JPH02129653A - Negatively chargeable toner for electrophotography - Google Patents
Negatively chargeable toner for electrophotographyInfo
- Publication number
- JPH02129653A JPH02129653A JP63281282A JP28128288A JPH02129653A JP H02129653 A JPH02129653 A JP H02129653A JP 63281282 A JP63281282 A JP 63281282A JP 28128288 A JP28128288 A JP 28128288A JP H02129653 A JPH02129653 A JP H02129653A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- toner
- polyester resin
- value
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 claims abstract description 50
- 229920001225 polyester resin Polymers 0.000 claims abstract description 41
- 239000004645 polyester resin Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003086 colorant Substances 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 150000002009 diols Chemical class 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004135 Bone phosphate Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 230000005611 electricity Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 26
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012643 polycondensation polymerization Methods 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 trimellitic acid Chemical class 0.000 description 4
- 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 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 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
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-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
- 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
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ARXSPTXFHDHTQQ-UHFFFAOYSA-N 2-ethylhexyl prop-2-enoate;methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1.CCCCC(CC)COC(=O)C=C ARXSPTXFHDHTQQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101100068867 Caenorhabditis elegans glc-1 gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 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
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006247 magnetic powder Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (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、静電記録、静電印刷等における静
電荷像を現像するための乾式電子写真用トナーに関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for dry electrophotography for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.
［従来の技術］
静電手段によって光導電材料の表面に像を形成し現像す
ることは従来周知である。BACKGROUND OF THE INVENTION It is well known in the art to form and develop images on the surface of photoconductive materials by electrostatic means.
すなわち米国特許第２，２８７，８９１号明細書、特公
昭４２−２３９１０号公報及び特公昭４３−２４７４８
号公報等、多数の方法が知られているが、一般には光導
電性物質を利用し、種々の手段により感光体上に電気的
潜像を形成し、次いで該潜像上にトナーと呼ばれる極〈
微細に粉砕された検電材料を付着させることによって静
電潜像に相当するトナー像を形成する。That is, U.S. Patent No. 2,287,891, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748.
Although a number of methods are known, such as those disclosed in Japanese Patent Publication No. 2003-12101, generally, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then a polar called toner is deposited on the latent image. <
A toner image corresponding to an electrostatic latent image is formed by depositing finely pulverized electrostatic material.
次いで必要に応じて紙の如き画像支持体表面にトナーを
転写した後、加熱、加圧あるいは溶剤蒸気などにより定
着し複写物を得るものである。またトナー画像を転写す
る工程を有する場合には、通常残余のトナーを除去する
ための工程が設けられる。Then, if necessary, the toner is transferred onto the surface of an image support such as paper, and then fixed by heating, pressure, solvent vapor, or the like to obtain a copy. Further, when a step of transferring a toner image is included, a step for removing residual toner is usually provided.
電気的潜像をトナーを用いて可視化する現像方法は、例
えば、米国特許第２，２２１，７７８号明細書に記載さ
れている粉末雲法、同第２，８１８，５５２号明細書に
記載されているカスケード現像法、同第２．８７４．０
８３号明細書に記載されている磁気ブラシ法、及び同第
３，９０９，２５８号明細書に記載されている導電性磁
性トナーを用いる方法などが知られている。Development methods for visualizing electrical latent images using toner include, for example, the powder cloud method described in U.S. Pat. No. 2,221,778, and the powder cloud method described in U.S. Pat. No. 2,818,552. Cascade development method, No. 2.874.0
The magnetic brush method described in Japanese Patent No. 83 and the method using conductive magnetic toner described in Japanese Patent No. 3,909,258 are known.
これらの現像法に適用されるトナーとしては一般には熱
可塑性樹脂に着色剤を混合分散後、微粉化したものが用
いられる。熱可塑性樹脂としては、ポリスチレン系樹脂
が最も一般的であるが、ポリエステル系樹脂、エポキシ
系樹脂、アクリル系樹脂、ウレタン系樹脂等も用いられ
る０着色剤としてはカーボンブラックが最も広く使用さ
れ、又磁性トナーの場合は、酸化鉄系の黒色の磁性粉が
多く用いられる。いわゆる二成分系現像剤を用いる方式
の場合には、トナーは通常ガラスピーズ、鉄粉などのキ
ャリア粒子と混合されて用いられる。Toners applied to these developing methods are generally prepared by mixing and dispersing a coloring agent in a thermoplastic resin and then pulverizing the mixture. As a thermoplastic resin, polystyrene resin is the most common, but polyester resin, epoxy resin, acrylic resin, urethane resin, etc. are also used.Carbon black is the most widely used colorant, and In the case of magnetic toner, iron oxide-based black magnetic powder is often used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder.
紙などの最終複写画像形成部材上のトナー像は、熱、圧
力等により支持体上に永久的に定着される。従来より、
この定着工程は熱によるものが多く採用されている。The toner image on the final copy imaging member, such as paper, is permanently affixed to the support by heat, pressure, or the like. Traditionally,
This fixing process often uses heat.
ここで鮮明な画像を得るためには、トナーはこれら各工
程において要求される諸条件を満足しなければならない
。すなわち、トナーとしては広い定着温度領域を持ち、
より低温定着が可能で、流動性に優れ、耐衝撃性、保存
安定性等の条件を同時に満たさなければならない、さら
に、現在複写機の汎用化に伴い、低温低湿、高温高湿等
苛酷な環境下に設置されることが多くなり、そのような
環境下においても通常環境下の画像と同様な鮮明な画像
が得られることが必要となっている。In order to obtain a clear image, the toner must satisfy various conditions required in each of these steps. In other words, as a toner, it has a wide fixing temperature range,
It must be possible to fix at a lower temperature, have excellent fluidity, and satisfy conditions such as impact resistance and storage stability.Furthermore, as copying machines have become more general-purpose, they can be used in harsh environments such as low temperature and low humidity, high temperature and high humidity, etc. In such environments, it is necessary to be able to obtain images as clear as images in normal environments.
［発明が解決しようとする課題］
すなわち、トナーとしては環境安定性と定着性、耐オフ
セット性とを同時に満足しなければならない。[Problems to be Solved by the Invention] That is, the toner must simultaneously satisfy environmental stability, fixing properties, and anti-offset properties.
