JPH01155360A - Electrophotographic developer composition - Google Patents
Electrophotographic developer compositionInfo
- Publication number
- JPH01155360A JPH01155360A JP62315525A JP31552587A JPH01155360A JP H01155360 A JPH01155360 A JP H01155360A JP 62315525 A JP62315525 A JP 62315525A JP 31552587 A JP31552587 A JP 31552587A JP H01155360 A JPH01155360 A JP H01155360A
- Authority
- JP
- Japan
- Prior art keywords
- binder resin
- mol
- acid
- resin
- formula
- 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
- 239000000203 mixture Substances 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 229920001225 polyester resin Polymers 0.000 claims abstract description 18
- 239000004645 polyester resin Substances 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005977 Ethylene Substances 0.000 claims abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- 239000006229 carbon black Substances 0.000 description 13
- 235000019241 carbon black Nutrition 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- -1 polyoxypropylene Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 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
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-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
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- CVRPSWGFUCJAFC-UHFFFAOYSA-N 4-[(2,5-dichlorophenyl)diazenyl]-N-(2,5-dimethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound ClC1=C(C=C(C=C1)Cl)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=C(C=CC(=C1)OC)OC)O CVRPSWGFUCJAFC-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 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
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 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
- 150000001875 compounds Chemical class 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
- 238000004132 cross linking Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 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
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- GWCHPNKHMFKKIQ-UHFFFAOYSA-N hexane-1,2,5-tricarboxylic acid Chemical compound OC(=O)C(C)CCC(C(O)=O)CC(O)=O GWCHPNKHMFKKIQ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 150000002739 metals Chemical class 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
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WRYWBRATLBWSSG-UHFFFAOYSA-N naphthalene-1,2,4-tricarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 WRYWBRATLBWSSG-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
- 230000003287 optical effect Effects 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—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
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、静電印刷などにおける
静電荷像を現像する為の現像剤組成物に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a developer composition for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.
従来電子写真法としては、米国特許第２２９７６９１号
、同第２３５７８０９号明細書等に記載されている如く
、光導電性絶縁層を一様に帯電させ、次いでその層を露
光せしめ、その露光された部分上の電荷を消散させる事
により電気的な潜像を形成し、更に該潜像にトナーと呼
ばれる着色された電荷をもった微粉末を付着せしめる事
によって可視化させ（現像工程）、得られた可視像を転
写紙等の転写材に転写せしめた後（転写工程）、加熱、
圧力或いはその他適当な定着法により永久定着せしめる
（定着工程）工程からなる。Conventional electrophotographic methods include uniformly charging a photoconductive insulating layer, then exposing the layer to light, as described in U.S. Pat. An electrical latent image is formed by dissipating the electric charge on the part, and is made visible by attaching a colored, electrically charged fine powder called toner to the latent image (development process). After the visible image is transferred to a transfer material such as transfer paper (transfer process), heating,
It consists of permanently fixing (fixing step) using pressure or other suitable fixing methods.
この様にトナーは単に現像工程のみならず、転写工程、
定着工程の各工程に於いて要求される機能を備えていな
ければならない。In this way, toner is used not only in the development process but also in the transfer process.
It must have the functions required in each step of the fixing process.
一般にトナーは現像装置内で機械的動作中に受ける剪断
力、衝撃力による機械的な摩擦力を受け、数十枚乃至数
万枚コピーする間に劣化する。この様なトナーの劣化を
防ぐには機械的な摩擦力に耐えうる分子量の大きな強靭
な樹脂を用いれば良いが、これらの樹脂は一般に軟化点
が高く、非接触定着方式であるオーブン定着、赤外線に
よるラジアント定着では熱効率が悪い為に定着が充分に
行われず、又、接触定着方式で熱効率が良い為、広く用
いられているヒートローラ一定着方式に於いても、充分
に定着させる為ヒートローラーの温度を高くする必要が
生じ、定着装置の劣化、紙のカール、消費エネルギーの
増大等の弊害を招くばかりでなく、この様な樹脂を使用
すると粉砕性が悪いため、トナーを製造する際、製造効
率が著しく低下する。Generally, toner is subjected to mechanical frictional force due to shearing force and impact force during mechanical operation in a developing device, and deteriorates during copying of tens to tens of thousands of sheets. To prevent such toner deterioration, it is best to use a strong resin with a large molecular weight that can withstand mechanical friction, but these resins generally have a high softening point and are suitable for non-contact fixing methods such as oven fixing and infrared fixing. With radiant fixing, the thermal efficiency is poor, so fixing is not sufficient.Also, since the contact fixing method has good thermal efficiency, even in the widely used heat roller constant fixing method, it is necessary to use the heat roller to achieve sufficient fixing. Not only does this require higher temperatures, which can cause problems such as deterioration of the fixing device, curling of paper, and increased energy consumption, but the use of such resins has poor pulverization properties, so when manufacturing toner, manufacturing Efficiency is significantly reduced.
その為、結着樹脂の重合度、更には軟化点も余り高いも
のは用いる事ができない。一方ヒートローラ一定着方式
は加熱ローラー表面と被定着シートのトナー像面が圧接
触する為、熱効率が著しく良く、低速から高速に至るま
で広く使用されているが、加熱ローラー面とトナー像面
が接触する際、トナーが加熱ローラー表面に付着して後
続の転写紙等に転写される、所謂オフセット現象が生じ
易い。この現象を防止する為、加熱ローラー表面を弗素
系樹脂等の離型性の優れた材料で加工するが、更に加熱
ローラー表面にシリコンオイル等の離型剤を塗布して対
処している。Therefore, it is not possible to use a binder resin whose polymerization degree and even softening point are too high. On the other hand, in the heat roller fixed fixing method, the heating roller surface and the toner image surface of the sheet to be fixed are in pressure contact, so the thermal efficiency is extremely high and it is widely used from low speeds to high speeds. When they come into contact, a so-called offset phenomenon tends to occur, in which toner adheres to the surface of the heating roller and is transferred to subsequent transfer paper or the like. In order to prevent this phenomenon, the surface of the heating roller is treated with a material with excellent mold release properties such as a fluorine-based resin, and in addition, a mold release agent such as silicone oil is coated on the surface of the heating roller.
