JP2010249938A - Nonmagnetic toner - Google Patents
Nonmagnetic toner Download PDFInfo
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- JP2010249938A JP2010249938A JP2009097155A JP2009097155A JP2010249938A JP 2010249938 A JP2010249938 A JP 2010249938A JP 2009097155 A JP2009097155 A JP 2009097155A JP 2009097155 A JP2009097155 A JP 2009097155A JP 2010249938 A JP2010249938 A JP 2010249938A
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- 239000002245 particle Substances 0.000 claims abstract description 109
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 52
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 52
- 239000006247 magnetic powder Substances 0.000 claims abstract description 40
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000003086 colorant Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 19
- 230000005291 magnetic effect Effects 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 6
- 230000007774 longterm Effects 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 description 48
- 239000001993 wax Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
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- 238000006243 chemical reaction Methods 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
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- 239000002184 metal Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004203 carnauba wax Substances 0.000 description 6
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- 238000005259 measurement Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 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 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GCOWTRMQPXDRQQ-UHFFFAOYSA-N [Mg].[Cu].[Zn] Chemical compound [Mg].[Cu].[Zn] GCOWTRMQPXDRQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 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
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 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
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
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- 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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
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Images
Abstract
Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられる非磁性トナーに関する。 The present invention relates to a non-magnetic toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
近年のプリントオンデマンドの発達により、トナーの定着工程後にメール・シーラー、バースター、折り機、ブックレットフィニッシャー、ステープルフィニッシャー等の印刷物加工工程が広く行なわれるようになったが、この後処置工程は、印刷物にかかるストレスが強く、特に紙同士が擦り合わせにより、画像品質が低下しやすい。そこで、この課題を解決するために、外添剤にフッ素系樹脂微粉末を用いるトナーが開示されている（特許文献１参照）。 Due to the recent development of print on demand, print processing processes such as mail sealers, bursters, folding machines, booklet finishers, staple finishers, etc. have been widely performed after the toner fixing process. The stress applied to the printed matter is strong, and the image quality tends to be deteriorated particularly by rubbing the papers together. In order to solve this problem, a toner using a fluororesin fine powder as an external additive has been disclosed (see Patent Document 1).
また、プリントオンデマンドのニーズから高速印刷を行うために非接触加熱定着方式が提案されている。しかしながら、非接触加熱定着方式は接触加熱定着方式に比べ、定着工程後の印刷面が平滑にならないために、擦り定着性が劣る。そこで、この課題を解決するために、トナー母粒子にフッ素系樹脂粉末を内添したトナーが開示されている（特許文献２参照） In addition, a non-contact heat fixing method has been proposed in order to perform high-speed printing from the needs of print on demand. However, the non-contact heating fixing method is inferior to the contact heating fixing method because the printed surface after the fixing step is not smooth, and thus the rubbing fixing property is inferior. In order to solve this problem, a toner in which a fluorine resin powder is internally added to toner base particles is disclosed (see Patent Document 2).
このようにフッ素系樹脂粒子を、外添剤として用いたトナーやトナー粒子に内添したトナーは、長時間にわたる連続印刷時にトナーの帯電量が大きく変化するため、安定な画像品質を得ることが困難である。 As described above, the toner using the fluororesin particles as an external additive or the toner internally added to the toner particles can obtain a stable image quality because the charge amount of the toner greatly changes during continuous printing over a long period of time. Have difficulty.
本発明の課題は、優れた擦り定着性を有するとともに、長期耐刷においても帯電量が安定し良好な画質を維持する非磁性トナーを提供することにある。 An object of the present invention is to provide a non-magnetic toner that has excellent rubbing and fixing properties and that maintains a good image quality with a stable charge amount even during long-term printing durability.
本発明は、少なくとも、結着樹脂、着色剤、ポリテトラフルオロエチレン粒子及び磁性粉を含んでなる非磁性トナーであって、前記磁性粉を前記結着樹脂100重量部に対して0.5〜15重量部含有してなる非磁性トナーに関する。 The present invention is a non-magnetic toner comprising at least a binder resin, a colorant, polytetrafluoroethylene particles, and magnetic powder, and the magnetic powder is added in an amount of 0.5 to 15 weights with respect to 100 parts by weight of the binder resin. The present invention relates to a non-magnetic toner containing part.
本発明の非磁性トナーは、優れた擦り定着性を有するとともに、長期耐刷においても帯電量が安定し良好な画質を維持することができる。 The non-magnetic toner of the present invention has excellent rubbing and fixing properties, and can maintain a good image quality with a stable charge amount even during long-term printing durability.
本発明の非磁性トナーは、少なくとも結着樹脂、着色剤、ポリテトラフルオロエチレン粒子及び特定量の磁性粉からなり、ポリテトラフルオロエチレン粒子により擦り定着性が向上し、さらに磁性粉との組み合わせにより、耐刷時の帯電安定性が向上する。なお、本発明において、非磁性トナーとは、795.8kA/mの印加磁場における飽和磁化が10.0Am2/kg以下のトナーである。 The non-magnetic toner of the present invention comprises at least a binder resin, a colorant, polytetrafluoroethylene particles, and a specific amount of magnetic powder. The polytetrafluoroethylene particles improve the rubbing fixability, and further, in combination with magnetic powder. In addition, charging stability during printing durability is improved. In the present invention, the non-magnetic toner is a toner having a saturation magnetization of 10.0 Am 2 / kg or less in an applied magnetic field of 795.8 kA / m.
本発明における結着樹脂は、トナーの低温定着性を向上させる観点から、ポリエステルを主成分とすることが好ましく、さらに低温定着性と保存安定性を両立させる観点から、結晶性ポリエステルと非晶質ポリエステルとを含有することがより好ましい。ここで、樹脂の結晶性は、軟化点と示差走査熱量計による吸熱の最高ピーク温度との比、即ち(軟化点／吸熱の最高ピーク温度)比で定義される結晶性指数によって表わされる。結晶性ポリエステルは、結晶性指数が0.6〜1.4、好ましくは0.7〜1.2、より好ましくは0.9〜1.2であり、非晶質ポリエステルは1.4を超えるか、0.6未満である。樹脂の結晶性は、原料モノマーの種類とその比率、及び製造条件(例えば、反応温度、反応時間、冷却速度)等により調整することができる。なお、吸熱の最高ピーク温度とは、観測される吸熱ピークのうち、最も高温側にあるピークの温度を指す。最高ピーク温度が軟化点に対して20℃以内の差であれば、最高ピーク温度を融点とし、軟化点との差が20℃を超える場合はガラス転移点とする。 The binder resin in the present invention is preferably composed mainly of polyester from the viewpoint of improving low-temperature fixability of the toner, and from the viewpoint of achieving both low-temperature fixability and storage stability, crystalline polyester and amorphous It is more preferable to contain polyester. Here, the crystallinity of the resin is expressed by the crystallinity index defined by the ratio between the softening point and the maximum peak temperature of the endotherm measured by the differential scanning calorimeter, that is, the ratio (softening point / maximum endothermic peak temperature). The crystalline polyester has a crystallinity index of 0.6 to 1.4, preferably 0.7 to 1.2, more preferably 0.9 to 1.2, and the amorphous polyester is more than 1.4 or less than 0.6. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. If the maximum peak temperature is within 20 ° C relative to the softening point, the maximum peak temperature is the melting point, and if the difference from the softening point exceeds 20 ° C, the glass transition point.