環境安定性改良を目的として、特開昭５５−４０４０７
号、特開昭５Ｅｔ−８５１４７号等に開示されるように
、酸価を調節することにより環境安定を図ろうとじてき
た。しかし、特開昭５５−４０４０７号においては、環
境安定性が得られる反面、ポリエステル樹脂の架橋剤と
して働く３価以上のカルボン酸、例えばトリメリット酸
等が含有されていないため、十分な定着温度領域は得ら
れない、また、特開昭５６−１３５１４７号では酸価の
みを調節しても、残存水酸基があるために、環境安定性
はある程度改良されるが、まだ十分ではない。For the purpose of improving environmental stability, JP-A-55-40407
As disclosed in Japanese Patent Application Laid-Open No. 5Et-85147, attempts have been made to achieve environmental stability by adjusting the acid value. However, although JP-A No. 55-40407 provides environmental stability, it does not contain trivalent or higher carboxylic acids, such as trimellitic acid, which act as a crosslinking agent for polyester resin, so it does not require a sufficient fixing temperature. Furthermore, even if only the acid value is adjusted in JP-A-56-135147, the environmental stability is improved to some extent due to the presence of residual hydroxyl groups, but it is still not sufficient.
他方、定着性、耐オフセツト性改良を目的として、酸価
調節する方法が、特開昭５９−１［８９号、特開昭５９
−２９２５５号、特開昭５９−２９２５６号に開示され
ているが、酸価が低く抑えられているにもかかわらず残
存水酸基があるために、高温高湿下での帯電量は小さく
なり、環境安定性が損われる。On the other hand, a method of adjusting the acid value for the purpose of improving fixing properties and offset resistance is disclosed in JP-A-59-1 [No. 89, JP-A-59].
-29255 and JP-A-59-29256, but even though the acid value is kept low, due to the residual hydroxyl groups, the amount of charge becomes small under high temperature and high humidity, and the environmental Stability is compromised.
そこで、本発明の目的は、これらの問題点特に環境安定
性を改良した新規なポリエステル樹脂を用いた負帯電ト
ナーを提供するものである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a negatively charged toner using a novel polyester resin that overcomes these problems, particularly in terms of environmental stability.
すなわち、定着性、耐オフセット性、低温定着性、流動
性に優れ、さらに高温高湿から低温低湿まで安定した摩
擦帯電量を有する熱ローラ定着用トナーを提供すること
にある。That is, the object of the present invention is to provide a toner for heat roller fixing that has excellent fixing properties, anti-offset properties, low-temperature fixing properties, and fluidity, and also has a stable triboelectric charge amount from high temperature and high humidity to low temperature and low humidity.
また、本発明の目的は１価のカルボン酸および／または
１価のアルコールで処理して得られるところの上記ポリ
エステル樹脂を用いた負帯電トナーを提供するものであ
る。Another object of the present invention is to provide a negatively charged toner using the above polyester resin obtained by treatment with a monovalent carboxylic acid and/or a monovalent alcohol.
［課題を解決するための手段及び作用］そこで、本発明
者らは、ポリエステル樹脂についての詳細な研究を行っ
た結果、ポリエステル樹脂のカルボキシル基のみならず
水酸基が環境安定性に大きく寄与していることを見出し
た。[Means and effects for solving the problem] Therefore, as a result of detailed research on polyester resins, the present inventors found that not only carboxyl groups but also hydroxyl groups of polyester resins greatly contribute to environmental stability. I discovered that.
すなわち、本発明は、ジオール成分とジカルボン酸成分
を主成分としたポリエステル樹脂および荷電制御剤およ
び着色剤とから成るトナーにおいて、該ポリエステル樹
脂が三価以上のアルコールおよび／または三価以上のカ
ルボン酸を含み、かつ酸価および水酸基価の総和が２０
ｍｇＫＯＨ／ｇ以下であることを特徴とする電子写真用
トナーにある。That is, the present invention provides a toner comprising a polyester resin containing a diol component and a dicarboxylic acid component as main components, a charge control agent, and a colorant, in which the polyester resin contains a trihydric or higher alcohol and/or a trivalent or higher carboxylic acid. and the sum of acid value and hydroxyl value is 20
The present invention provides an electrophotographic toner characterized by having a concentration of mgKOH/g or less.
また、該ポリエステル樹脂の酸価および水酸基価の総和
が２０閤ｇＫＯＨ／ｇ以下となるように一価のカルポン
酸および／または一価のアルコールで処理して得られる
ポリエステル樹脂を特徴とする電子写真用トナーにある
。Moreover, an electrophotographic image characterized by a polyester resin obtained by treating the polyester resin with a monovalent carboxylic acid and/or a monovalent alcohol so that the sum of the acid value and hydroxyl value of the polyester resin becomes 20 gKOH/g or less. It is in the toner for use.
本発明により、耐オフセット性、定着性に優れ、かつ、
環境安定性のあるトナーを提供できる。この理由を本発
明者らは、以下のように推察した。The present invention provides excellent offset resistance and fixing properties, and
Can provide toner with environmental stability. The inventors of the present invention inferred the reason for this as follows.
すなわち、酸価を下げることにより、ポリエステル樹脂
中のカルボキシル基の量が減少し、高湿下においてトナ
ーは吸湿しにくくなる。これにより高湿下での帯電の低
下はある程度抑えられる。That is, by lowering the acid value, the amount of carboxyl groups in the polyester resin decreases, making it difficult for the toner to absorb moisture under high humidity conditions. This suppresses a decrease in charging to some extent under high humidity conditions.
しかし、それ以上の環境安定性を改良するにあたり、酸
価が小さいときには水酸基価の環境安定性への寄与が大
きくなることを把握した。つまり、カルボキシル基に比
較して水酸基が過剰にある場合、水酸基が水和をおこし
高湿下での帯電量低下が起こり、環境安定性は損われる
。However, in order to further improve the environmental stability, we found that when the acid value is small, the contribution of the hydroxyl value to the environmental stability increases. In other words, when there is an excess of hydroxyl groups compared to carboxyl groups, the hydroxyl groups cause hydration, resulting in a decrease in the amount of charge under high humidity, which impairs environmental stability.
そこで本発明者らは、酸価および水酸基価の総和を２０
ｍｇＫＯＨ／ｇ以下、好ましくは１５扉ｇＫＤＨ／ｇ以
下、さらに好ましくは１０ｍｇＫＯＨ／ｇ以下にするこ
とにより十分な帯電の環境安定性を有するトナーの発明
に至った。Therefore, the present inventors determined that the sum of the acid value and hydroxyl value was 20
By setting the charge to less than mgKOH/g, preferably less than 15 gKDH/g, more preferably less than 10 mgKOH/g, a toner having sufficient environmental stability of charging has been invented.
尚、水酸基価／酸価の値が１．０以下であるのが特に好
ましい。In addition, it is particularly preferable that the value of hydroxyl value/acid value is 1.0 or less.
