUGJX-UHFFFAOYSA-N 0.000 description 1
- JTWBYEWVFCYRSF-UHFFFAOYSA-N 2-(6-methylheptyl)butanedioic acid Chemical compound CC(C)CCCCCC(C(O)=O)CC(O)=O JTWBYEWVFCYRSF-UHFFFAOYSA-N 0.000 description 1
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- ZNLXEDDUXFMEML-UHFFFAOYSA-N 2-[5-(2-chloroacetyl)thiophen-2-yl]acetic acid Chemical compound OC(=O)CC1=CC=C(C(=O)CCl)S1 ZNLXEDDUXFMEML-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- CGDAWEVRGAIHJH-UHFFFAOYSA-N 3-carbamoylpyridine-2-carboxylic acid Chemical compound NC(=O)C1=CC=CN=C1C(O)=O CGDAWEVRGAIHJH-UHFFFAOYSA-N 0.000 description 1
- XJFABQUUYAJFFJ-UHFFFAOYSA-N 3-propoxypyridine-2-carboxylic acid Chemical compound CCCOC1=CC=CN=C1C(O)=O XJFABQUUYAJFFJ-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- CVRPSWGFUCJAFC-UHFFFAOYSA-N 4-[(2,5-dichlorophenyl)diazenyl]-N-(2,5-dimethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound ClC1=C(C=C(C=C1)Cl)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=C(C=CC(=C1)OC)OC)O CVRPSWGFUCJAFC-UHFFFAOYSA-N 0.000 description 1
- XTLJJHGQACAZMS-UHFFFAOYSA-N 4-oxo-1h-pyridine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CC(=O)C=C(C(O)=O)N1 XTLJJHGQACAZMS-UHFFFAOYSA-N 0.000 description 1
- LTUUGSGSUZRPRV-UHFFFAOYSA-N 6-methylpyridine-2-carboxylic acid Chemical compound CC1=CC=CC(C(O)=O)=N1 LTUUGSGSUZRPRV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RTCOLHPAQIGCEQ-UHFFFAOYSA-N CCCC(O)CO.CCC(O)CCO Chemical compound CCCC(O)CO.CCC(O)CCO RTCOLHPAQIGCEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 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
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- XAAKCCMYRKZRAK-UHFFFAOYSA-N isoquinoline-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=NC=CC2=C1 XAAKCCMYRKZRAK-UHFFFAOYSA-N 0.000 description 1
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- 239000012188 paraffin wax Substances 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- VXGYRCVTBHVXMZ-UHFFFAOYSA-N quinoline-6-carboxylic acid Chemical compound N1=CC=CC2=CC(C(=O)O)=CC=C21 VXGYRCVTBHVXMZ-UHFFFAOYSA-N 0.000 description 1
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- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
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- RLEBKHAOAHYZHT-UHFFFAOYSA-M sodium;pyridine-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=N1 RLEBKHAOAHYZHT-UHFFFAOYSA-M 0.000 description 1
- PLTCLMZAIZEHGD-UHFFFAOYSA-M sodium;quinoline-2-carboxylate Chemical compound [Na+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 PLTCLMZAIZEHGD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- FBZONXHGGPHHIY-UHFFFAOYSA-N xanthurenic acid Chemical compound C1=CC=C(O)C2=NC(C(=O)O)=CC(O)=C21 FBZONXHGGPHHIY-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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トナー用結着樹脂及び該結着樹脂を含有した電子写真用トナーに関する。 The present invention relates to a binder resin for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner containing the binder resin.
近年、プリンターやコピー機の高速化が進む中で、低温定着性に優れたトナーが望まれており、樹脂を低分子量化する傾向にあるが、一方で、保存性の観点からは高いガラス転移点が望まれている。 In recent years, as the speed of printers and copiers has increased, toners with excellent low-temperature fixability have been demanded, and there is a tendency to lower the molecular weight of the resin. A point is desired.
これらの特性を両立するために、芳香族化合物(ベンゼン環を含む化合物)を用いて得られるポリエステルが検討されている。例えば、特許文献１には、ビスフェノールＡのエチレンオキサイド付加物を全アルコール成分中50モル％以上含有したアルコール成分と、テレフタル酸を、2価のカルボン酸成分中80モル％以上、かつ全カルボン酸成分中70モル％以上含有したカルボン酸成分とを縮重合させて得られるポリエステルであって、軟化点が130℃以上のポリエステルを含有したトナー用結着樹脂が開示されている。 In order to achieve both of these properties, polyesters obtained using aromatic compounds (compounds containing a benzene ring) have been studied. For example, Patent Document 1 discloses that an alcohol component containing 50 mol% or more of an ethylene oxide adduct of bisphenol A in a total alcohol component, terephthalic acid, 80 mol% or more in a divalent carboxylic acid component, and a total carboxylic acid. A binder resin for toner containing a polyester obtained by polycondensation with a carboxylic acid component contained in a component at 70 mol% or more and having a softening point of 130 ° C. or more is disclosed.
しかし、さらなる低温定着性の向上が望まれている。 However, further improvement in low-temperature fixability is desired.
本発明の課題は、低温定着性と保存性との両立が可能なトナー用結着樹脂及び該結着樹脂を含有した電子写真用トナーを提供することにある。 An object of the present invention is to provide a toner binder resin capable of achieving both low-temperature fixability and storage stability, and an electrophotographic toner containing the binder resin.
本発明は、
〔１〕 アルコール成分と、分子中にピリジン骨格を有するカルボン酸化合物を20モル％以上含有するカルボン酸成分とを縮重合させて得られるポリエステルを含むトナー用結着樹脂、並びに
〔２〕 前記〔１〕記載の結着樹脂を含有してなる電子写真用トナー
に関する。
The present invention
[1] A binder resin for toner containing polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing 20 mol% or more of a carboxylic acid compound having a pyridine skeleton in the molecule; and [2] the above [ 1] An electrophotographic toner comprising the binder resin as described above.
本発明のトナー用結着樹脂を含有した電子写真用トナーは、低温定着性と保存性のいずれにも優れるという効果を奏するものである。 The electrophotographic toner containing the binder resin for toner of the present invention has an effect of being excellent in both low-temperature fixability and storage stability.
