JPH04254863A - Toner for electrostatic charge development - Google Patents
Toner for electrostatic charge developmentInfo
- Publication number
- JPH04254863A JPH04254863A JP3035051A JP3505191A JPH04254863A JP H04254863 A JPH04254863 A JP H04254863A JP 3035051 A JP3035051 A JP 3035051A JP 3505191 A JP3505191 A JP 3505191A JP H04254863 A JPH04254863 A JP H04254863A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- molecular weight
- acid
- parts
- polyester resin
- 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
- 238000011161 development Methods 0.000 title abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001225 polyester resin Polymers 0.000 claims abstract description 24
- 239000004645 polyester resin Substances 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 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 11
- 239000000178 monomer Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000010186 staining Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant 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
- 238000011156 evaluation Methods 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 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
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 229920006249 styrenic copolymer Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 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
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 229940084778 1,4-sorbitan Drugs 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- XYHGSPUTABMVOC-UHFFFAOYSA-N 2-methylbutane-1,2,4-triol Chemical compound OCC(O)(C)CCO XYHGSPUTABMVOC-UHFFFAOYSA-N 0.000 description 1
- SZJXEIBPJWMWQR-UHFFFAOYSA-N 2-methylpropane-1,1,1-triol Chemical compound CC(C)C(O)(O)O SZJXEIBPJWMWQR-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
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene 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
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 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
- NWLCFADDJOPOQC-UHFFFAOYSA-N [Mn].[Cu].[Sn] Chemical compound [Mn].[Cu].[Sn] NWLCFADDJOPOQC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-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
- 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
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 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
- 229910001291 heusler alloy Inorganic materials 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
- 229910052742 iron Inorganic materials 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
- 239000006233 lamp black Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229940002712 malachite green oxalate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture 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
- 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
- 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
- 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
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 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
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 235000013799 ultramarine blue Nutrition 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は静電荷現像用トナーに関
し、特に熱ロール定着を採用している複写機又はプリン
ター用の静電荷現像用トナーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge developing toner, and more particularly to an electrostatic charge developing toner for copying machines or printers employing hot roll fixing.
【０００２】0002
【従来の技術】近年、電子写真方式を用いた複写機及び
プリンターはその普及が広まるにつれて、家庭への普及
及び複写機又はプリンターの多機能化を主な目的とした
低エネルギー化、印刷機と複写機との境に位置するいわ
ゆるグレイエリアへの普及を目的とした高速化、あるい
は機械コストを下げるための定着ロールの簡素化のため
の低ロール圧力化が望まれており、また、複写機の高級
化にともない両面コピー機能や原稿自動送り装置の搭載
された複写機が広く普及されてきたため、複写機及びプ
リンターに使用されるトナーには定着温度が低く、耐オ
フセット性が優れて、且つ両面コピー時の汚れや、原稿
自動送り装置における汚れの発生しないことが要求され
ている。[Prior Art] In recent years, as copying machines and printers using electrophotography have become more popular, energy saving and printing machines have been developed with the main purpose of popularizing them in homes and increasing the functionality of copying machines and printers. There is a desire for higher speeds for the purpose of spreading to so-called gray areas located on the border with copying machines, or for lower roll pressure to simplify the fixing roll to reduce machine costs. Copying machines equipped with double-sided copying functions and automatic document feeders have become widespread as the technology has become more sophisticated.As a result, the toner used in copiers and printers has a low fusing temperature, excellent offset resistance, and It is required that no stains occur during double-sided copying or in automatic document feeders.
【０００３】上記の要求に対して従来技術では、下記の
ように結着樹脂の分子量や分子量分布を改良したもの、
結着樹脂中に添加剤を加える等の提案がなされている。[0003] In order to meet the above requirements, the prior art has developed binder resins with improved molecular weight and molecular weight distribution as described below.
Proposals have been made to add additives to the binder resin.
【０００４】前記トナーの結着樹脂の分子量あるいはそ
の分布を変える方法としては、低分子部分の分子量を下
げ高分子部分の分子量を上げることにより分子量の分布
を広くする方法や、あるいは高分子部分を架橋させたり
することが行なわれている。しかしながら、この方法に
於いては定着性を充分に持たせるために、樹脂のガラス
転移点を下げざるを得ずトナーとしたときの保存性を損
なうことが避けられない。また、結着樹脂の低分子部分
を多くするとトナー自体が脆くなり両面コピー時の汚れ
や、原稿自動送り装置における汚れが発生していた。Methods for changing the molecular weight or its distribution of the binder resin of the toner include a method of widening the molecular weight distribution by lowering the molecular weight of the low molecular weight part and increasing the molecular weight of the high molecular weight part, or a method of widening the molecular weight distribution by lowering the molecular weight of the low molecular weight part and increasing the molecular weight of the high molecular weight part. Crosslinking is also performed. However, in this method, in order to provide sufficient fixing properties, the glass transition point of the resin must be lowered, which inevitably impairs the storage stability of the toner. Furthermore, when the low molecular weight portion of the binder resin is increased, the toner itself becomes brittle, causing stains during double-sided copying and stains in an automatic document feeder.