結晶性ポリエステルの原料モノマーとしては、結晶性を高める観点から、炭素数が2〜6、好ましくは4〜6の脂肪族ジオールを含有したアルコール成分と、炭素数が2〜8、好ましくは4〜6、より好ましくは4の脂肪族ジカルボン酸化合物、又は炭素数が8の芳香族ジカルボン酸化合物を含有したカルボン酸成分が好ましい。なお、ジカルボン酸化合物とは、ジカルボン酸、その無水物及びそのアルキル(炭素数1〜8)エステルを指す。また、好ましい炭素数とは、ジカルボン酸化合物のジカルボン酸部分の炭素数を意味する。 As a raw material monomer of the crystalline polyester, from the viewpoint of enhancing crystallinity, an alcohol component containing an aliphatic diol having 2 to 6, preferably 4 to 6 carbon atoms, and 2 to 8, preferably 4 to 4 carbon atoms. A carboxylic acid component containing an aliphatic dicarboxylic acid compound having 6 carbon atoms, more preferably 4 or an aromatic dicarboxylic acid compound having 8 carbon atoms is preferable. In addition, a dicarboxylic acid compound refers to dicarboxylic acid, its anhydride, and its alkyl (C1-C8) ester. Moreover, a preferable carbon number means the carbon number of the dicarboxylic acid part of a dicarboxylic acid compound.
炭素数2〜6の脂肪族ジオールとしては、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、1,4-ブテンジオール等が挙げられ、なかでも、結晶性を高める観点から、1,4-ブタンジオール及び1,6-ヘキサンジオールが好ましい。 Examples of the aliphatic diol having 2 to 6 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples thereof include neopentyl glycol and 1,4-butenediol. Among these, 1,4-butanediol and 1,6-hexanediol are preferable from the viewpoint of enhancing crystallinity.
炭素数2〜6の脂肪族ジオールは、結晶性を高める観点から、アルコール成分中に、好ましくは60モル％以上、より好ましくは80〜100モル％、さらに好ましくは90〜100モル％含有されているのが望ましい。 The aliphatic diol having 2 to 6 carbon atoms is preferably contained in the alcohol component in an amount of 60 mol% or more, more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%, from the viewpoint of enhancing crystallinity. It is desirable.
アルコール成分には、炭素数2〜6の脂肪族ジオール以外の多価アルコール成分が含有されていてもよく、式(I)： The alcohol component may contain a polyhydric alcohol component other than the aliphatic diol having 2 to 6 carbon atoms.
（式中、ＲＯ及びＯＲはオキシアルキレン基であり、Ｒはエチレン及び／又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの付加モル数を示し、それぞれ正の数であり、ｘとｙの和の平均値は1〜16が好ましく、1〜8がより好ましく、1.5〜4がさらに好ましい）
で表されるビスフェノールＡのアルキレンオキサイド付加物等の芳香族ジオール；グリセリン、ペンタエリスリトール、トリメチロールプロパン、ソルビトール、1,4-ソルビタン等の3価以上のアルコール等が挙げられる。
(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y represent the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable)
An aromatic diol such as an alkylene oxide adduct of bisphenol A represented by the formula: trivalent or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, 1,4-sorbitan, and the like.
炭素数2〜8の脂肪族ジカルボン酸化合物としては、シュウ酸、マロン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、コハク酸、アジピン酸が挙げられ、結晶性を高める観点から、フマル酸及びアジピン酸が好ましく、フマル酸がより好ましい。炭素数8の芳香族ジカルボン酸化合物としては、フタル酸、テレフタル酸、イソフタル酸が挙げられ、結晶性を高める観点から、テレフタル酸が好ましい。ジカルボン酸化合物の中では、ジカルボン酸が好ましい。 Examples of the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid, from the viewpoint of increasing crystallinity. Fumaric acid and adipic acid are preferred, and fumaric acid is more preferred. Examples of the aromatic dicarboxylic acid compound having 8 carbon atoms include phthalic acid, terephthalic acid, and isophthalic acid, and terephthalic acid is preferable from the viewpoint of improving crystallinity. Of the dicarboxylic acid compounds, dicarboxylic acids are preferred.
炭素数2〜8の脂肪族ジカルボン酸化合物、炭素数8の芳香族ジカルボン酸は、結晶性を高める観点から、カルボン酸成分中に、好ましくは60モル％以上、より好ましくは80〜100モル％、さらに好ましくは90〜100モル％含有されているのが望ましい。特に、その中の1種の脂肪族ジカルボン酸化合物が、カルボン酸成分中の好ましくは60モル％以上、より好ましくは70〜100モル％、さらに好ましくは80〜100モル％を占めているのが望ましい。なかでも、フマル酸が、カルボン酸成分中、好ましくは60モル％以上、より好ましくは70〜100モル％、さらに好ましくは80〜100モル％含有されているのが望ましい。 From the viewpoint of enhancing crystallinity, the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms and the aromatic dicarboxylic acid having 8 carbon atoms are preferably 60 mol% or more, more preferably 80 to 100 mol%, in the carboxylic acid component. More preferably, the content is 90 to 100 mol%. In particular, one aliphatic dicarboxylic acid compound in the carboxylic acid component preferably accounts for 60 mol% or more, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%. desirable. Among them, it is desirable that fumaric acid is contained in the carboxylic acid component in an amount of preferably 60 mol% or more, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%.
カルボン酸成分には、炭素数2〜8の脂肪族ジカルボン酸化合物、炭素数8の芳香族ジカルボン酸化合物以外の多価カルボン酸成分が含有されていてもよく、該多価カルボン酸成分としては、セバシン酸、アゼライン酸、n-ドデシルコハク酸、n-ドデセニルコハク酸等の脂肪族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；トリメリット酸、ピロメリット酸等の3価以上の多価カルボン酸；及びこれらの酸無水物、アルキル(炭素数1〜8)エステル等が挙げられる。 The carboxylic acid component may contain a polyvalent carboxylic acid component other than the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms and the aromatic dicarboxylic acid compound having 8 carbon atoms. , Sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid and other aliphatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; trimellitic acid, pyromellitic acid and more Carboxylic acids; and their acid anhydrides, alkyl (C 1-8) esters, and the like.