しかしながら、特開昭８２−１９５８７１３ 、特開昭
６２−１９５１１ｉ７８、特開昭８２−１９５Ｅｔ８０
、特開昭８２−１９５８８１、特開昭６２−１９５８
８２等によると、末端基量特にカルボキシル基量を減ら
し過ぎるとポリエステル樹脂の帯電量は低下すると述べ
られているが、本発明者らはトナー化する際に好ましい
適当な荷電ル制御剤を含有することにより、帯電量は十
分な値をとることを見出した。また、前述の公報による
と流動性向上および最低定着温度を下げる目的で水酸基
価と酸価との比を１．２以上に調節することも述べられ
ている。が、この場合、酸価に比べ水酸基価が大きくな
り、先述のごとく十分な環境安定性は得られない。However, JP-A-82-1958713, JP-A-62-19511i78, JP-A-82-195Et80
, JP-A-82-195881, JP-A-62-1958
82 etc., it is stated that if the amount of terminal groups, especially the amount of carboxyl groups, is reduced too much, the amount of charge of the polyester resin decreases.However, the present inventors have determined that the amount of charge of the polyester resin will decrease when the amount of terminal groups, especially the amount of carboxyl groups, is reduced. It has been found that by doing so, the amount of charge can take a sufficient value. The above-mentioned publication also states that the ratio of the hydroxyl value to the acid value is adjusted to 1.2 or more for the purpose of improving fluidity and lowering the minimum fixing temperature. However, in this case, the hydroxyl value becomes larger than the acid value, and as mentioned above, sufficient environmental stability cannot be obtained.
また環境安定性を目的として、特開昭６２−２９１Ｈ８
に開示されるように酸価、水酸基価を調節し、特に酸価
を５■ｇにＯＨ１ｇ以下にすることによりポリエステル
樹脂の帯電を中性化し、正帯電用荷電制御剤と併用する
ことで正帯電トナーとして用いる方法があるが、負帯電
トナーにおいてこの特開昭６２−２９１６６８の実施例
に示されるような酸価および水酸基価のように、酸価に
比べ水酸基価が大きいと、キャリアとの摩擦混合におけ
る立上りが悪く、帯電の環境安定性が得られない。In addition, for the purpose of environmental stability, JP-A-62-291H8
By adjusting the acid value and hydroxyl value, and in particular by adjusting the acid value to 5 g and 1 g of OH or less as disclosed in There is a method of using it as a charged toner, but if a negatively charged toner has a higher acid value and hydroxyl value than the acid value as shown in the example of JP-A-62-291668, it may cause problems with the carrier. The rise in frictional mixing is poor, and environmental stability of charging cannot be obtained.
ところで、環境安定性のみならず定着性、耐オフセット
性を兼備することが必要であることは先述したが、その
対応策として特開昭６２−４５６２２に開示されるごと
くポリエステル樹脂中にモノカルボン酸を含有させ、ポ
リエステル樹脂の架橋をコントロールする方法がある。By the way, as mentioned above, it is necessary to have not only environmental stability but also fixing properties and offset resistance. There is a method of controlling the crosslinking of polyester resin by containing it.
これについては、低温定着性、耐オフセット性は良好に
なる反面、水酸基のみ減少させ、残留カルボキシル基が
多量にあるために環境依存性が悪くなる。Regarding this, although low-temperature fixing properties and anti-offset properties are improved, only hydroxyl groups are reduced and there are a large amount of residual carboxyl groups, resulting in poor environmental dependence.
すなわち、環境安定性および定着性、耐オフセット性を
満足させるために、ポリエステル樹脂成分として、３価
以上のカルボン酸、および／または３価以上のアルコー
ルを含有しかつ、カルボキシル基量、水醸基量が少ない
ことが望まれる。That is, in order to satisfy environmental stability, fixing properties, and anti-offset properties, the polyester resin component contains a trivalent or higher carboxylic acid and/or a trivalent or higher alcohol, and the amount of carboxyl group, aqueous group is It is desirable that the amount be small.
本発明のポリエステル樹脂の製造方法は、２価以上の酸
及びアルコールによる重縮合反応終了後に酸価および水
酸基価を測定し、それとほぼ等モルの１価のカルボン酸
および／または１価のアルコールを反応系中に加え、処
理することにより酸価および水酸基価の総和を２０ｍｇ
ＫＯＨ／ｇ以下にする。このポリエステル樹脂を用いた
トナーは定着性、耐オフセット性に優れ、かつ環境安定
性に優れ、流動性、耐ブロッキング性が良くなり、劣化
しにくいことが可能となった。The method for producing a polyester resin of the present invention involves measuring the acid value and hydroxyl value after the completion of the polycondensation reaction using a divalent or higher acid and an alcohol, and then adding approximately equimolar amounts of a monovalent carboxylic acid and/or a monovalent alcohol to the acid value and the hydroxyl value. By adding it to the reaction system and treating it, the total acid value and hydroxyl value can be reduced to 20 mg.
Keep it below KOH/g. A toner using this polyester resin has excellent fixing properties, anti-offset properties, excellent environmental stability, improved fluidity and anti-blocking properties, and is resistant to deterioration.
本発明に用いられるポリエステル樹脂の多価アルコール
成分としては、エチレングリコール、プロピレングリコ
ール、１．３−ブタンジオール、１．４−ブタンジオー
ル、２，３−ブタンジオール、ジエチレングリコール、
ジプロピレングリコール、トリエチレングリコール、１
．５−ベンタンジオール、 １．６−ヘキサンジオール
、ネオペンチルグリコール、ペンタエリスリトールジア
リルエーテル、トリメチレンゲリコール、２−エチル−
１，３−ヘキサンジオール、水素化ビスフェノールＡ、
又次式で表わされるビスフェノール誘導体；
次式
（式中Ｒはエチレンまたはプロピレン基であり、ｘ、ｙ
はそれぞれ１以上の整数↑あり、かつＸ＋ｙの平均値は
２〜１０である。）
等のジオール類が挙げられる。The polyhydric alcohol component of the polyester resin used in the present invention includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol,
Dipropylene glycol, triethylene glycol, 1
．． 5-bentanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene gellicol, 2-ethyl-
1,3-hexanediol, hydrogenated bisphenol A,
Bisphenol derivatives represented by the following formula;
are each an integer ↑ greater than or equal to 1, and the average value of X+y is 2 to 10. ) and other diols.
又、酸成分としてはフマル酸、マレイン酸、シトラコン
酸、イタコン酸などの不飽和ジカルボン酸類、又はこれ
らの酸無水物、コ／＼り酸、アジピン酸、セバシン酸、
アゼライン酸などのジカルボン酸類又はこれらの酸無水
物、フタル酸、テレフタル酸等の芳香族系ジカルボン酸
などが挙げられる。In addition, as acid components, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or acid anhydrides thereof, co/\hydric acid, adipic acid, sebacic acid,
Examples include dicarboxylic acids such as azelaic acid, acid anhydrides thereof, and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.