【０００５】一方、ポリエチレン系ワックス、カルナウ
バワックスの如き天然のワックスやエチレン・酢酸ビニ
ル共重合体等の添加剤を加える方法では、いずれも保存
安定性や、粉体としての流動性に問題を生じていた。On the other hand, with the methods of adding natural waxes such as polyethylene wax and carnauba wax, and additives such as ethylene/vinyl acetate copolymers, there are problems with storage stability and fluidity of the powder. was occurring.
【０００６】[0006]
【発明が解決しようとする課題】したがって、本発明の
目的は低い定着温度で定着することができ、オフセット
性においても実用上なんら問題を発生せず、更には両面
コピー時の汚れや、原稿自動送り装置における汚れ（す
なわち耐こすれ性）の発生しない静電荷現像用トナーを
提供することにある。[Problems to be Solved by the Invention] Therefore, the object of the present invention is to be able to fix at a low fixing temperature, to cause no practical problems in terms of offset, and to prevent smudges during double-sided copying, and to reduce the problem of automatic document automatic copying. It is an object of the present invention to provide an electrostatic charge developing toner that does not cause stains (ie, scratch resistance) on a feeding device.
【０００７】[0007]
【課題を解決するための手段】本発明は、ポリエステル
樹脂５０〜１０重量部とスチレン系共重合体５０〜９０
重量部とを結着樹脂（但し、ポリエステル樹脂とスチレ
ン系共重合体との総量は１００重量部である）として含
有し、ＧＰＣクロマトグラムにおける該ポリエステル樹
脂及びスチレン系共重合体の分子量のピーク位置が各々
８×１０２ 〜５×１０４ 及び１０４ 〜５×１０５
の領域にあることを特徴とする静電荷現像用トナーで
ある。すなわち、本発明はスチレン系共重合体に比べ弾
性的性質が大であるポリエステル樹脂を結着樹脂の低分
子量領域に用いることによって、トナーの定着後におけ
る耐こすれ性を強くし、高分子量領域にスチレン系共重
合体を使用することにより耐オフセット性を良好になら
しめるものである。[Means for Solving the Problems] The present invention consists of 50 to 10 parts by weight of a polyester resin and 50 to 90 parts by weight of a styrene copolymer.
parts by weight as a binder resin (however, the total amount of the polyester resin and styrene copolymer is 100 parts by weight), and the peak position of the molecular weight of the polyester resin and styrene copolymer in the GPC chromatogram. are respectively 8×102 ~ 5×104 and 104 ~ 5×105
This is an electrostatic charge developing toner characterized by being in the range of . That is, the present invention uses polyester resin, which has greater elasticity than styrene-based copolymers, in the low molecular weight region of the binder resin to strengthen the rubbing resistance after fixing the toner, and to strengthen the rubbing resistance in the high molecular weight region. By using a styrene copolymer, offset resistance is improved.
【０００８】本発明におけるポリエステル樹脂はゲルパ
ーミエーションクロマトグラフィー（以下ＧＰＣと言う
）によって測定されるクロマトグラムにて分子量８×１
０２ 〜５×１０４ の領域に少なくとも１つのピーク
位置を有するものであり、該領域の範囲外にピーク位置
を有することはない。この場合、分子量のピーク位置が
８×１０２ 未満にあるものでは結着樹脂としての分子
量が低くなりすぎて結着樹脂が脆くなり、トナーの定着
後のこすれに対して弱くなる。一方、分子量のピーク位
置が５×１０４ を越えると分子量が高いために、トナ
ーは定着ロールによって溶融してもトナーが転写紙の繊
維への絡みが生じないため、アンカー効果が生まれず定
着後のこすれに対しほとんどのトナーが転写紙より剥が
れ落ちてしまう現象が生じる。また、本発明におけるス
チレン系共重合体はＧＰＣクロマトグラムにて分子量１
０４ 〜５×１０５ の領域に少なくとも１つのピーク
位置を有するものであり、該領域の範囲外にピーク位置
を有することはない。この場合、分子量のピーク位置が
１０４ 未満では、耐オフセット性を良好に保つことは
困難となる。
一方、分子量のピーク位置が５×１０５ を越えて存在
すると定着ロールによってトナーが十分に溶けず、低温
オフセットと同様な状態となる。The polyester resin in the present invention has a molecular weight of 8×1 in a chromatogram measured by gel permeation chromatography (hereinafter referred to as GPC).