さらに、樹脂の分子量調整等の観点から、1価のアルコールがアルコール成分に、1価のカルボン酸化合物がカルボン酸成分に、本発明の効果を損なわない範囲で適宜含有されていてもよい。 Furthermore, from the viewpoint of adjusting the molecular weight of the resin, a monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component as long as the effects of the present invention are not impaired.
なお、結晶性ポリエステルにおけるカルボン酸成分とアルコール成分のモル比(カルボン酸成分／アルコール成分)は、製造安定性の観点から、さらにアルコール成分が多い場合には、減圧反応時に蒸発により樹脂の分子量を容易に調整できる観点から、0.9〜1.0が好ましく、0.95以上1.0未満がより好ましい。 Note that the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) in the crystalline polyester is such that the molecular weight of the resin is reduced by evaporation during a reduced pressure reaction in the case where there are more alcohol components from the viewpoint of production stability. From the viewpoint of easy adjustment, 0.9 to 1.0 is preferable, and 0.95 or more and less than 1.0 is more preferable.
結晶性ポリエステルとしては、非晶質ポリエステルとの相溶性の観点から、ワックスの存在下で原料モノマーを重合させて得られる結晶性ポリエステルが好ましい。 The crystalline polyester is preferably a crystalline polyester obtained by polymerizing a raw material monomer in the presence of a wax from the viewpoint of compatibility with an amorphous polyester.
結晶性ポリエステルの原料モノマー重合時に使用されるワックスとしては、炭化水素系ワックス、エステル系ワックス、アミド系ワックス等のいずれでもよいが、結晶性ポリエステルとの相溶性及び離型性の観点から、炭化水素系ワックスが好ましい。炭化水素系ワックスは、一般に-(CH2-CH(R))n-（式中、Ｒは水素原子又は炭素数1〜3の炭化水素基を示す）で表される主骨格を有し、具体的には、フィッシャートロプシュワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリエチレン−ポリプロピレンワックス、マイクロクリスタリンワックス、パラフィンワックスが挙げられ、これらの中では、結晶性ポリエステルの粉砕性向上の観点から、ポリエチレンワックス及びポリプロピレンワックスが好ましく、ポリプロピレンワックスがより好ましい。 The wax used during the polymerization of the raw material monomer of the crystalline polyester may be any of hydrocarbon wax, ester wax, amide wax, etc., but from the viewpoint of compatibility with the crystalline polyester and releasability. Hydrogen wax is preferred. The hydrocarbon wax generally has a main skeleton represented by — (CH 2 —CH (R)) n — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms), Specific examples include Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polyethylene-polypropylene wax, microcrystalline wax, and paraffin wax. Among these, polyethylene wax and polypropylene are used from the viewpoint of improving the pulverizability of crystalline polyester. Wax is preferred and polypropylene wax is more preferred.
結晶性ポリエステルの原料モノマー重合時に使用されるワックスの量は、結晶性ポリエステルの原料モノマー100重量部に対して、0.1〜20重量部が好ましく、0.5〜15重量部がより好ましく、1〜12重量部がさらに好ましい。 The amount of wax used during the polymerization of the raw material monomer of the crystalline polyester is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and 1 to 12 parts by weight based on 100 parts by weight of the raw material monomer of the crystalline polyester. Part is more preferable.
結晶性ポリエステルは、例えば、アルコール成分とカルボン酸成分とを不活性ガス雰囲気中にて、必要に応じてエステル化触媒、重合禁止剤等の存在下、180〜250℃程度の温度で縮重合させて製造することができる。エステル化触媒としては、酸化ジブチル錫、2-エチルヘキサン酸錫(II)等の錫化合物、チタンジイソプロピレートビストリエタノールアミネート等のチタン化合物等が挙げられる。エステル化触媒の使用量は、アルコール成分100重量部に対して、0.01〜1重量部が好ましく、0.1〜0.6重量部がより好ましい。 For example, the crystalline polyester is obtained by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere at a temperature of about 180 to 250 ° C. in the presence of an esterification catalyst or a polymerization inhibitor as necessary. Can be manufactured. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of esterification catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the alcohol component.
結晶性ポリエステルの吸熱の最高ピーク温度は、トナーの保存性、耐久性を向上させる観点から、60℃以上が好ましく、80℃以上がより好ましく、100℃以上がさらに好ましい。また、トナーの低温定着性を向上させる観点から、150℃以下が好ましく、140℃以下がよりに好ましく、130℃以下がさらに好ましい。すなわち、これらの観点を総合すると、結晶性ポリエステルの吸熱の最高ピーク温度は、60〜150℃が好ましく、80〜140℃がより好ましく、100〜130℃がさらに好ましい。 The maximum endothermic peak temperature of the crystalline polyester is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher from the viewpoint of improving the storage stability and durability of the toner. Further, from the viewpoint of improving the low-temperature fixability of the toner, 150 ° C. or lower is preferable, 140 ° C. or lower is more preferable, and 130 ° C. or lower is further preferable. That is, taking these viewpoints together, the maximum peak temperature of the endotherm of the crystalline polyester is preferably 60 to 150 ° C, more preferably 80 to 140 ° C, and even more preferably 100 to 130 ° C.
結晶性ポリエステルの軟化点は、トナーの保存性及び耐久性を向上させる観点から、50℃以上が好ましく、70℃以上がより好ましく、90℃以上がさらに好ましい。また、トナーの低温定着性を向上させる観点から、160℃以下が好ましく、140℃以下がより好ましく、130℃以下がさらに好ましい。すなわち、これらの観点を総合すると、結晶性ポリエステルの軟化点は、50〜160℃が好ましく、70〜140℃がより好ましく、90〜130℃がさらに好ましい。 The softening point of the crystalline polyester is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 90 ° C. or higher, from the viewpoint of improving the storage stability and durability of the toner. Further, from the viewpoint of improving the low-temperature fixability of the toner, it is preferably 160 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. That is, taking these viewpoints together, the softening point of the crystalline polyester is preferably 50 to 160 ° C, more preferably 70 to 140 ° C, and further preferably 90 to 130 ° C.
結晶性ポリエステルの含有量は、トナーの低温定着性を向上させる観点から、結着樹脂中、1〜40重量％が好ましく、3〜20重量％がより好ましい。 The content of the crystalline polyester is preferably 1 to 40% by weight and more preferably 3 to 20% by weight in the binder resin from the viewpoint of improving the low-temperature fixability of the toner.