また三価以上のアルコールとしてグリセリン、ソルビッ
ト、ソルビタン等、三価以上の酸としてはトリメリット
酸、ピロメリット酸等及びこれらの酸無水物等が挙げら
れ、これらは、三価のアルコールおよび三価の酸を含ん
だ２種以上の混合物で用いられる。Trivalent or higher alcohols include glycerin, sorbitol, sorbitan, etc.; trivalent or higher acids include trimellitic acid, pyromellitic acid, etc., and their acid anhydrides; It is used in a mixture of two or more acids.
本発明に用いられるアルコール成分としては４０〜８０
ｍｏＲ％、好ましくは４５〜５５腸ＯＰ％、酸成分と
しては８０〜４０■Ｏｐ％、好ましくは５５〜４５ ｍ
ｏＲ％であることが望ましい。The alcohol component used in the present invention is 40 to 80
moR%, preferably 45-55 intestine OP%, acid component 80-40 OP%, preferably 55-45 m
oR% is desirable.
本発明に用いられる一価のカルボン酸としては、−船人
Ｒ−ＣＯＯＨで示される。ここでＲはアルキル基、アル
ケニル基などの脂肪族系、または芳香族系、または複素
環系、などであり、具体的には以下に示すような化合物
である。The monovalent carboxylic acid used in the present invention is represented by -FuneninR-COOH. Here, R is an aliphatic group such as an alkyl group or an alkenyl group, an aromatic group, a heterocyclic group, etc., and specifically, the compounds shown below.
ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、
ビバル酸、ラウリル酸、ミリスチン酸、パルミチン酸、
ステアリン酸、アクリル酸、プロピオル酸、メタクリル
酸、クロトン酸、オレイン酸、安息香酸、トルイル酸、
ナフトエ酸、ケイ皮酸、２−フル酸、ニコチン酸、イソ
ニコチン酸などがあり、中でも好ましくは酢酸、プロピ
オン酸、酪酸、イソ酪酸、吉草酸、ピバル酸、ラウリル
酸、プロピオル酸、メタクリル酸、ステアリン酸、安息
香酸、トルイル酸、ナフトエ酸、２−フル酸であり、さ
らに好ましくは酢酸、プロピオン酸、吉草酸、安息香酸
である。Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid,
Bivalic acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, oleic acid, benzoic acid, toluic acid,
These include naphthoic acid, cinnamic acid, 2-furic acid, nicotinic acid, and isonicotinic acid, among which preferred are acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, propiolic acid, methacrylic acid, These include stearic acid, benzoic acid, toluic acid, naphthoic acid, and 2-furic acid, and more preferably acetic acid, propionic acid, valeric acid, and benzoic acid.
また本発明に用いられる一価のアルコールとしては、−
船人Ｒ−０）！で示される。ここでＲはアルキル基、ア
ルケニル基などの脂肪族系、または芳香族系、または複
素環系などであり、具体的には以下に示すような化合物
が使用される。Furthermore, the monohydric alcohol used in the present invention includes -
Shipman R-0)! It is indicated by. Here, R is an aliphatic group such as an alkyl group or an alkenyl group, an aromatic group, or a heterocyclic group, and specifically, the compounds shown below are used.
メチルアルコール、エチルアルコール、プロピルアルコ
ール、イソプロピルアルコール、ブチルアルコール、イ
ソブチルアルコール、５ｅｃ−ブチルアルコール、ｔｅ
ｒｔ−ブチルアルコール、ｎ−アミルアルコール、イソ
アミルアルコール、ヘキシルアルコール、ヘプチルアル
コール、オクチルアルコール、カプリルアルコール、ア
リルアルコール、クロチルアルコール、プロパルギルア
ルコール、シクロペンタノール、シクロヘキサノール。Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 5ec-butyl alcohol, te
rt-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, caprylic alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol.
ベンジルアルコール、シンナミルアルコール、フルフリ
ルアルコール、中でも好ましくはメチルアルコール、エ
チルアルコール、イソブチルアルコール、５ｅｃ−ブチ
ルアルコール、 ｔｅｒｔ−ブチルアルコール、ｎ−ア
ミルアルコール、イソアミルアルコール、アリルアルコ
ール、クロチルアルコール、シクロペンタノール、ベン
ジルアルコールであり、さらに好ましくは、メチルアル
コール、エチルアルコール、イソブチルアルコール、ア
リルアルコール、ベンジルアルコールである。Benzyl alcohol, cinnamyl alcohol, furfuryl alcohol, preferably methyl alcohol, ethyl alcohol, isobutyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, allyl alcohol, crotyl alcohol, cyclopene Tanol and benzyl alcohol, more preferably methyl alcohol, ethyl alcohol, isobutyl alcohol, allyl alcohol, and benzyl alcohol.
本発明に用いられる一価のカルボン酸または一価のアル
コールの分子量が大きくなると、ポリエステル樹脂の末
端基においてその部分にソフトセグメントを形成するた
めに耐オフセット性やキャリアのスペント化など不都合
を生じる。ここでＲは炭素数が１−ｔｏであることが望
ましい。When the molecular weight of the monohydric carboxylic acid or monohydric alcohol used in the present invention becomes large, soft segments are formed at the end groups of the polyester resin, resulting in disadvantages such as offset resistance and spent carrier formation. Here, it is desirable that R has 1 to carbon number.
１価のカルボン酸または１価のアルコールの添加量は次
式（１）、（２）により求めた。添加量は酸価または水
酸基価とほぼ等モルになるようにする。The amount of monovalent carboxylic acid or monovalent alcohol added was determined using the following formulas (1) and (2). The amount added should be approximately equimolar to the acid value or hydroxyl value.
アルコール ポリエステル樹脂の製造方法は以下の通りである。alcohol The method for producing polyester resin is as follows.
不活性ガス雰囲気下（多くの場合は窒素ガス存在下）常
圧〜減圧下（θ〜ー７６０層１Ｈ２０）で反応を行う．
攪拌しながら６０〜２７０℃好ましくは８０〜２２０℃
まで昇温し、１０〜３０時間反応を行う．縮合重合によ
り生成された水またはアルコール類は不活性ガスを系内
に供給しつつ不活性ガスと共に系外に連続的に排出され
、縮合重合が進む様にする．例えば攪拌機、コンデンサ
−１温度計及び不活性ガス導入管を具備した反応容器に
酸、アルコールを仕込む．次いで不活性ガスを導入して
ガス置換を行う．ガス置換終了後も不活性ガスを流し続
は反応温度を所定温度にまで昇温し、１０〜３０蒔間攪
拌しなから縮合重合反応を行う．縮合重合反応により生
成された木またはアルコールは系外でコンデンサーにて
凝縮させ回収する．反応終了時点で酸価，水酸基価を７
１１足し、上記式（１）。The reaction is carried out under an inert gas atmosphere (often in the presence of nitrogen gas) at normal pressure to reduced pressure (θ~-760 layer 1H20).
