JPH01201675A - Toner composition - Google Patents
Toner compositionInfo
- Publication number
- JPH01201675A JPH01201675A JP63027205A JP2720588A JPH01201675A JP H01201675 A JPH01201675 A JP H01201675A JP 63027205 A JP63027205 A JP 63027205A JP 2720588 A JP2720588 A JP 2720588A JP H01201675 A JPH01201675 A JP H01201675A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- polyester resin
- toner
- charge control
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 20
- 239000004645 polyester resin Substances 0.000 claims abstract description 26
- 229920001225 polyester resin Polymers 0.000 claims abstract description 26
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 claims abstract description 23
- 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 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 abstract description 7
- 150000007519 polyprotic acids Polymers 0.000 abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 238000007323 disproportionation reaction Methods 0.000 abstract 3
- 239000011230 binding agent Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 n-dodecylamino Chemical group 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 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
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GBURUDXSBYGPBL-UHFFFAOYSA-N 2,2,3-trimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)C(C)CCC(O)=O GBURUDXSBYGPBL-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- GZZLQUBMUXEOBE-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diol Chemical compound OCCC(C)CC(C)(C)CO GZZLQUBMUXEOBE-UHFFFAOYSA-N 0.000 description 1
- PKKDWPSOOQBWFB-UHFFFAOYSA-N 2,4-dichloro-6-[(3,5-dichloro-2-hydroxyphenyl)methyl]phenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1CC1=CC(Cl)=CC(Cl)=C1O PKKDWPSOOQBWFB-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
- HECNJWVSWIBMGG-UHFFFAOYSA-N 2-(cyclohexylcarbamoyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)NC1CCCCC1 HECNJWVSWIBMGG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-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
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- BUYHVRZQBLVJOO-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexane-1,3-diol Chemical compound CCC(C)C(O)C(C)(CC)CO BUYHVRZQBLVJOO-UHFFFAOYSA-N 0.000 description 1
- QNKRHLZUPSSIPN-UHFFFAOYSA-N 2-ethyl-2-(2-methylpropyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CC(C)C QNKRHLZUPSSIPN-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- RGUZWBOJHNWZOK-UHFFFAOYSA-N 3,6-dimethylbenzene-1,2-diol Chemical compound CC1=CC=C(C)C(O)=C1O RGUZWBOJHNWZOK-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- FYGVLURPKLFVAB-UHFFFAOYSA-N 4-methylcyclohexane-1,2,3-tricarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1C(O)=O FYGVLURPKLFVAB-UHFFFAOYSA-N 0.000 description 1
- CDUACMUYDHRMBX-UHFFFAOYSA-N 6-(oxomethylidene)cyclohexa-2,4-diene-1-carboxylic acid Chemical compound OC(=O)C1C=CC=CC1=C=O CDUACMUYDHRMBX-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PJGXSCHDOCZUNR-UHFFFAOYSA-N azanium;2-sulfobenzoate Chemical compound [NH4+].OC(=O)C1=CC=CC=C1S([O-])(=O)=O PJGXSCHDOCZUNR-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- VCVOSERVUCJNPR-UHFFFAOYSA-N cyclopentane-1,2-diol Chemical compound OC1CCCC1O VCVOSERVUCJNPR-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- VDNLFJGJEQUWRB-UHFFFAOYSA-N rose bengal free acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 VDNLFJGJEQUWRB-UHFFFAOYSA-N 0.000 description 1
- HFPGULMERUXXDW-UHFFFAOYSA-M sodium;2-carboxybenzenesulfonate Chemical compound [Na+].OS(=O)(=O)C1=CC=CC=C1C([O-])=O HFPGULMERUXXDW-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電子写真法、静電写真法、静電記録法等にお
いて形成される静電画像を現像するために使用されるト
ナー組成物、殊に、プラス帯電用に使用できる組成物に
関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a toner composition used for developing electrostatic images formed in electrophotography, electrostatic photography, electrostatic recording, etc. In particular, it relates to compositions that can be used for positive charging.
［従来の技術］
一般に静電画像は、着色粉体であるトナーにより現像さ
れてトナー像とされ、このトナー像がそのままあるいは
転写紙等に転写された上で定着される。[Prior Art] Generally, an electrostatic image is developed with toner, which is a colored powder, to form a toner image, and this toner image is fixed as it is or after being transferred to a transfer paper or the like.
通常トナーは、バインダー成分及び着色成分、荷電制御
剤を配合し、加熱下に溶融、混合した後、所定の粒度に
粉砕することにより調製される。A toner is usually prepared by blending a binder component, a coloring component, and a charge control agent, melting and mixing the mixture under heating, and then pulverizing the mixture to a predetermined particle size.
トナーの性能はバインダー成分に大きく影響される。Toner performance is greatly influenced by binder components.
この場合、マイナス帯電型トナーとするにはバインダー
樹脂に酸価を持たせ、プラス帯電型トナーとするにはバ
インダー樹脂にアミン基や第４級アンモニウム塩基を導
入すればよい。In this case, to make a negatively charged toner, the binder resin may have an acid value, and to make a positively charged toner, an amine group or a quaternary ammonium base may be introduced into the binder resin.