It has at least one peak position in the range of 02 to 5 x 104, and does not have any peak position outside the range. In this case, if the peak position of the molecular weight is less than 8×10 2 , the molecular weight of the binder resin will be too low, making the binder resin brittle and susceptible to rubbing after toner fixation. On the other hand, when the peak position of the molecular weight exceeds 5 x 104, the molecular weight is high, so even if the toner is melted by the fixing roll, the toner does not get entangled with the fibers of the transfer paper, so an anchor effect does not occur and the A phenomenon occurs in which most of the toner peels off from the transfer paper due to rubbing. In addition, the styrene copolymer in the present invention has a molecular weight of 1 in GPC chromatogram.
It has at least one peak position in the region of 0.04 to 5.times.105, and does not have a peak position outside the range. In this case, if the molecular weight peak position is less than 104, it is difficult to maintain good offset resistance. On the other hand, if the peak position of the molecular weight exceeds 5×10 5 , the toner will not be sufficiently melted by the fixing roll, resulting in a state similar to low-temperature offset.
【０００９】このようなポリエステル樹脂とスチレン系
共重合体は、トナーの製造時に乾式混合して熱溶融後、
機械的に混合し結着樹脂として形成せしめてもよいし、
適当な溶媒中に両者を添加し溶解して充分に混合した後
、溶媒を除去して結着樹脂を作成してもよい。[0009] Such a polyester resin and a styrene copolymer are dry mixed during toner production, and after being heated and melted,
It may be mechanically mixed to form a binder resin, or
A binder resin may be prepared by adding and dissolving both in a suitable solvent and mixing thoroughly, and then removing the solvent.
【００１０】本発明においてポリエステル樹脂とスチレ
ン系共重合体の分子量分布のピーク位置の分子量を測定
するには、公知の通常の方法が用いられ、ＧＰＣによっ
て次の条件で測定された値である。すなわち、温度２５
℃において溶媒（テトラヒドロフラン）を毎分１ｍｌの
流速で流し、濃度０．４ｇｒ／ｄｌのテトラヒドロフラ
ン試料溶液を試料重量として８ｍｇ注入し測定する。又
、試料の分子量測定にあたっては、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
製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。又、本測定
にあたり、測定の信頼性は上述の測定条件で行ったＮＢ
Ｓ７０６ポリスチレン標準試料（Ｍｗ＝２８．８×１０
４ ，Ｍｎ＝１３．７×１０４ ，Ｍｗ／Ｍｎ＝２．１
１）のＭｗ／Ｍｎが、２．１１±０．１０となる事によ
り確認し得る。In the present invention, a known conventional method is used to measure the molecular weight at the peak position of the molecular weight distribution of the polyester resin and styrene copolymer, and the value is measured by GPC under the following conditions. That is, temperature 25
A solvent (tetrahydrofuran) is flowed at a flow rate of 1 ml per minute at a temperature of .degree. C., and a sample weight of 8 mg of a tetrahydrofuran sample solution having a concentration of 0.4 gr/dl is injected and measured. In addition, when measuring the molecular weight of a sample, the measurement conditions are such that the molecular weight distribution of the sample falls within a range where the logarithm of the molecular weight and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples are linear. Select. In addition, in this measurement, the reliability of the measurement was determined by the NB performed under the above measurement conditions.
S706 polystyrene standard sample (Mw=28.8×10
4, Mn=13.7×104, Mw/Mn=2.1
This can be confirmed by the fact that Mw/Mn of 1) is 2.11±0.10.
【００１１】本発明において結着樹脂として用いるポリ
エステル樹脂はアルコールとカルボン酸との縮重合によ
って得られるが、用いられる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、及びビスフェノールＡ、水素添加ビスフェ
ノールＡ、ポリオキシエチレン化ビスフェノールＡ、ポ
リオキシプロピレン化ビスフェノールＡ等のエーテル化
ビスフェノール類、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。The polyester resin used as the binder resin in the present invention is obtained by polycondensation of alcohol and carboxylic acid, and the alcohols used include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1
, 3-propylene glycol, 1,4-butanediol, neopentyl glycol, diols such as 1,4-butenediol, 1,4-bis(hydroxymethyl)cyclohexane, and bisphenol A, hydrogenated bisphenol A, polyoxy Examples include etherified bisphenols such as ethyleneated bisphenol A and polyoxypropylenated bisphenol A, and other dihydric alcohol monomers.