60-270℃ while stirring, preferably 80-220℃
Raise the temperature to 100°C and carry out the reaction for 10 to 30 hours. The water or alcohol produced by condensation polymerization is continuously discharged from the system together with the inert gas while supplying an inert gas into the system, allowing the condensation polymerization to proceed. For example, acid and alcohol are charged into a reaction vessel equipped with a stirrer, a condenser 1 thermometer, and an inert gas introduction tube. Next, inert gas is introduced to perform gas replacement. After the completion of gas replacement, the inert gas is continued to flow, and the reaction temperature is raised to a predetermined temperature, and the condensation polymerization reaction is carried out while stirring for 10 to 30 minutes. The wood or alcohol produced by the condensation polymerization reaction is condensed and recovered in a condenser outside the system. At the end of the reaction, the acid value and hydroxyl value are 7.
Add 11 and get the above formula (1).
（２）で示されるカルボン酸，アルコールを加える．こ
こで七ツマ−にカルボン酸およびアルコールを用いた場
合、カルボキシル基と水酸基をアルコールおよび／また
はカルボン酸により処理する。Add the carboxylic acid and alcohol shown in (2). When a carboxylic acid and an alcohol are used as the 7-mer, the carboxyl group and the hydroxyl group are treated with the alcohol and/or the carboxylic acid.
反応終了後、生成水または加えたカルボン酸またはアル
コールが過剰である場合の残存カルボン酸またはアルコ
ールは減圧下で蒸発させ系外でコンデンサーにより凝縮
させ回収する．そののち、室温まで温度を下げポリエス
テル樹脂を得る。After the reaction is complete, the water produced or the residual carboxylic acid or alcohol added if it is in excess is evaporated under reduced pressure and condensed outside the system using a condenser and recovered. Thereafter, the temperature is lowered to room temperature to obtain a polyester resin.
ここで、本発明におけるポリエステル樹脂は、その性質
上、酸価と水酸基価の総和が２０ｍｇＫＯＨ／ｇ以下と
なることが必要で、２０ｔｍｇＫＯＨ／ｇを越える場合
は、カルボキシル基または水酸基が増え、帯電の環境依
存性が大きくなり、または分子量の減少を招き、定着温
度領域が狭くなる等支障をきたす。Here, due to the nature of the polyester resin used in the present invention, the sum of the acid value and hydroxyl value must be 20 mgKOH/g or less, and if it exceeds 20 tmgKOH/g, the number of carboxyl groups or hydroxyl groups will increase, resulting in less charging. This may lead to increased environmental dependence or a decrease in molecular weight, resulting in problems such as a narrowing of the fixing temperature range.
本発明における添加しうる荷電制御剤としては、トナー
の色調に影響を与えない無色または淡色のものが好まし
い．負の荷電制御剤としては、例えばアルキル置換サリ
チル酸の金属錯体、ジターシャリ−ブチルサリチル酸の
クロム錯体または亜鉛錯体の如き有機金属錯体が挙げら
れる．負の荷電制御剤をトナーに配合する場合には、結
着樹脂１００重量部に対して０．１−１０重量部、好ま
しくは０．５〜８重量部添加するのが良い。The charge control agent that can be added in the present invention is preferably a colorless or light-colored one that does not affect the color tone of the toner. Examples of the negative charge control agent include organometallic complexes such as metal complexes of alkyl-substituted salicylic acid, chromium complexes or zinc complexes of ditertiary-butylsalicylic acid. When a negative charge control agent is added to the toner, it is preferably added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, per 100 parts by weight of the binder resin.
また、本発明において使用できる着色剤は、黒色トナー
の場合、ファ°ーネスブラック、チャンネルブラック、
アセチレンブラック等のカーボンブラック、カラートナ
ーの場合、ジスアゾ系顔料、不溶性アゾ顔料、銅フタロ
シアニン等の顔料系のものと塩基性染料，油溶性染料等
の染料がある。In addition, in the case of black toner, colorants that can be used in the present invention include furnace black, channel black,
In the case of carbon black such as acetylene black and color toners, there are pigment-based ones such as disazo pigments, insoluble azo pigments, and copper phthalocyanine, and dyes such as basic dyes and oil-soluble dyes.
これらを該結着樹脂と負の荷電制御剤とともに混合し、
混練したのち平均粒径ｌ〜３０μ■の微粉体、すなわち
トナーとして使用する。乾式２成分現像剤として該トナ
ーはキャリアと適当量ブレンドし，現像剤として使用さ
れる。Mixing these together with the binder resin and a negative charge control agent,
After kneading, the mixture is used as a fine powder having an average particle size of 1 to 30 .mu.m, that is, a toner. The toner is blended with an appropriate amount of carrier and used as a dry two-component developer.
本発明に使用されるキャリアとしては、例えば表面酸化
または未酸化の鉄，ニッケル、銅、亜鉛、コバルト、マ
ンガン、クロム、希土類等の金属およびそれらの合金ま
たは酸化物およびフェライトなどが使用できる。As carriers used in the present invention, surface-oxidized or unoxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, alloys or oxides thereof, and ferrites can be used.
また本発明に支障をきたさない範囲で流動向上剤として
、例えばフッ素系樹脂粉末、脂肪酸全屈塩、金属酸化物
、微粉末シリカ等を使用できる。Further, as the fluidity improver, for example, fluororesin powder, fatty acid total salt, metal oxide, finely powdered silica, etc. can be used within the range that does not interfere with the present invention.
本発明に用いた酸価および水酸基価の測定方法を以下に
示す。The method for measuring acid value and hydroxyl value used in the present invention is shown below.
サンプル２〜１０ｇを２００〜３００ｍｊ’の三角フラ
スコに秤量し、メタノール：トルエン＝ ３０ ： ７
０（７）ｉ合溶奴約５０ｍｊｌ加えて樹脂を溶解する．
溶解性がわるいようであれば少量のアセトンを加えても
よい、 ０．１％のブロムチモールブルーとフェノール
レッドの混合指示薬を用い、あらかじめ標定されたＮ／
１０力性カリ〜アルコール溶液で滴定し、アルコールカ
リ液の消費量からつぎの計算式（３）で酸価を求める。Weigh 2 to 10 g of the sample into a 200 to 300 mj' Erlenmeyer flask, and methanol:toluene = 30:7.
Add about 50 mjl of 0(7)i mixture and dissolve the resin.
If the solubility is poor, a small amount of acetone may be added. Use a mixed indicator of 0.1% bromothymol blue and phenol red to pre-standardize N/N.