トナーのバインダー成分としては種々の樹脂が知られて
いるが、最近では、帯電性が大きくかつ低温定着性にす
ぐれているため高速複写用に適性を有し、しかも塩化ビ
ニルシート、フィルム等に印刷物が積層されたときに可
塑剤により印刷面が不鮮明化することがない（つまり耐
可塑剤性にすぐれている）ポリエステル樹脂系パインダ
ーが注目されている。Various resins are known as binder components for toners, but recently, they are suitable for high-speed copying due to their high chargeability and excellent low-temperature fixing properties, and are also suitable for printing on vinyl chloride sheets, films, etc. Polyester resin binders are attracting attention because they do not cause the printed surface to become unclear due to plasticizers when they are laminated (in other words, they have excellent plasticizer resistance).
ポリエステル樹脂をトナー用のバインダー樹脂とする出
願として、例えば次にあげるものがある。Examples of applications using polyester resin as a binder resin for toner include the following.
■ 特開昭５９．７９６０号公報には、（Ａ）アルキル
置換ジカルボン酸類及び／又はアルキル置換ジオール、
（Ｂ）３価以上のポリカルボン酸類及び／又は３価以上
のポリオール類、（Ｃ）ジカルボン酸類、（Ｄ）エーテ
ル化ジフェノール類、を含有する成分から得られる酸価
１０〜６０の非線状低融点ポリエステルを含有する熱定
着性乾式トナーが示されている。■ JP-A-59-7960 discloses (A) alkyl-substituted dicarboxylic acids and/or alkyl-substituted diols;
(B) A nonlinear acid value of 10 to 60 obtained from a component containing trivalent or higher polycarboxylic acids and/or trivalent or higher polyols, (C) dicarboxylic acids, and (D) etherified diphenols. A heat-fixable dry toner containing a low melting point polyester is disclosed.
■ 特公昭５２−２５４２０号公報（特開昭４７−１２
３３４号公報）には、ジカルボン酸と特定のエーテル化
ジフェノールとから得られる１１０℃よりも低い流動点
及び約６０℃以上の粘着点を有するポリエステル樹脂を
含有するトナーが示されている。■ Japanese Patent Publication No. 52-25420 (Japanese Patent Publication No. 47-12
No. 334) discloses a toner containing a polyester resin obtained from a dicarboxylic acid and a specific etherified diphenol and having a pour point below 110°C and a stick point above about 60°C.
■ 特開昭５９−２９２５６号公報には、プロポキシ化
及び／又はエトキシ化されていてプロポキシ基か５０％
以上であるエーテル化ジフェノールと、３価以上の芳香
族カルボン酸を４０モル％まで含むフタル酸類とを反応
させて得られる酸価１０〜１００の無定形ポリエステル
を用いたトナーが示されている。■ JP-A No. 59-29256 discloses that propoxylated and/or ethoxylated and 50% of the propoxy group is
A toner using an amorphous polyester with an acid value of 10 to 100 obtained by reacting the above etherified diphenol with a phthalic acid containing up to 40 mol% of trivalent or higher aromatic carboxylic acid is disclosed. .
■ 特開昭６２−４５６２２号公報には、不揮発性のモ
ノカルボン酸成分、具体的にはスルホ安息香酸モノアン
モニウム塩、スルホ安息香酸モノナトリウム塩、シクロ
へキシルアミノカルボニル安息香酸、ｎ−ドデシルアミ
ノカルボニル安息香酸などを含有するポリエステル樹脂
であって、ガラス転移温度が５０℃でしかも軟化温度が
９０〜１７０℃であるトナー用ポリエステル樹脂につい
て開示がある。■ JP-A-62-45622 discloses non-volatile monocarboxylic acid components, specifically sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylamino There is a disclosure of a polyester resin for toner that contains carbonylbenzoic acid or the like and has a glass transition temperature of 50°C and a softening temperature of 90 to 170°C.
［発明が解決しようとする問題点］
上述のポリエステル樹脂系トナー用バインダー樹脂のう
ち■、■及び■は、その酸価が大きいことから、マイナ
ス帯電用に限られることがわかる。[Problems to be Solved by the Invention] Among the above-mentioned binder resins for polyester resin toners, it can be seen that ■, ■, and ■ are limited to negative charging applications because of their large acid values.
上述の■のポリエステル樹脂においては、過剰に存在す
る水酸基が安息香酸系モノカルボン酸で部分的に封鎖さ
れているが、量的割合から見て封鎖されていない末端水
酸基がかなり多量に存在しているものと考えられる。In the above polyester resin (2), the excess hydroxyl groups are partially blocked with benzoic monocarboxylic acids, but in terms of quantitative ratio, there are quite a large amount of unblocked terminal hydroxyl groups. It is thought that there are.