非晶質ポリエステルも、結晶性ポリエステルと同様に、アルコール成分とカルボン酸成分とを不活性ガス雰囲気中にて、必要に応じて、エステル化触媒、重合禁止剤等の存在下、180〜250℃程度の温度で縮重合させて製造することができる。ただし、非晶質ポリエステルとするためには、
(1) 炭素数2〜6の脂肪族ジオール、炭素数2〜8の脂肪族カルボン酸化合物等の樹脂の結晶化を促進するモノマーを用いる場合は、これらのモノマーをそれぞれ２種以上併用して結晶化を抑制すること、即ちアルコール成分及びカルボン酸成分のいずれにおいても、これらのモノマーの1種が各成分中10〜70モル％、好ましくは20〜60モル％を占め、かつこれらのモノマーが2種以上、好ましくは2〜4種用いられていること、又は
(2) 樹脂の非晶質化を促進するモノマー、好ましくはアルコール成分ではビスフェノールＡのアルキレンオキサイド付加物が、またはカルボン酸成分ではアルキル基もしくはアルケニル基で置換されたコハク酸が、それぞれアルコール成分中又はカルボン酸成分中、少なくとも一方の成分において、好ましくは両成分のそれぞれにおいて、30〜100モル％、好ましくは50〜100モル％用いられていることが好ましい。
As with the crystalline polyester, the amorphous polyester also has an alcohol component and a carboxylic acid component in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, a polymerization inhibitor, etc. at 180 to 250 ° C. It can be produced by polycondensation at a moderate temperature. However, in order to make amorphous polyester,
(1) When using monomers that promote crystallization of resins such as aliphatic diols having 2 to 6 carbon atoms and aliphatic carboxylic acid compounds having 2 to 8 carbon atoms, two or more of these monomers are used in combination. Inhibiting crystallization, that is, in any of the alcohol component and the carboxylic acid component, one of these monomers accounts for 10 to 70 mol%, preferably 20 to 60 mol% in each component, and these monomers 2 or more, preferably 2 to 4 are used, or
(2) A monomer that promotes amorphization of the resin, preferably an alkylene oxide adduct of bisphenol A in the alcohol component, or a succinic acid substituted with an alkyl group or alkenyl group in the alcohol component, respectively in the alcohol component. Alternatively, in at least one component in the carboxylic acid component, preferably 30 to 100 mol%, preferably 50 to 100 mol% is used in each of both components.
非晶質ポリエステルの酸価は、高温高湿環境での帯電安定性の観点から、30mgKOH/g以下が好ましく、20mgKOH/g以下がより好ましく、10mgKOH/g以下がさらに好ましい。 The acid value of the amorphous polyester is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and even more preferably 10 mgKOH / g or less, from the viewpoint of charging stability in a high temperature and high humidity environment.
本発明において、アルコール成分とカルボン酸成分とを縮重合させて得られるポリエステル成分を有する非晶質ポリエステルには、ポリエステルのみならず、その変性樹脂も含まれる。 In the present invention, the amorphous polyester having a polyester component obtained by condensation polymerization of an alcohol component and a carboxylic acid component includes not only the polyester but also a modified resin thereof.
ポリエステルの変性樹脂としては、例えば、ポリエステルがウレタン結合で変性されたウレタン変性ポリエステル、ポリエステルがエポキシ結合で変性されたエポキシ変性ポリエステル、ポリエステル成分を含む2種以上の樹脂成分を有するハイブリッド樹脂等が挙げられる。 Examples of the polyester-modified resin include urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and a hybrid resin having two or more resin components including a polyester component. It is done.
非晶質ポリエステルの軟化点は、トナーの保存安定性及び耐久性を向上させる観点から、70℃以上が好ましく、100℃以上がより好ましい。また、トナーの低温定着性を向上させる観点から180℃以下が好ましく、160℃以下がより好ましい。すなわち、これらの観点を総合すると、非晶質ポリエステルの軟化点は、70〜180℃が好ましく、100〜160℃がより好ましい。また、ガラス転移点は、トナーの保存安定性及び耐久性を向上させる観点から、45℃以上が好ましく、55℃以上がより好ましい。また、トナーの低温定着性を向上させる観点から、80℃以下が好ましく、75℃以下がより好ましい。すなわち、これらの観点を総合すると、非晶質ポリエステルのガラス転移点は、好ましくは45〜80℃、より好ましくは55〜75℃である。なお、ガラス転移点は非晶質樹脂に特有の物性であり、吸熱の最高ピーク温度とは区別される。 The softening point of the amorphous polyester is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of improving the storage stability and durability of the toner. Further, from the viewpoint of improving the low-temperature fixability of the toner, 180 ° C. or lower is preferable, and 160 ° C. or lower is more preferable. That is, taking these viewpoints together, the softening point of the amorphous polyester is preferably 70 to 180 ° C, more preferably 100 to 160 ° C. The glass transition point is preferably 45 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of improving the storage stability and durability of the toner. Further, from the viewpoint of improving the low-temperature fixability of the toner, it is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower. That is, taking these viewpoints together, the glass transition point of the amorphous polyester is preferably 45 to 80 ° C, more preferably 55 to 75 ° C. The glass transition point is a physical property peculiar to an amorphous resin, and is distinguished from the maximum peak temperature of endotherm.
結晶性ポリエステルと非晶質ポリエステルの重量比(結晶性ポリエステル／非晶質ポリエステル)は、低温定着性と耐久性の両立の観点から1/99〜50/50が好ましく、3/97〜45/55がより好ましく、5/95〜40/60がさらに好ましい。 The weight ratio of crystalline polyester to amorphous polyester (crystalline polyester / amorphous polyester) is preferably 1/99 to 50/50 from the viewpoint of achieving both low temperature fixability and durability, and 3/97 to 45 / 55 is more preferable, and 5/95 to 40/60 is more preferable.
結着樹脂には、結晶性ポリエステルと非晶質ポリエステル以外の結着樹脂が、本発明の効果を損なわない範囲で含まれていてもよい。結晶性ポリエステルと非晶質ポリエステル以外の結着樹脂としては、ビニル系樹脂、エポキシ系樹脂、ポリカーボネート、ポリウレタン等が挙げられる。 The binder resin may contain a binder resin other than the crystalline polyester and the amorphous polyester as long as the effects of the present invention are not impaired. Examples of binder resins other than crystalline polyester and amorphous polyester include vinyl resins, epoxy resins, polycarbonates, polyurethanes, and the like.
本発明のトナーの着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができる。 As the colorant of the toner of the present invention, all of dyes, pigments and the like used as toner colorants can be used.