しかしながら、シリコンオイル等を塗布する方式は、定
着装置が大きくなりコスト高となるばかりでなく複雑に
なる為、トラブルの原因にもなり易く好ましいものでは
ない。However, the method of applying silicone oil or the like is not preferable because the fixing device becomes large and not only expensive but also complicated, which tends to cause trouble.
又、特公昭５５−６８９５号、特開昭５６−９８２０２
号公報に記載の如く、結着樹脂の分子量分布幅を広くす
る事によりオフセット現象を改良する方法もあるが、一
般に樹脂の重合度が高くなり使用定着温度も高く設定す
る必要がある。Also, Japanese Patent Publication No. 55-6895, Japanese Patent Publication No. 56-98202
As described in the above publication, there is a method of improving the offset phenomenon by widening the molecular weight distribution width of the binder resin, but generally the degree of polymerization of the resin increases and the fixing temperature used also needs to be set high.
更に改良された方法として、特公昭５７−４９３号、特
開昭５０−４４８３６号、特開昭５７−３７３５３号公
報記載の如く、樹脂を非対称化、架橋化せしめる事によ
ってオフセット現象を改善する方法があるが定着点は改
善されていない。As a further improved method, as described in Japanese Patent Publication No. 57-493, Japanese Patent Application Laid-open No. 50-44836, and Japanese Patent Application Publication No. 57-37353, there is a method of improving the offset phenomenon by making the resin asymmetrical and crosslinking it. However, the retention point has not improved.
一般に、最低定着温度は低温オフセットと高温オフセッ
トの間にある為、使用可能温度領域は、最低定着温度と
高温オフセットとの間となり、最低定着温度をできるだ
け下げる事、高温オフセット発生温度をできるだけ上げ
る事により使用定着温度を下げる事ができると共に使用
可能温度領域を広げる事ができ、省エネルギー化、高速
定着化、紙のカールを防ぐ事ができる。Generally, the minimum fusing temperature is between the low temperature offset and the high temperature offset, so the usable temperature range is between the minimum fusing temperature and the high temperature offset.The minimum fusing temperature should be lowered as much as possible, and the temperature at which high temperature offset occurs should be raised as much as possible. This makes it possible to lower the usable fixing temperature and widen the usable temperature range, resulting in energy savings, high-speed fixing, and prevention of paper curl.
又、両面コピーがトラブルなくできる為、複写機のイン
テリジェント化、定着装置の温度コントロールの精度、
許容幅の緩和等数々の利点がある。In addition, in order to be able to make double-sided copies without any trouble, the copiers have become more intelligent, the temperature control of the fixing device has become more accurate, and
There are many advantages such as relaxing the tolerance range.
その為、常に定着性、耐オフセット性の良い樹脂、トナ
ーが望まれている。Therefore, resins and toners with good fixing properties and offset resistance are always desired.
この様な要求を達成する為スチレン系の結着樹脂を使用
する場合には特開昭４９−６５２３２号、特開昭５０−
２８８４０号、特開昭５０−８１３４２号公報記載の如
く、パラフィンワックス、低分子量ポリオレフィン等を
オフセット防止剤として添加する方 □法が知
られているが、添加量が少ないと効果がなく、多いと現
像剤の劣化が早い事も確認されている。When using a styrene-based binder resin to meet such requirements, Japanese Patent Application Laid-Open Nos. 49-65232 and 1977-
As described in No. 28840 and JP-A No. 50-81342, a method of adding paraffin wax, low molecular weight polyolefin, etc. as an anti-offset agent is known. It has also been confirmed that the developer deteriorates quickly.
ポリエステル樹脂は本質的に定着性が良く、米国特許第
３５９００００号明細書記載の如く、非接触定着方式に
於いても充分に定着されるが、オフセット現象が発生し
易くヒートローラ一定着方式には使用が困難であった。Polyester resin inherently has good fixing properties, and can be sufficiently fixed even in a non-contact fixing method, as described in U.S. Pat. It was difficult to use.
特開昭５０−４４８３６号、特開昭５７−３７３５３号
、特開昭５７−１０９８７５号公報記載の如く、多価カ
ルボン酸を使用し耐オフセット性を改良したポリエステ
ル樹脂は、使用するに充分な耐オフセット性を有してい
ないか、又は有しているものはポリエステル樹脂が本来
有している低温定着性を犠牲にしている場合が多く、問
題があった。As described in JP-A-50-44836, JP-A-57-37353, and JP-A-57-109875, polyester resins with improved anti-offset properties using polyhydric carboxylic acids have sufficient properties for use. There is a problem in that either they do not have anti-offset properties, or those that do do so at the expense of the low-temperature fixing properties that polyester resins inherently have.
本発明はこれらの要求を満たす為になされたものであり
、その目的はヒートローラ一定着方式に於いてオフセッ
ト防止液を塗布することなく、オフセットが防止され、
かつより低い定着温度で定着できる現像剤を提供する事
にある。The present invention has been made to meet these demands, and its purpose is to prevent offset without applying an anti-offset liquid in a heat roller fixed fixing method.
Another object of the present invention is to provide a developer that can be fixed at a lower fixing temperature.
本発明の他の目的は、ブロッキングの生じない、かつ寿
命の長い（劣化し難い）現像剤を提供する事にある。Another object of the present invention is to provide a developer that does not cause blocking and has a long life (hard to deteriorate).
本発明の更なる目的は粉砕性の良好な樹脂及びトナーを
提供する事にある。A further object of the present invention is to provide a resin and a toner with good pulverizability.