本発明者らの研究によれば、末端水酸基を有するポリエ
ステル樹脂は、マイナスの荷電制御剤の添加でマイナス
の帯ｉｔは大きくなることが期待できるが、プラスの荷
電制御剤を添加してもそのプラスの荷電量は小さい範囲
にとどまり、実用化にまで至らないという問題がある。According to the research of the present inventors, it is expected that the addition of a negative charge control agent will increase the negative band IT of polyester resins having terminal hydroxyl groups; however, even if a positive charge control agent is added, The problem is that the amount of positive charge remains within a small range, making it difficult to put it into practical use.
また、上述の■のポリエステル樹脂をバインダー樹脂と
するトナーは、低温定着性、耐オフセット性の点で、必
ずしも満足し得るものではなかった。なおオフセット現
象とは、トナーの一部が熱ローラーに転移して、その後
に供給されてくる転写用紙の表面を汚したり、更には熱
ローラーに押圧されている圧接ローラーに転移したトナ
ーにより、転写用紙の裏面が汚される現象である。Further, the toner using the above polyester resin as the binder resin was not necessarily satisfactory in terms of low-temperature fixing properties and anti-offset properties. The offset phenomenon is caused by some of the toner transferring to the heated roller and staining the surface of the transfer paper that is subsequently fed, or by toner transferring to the pressure roller that is pressed by the heated roller, causing the transfer This is a phenomenon in which the back side of the paper becomes dirty.
かかる問題点を解決するために、本出願人は先にロジン
で変性したポリエステル樹脂をバインダーとするトナー
について特許出願した。（特願昭６２−１８４６１７号
）しかし、該トナーはプラス帯電性の面で更に改良する
必要が明らかになり、本発明者等は鋭意研究を行った。In order to solve this problem, the present applicant previously filed a patent application for a toner using a polyester resin modified with rosin as a binder. (Japanese Patent Application No. 62-184617) However, it became clear that the toner needed to be further improved in terms of positive chargeability, and the inventors of the present invention conducted extensive research.
即ち、本発明は保存安定性、低温定着性や耐オフセット
性を維持しながらプラス帯電性が著しく向上したトナー
組成物を提供することを目的とするものである。That is, an object of the present invention is to provide a toner composition that has significantly improved positive chargeability while maintaining storage stability, low-temperature fixability, and offset resistance.
［問題点を解決するための手段］
本発明は不均化ロジンを縮合成分とするポリエステル樹
脂及び−殺人
（但しＲ１；炭素数１〜８のアルキル基、ＲＩＲ３：炭
素数１〜１８のアルキル基、Ｒ４：炭素数１〜８のアル
キル基又はベンジル基を示す）で表される荷電制御剤を
含んでなるトナー組成物を提供する。[Means for Solving the Problems] The present invention provides a polyester resin containing a disproportionated rosin as a condensation component and a polyester resin (wherein R1: an alkyl group having 1 to 8 carbon atoms; , R4: represents an alkyl group having 1 to 8 carbon atoms or a benzyl group).
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いるポリエステル樹脂は、多塩基酸成分と多
価アルコール及び不均化ロジンとを反応させることによ
り得られる。The polyester resin used in the present invention is obtained by reacting a polybasic acid component, a polyhydric alcohol, and a disproportionated rosin.
多塩基酸成分としては、テレフタル酸、イソフタル酸、
フタル酸、マロン酸、ジメチルマロン酸、コハク酸、ゲ
ルタール酸、アジピン酸、トリメチルアジピン酸、ピメ
リン酸、２，２−ジメチルグルクール酸、アゼライン酸
、セバシン酸、フマール酸、マレイン酸、イタコン酸、
ｌ、３−シクロペンタンジカルボン酸、１．２−シクロ
ヘキサンジカルボン酸、１．３−シクロペンタンジカル
ボンＬｌ、４−シクロヘキサンジカルボン酸、２．５−
ノルボルナンジカルボン酸、１．４−ナフタール酸、シ
フエニン酸、４，４°−オキシ安息香酸、ジグリコール
酸、チオジプロピオン酸、２．５−ナフタレンジカルボ
ン酸などがあげられる。これらの多塩基酸は、酸無水物
、エステル、クロライドなどであってもよい。Polybasic acid components include terephthalic acid, isophthalic acid,
Phthalic acid, malonic acid, dimethylmalonic acid, succinic acid, geltaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglucuric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid,
l, 3-cyclopentanedicarboxylic acid, 1.2-cyclohexanedicarboxylic acid, 1.3-cyclopentanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, 2.5-
Examples include norbornane dicarboxylic acid, 1,4-naphthalic acid, siphenic acid, 4,4°-oxybenzoic acid, diglycolic acid, thiodipropionic acid, and 2,5-naphthalene dicarboxylic acid. These polybasic acids may be acid anhydrides, esters, chlorides, etc.
