JPS6360905B2 - - Google Patents
Info
- Publication number
- JPS6360905B2 JPS6360905B2 JP56112115A JP11211581A JPS6360905B2 JP S6360905 B2 JPS6360905 B2 JP S6360905B2 JP 56112115 A JP56112115 A JP 56112115A JP 11211581 A JP11211581 A JP 11211581A JP S6360905 B2 JPS6360905 B2 JP S6360905B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- resin
- molecular weight
- carrier
- weight
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 229920001225 polyester resin Polymers 0.000 claims description 30
- 239000004645 polyester resin Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 26
- 229920005792 styrene-acrylic resin Polymers 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000007771 core particle Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 34
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 vinyl halides Chemical class 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 108091008695 photoreceptors Proteins 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- 239000000049 pigment Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-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
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
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- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
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- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
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- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
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- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
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- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- SZJXEIBPJWMWQR-UHFFFAOYSA-N 2-methylpropane-1,1,1-triol Chemical compound CC(C)C(O)(O)O SZJXEIBPJWMWQR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
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- 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
- 101000760987 Homo sapiens 5'-AMP-activated protein kinase subunit gamma-2 Proteins 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- SQAMZFDWYRVIMG-UHFFFAOYSA-N [3,5-bis(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC(CO)=CC(CO)=C1 SQAMZFDWYRVIMG-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- DFYKHEXCUQCPEB-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C(C)=C DFYKHEXCUQCPEB-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 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
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 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
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- RLMXGBGAZRVYIX-UHFFFAOYSA-N hexane-1,2,3,6-tetrol Chemical compound OCCCC(O)C(O)CO RLMXGBGAZRVYIX-UHFFFAOYSA-N 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 201000010517 hypertrophic cardiomyopathy 6 Diseases 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000696 magnetic material 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 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
- LATKICLYWYUXCN-UHFFFAOYSA-N naphthalene-1,3,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 LATKICLYWYUXCN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- WDAISVDZHKFVQP-UHFFFAOYSA-N octane-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CCCCC(C(O)=O)CC(O)=O WDAISVDZHKFVQP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000859 α-Fe 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
- G03G9/087—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
-
- 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
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
Description
本発明は、電子写真法、静電記録法、静電印刷
法などにおける静電荷像を現像するための現像剤
に関する。
電子写真法においては光導電性要素よりなる感
光体に暗所にて均一な表面電荷を与えた後、露光
を行つて静電荷像を形成し、しかる後に現像して
可視像を形成する。
一般に斯かる静電荷像を現像する方法は、液体
現像法と乾式現像法とに大別される。液体現像法
は絶縁性有機液体中に各種の顔料や染料を微細粒
子として分散して成る液体現像剤を用いて現像す
る方法であり、又乾式現像法は天然又は合成の樹
脂中にカーボンブラツク等の着色剤を分散含有し
てなるトナーと、鉄、ガラスビーズ等のキヤリア
とからなる混合体を使用する現像法である。又一
般にキヤリアは絶縁性キヤリアと導電性キヤリア
に分ける事ができる。導電性キヤリアとしては酸
化された又は未酸化の鉄粉が用いられる。又絶縁
性キヤリアとしては鉄、ニツケル、コバルト、フ
エライト等の磁性体よりなるキヤリア用核体粒子
の表面が絶縁性樹脂により被覆されたキヤリアが
代表的なものである。
又乾式現像法には前記トナーのみを主成分とし
た現像剤を用いる所謂毛ブラシ法、インプレツシ
ヨン法、パウダークラウド法のほか、鉄粉或いは
ガラスビーズ等よりなるキヤリアとトナーとの混
合体を現像剤として用いる所謂磁気ブラシ法、カ
スケード法がある。
これらの現像法により、現像剤中に含有される
電荷を有するトナー粒子等の検電粒子が静電荷像
に付着して可視像が形成される。この可視像は
熱、圧力、溶媒蒸気等によりそのまま感光体上に
或いは紙等の他の像支持体に転写され、その後に
定着される。
本発明は、上記現像方法のうち磁気ブラシ法及
びカスケード法に用いる現像剤、即ちトナー及び
キヤリアによつて構成される静電荷像現像剤に関
するものである。
従来定着は、静電荷像を支持している光導電性
感光体、もしくは静電記録体上に、現像によつて
得られたトナー像を直接融着させるか、或いは現
像によつて得られたトナー像を光導電性感光体も
しくは静電記録体上から紙などの転写シート上に
一旦転写した後これを融着させる事によつて行わ
れる。その際トナー像の融着は溶媒蒸気との接触
又は加熱方式の何れかによつて行なわれている。
加熱方式としては電気炉による非接触加熱方式及
び加熱ローラによる圧着加熱方式が一般に採用さ
れている。
加熱ローラによる圧着加熱方式は、トナーに対
して離型性を有する材料で表面を形成した加熱ロ
ーラの表面に被定着シートのトナー像面を圧接触
させながら通過させる事により定着を行うもので
あり、一般に加熱ローラ定着法と呼ばれている。
この方法は加熱ローラの表面と被定着シートのト
ナー像面とが圧接触するため、トナー像を被定着
シート上に融着する際の熱効率が極めて良好であ
り、迅速に定着を行う事ができるので特に高速複
写を目的とする転写方式の電子写真複写機には極
めて有効である。
しかしながらこの方法においては加熱ローラ表
面とトナー像とが加熱溶融状態で圧接触するた
め、トナー像の一部が加熱ローラ表面に付着して
移転し、次の被定着シート上に汚れを発生せしめ
る事がある。所謂オフセツト現象である。その為
加熱ローラ表面に対してトナーが付着しないよう
にする事が加熱定着法における必須要件の一つと
されている。
従来加熱ローラ表面にトナーを付着させないた