即ち本発明は、結着樹脂及び着色剤並びに所望に応じて
他の添加剤を含有する電子写真用現像剤組成物に於いて
、該結着樹脂の主成分がポリエステル樹脂より成り、該
ポリエステル樹脂部分は、少なくとも
（イ）次式
（式中、Ｒはエチレン又はプロピレン基、Ｘ。That is, the present invention provides an electrophotographic developer composition containing a binder resin, a colorant, and other additives as desired, in which the main component of the binder resin is a polyester resin; The moiety has at least (a) the following formula (wherein R is ethylene or propylene group, X.
ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値
は２〜７である。）
で表されるジオール成分を全構成成分中１０モル％以上
３０モル％以下と、
（ロ） 次式
％式％
（式中、ｎは２ないし６の整数である。）で表されるジ
オール成分を全構成成分中１０モル％以上２５モル％未
満と、
（ハ）２価のカルボン酸又はその酸無水物又はその低級
アルキルエステルと、
（ニ）３価以上の多価カルボン酸又はその酸無水物又は
その低級アルキルエステルを全構成成分中２．５モル％
以上１５モル％未満
とを共縮重合したポリエステル樹脂であることを特徴と
する電子写真用現像剤組成物に係わるものである。Each y is an integer of 1 or more, and the average value of x+y is 2 to 7. ) A diol component represented by 10 mol % or more and 30 mol % or less of the total constituent components, and (b) a diol represented by the following formula % (wherein n is an integer from 2 to 6). 10 mol% or more and less than 25 mol% of the total components; (c) divalent carboxylic acid or its acid anhydride or its lower alkyl ester; (d) trivalent or higher polyhydric carboxylic acid or its acid. 2.5 mol% of anhydride or its lower alkyl ester in all components
This invention relates to an electrophotographic developer composition characterized in that it is a polyester resin cocondensed with less than 15 mol% of the above.
本発明において結着樹脂の主成分として用いられる樹脂
中のポリエステル部分は、アルコールとカルボン酸、も
しくはカルボン酸エステル、カルボン酸無水物との縮重
合により得られるが、アルコール成分の内（イ）のジオ
ール成分としては、ポリオキシプロピレン（２，２）−
２，２−ビス（４−ヒドロキシフェニル）プロパン、ポ
リオキシプロピレン（３，３）−２，２−ビス（４−ヒ
ドロキシフェニル）プロパン、ポリオキシエチレン（２
，０）−２，２−ビス（４−ヒドロキシフェニル）プロ
パン、ポリオキシプロピレン（２，０）−ポリオキシエ
チレン（２，０）−２，２−ビス（４−ヒドロキシフェ
ニル）プロパン、ポリオキシプロピレン（６）−２，２
−ビス（４−ヒドロキシフェニル）プロパン等を挙げる
ことができる。The polyester moiety in the resin used as the main component of the binder resin in the present invention is obtained by condensation polymerization of alcohol and carboxylic acid, carboxylic acid ester, or carboxylic acid anhydride. As a diol component, polyoxypropylene (2,2)-
2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3,3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2
,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2,0)-polyoxyethylene(2,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxy Propylene (6)-2,2
-bis(4-hydroxyphenyl)propane and the like.
（イ）のジオール成分は全構成成分中１０モル％以上３
０モル％以下で使用されるが、１０モル％未満ではポリ
エステル樹脂の負帯電性が減少し、３０モル％を超える
と、樹脂及びトナーの粉砕性が悪化し好ましくない。The diol component in (a) is 10 mol% or more in all components3
It is used in an amount of 0 mol % or less, but if it is less than 10 mol %, the negative chargeability of the polyester resin decreases, and if it exceeds 30 mol %, the crushability of the resin and toner deteriorates, which is not preferable.
（ロ）のジオール成分としては、エチレングリコール、
１．３−プロピレングリコール、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
ールを挙げることができる。The diol component in (b) is ethylene glycol,
Mention may be made of 1,3-propylene glycol, 1,4-butanediol, 1,5-bentanediol, and 1,6-hexanediol.
中でもエチレングリコール、１．３−プロピレングリコ
ール、１，４−ブタンジオールが好ましく用いられる。Among them, ethylene glycol, 1,3-propylene glycol, and 1,4-butanediol are preferably used.
（ロ）のジオール成分は全構成成分中１０モル％以上２
５モル％未満で使用されるが、１０モル、％未満ではト
ナーの最低定着温度が高くなり、２５モル％以上では樹
脂が結晶性を帯びてきて、特公昭５７−４９３号公報に
記載の如く、好ましくない。The diol component (b) is 10 mol% or more of the total components2.
It is used in an amount of less than 5 mol%, but if it is less than 10 mol%, the minimum fixing temperature of the toner becomes high, and if it is more than 25 mol%, the resin becomes crystalline, as described in Japanese Patent Publication No. 57-493. , undesirable.
又、場合により他のジオール、例えばジエチレングリコ
ール、トリエチレングリコール、１゜２−プロピレング
リコール、ネオペンチルグリコール、１．４−７’テン
ジオール等のジオール類、ビスフェノールＡ、水素添加
ビスフェノールＡ１その他の２価のアルコールを加える
事ができる。In addition, other diols such as diethylene glycol, triethylene glycol, 1゜2-propylene glycol, neopentyl glycol, 1,4-7'tenediol, bisphenol A, hydrogenated bisphenol A1 and other divalent diols may be used as necessary. Alcohol can be added.