本発明のトナー用結着樹脂は、ポリエステルのカルボン酸成分が、分子中にピリジン骨格を有するカルボン酸化合物を特定量含有するものである点に大きな特徴を有しており、これによりトナーの低温定着性と保存性の両立が達成される。即ち、本発明の結着樹脂は、ベンゼン環を有するポリエステルを含有する結着樹脂と同様にトナーの保存性に優れ、そのうえトナーの低温定着性にも優れていることを見出したものである。これは、ポリエステルのベンゼン環に窒素原子が挿入されることで、ベンゼン環を有するポリエステルと比較して、ガラス転移点を適度に低下させていることによるものと推定される。 The binder resin for toner of the present invention has a great feature in that the carboxylic acid component of the polyester contains a specific amount of a carboxylic acid compound having a pyridine skeleton in the molecule. Compatibility between fixability and storage stability is achieved. That is, the binder resin of the present invention has been found to be excellent in the storage stability of the toner as well as in the low-temperature fixability of the toner, like the binder resin containing a polyester having a benzene ring. This is presumably due to the fact that the glass transition point is appropriately reduced by inserting nitrogen atoms into the benzene ring of the polyester as compared with the polyester having a benzene ring.
分子中にピリジン骨格を有するカルボン酸化合物としては、ピコリン酸、ピコリン酸ナトリウム、3-ヒドロキシピコリン酸、3-カルバモイルピコリン酸、6-メチルピコリン酸、3-n-プロポキシピコリン酸、6-キノリンカルボン酸、イソキノリン-1-カルボン酸、イソキノリン-3-カルボン酸一水和物、４-ヒドロキシキノリン-2-カルボン酸（キヌレン酸）、キナルジン酸、キナルジン酸ナトリウム、キサンツレン酸等のモノカルボン酸又はそれらの低級アルキル(炭素数1〜3)エステル；2,6-ピリジンジカルボン酸、2,4-ピリジンジカルボン酸水和物、2,5-ピリジンジカルボン酸、2,3-ピリジンジカルボン酸、4-ヒドロキシピリジン-2,6-ジカルボン酸(ケリダム酸)一水和物、2,6-ジアセチルピリジン、3,5-ピリジンジカルボン酸、3,4-ピリジンジカルボン酸等のジカルボン酸又はそれらの低級アルキル(炭素数1〜3)エステル等が挙げられる。本発明においては、カルボン酸、酸無水物、低級アルキルエステル等の誘導体等を含め、総称してカルボン酸化合物という。これらのなかでは、低温定着性と保存性及び縮重合の反応性の観点から、ジカルボン酸化合物が好ましい。 Examples of carboxylic acid compounds having a pyridine skeleton in the molecule include picolinic acid, sodium picolinate, 3-hydroxypicolinic acid, 3-carbamoylpicolinic acid, 6-methylpicolinic acid, 3-n-propoxypicolinic acid, and 6-quinolinecarboxylic acid. Monocarboxylic acids such as acid, isoquinoline-1-carboxylic acid, isoquinoline-3-carboxylic acid monohydrate, 4-hydroxyquinoline-2-carboxylic acid (quinurenic acid), quinaldic acid, sodium quinaldate, xanthurenic acid or the like Lower alkyl (1 to 3 carbon atoms) ester of 2,6-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid hydrate, 2,5-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 4-hydroxy Dicarboxylic acids such as pyridine-2,6-dicarboxylic acid (chelidamic acid) monohydrate, 2,6-diacetylpyridine, 3,5-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, etc. Phosphate or their lower alkyl esters thereof (C1 to C3). In the present invention, the term “carboxylic acid compound” is used generically, including derivatives such as carboxylic acid, acid anhydride, and lower alkyl ester. Of these, dicarboxylic acid compounds are preferred from the viewpoints of low-temperature fixability, storage stability, and condensation polymerization reactivity.
分子中にピリジン骨格を有するカルボン酸化合物の含有量は、低温定着性と保存性の観点から、カルボン酸成分中、20モル％以上であり、好ましくは30〜90モル％、より好ましくは40〜80モル％である。 The content of the carboxylic acid compound having a pyridine skeleton in the molecule is 20 mol% or more, preferably 30 to 90 mol%, more preferably 40 to 40 mol% in the carboxylic acid component from the viewpoint of low-temperature fixability and storage stability. 80 mol%.
本発明の結着樹脂に含まれるポリエステルは、前記の分子中にピリジン骨格を有するカルボン酸化合物を含むカルボン酸成分と、アルコール成分とを縮重合させて得られる。 The polyester contained in the binder resin of the present invention is obtained by polycondensing a carboxylic acid component containing a carboxylic acid compound having a pyridine skeleton in the molecule and an alcohol component.
アルコール成分としては、式(I)： As the alcohol component, the formula (I):
（式中、Ｒ1Ｏ及びＯＲ1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、1.5〜5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又は脂肪族ジオールが好ましい。
(In the formula, R 1 O and OR 1 are oxyalkylene groups, R 1 is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1-16, more preferably 1-8, and even more preferably 1.5-5)
An alkylene oxide adduct or aliphatic diol of bisphenol A represented by
ビスフェノールＡのアルキレンオキサイド付加物は、保存性の観点から好ましい。 The alkylene oxide adduct of bisphenol A is preferable from the viewpoint of storage stability.
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の具体例としては、2,2-ビス(4-ヒドロキシフェニル)プロパンのポリオキシプロピレン付加物、及び2,2-ビス(4-ヒドロキシフェニル)プロパンのポリオキシエチレン付加物等のビスフェノールＡのアルキレンオキサイド付加物等が挙げられる。 Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy). And an alkylene oxide adduct of bisphenol A such as a polyoxyethylene adduct of phenyl) propane.
前記ビスフェノールＡのアルキレンオキサイド付加物の含有量は、前記観点から、アルコール成分中、好ましくは20〜100モル％、より好ましくは30〜100モル％、さらに好ましくは50〜100モル％である。 From the above viewpoint, the content of the alkylene oxide adduct of bisphenol A is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, and still more preferably 50 to 100 mol% in the alcohol component.
脂肪族ジオール、好ましくは炭素数2〜8、より好ましくは炭素数2〜6の脂肪族ジオールは、トナーの低温定着性の観点から好ましい。 An aliphatic diol, preferably an aliphatic diol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, is preferable from the viewpoint of low-temperature fixability of the toner.