めに、例えば加熱ローラの表面をフツ素系樹脂な
どの離型性の優れた材料で構成するとともにその
表面にさらにシリコンオイルなどのオフセツト防
止用液体を供給して液体の薄膜により加熱ローラ
の表面を被覆する事が行なわれている。
この方法はオフセツト現象を防止する点では極
めて有効なものであるが、オフセツト防止用液体
が加熱される事により臭気を発生し、又オフセツ
ト防止用液体を供給するための装置を必要とする
ので、複写装置の機構が複雑になると共に、安定
性の良い結果を得るためには高い精度が要求され
るので、複写装置が高価なものになるという欠点
がある。
一方、ポリエステル樹脂は一般にガラス転移点
が高いにも拘らず低軟化点の樹脂を得やすい。つ
まり加熱溶融した時の転写紙等への支持体に対す
る「濡れ」が良く、ビニル系重合体のトナーに比
べるとより低い温度で十分な定着を行なう事がで
きる。
しかしながら従来トナーとして用いられている
ポリエステル樹脂ではオフセツト発生温度が低い
ために広い定着可能温度域を得る事は困難であつ
た。
又軟化点が低くてオフセツト発生温度が高く、
従つて定着可能温度域が広くしかもその高さが好
適な、ポリエステル樹脂をバインダーとするトナ
ーについては特許出願がなされており、このトナ
ーによれば、そのバインダーが特定量のクロロホ
ルムに不溶な高分子量成分と、軟化点を下げて定
着を容易にする低分子量成分とを含有するポリエ
ステル樹脂より成るものであるため、低い軟化点
と高いオフセツト発生温度とを有し、しかもそれ
らの温度が適当な高さに有り、従つて広くて高さ
の好適な定着可能温度域が得られる。
この結果オフセツト現象を生ぜずに十分な定着
を達成するための定着器の熱ローラの不均一さに
基くオフセツト現象の発生及び定着の不完全さを
伴う事なく、常に良好な定着を確実に達成する事
が可能となる。
しかしながらポリエステル樹脂は、強い負の摩
擦帯電性を有し、現像剤として用いた時に帯電量
が過大となつて好適な画像濃度を得ることができ
ないことも多い。よつて適度な帯電量を有する現
像剤を得るためには他の適当な樹脂をブレンド
し、摩擦帯電性を調節するのが容易な方法である
が、オフセツト防止効果を得るためには、添加す
る樹脂もオフセツト防止特性を持つていなければ
ならない。
特公昭55−6895号公報には、オフセツト防止特
性の優れた樹脂に関する記載があり、これはα―
β不飽和スチレン系単量体を構成単位として含有
し、かつ数平均分子量Mnに対する重量平均分子
量Mwの比Mw／Mnの値が3.5〜40の樹脂を主要
成分として含有する静電荷像現像用トナーに関す
るものである。このMw／Mnの値が3.0〜40の樹
脂は、高分子状のポリマーと低分子状のポリマー
とが混合された形のものである。しかし、更にオ
フセツト防止特性を得るためには、特に分子量が
100000以上の高分子量成分を含有することが必要
であり、又低軟化点化するためには低分子量成分
を混入させなくてはならない。
即ち、オフセツト防止特性を有する為には、バ
インダーの成分であるすべての樹脂が必ずオフセ
ツト防止特性を持つていなければならず、又同時
にトナーとした場合に適度な摩擦帯電特性を持つ
ていなければならない。ましてや定着を容易にす
るための適度な軟化点を持つていなければならな
い。そのためには前述した如く、低分子量成分を
混入しなくてはならない。しかしながらこの低分
子量成分が現像剤の耐久性に大まかな影響を与え
ていた。（即ち、従来の未被覆の鉄粉キヤリアで
は低分子量成分のポリマーが未被覆の鉄粉キヤリ
アの表面に付着しやすく、現像剤としての摩擦帯
電特性及び、バイアス効果を変化させてしまい、
使用に耐えないものであつた。）よつて上記欠点
を克服した現像剤の出現が強く望まれていた。
本発明の目的は、その表面にオフセツト防止用
液体を供給しない定着ローラを使用した場合に
も、オフセツト現象を発生させずに効率良く良好
な加熱ローラ定着を行なう事ができる静電荷像現
像用トナーを用いた高耐久性の現像剤を提供する
にある。
本発明者等は、キヤリア及びトナーによつて構
成される静電荷像現像剤であつて、キヤリアは鉄
粉等の核体粒子が樹脂により被覆されてなり、ト
ナーは、三官能以上の多官能性単量体による成分
を含有するポリエステル樹脂及び分子量が100000
以上の高分子量成分を10重量％以上含有するスチ
レン―アクリル樹脂をバインダーとして含み、該
ポリエステル樹脂が５〜25重量％のクロロホルム
不溶分を有する熱ローラ定着用トナーである静電
荷像現像剤が前記目的を達成するものである事を
見出した。即ち、本発明の現像剤は、その構成に
おいて、トナーのバインダー中に含まれている低
分子量成分が樹脂被覆されたキヤリア表面に転移
もしくは融着する事が未被覆のキヤリアを用いた
場合に比べて著しく少なく、耐久性に優れている
点で特に高速の電子複写機に好適であるという事
を見出したのである。
本発明において、キヤリアの被覆を形成するた
めの樹脂としては、ｐ―クロルスチレン、メチル
スチレン等のスチレン類；塩化ビニル、臭化ビニ
ル、フツ化ビニル等のハロゲン化ビニル類；酢酸
ビニル、プロピオン酸ビニル、ベンゾエ酸ビニ
ル、酪酸ビニル等のビニルエステル類；アクリル
酸メチル、アクリル酸エチル、アクリル酸ｎ―ブ
チル、アクリル酸イソブチル、アクリル酸ドデシ
ル、アクリル酸ｎ―オクチル、アクリル酸３―ク
ロルエチル、アクリル酸フエニル、α―クロルア
クリル酸メチル、メタアクリル酸メチル、メタア
クリル酸エチル、メタアクリル酸ブチル等のα―
メチレン脂肪族モノカルボン酸のエステル類；ア
クリロニトリル、メタアクリロニトル、アクリル
アミド、ビニルメチルエーテル、ビニルイソブチ
ルエーテル、ビニルエチルエーテル等のビニルエ
ーテル類；ビニルメチルケトン、ビニルヘキシル
ケトン、メチルイソプロペニルケトン等のビニル
ケトン類などの単量体を重合させたホモポリマー
或いは、この他の樹脂としてエポキシ樹脂、ロジ
ン変性フエノールホルマリン樹脂、セルローズ樹
脂、ポリエーテル樹脂、ポリビニルブチラール樹
脂、ポリエステル樹脂、スチレン―ブタジエン樹
脂、ポリウレタン樹脂、ポリビニルホルマール樹
脂、メラミン樹脂、ポリカーボネート樹脂、テフ
ロン等のフツ素樹脂等の樹脂を単独で若しくはブ
レンドして使用することができる。
このうち、スチレン―アクリル系樹脂（例えば
スチレン―メチルメタアクリレート、スチレン―
ブチルメタアクリレート等）、エポキシ樹脂、ス
チレン―ブタジエン樹脂、ブチラール樹脂、セル
ローズ樹脂等が特に有用である。
又感光体が有機光導電物質、硫化カドミウム等
より成る負帯電特性のものである場合には、テフ
ロン等のフツ素樹脂、塩化ビニル酢酸ビニル樹
脂、ポリエステル樹脂のような樹脂が好適であ
る。
本発明において用いるキヤリアを製造するため
には、前述した樹脂を溶剤に溶解し塗布液を作
り、この塗布液をキヤリア用核体粒子の表面に塗
布する。この塗布のためには浸漬法、スプレー法
等を用いることができるが、特に流動化ベツド法
によるのが好適である。この流動化ベツド法は、
流動化ベツド装置内において上昇する加圧ガス流
により、核体粒子を平衡高さに迄上昇浮遊させ、
当該核体粒子が再び落下する迄の間に前記塗布液
を上方からスプレーして各粒子に塗布し、これを
繰返して所望の厚さの塗膜を形成する方法であ
り、この方法により各粒子に均一な塗布を行なう
ことができる。前記塗布液には相溶性の良い他の
樹脂を混合し溶解しても良い。
以上において用いられる溶剤としては、前記樹
脂を溶解するものであればよく、例えばメタノー
ル、エタノール、ブタノール、イソプロパノール
等のアルコール類；ジクロルエタン、トリクロル
エチレン等のハロゲン化炭化水素類；トルエン、
キシレン等の芳香族炭化水素類；アセトン、メチ
ルエチルケトン等のケトン類；その他テトラヒド
ロフラン、ジオキサン等の有機溶剤又はこれらの
混合溶剤が用いられる。
以上において、核体粒子は、その粒径が10〜
1000ミクロン、特に20〜300ミクロンのものが好
ましく、又樹脂被覆層の厚さは、0.1〜10ミクロ
ン、特に0.2〜５ミクロンであることが好ましい。
斯くして得られるキヤリアは、絶縁性であつて
球形であることが好ましいが、導電性或いは非球
形であつても本発明の効果が失われるものではな
い。
本発明におけるトナーのバインダーとして用い
るポリエステル樹脂は、三官能以上の多官能性単
量体による成分を含有するものである。即ち、一
般にポリエステル樹脂は各々二官能以上のアルコ
ール単量体とカルボン酸単量体との縮重合によつ
て得られるが、本発明においては、アルコール単
量体及びカルボン酸単量体の少なくとも一方が三
官能以上の多官能性単量体成分を含有することが
必要である。
このようなポリエステル樹脂を得るために用い
られる二官能性アルコールとしては、例えばエチ
レングリコール、ジエチレングリコール、トリエ
チレングリコール、１，２―プロピレングリコー
ル、１，３―プロピレングリコール、１，４―ブ
タンジオール、ネオペンチルグリコール、１，４
―ブテンジオール等のジオール類、１，４―ビス
（ヒドロキシメチル）シクロヘキサン、及びビス
フエノールＡ、水素添加ビスフエノールＡ、ポリ
オキシエチレン化ビスフエノールＡ、ポリオキシ
プロピレン化ビスフエノールＡ等のエーテル化ビ
スフエノール類、その他の二価のアルコール単量
体を挙げることができる。
又二官能性カルボン酸単量体としては、例えば
マレイン酸、フマール酸、メサコニン酸、シトラ
コン酸、イタコン酸、グルタコン酸、フタル酸、
イソフタル酸、テレフタル酸、シクロヘキサンジ
カルボン酸、コハク酸、アジピン酸、セバチン
酸、マロン酸、これらの酸の無水物、低級アルキ
ルエステルとリノレイン酸の二量体、その他の二
価の有機酸単量体を挙げることができる。
又三官能以上の多官能性単量体としては、三価
以上の多価アルコール単量体又は三価以上の多価
カルボン酸単量体が用いられる。ここに三価以上
の多価アルコール単量体としては、例えばソルビ
トール、１，２，３，６―ヘキサンテトロール、
１，４―ソルビタン、ペンタエリスリトール、ジ
ペンタエリスリトール、トリペンタエリスリトー
ル、蔗糖、１，２，４―ブタントリオール、１，
２，５―ペンタントリオール、グリセロール、２
―メチルプロパントリオール、２―メチル―１，
２，４―ブタントリオール、トリメチロールエタ
ン、トリメチロールプロパン、１，３，５―トリ
ヒドロキシメチルベンゼン、その他を挙げること
ができる。
又三価以上の多価カルボン酸単量体としては、
例えば１，２，４―ベンゼントリカルボン酸、
１，２，５―ベンゼントリカルボン酸、１，２，
４―シクロヘキサントリカルボン酸、２，５，７
―ナフタレントリカルボン酸、１，２，４―ナフ
タレントリカルボン酸、１，２，４―ブタントリ
カルボン酸、１，２，５―ヘキサントリカルボン
酸、１，３―ジカルボキシル―２―メチル―２―
メチレンカルボキシプロパン、テトラ（メチレン
カルボキシル）メタン、１，２，７，８―オクタ
ンテトラカルボン酸、エンポール三量体酸、及び
これらの酸無水物、その他を挙げることができ
る。
以上のような多官能性単量体による成分は、重
合体における構造単位としてのアルコール成分又
は酸成分の各々における20〜30モル％の割合で含
有されるのが望ましい。
本発明において用いるポリエステル樹脂は、ク
ロロホルム不溶分が５重量％以上のものである。
ここにクロロホルム不溶分とは、試料をクロロホ
ルムに溶解したときの紙不透過分をいい、次の
ようにして求められる。
樹脂試料を微粉砕し、40メツシユの篩を通過し
た試料粉体5.00ｇを採取し、過助剤ラジオライ
ト（＃700）5.00ｇと共に容量150mlの容器に入