ジカルボン酸のほかに、少量であるならば３価以上の多
価カルボン酸、例えばトリメリット酸、無水トリメリッ
ト酸、ピロメリット酸、無水ピロメリット酸、４−メチ
ルシクロヘキサン−１，２，３−トリカルボン酸無水物
、トリメシン酸、５−（２，５−ジオキソテトラヒドロ
フルフリル）−３−メチル−３−シクロヘキセン−１，
２−ジカルボン酸無水物などを併用することもできる。In addition to dicarboxylic acids, small amounts of trivalent or higher polyhydric carboxylic acids, such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexane-1,2,3- Tricarboxylic acid anhydride, trimesic acid, 5-(2,5-dioxotetrahydrofurfuryl)-3-methyl-3-cyclohexene-1,
2-dicarboxylic acid anhydride and the like can also be used in combination.
多価アルコール成分としては、エチレングリコール、ジ
エチレングリコール、プロピレングリコール、ｌ、３−
プロパンジオール、１．３−ブタンジオール、ｌ、４−
ブタンジオール、１．５−ベンタンジオール、１．６−
ヘキサンジオール、１．７−へブタンジオール、１．８
−オクタンジオール、１．９−ノナンジオール、１．１
０−デカンジオール、２．４−ジメチル−２−エチルヘ
キサン−１，３−ジオール、２，２−ジメチル−１，３
−プロパンジオール（ネオペンチルグリコール）、２−
エチル−２−ブチル−１，３−プロパンジオール、２−
エチル−２−イソブチル−１，３−プロパンジオール、
３−メチル−１，５−ペンタジオール、２，２．４−ト
リメチル−１，６−ヘキサンジオール、ｌ、２−シクロ
ヘキサンジメタツール、１．３−シクロヘキサンジメタ
ツール、１．４−シクロヘキサンジメタツール、２，２
，４．４−テトラメチル−１，３−シクロブタンジオー
ル、４．４゜−チオジフェノール、４．４°−メチレン
ジフェノール、４．４°−（２−ノルボルニリデン）ジ
フェノール、４．４′−ジヒドロキシビフェノール、ｏ
−、ｍ−及びｐ−ジヒドロキシベンゼン、４，４゛−
イソプロピリデンフェノール、４，４°−イソプロピリ
デンビス（２，６−ジクロロフェノール）、２．５−ナ
フタレンジオール、ｐ−キシレンジオール、シクロペン
タン−１，２−ジオール、シクロヘキサン−１，４−ジ
オール、ビスフェノールＡ−アルキレンオキサイド付加
物等のエーテル化ジフェノールなどがあげられる。場合
により少量の３価以上の多価アルコールを併用すること
もできる。Polyhydric alcohol components include ethylene glycol, diethylene glycol, propylene glycol, l, 3-
Propanediol, 1,3-butanediol, l,4-
Butanediol, 1.5-bentanediol, 1.6-
Hexanediol, 1.7-hebutanediol, 1.8
-octanediol, 1.9-nonanediol, 1.1
0-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3
-Propanediol (neopentyl glycol), 2-
Ethyl-2-butyl-1,3-propanediol, 2-
ethyl-2-isobutyl-1,3-propanediol,
3-Methyl-1,5-pentadiol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, 1,4-cyclohexane dimethatol Metatool, 2,2
, 4.4-tetramethyl-1,3-cyclobutanediol, 4.4°-thiodiphenol, 4.4°-methylenediphenol, 4.4°-(2-norbornylidene)diphenol, 4.4' -dihydroxybiphenol, o
-, m- and p-dihydroxybenzene, 4,4゛-
Isopropylidenephenol, 4,4°-isopropylidenebis(2,6-dichlorophenol), 2,5-naphthalene diol, p-xylene diol, cyclopentane-1,2-diol, cyclohexane-1,4-diol, Examples include etherified diphenols such as bisphenol A-alkylene oxide adducts. Depending on the case, a small amount of trihydric or higher polyhydric alcohol may also be used in combination.
３価以上の多価アルコールとしては、グリセリン、トリ
メチロールプロパン、１，２．６−ヘキサンジオール、
トリメチロールエタン、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、ソルビ
トールなどが例示できる。Examples of trivalent or higher polyhydric alcohols include glycerin, trimethylolpropane, 1,2.6-hexanediol,
Examples include trimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol.
不均化ロジンとは、主成分としてアビエチン酸を含むロ
ジンを貴金属触媒あるいはハロゲン触媒の存在下で高温
加熱することによって、分子内の不安定な共役二重結合
を消失させたもので、主成分として、ジヒドロアビエチ
ン酸とジヒドロアビエチン酸との混合物を意味する。Disproportionated rosin is a rosin containing abietic acid as its main component, which is heated at high temperature in the presence of a noble metal catalyst or a halogen catalyst to eliminate unstable conjugated double bonds within the molecule. means a mixture of dihydroabietic acid and dihydroabietic acid.
本発明ではかかる特定のロジンを用いる点に大きな特徴
をもち、ガムロジンや水添ロジンを用いても大巾なプラ
ス帯電性向上効果は認められない。The present invention is characterized by the use of such a specific rosin, and even when gum rosin or hydrogenated rosin is used, no significant positive chargeability improvement effect is observed.