又、本発明における（ハ）のカルボン酸成分としては、
例えば、マレイン酸、フマール酸、シトラコン酸、イタ
コン酸、グルタコン酸、フタル酸、イソフタル酸、テレ
フタル酸、シクロヘキサンジカルボン酸、コハク酸、ア
ジピン酸、セバシン酸、アゼライン酸、マロン酸、又は
ｎ−ドデセニルコハク酸、ｎ−ドデシルコハク酸等のア
ルケニルコハク酸、もしくはアルキルコハク酸、これら
の酸の無水物、低級アルキルエステル、その他の２価の
カルボン酸を挙げることができる。In addition, as the carboxylic acid component (c) in the present invention,
For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or n-dodecenylsuccinic acid. , alkenylsuccinic acids such as n-dodecylsuccinic acid, or alkylsuccinic acids, anhydrides of these acids, lower alkyl esters, and other divalent carboxylic acids.
これらのうち、テレフタル酸、又はその低級アルキルエ
ステルが特に好ましい。Among these, terephthalic acid or its lower alkyl ester is particularly preferred.
又、本発明における（二）の３価以上の多価カルボン酸
又はその誘導体は、オフセット現象を改良する好ましい
成分であるが、少ないと効果がうすく、又、ポリエステ
ル樹脂及びトナーの粉砕性が悪化し、多い場合は反応の
コントロールが難しく、安定した性能のポリエステル樹
脂が得難いばかりでな（、最低定着温度が高くなる等、
好ましくない現象が発生する。従って（ニ）の３価以上
の多価カルボン酸又はその誘導体の使用量は全構成成分
中２．５モル％以上１５モル％未満が望ましい。具体的
に（ニ）の３価以上の多価カルボン酸又はその誘導体と
しては、１．２．４−ベンゼントリカルボン酸、２，５
．７−ナフタレントリカルボン酸、１，２．４−ナフタ
レントリカルボン酸、１．２．４−ブタントリカルボン
酸、１，２．５−ヘキサントリカルボン酸、１．３−ジ
カルボキシル−２−メチル−２−メチレンカルボキシプ
ロパン、テトラ（メチレンカルボキシル）メタン、１．
２．７．８−オクタンテトラカルボン酸、エンボール二
量体酸、及びこれらの無水物、低級アルキルエステル、
その他の３価以上のカルボン酸を挙げることができる。In addition, the (2) trivalent or higher polycarboxylic acid or its derivative in the present invention is a preferable component for improving the offset phenomenon, but if the amount is small, the effect is weak, and the pulverizability of the polyester resin and toner deteriorates. However, if there is a large amount, it is difficult to control the reaction, and it is difficult to obtain a polyester resin with stable performance (e.g., the minimum fixing temperature becomes high, etc.).
Undesirable phenomena occur. Therefore, the amount of the trivalent or higher polyhydric carboxylic acid or its derivative (d) used is preferably 2.5 mol% or more and less than 15 mol% of the total components. Specifically, (d) trivalent or higher polyhydric carboxylic acids or derivatives thereof include 1.2.4-benzenetricarboxylic acid, 2,5
．． 7-naphthalenetricarboxylic acid, 1,2.4-naphthalenetricarboxylic acid, 1.2.4-butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, 1.3-dicarboxyl-2-methyl-2-methylene Carboxypropane, tetra(methylenecarboxyl)methane, 1.
2.7.8-octane tetracarboxylic acid, embol dimer acid, and anhydrides thereof, lower alkyl esters,
Other trivalent or higher carboxylic acids can be mentioned.
本発明において用いられる結着樹脂としては、軟化点が
１０６℃以上１６０℃以下、ガラス転移温度が５０℃以
上８０℃以下のものが好ましいが、軟化点が１０６℃未
満では充分な非オフセット域を得るのに効果がなく、１
６０″Ｃを越えれば最低定着温度が高くなる等、好まし
くない現象が発生する。一方、ガラス転移温度が５０℃
未満ではトナー化後の保存安定性が悪くなり、８０℃を
越えれば定着性に悪影響を及ぼすようになり、好ましく
ない。The binder resin used in the present invention preferably has a softening point of 106°C or higher and 160°C or lower and a glass transition temperature of 50°C or higher and 80°C or lower. However, if the softening point is lower than 106°C, a sufficient non-offset area is not obtained. It has no effect on obtaining 1
If the temperature exceeds 60"C, undesirable phenomena such as an increase in the minimum fixing temperature will occur. On the other hand, if the glass transition temperature is 50"C.
If it is less than 80° C., the storage stability after forming a toner will be poor, and if it exceeds 80° C., it will have an adverse effect on fixing properties, which is not preferable.
くない。Not.
本発明に使用するポリエステル樹脂は多価カルボン酸成
分とポリオール成分とを不活性ガス雰囲気中にて１８０
〜２５０℃の温度で縮重合する事により製造する事がで
きる。この際、反応を促進せしめる為通常使用されてい
るエステル化触媒、例えば酸化亜鉛、酸化第一錫、ジプ
チル錫オキシド、ジブチル錫ジラウレート等を使用する
事ができる。又同様の目的の為減圧下にて製造する事も
できる。The polyester resin used in the present invention is prepared by combining a polyhydric carboxylic acid component and a polyol component in an inert gas atmosphere.
It can be produced by polycondensation at a temperature of ~250°C. At this time, commonly used esterification catalysts such as zinc oxide, stannous oxide, diptyltin oxide, dibutyltin dilaurate, etc. can be used to accelerate the reaction. It can also be produced under reduced pressure for the same purpose.
本発明に係るポリエステル樹脂を結着樹脂の主成分とし
て用いてトナーを得るが、例えばトナー化での粉砕性を
更に向上させるべく、数平均分子量が１１ 、０００以
下のスチレンもしくはスチレン−アクリル系樹脂等、他
の樹脂を結着樹脂中の３０重量％まで用いてもよい。ト
ナー調製時には着色剤、必要に応じて電荷制御剤、磁性
体が添加される以外にオフセット防止剤としてワックス
、流動性向上剤として疎水性シリカ等、特性改良剤が添
加されるが、本発明に係るポリエステル樹脂を結着樹脂
として用いた場合、該特性改良剤を加えなくても良く、
又、添加する場合でも添加量は少なくて済む。A toner is obtained by using the polyester resin according to the present invention as the main component of a binder resin. Other resins may be used up to 30% by weight of the binder resin. At the time of toner preparation, in addition to colorants, charge control agents and magnetic substances as required, property improvers such as wax as an anti-offset agent and hydrophobic silica as a fluidity improver are added. When such a polyester resin is used as a binder resin, it is not necessary to add the property improver,
Moreover, even if it is added, the amount added can be small.