れ、この容器内にクロロホルム100ｇを注入し、
ボールミル架台に載せ５時間以上に亘つて回転せ
しめて充分に試料をクロロホルムに溶解せしめ
る。一方加圧過器内に直径７cmの紙（No.２の
もの）を置き、その上に5.00ｇのラジオライトを
均一にプレコートし、少量のクロロホルムを加え
て紙を過器に密着させた後、前記容器の内容
物を過器内に流し込む。更に容器を100mlのク
ロロホルムにより充分に洗浄して過器に流し込
み、容器の器壁に付着物が残留しないようにす
る。その後過器の上蓋を閉じ、過を行なう。
過は４Kg／cm2以下の加圧下にて行ない、クロロ
ホルムの流出が止まつた後に新たにクロロホルム
100mlを加えて紙上の残留物を洗浄し、再び加
圧過を行なう。
以上の操作が完了した後、紙及びその上の残
渣並びにラジオライトのすべてをアルミホイル上
に載せて真空乾燥器内に入れ、温度80〜100℃、
圧力100mmHgの条件下で10時間乾燥せしめ、斯く
して得られた乾固物の総重量(a)を測定し、次式に
よりクロロホルム不溶分ｘ（重量％）を求める。
ｘ（重量％）＝ａ(g)−紙の重量(g)−ラジオライトの
重量（10.00ｇ）／サンプリング重量（5.00ｇ）×100
このようにして求められるクロロホルム不溶分
は、ポリエステル樹脂においては、高分子量の重
合体成分若しくは架橋された重合体成分であり、
その分子量はおよそ200000以上であると考えられ
る。
以上の如きクロロホルム不溶分は、既述のアル
コールとカルボン酸との重合反応において、反応
条件を適当に選ぶことにより、或いは適当な架橋
剤を反応系に存在せしめることにより、相当程度
制御された割合で形成することができる。
本発明においては、前記クロロホルム不溶分が
５重量％以上のポリエステル樹脂を用いるが、ク
ロロホルム不溶分が５重量％未満のポリエステル
樹脂を用いると、得られるトナーは非オフセツト
性が低く、又これによる現像剤の耐久性が不十分
となる。又クロロホルム不溶分が多くなると軟化
点が高くなるので、25重量％以下であることが好
ましい。
以上のポリエステル樹脂と共にバインダーを構
成するスチレン―アクリル樹脂は、スチレン単量
体とアクリル単量体との共重合体である。ここに
用いることのできるスチレン単量体としては、例
えばスチレン、ｏ―メチルスチレン、ｍ―メチル
スチレン、ｐ―メチルスチレン、α―メチルスチ
レン、ｐ―エチルスチレン、２，４―ジメチルス
チレン、ｐ―ｎ―ブチルスチレン、ｐ―tert―ブ
チルスチレン、ｐ―ｎ―ヘキシルスチレン、ｐ―
ｎ―オクチルスチレン、ｐ―ｎ―ノニルスチレ
ン、ｐ―ｎ―デシルスチレン、ｐ―ｎ―ドデシル
スチレン、ｐ―メトキシスチレン、ｐ―フエニル
スチレン、ｐ―クロルスチレン、３，４―ジクロ
ルスチレン等を挙げることができる。
又アクリル単量体としては、例えばアクリル酸
メチル、アクリル酸エチル、アクリル酸ｎ―ブチ
ル、アクリル酸イソブチル、アクリル酸プロピ
ル、アクリル酸ｎ―オクチル、アクリル酸ドデシ
ル、アクリル酸ラウリル、アクリル酸２―エチル
ヘキシル、アクリル酸ステアリル、アクリル酸２
―クロルエチル、アクリル酸フエニル、α―クロ
ルアクリル酸メチル、メタアクリル酸メチル、メ
タアクリル酸エチル、メタアクリル酸プロピル、
メタアクリル酸ｎ―ブチル、メタアクリル酸イソ
ブチル、メタアクリル酸ｎ―オクチル、メタアク
リル酸ドデシル、メタアクリル酸ラウリル、メタ
アクリル酸２―エチルヘキシル、メタアクリル酸
ステアリル、メタアクリル酸フエニル、メタアク
リル酸ジメチルアミノエチル、メタアクリル酸ジ
エチルアミノエチル等のα―メチレン脂肪族モノ
カルボン酸エステル類；アクリロニトリル、メタ
アクリロニトリル、アクリルアミド等のアクリル
酸もしくはメタアクリル酸誘導体、その他を挙げ
ることができる。これらの単量体は単独で或いは
複数のものを組合せて用いることができる。
以上のスチレン―アクリル樹脂は、分子量が
100000以上の高分子量成分を10重量％以上含有す
るものであることが必要であり、そうでないもの
を用いたときには、高いオフセツト発生温度が得
られない。斯かる高分子量成分を含有するスチレ
ン―アクリル樹脂は、その重合条件を適当に選択
することにより、或いは架橋剤等を利用して架橋
重合体とすることによつて容易に得ることができ
る。
トナーのバインダーにおける前記ポリエステル
樹脂及びスチレン―アクリル樹脂の含有割合は、
それぞれ50〜90重量％及び10〜50重量％の範囲内
であることが好ましい。
本明細書における分子量は、下記条件における
ゲル・パーミエーシヨン・クロマトグラフイ
（Gel Permeation Chromatography）法により
求められるものである。即ち、温度25℃において
テトラヒドロフランを１ml／分の流速で流し、濃
度0.4ｇ／dlのテトラヒドロフラン溶液を試料重
量として８mg注入し測定を行う。試料の分子量測
定に当つては、該試料の有する分子量分布が、数
種の単分散ポリスチレン標準試料により、作成さ
れた検量線の分子量の対数とカウント数が直線と
なる範囲内に包含される測定条件を選択する。上
記測定は東洋曹達株式会社製HLC―802UR装置
を用い、カラムはTSK―GEL／CMH6を使用し
た。
分子量が100000以上の高分子量成分を10重量％
以上含有するようなスチレン―アクリル樹脂は、
例えば次のようにして製造することができる。
合成例
容量１のセパラブルフラスコにポリビニルア
ルコール部分ケン化物「ゴーセノールGH―17」
（日本合成社製）0.1ｇを入れ、蒸留水100mlに溶
解し、その中に下表のモノマー混合物Ａを添加
し、懸濁分散させ、気相を窒素ガスにて置換した
後80℃に昇温し、15時間この温度に保つて重合せ
しめる。その後温度40℃まで冷却し、その中に下
表のモノマー混合物Ｂを添加し、温度40℃におい
て２時間撹拌を続ける。次いで、ポリビニルアル
コール部分ケン化物「ゴーセノールGH―17」0.4
ｇを含む蒸留水100mlを別に調製し、その水溶液
を懸濁系に追加する。その後80℃に再度昇温し、
８時間この温度に保つて重合を行ない、さらに95
℃に昇温して２時間保ち、重合を完結する。その
後冷却し、脱水、洗浄を繰り返し、乾燥して樹脂
を得る。この樹脂は数平均分子量Mnが1.1×104、
数平均分子量Mnに対する重量平均分子量Mwの
比Mw／Mnが4.5、JISK2531―1960に規定される
環球法により測定したときの軟化点が140±２℃
のものであつた。
The present invention relates to a developer for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like. In electrophotography, a photoreceptor comprising a photoconductive element is provided with a uniform surface charge in the dark, exposed to light to form an electrostatic charge image, and then developed to form a visible image. Generally, methods for developing such electrostatic images are broadly classified into liquid development methods and dry development methods. The liquid development method uses a liquid developer made by dispersing various pigments and dyes as fine particles in an insulating organic liquid, while the dry development method uses a liquid developer made by dispersing various pigments and dyes as fine particles in an insulating organic liquid. This is a developing method that uses a mixture of a toner containing a colorant dispersed therein and a carrier such as iron or glass beads. In general, carriers can be divided into insulating carriers and conductive carriers. Oxidized or unoxidized iron powder is used as the conductive carrier. A typical example of an insulating carrier is a carrier in which the surface of carrier core particles made of a magnetic material such as iron, nickel, cobalt, or ferrite is coated with an insulating resin. Dry development methods include the so-called bristle brush method, impression method, and powder cloud method that use a developer containing only the above-mentioned toner as a main component, as well as a mixture of toner and a carrier made of iron powder or glass beads. There are a so-called magnetic brush method and a cascade method which are used as a developer. By these developing methods, electrostatic particles such as charged toner particles contained in the developer adhere to the electrostatic charge image to form a visible image. This visible image is transferred directly onto a photoreceptor or onto another image support such as paper by heat, pressure, solvent vapor, etc., and then fixed. The present invention relates to a developer used in the magnetic brush method and the cascade method among the above-mentioned developing methods, that is, an electrostatic image developer composed of toner and carrier. Conventionally, fixing involves directly fusing a toner image obtained by development onto a photoconductive photoreceptor or electrostatic recording medium supporting an electrostatic charge image, or by directly fusing a toner image obtained by development. This is carried out by first transferring a toner image from a photoconductive photoreceptor or an electrostatic recording medium onto a transfer sheet such as paper, and then fusing this. The fusing of the toner image takes place either by contact with solvent vapor or by heating.