【００１２】又カルボン酸としては、例えばマレイン酸
、フマール酸、メサコン酸、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。Examples of carboxylic acids 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, Mention may be made of malonic acid, anhydrides of these acids, dimers of lower alkyl esters and linoleic acid, and other divalent organic acid monomers.
【００１３】本発明において用いるポリエステル樹脂と
しては、以上の二官能性単量体のみによる重合体のみで
なく、三官能以上の多官能性単量体による成分を含有す
る重合体を用いることも好適である。斯かる多官能性単
量体である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。[0013] As the polyester resin used in the present invention, it is preferable to use not only a polymer composed only of the above difunctional monomers, but also a polymer containing a component composed of trifunctional or higher polyfunctional monomers. It is. As such polyfunctional monomers, trivalent or higher polyhydric alcohol monomers,
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentane triol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1
, 3,5-trihydroxymethylbenzene, and others.
【００１４】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。Examples of trivalent or higher polycarboxylic acid monomers include 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-methylenecarboxypropane, tetra(methylenecarboxyl)methane, 1,2,7, Mention may be made of 8-octanetetracarboxylic acid, Empol trimer acid, their acid anhydrides, and others.
【００１５】以上のような三官能以上の多官能性単量体
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３０〜８０モル％の
割合で含有されるのが望ましい。[0015] It is desirable that the above-mentioned component of trifunctional or higher polyfunctional monomer is contained in a proportion of 30 to 80 mol% in each of the alcohol component or acid component as a structural unit in the polymer. .
【００１６】また、スチレン系共重合体は、下記に示す
単量体を懸濁重合法、乳化重合法、溶液重合法、塊状重
合法等によって合成するものである。単量体としてはス
チレン、α−メチルスチレン、クロルスチレン等のスチ
レン類、アクリル酸メチル、アクリル酸エチル、アクリ
ル酸プロピル、アクリル酸ブチル、アクリル酸オクチル
、アクリル酸アルキルエステル等のアクリル酸エステル
類、メタクリル酸メチル、メタクリル酸エチル、メタク
リル酸プロピル、メタクリル酸ブチル、メタクリル酸オ
クチル、メタクリル酸ステアリル、メタクリル酸グリシ
ジル、メタクリル酸アルキルエステル等のメタクリル酸
エステル類等を挙げることができる。その他の共重合成
分としてはアクリロニトリル、マレイン酸、マレイン酸
エステル、メタクリル酸メチル、アクリル酸メチル、塩
化ビニル、酢酸ビニル、安息香酸ビニル、ビニルメチル
ケトン、ビニルヘキシルケトン、ビニルメチルエーテル
、ビニルエチルエーテル、ビニルイソブチルエーテル等
のビニル単量体を重量体に対して３０重量％以下で含有
してもよい。The styrenic copolymer is synthesized from the following monomers by suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, or the like. Monomers include styrenes such as styrene, α-methylstyrene, and chlorostyrene; acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, and alkyl acrylate; Examples include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, stearyl methacrylate, glycidyl methacrylate, and alkyl methacrylate. Other copolymerization components include acrylonitrile, maleic acid, maleic ester, methyl methacrylate, methyl acrylate, vinyl chloride, vinyl acetate, vinyl benzoate, vinyl methyl ketone, vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, A vinyl monomer such as vinyl isobutyl ether may be contained in an amount of 30% by weight or less based on the weight.
【００１７】結着樹脂中におけるポリエステル樹脂とス
チレン系共重合体との割合は、両者の共重合体の総量を
１００重量部とすると、ポリエステル樹脂が５０〜１０
重量部であり、スチレン系共重合体が５０〜９０重量部
である。ポリエステル樹脂の割合が５０重量部より多い
場合は耐オフセット性が低下する。一方スチレン系共重
合体の割合が９０重量部より多い場合は耐こすれ性が低
下する。The ratio of the polyester resin and the styrene copolymer in the binder resin is 50 to 10 parts by weight, assuming that the total amount of both copolymers is 100 parts by weight.
The amount of the styrene copolymer is 50 to 90 parts by weight. If the proportion of the polyester resin is more than 50 parts by weight, the offset resistance will decrease. On the other hand, if the proportion of the styrene copolymer is more than 90 parts by weight, the abrasion resistance will decrease.