脂肪族ジオールとしては、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,2-ペンタンジオール、1,3-ペンタンジオール、1,4-ペンタンジオール、1,5-ペンタンジオール、1,2-ヘキサンジオール、1,3-ヘキサンジオール、1,4-ヘキサンジオール、1,5-ヘキサンジオール、1,6-ヘキサンジオール、1,4-ブテンジオール、ネオペンチルグリコール、2,3-ブタンジオール、2,3-ペンタンジオール、2,4-ペンタンジオール、2,3-ヘキサンジオール、3,4-ヘキサンジオール、2,4-ヘキサンジオール、2,5-ヘキサンジオール等が挙げられる。 Aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentanediol, 2,3-hexanediol, 3,4- Examples include hexanediol, 2,4-hexanediol, and 2,5-hexanediol.
これらの中では、トナーの低温定着性と保存性とに優れる観点から、第二級炭素原子に結合した水酸基を有する脂肪族ジオールが好ましい。かかる脂肪族ジオールの炭素数は、トナーの低温定着性と保存性の観点から、炭素数3〜8が好ましく、炭素数3〜6がより好ましい。具体的には、1,2-プロパンジオール、2,3-ブタンジオール、2,3-ペンタンジオール、2,4-ペンタンジオール、2,3-ヘキサンジオール、3,4-ヘキサンジオール、2,4-ヘキサンジオール、2,5-ヘキサンジオール等が挙げられる。 Among these, an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferable from the viewpoint of excellent low-temperature fixability and storage stability of the toner. The carbon number of the aliphatic diol is preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, from the viewpoint of low-temperature fixability and storage stability of the toner. Specifically, 1,2-propanediol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentanediol, 2,3-hexanediol, 3,4-hexanediol, 2,4 -Hexanediol, 2,5-hexanediol and the like.
脂肪族ジオールの含有量は、前記観点から、アルコール成分中、好ましくは20〜100モル％、より好ましくは30〜100モル％、さらに好ましくは50〜100モル％である。 From the above viewpoint, the content of the aliphatic diol is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, and still more preferably 50 to 100 mol% in the alcohol component.
分子中にピリジン骨格を有するカルボン酸化合物以外のカルボン酸成分としては、シュウ酸、マロン酸、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、アジピン酸、セバシン酸、アゼライン酸、コハク酸(例えば、n-ドデセニルコハク酸、イソドデセニルコハク酸、n-ドデシルコハク酸、イソオクテニルコハク酸、イソオクチ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)等の脂肪族ジカルボン酸；フタル酸、イソフタル酸、テレフタル酸、1,2,4-ベンゼントリカルボン酸(トリメリット酸)、2,5,7-ナフタレントリカルボン酸、ピロメリット酸等の芳香族多価カルボン酸；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；ロジン；フマル酸、マレイン酸又はアクリル酸等で変性されたロジン等並びにこれらの酸の無水物及び低級アルキル(炭素数1〜3)エステル等が挙げられる。 As carboxylic acid components other than carboxylic acid compounds having a pyridine skeleton in the molecule, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, adipic acid, sebacic acid, azelaic acid, succinic acid (For example, substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, etc. Aliphatic dicarboxylic acids such as succinic acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, etc. Aromatic polycarboxylic acids such as cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, rosin, fumaric acid, maleic acid, acrylic acid, etc. Sex rosin, etc. and anhydrides and lower alkyl of these acids (1-3 carbon atoms) esters, and the like.
これらの中では、トナーの保存性の観点からは、芳香族多価カルボン酸化合物が好ましく、トナーの保存性と分子中にピリジン骨格を有するカルボン酸化合物の縮重合反応の反応性を向上させる観点から、トリメリット酸、ピロリメット酸、これらの酸の無水物及び低級アルキル(炭素数1〜3)エステル等の3価以上の芳香族カルボン酸化合物がより好ましい。 Among these, an aromatic polyvalent carboxylic acid compound is preferable from the viewpoint of the storage stability of the toner, and the viewpoint of improving the storage stability of the toner and the reactivity of the condensation polymerization reaction of the carboxylic acid compound having a pyridine skeleton in the molecule. Therefore, trimellitic acid, pyrrolmet acid, anhydrides of these acids, and trivalent or higher aromatic carboxylic acid compounds such as lower alkyl (C1-3) esters are more preferable.
3価以上の芳香族カルボン酸化合物と分子中にピリジン骨格を有するカルボン酸化合物とのモル比(3価以上の芳香族カルボン酸化合物／分子中にピリジン骨格を有するカルボン酸化合物)は、トナーの保存性と分子中にピリジン骨格を有するカルボン酸化合物の縮重合反応の反応性を向上させる観点から、1/10〜1/1が好ましく、1/8〜2/3がより好ましく、1/4〜1/2がさらに好ましい。 The molar ratio of the trivalent or higher aromatic carboxylic acid compound to the carboxylic acid compound having a pyridine skeleton in the molecule (trivalent or higher aromatic carboxylic acid compound / carboxylic acid compound having a pyridine skeleton in the molecule) From the viewpoint of improving the storage stability and the reactivity of the polycondensation reaction of the carboxylic acid compound having a pyridine skeleton in the molecule, 1/10 to 1/1 is preferable, 1/8 to 2/3 is more preferable, and 1/4 ~ 1/2 is more preferred.
また、トナーの低温定着性の観点からは、脂肪族ジカルボン酸化合物が好ましい。 From the viewpoint of low-temperature fixability of the toner, an aliphatic dicarboxylic acid compound is preferable.
なお、アルコール成分には1価のアルコールが、カルボン酸成分には1価のカルボン酸化合物が、分子量調整や耐オフセット性向上の観点から、適宜含有されていてもよい。 The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoints of molecular weight adjustment and offset resistance improvement.
カルボン酸成分とアルコール成分のモル比(カルボン酸成分／アルコール成分)は、重合性を高め、保存性を高め、酸価を調整する観点から、0.9〜1.2が好ましく、0.95〜1.1がより好ましい。 The molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is preferably from 0.9 to 1.2, more preferably from 0.95 to 1.1, from the viewpoints of improving the polymerizability, improving the storage stability and adjusting the acid value.