As a heating method, a non-contact heating method using an electric furnace and a pressure heating method using a heating roller are generally adopted. The pressure heating method using a heating roller performs fixing by passing the toner image surface of the sheet to be fixed while being in pressure contact with the surface of the heating roller whose surface is made of a material that has releasability for toner. This method is generally called the heated roller fixing method.
In this method, the surface of the heating roller and the toner image surface of the fixing sheet come into pressure contact, so the thermal efficiency when fusing the toner image onto the fixing sheet is extremely good, and the fixing can be performed quickly. Therefore, it is extremely effective particularly for transfer type electrophotographic copying machines intended for high-speed copying. However, in this method, since the heating roller surface and the toner image come into pressure contact in a heated and molten state, a part of the toner image adheres to the heating roller surface and is transferred, causing stains on the next sheet to be fixed. There is. This is a so-called offset phenomenon. Therefore, one of the essential requirements in the heat fixing method is to prevent toner from adhering to the surface of the heating roller. Conventionally, in order to prevent toner from adhering to the surface of the heating roller, for example, the surface of the heating roller was made of a material with excellent mold release properties such as fluororesin, and an offset prevention liquid such as silicone oil was further supplied to the surface. The surface of the heating roller is coated with a thin film of liquid. Although this method is extremely effective in preventing the offset phenomenon, it generates an odor due to heating of the offset prevention liquid and requires a device for supplying the offset prevention liquid. This has the disadvantage that the mechanism of the copying device becomes complex and high precision is required to obtain stable results, making the copying device expensive. On the other hand, although polyester resin generally has a high glass transition point, it is easy to obtain a resin with a low softening point. That is, when heated and melted, it "wets" well to a support such as a transfer paper, and can be sufficiently fixed at a lower temperature than toners made of vinyl polymers. However, with polyester resins conventionally used as toners, it has been difficult to obtain a wide fixable temperature range because the temperature at which offset occurs is low. Also, the softening point is low and the offset generation temperature is high.
Therefore, a patent application has been filed for a toner using a polyester resin as a binder, which has a wide fixable temperature range and a suitable temperature range.According to this toner, the binder has a high molecular weight that is insoluble in a specific amount of chloroform. Because it is made of a polyester resin containing a low molecular weight component that lowers the softening point and facilitates fixing, it has a low softening point and a high offset generation temperature. Therefore, a wide and high suitable fixing temperature range can be obtained. As a result, it is possible to always achieve good fixing without causing offset phenomena and incomplete fixing due to the unevenness of the heat roller of the fixing device. It becomes possible to do so. However, polyester resins have a strong negative triboelectric chargeability, and when used as a developer, the amount of charge becomes excessive and it is often impossible to obtain a suitable image density. Therefore, in order to obtain a developer with an appropriate amount of charge, it is easy to blend other suitable resins to adjust the triboelectric charging properties, but in order to obtain the effect of preventing offset, it is necessary to add The resin must also have anti-offset properties. Japanese Patent Publication No. 55-6895 describes a resin with excellent anti-offset properties, which is
A toner for developing electrostatic images containing a resin as a main component, which contains a β-unsaturated styrenic monomer as a constituent unit, and has a ratio Mw/Mn of weight average molecular weight Mw to number average molecular weight Mn of 3.5 to 40. It is related to. The resin having a Mw/Mn value of 3.0 to 40 is a mixture of a high molecular weight polymer and a low molecular weight polymer. However, in order to obtain even more anti-offset properties, it is necessary to increase the molecular weight in particular.