【００１８】本発明のトナーの結着樹脂としては前記重
合体の他にエポキシ樹脂、シリコーン樹脂、ポリスチレ
ン、ポリアミド樹脂、ポリウレタン樹脂、アクリル酸等
の樹脂を添加してもよい。In addition to the above polymers, resins such as epoxy resin, silicone resin, polystyrene, polyamide resin, polyurethane resin, and acrylic acid may be added as the binder resin for the toner of the present invention.
【００１９】本発明のトナーは、上述の如き結着樹脂に
その他のトナー成分例えば着色剤、磁性体、特性改良剤
等を分散含有せしめてなる粉体物であり、その平均粒子
径は５〜３０μｍの範囲である。またこのようにして得
られる粉体物にシリカ微粉体等よりなる流動向上剤を添
加混合してトナーを構成してもよい。着色剤としては、
カーボンブラック、ニグロシン染料、アニリンブルー、
カルコオイルブルー、クロムイエロー、ウルトラマリン
ブルー、デュポンオイルレッド、キノリンイエロー、メ
チレンブルークロライド、フタロシアニンブルー、マラ
カイトグリーンオクサレート、ランプブラックローズベ
ンガル、これらの混合物、その他を挙げることができる
。これらの着色剤は、十分な濃度の可視像が形成される
に十分な割合で含有されることが必要であり、通常結着
樹脂１００重量部に対して１〜２０重量部程度の割合と
される。The toner of the present invention is a powder material in which other toner components such as a colorant, a magnetic substance, a property improver, etc. are dispersed in the above-mentioned binder resin, and the average particle size thereof is 5 to 5. The range is 30 μm. Further, a toner may be formed by adding and mixing a fluidity improver such as fine silica powder to the powder thus obtained. As a coloring agent,
carbon black, nigrosine dye, aniline blue,
Mention may be made of calco oil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black rose bengal, mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image with sufficient concentration, and are usually contained in a proportion of about 1 to 20 parts by weight per 100 parts by weight of the binder resin. be done.
【００２０】前記磁性体としては、フェライト、マグネ
タイトを始めとする鉄、コバルト、ニッケルなどの強磁
性を示す金属若しくは合金又はこれらの元素を含む化合
物、或いは強磁性元素を含まないが適当な熱処理を施す
ことによって強磁性を示すようになる合金、例えばマン
ガン−銅−アルミニウム、マンガン−銅−錫などのマン
ガンと銅とを含むホイスラー合金と呼ばれる種類の合金
、又は二酸化クロム、その他を挙げることができる。
これらの磁性体は平均粒径０．１〜１ミクロンの微粉末
の形で結着樹脂中に均一に分散される。そしてその含有
量は、トナー１００重量部当り２０〜７０重量部、好ま
しくは４０〜７０重量部である。[0020] The magnetic material may be a ferromagnetic metal or alloy such as iron, cobalt, or nickel, including ferrite and magnetite, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Alloys that exhibit ferromagnetic properties when subjected to ferromagnetism, such as a type of alloy called Heusler alloy containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, etc. . These magnetic substances are uniformly dispersed in the binder resin in the form of fine powder with an average particle size of 0.1 to 1 micron. The content thereof is 20 to 70 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of toner.
【００２１】前記特性改良剤としては、荷電制御剤、オ
フセット防止剤、流動性改善用滑剤その他がある。[0021] Examples of the property improving agent include a charge control agent, an anti-offset agent, a lubricant for improving fluidity, and others.
【００２２】本発明トナーは、鉄粉、ガラスビーズ等よ
り成るキャリアと混合されて二成分現像剤とされるが、
磁性体が含有されるときはそのまま一成分現像剤として
静電荷像の現像に供される。The toner of the present invention is mixed with a carrier consisting of iron powder, glass beads, etc. to form a two-component developer.
When a magnetic substance is contained, it is used as is for developing electrostatic images as a one-component developer.
【００２３】[0023]
【作用】一般に転写紙上のトナーの定着強度、両面コピ
ー時の汚れは、結着樹脂の低分子領域が弾性的であるか
粘性的であるかによって大きく異なる。すなわち、弾性
的性質が強ければ定着後のこすれに対し強くなり、粘性
的性質が強ければこすれに対し弱くなる。[Operation] Generally, the fixing strength of toner on transfer paper and the staining during double-sided copying vary greatly depending on whether the low molecular weight region of the binder resin is elastic or viscous. That is, if the elastic property is strong, it will be strong against rubbing after fixing, and if the viscous property is strong, it will be weak against rubbing.