本発明に用いられる着色剤としては、サーマ
゛ルブラツク法、アセチレンブラック法、チャンネルブ
ラック法、ランプブラック法等により製造される各種の
カーボンブラック、フタロシアニンブルー、パーマネン
トブラウンＦＧ、ブリリアントファーストスカーレット
、ピグメントグリーンＢ、ローダミン−Ｂベース、ソル
ベントレッド４９、ソルベントレッド１４６、ソルベン
トブルー３５等及びそれらの混合物等を挙げる事ができ
、通常、結着樹脂１００重景部に対し１〜１５重量部程
度が使用される。The colorant used in the present invention includes Therma
Various carbon blacks produced by the Rubrack method, Acetylene black method, Channel black method, Lamp black method, etc., Phthalocyanine blue, Permanent brown FG, Brilliant first scarlet, Pigment green B, Rhodamine-B base, Solvent red 49, Solvent Examples include Red 146, Solvent Blue 35, and mixtures thereof, and are usually used in an amount of about 1 to 15 parts by weight per 100 parts of the binder resin.
本発明のポリエステル樹脂は樹脂自体が負の摩擦帯電性
を有するので、荷電制御剤を用いずに負帯電性トナーを
得る事が出来るが、初期から帯電量を確保する目的で負
帯電性の荷電制御剤を、又、帯電量の経時安定性を確保
する目的で正帯電性の荷電制御剤を併用しても良い。Since the polyester resin of the present invention has negative triboelectric chargeability itself, it is possible to obtain a negatively chargeable toner without using a charge control agent. The control agent may also be used in combination with a positively chargeable charge control agent for the purpose of ensuring stability of the charge amount over time.
正の荷電制御剤の具体例としては、ニグロシン系染料、
例えば「ニグロシンベースＥＸＪ、［オイルブラックＢ
ＳＪ、「オイルブラックＳＯＪ、「ボントロンＮ−０１
Ｊ、「ボントロンＮ−１１Ｊ（以上、オリエント化学社
製）等、三級アミンを側鎖として含有するトリフェニル
メタン系染料、四級アンモニウム塩化合物、例えば「ボ
ントロンＰ−５１Ｊ（オリエント化学社製）、セチルト
リメチルアンモニウムプロミド等、ポリアミン樹脂、例
えばｒＡＦＰ−ＢＪ （オリエント化学社製）等、そ
の他を挙げることができる。Specific examples of positive charge control agents include nigrosine dyes,
For example, "Nigrosine Base EXJ, [Oil Black B
SJ, “Oil Black SOJ,” Bontron N-01
J, "Bontron N-11J (manufactured by Orient Chemical Co., Ltd.), triphenylmethane dye containing a tertiary amine as a side chain, quaternary ammonium salt compound, such as "Bontron P-51J (manufactured by Orient Chemical Co., Ltd.) , cetyltrimethylammonium bromide, polyamine resins such as rAFP-BJ (manufactured by Orient Chemical Co., Ltd.), and others.
負の荷電制御剤としては、含金属アブ染料、例えば「パ
リファーストブラック３８０４ Ｊ、「ボントロンＳ−
３１Ｊ、「ボントロンＳ−３２Ｊ、「ボントロンＳ−３
４Ｊ、ｒボントロンＳ−３６Ｊ、（以上オリエント化学
社製）、「アイゼン スピロンブラックＴＶＩＩＪ
（採土ケ谷化学社製）等、銅フタロシアニン染料、サリ
チル酸のアルキル誘導体の金属錯体、例えば［ボントロ
ンＥ −８２Ｊ、「ボントロンＥ−８４Ｊ、「ボントロ
ンＥ−８５Ｊ（以上、オリエント化学社製）等、その他
を挙げることができる。As the negative charge control agent, metal-containing ab dyes such as "Pali Fast Black 3804 J" and "Bontron S-
31J, "Bontron S-32J," Bontron S-3
4J, r Bontron S-36J, (manufactured by Orient Chemical Co., Ltd.), "Eisen Spiron Black TVIIJ
Copper phthalocyanine dyes such as (manufactured by Odugaya Chemical Co., Ltd.), metal complexes of alkyl derivatives of salicylic acid, such as [Bontron E-82J, Bontron E-84J, Bontron E-85J (manufactured by Orient Chemical Co., Ltd.), etc. can be mentioned.
以上の荷電制御剤は結着樹脂に対して、０．１〜８．０
重量％、好ましくは０．２〜５．０重量％含有される。The above charge control agent has a charge control agent of 0.1 to 8.0 with respect to the binder resin.
It is contained in an amount of 0.2 to 5.0% by weight, preferably 0.2 to 5.0% by weight.
本発明におけるポリエステル樹脂を必須成分、 とし
て、着色剤と、場合によっては特性改良剤とを均一分散
後、公知の方法にて溶融混練、冷却、粉砕、分級後、平
均粒径５〜１５−のトナーを得るが、該トナーは磁性粉
体、即ち、酸化鉄系キャリアー、真球状酸化鉄系キャリ
アー、又はフェライト系キャリアーを樹脂等でコートし
たものと混合することにより、乾式２成分現像剤として
用い、られる。The polyester resin of the present invention is used as an essential component, and after uniformly dispersing a coloring agent and, in some cases, a property improving agent, melt-kneading, cooling, pulverizing, and classifying by a known method, the polyester resin has an average particle size of 5 to 15. A toner is obtained, and the toner is used as a dry two-component developer by mixing magnetic powder, that is, an iron oxide carrier, a true spherical iron oxide carrier, or a ferrite carrier coated with a resin or the like. , can be done.