本発明において、分子中にピリジン骨格を有するカルボン酸化合物以外のカルボン酸化合物を含むカルボン酸成分を用いる場合には、分子中にピリジン骨格を有するカルボン酸化合物の重合性を高め、保存性を高める観点から、分子中にピリジン骨格を有するカルボン酸化合物とアルコール成分とを縮重合させ、反応率が好ましくは60〜98％、より好ましくは70〜95％に達した後、他のカルボン酸化合物を添加して縮重合させることが好ましい。なお、本発明において、反応率とは、理論反応水量の排出を反応率100％とした時の割合をいい、上記の場合、分子中にピリジン骨格を有するカルボン酸化合物とアルコール成分との理論反応水量の排出を反応率100％とした時の割合である。 In the present invention, when a carboxylic acid component containing a carboxylic acid compound other than a carboxylic acid compound having a pyridine skeleton in the molecule is used, the polymerizability of the carboxylic acid compound having a pyridine skeleton in the molecule is increased and the storage stability is improved. From the viewpoint, the carboxylic acid compound having a pyridine skeleton in the molecule and an alcohol component are subjected to condensation polymerization, and after the reaction rate reaches 60 to 98%, more preferably 70 to 95%, another carboxylic acid compound is added. It is preferable to add and perform condensation polymerization. In the present invention, the reaction rate refers to the rate when the discharge of the theoretical reaction water amount is 100%, and in the above case, the theoretical reaction between the carboxylic acid compound having a pyridine skeleton in the molecule and the alcohol component. This is the rate when the amount of water discharged is 100% reaction rate.
アルコール成分とカルボン酸成分との縮重合は、錫化合物、チタン化合物等のエステル化触媒の存在下、不活性ガス雰囲気中にて、180〜250℃の温度で行うことが好ましい。 The polycondensation of the alcohol component and the carboxylic acid component is preferably performed at a temperature of 180 to 250 ° C. in an inert gas atmosphere in the presence of an esterification catalyst such as a tin compound or a titanium compound.
錫化合物としては、例えば、酸化ジブチル錫が知られているが、本発明では、ポリエステル中での分散性が良好である観点から、Ｓｎ-Ｃ結合を有していない錫(II)化合物が好ましい。 As the tin compound, for example, dibutyltin oxide is known, but in the present invention, a tin (II) compound having no Sn—C bond is preferable from the viewpoint of good dispersibility in the polyester. .
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、(Ｒ2ＣＯＯ)2Ｓｎ(ここでＲ2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)、(Ｒ3Ｏ)2Ｓｎ(ここでＲ3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、(Ｒ2ＣＯＯ)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 2 COO) 2 Sn (wherein R 2 represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 3 O) 2 Sn (where R 3 Is C 6-20 alk Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by a group or an alkenyl group), (R 2 COO) fatty tin represented by 2 Sn (II) and tin oxide ( II) is more preferable, and tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferable.
チタン化合物の具体例としては、チタンジイソプロピレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ3Ｈ7Ｏ)2〕、チタンジイソプロピレートビスジエタノールアミネート〔Ｔｉ(Ｃ4Ｈ10Ｏ2Ｎ)2(Ｃ3Ｈ7Ｏ)2〕、チタンジペンチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ5Ｈ11Ｏ)2〕、チタンジエチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ2Ｈ5Ｏ)2〕、チタンジヒドロキシオクチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(ＯＨＣ8Ｈ16Ｏ)2〕、チタンジステアレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ18Ｈ37Ｏ)2〕、チタントリイソプロピレートトリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)(Ｃ3Ｈ7Ｏ)3〕、チタンモノプロピレートトリス(トリエタノールアミネート)〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)3(Ｃ3Ｈ7Ｏ)〕等が挙げられ、これらの中ではチタンジイソプロピレートビストリエタノールアミネート、チタンジイソプロピレートビスジエタノールアミネート及びチタンジペンチレートビストリエタノールアミネートが好ましく、これらは、例えばマツモト交商(株)の市販品としても入手できる。 Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 3 H 7 O) 2 ], titanium diisopropylate bisdiethanolamate [Ti (C 4 H 10 O 2 N) 2 (C 3 H 7 O) 2 ], titanium dipentylate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 5 H 11 O) 2 ], titanium diety rate bis triethanolaminate [Ti (C 6 H 14 O 3 N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate [Ti (C 6 H 14 O 3 N) 2 (OHC 8 H 16 O) 2 ], titanium distearate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 18 H 37 O) 2 ], titanium triisopropylate triethanolamate [Ti (C 6 H 14 O 3 N) (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) [Ti (C 6 H 14 O 3 N) 3 (C 3 H 7 O)] and the like, among these, titanium diisopropylate bistri Ethanolaminate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd., for example.
他の好ましいチタン化合物の具体例としては、テトラ-ｎ-ブチルチタネート〔Ｔｉ(Ｃ4Ｈ9Ｏ)4〕、テトラプロピルチタネート〔Ｔｉ(Ｃ3Ｈ7Ｏ)4〕、テトラステアリルチタネート〔Ｔｉ(Ｃ18Ｈ37Ｏ)4〕、テトラミリスチルチタネート〔Ｔｉ(Ｃ14Ｈ29Ｏ)4〕、テトラオクチルチタネート〔Ｔｉ(Ｃ8Ｈ17Ｏ)4〕、ジオクチルジヒドロキシオクチルチタネート〔Ｔｉ(Ｃ8Ｈ17Ｏ)2(ＯＨＣ8Ｈ16Ｏ)2〕、ジミリスチルジオクチルチタネート〔Ｔｉ(Ｃ14Ｈ29Ｏ)2(Ｃ8Ｈ17Ｏ)2〕等が挙げられ、これらの中ではテトラステアリルチタネート、テトラミリスチルチタネート、テトラオクチルチタネート及びジオクチルジヒドロキシオクチルチタネートが好ましい。これらは、例えばハロゲン化チタンを対応するアルコールと反応させることにより得ることができ、又は、ニッソー社等の市販品としても入手できる。 Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C 4 H 9 O) 4 ], tetrapropyl titanate [Ti (C 3 H 7 O) 4 ], tetrastearyl titanate [Ti ( C 18 H 37 O) 4 ], tetramyristyl titanate [Ti (C 14 H 29 O) 4 ], tetraoctyl titanate [Ti (C 8 H 17 O) 4 ], dioctyl dihydroxyoctyl titanate [Ti (C 8 H 17 O) 2 (OHC 8 H 16 O) 2 ], dimyristyl dioctyl titanate [Ti (C 14 H 29 O) 2 (C 8 H 17 O) 2 ] and the like. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.