本発明で用いるポリエステル樹脂は、要は不均化ロジン
を縮合成分として含有していればよく、その製造法に制
限はないが、以下の如き方法が代表的である。The polyester resin used in the present invention only needs to contain disproportionated rosin as a condensation component, and there are no restrictions on the method for producing it, but the following method is typical.
（イ）多塩基酸と多価アルコールとを後者が過剰となる
割合で一括仕込みし、併せて不均化ロジンを仕込む。エ
ステル化反応を常法で行い、ついで高真空で重縮合する
ことにより目的とするポリエステル樹脂を得る。(a) A polybasic acid and a polyhydric alcohol are charged at once in such a proportion that the latter is in excess, and the disproportionated rosin is also charged. The desired polyester resin is obtained by carrying out an esterification reaction in a conventional manner and then polycondensing in a high vacuum.
（ロ）多塩基酸と多価アルコールとを後者が過剰となる
割合で仕込んで通常のポリエステル化反応を行う。次に
不均化ロジンを仕込んで過剰の水酸基と反応させ、つい
で必要に応じ１価のアルコールを加えて過剰の不均化ロ
ジンと反応させ、ついで中程度の真空で過剰の追加原料
を追い出し、目的とするポリエステル樹脂を得る。(b) A normal polyesterification reaction is carried out by charging a polybasic acid and a polyhydric alcohol in such a ratio that the latter is in excess. The disproportionated rosin is then charged and reacted with the excess hydroxyl groups, then a monohydric alcohol is added as needed to react with the excess disproportionated rosin, and the excess additional material is then driven off with a medium vacuum. Obtain the desired polyester resin.
上記（イ）、（ロ）に代表される反応を行うときは、得
られるポリエステル樹脂の酸価が４ ＫＯＩＩｍｇ／ｇ
以下、水酸基価が２０ ＫＯ１１ｍｇ／ｇ以下となるよ
うに各成分の仕込み割合、その他の反応条件を定めるの
が好ましい。酸価又は水酸基価のいずれか一方でもこの
上限値を上まわると、期待する性質を有するトナーが得
られない。特に好ましい範囲は、酸価か２ ＫＯＩＩｍ
ｇ／ｇ以下、水酸基価が１２ ＫＯＩ１ｍｇ／ｇ以下で
ある。When carrying out the reactions represented by (a) and (b) above, the acid value of the resulting polyester resin is 4 KOIImg/g.
Hereinafter, it is preferable to determine the charging ratio of each component and other reaction conditions so that the hydroxyl value is 20 KO11 mg/g or less. If either the acid value or the hydroxyl value exceeds this upper limit, a toner having the expected properties cannot be obtained. A particularly preferable range is an acid value of 2 KOIIm
g/g or less, and the hydroxyl value is 12 KOI 1 mg/g or less.
次に本発明で用いる荷電制御剤は一般式％式％
ここでＲ１は炭素数ｌ〜８のアルキル基、例えばメチル
基、エチル基、プロピル基、ブチル基、アミル基、へキ
シル基、オクチル基であり、Ｒｔ、Ｒｓは炭素数１〜１
８のアルキル基である。Ｉ（ｔ、Ｒ３の具体例としては
Ｒ，と同様なもの以外にデシル基、ドデシル基、テトラ
デシル基、ヘキサデシル基である。Ｒ４はＲ，＆同−又
はベンジル基である。Next, the charge control agent used in the present invention has the general formula % where R1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group. , Rt and Rs have 1 to 1 carbon atoms
8 alkyl group. Specific examples of I(t and R3 are decyl group, dodecyl group, tetradecyl group, and hexadecyl group in addition to those similar to R. R4 is R, &same- or benzyl group.
市販品としてはボントロンＰ−５１（オリエント化学工
業株式会社製）等が著名である。As a commercially available product, Bontron P-51 (manufactured by Orient Chemical Industry Co., Ltd.) is well-known.
前記構造式で示される荷電制御剤の具体例としては次の
ものが挙げられる。Specific examples of the charge control agent represented by the above structural formula include the following.
トナー組成物の調製は、上記ポリエステル樹脂、着色剤
および荷電制御剤に、必要に応じ流動性改良剤、離型剤
、可塑剤などの添加剤を配合して溶融混合した後、所定
の粒度にまで粉砕することにより達成できる。なお、本
発明の趣旨を損なわない範囲で、上記のポリエステル樹
脂と共に他のポリエステル系又はポリエステル系以外の
トナー用バインダー樹脂を併用することもできる。The toner composition is prepared by melt-mixing the above polyester resin, colorant, and charge control agent with additives such as a fluidity improver, a mold release agent, and a plasticizer, if necessary, and then adjusting the mixture to a predetermined particle size. This can be achieved by crushing to Note that other polyester-based or non-polyester-based toner binder resins may be used in combination with the above-mentioned polyester resin as long as the spirit of the present invention is not impaired.