イエロー着色剤としては、縮合アゾ化合物、イソインドリノン化合物、アンスラキノン化合物、アゾ金属錯体メチン化合物、アリルアミド化合物等が挙げられる。具体的には、C.I.ピグメントイエロー3、7、10、12〜15、17、23、24、60、62、74、75、83、93〜95、99、100、101、104、108〜111、117、123、128、129、138、139、147、148、150、166、168〜177、179、180、181、183、185、191:1、191、192、193、199等が挙げられる。
Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds. Specifically,
マゼンタ着色剤としては、縮合アゾ化合物、ジケトピロロピロール化合物、アントラキノン、キナクリドン化合物、塩基染料レーキ化合物、ナフトール化合物、ベンズイミダゾロン化合物、チオインジゴ化合物、ペリレン化合物等が挙げられる。具体的には、C.I.ピグメントレッド2、3、5〜7、23、48:2、48:3、48:4、57:1、81:1、122、146、166、169、177、184、185、202、206、220、221、254、C.I.ピグメントバイオレッド19等が挙げられる。 Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, CI Pigment Red 2, 3, 5-7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, CI Pigment Bio Red 19 and the like.
シアン着色剤としては、銅フタロシアニン化合物及びその誘導体、アントラキノン化合物、塩基染料レーキ化合物等が挙げられる。具体的には、C.I.ピグメントブルー1、7、15、15:1、15:2、15:3、15:4、60、62、66等が挙げられる。
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specific examples include C.I.
黒トナー用着色剤としては、カーボンブラック、アニリンブラック、マグネタイト、Ｔｉ／Ｆｅ系の複合酸化物等が挙げられる。 Examples of the colorant for black toner include carbon black, aniline black, magnetite, and Ti / Fe based composite oxide.
着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、2〜10重量部がより好ましい。 The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
ポリテトラフルオロエチレン粒子としては、分子量が高く、耐刷性が向上する観点から、乳化重合により製造された球形に近い形状のものが好ましい。 The polytetrafluoroethylene particles preferably have a shape close to a sphere produced by emulsion polymerization from the viewpoint of high molecular weight and improved printing durability.
ポリテトラフルオロエチレン粒子の平均粒径は、トナーの擦り定着性を向上させる観点から、0.01μｍ以上が好ましく、0.1μｍ以上がより好ましい。また、耐刷時のトナーの帯電安定性を向上させる観点から、1.0μｍ以下が好ましく、0.8μｍ以下がより好ましい。すなわち、これらの観点を総合すると、ポリテトラフルオロエチレン粒子の平均粒径は、0.01〜1.0μｍが好ましく、0.1〜0.8μｍがより好ましい。 The average particle size of the polytetrafluoroethylene particles is preferably 0.01 μm or more, and more preferably 0.1 μm or more, from the viewpoint of improving the rubbing fixability of the toner. Further, from the viewpoint of improving the charging stability of the toner during printing durability, it is preferably 1.0 μm or less, and more preferably 0.8 μm or less. That is, taking these viewpoints together, the average particle size of the polytetrafluoroethylene particles is preferably 0.01 to 1.0 μm, and more preferably 0.1 to 0.8 μm.
このような形状及び平均粒径を有するポリテトラフルオロエチレン粒子の市販品としては、「ルブロン L2」(ダイキン工業社製、平均粒径0.3μｍ)、「ルブロン L5F」(ダイキン工業社製、平均粒径0.2μｍ)、「KTL-500F」(喜多村社製、平均粒径0.5μｍ)等が挙げられる。 Commercially available polytetrafluoroethylene particles having such a shape and average particle size include “Lublon L2” (Daikin Industries, average particle size 0.3 μm), “Lublon L5F” (Daikin Industries, average particle size) Diameter 0.2 μm), “KTL-500F” (manufactured by Kitamura Co., Ltd., average particle size 0.5 μm), and the like.
本発明のトナーは、少なくとも、結着樹脂、着色剤、ポリテトラフルオロエチレン粒子及び磁性粉を溶融混練する工程を含む方法により得られるもの(ポリテトラフルオロエチレン粒子がトナー粒子(トナー母粒子)中に内添された態様)でもよいし、結着樹脂、着色剤及び磁性粉を含むトナー母粒子の表面に、ポリテトラフルオロエチレン粒子が外添されたものであってもよいが、トナーの耐刷時の帯電安定性と擦り定着性を両立させる観点から、前者の態様が好ましい。 The toner of the present invention is obtained by a method including a step of melt-kneading at least a binder resin, a colorant, polytetrafluoroethylene particles, and magnetic powder (polytetrafluoroethylene particles in toner particles (toner mother particles)). May be added to the surface of the toner base particles containing the binder resin, the colorant and the magnetic powder. From the viewpoint of achieving both charging stability during printing and rubbing and fixing properties, the former mode is preferred.
ポリテトラフルオロエチレン粒子をトナー粒子中に内添させる場合、ポリテトラフルオロエチレン粒子の含有量は、トナーの擦り定着性を向上させる観点から、結着樹脂100重量部に対して、0.5重量部以上が好ましく、1重量部以上がより好ましく、2重量部以上がさらに好ましい。また、トナーの耐刷時の帯電安定性及び低温定着性を向上させる観点から、結着樹脂100重量部に対して、10重量部以下が好ましく、6重量部以下がより好ましく、4重量部以下がさらに好ましい。すなわち、これらの観点を総合すると、ポリテトラフルオロエチレン粒子の含有量は、結着樹脂100重量部に対して、0.5〜10重量部が好ましく、1〜6重量部がより好ましく、2〜4重量部がさらに好ましい。 When polytetrafluoroethylene particles are internally added to the toner particles, the content of the polytetrafluoroethylene particles is 0.5 parts by weight or more with respect to 100 parts by weight of the binder resin from the viewpoint of improving the rubbing fixability of the toner. Is preferred, 1 part by weight or more is more preferred, and 2 parts by weight or more is more preferred. Further, from the viewpoint of improving the charging stability and low-temperature fixability at the time of printing of the toner, it is preferably 10 parts by weight or less, more preferably 6 parts by weight or less, and more preferably 4 parts by weight or less with respect to 100 parts by weight of the binder resin. Is more preferable. That is, taking these viewpoints together, the content of the polytetrafluoroethylene particles is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, and 2 to 4 parts by weight with respect to 100 parts by weight of the binder resin. Part is more preferable.