エステル化触媒の存在量は、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、0.01〜2.0重量部が好ましく、0.1〜1.5重量部がより好ましく、0.2〜1.0重量部がさらに好ましい。ここで、エステル化触媒の存在量とは、縮重合反応に供した触媒の全配合量を意味する。 The amount of the esterification catalyst is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and still more preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component. Here, the abundance of the esterification catalyst means the total amount of the catalyst subjected to the condensation polymerization reaction.
ポリエステルの軟化点は、トナーの低温定着性、保存性及び耐久性の観点から、90〜160℃が好ましく、100〜150℃がより好ましく、105〜140℃がさらに好ましい。 The softening point of the polyester is preferably from 90 to 160 ° C, more preferably from 100 to 150 ° C, and even more preferably from 105 to 140 ° C, from the viewpoint of low-temperature fixability, storage stability, and durability of the toner.
ポリエステルは、軟化点の高い樹脂と低い樹脂とを併用することで、トナーの低温定着性と保存性の点において、より優れる。具体的に、結着樹脂は、上記観点から、軟化点が好ましくは10℃以上、より好ましくは20〜60℃異なる高軟化点ポリエステルと低軟化点ポリエステルとからなることが好ましい。高軟化点ポリエステルの軟化点は、好ましくは125〜160℃、より好ましくは130〜150℃であり、低軟化点ポリエステルの軟化点は、好ましくは90〜120℃、より好ましくは90〜110℃である。高軟化点ポリエステルの低軟化点ポリエステルに対する重量比(高軟化点ポリエステル／低軟化点ポリエステル)は、1/3〜3/1が好ましく、1/2〜2/1がより好ましい。 Polyester is more excellent in terms of low-temperature fixability and storage stability of toner by using a resin having a high softening point and a resin having a low softening point. Specifically, the binder resin is preferably composed of a high softening point polyester and a low softening point polyester having a softening point of preferably 10 ° C. or higher, more preferably 20 to 60 ° C. from the above viewpoint. The softening point of the high softening point polyester is preferably 125 to 160 ° C, more preferably 130 to 150 ° C, and the softening point of the low softening point polyester is preferably 90 to 120 ° C, more preferably 90 to 110 ° C. is there. The weight ratio of the high softening point polyester to the low softening point polyester (high softening point polyester / low softening point polyester) is preferably 1/3 to 3/1, and more preferably 1/2 to 2/1.
ポリエステルのガラス転移点は、トナーの低温定着性、保存性及び耐久性の観点から、45〜85℃が好ましく、50〜80℃がより好ましい。 The glass transition point of the polyester is preferably 45 to 85 ° C, more preferably 50 to 80 ° C, from the viewpoints of low-temperature fixability, storage stability and durability of the toner.
また、トナーの低温定着性の観点から、酸価は、15mgKOH/g以上が好ましく、15〜80mgKOH/gがより好ましく、15〜70mgKOH/gがさらに好ましい。酸価を15mgKOH/g以上とするには縮重合反応に用いられるカルボン酸成分とアルコール成分のモル比を前述のとおりに調整したり、ポリエステルの縮重合反応を調整する方法がある。縮重合反応が進行するにつれて、樹脂の分子量が大きくなるとともに、酸価は低くなる。 In view of low-temperature fixability of the toner, the acid value is preferably 15 mgKOH / g or more, more preferably 15 to 80 mgKOH / g, and further preferably 15 to 70 mgKOH / g. In order to increase the acid value to 15 mgKOH / g or more, there are methods of adjusting the molar ratio of the carboxylic acid component and the alcohol component used in the condensation polymerization reaction as described above, or adjusting the condensation polymerization reaction of polyester. As the polycondensation reaction proceeds, the molecular weight of the resin increases and the acid value decreases.
本発明の結着樹脂は、アルコール成分とカルボン酸成分の縮重合によるポリエステルを含む樹脂であり、ポリエステルだけでなく、ポリエステル変性樹脂も含まれるが、トナーの耐久性及び帯電立ち上がり性の観点から、ポリエステルが好ましい。 The binder resin of the present invention is a resin containing a polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component, and includes not only a polyester but also a polyester-modified resin. From the viewpoint of toner durability and charge rising property, Polyester is preferred.
ポリエステルの含有量は、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い。 The polyester content is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more in the binder resin.
ポリエステル変性樹脂としては、例えば、ポリエステル・ポリアミド、ポリエステルがウレタン結合で変性されたウレタン変性ポリエステル、ポリエステルがエポキシ結合で変性されたエポキシ変性ポリエステル、及びポリエステル成分とビニル系樹脂成分を含む２種以上の樹脂成分を有する複合樹脂等が挙げられる。 Examples of the polyester-modified resin include polyester / polyamide, urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and two or more kinds including a polyester component and a vinyl resin component. Examples thereof include a composite resin having a resin component.
ポリエステル成分の含有量は、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い。 The content of the polyester component is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more in the binder resin.
本発明の結着樹脂には、本発明の効果を損なわない範囲で、公知の結着樹脂、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、前記ポリエステルの含有量は、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。 In the binder resin of the present invention, a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like is used in combination as long as the effects of the present invention are not impaired. However, the content of the polyester in the binder resin is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and substantially 100% by weight. More preferably.
本発明の結着樹脂を用いて、低温定着性と保存性のいずれにも優れた電子写真用トナーが得られる。 By using the binder resin of the present invention, an electrophotographic toner excellent in both low-temperature fixability and storage stability can be obtained.
本発明のトナーには、さらに、着色剤、離型剤、荷電制御剤、荷電制御樹脂、磁性粉、流動性向上剤、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、クリーニング性向上剤等の添加剤が適宜含有されていてもよい。 The toner of the present invention further includes a colorant, a release agent, a charge control agent, a charge control resin, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an oxidation Additives such as an inhibitor, an anti-aging agent, and a cleaning property improver may be appropriately contained.
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、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンB、ローダミン−Bベース、ソルベントレッド49、ソルベントレッド146、ソルベントブルー35、キナクリドン、カーミン6B、ジスアゾエロー等が用いることができ、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、2〜10重量部がより好ましい。 As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
離型剤としては、ポリオレフィンワックス、パラフィンワックス、シリコーン類；オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、ステアリン酸アミド等の脂肪酸アミド類；カルナバロウワックス、ライスワックス、キャンデリラワックス、木ロウ、ホホバ油等の植物系ワックス；ミツロウ等の動物系ワックス；モンタンワックス、オゾケライト、セレシン、マイクロクリスタリンワックス、フィッシャートロプシュワックス等の鉱物・石油系ワックス等のワックスが挙げられ、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る。 Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oils; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more Can be mixed and used.