着色剤としては、例えば、カーボンブラック、ニグロシ
ン染料、アニリンブラック、カルコオイルブルー、クロ
ムイエロー、ウルトラマリンブルー、デュポンオイルレ
ッド、キノリンイエロー、メチレンブルークロライド、
フタロシアニンブルー、マラカイトグリーンオフサレー
ト、ランプブラック、ローズベンガルなどが挙げられる
。これらの中では、特にカーボンブラックが重要である
。Examples of colorants include carbon black, nigrosine dye, aniline black, calco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride,
Examples include phthalocyanine blue, malachite green offsalate, lamp black, and rose bengal. Among these, carbon black is particularly important.
磁性トナーを得る場合は、磁性を示すが磁化可能な磁性
材料、例えば、鉄、マンガン、ニッケル、コバルト、ク
ロムなどの金属の微粉末、フェライト、パーマロイなど
をトナーに配合すればよい。When obtaining a magnetic toner, a magnetic material that exhibits magnetism but can be magnetized, such as fine powder of metals such as iron, manganese, nickel, cobalt, and chromium, ferrite, and permalloy, may be blended into the toner.
必要に応じて他種の荷電制御剤の併用も可能である。If necessary, other types of charge control agents can also be used in combination.
本発明のトナー組成物中における各成分の割合はポリエ
ステル樹脂８０〜９５重量部、荷電制御剤０．５〜ｌＯ
重量部、着色剤５〜１５重量部か適当である。The ratio of each component in the toner composition of the present invention is 80 to 95 parts by weight of polyester resin, 0.5 to 10 parts by weight of charge control agent.
5 to 15 parts by weight of the colorant is appropriate.
［作用および発明の効果コ
本発明のトナー用バインダー樹脂は、ポリエステルポリ
オールの分子末端の水酸基の全部又は大部分が不均化ロ
ジンで封鎖されているため、低酸価および低水酸基価に
抑えられており、実質的に中性の樹脂である。かかる樹
脂と特定の荷電制御剤との組合せによって、他のバイン
ダー樹脂、あるいはガムロジン変性ポリエステル樹脂、
水添ロジン変性ポリエステル樹脂では得られないすぐれ
たプラス帯電性が発揮されるのである。[Function and Effects of the Invention] The toner binder resin of the present invention has a low acid value and a low hydroxyl value because all or most of the hydroxyl groups at the molecular terminals of the polyester polyol are blocked with a disproportionated rosin. It is a substantially neutral resin. Depending on the combination of such resin and a specific charge control agent, other binder resins, gum rosin modified polyester resins,
It exhibits excellent positive chargeability that cannot be obtained with hydrogenated rosin-modified polyester resin.
［実施例］
次に実施例をあげて本発明のトナー組成物をさらに説明
する。以下「部」、「％」とあるのは、重量基準で表し
たものである。[Example] Next, the toner composition of the present invention will be further explained with reference to Examples. Hereinafter, "parts" and "%" are expressed on a weight basis.
くバインダー、樹脂の製造〉
実施例１
充填塔付きフラスコに、テレフタル酸０．９モル、エチ
レングリコール ０．８５モル、ビスフェノールＡ−エ
チレンオキサイド付加物 ０．５モル、グリセリン０．
１モルおよび不均化ロジン（播磨化学工業（株）製ハリ
タックＧＸ）０．２モルを仕込み、ｎ−ブチルスズオキ
サイドを触媒として、１８０〜２５０℃で撹拌下に反応
させた。Production of binder and resin> Example 1 In a flask equipped with a packed tower, 0.9 mol of terephthalic acid, 0.85 mol of ethylene glycol, 0.5 mol of bisphenol A-ethylene oxide adduct, and 0.5 mol of glycerin were added.
1 mol and 0.2 mol of disproportionated rosin (Haritak GX, manufactured by Harima Chemical Industry Co., Ltd.) were charged, and the mixture was reacted with n-butyltin oxide as a catalyst at 180 to 250°C with stirring.
留出水が出なくなった時点で重縮合触媒として三酸化ア
ンチモンを加え、充填塔を外し、１ ｍｍｔｌｇの減圧
下に脱グリコールしなから重縮合し、グリコールの留出
の止まった時点で反応を終了した。When distilled water stopped coming out, antimony trioxide was added as a polycondensation catalyst, the packed tower was removed, and polycondensation was carried out without deglycol under a reduced pressure of 1 mmtlg. When the distillation of glycol stopped, the reaction was stopped. finished.
実施例２
ブチルスズオキサイドを触媒として、１８０〜２５０℃
で撹拌下に反応させた。Example 2 Butyltin oxide as a catalyst, 180-250°C
The reaction was carried out under stirring.
留出水が出なくなった時点で不均化ロジン２モルを仕込
んで１時間反応を続け、更にベンジルアルコール０．３
モルを仕込んで１時間反応させた。充填塔をはずしてｌ
ＯＯｍｍ１１ｇに減圧し、未反応物を追い出し、反応
を終了した。When distilled water stopped coming out, 2 moles of disproportionated rosin were charged and the reaction was continued for 1 hour, and then 0.3 moles of benzyl alcohol was added.
mol was charged and allowed to react for 1 hour. Remove the packed tower
The pressure was reduced to 11 g of OOmm, unreacted substances were expelled, and the reaction was completed.