It is necessary to contain a high molecular weight component of 100,000 or more, and in order to lower the softening point, a low molecular weight component must be mixed. That is, in order to have anti-offset properties, all the resins that are components of the binder must have anti-offset properties, and at the same time, when used as a toner, they must have appropriate triboelectric properties. . Furthermore, it must have an appropriate softening point to facilitate fixation. For this purpose, as mentioned above, it is necessary to mix low molecular weight components. However, this low molecular weight component had a rough influence on the durability of the developer. (In other words, in conventional uncoated iron powder carriers, polymers with low molecular weight components tend to adhere to the surface of the uncoated iron powder carrier, changing the triboelectric charging characteristics and bias effect as a developer.
It was unusable. ) Therefore, it has been strongly desired to develop a developer that overcomes the above-mentioned drawbacks. An object of the present invention is to provide a toner for developing electrostatic images that can be efficiently and well fixed by a heating roller without causing an offset phenomenon even when a fixing roller that does not supply an offset prevention liquid to the surface thereof is used. The purpose of the present invention is to provide a highly durable developer using. The present inventors have proposed an electrostatic image developer composed of a carrier and a toner. polyester resin containing components based on monomers and a molecular weight of 100,000
The electrostatic image developer described above is a heat roller fixing toner containing a styrene-acrylic resin containing 10% by weight or more of the above-mentioned high molecular weight components as a binder, and in which the polyester resin has a chloroform-insoluble content of 5 to 25% by weight. I found that it achieved the purpose. That is, the developer of the present invention has a structure in which the low molecular weight components contained in the toner binder are less likely to be transferred or fused to the resin-coated carrier surface than when an uncoated carrier is used. They found that it is particularly suitable for high-speed electronic copying machines because it has a significantly low amount of carbon dioxide and has excellent durability. In the present invention, the resin for forming the carrier coating includes styrenes such as p-chlorostyrene and methylstyrene; vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, propionic acid, etc. Vinyl esters such as vinyl, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 3-chloroethyl acrylate, acrylic acid α- such as phenyl, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.
Esters of methylene aliphatic monocarboxylic acids; vinyl ethers such as acrylonitrile, methacrylonitrile, acrylamide, vinyl methyl ether, vinyl isobutyl ether, and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone Homopolymers made by polymerizing monomers such as epoxy resins, rosin-modified phenol-formalin resins, cellulose resins, polyether resins, polyvinyl butyral resins, polyester resins, styrene-butadiene resins, polyurethane resins, Resins such as polyvinyl formal resin, melamine resin, polycarbonate resin, and fluororesin such as Teflon can be used alone or in a blend. Of these, styrene-acrylic resins (e.g. styrene-methyl methacrylate, styrene-acrylic resins)
butyl methacrylate, etc.), epoxy resins, styrene-butadiene resins, butyral resins, cellulose resins, etc. are particularly useful. When the photoreceptor is made of an organic photoconductive substance, cadmium sulfide, or the like and is negatively charged, resins such as fluorocarbon resins such as Teflon, vinyl chloride vinyl acetate resins, and polyester resins are suitable. In order to manufacture the carrier used in the present invention, the above-mentioned resin is dissolved in a solvent to prepare a coating liquid, and this coating liquid is applied to the surface of the carrier core particles. For this application, a dipping method, a spray method, etc. can be used, but a fluidized bed method is particularly preferred. This fluidized bed method is
The rising pressurized gas flow within the fluidization bed device causes the nuclear particles to rise and float to an equilibrium height.
This is a method in which the coating liquid is sprayed from above and applied to each particle until the core particles fall again, and this is repeated to form a coating film of a desired thickness. Uniform coating can be achieved. Other resins with good compatibility may be mixed and dissolved in the coating liquid. The solvent used in the above may be any solvent as long as it dissolves the resin, such as alcohols such as methanol, ethanol, butanol, and isopropanol; halogenated hydrocarbons such as dichloroethane and trichloroethylene; toluene,
Aromatic hydrocarbons such as xylene; ketones such as acetone and methyl ethyl ketone; organic solvents such as tetrahydrofuran and dioxane, or mixed solvents thereof are used. In the above, the nuclear particles have a particle size of 10 to
The thickness of the resin coating layer is preferably 1000 microns, especially 20 to 300 microns, and the thickness of the resin coating layer is preferably 0.1 to 10 microns, especially 0.2 to 5 microns. The carrier thus obtained is preferably insulative and spherical, but the effects of the present invention will not be lost even if the carrier is conductive or non-spherical. The polyester resin used as the binder of the toner in the present invention contains a component of a trifunctional or higher polyfunctional monomer. That is, polyester resins are generally obtained by condensation polymerization of difunctional or higher-functional alcohol monomers and carboxylic acid monomers, but in the present invention, at least one of the alcohol monomers and the carboxylic acid monomers is used. It is necessary that the monomer component contains a trifunctional or higher polyfunctional monomer component. Examples of difunctional alcohols used to obtain such polyester resins include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and Pentyl glycol, 1,4
- Diols such as butene diol, 1,4-bis(hydroxymethyl)cyclohexane, and etherified bisphenols such as bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, and polyoxypropylenated bisphenol A. Examples include phenols and other dihydric alcohol monomers. Examples of difunctional carboxylic acid monomers include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid,
Isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, anhydrides of these acids, dimers of lower alkyl esters and linoleic acid, other divalent organic acid monomers can be mentioned. As the trifunctional or higher polyfunctional monomer, a trivalent or higher polyhydric alcohol monomer or a trivalent or higher polyvalent carboxylic acid monomer is used. Examples of trihydric or higher polyhydric alcohol monomers include sorbitol, 1,2,3,6-hexanetetrol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,
2,5-pentanetriol, glycerol, 2
-Methylpropanetriol, 2-methyl-1,
Examples include 2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and others. In addition, as trivalent or higher polyvalent carboxylic acid monomers,
For example, 1,2,4-benzenetricarboxylic acid,
1,2,5-benzenetricarboxylic acid, 1,2,
4-cyclohexanetricarboxylic 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-
Examples include methylenecarboxypropane, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, Empol trimer acid, acid anhydrides thereof, and others. It is desirable that the above-mentioned polyfunctional monomer component is contained in a proportion of 20 to 30 mol% in each of the alcohol component or acid component as a structural unit in the polymer. The polyester resin used in the present invention has a chloroform-insoluble content of 5% by weight or more.
The chloroform-insoluble content herein refers to the paper-insoluble content when a sample is dissolved in chloroform, and is determined as follows. Finely crush the resin sample, collect 5.00g of sample powder that passed through a 40-mesh sieve, and place it in a 150ml container with 5.00g of super-aiding agent Radiolite (#700), and inject 100g of chloroform into this container. death,
The sample was placed on a ball mill stand and rotated for 5 hours or more to sufficiently dissolve the sample in chloroform. On the other hand, place a piece of paper (No. 2) with a diameter of 7 cm in the pressurizer, pre-coat 5.00g of Radiolite uniformly on it, and add a small amount of chloroform to make the paper adhere to the pressurizer. , the contents of the container are poured into a strainer. Furthermore, thoroughly wash the container with 100 ml of chloroform and pour it into a filter to prevent any deposits from remaining on the walls of the container. After that, close the top lid of the filtration vessel and carry out filtration.
The filtration is carried out under a pressure of 4 kg/ cm2 or less, and after the chloroform has stopped flowing out, fresh chloroform is added.
Add 100 ml to wash the residue on the paper and perform pressure filtration again. After the above operations are completed, the paper, the residue on it, and the radiolite are all placed on aluminum foil and placed in a vacuum dryer at a temperature of 80 to 100℃.