本発明に係る結着樹脂を用いて磁性トナーとする場合、
磁性体としては、鉄、コバルト、ニッケル等の強磁性金
属の粉末もしくはフェライト、ヘマタイト、マグネタイ
ト等強磁性を示す元素を含む合金あるいは化合物を挙げ
る事ができ、該磁性体は平均粒径０．１〜１ｊ１ｍの微
粉末の形で、結着樹脂１００重量部に対して４０〜７０
重量部程度を分散せしめて用いる事ができる。When making a magnetic toner using the binder resin according to the present invention,
Examples of the magnetic material include powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys or compounds containing ferromagnetic elements such as ferrite, hematite, and magnetite, and the magnetic material has an average particle size of 0.1 ~1j1m fine powder form, 40-70 parts per 100 parts by weight of binder resin.
It can be used by dispersing about parts by weight.
以下、結着樹脂の製造例及び本発明の実施例について述
べるが、本発明はこれらの例に限定されるものではない
。Examples of manufacturing the binder resin and examples of the present invention will be described below, but the present invention is not limited to these examples.
尚、実施例に示す組成割合はすべて重量部で表すもので
ある。It should be noted that all composition ratios shown in Examples are expressed in parts by weight.
製造例１
ポリオキシプロピレン（２，２）−２，２−ビス（４−
ヒドロキシフェニル）プロパン４６０ ｇ 、エチレン
グリコール７２ｇ、テレフタル酸３０６ｇ、１゜２．４
−ベンゼントリカルボン酸無水物（無水トリメリット酸
）９０ｇ、及び１．２ｇのジブチル錫オキシドをガラス
製２１の４つロフラスコに入れ、温度計、ステンレス製
撹拌棒、流下式コンデンサー、及び窒素導入管を取り付
け、マントルヒーター中で窒素気流下にて１９０″Ｃに
て５時間、その後２２０℃にて撹拌しつつ反応せしめた
。Production Example 1 Polyoxypropylene (2,2)-2,2-bis(4-
Hydroxyphenyl)propane 460 g, ethylene glycol 72 g, terephthalic acid 306 g, 1°2.4
- Place 90 g of benzenetricarboxylic anhydride (trimellitic anhydride) and 1.2 g of dibutyltin oxide in a 21-inch glass four-bottle flask, and attach a thermometer, stainless steel stirring bar, falling condenser, and nitrogen inlet tube. The mixture was attached and reacted in a mantle heater under a nitrogen stream at 190''C for 5 hours, and then at 220°C with stirring.
重合度はＡＳＴＭ Ｅ ２８−５１Ｔに準する軟化点よ
り追跡を行い、軟化点が１３０℃に達した時反応を終了
した。The degree of polymerization was monitored from the softening point according to ASTM E 28-51T, and the reaction was terminated when the softening point reached 130°C.
得られた樹脂は淡黄色の固体であり、ＤＳＣ（示差熱量
計）によるガラス転移温度は表１に示した。当該樹脂を
結着樹脂（１）とする。The obtained resin was a pale yellow solid, and the glass transition temperature measured by DSC (differential calorimeter) is shown in Table 1. This resin is referred to as a binder resin (1).
製造例２〜１２
表１に示した原料組成にて製造例１と同様の操作を行い
、結着樹脂（２）〜０２１を製造した。Production Examples 2 to 12 Binder resins (2) to 021 were produced by performing the same operations as in Production Example 1 using the raw material compositions shown in Table 1.
但し、結着樹脂（５）については、反応初期は１７０℃
で脱メタノールさせ、後半は２２０℃で反応を進行せし
めた。However, for the binder resin (5), the initial temperature of the reaction is 170°C.
The mixture was demethanoled, and the reaction was allowed to proceed at 220° C. in the second half.
得られた樹脂の物性を表１に示した。Table 1 shows the physical properties of the obtained resin.
実施例１〜６、参考例１〜３及び比較例１〜４下記組成
の材料をヘンシェルミキサーで混合後、２軸押し出し機
にて溶融混練し、冷却後、通常の粉砕・分級工程を経て
平均粒径１１−のトナーを調整した。Examples 1 to 6, Reference Examples 1 to 3, and Comparative Examples 1 to 4 Materials with the following compositions were mixed in a Henschel mixer, then melted and kneaded in a twin-screw extruder, cooled, and then subjected to normal crushing and classification processes to obtain an average A toner having a particle size of 11 was prepared.