比較例１〜２
不均化ロジンに代えて水添ロジン（理化バーキュレス製
ステビライトレジン）を（比較例１）、並びにガムロジ
ンを（比較例２）それぞれ用いて実施例１と同様の反応
を行った。Comparative Examples 1 to 2 The same reaction as in Example 1 was carried out using hydrogenated rosin (Stabilite Resin manufactured by Rika Vercules) (Comparative Example 1) and gum rosin (Comparative Example 2) in place of the disproportionated rosin. went.
上記実施例１〜２および比較例１〜２で得られた樹脂の
特性値を第１表に示す。Table 1 shows the characteristic values of the resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
第 １ 表 くトナーの調製および評価〉 プラス用荷電制御剤として次のものを準備した。Table 1 Preparation and evaluation of toner> The following was prepared as a positive charge control agent.
（り
上記で得たポリエステル樹脂９０部、カーボンブラック
（三菱化成工業株式会社製カーボンブラック＃４４）８
部、荷電制御剤２部を粉体混合し、２軸型混練機（池貝
鉄工株式会社製ＰＣＭ３０）に供給して、１００〜１６
０℃の範囲で上記混合物の溶融粘度カ月００００〜５０
０００ボイズになる温度で回転数１０ Ｏｒｐｍの条件
にて混練し、ついで冷却ロールを通して冷却した後、ハ
ンマーミルで粒子径０ 、８ ｍｍ以下に粗粉砕した。(90 parts of the polyester resin obtained above, carbon black (carbon black #44 manufactured by Mitsubishi Chemical Corporation) 8
1 part and 2 parts of the charge control agent were mixed in powder form and fed to a twin-screw kneader (PCM30 manufactured by Ikegai Iron Works Co., Ltd.) to give a powder of 100 to 16 parts.
The melt viscosity of the above mixture in the range of 0°C is 0,000 to 50
The mixture was kneaded at a temperature of 0.000 voids at a rotational speed of 10 rpm, cooled through a cooling roll, and then coarsely pulverized with a hammer mill to a particle size of 0.8 mm or less.
次にこの粉末を分級機付き超音速ジェット粉砕機（日本
ニューマチック工業株式会社製ＬＡＢＯＪＥＴ）を用い
て２００９／ｈｒで微粉砕した後、旋回気流型分級機で
分級し、平均粒径５〜１５μのトナー組成物を得た。Next, this powder was finely pulverized at 2009/hr using a supersonic jet pulverizer equipped with a classifier (LABOJET, manufactured by Japan Pneumatic Industries Co., Ltd.), and then classified using a swirling airflow classifier, with an average particle size of 5 to 15μ. A toner composition was obtained.
得られたトナ組成物につき、下記のようにして５０°Ｃ
放置安定性、帯電量を調べた。The obtained toner composition was heated to 50°C as follows.
The storage stability and amount of charge were investigated.
５０℃放置安定性
上記で得たトナー組成物１５９を７０ｃｃの広口ガラス
ピンにいれて密封し、５０±０．５℃に保った恒温槽に
２４時間放置し、ついで取り出して、トナーの流動性が
保存されているか否かを目視で判定した。Stability at 50°C The toner composition 159 obtained above was placed in a 70cc wide-mouthed glass pin, sealed, and left in a constant temperature bath kept at 50±0.5°C for 24 hours, then taken out to determine the fluidity of the toner. It was visually determined whether or not the data had been preserved.
帯電性
上記で得たトナー組成物５部と鉄粉（日本鉄粉株式会社
製ＴＥＦＶ−２００／３００）９５部とを広口ガラスピ
ンに入れ、ローリングミキサー（サーマル化学産業株式
会社製）で３分間撹拌した後、ブローオフ粉体帯電量測
定装置（東芝ケミカル株式会社製ＭＯＤＥＬ Ｔｌ３
−２００型）を用いて帯Ｎ量を測定した。Chargeability 5 parts of the toner composition obtained above and 95 parts of iron powder (TEFV-200/300 manufactured by Nippon Tetsuko Co., Ltd.) were placed in a wide-mouthed glass pin, and mixed for 3 minutes with a rolling mixer (manufactured by Thermal Kagaku Sangyo Co., Ltd.). After stirring, a blow-off powder charge measuring device (MODEL Tl3 manufactured by Toshiba Chemical Corporation) was used.
-200 type) was used to measure the band N amount.
試験結果
５０℃放置安定性および帯電量の試験結果を第２表にそ
れぞれ示す。Test Results Table 2 shows the test results for storage stability at 50° C. and charge amount.
第 ２ 表
［効 果コ
本発明のトナー組成物は、プラス帯電量が著しく向上す
る。Table 2 [Effects] The toner composition of the present invention significantly improves the amount of positive charge.