Dry for 10 hours under a pressure of 100 mmHg, measure the total weight (a) of the dried product thus obtained, and calculate the chloroform insoluble content x (% by weight) using the following formula. x (weight%) = a (g) - weight of paper (g) - weight of radiolite (10.00g) / sampling weight (5.00g) x 100 The chloroform insoluble content determined in this way is , a high molecular weight polymer component or a crosslinked polymer component,
Its molecular weight is believed to be approximately 200,000 or more. The proportion of the above-mentioned chloroform-insoluble components can be controlled to a considerable extent by appropriately selecting the reaction conditions or by allowing an appropriate crosslinking agent to exist in the reaction system in the polymerization reaction between alcohol and carboxylic acid mentioned above. can be formed with. In the present invention, a polyester resin having a chloroform-insoluble content of 5% by weight or more is used. However, if a polyester resin having a chloroform-insoluble content of less than 5% by weight is used, the resulting toner will have low non-offset properties, and the resulting toner will have low non-offset properties. The durability of the agent becomes insufficient. Further, as the chloroform-insoluble content increases, the softening point increases, so it is preferably 25% by weight or less. The styrene-acrylic resin that constitutes the binder together with the above polyester resin is a copolymer of styrene monomer and acrylic monomer. Examples of styrene monomers that can be used here include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-
n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, etc. can be mentioned. Examples of acrylic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , stearyl acrylate, acrylic acid 2
- Chlorethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate α-methylene aliphatic monocarboxylic acid esters such as aminoethyl and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, and others. These monomers can be used alone or in combination. The above styrene-acrylic resins have a molecular weight of
It is necessary that the material contains 10% by weight or more of a high molecular weight component of 100,000 or more, and if it is not used, a high offset generation temperature cannot be obtained. A styrene-acrylic resin containing such a high molecular weight component can be easily obtained by appropriately selecting polymerization conditions or by forming a crosslinked polymer using a crosslinking agent or the like. The content ratio of the polyester resin and styrene-acrylic resin in the toner binder is:
Preferably, the amounts are in the ranges of 50 to 90% by weight and 10 to 50% by weight, respectively. The molecular weight in this specification is determined by gel permeation chromatography under the following conditions. That is, at a temperature of 25° C., tetrahydrofuran is flowed at a flow rate of 1 ml/min, and a sample weight of 8 mg of a tetrahydrofuran solution with a concentration of 0.4 g/dl is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is measured to be within a range where the logarithm of the molecular weight and the count number of the calibration curve created using several types of monodisperse polystyrene standard samples are linear. Select conditions. The above measurement was carried out using an HLC-802UR device manufactured by Toyo Soda Co., Ltd., and a TSK-GEL/CMH6 column was used. 10% by weight of high molecular weight components with a molecular weight of 100,000 or more
Styrene-acrylic resins containing the above
For example, it can be manufactured as follows. Synthesis example: Partially saponified polyvinyl alcohol "Gohsenol GH-17" in a separable flask with a capacity of 1
(manufactured by Nippon Gosei Co., Ltd.), dissolved in 100 ml of distilled water, added monomer mixture A shown in the table below, suspended and dispersed, and after replacing the gas phase with nitrogen gas, heated to 80°C. Heat and keep at this temperature for 15 hours to polymerize. Thereafter, the mixture was cooled to a temperature of 40°C, and monomer mixture B shown in the table below was added thereto, and stirring was continued for 2 hours at a temperature of 40°C. Next, partially saponified polyvinyl alcohol "Gohsenol GH-17" 0.4
Separately prepare 100 ml of distilled water containing g and add that aqueous solution to the suspension system. After that, the temperature was raised again to 80℃,
Polymerization was carried out by keeping at this temperature for 8 hours, and then 95
The temperature was raised to ℃ and maintained for 2 hours to complete the polymerization. Thereafter, it is cooled, dehydrated, washed repeatedly, and dried to obtain a resin. This resin has a number average molecular weight Mn of 1.1×10 4 ,
The ratio Mw/Mn of weight average molecular weight Mw to number average molecular weight Mn is 4.5, and the softening point is 140 ± 2°C when measured by the ring and ball method specified in JISK2531-1960.
It was from.
１ キヤリア１
平均分子量15万のスチレン―メチルメタアクリ
レート樹脂５ｇをメチルエチルケトン300ml中に
溶解して塗布液を調製し、200〜300メツシユの焼
結鉄粉「EFVS」（日本鉄粉社製）１Kgを前記塗
布液中に入れ、上澄液を除去した後写真用バツト
中で撹拌しながら熱風を吹き付けて乾燥し、次に
粉体を温度100℃のオーブン中で２時間熱処理し、
以つて樹脂被膜を有するキヤリア１を得た。この
キヤリア１の体積固有抵抗は2.3×109Ω・cmであ
つた。
なお、「体積固有抵抗」は、面積１cm2、深さ１
cmの凹所を有し内円底面が真鍮の電極板とされた
容器内に試料１ｇを入れ、上方から重さ１Kgの真
鍮電極を試料層上に載せた条件下で測定された値
である。
２ キヤリア２
酢酸酪酸セルロース樹脂３ｇをメチルエチルケ
トン300ml中に溶解して塗布液を調製し、200〜
300メツシユのスチール鉄粉「DSP―179D」（同
和鉄粉社製）１Kgを前記塗布液中に入れ、上澄液
を除去した後写真用バツト内中で撹拌しながら熱
風を吹き付けて乾燥し、次に粉体を温度120℃の
オーブン中で１時間熱処理し、以つて樹脂被膜を
有するキヤリア２を得た。このキヤリア２の体積
固有抵抗は4.5×108Ω・cmであつた。
３ キヤリア３
平均分子量10万のメタアクリル酸メチル―アク
リル酸エチルの共重合体樹脂３ｇをメチルエチル
ケトン300ml中に溶解した塗布液を用い、200〜
300メツシユの焼結鉄粉「TEFVS」（日本鉄粉社
製）１Kgを用いたほかは、キヤリア１の製造と同
様にして、樹脂被膜を有するキヤリア３を得た。
このキヤリア３の体積固有抵抗は1.8×106Ω・cm
であつた。
４ キヤリア４
エポキシ樹脂20ｇをメチルエチルケトン300ml
中に溶解して塗布液を調製し、流動化ベツド装置
を用いて平均粒径100ミクロンの球形鋼シヨツト
１Kgに、流動乾燥温度を60℃とした条件下でスプ
レーし、次に粉体を温度100℃のオーブン中で２
時間熱処理し、以つて樹脂被膜を有するキヤリア
４を得た。このキヤリア４の体積固有抵抗は1014
Ω・cm以上であつた。
５ キヤリア５
エポキシ樹脂の代りにポリビニルブチラール樹
脂「エスレツクＢ」（積水化学社製）を用いたほ
かは、キヤリア４の製造と同様にして、樹脂被膜
を有するキヤリア５を得た。このキヤリア５の体
積固有抵抗は6.8×1013Ω・cmであつた。
６ キヤリア６
平均分子量13万のスチレン―ブチルメタアクリ
レート樹脂を被覆用樹脂として用い、鉄粉
「DSP−135C」（同和鉄粉社製）を用いたほかは、
キヤリア４の製造と同様にして、樹脂被膜を有す
るキヤリア６を得た。このキヤリア６の体積固有
抵抗は、1014Ω・cm以上であつた。
〔トナーの製造〕
１ トナー１
テレフタル酸299ｇと、ポリオキシプロピレン
（２，２）―２，２―ビス（４―ヒドロキシフエ
ニル）プロパン211ｇと、ペンタエリスリトール
82ｇとを、温度計、ステンレススチール製撹拌
器、ガラス製窒素ガス導入管及び流下式コンデン
サを備えた丸底フラスコ内に入れ、このフラスコ
をマントルヒーターにセツトし、窒素ガス導入官
より窒素ガスを導入してフラスコ内を不活性雰囲
気に保つた状態で昇温せしめた。そして0.05ｇの