〈組 成〉
実施例１
結着樹脂（］） ９３ 部実
施例２−
結着樹脂（２） ９３ 部カ
ーボンブラックｒ＃４４ Ｊ ７ 部実施
例３
結着樹脂（３）９３ 部
カーボンブラックｒｔｔ４４ Ｊ ７ 部
実施例４
結着樹脂（４） ９３ 部カ
ーボンブラックｒ＃４４ Ｊ ７ 部実施
例５
結着樹脂（５） ９３ 部カ
ーボンブラックｒｌ１４４ Ｊ ７ 部実
施例６
結着樹脂（６） ９３ 部カ
ーボンブラックｒ＃４４」７ 部
参考例１
結着樹脂（力 ９３ 部カーボ
ンブラックｒ＃４４ Ｊ ７ 部参考例２
結着樹脂（８） ９３ 部カ
ーボンブラックｒｊ１４４ Ｊ ７ 部参
考例３
結着樹脂（７） ９３ 部カ
ーボンブラックｒ１４４ Ｊ ７ 部比較
例１
結着樹脂（９） ９３ 部カ
ーボンブラックｒｌ１４４ Ｊ ７ 部比
較例２
結着樹脂Ｏｎ） ９３ 部カ
ーボンブラックｒｌ１４４ Ｊ ７ 部比
較例３
結着樹脂（ＩＩ） ９３ 部
カーボンブラックｒ＃４４」７ 部
比較例４
結着樹脂θ２） ９３ 部カ
ーボンブラックｒｌｔ４４」７ 部以上の実施例１〜
６で得られたトナーをそれぞれトナー１〜トナー６とし
、参考例１〜３で得られたトナーをそれぞれ参考トナー
１〜参考トナー３、比較例１〜４で得られたトナーをそ
れぞれ比較トナー１〜比較トナー４とする。<Composition> Example 1 Binder resin (]) 93 parts Example 2 - Binder resin (2) 93 parts Carbon black r#44 J 7 parts Example 3 Binder resin (3) 93 parts Carbon black RTT44 J 7 parts Example 4 Binder resin (4) 93 parts Carbon black r#44 J 7 parts Example 5 Binder resin (5) 93 parts Carbon black RL144 J 7 parts Example 6 Binder resin (6) 93 parts Carbon Black r#44'' 7 parts Reference example 1 Binder resin (force 93 parts Carbon black r#44 J 7 parts Reference example 2 Binder resin (8) 93 parts Carbon black rj144 J 7 parts Reference example 3 Binder resin (7 ) 93 parts Carbon black r144 J 7 parts Comparative example 1 Binder resin (9) 93 parts Carbon black rl144 J 7 parts Comparative example 2 Binder resin On) 93 parts Carbon black rl144 J 7 parts Comparative example 3 Binder resin (II ) 93 parts carbon black r#44'' 7 parts Comparative Example 4 Binder resin θ2) 93 parts carbon black rlt44'' 7 parts or more Examples 1 to
The toners obtained in Example 6 are designated as Toner 1 to Toner 6, respectively, the toners obtained in Reference Examples 1 to 3 are designated as Reference Toner 1 to Reference Toner 3, respectively, and the toners obtained in Comparative Examples 1 to 4 are designated as Comparative Toner 1, respectively. - Comparison toner 4.
以上のトナー各々３９部と樹脂被覆された鉄粉１２６１
部とを混合して現像剤を調製し、市販の電子写真複写機
（感光体はアモルファスセレン、定着ローラーの回転速
度は２５５ｍｍ／ｓｅｃ、定着装置中のヒートローラー
温度を可変にし、オイル塗布装置を除去したもの）にて
画像出しを行った。39 parts of each of the above toners and 1261 parts of resin-coated iron powder
A commercially available electrophotographic copying machine (the photoconductor is amorphous selenium, the rotation speed of the fixing roller is 255 mm/sec, the heat roller temperature in the fixing device is variable, and the oil coating device is (removed)).
定着温度を１２０℃〜２２０℃にコントロールし、画像
の定着性、オフセット性を評価した結果を表２に示す。The fixing temperature was controlled at 120° C. to 220° C., and the fixing properties and offset properties of the image were evaluated. The results are shown in Table 2.
ここでの最低定着温度とは底面が１５ｍｍ Ｘ ７．５
ｍａ＋の砂消しゴムに５００ｇの荷重を載せ、定着機を
通して定着された画像の上を５往復こすり、こする前後
でマクベス社の反射濃度計にて光学反射密度を測定し、
以下の定義による定着率が７０％を越える際の定着ロー
ラーの温度をいう。The minimum fixing temperature here is 15 mm x 7.5 mm on the bottom.
A load of 500 g was placed on a MA+ sand eraser, and the image fixed through the fixing machine was rubbed back and forth 5 times, and the optical reflection density was measured using a Macbeth reflection densitometer before and after rubbing.
It refers to the temperature of the fixing roller when the fixing rate exceeds 70% as defined below.
又、保存安定性については、各トナーの５０℃１相対湿
度４０％の条件下で２４時間放置したときの凝集の発生
の程度を評価した。その結果も表２に示す。Regarding storage stability, the degree of aggregation was evaluated when each toner was left for 24 hours at 50° C. and 40% relative humidity. The results are also shown in Table 2.
注）
傘樹脂の粉砕性：
簡易粉砕試験により評価した。即ち、通常の粉砕工程を
終わった樹脂を篩にかけ、１６メツシユを通過し、２０
メツシユは通過しない樹脂粉体を得る。上記の分級され
た樹脂粉体を３０．００ ｇ精秤し、コーヒーミル（Ｐ
１１ＬＩＰＳ社製＋１Ｒ−２１７０タイプ）にて１５秒
間粉砕後、３２メツシユの篩にかけ、通過しない樹脂の
重ｆｆｉ（Ａ）ｇを精秤する。Note) Crushability of umbrella resin: Evaluated by simple crushing test. That is, the resin that has undergone the normal crushing process is passed through a sieve, passed through 16 meshes, and then
A resin powder is obtained that does not pass through the mesh. Precisely weigh 30.00 g of the above classified resin powder, and place it in a coffee mill (P
After pulverizing for 15 seconds using a 1R-2170 type (manufactured by 11LIPS), the resin was sieved through a 32-mesh sieve, and the weight of the resin that did not pass was precisely weighed (ffi(A) g).
次式
％式％（）
により残存率を求めるが、以上の操作を３回行い平均し
、平均残存率が０〜１５．０％を〔◎） 、１５．１〜
３０．０％を〔○） 、３０．１〜４５．０％を〔Δ〕
、４５．１〜１ｏｏ％を〔×〕と表示する。The remaining rate is calculated using the following formula % formula % (). The above operation is performed three times and averaged, and the average remaining rate is 0 to 15.0% [◎), 15.1 to
30.0% [○], 30.1-45.0% [Δ]
, 45.1 to 1oo% is indicated as [x].