離型剤の融点は、トナーの低温定着性と耐オフセット性の観点から、60〜160℃が好ましく、60〜150℃がより好ましい。 The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoints of low-temperature fixability and offset resistance of the toner.
離型剤の含有量は、結着樹脂100重量部に対して、結着樹脂中への分散性の観点から、0.5〜10重量部が好ましく、0.8〜5重量部がより好ましい。 The content of the release agent is preferably 0.5 to 10 parts by weight and more preferably 0.8 to 5 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of dispersibility in the binder resin.
荷電制御剤としては、特に限定されないが、負帯電性荷電制御剤としては、含金属アゾ染料、例えば「ボントロンS-28」(オリエント化学工業社製)、「T-77」(保土谷化学工業社製)、「ボントロンS-34」 (オリエント化学工業社製)、「アイゼンスピロンブラックTRH」(保土谷化学工業社製)等；銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、例えば「ボントロンE-81」、「ボントロンE-84」、「ボントロンE-304」(以上、オリエント化学工業社製)等；ニトロイミダゾール誘導体；ベンジル酸ホウ素錯体、例えば、「LR-147」(日本カーリット社製)等；無金属系荷電調整剤、例えば「ボントロンF-21」、「ボントロンE-89」(以上、オリエント化学工業社製)、「T-8」(保土ヶ谷化学工業社製)、「FCA-2521NJ」、「FCA-2508N」(以上、藤倉化成社製)等が挙げられる。 The charge control agent is not particularly limited. Examples of the negative charge control agent include metal-containing azo dyes such as “Bontron S-28” (manufactured by Orient Chemical Co., Ltd.), “T-77” (Hodogaya Chemical Co., Ltd.). , Bontron S-34 (produced by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH” (made by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes, metal complexes of salicylic acid alkyl derivatives such as “Bontron” E-81 ”,“ Bontron E-84 ”,“ Bontron E-304 ”(manufactured by Orient Chemical Industry Co., Ltd.), etc .; Nitroimidazole derivatives; Boron benzylate complexes, such as“ LR-147 ”(manufactured by Nippon Carlit Non-metallic charge control agents such as “Bontron F-21”, “Bontron E-89” (manufactured by Orient Chemical Co., Ltd.), “T-8” (Hodogaya Chemical Co., Ltd.), “FCA- 2521NJ, FCA-2508N (Fujikura Kasei Co., Ltd.) It is below.
正帯電性荷電制御剤としては、ニグロシン染料、例えば「ボントロンN-01」、「ボントロンN-04」、「ボントロンN-07」(以上、オリエント化学工業社製)、「CHUO CCA-3」(中央合成社製)等；3級アミンを側鎖として含有するトリフェニルメタン系染料；4級アンモニウム塩化合物、例えば「ボントロンP-51」(オリエント化学工業社製)、「TP-415」(保土谷化学工業社製)、セチルトリメチルアンモニウムブロミド、「COPYCHARGEPXVP435」(ヘキスト社製)等が挙げられる。 Examples of positively chargeable charge control agents include nigrosine dyes such as `` Bontron N-01 '', `` Bontron N-04 '', `` Bontron N-07 '' (above, manufactured by Orient Chemical Industries), `` CHUO CCA-3 '' ( Chuo Gosei Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains; Quaternary ammonium salt compounds such as “Bontron P-51” (Orient Chemical Industries), “TP-415” (Tsuchiya Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, “COPYCHARGEPXVP435” (Hoechst) and the like.
荷電制御剤の含有量は、結着樹脂100重量部に対して、0.1〜8重量部が好ましく、0.5〜7重量部がより好ましい。 The content of the charge control agent is preferably 0.1 to 8 parts by weight and more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーは、溶融混練法、乳化転相法、重合法等の従来より公知のいずれの方法により得られたトナーであってもよいが、生産性や着色剤の分散性の観点から、溶融混練法による粉砕トナーが好ましい。溶融混練法による粉砕トナーの場合、例えば、結着樹脂、着色剤、荷電制御剤等の原料をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー、１軸もしくは２軸の押出機、オープンロール型混練機等で溶融混練し、冷却、粉砕、分級して製造することができる。一方、トナーの小粒径化の観点からは、重合法によるトナーが好ましい。 The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by melt kneading is preferred. In the case of pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetically sealed kneader, a single or twin screw extruder It can be produced by melt-kneading with an open roll kneader or the like, cooling, pulverizing and classifying. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.
本発明のトナーの体積中位粒径(Ｄ50)は、3〜15μｍが好ましく、3〜10μmがより好ましい。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 3 to 15 μm, more preferably 3 to 10 μm. 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.
本発明のトナーには、転写性を向上させるために、無機微粒子を外添剤として用いるのが好ましい。具体的には、シリカ、アルミナ、チタニア、ジルコニア、酸化錫、及び酸化亜鉛からなる群から選ばれる１種以上が好ましく挙げられ、これらの中では、シリカが好ましく、埋め込み防止の観点から、比重の小さいシリカが含有されているのがより好ましい。 In the toner of the present invention, it is preferable to use inorganic fine particles as an external additive in order to improve transferability. Specifically, at least one selected from the group consisting of silica, alumina, titania, zirconia, tin oxide, and zinc oxide is preferable. Among these, silica is preferable, and from the viewpoint of preventing embedding, the specific gravity is More preferably, small silica is contained.
シリカは、トナーの転写性の観点から、疎水化処理された疎水性シリカであるのが好ましい。 Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.
外添剤の含有量は、外添剤で処理する前のトナー粒子100重量部に対して、好ましくは0.05〜5重量部であり、より好ましくは0.1〜3重量部であり、さらに好ましくは0.3〜3重量部である。 The content of the external additive is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and still more preferably 0.3 to 100 parts by weight of toner particles before being processed with the external additive. ~ 3 parts by weight.
本発明の電子写真用トナーは、一成分現像用トナーとして、又はキャリアと混合して二成分現像剤として用いることができる。 The electrophotographic toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.
〔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、試料の半量が流出した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, and a 1.96 MPa load is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔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、試料を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 from that temperature to 0 ° C at a rate of 10 ° C / min. The temperature of the cooled sample is raised at a heating rate of 10 ° C / min, and the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent that indicates the maximum slope from the peak rise to the peak apex To do.
〔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)).