【００２４】本発明はポリエステル樹脂がスチレンアク
リル系共重合体に比べ弾性的性質を強く有しているとい
う知見からなしえたものである。すなわち、ポリエステ
ル樹脂はスチレンアクリル系共重合体と比較すると分子
の密度が高いため、トナー定着時において転写紙内には
いった樹脂の分子同志が強固に結合し、アンカー効果を
形成せしめるため耐こすれ性に優れていると推察される
。The present invention was made based on the knowledge that polyester resins have stronger elastic properties than styrene-acrylic copolymers. In other words, polyester resin has a higher molecular density than styrene-acrylic copolymers, so when the toner is fixed, the resin molecules that enter the transfer paper strongly bond to each other, creating an anchor effect and improving scratch resistance. It is presumed to be excellent in
【００２５】[0025]
【実施例】以下本発明の実施例について説明する。なお
「部」とは重量部を表わす。
実施例１
ポリエステル樹脂
５０部 （ビスフェノールＡ／テレフタル酸，Ｍｗ＝
８×１０３ ，Ｍｎ＝６×１０３ ，Ｍｗ／Ｍｎ＝１．
３，ピーク位置は８×１０３ に有する） スチレン
系共重合体
５０部 （Ｓ
ｔ／ＢＡ，Ｍｗ＝１×１０５ ，Ｍｎ＝１．５×１０４
，Ｍｗ／Ｍｎ＝６．７，ピーク位置は１×１０５ に
有する） カーボンブラック
５部 （三菱化成工業社製 ＭＡ−１
００） クロム含金属染料
１部 （オリエント化学工業社製 ボン
トロンＳ−３４）上記配合の材料を２本ロールの混練機
で溶融混練をおこないジェットミルで粉砕をして分級し
、平均粒子径１２μｍの本発明の静電荷現像用トナーを
得た。[Examples] Examples of the present invention will be described below. Note that "parts" represent parts by weight. Example 1 Polyester resin
50 parts (bisphenol A/terephthalic acid, Mw=
8×103, Mn=6×103, Mw/Mn=1.
3. Peak position is at 8 x 103) Styrenic copolymer
50 copies (S
t/BA, Mw=1×105, Mn=1.5×104
, Mw/Mn=6.7, peak position is at 1×105) carbon black
5 parts (manufactured by Mitsubishi Chemical Industries, Ltd. MA-1
00) Chromium-containing metal dye
1 part (Bontron S-34 manufactured by Orient Chemical Industry Co., Ltd.) The above-mentioned blended materials were melt-kneaded in a two-roll kneader, pulverized and classified in a jet mill, and the electrostatic charge developing material of the present invention having an average particle size of 12 μm was prepared. I got a toner for use.
【００２６】実施例２
実施例１のポリエステル樹脂の配合量を１０部及びスチ
レン系共重合体の配合量を９０部にした他は実施例１と
同様にして本発明の静電荷現像用トナーを得た。Example 2 The toner for electrostatic charge development of the present invention was prepared in the same manner as in Example 1 except that the amount of the polyester resin in Example 1 was changed to 10 parts and the amount of the styrene copolymer was changed to 90 parts. Obtained.
【００２７】実施例３
実施例１のポリエステル樹脂の配合量を３０部及びスチ
レン系共重合体の配合量を７０部にした他は実施例１と
同様にして本発明の静電荷現像用トナーを得た。Example 3 The toner for electrostatic charge development of the present invention was prepared in the same manner as in Example 1 except that the amount of the polyester resin in Example 1 was changed to 30 parts and the amount of the styrene copolymer was changed to 70 parts. Obtained.
【００２８】比較例１
実施例１の結着樹脂をポリエステル樹脂（ビスフェノー
ルＡ／テレフタル酸，Ｍｗ＝９×１０４ ，Ｍｎ＝６×
１０３ ，Ｍｗ／Ｍｎ＝１５．３，ピーク位置は９×１
０３ と５×１０５ に有する）１００部にした他は実
施例１と同様にして比較用の静電荷現像用トナーを得た
。Comparative Example 1 The binder resin of Example 1 was replaced with a polyester resin (bisphenol A/terephthalic acid, Mw=9×104, Mn=6×
103, Mw/Mn=15.3, peak position is 9×1
A toner for electrostatic charge development for comparison was obtained in the same manner as in Example 1, except that 100 parts of the toner (having 0.03 and 5.times.10.sup.5) were used.