表２から明らかな様に本発明に係わるトナー１〜６につ
いては最低定着温度が低く、非オフセット域も広（、保
存安定性も良好で、樹脂の粉砕性も良好であり、ひいて
はトナー化での粉砕性も良好であった。しかし、参考ト
ナー１は最低定着温度は低いものの非オフセット域が狭
く、それにワックスを添加して非オフセット域を広げた
参考トナー３では最低定着温度が高くなってしまった。As is clear from Table 2, toners 1 to 6 according to the present invention have a low minimum fixing temperature, a wide non-offset range (also have good storage stability, good resin pulverization properties, and can be easily converted into toners). The pulverizability of the toner was also good. However, although reference toner 1 had a low minimum fixing temperature, the non-offset area was narrow, and reference toner 3, in which wax was added to widen the non-offset area, had a high minimum fixing temperature. Oops.
参考トナー２及び比較トナー１、４は最低定着温度が高
かった。比較トナー２゜３は樹脂の粉砕性、ひいてはト
ナーの粉砕性が悪かった。又、比較トナー４に用いた結
着樹脂（１２１は製造安定性の悪いものであった。Reference Toner 2 and Comparative Toners 1 and 4 had a high minimum fixing temperature. Comparative toner 2.3 had poor resin pulverization properties and, by extension, poor toner pulverization properties. Furthermore, the binder resin (121) used in Comparative Toner 4 had poor manufacturing stability.
出願人代理人 古 谷 馨Applicant's agent Kaoru Furutani
Claims (1)
を含有する電子写真用現像剤組成物に於いて、該結着樹
脂の主成分がポリエステル樹脂より成り、該ポリエステ
ル樹脂部分は、少なくとも （イ）次式 ▲数式、化学式、表等があります▼ （式中、Ｒはエチレン又はプロピレン基、 ｘ、ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平
均値は２〜７である。） で表されるジオール成分を全構成成分中１０モル％以上
３０モル％以下と、 （ロ）次式 ▲数式、化学式、表等があります▼ （式中、ｎは２ないし６の整数である。） で表されるジオール成分を全構成成分中１０モル％以上
２５モル％未満と、 （ハ）２価のカルボン酸又はその酸無水物又はその低級
アルキルエステルと、 （ニ）３価以上の多価カルボン酸又はその酸無水物又は
その低級アルキルエステルを全構成成分中２．５モル％
以上１５モル％未満 とを共縮重合したポリエステル樹脂であることを特徴と
する電子写真用現像剤組成物。 ２、前記２価カルボン酸の主成分がテレフタル酸又はそ
の低級アルキルエステルであることを特徴とする特許請
求の範囲第１項記載の電子写真用現像剤組成物。 ３、結着樹脂の軟化点が１０６℃以上１６０℃以下であ
って、ガラス転移温度が５０℃以上８０℃以下であるこ
とを特徴とする特許請求の範囲第１項記載の電子写真用
現像剤組成物。[Scope of Claims] 1. In an electrophotographic developer composition containing a binder resin, a colorant, and other additives as desired, the main component of the binder resin is a polyester resin, The polyester resin part has at least the following formula (a) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of is 2 to 7.) The diol component represented by 10 mol% or more and 30 mol% or less of the total constituent components, and (b) The following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n is 10 mol% or more and less than 25 mol% of the diol component represented by (an integer from 2 to 6) in the total constituent components; (c) a divalent carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof; (d) 2.5 mol% of trivalent or higher polycarboxylic acid, its acid anhydride, or its lower alkyl ester based on the total components
An electrophotographic developer composition characterized in that it is a polyester resin cocondensed with less than 15 mol% of the above. 2. The electrophotographic developer composition according to claim 1, wherein the main component of the divalent carboxylic acid is terephthalic acid or a lower alkyl ester thereof. 3. The electrophotographic developer according to claim 1, wherein the binder resin has a softening point of 106°C or more and 160°C or less, and a glass transition temperature of 50°C or more and 80°C or less. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315525A JPH01155360A (en) | 1987-12-14 | 1987-12-14 | Electrophotographic developer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315525A JPH01155360A (en) | 1987-12-14 | 1987-12-14 | Electrophotographic developer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01155360A true JPH01155360A (en) | 1989-06-19 |
Family
ID=18066393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62315525A Pending JPH01155360A (en) | 1987-12-14 | 1987-12-14 | Electrophotographic developer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01155360A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0371824A2 (en) * | 1988-12-01 | 1990-06-06 | Mitsubishi Rayon Co., Ltd. | Toner |
| US5266432A (en) * | 1991-03-01 | 1993-11-30 | Kao Corporation | Hydrophobic polyester toner composition |
| 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 |
| JP2010271469A (en) * | 2009-05-20 | 2010-12-02 | Mitsubishi Rayon Co Ltd | Method for producing polyester resin, polyester resin for toner, and toner |
| WO2023243701A1 (en) * | 2022-06-17 | 2023-12-21 | 株式会社クラレ | Polyester and molded article composed of same |
-
1987
- 1987-12-14 JP JP62315525A patent/JPH01155360A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0371824A2 (en) * | 1988-12-01 | 1990-06-06 | Mitsubishi Rayon Co., Ltd. | Toner |
| US5153301A (en) * | 1988-12-01 | 1992-10-06 | Mitsubishi Rayon Company Ltd. | Polyester resin for toner |
| US5266432A (en) * | 1991-03-01 | 1993-11-30 | Kao Corporation | Hydrophobic polyester toner composition |
| 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 |
| JP2010271469A (en) * | 2009-05-20 | 2010-12-02 | Mitsubishi Rayon Co Ltd | Method for producing polyester resin, polyester resin for toner, and toner |
| WO2023243701A1 (en) * | 2022-06-17 | 2023-12-21 | 株式会社クラレ | Polyester and molded article composed of same |
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