〔離型剤の融点〕
示差走査熱量計（セイコー電子工業社製、DSC210）を用いて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、融解熱の最大ピーク温度を融点とする。
[Melting point of release agent]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.
〔トナーの体積中位粒径（Ｄ50）〕
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：50μｍ
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％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：ビーカーに電解液100mlと分散液を加え、3万個の粒子の粒径を20秒で測定できる濃度で、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 diameter of toner (D 50 )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D 50).
樹脂製造例１〔樹脂Ａ、Ｉ〕
表１、２に示す2,6-ピリジンジカルボン酸とアルコール成分、及びエステル化触媒を、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装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、200℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。150℃まで冷却し、表１、２に示すテレフタル酸を仕込み、230℃、常圧にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。210℃まで冷却したのち、表１、２に示す無水トリメリット酸を添加し、1時間常圧にて反応させた後、8kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ａ、Ｉ)を得た。
Resin Production Example 1 [Resin A, I]
Place 2,6-pyridinedicarboxylic acid, alcohol component, and esterification catalyst shown in Tables 1 and 2 in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube. The reaction was continued in a mantle heater in a nitrogen atmosphere at 200 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, and further reacted at 8 kPa for 1 hour. After cooling to 150 ° C., terephthalic acid shown in Tables 1 and 2 was charged, and the reaction was continued at 230 ° C. and normal pressure until the reaction rate reached 90%, and then further reacted at 8 kPa for 1 hour. After cooling to 210 ° C., trimellitic anhydride shown in Tables 1 and 2 was added, reacted at normal pressure for 1 hour, then reacted to the desired softening point at 8 kPa, and polyester (resins A and I) Got.
樹脂製造例２〔樹脂Ｂ、Ｃ〕
表１に示す無水トリメリット酸を除くカルボン酸成分、アルコール成分、及びエステル化触媒を、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装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、200℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。表１に示す無水トリメリット酸を添加し、210℃、1時間常圧にて反応させた後、8kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ｂ、Ｃ)を得た。
Resin Production Example 2 [Resin B, C]
Put the carboxylic acid component, alcohol component, and esterification catalyst except trimellitic anhydride shown in Table 1 into a 5 liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a flow-down condenser and a nitrogen inlet tube. The reaction was continued in a mantle heater in a nitrogen atmosphere at 200 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, and further reacted at 8 kPa for 1 hour. Trimellitic anhydride shown in Table 1 was added and reacted at 210 ° C. for 1 hour at normal pressure, and then reacted at 8 kPa to the desired softening point to obtain polyesters (resins B and C).
樹脂製造例３〔樹脂Ｄ〕
表１に示す2,6-ピリジンジカルボン酸とアルコール成分、及びエステル化触媒を、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装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、200℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。180℃に冷却し、表１に示すフマル酸及び重合禁止剤(t-ブチルカテコール)を添加し、210℃まで4時間かけて昇温し、210℃にて1時間常圧にて反応させた後、8kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ｄ)を得た。
Resin Production Example 3 [Resin D]
The 2,6-pyridinedicarboxylic acid and alcohol component shown in Table 1 and the esterification catalyst were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The reaction was carried out in a mantle heater in an atmosphere at 200 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, and further reacted at 8 kPa for 1 hour. After cooling to 180 ° C., fumaric acid and a polymerization inhibitor (t-butylcatechol) shown in Table 1 were added, the temperature was raised to 210 ° C. over 4 hours, and the reaction was carried out at 210 ° C. for 1 hour at normal pressure. Thereafter, the reaction was carried out to a desired softening point at 8 kPa to obtain polyester (resin D).
樹脂製造例４〔樹脂Ｅ〕
表１に示す2,6-ピリジンジカルボン酸とアルコール成分、及びエステル化触媒を、温度計、ステンレス製攪拌棒、流下式コンデンサー、精留塔及び窒素導入管を装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、180℃まで昇温し、200℃まで5時間かけて昇温を行った。200℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに40kPaにて1時間反応させた。表１に示す無水トリメリット酸を添加し、210℃、1時間常圧にて反応させた後、40kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ｅ)を得た。
Resin Production Example 4 [Resin E]
A 5-liter four-necked flask equipped with a 2,6-pyridinedicarboxylic acid, an alcohol component, and an esterification catalyst shown in Table 1 equipped with a thermometer, a stainless steel stirring rod, a falling condenser, a rectification column, and a nitrogen introduction tube The temperature was raised to 180 ° C. in a mantle heater in a nitrogen atmosphere, and the temperature was raised to 200 ° C. over 5 hours. The reaction was continued at 200 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, and then further reacted at 40 kPa for 1 hour. Trimellitic anhydride shown in Table 1 was added and reacted at 210 ° C. for 1 hour at normal pressure, and then reacted to a desired softening point at 40 kPa to obtain polyester (resin E).
樹脂製造例５〔樹脂Ｆ、Ｇ〕
表２に示すテレフタル酸、アルコール成分、及びエステル化触媒を、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装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、230℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。表２に示す無水トリメリット酸を添加し、210℃、1時間常圧にて反応させた後、8kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ｆ、Ｇ)を得た。
Resin Production Example 5 [Resin F, G]
Put the terephthalic acid, alcohol component and esterification catalyst shown in Table 2 into a 5 liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a flow-down condenser and a nitrogen inlet tube, and mantle heater in a nitrogen atmosphere. The reaction was continued at 230 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, followed by further reaction at 8 kPa for 1 hour. Trimellitic anhydride shown in Table 2 was added and reacted at 210 ° C. for 1 hour at normal pressure, and then reacted at 8 kPa to the desired softening point to obtain polyesters (resins F and G).
樹脂製造例６〔樹脂Ｈ〕
表２に示す2,5-ピリジンジカルボン酸とアルコール成分、及びエステル化触媒を、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装備した5リットルの四つ口フラスコに入れ、窒素雰囲気にてマントルヒーター中で、200℃、常圧(101.3kPa)にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。150℃まで冷却し、表２に示すテレフタル酸を仕込み、230℃、常圧にて反応率が90％に到達するまで反応させたのち、さらに8kPaにて1時間反応させた。210℃まで冷却したのち、表２に示す無水トリメリット酸を添加し、1時間常圧にて反応させた後、8kPaにて所望の軟化点まで反応させ、ポリエステル(樹脂Ｈ)を得た。
Resin Production Example 6 [Resin H]
The 2,5-pyridinedicarboxylic acid and alcohol component shown in Table 2 and the esterification catalyst were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The reaction was carried out in a mantle heater in an atmosphere at 200 ° C. and normal pressure (101.3 kPa) until the reaction rate reached 90%, and further reacted at 8 kPa for 1 hour. The mixture was cooled to 150 ° C., charged with terephthalic acid shown in Table 2, reacted at 230 ° C. and normal pressure until the reaction rate reached 90%, and further reacted at 8 kPa for 1 hour. After cooling to 210 ° C., trimellitic anhydride shown in Table 2 was added and reacted at normal pressure for 1 hour, and then reacted to a desired softening point at 8 kPa to obtain a polyester (resin H).