ポリテトラフルオロエチレン粒子をトナー粒子に表面に外添させる場合、ポリテトラフルオロエチレン粒子の含有量は、トナーの擦り定着性を向上させる観点から、トナー母粒子100重量部に対して、0.1重量部以上が好ましく、0.2重量部以上がより好ましく、0.3重量部以上がさらに好ましい。また、トナーの耐刷時の帯電安定性を向上させる観点から、トナー母粒子100重量部に対して、2重量部以下が好ましく、1.5重量部以下がより好ましく、1重量部以下がさらに好ましい。すなわち、これらの観点を総合すると、ポリテトラフルオロエチレン粒子の含有量は、トナー母粒子100重量部に対して、0.1〜2重量部が好ましく、0.2〜1.5重量部がより好ましく、0.3〜1重量部がさらに好ましい。 When polytetrafluoroethylene particles are externally added to the toner particles, the content of the polytetrafluoroethylene particles is 0.1 parts by weight with respect to 100 parts by weight of the toner base particles from the viewpoint of improving the rubbing fixability of the toner. The above is preferable, 0.2 parts by weight or more is more preferable, and 0.3 parts by weight or more is more preferable. Further, from the viewpoint of improving the charging stability of the toner during printing durability, the amount is preferably 2 parts by weight or less, more preferably 1.5 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the toner base particles. That is, taking these viewpoints together, the content of the polytetrafluoroethylene particles is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1.5 parts by weight, and more preferably 0.3 to 1 part by weight with respect to 100 parts by weight of the toner base particles. Part is more preferable.
本発明において磁性粉とは、磁場の中に置かれて磁化される物質であり、鉄、コバルト、ニッケル等の強磁性金属の粉末や、マグネタイト、ヘマタイト、フェライト、γ-酸化鉄のような、酸化鉄を主成分とする化合物等が挙げられる。酸化鉄を主成分とする化合物は、リン、コバルト、ニッケル、銅、マグネシウム、マンガン、アルミニウム、珪素等の元素を含んでいてもよい。磁性粉の形状は、球状、定形及び不定形のいずれであってもよい。トナーの耐刷時の帯電安定性を向上させる観点から、酸化鉄を主成分とする化合物が好ましく、酸化鉄を30重量％以上含有する化合物がより好ましく、マグネタイト及びフェライトがさらに好ましい。 In the present invention, magnetic powder is a substance that is magnetized by being placed in a magnetic field, such as powders of ferromagnetic metals such as iron, cobalt, nickel, magnetite, hematite, ferrite, γ-iron oxide, The compound etc. which have iron oxide as a main component are mentioned. The compound containing iron oxide as a main component may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. The shape of the magnetic powder may be spherical, regular or irregular. From the viewpoint of improving the charging stability of the toner during printing durability, a compound containing iron oxide as a main component is preferable, a compound containing 30% by weight or more of iron oxide is more preferable, and magnetite and ferrite are more preferable.
磁性粉の平均粒径は、結着樹脂中への分散性を向上させ、トナーの耐刷時の帯電安定性を向上させる観点から、0.02μm以上が好ましく、0.05μｍ以上がより好ましく、0.1μｍ以上がさらに好ましい。また、トナーの擦り定着性を向上させる観点から、2.0μm以下が好ましく、1.0μｍ以下がより好ましく、0.5μｍ以下がさらに好ましい。すなわち、これらの観点を総合すると、磁性粉の平均粒径は、0.02〜3.0μｍが好ましく、0.02〜2.5μｍがより好ましく、0.05〜2.0μｍがさらに好ましい。 The average particle diameter of the magnetic powder is preferably 0.02 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm from the viewpoint of improving the dispersibility in the binder resin and improving the charging stability of the toner during printing. The above is more preferable. Further, from the viewpoint of improving the rubbing fixability of the toner, it is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.5 μm or less. That is, taking these viewpoints together, the average particle size of the magnetic powder is preferably 0.02 to 3.0 μm, more preferably 0.02 to 2.5 μm, and even more preferably 0.05 to 2.0 μm.
磁性粉の含有量は、トナーの耐刷時の帯電安定性を向上させる観点から、結着樹脂100重量部に対して、0.5重量部以上が好ましく、1重量部以上がより好ましく、3重量部以上がさらに好ましく、4重量部以上がよりさらに好ましい。また、トナーの擦り定着性及び低温定着性を向上させる観点から、結着樹脂100重量部に対して、15重量部以下が好ましく、12重量部以下がより好ましく、10重量部以下がさらに好ましく、8重量部以下がよりさらに好ましい。すなわち、これらの観点を総合すると、磁性粉の含有量は、結着樹脂100重量部に対して、0.5〜15重量部が好ましく、1〜12重量部がより好ましく、3〜10重量部がさらに好ましく、4〜8重量部がよりさらに好ましい。 The content of the magnetic powder is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and 3 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of improving the charging stability of the toner during printing durability. The above is more preferable, and 4 parts by weight or more is even more preferable. Further, from the viewpoint of improving the rubbing fixing property and low temperature fixing property of the toner, it is preferably 15 parts by weight or less, more preferably 12 parts by weight or less, still more preferably 10 parts by weight or less, relative to 100 parts by weight of the binder resin. Even more preferably 8 parts by weight or less. That is, taking these viewpoints together, the content of the magnetic powder is preferably 0.5 to 15 parts by weight, more preferably 1 to 12 parts by weight, and further 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin. Preferably, 4 to 8 parts by weight is even more preferable.
ポリテトラフルオロエチレン粒子の含有量により、トナーの耐刷時の帯電安定性の程度が大きく異なる。また、詳細は明らかではないが、ポリテトラフルオロエチレン粒子と磁性粉の相互作用によって、トナーの耐刷時の帯電安定性が向上すると推定される。かかる観点から、ポリテトラフルオロエチレン粒子と磁性粉の重量比を制御することが好ましい。 Depending on the content of the polytetrafluoroethylene particles, the degree of charging stability of the toner during printing durability varies greatly. Although details are not clear, it is presumed that the charging stability of the toner during printing durability is improved by the interaction between the polytetrafluoroethylene particles and the magnetic powder. From this viewpoint, it is preferable to control the weight ratio between the polytetrafluoroethylene particles and the magnetic powder.
ポリテトラフルオロエチレン粒子と磁性粉の重量比(ポリテトラフルオロエチレン粒子／磁性粉)は、ポリテトラフルオロエチレン粒子をトナー母粒子に内添させる場合は、トナーの耐刷時の帯電安定性を向上させる観点、及びトナーの擦り定着性を向上させる観点から、70/30〜10/90が好ましく、50/50〜15/85がより好ましく、40/60〜20/80がさらに好ましい。 The weight ratio of polytetrafluoroethylene particles to magnetic powder (polytetrafluoroethylene particles / magnetic powder) improves the charging stability of the toner during printing durability when polytetrafluoroethylene particles are internally added to the toner base particles. From the viewpoints of improving the toner rubbing and fixing properties, the ratio is preferably 70/30 to 10/90, more preferably 50/50 to 15/85, and still more preferably 40/60 to 20/80.