ジブチル錫オキシドを加え、軟化点において反応
を追跡しながら温度200℃で反応せしめ、以つて
クロロホルム不溶分17重量％のポリエステル樹脂
を製造した。このポリエステル樹脂の環球軟化点
（JISK2531−1960の方法による。以下において同
じ。）は131℃であつた。
一方、前述したスチレン―アクリル樹脂の合成
例に従い、分子量が100000以上の高分子量成分を
16重量％含有し、環球軟化点が130℃のスチレン
―アクリル樹脂を製造した。
前記ポリエステル樹脂70重量部と、前記スチレ
ン−アクリル樹脂30重量部と、カーボンブラツク
10重量部とを混合し、練肉、粉砕、分級の各工程
による通常のトナーの製造方法に従い、平均粒径
12.3ミクロンのトナー１を製造した。
２ トナー２
イソフタル酸299ｇと、ポリオキシプロピレン
（２，２）―２，２―ビス（４―ヒドロキシフエ
ニル）プロパン211ｇと、グリセロール74ｇとを
用い、トナー１に係るポリエステル樹脂の製造と
同様にして温度180℃で反応させ、クロロホルム
不溶分21重量％、環球軟化点135℃のポリエステ
ル樹脂を製造した。
一方、前述したスチレン―アクリル樹脂の合成
例に従い、分子量が100000以上の高分子量成分を
23重量％含有し、環球軟化点が130℃のスチレン
―アクリル樹脂を製造した。
前記ポリエステル樹脂60重量部と、前記スチレ
ン―アクリル樹脂60重量部と、カーボンブラツク
10重量部とを混合し、練肉、粉砕、分級の各工程
による通常のトナーの製造方法に従い、平均粒径
13.6ミクロンのトナー２を製造した。
３ トナー３
１，４―ブタンジオール270ｇと、テレフタル
酸150ｇと、ベンゼン―１，２，４―トリカルボ
ン酸231ｇとを用い、トナー１に係るポリエステ
ル樹脂の製造と同様にして温度200℃で反応させ、
クロロホルム不溶分12重量％、環球軟化点128℃
のポリエステル樹脂を製造した。
一方、前述したスチレン―アクリル樹脂の合成
例に従い、分子量が100000以上の高分子量成分を
40重量％含有し、環球軟化点が130のスチレン―
アクリル樹脂を製造した。
前記ポリエステル樹脂85重量部と、前記スチレ
ン―アクリル樹脂15重量部と、カーボンブラツク
10重量部と、低軟化点ポリプロピレン「ビスコー
ル660P」（三洋化成工業社製）４重量部とを混合
し、練肉、粉砕、分級の各工程による通常のトナ
ーの製造方法に従い、平均粒径13.1ミクロンの粉
末を得、これに流動性向上剤として疎水性シリカ
「Ｒ―972」（日本アエロジル社製）を0.8重量％添
加してトナー３を得た。
実施例
以上のキヤリア１〜６のうちの一種と、トナー
１〜３のうちの一種とを次表に示す組合せによ
り、同表に示すトナー濃度（重量％）となる割合
で混合して合計６種の本発明静電荷像現像剤を作
り、電子写真複写機「Ｕ―BixW（改造型）」（小
西六写真工業社製）を用いて各現像剤について連
続複写による耐久性試験を行なつた。結果は表に
示す通りである。尚表中「不溶分」とは、トナー
のバインダーにおけるポリエステル樹脂のクロロ
ホルム不溶分、「高分子量成分」とは同じくスチ
レン―アクリル樹脂の分子量が100000以上の成分
を表わす。
1 Carrier 1 Prepare a coating solution by dissolving 5 g of styrene-methyl methacrylate resin with an average molecular weight of 150,000 in 300 ml of methyl ethyl ketone, and add 1 kg of sintered iron powder "EFVS" (manufactured by Nippon Iron Powder Co., Ltd.) of 200 to 300 meshes. After putting it in the coating solution and removing the supernatant liquid, it was dried by blowing hot air while stirring in a photographic vat, and then the powder was heat-treated in an oven at a temperature of 100°C for 2 hours,
Thus, a carrier 1 having a resin coating was obtained. The volume resistivity of this carrier 1 was 2.3×10 9 Ω·cm. In addition, "volume specific resistance" is defined as 1cm 2 in area and 1cm in depth.
This is a value measured under conditions in which 1 g of a sample is placed in a container with a recess of cm and a circular bottom with a brass electrode plate, and a brass electrode weighing 1 kg is placed on the sample layer from above. . 2 Carrier 2 Prepare a coating solution by dissolving 3 g of cellulose acetate butyrate resin in 300 ml of methyl ethyl ketone.
1 kg of 300 mesh steel iron powder "DSP-179D" (manufactured by Dowa Iron Powder Co., Ltd.) was added to the coating solution, and after removing the supernatant liquid, it was dried by blowing hot air while stirring in a photographic vat. Next, the powder was heat treated in an oven at a temperature of 120° C. for 1 hour to obtain a carrier 2 having a resin coating. The volume resistivity of this carrier 2 was 4.5×10 8 Ω·cm. 3 Carrier 3 Using a coating solution prepared by dissolving 3 g of methyl methacrylate-ethyl acrylate copolymer resin with an average molecular weight of 100,000 in 300 ml of methyl ethyl ketone,
Carrier 3 having a resin coating was obtained in the same manner as Carrier 1 except that 1 kg of 300 mesh sintered iron powder "TEFVS" (manufactured by Nippon Tetsuko Co., Ltd.) was used.
The volume resistivity of this Carrier 3 is 1.8×10 6 Ω・cm
It was hot. 4 Carrier 4 20g of epoxy resin and 300ml of methyl ethyl ketone
A coating solution is prepared by dissolving the powder in a fluidized bed device, and sprayed onto 1 kg of spherical steel shot with an average particle size of 100 microns at a fluidized drying temperature of 60°C. 2 in the oven at 100℃
A carrier 4 having a resin coating was obtained by heat treatment for a period of time. The volume resistivity of this carrier 4 is 10 14
It was over Ω・cm. 5 Carrier 5 A carrier 5 having a resin coating was obtained in the same manner as in the production of carrier 4, except that polyvinyl butyral resin "Eslec B" (manufactured by Sekisui Chemical Co., Ltd.) was used instead of the epoxy resin. The volume resistivity of this carrier 5 was 6.8×10 13 Ω·cm. 6 Carrier 6 Styrene-butyl methacrylate resin with an average molecular weight of 130,000 was used as the coating resin, and iron powder "DSP-135C" (manufactured by Dowa Iron Powder Co., Ltd.) was used.
A carrier 6 having a resin coating was obtained in the same manner as in the production of carrier 4. The volume resistivity of this carrier 6 was 10 14 Ω·cm or more. [Manufacture of toner] 1 Toner 1 299 g of terephthalic acid, 211 g of polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane, and pentaerythritol
Place 82g of the sample into a round-bottomed flask equipped with a thermometer, a stainless steel stirrer, a glass nitrogen gas inlet tube, and a flow-down condenser, set the flask on a mantle heater, and introduce nitrogen gas from the nitrogen gas inlet. The temperature was raised while maintaining an inert atmosphere inside the flask. Then, 0.05 g of dibutyltin oxide was added, and the reaction was allowed to proceed at 200° C. while monitoring the reaction at the softening point, thereby producing a polyester resin with a chloroform-insoluble content of 17% by weight. The ring and ball softening point (according to the method of JISK2531-1960; the same applies hereinafter) of this polyester resin was 131°C. On the other hand, according to the synthesis example of styrene-acrylic resin mentioned above, a high molecular weight component with a molecular weight of 100,000 or more was added.
A styrene-acrylic resin containing 16% by weight and having a ring and ball softening point of 130°C was produced. 70 parts by weight of the polyester resin, 30 parts by weight of the styrene-acrylic resin, and carbon black.
10 parts by weight, and the average particle size
A 12.3 micron Toner 1 was produced. 2 Toner 2 Using 299 g of isophthalic acid, 211 g of polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane, and 74 g of glycerol, the same procedure as in the production of the polyester resin related to Toner 1 was carried out. The mixture was reacted at a temperature of 180°C to produce a polyester resin having a chloroform insoluble content of 21% by weight and a ring and ball softening point of 135°C. On the other hand, according to the synthesis example of styrene-acrylic resin mentioned above, a high molecular weight component with a molecular weight of 100,000 or more was added.