Claims (1)
般式 ▲数式、化学式、表等があります▼ （但しＲ＿１：炭素数１〜８のアルキル基、Ｒ＿２、Ｒ
＿３：炭素数１〜１８のアルキル基、Ｒ＿４：炭素数１
〜８のアルキル基又はベンジル基を示す）で表される荷
電制御剤を含んでなるトナー組成物。[Claims] Polyester resin containing disproportionated rosin as a condensation component and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1: an alkyl group having 1 to 8 carbon atoms, R_2, R
_3: Alkyl group having 1 to 18 carbon atoms, R_4: 1 carbon number
-8 alkyl group or benzyl group) A toner composition comprising a charge control agent represented by the following formula.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63027205A JPH01201675A (en) | 1988-02-08 | 1988-02-08 | Toner composition |
| US07/221,074 US4968575A (en) | 1987-07-23 | 1988-07-19 | A toner composition comprising a rosin-containing polyester |
| DE3824655A DE3824655C2 (en) | 1987-07-23 | 1988-07-20 | Binder resin for toner |
| GB8817439A GB2207438B (en) | 1987-07-23 | 1988-07-21 | A toner comprising a rosin containing polyester |
| FR888809958A FR2618574B1 (en) | 1987-07-23 | 1988-07-22 | RESIN FORMING BINDER FOR TONERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63027205A JPH01201675A (en) | 1988-02-08 | 1988-02-08 | Toner composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01201675A true JPH01201675A (en) | 1989-08-14 |
| JPH059788B2 JPH059788B2 (en) | 1993-02-05 |
Family
ID=12214599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63027205A Granted JPH01201675A (en) | 1987-07-23 | 1988-02-08 | Toner composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01201675A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03278068A (en) * | 1990-03-28 | 1991-12-09 | Canon Inc | Color toner and image forming method using the same |
| JPH043073A (en) * | 1990-04-20 | 1992-01-08 | Canon Inc | Color toner |
| JPH0432851A (en) * | 1990-05-30 | 1992-02-04 | Canon Inc | Toner and image forming method |
| JPH0440469A (en) * | 1990-06-07 | 1992-02-10 | Canon Inc | Toner and image forming method |
| WO2004059396A1 (en) * | 2002-12-25 | 2004-07-15 | Toyo Ink Manufacturing Co., Ltd. | Polyester resin for toner, toner for developing electrostatic charge image and method for forming image |
| WO2013038955A1 (en) * | 2011-09-16 | 2013-03-21 | 富士フイルム株式会社 | Resin composition and method for manufacturing same, and toner using same |
| JP2015081349A (en) * | 2013-10-22 | 2015-04-27 | ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ | Sustainable toner and optimized process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204848A (en) * | 1983-05-09 | 1984-11-20 | Arakawa Chem Ind Co Ltd | Toner composition for electrophotography |
| JPS60153057A (en) * | 1984-01-21 | 1985-08-12 | Arakawa Chem Ind Co Ltd | Positively electrostatic chargeable electrophotographic toner |
| JPS60169857A (en) * | 1984-02-13 | 1985-09-03 | Orient Kagaku Kogyo Kk | Electrostatic charge image developing toner |
-
1988
- 1988-02-08 JP JP63027205A patent/JPH01201675A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204848A (en) * | 1983-05-09 | 1984-11-20 | Arakawa Chem Ind Co Ltd | Toner composition for electrophotography |
| JPS60153057A (en) * | 1984-01-21 | 1985-08-12 | Arakawa Chem Ind Co Ltd | Positively electrostatic chargeable electrophotographic toner |
| JPS60169857A (en) * | 1984-02-13 | 1985-09-03 | Orient Kagaku Kogyo Kk | Electrostatic charge image developing toner |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03278068A (en) * | 1990-03-28 | 1991-12-09 | Canon Inc | Color toner and image forming method using the same |
| JPH043073A (en) * | 1990-04-20 | 1992-01-08 | Canon Inc | Color toner |
| JPH0432851A (en) * | 1990-05-30 | 1992-02-04 | Canon Inc | Toner and image forming method |
| JPH0440469A (en) * | 1990-06-07 | 1992-02-10 | Canon Inc | Toner and image forming method |
| WO2004059396A1 (en) * | 2002-12-25 | 2004-07-15 | Toyo Ink Manufacturing Co., Ltd. | Polyester resin for toner, toner for developing electrostatic charge image and method for forming image |
| US7569320B2 (en) | 2002-12-25 | 2009-08-04 | Toyo Ink Mfg. Co., Ltd | Polyester resin for toner, toner for developing electrostatic charge image and method for forming image |
| WO2013038955A1 (en) * | 2011-09-16 | 2013-03-21 | 富士フイルム株式会社 | Resin composition and method for manufacturing same, and toner using same |
| JP2013064067A (en) * | 2011-09-16 | 2013-04-11 | Fujifilm Corp | Resin composition and method for producing the same, and toner using the same |
| JP2015081349A (en) * | 2013-10-22 | 2015-04-27 | ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ | Sustainable toner and optimized process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH059788B2 (en) | 1993-02-05 |
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