Titration is carried out with a 10-potassium to alcohol solution, and the acid value is determined from the consumption amount of the alcoholic potash solution using the following formula (3).
酸価＝ ＫＯＨ（＋ｓｊ？数）ＸＮＸ５６．１／試料重
量・・・（３）
（ただしＮはＮ／１０ ＫＯＨのファクター）また、試
料を過剰のアセチル化剤、たとえば無水酢酸と加熱して
アセチル化を行い、生成したアセチル化物のケン化価を
測定したのち、次の式（４）に従って水酸基価を計算す
る。Acid value = KOH (+sj? number) After measuring the saponification value of the acetylated product produced, the hydroxyl value is calculated according to the following formula (4).
（ただしＡはアセチル化後のケン化価、Ｂはアセチル化
前のケン化価を表わす。）
本発明に用いた帯電量の測定方法を以下に示す・
摩擦帯電量測定（ブローオフ法）
測定法を図面を用いて詳述する。(However, A represents the saponification value after acetylation, and B represents the saponification value before acetylation.) The method for measuring the amount of charge used in the present invention is shown below. Measuring the amount of triboelectric charge (blow-off method) Measuring method will be explained in detail using drawings.
第１図はトナーのトリポ電荷量を測定する装置の説明図
である。先ず、底に５００メツシユのスクリーン３のあ
る金属製の測定容器２に摩擦帯電量を測定しようとする
トナーとキャリヤの重量比ｌ：９の混合物を５０〜１０
〇−容量のポリエチレン製のビンに入れ、約１０〜４０
秒間手で振盪し、該混合物（現像剤）約０．５〜１．５
ｇを入れ金属製のフタ４をする。このときの測定容器
２全体の重量を秤りＷ＋ （ｇ）とする０次に、吸引機
１（測定容器２と接する部分は少なくとも絶縁体）にお
いて、吸引ロアから吸引し風量調節弁６を調整して真空
計５の圧力を２５０１■Ａｑとする。この状態で充分、
好ましくは２分間吸引を行いトナーを吸引除去する。こ
のときの電位計９の電位をＶ（ボルト）とする、ここで
８はコンデンサーであり容量をＣ（ｐＦ）とする、また
、吸引後の測定容器全体の重量を秤りＷ？（ｇ）とする
、このトナーの摩擦帯電量（ｐｃ／ｇ）は下式（５）の
如く計算される。FIG. 1 is an explanatory diagram of an apparatus for measuring the amount of toner charge. First, a mixture of toner and carrier whose weight ratio is 1:9, whose amount of triboelectric charge is to be measured, is placed in a metal measuring container 2 with a 500-mesh screen 3 at the bottom.
〇-Put in a polyethylene bottle with a capacity of about 10 to 40
The mixture (developer) is shaken by hand for about 0.5 to 1.5 seconds.
g and put on the metal lid 4. Weigh the entire weight of the measuring container 2 at this time and let it be W+ (g).Next, in the suction device 1 (at least the part in contact with the measuring container 2 is an insulator), suck it from the suction lower and adjust the air volume control valve 6. Then, the pressure of the vacuum gauge 5 is set to 2501 Aq. This condition is sufficient,
Preferably, suction is performed for 2 minutes to remove the toner. The potential of the electrometer 9 at this time is assumed to be V (volts), where 8 is a capacitor whose capacity is C (pF), and the weight of the entire measurement container after suction is weighed. The triboelectric charge amount (pc/g) of this toner, which is expressed as (g), is calculated as shown in the following equation (5).
（但し、測定条件は２３℃、６０％ＲＨとする。）また
測定に用いるキャリアは２５０メツシユパス、３５０メ
ツシユオンのキャリア粒子が７０〜９０重量％有するフ
ッ素系樹脂−スチレン系樹脂コートフェライトキャリア
を使用する。すなわち、ビニリデンフルオライド−テト
ラフルオロエチレン共重合体とスチレン−アクリル酸２
−エチルヘキシル−メタクリル酸メチルの５＝５の混合
物で０．２〜０．７重量パーセントコートされているフ
ェライトキャリアを使用する。(However, the measurement conditions are 23° C. and 60% RH.) The carrier used for the measurement is a fluororesin-styrene resin coated ferrite carrier containing 70 to 90% by weight of carrier particles of 250 mesh pass and 350 mesh pass. . That is, vinylidene fluoride-tetrafluoroethylene copolymer and styrene-acrylic acid 2
A ferrite carrier coated with 0.2 to 0.7 weight percent of a 5=5 mixture of -ethylhexyl-methyl methacrylate is used.
測定に用いる試料トナー及びキャリアは２３℃。The sample toner and carrier used in the measurement were at 23°C.
６０％Ｒ）Ｉ環境下最低１２時間放置後１帯電量測定に
使用する。60%R)I After being left in an environment for at least 12 hours, it is used to measure the amount of charge.
また摩擦帯電量測定は、２３℃、６０％Ｒ）ｌ環境下で
行う。Further, the measurement of the amount of triboelectric charge is carried out at 23° C. in an environment of 60% R).
［実施例］
以下に実施例（ポリエステル樹脂の製造例及び該樹脂を
用いたトナーの実施例）をもって本発明の詳細な説明す
る。[Examples] The present invention will be described in detail below using Examples (manufacturing examples of polyester resins and examples of toners using the resins).
（ビスフェノールＡエトキシ付加物 １７２０ ／／
上記の化合物を温度計、テフロンコーティング攪拌翼、
ガラス製窒素導入管、コンデンサー、及び減圧装置を備
えた２文容量の４つ日丸底フラスコに入れた。ガラス導
入管より窒素ガスを導入して反応器内を不活性雰囲気に
したあと、窒素ガス導入バルブと減圧調整バルブの開度
を調節することにより、系内を一７５０層■Ｈ２０に保
った。その後マントルヒーター中に反応器をおき、１７
０℃に保ち２５時間縮合重合反応を行った。このときの
圧力も一７５０■１ＩＨ２０に保った。(Bisphenol A ethoxy adduct 1720 //
Add the above compound to a thermometer, a Teflon-coated stirring blade,
It was placed in a 4-day round bottom flask with a 2-liter capacity equipped with a glass nitrogen inlet tube, a condenser, and a vacuum device. After nitrogen gas was introduced through the glass introduction tube to create an inert atmosphere inside the reactor, the inside of the system was maintained at 1750 μm H20 by adjusting the opening degrees of the nitrogen gas introduction valve and the pressure reduction adjustment valve. After that, place the reactor in the mantle heater and
The condensation polymerization reaction was carried out at 0° C. for 25 hours. The pressure at this time was also maintained at 1750 cm 1 IH20.