A styrene-acrylic resin containing 23% by weight and having a ring and ball softening point of 130°C was produced. 60 parts by weight of the polyester resin, 60 parts by weight of the styrene-acrylic resin, and carbon black.
10 parts by weight, and the average particle size
A 13.6 micron Toner 2 was produced. 3 Toner 3 270 g of 1,4-butanediol, 150 g of terephthalic acid, and 231 g of benzene-1,2,4-tricarboxylic acid were reacted at a temperature of 200°C in the same manner as in the production of the polyester resin related to Toner 1. ,
Chloroform insoluble content 12% by weight, ring and ball softening point 128℃
Polyester resin was produced. On the other hand, according to the synthesis example of styrene-acrylic resin mentioned above, a high molecular weight component with a molecular weight of 100,000 or more was added.
Styrene containing 40% by weight and having a ring and ball softening point of 130.
Acrylic resin was produced. 85 parts by weight of the polyester resin, 15 parts by weight of the styrene-acrylic resin, and carbon black.
10 parts by weight and 4 parts by weight of low softening point polypropylene "Viscol 660P" (manufactured by Sanyo Chemical Industries, Ltd.) were mixed, and the average particle size was 13.1 according to the usual toner manufacturing method using each process of kneading, crushing, and classification. Micron powder was obtained, and toner 3 was obtained by adding 0.8% by weight of hydrophobic silica "R-972" (manufactured by Nippon Aerosil Co., Ltd.) as a fluidity improver. Example One of the above carriers 1 to 6 and one of the toners 1 to 3 are mixed in the combination shown in the following table in a ratio that gives the toner concentration (weight %) shown in the same table, and a total of 6 Various electrostatic charge image developers of the present invention were prepared, and durability tests were conducted on each developer by continuous copying using an electrophotographic copying machine "U-BixW (modified model)" (manufactured by Konishiroku Photo Industry Co., Ltd.). . The results are shown in the table. In the table, "insoluble content" refers to the chloroform-insoluble content of the polyester resin in the toner binder, and "high molecular weight component" refers to the styrene-acrylic resin component having a molecular weight of 100,000 or more.
【表】
以上の結果からも理解されるように、本発明静
電荷像現像剤は、多数回に亘る現像に供されても
カブリが生ずることがなくて良好な現像を達成す
ることができて大きな耐久性を有し、しかもオフ
セツト現象による画像汚れもなく、優れた複写画
像が得られる。
一方、既述の実施例におけるトナーのバインダ
ーがポリエステル樹脂のみより成る場合は、実施
例のものに比して耐久性が劣り、又スチレン―ア
クリル樹脂のみより成る場合は、定着性が低くて
優れた画像を得ることが困難であつた。[Table] As can be understood from the above results, the electrostatic image developer of the present invention can achieve good development without causing fogging even after being subjected to development many times. It has great durability and is free from image stains due to offset phenomenon, making it possible to obtain excellent copied images. On the other hand, when the binder of the toner in the above-mentioned examples is made only of polyester resin, the durability is inferior to that of the example, and when it is made only of styrene-acrylic resin, the fixing properties are low and excellent. It was difficult to obtain a clear image.
Claims (1)
荷像現像剤において、 キヤリアは、核体粒子が樹脂により被覆されて
なり、 トナーは、三官能以上の多官能性単量体による
成分を含有するポリエステル樹脂及び分子量が
100000以上の高分子量成分を10重量％以上含有す
るスチレン―アクリル樹脂をバインダーとして含
み、該ポリエステル樹脂が５〜25重量％のクロロ
ホルム不溶分を有する熱ローラ定着用トナーであ
ることを特徴とする静電荷像現像剤。[Claims] 1. In an electrostatic image developer composed of a carrier and a toner, the carrier is made up of core particles coated with a resin, and the toner is made of a trifunctional or higher polyfunctional monomer. Polyester resin containing components and molecular weight according to
A static toner for hot roller fixing, which contains as a binder a styrene-acrylic resin containing 10% by weight or more of a high molecular weight component of 100,000 or more, and the polyester resin has a chloroform-insoluble content of 5 to 25% by weight. Charge image developer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112115A JPS5814147A (en) | 1981-07-20 | 1981-07-20 | Electrostatic image developing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112115A JPS5814147A (en) | 1981-07-20 | 1981-07-20 | Electrostatic image developing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5814147A JPS5814147A (en) | 1983-01-26 |
| JPS6360905B2 true JPS6360905B2 (en) | 1988-11-25 |
Family
ID=14578539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56112115A Granted JPS5814147A (en) | 1981-07-20 | 1981-07-20 | Electrostatic image developing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5814147A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60136753A (en) * | 1983-12-26 | 1985-07-20 | Hitachi Ltd | Positively charge type heat roll fixable toner |
| JPS60263954A (en) * | 1984-06-13 | 1985-12-27 | Hitachi Metals Ltd | Toner for heat fixing |
| EP0216461B1 (en) * | 1985-09-20 | 1992-12-09 | Molex Incorporated | Apparatus for electrical harness manufacture |
| JPS6368854A (en) * | 1986-09-10 | 1988-03-28 | Kao Corp | Electrophotographic developer composition |
| FR2720843B1 (en) * | 1994-06-03 | 1997-05-23 | Tomoegawa Paper Co Ltd | Toner for developing static charge images, and process for preparing it |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5044836A (en) * | 1973-07-18 | 1975-04-22 | ||
| JPS5075043A (en) * | 1973-10-26 | 1975-06-20 | ||
| US3938992A (en) * | 1973-07-18 | 1976-02-17 | Eastman Kodak Company | Electrographic developing composition and process using a fusible, crosslinked binder polymer |
| JPS5123354A (en) * | 1974-08-20 | 1976-02-24 | Silver Seiko | AMIKI |
| JPS5486342A (en) * | 1977-12-21 | 1979-07-09 | Hitachi Chemical Co Ltd | Toner for static charge picture development |
| JPS54114245A (en) * | 1978-02-27 | 1979-09-06 | Fuji Xerox Co Ltd | Electrophotographic toner composition |
| JPS55147639A (en) * | 1979-05-08 | 1980-11-17 | Canon Inc | Toner for development |
| JPS5737353A (en) * | 1980-08-15 | 1982-03-01 | Konishiroku Photo Ind Co Ltd | Toner for developing electrostatic charge image |
| DE3222928A1 (en) * | 1981-06-19 | 1983-01-27 | Konishiroku Photo Industry Co., Ltd., Tokyo | TONER FOR DEVELOPING LATEN ELECTROSTATIC IMAGES |
-
1981
- 1981-07-20 JP JP56112115A patent/JPS5814147A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5044836A (en) * | 1973-07-18 | 1975-04-22 | ||
| US3938992A (en) * | 1973-07-18 | 1976-02-17 | Eastman Kodak Company | Electrographic developing composition and process using a fusible, crosslinked binder polymer |
| JPS5075043A (en) * | 1973-10-26 | 1975-06-20 | ||
| JPS5123354A (en) * | 1974-08-20 | 1976-02-24 | Silver Seiko | AMIKI |
| JPS5486342A (en) * | 1977-12-21 | 1979-07-09 | Hitachi Chemical Co Ltd | Toner for static charge picture development |
| JPS54114245A (en) * | 1978-02-27 | 1979-09-06 | Fuji Xerox Co Ltd | Electrophotographic toner composition |
| JPS55147639A (en) * | 1979-05-08 | 1980-11-17 | Canon Inc | Toner for development |
| JPS5737353A (en) * | 1980-08-15 | 1982-03-01 | Konishiroku Photo Ind Co Ltd | Toner for developing electrostatic charge image |
| DE3222928A1 (en) * | 1981-06-19 | 1983-01-27 | Konishiroku Photo Industry Co., Ltd., Tokyo | TONER FOR DEVELOPING LATEN ELECTROSTATIC IMAGES |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5814147A (en) | 1983-01-26 |
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