また、ポリテトラフルオロエチレン粒子をトナー母粒子に外添させる場合、ポリテトラフルオロエチレン粒子と磁性粉の重量比(ポリテトラフルオロエチレン粒子／磁性粉)は、トナーの耐刷時の帯電安定性を向上させる観点、及びトナーの擦り定着性を向上させる観点から、30/70〜1/99が好ましく、15/85〜2/98がより好ましく、8/92〜3/97がさらに好ましい。 In addition, when polytetrafluoroethylene particles are externally added to the toner base particles, the weight ratio of the polytetrafluoroethylene particles to the magnetic powder (polytetrafluoroethylene particles / magnetic powder) determines the charging stability of the toner during printing durability. 30/70 to 1/99 is preferable, 15/85 to 2/98 is more preferable, and 8/92 to 3/97 is more preferable from the viewpoint of improving and improving the rubbing fixability of the toner.
本発明のトナーは、さらに離型剤及び荷電制御剤を含有していることが好ましい。 The toner of the present invention preferably further contains a release agent and a charge control agent.
離型剤としては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、カルナウバワックス、モンタンワックス、サゾールワックス及びそれらの脱酸ワックス、脂肪酸エステルワックス等のエステル系ワックス、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられる。これらのなかでは、トナーの低温定着性及び保存安定性を向上させる観点から、脂肪族炭化水素系ワックス及びエステル系ワックスが好ましく、同様の観点から、エステル系ワックスでは、カルナウバワックスがさらに好ましく、脂肪族炭化水素系ワックスでは、ポリプロピレンワックスが好ましい。これらは単独で又は2種以上を混合して用いられていてもよく、脂肪族炭化水素系ワックスとエステル系ワックスを併用するのが好ましい。 As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax and their oxides, carnauba wax, Examples thereof include montan wax, sazol wax and their deoxidized wax, ester waxes such as fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. Among these, aliphatic hydrocarbon waxes and ester waxes are preferable from the viewpoint of improving low-temperature fixability and storage stability of the toner. From the same viewpoint, carnauba wax is more preferable as the ester wax. Of the aliphatic hydrocarbon waxes, polypropylene wax is preferred. These may be used alone or in admixture of two or more, and it is preferable to use an aliphatic hydrocarbon wax and an ester wax in combination.
離型剤の含有量は、トナーのオフセット防止の観点と、トナーの流動性低下の防止の観点から、結着樹脂100重量部に対して、0.5〜4.0重量部が好ましく、1.0〜3.0重量部がより好ましく、1.8〜2.8重量部がさらに好ましい。 The content of the release agent is preferably 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoints of preventing toner offset and preventing toner fluidity from decreasing. Is more preferable, and 1.8 to 2.8 parts by weight is even more preferable.
荷電制御剤としては、特に限定されないが、負帯電性荷電制御剤としては、含金属アゾ染料、例えば「ボントロンS-28」(オリエント化学工業社製)、「T-77」(保土谷化学工業社製)、「ボントロンS-34」 (オリエント化学工業社製)、「アイゼンスピロンブラックTRH」(保土谷化学工業社製)等；銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、例えば「ボントロンE-81」、「ボントロンE-84」、「ボントロンE-304」(以上、オリエント化学工業社製)等；ニトロイミダゾール誘導体；ベンジル酸ホウ素錯体、例えば、「LR-147」(日本カーリット社製)等；無金属系荷電調整剤、例えば「ボントロンF-21」、「ボントロンE-89」(以上、オリエント化学工業社製)、「T-8」(保土ヶ谷化学工業社製)、「FCA-2521NJ」、「FCA-2508N」(以上、藤倉化成社製)等が挙げられる。 The charge control agent is not particularly limited. Examples of the negative charge control agent include metal-containing azo dyes such as “Bontron S-28” (manufactured by Orient Chemical Co., Ltd.), “T-77” (Hodogaya Chemical Co., Ltd.). , Bontron S-34 (Orient Chemical Co., Ltd.), “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes, metal complexes of salicylic acid alkyl derivatives, such as “Bontron” E-81 ”,“ Bontron E-84 ”,“ Bontron E-304 ”(manufactured by Orient Chemical Co., Ltd.), etc .; Nitroimidazole derivatives; Boron benzylate complexes, such as“ LR-147 ”(manufactured by Nippon Carlit Non-metallic charge control agents such as “Bontron F-21”, “Bontron E-89” (manufactured by Orient Chemical Co., Ltd.), “T-8” (Hodogaya Chemical Co., Ltd.), “FCA- 2521NJ, FCA-2508N (Fujikura Kasei Co., Ltd.) It is below.
正帯電性荷電制御剤としては、ニグロシン染料、例えば「ボントロンN-01」、「ボントロンN-04」、「ボントロンN-07」(以上、オリエント化学工業社製)、「CHUO CCA-3」(中央合成社製)等；3級アミンを側鎖として含有するトリフェニルメタン系染料；4級アンモニウム塩化合物、例えば「ボントロンP-51」(オリエント化学工業社製)、「TP-415」(保土谷化学工業社製)、セチルトリメチルアンモニウムブロミド、「COPYCHARGEPXVP435」(ヘキスト社製)等が挙げられる。 Examples of positively chargeable charge control agents include nigrosine dyes such as `` Bontron N-01 '', `` Bontron N-04 '', `` Bontron N-07 '' (above, manufactured by Orient Chemical Industries), `` CHUO CCA-3 '' ( Chuo Gosei Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains; Quaternary ammonium salt compounds such as “Bontron P-51” (Orient Chemical Industries), “TP-415” (Tsuchiya Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, “COPYCHARGEPXVP435” (Hoechst) and the like.
荷電制御剤の含有量は、トナーの耐刷時の帯電安定性を向上させる観点から、結着樹脂100重量部に対して、0.3重量部以上が好ましく、より好ましくは0.5重量部以上である。また、耐刷時の画像濃度を安定させる観点から、結着樹脂100重量部に対して、5重量部以下が好ましく、より好ましくは3重量部以下である。すなわち、これらの観点を総合すると、荷電制御剤の含有量は、結着樹脂100重量部に対して、0.3〜5重量部が好ましく、0.5〜3重量部がより好ましい。 The content of the charge control agent is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the binder resin, from the viewpoint of improving the charging stability of the toner during printing durability. Further, from the viewpoint of stabilizing the image density at the time of printing durability, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the binder resin. That is, taking these viewpoints together, the content of the charge control agent is preferably 0.3 to 5 parts by weight and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーには、さらに、流動性向上剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、クリーニング性向上剤等の添加剤が適宜含有されていてもよい。 The toner of the present invention further contains additives such as fluidity improvers, conductivity modifiers, extender pigments, reinforcing fillers such as fibrous substances, antioxidants, antioxidants, and cleaning improvers as appropriate. May be.