実施例１〜８及び比較例１、２（実施例５〜７は参考例である）
表３に示す結着樹脂100重量部、カーボンブラック「MOGUL L」(キャボット社製)4重量部、負帯電性荷電制御剤「ボントロン S-34」(オリエント化学工業社製)1重量部及びポリプロピレンワックス「NP-105」(三井化学社製、融点:140℃)1重量部をヘンシェルミキサーで十分混合した後、同方向回転二軸押出し機を用い、ロール回転速度200r/min、ロール内の加熱温度80℃で溶融混練した。得られた溶融混練物を冷却、粗粉砕した後、ジェットミルにて粉砕し、分級して、体積中位粒径(Ｄ50)が7.5μmのトナー粒子を得た。
Examples 1 to 8 and Comparative Examples 1 and 2 (Examples 5 to 7 are reference examples)
100 parts by weight of binder resin shown in Table 3, 4 parts by weight of carbon black “MOGUL L” (Cabot), 1 part by weight of negative charge control agent “Bontron S-34” (Orient Chemical Industries) and polypropylene After thoroughly mixing 1 part by weight of wax “NP-105” (Mitsui Chemicals, melting point: 140 ° C.) with a Henschel mixer, using a co-rotating twin screw extruder, roll rotation speed 200r / min, heating in the roll Melt kneading was performed at a temperature of 80 ° C. The obtained melt-kneaded product was cooled, coarsely pulverized, then pulverized by a jet mill, and classified to obtain toner particles having a volume median particle size (D 50 ) of 7.5 μm.
得られたトナー粒子100重量部に、外添剤として「アエロジル R-972」(日本アエロジル社製)1.0重量部を添加し、ヘンシェルミキサーで混合してトナーを得た。 To 100 parts by weight of the obtained toner particles, 1.0 part by weight of “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) was added as an external additive and mixed with a Henschel mixer to obtain a toner.
試験例１〔低温定着性〕
複写機「AR-505」(シャープ(株)製)の定着機を装置外での定着が可能なように改良した装置にトナーを実装し、未定着画像を得た。総定着圧が40kgfになるように調整した定着機(定着速度390mm/sec)を用い、定着ローラーの温度を100℃から240℃へと10℃ずつ順次上昇させながら、各温度で未定着画像の定着試験を行った。定着画像に「ユニセフセロハン」(三菱鉛筆社、幅：18mm、JISZ-1522)を貼り付け、30℃に設定した定着ローラーに通過させた後、テープを剥がした。テープを貼る前と剥がした後の光学反射密度を反射濃度計「RD-915」(マクベス社製)を用いて測定し、両者の比率(剥離後／貼付前×100)が最初に90％を越える定着ローラーの温度を最低定着温度とし、以下の評価基準に従って、低温定着性を評価した。結果を表３に示す。なお、定着試験に用いた紙は、シャープ(株)製のCopyBond SF-70NA(75g/m2)であった。
Test Example 1 [low temperature fixability]
Toner was mounted in an apparatus in which the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) was modified so that fixing was possible outside the apparatus, and an unfixed image was obtained. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure is 40kgf, the temperature of the fixing roller is gradually increased from 100 ° C to 240 ° C in 10 ° C increments. A fixing test was conducted. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was pasted on the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The fixing roller temperature exceeding the minimum fixing temperature was used, and the low temperature fixing property was evaluated according to the following evaluation criteria. The results are shown in Table 3. The paper used in the fixing test was CopyBond SF-70NA (75 g / m 2 ) manufactured by Sharp Corporation.
〔評価基準〕
Ａ：最低定着温度が160℃未満である。
Ｂ：最低定着温度が160℃以上、180℃未満である。
Ｃ：最低定着温度が180℃以上である。
〔Evaluation criteria〕
A: The minimum fixing temperature is less than 160 ° C.
B: The minimum fixing temperature is 160 ° C. or higher and lower than 180 ° C.
C: The minimum fixing temperature is 180 ° C. or higher.
試験例２〔保存性〕
トナー4gを温度50℃、湿度60％の環境下で48時間放置した。放置後、トナー凝集の発生程度を目視にて観察し、以下の評価基準に従って、保存性を評価した。結果を表３に示す。
Test Example 2 [Preservation]
4 g of toner was left for 48 hours in an environment of temperature 50 ° C. and humidity 60%. After standing, the degree of occurrence of toner aggregation was visually observed, and storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
〔評価基準〕
Ａ：凝集は全く認められない。
Ｂ：わずかに凝集が認められる。
Ｃ：明らかに凝集が認められる。
〔Evaluation criteria〕
A: Aggregation is not recognized at all.
B: Slight aggregation is observed.
C: Aggregation is clearly observed.
以上の結果より、実施例１〜８のトナーは、比較例１、２のトナーと対比して、トナーの低温定着性と保存性のいずれもが良好であることが分かる。 From the above results, it can be seen that the toners of Examples 1 to 8 are excellent in both the low-temperature fixability and the storage stability of the toner as compared with the toners of Comparative Examples 1 and 2.
本発明のトナー用結着樹脂は、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用いられる電子写真用トナーの結着樹脂として好適に用いられる。 The binder resin for toner of the present invention is suitably used as a binder resin for an electrophotographic toner used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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| JP3393085B2 (en) * | 1999-05-14 | 2003-04-07 | 株式会社巴川製紙所 | Electrophotographic toner |
| JP2005215607A (en) * | 2004-02-02 | 2005-08-11 | Seiko Epson Corp | Electrophotographic toner |
| JP2008281709A (en) * | 2007-05-09 | 2008-11-20 | Fuji Xerox Co Ltd | Toner for electrostatic charge image development, developer for electrostatic charge image development, cartridge and image forming apparatus |
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