このときの酸価は２．０■ｇＫＯＨ／ｇ、水酸基価は２
５．６ｍｇＫＯＨ／ｇであった。これをポリエステル樹
脂Ａとする。また、こののち系内に酢酸を１８０ｍｊ）
加え、反応生成水および残存酢酸を系外に除外しポリエ
ステル樹脂Ｂを得た。このときの酸価は２．３ｍｇＫＯ
Ｈ／ｇ、水酸基価は１．０ｍｇＫＯＨ／ｇであった。At this time, the acid value was 2.0 gKOH/g, and the hydroxyl value was 2.
It was 5.6 mgKOH/g. This is called polyester resin A. Also, after this, 180 mj of acetic acid was added to the system)
In addition, reaction product water and residual acetic acid were removed from the system to obtain polyester resin B. The acid value at this time was 2.3mgKO
H/g and hydroxyl value were 1.0 mgKOH/g.
上記の化合物を温度計、テフロンコーティング攪拌翼、
ガラス製窒素導入管、コンデンサー、及び減圧装置を備
えた２交容量の４つ目丸底フラスコに入れた。ガラス導
入管より窒素ガスを導入して反応鼻内を不活性雰囲気に
したあと、窒素ガス導入バルブと減圧調整バルブの開度
を調節することにより、系内を一７５０ｓｎＨ２０に保
った。その後マントルヒーター中に反応器をおき、１７
０℃に保ち２０時間縮合重合反応を行った。このときの
圧力も一７５０■濡８２０に保った。Add the above compound to a thermometer, a Teflon-coated stirring blade,
The mixture was placed in a fourth round bottom flask with two exchange volumes equipped with a glass nitrogen inlet tube, condenser, and vacuum device. After nitrogen gas was introduced through the glass introduction tube to create an inert atmosphere inside the reaction nostril, the inside of the system was maintained at -750 snH20 by adjusting the opening degrees of the nitrogen gas introduction valve and the pressure reduction adjustment valve. After that, place the reactor in the mantle heater and
The condensation polymerization reaction was carried out at 0° C. for 20 hours. The pressure at this time was also kept at 1,750 cm and 820 cm.
このときの酸価は７．９■ｇＫＯＨ／ｇ、水酸基価は２
０、１ｒａｇＫＯＨ／ｇであった。これをポリエステル
樹脂Ｃとする。また、こののち系内に酢酸を１２５１加
え、反応生成水および残存酢酸は系外に除いてポリエス
テル樹脂りを得た。このときの酸価は８．９厘ｇＫＤＨ
／ｇ、水酸基価は２．７■ｇに０）１／ｇであった。At this time, the acid value was 7.9 gKOH/g, and the hydroxyl value was 2.
It was 0.1 ragKOH/g. This will be referred to as polyester resin C. After that, 1251 grams of acetic acid was added to the system, and the water produced by the reaction and the remaining acetic acid were removed from the system to obtain a polyester resin. The acid value at this time is 8.9 gKDH
/g, and the hydroxyl value was 2.7 g to 0)1/g.
樹脂製造例３
ｒテレフタル酸 １１６２重量部上
記の化合物を樹脂製造例１と同様にしてポリエステル樹
脂Ｅを得た。このときの酸価は１８．３■ｇＫＯＨ／ｇ
、水酸基価は２９．４ｍｇＫＯＨ／ｇであった。さら
に、こののち系内に酢酸を１８０層！、エタノールを８
５腸で加え、反応生成水および残存酢酸。Resin Production Example 3 rTerephthalic acid 1162 parts by weight Polyester resin E was obtained using the above compound in the same manner as in Resin Production Example 1. The acid value at this time was 18.3 gKOH/g
The hydroxyl value was 29.4 mgKOH/g. Furthermore, after this, 180 layers of acetic acid were added to the system! , 8 ethanol
5. Add reaction product water and residual acetic acid.
エタノールは系外に除去しポリエステル樹脂Ｆを得た。Ethanol was removed from the system to obtain polyester resin F.
このときの酸価３．１■ｇＫＯＨ／ｇ、水酸基価１．５
■ｇＫＯＨ／ｇであった・
上記化合物を樹脂製造例１と同様にしてポリエステル樹
脂Ｇを得た。このときの酸価は２３．１ｍｇＫＯ）Ｉ／
３ 、水＃基価は３．２ｍｇＫＯＨ／ｇテあった。At this time, the acid value was 3.1 gKOH/g, and the hydroxyl value was 1.5.
■gKOH/g Polyester resin G was obtained using the above compound in the same manner as in Resin Production Example 1. The acid value at this time was 23.1mgKO)I/
3. The water value was 3.2 mgKOH/g.
さらに、こののち系内にプロパツールを１４５１ｅ加え
、反応生成水および残存プロパツールを系外に除去しボ
リエ・ステル樹脂Ｈを得た。このときの酸価は３．１ｍ
ｇＫＯＨ／ｇであり、水酸基価は２．５ｍｇＫＯＨ／ｇ
であった。Furthermore, after this, Propatol 1451e was added to the system, and the water produced by the reaction and the remaining Propatol were removed from the system to obtain Bolier-Stell resin H. The acid value at this time was 3.1m
gKOH/g, and the hydroxyl value is 2.5 mgKOH/g
Met.
以下に前記のポリエステル樹脂を用いた実施例を示す。Examples using the above polyester resin are shown below.
以下実施例２〜６および比較例１〜４を表１に示す処方
量を用いトナーを得た。Toners of Examples 2 to 6 and Comparative Examples 1 to 4 were obtained using the prescribed amounts shown in Table 1.
（以下余白）
上記トナーの製造方法は、前記の各処方量を充分ヘンシ
ェルミキサーにより予備混合を行い、３本ロールミルで
少なくとも２回以上溶融混練し、冷却後ハンマーミルを
用いて約１〜２ｍ１１程度に粗粉砕し次いでエアージェ
ット方式による微粉砕機で４０ｐｍ以下の粒径に微粉砕
した。さらに得られた微粉砕物を分級して、本発明の粒
度分布となるように２〜２３ルを選択し、流動向上剤と
してヘキサメチルジシラザンで処理したシリカ微粉末な
各分級品１００重量部に０．５重量部外添添加しトナー
とした。(Left below) The method for producing the above toner is to premix the above-mentioned amounts in a Henschel mixer, melt and knead at least twice in a three-roll mill, and after cooling, use a hammer mill to approximately 1 to 2 m11. The mixture was coarsely pulverized and then pulverized to a particle size of 40 pm or less using an air jet type pulverizer. Further, the obtained finely pulverized product was classified, 2 to 23 particles were selected so as to have the particle size distribution of the present invention, and 100 parts by weight of each classified product was a finely divided silica powder treated with hexamethyldisilazane as a flow improver. A toner was prepared by adding 0.5 part by weight externally.