【００２９】比較例２
実施例１の結着樹脂をスチレン系共重合体（Ｓｔ／ＢＡ
，Ｍｗ＝２．４×１０５ ，Ｍｎ＝８．９×１０３ ，
Ｍｗ／Ｍｎ＝２７．２，ピーク位置は１．１×１０４
と９×１０５ に有する）１００部にした他は実施例１
と同様にして比較用の静電荷現像用トナーを得た。Comparative Example 2 The binder resin of Example 1 was replaced with a styrene copolymer (St/BA
, Mw=2.4×105 , Mn=8.9×103 ,
Mw/Mn=27.2, peak position is 1.1×104
Example 1 except that the number of copies was 100 (9×105)
A comparative electrostatic charge developing toner was obtained in the same manner as above.
【００３０】比較例３
実施例１のポリエステル樹脂の配合量を５部及びスチレ
ン系共重合体の配合量を９５部にした他は実施例１と同
様にして比較用の静電荷現像用トナーを得た。Comparative Example 3 A comparative electrostatic charge developing toner was prepared in the same manner as in Example 1, except that the blending amount of the polyester resin in Example 1 was changed to 5 parts and the blending amount of the styrene copolymer was changed to 95 parts. Obtained.
【００３１】比較例４
実施例１のポリエステル樹脂の配合量を６０部及びスチ
レン系共重合体の配合量を４０部にした他は実施例１と
同様にして比較用の静電荷現像用トナーを得た。Comparative Example 4 A comparative electrostatic charge developing toner was prepared in the same manner as in Example 1 except that the amount of the polyester resin in Example 1 was changed to 60 parts and the amount of the styrene copolymer was changed to 40 parts. Obtained.
【００３２】以上の実施例１〜３及び比較例１〜４につ
いて次の項目の試験を行い、その評価結果を表１に示す
。The following tests were carried out for Examples 1 to 3 and Comparative Examples 1 to 4, and the evaluation results are shown in Table 1.
【００３３】（１）定着強度
表層がテフロンで形成された熱ローラと、表層がシリコ
ンゴムで形成された圧着ローラとより成る定着器をロー
ル圧力が３０ｋｇ／ｃｍ及びロールスピードが１７０ｍ
ｍ／ｓｅｃ になるように調節し、該熱ローラの設定温
度を段階的に変化させて、各設定温度において転写紙に
転写せしめた試料トナーによるトナー像の定着を行い、
定着後の画像の画像濃度（定着画像濃度）をマクベス反
射濃度計により測定する。次に形成された定着画像に対
して綿パッド（ダイニック社製商品名ＰＰＣパッド）に
よって摺擦を施し、摺擦後の定着画像の画像濃度（摺擦
画像濃度）をマクベス反射濃度計により測定し、下記式
によって定着強度を算出した。
定着強度＝（摺擦画像濃度／定着画像濃度）×１００〔
％〕(1) Fixing strength A fixing device consisting of a heat roller whose surface layer is made of Teflon and a pressure roller whose surface layer is made of silicone rubber is used at a roll pressure of 30 kg/cm and a roll speed of 170 m.
m/sec, and by changing the set temperature of the heat roller in stages, fixing the toner image by the sample toner transferred to the transfer paper at each set temperature,
The image density of the image after fixing (fixed image density) is measured using a Macbeth reflection densitometer. Next, the formed fixed image was rubbed with a cotton pad (product name: PPC pad manufactured by Dynic), and the image density of the fixed image after rubbing (rubbing image density) was measured using a Macbeth reflection densitometer. The fixing strength was calculated using the following formula. Fixing strength = (rubbed image density/fixed image density) x 100 [
%〕
【００３４】（２）非オフセット温度幅転写紙上にトナ
ー像を転写して上記の定着器により定着処理を行い、該
転写紙余白部分にトナー汚れが生ずるか否かの観察する
操作を、前記定着器の熱ローラの設定温度を変化させた
状態で繰り返し行ない、トナーによる汚れの生じない温
度をもって非オフセット温度幅とした。(2) Transferring a toner image onto a non-offset temperature range transfer paper, performing a fixing process using the above-mentioned fixing device, and observing whether or not toner stains occur in the margin area of the transfer paper. The test was repeated while changing the set temperature of the heat roller of the device, and the temperature at which no toner staining occurred was defined as the non-offset temperature range.