また、このトナー８〜１２重量部に対しビニリデンフル
オライド−テトラフルオロエチレン共重合体（共重合重
量比８：２）とスチレン−アクリル酸２−エチルヘキシ
ル−メタグリル酸メチル（共重合重量比４５ ： ２０
： ３５）を５０：５０の重址比率で約０．５重量％
コーティングした。 Ｃｕ−Ｚｎ−Ｆｅ系フェライトキ
ャリア（平均粒径４８μｍ：２５０メツシユパス、３５
０メツシュオン７９重量％； 真ｓ度４．５ｇ／ｃ腸３
）を総量１００重量部になるように混合し現像剤とした
。各トナーの現像剤濃度（％）は表１中に示した。この
現像剤の摩擦帯電量をブローオフ法により測定した。Additionally, vinylidene fluoride-tetrafluoroethylene copolymer (copolymerization weight ratio 8:2) and styrene-2-ethylhexyl acrylate-methyl methacrylate (copolymerization weight ratio 45:20) were added to 8 to 12 parts by weight of this toner.
: Approximately 0.5% by weight of 35) at a weight ratio of 50:50
Coated. Cu-Zn-Fe-based ferrite carrier (average particle size 48 μm: 250 mesh passes, 35
0 Metschone 79% by weight; s degree 4.5g/c intestinal 3
) were mixed in a total amount of 100 parts by weight to prepare a developer. The developer concentration (%) of each toner is shown in Table 1. The amount of triboelectric charge of this developer was measured by a blow-off method.
また、これを市販の電子写真複写機（キャノン製ＭＰ−
８５００スーパーおよびＧＬＣ−１カラーレーザーコピ
アＩ）を用いて画出しを行い、定着温度を１００〜２５
０℃にコントロールし、定着上ローラーにＲＴＶシリコ
ンゴムローラーを用い定着下ローラーとしてフルオルア
ルコキシコーティングしたフッ素系ローラーを用いた外
部駆動定着塁を使用して、画像の定着性およびオフセッ
ト性を評価した。In addition, we used a commercially available electrophotographic copying machine (Canon MP-
8500 Super and GLC-1 Color Laser Copier
The fixing and offset properties of the image were evaluated using an externally driven fixing base controlled at 0°C and using an RTV silicone rubber roller as the upper fixing roller and a fluorine-based roller coated with fluoroalkoxy as the lower fixing roller. .
環境依存性は先述した摩擦帯電量測定を用いて評価した
。それぞれの環境は低温低湿（１５℃。Environmental dependence was evaluated using the triboelectric charge measurement described above. Each environment was low temperature and low humidity (15℃).
１０％ＲＨ） 、高温高湿（３５℃、８５％ＲＨ）とし
た。環境安定性の評価として、高温高湿での帯電量と低
温低湿での帯電量の差の絶対値が１０以内を良とし２０
以上となるものを不可とした。10% RH) and high temperature and high humidity (35° C., 85% RH). As an evaluation of environmental stability, the absolute value of the difference between the amount of charge at high temperature and high humidity and the amount of charge at low temperature and low humidity is considered to be within 10.
Items that exceed the above were not allowed.
以上の結果を表２に示す。The above results are shown in Table 2.
［発明の効果］
以上述べたように本発明によれば、３価のカルボン酸お
よび／または３価のアルコールを含むポリエステル樹脂
において、末端基のカルボキシル基、水酸基を処理し、
酸価および水酸基価の総和を２０以下にすることにより
定着性のよい耐オフセット性でかつ環境安定性に優れた
トナーを得ることができる。[Effects of the Invention] As described above, according to the present invention, in a polyester resin containing a trivalent carboxylic acid and/or a trivalent alcohol, the terminal carboxyl group and hydroxyl group are treated,
By setting the sum of the acid value and hydroxyl value to 20 or less, a toner with good fixing properties, offset resistance, and excellent environmental stability can be obtained.
第１図は、実施例で用いたトナーの帯電量を測定する装
置の概略図である。
１・・・吸引機 ２・・・測定容器３・・・ス
クリーン ４・・・フタ５・・・真空計
６・・・風量調節弁７・・・吸引口 ８・・・
コンデンサー９・・・電位計FIG. 1 is a schematic diagram of an apparatus for measuring the amount of charge of toner used in Examples. 1... Suction machine 2... Measuring container 3... Screen 4... Lid 5... Vacuum gauge
6... Air volume control valve 7... Suction port 8...
Capacitor 9...Electrometer
Claims (2)
合成されるポリエステル樹脂および荷電制御剤および着
色剤とから成るトナーにおいて、該ポリエステル樹脂が
三価以上のアルコールおよび／または三価以上のカルボ
ン酸を含み、かつ酸価および水酸基価の総和が２０以下
であることを特徴とする電子写真用負帯電トナー。(1) In a toner comprising a polyester resin synthesized with a diol component and a dicarboxylic acid component as main components, a charge control agent, and a colorant, the polyester resin contains a trihydric or higher alcohol and/or a trivalent or higher carboxylic acid. 1. A negatively charged toner for electrophotography, characterized in that the sum of acid value and hydroxyl value is 20 or less.
が２０以下となるように、一価の酸および／または一価
のアルコールにより処理して得られるポリエステル樹脂
より成る請求項１記載の電子写真用負帯電トナー。(2) The electrophotographic photograph according to claim 1, comprising a polyester resin obtained by treating with a monovalent acid and/or a monovalent alcohol so that the sum of the acid value and hydroxyl value of the polyester resin is 20 or less. Negatively charged toner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63281282A JPH02129653A (en) | 1988-11-09 | 1988-11-09 | Negatively chargeable toner for electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63281282A JPH02129653A (en) | 1988-11-09 | 1988-11-09 | Negatively chargeable toner for electrophotography |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02129653A true JPH02129653A (en) | 1990-05-17 |
Family
ID=17636900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63281282A Pending JPH02129653A (en) | 1988-11-09 | 1988-11-09 | Negatively chargeable toner for electrophotography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02129653A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716351A2 (en) | 1994-11-28 | 1996-06-12 | Canon Kabushiki Kaisha | Toner for developing electrostatic image |
| US5578409A (en) * | 1993-01-11 | 1996-11-26 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, one component-type developer and two-component type developer |
-
1988
- 1988-11-09 JP JP63281282A patent/JPH02129653A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578409A (en) * | 1993-01-11 | 1996-11-26 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, one component-type developer and two-component type developer |
| EP0716351A2 (en) | 1994-11-28 | 1996-06-12 | Canon Kabushiki Kaisha | Toner for developing electrostatic image |
| US5660963A (en) * | 1994-11-28 | 1997-08-26 | Canon Kabushiki Kaisha | Toner for developing electrostatic image |
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