【００３５】（３）コピー試験
実施例１〜３、比較例１〜４のトナーを各々３部とフェ
ライトにシリコーン樹脂をコートしたキャリア１００部
とを混合して二成分系現像剤を作成し、市販の複写機（
シャープ社製 ＳＦ−９８００）にセットして２万枚
までのコピー試験を行った。表中の画像濃度及び地カブ
リはマクベス反射濃度計により測定した値である。(3) Copy Test A two-component developer was prepared by mixing 3 parts each of the toners of Examples 1 to 3 and Comparative Examples 1 to 4 with 100 parts of a carrier made of ferrite coated with silicone resin. Commercially available copier (
A copying test of up to 20,000 copies was conducted by setting the copy in a Sharp Corporation SF-9800. The image density and background fog in the table are values measured using a Macbeth reflection densitometer.
【００３６】（４）両面コピー性
項目（３）における二成分系現像剤及び複写機を用いて
両面コピーを行い、両面コピー後の画像を下記の評価基
準をもって目視により評価した。
◎：定着画像に対する給紙ローラーのこすれによる汚れ
は全く発生しなかった。
○：定着画像に対する給紙ローラーのこすれによる汚れ
が僅かに発生した。
×：定着画像に対する給紙ローラーのこすれによる汚れ
が極度に発生した。(4) Double-sided copyability Double-sided copying was performed using the two-component developer and copying machine in item (3), and the images after double-sided copying were visually evaluated using the following evaluation criteria. ◎: There was no staining caused by rubbing of the paper feed roller against the fixed image. ○: Slight staining caused by rubbing of the paper feed roller against the fixed image occurred. ×: Extreme staining caused by rubbing of the paper feed roller against the fixed image occurred.
【００３７】[0037]
【表１】[Table 1]
【００３８】表１の評価結果から明らかなように本発明
の静電荷現像用トナーは非オフセット温度幅が広く、低
い定着温度（１６０℃）で定着強度も十分にあり、両面
コピー性についても何ら問題がなく、２万枚まで画像濃
度、地カブリ共良好な特性を示してした。一方、比較例
１及び比較例４については２万枚において画像濃度が低
下し、地カブリも多い画像であった。また、比較例２及
び比較例３については定着強度、両面コピー性が悪く、
非オフセット温度幅も狭いものであった。As is clear from the evaluation results in Table 1, the electrostatic charge developing toner of the present invention has a wide non-offset temperature range, has sufficient fixing strength at a low fixing temperature (160° C.), and has no double-sided copyability. There were no problems and the image density and background fog showed good characteristics up to 20,000 copies. On the other hand, in Comparative Example 1 and Comparative Example 4, the image density decreased at 20,000 sheets, and the images had a lot of background fog. In addition, Comparative Examples 2 and 3 had poor fixing strength and double-sided copyability;
The non-offset temperature range was also narrow.
【００３９】[0039]
【発明の効果】本発明は低い定着温度で十分な定着強度
を有し、非オフセット温度幅も広く、両面コピー性及び
原稿自動送り装置での汚れもなく、繰り返しコピーに対
しても画像の劣化のない静電荷現像用トナーを提供する
ことができる。Effects of the Invention: The present invention has sufficient fixing strength at low fixing temperatures, has a wide non-offset temperature range, has double-sided copyability, does not get smeared by automatic document feeder, and does not cause image deterioration even with repeated copying. It is possible to provide a toner for developing electrostatic charge free of electrostatic charges.
Claims (1)
スチレン系共重合体５０〜９０重量部とを結着樹脂（但
し、ポリエステル樹脂とスチレン系共重合体との総量は
１００重量部である）として含有し、ＧＰＣクロマトグ
ラムにおける該ポリエステル樹脂及びスチレン系共重合
体の分子量のピーク位置が各々８×１０２ 〜５×１０
４ 及び１０４ 〜５×１０５ の領域にあることを特
徴とする静電荷現像用トナー。Claim 1: 50 to 10 parts by weight of a polyester resin and 50 to 90 parts by weight of a styrene copolymer are used as a binder resin (however, the total amount of the polyester resin and styrene copolymer is 100 parts by weight). content, and the peak positions of the molecular weights of the polyester resin and styrene copolymer in the GPC chromatogram are 8 x 102 to 5 x 10, respectively.
4 and 104 to 5×105.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3035051A JPH04254863A (en) | 1991-02-06 | 1991-02-06 | Toner for electrostatic charge development |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3035051A JPH04254863A (en) | 1991-02-06 | 1991-02-06 | Toner for electrostatic charge development |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04254863A true JPH04254863A (en) | 1992-09-10 |
Family
ID=12431243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3035051A Pending JPH04254863A (en) | 1991-02-06 | 1991-02-06 | Toner for electrostatic charge development |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04254863A (en) |
-
1991
- 1991-02-06 JP JP3035051A patent/JPH04254863A/en active Pending
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20011002 |