本発明のトナーは、溶融混練法、乳化転相法、重合法等の従来より公知のいずれの方法により得られたトナーであってもよいが、生産性や着色剤の分散性の観点から、溶融混練法による粉砕トナーが好ましい。具体的には、結着樹脂、着色剤、磁性粉、荷電制御剤、離型剤等の原料、さらにポリテトラフルオロエチレン粒子を内添させる場合には、ポリテトラフルオロエチレン粒子をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー、１軸もしくは２軸の押出機、オープンロール型混練機等で溶融混練し、冷却後、所定の体積中位粒径(Ｄ50)、粒度分布になるように、粉砕、分級を行ってトナー母粒子を製造することができる。一方、トナーの小粒径化の観点からは、重合法によるトナーが好ましい。 The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. Specifically, when adding raw materials such as a binder resin, a colorant, magnetic powder, a charge control agent, a release agent, and further polytetrafluoroethylene particles, the polytetrafluoroethylene particles are added to a Henschel mixer or the like. After mixing uniformly with a mixer, melt kneading with a closed kneader, a single or twin screw extruder, an open roll kneader, etc., and after cooling, a predetermined volume-median particle size (D 50 ), particle size distribution Thus, the toner base particles can be produced by pulverization and classification. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.
トナー母粒子の体積中位粒径(Ｄ50)は、画像品質を向上させる観点から、3〜15μmが好ましく、4〜12μmがより好ましい。なお、本明細書において、体積中位粒径(Ｄ50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になる粒径を意味する。 The volume median particle size (D 50 ) of the toner base particles is preferably 3 to 15 μm and more preferably 4 to 12 μm from the viewpoint of improving the image quality. In the present specification, the volume-median particle size (D 50 ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.
ポリテトラフルオロエチレン粒子をトナー母粒子の表面に外添させる場合は、粉砕、分級工程後、トナー母粒子とポリテトラフルオロエチレン粒子を混合し、トナー母粒子に樹脂粒子を付着させる。 When polytetrafluoroethylene particles are externally added to the surface of the toner base particles, the toner base particles and the polytetrafluoroethylene particles are mixed after the pulverization and classification steps, and the resin particles are adhered to the toner base particles.
また、ポリテトラフルオロエチレン粒子をトナー母粒子の表面に外添する際に、外添剤として無機粒子等をともに用いてもよい。 In addition, when polytetrafluoroethylene particles are externally added to the surface of the toner base particles, inorganic particles or the like may be used as external additives.
無機粒子としては、二酸化ケイ素(シリカ)、二酸化チタン、酸化アルミニウム、酸化亜鉛、酸化マグネシウム、酸化セリウム、酸化スズ等が挙げられ、帯電性付与の観点から、シリカ及び二酸化チタンが好ましく、シリカがより好ましい。また、無機粒子は、単独で、又は2種類以上を混合してもよく、帯電安定性の観点から2種類以上のシリカを混合するのが好ましい。 Examples of the inorganic particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, tin oxide, etc., and silica and titanium dioxide are preferable from the viewpoint of imparting charging properties, and silica is more preferable. preferable. Further, the inorganic particles may be used alone or in combination of two or more, and it is preferable to mix two or more types of silica from the viewpoint of charging stability.
トナー母粒子とポリテトラフルオロエチレン粒子等の外添剤を混合する際に用いられる混合機としては、ヘンシェルミキサー、スーパーミキサー等の高速攪拌機、Ｖ型ブレンダー等の乾式混合に用いる攪拌装置が好ましい。外添剤は、あらかじめ混合して高速攪拌機やＶ型ブレンダーに添加してもよく、また別々に添加してもよい。 As a mixer used when mixing toner base particles and external additives such as polytetrafluoroethylene particles, a high-speed stirrer such as a Henschel mixer or a super mixer, or a stirrer used for dry mixing such as a V-type blender is preferable. The external additives may be mixed in advance and added to a high-speed stirrer or a V-type blender, or may be added separately.
本発明のトナーは、非磁性一成分現像用トナーとして、もしくはキャリアと混合される二成分現像用トナーとして、特に限定されることなく、いずれの現像方法にも用いることができる。 The toner of the present invention is not particularly limited as a non-magnetic one-component developing toner or a two-component developing toner mixed with a carrier, and can be used in any developing method.
キャリアのコア材としては、公知の材料からなるものを特に限定することなく用いることができ、例えば、鉄、コバルト、ニッケル等の強磁性金属、マグネタイト、ヘマタイト、フェライト、銅-亜鉛-マグネシウムフェライト、マンガンフェライト、マグネシウムフェライト等の合金や化合物、ガラスビーズ等が挙げられ、これらの中では、帯電性の観点から、マグネタイト、フェライト、銅-亜鉛-マグネシウムフェライト及びマンガンフェライトが好ましい。 As the core material of the carrier, those made of known materials can be used without particular limitation, for example, ferromagnetic metals such as iron, cobalt, nickel, magnetite, hematite, ferrite, copper-zinc-magnesium ferrite, Examples thereof include alloys and compounds such as manganese ferrite and magnesium ferrite, and glass beads. Among these, magnetite, ferrite, copper-zinc-magnesium ferrite, and manganese ferrite are preferable from the viewpoint of chargeability.
キャリアの表面は、スペント防止の観点から樹脂で被覆されていてもよい。キャリア表面を被覆する樹脂としては、トナー材料により異なるが、例えばポリテトラフルオロエチレン、モノクロロトリフルオロエチレン重合体、ポリフッ化ビニリデン等のフッ素樹脂、ポリジメチルシロキサン等のシリコーン樹脂、ポリエステル、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、アミノアクリレート樹脂等が挙げられ、これらは単独であるいは２種以上を併用して用いることができるが、樹脂によるコア材の被覆方法は、例えば、樹脂等の被覆材を溶剤中に溶解もしくは懸濁させて塗布し、コア材に付着させる方法、単に粉体で混合する方法等、特に限定されない。 The surface of the carrier may be coated with a resin from the viewpoint of preventing spent. The resin that coats the carrier surface varies depending on the toner material. For example, fluororesin such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin such as polydimethylsiloxane, polyester, styrenic resin, Acrylic resin, polyamide, polyvinyl butyral, amino acrylate resin, etc. can be mentioned, and these can be used alone or in combination of two or more. There is no particular limitation such as a method in which the material is dissolved or suspended in a solvent and applied to the core material, or a method of simply mixing with powder.
トナーとキャリアとを混合して得られる二成分現像剤において、トナーの含有量は、現像剤の流動性及びカブリやダスト低減の観点から、キャリア100重量部に対して、0.5〜10重量部が好ましく、2〜8重量部がより好ましい。 In the two-component developer obtained by mixing the toner and the carrier, the toner content is 0.5 to 10 parts by weight with respect to 100 parts by weight of the carrier from the viewpoint of developer fluidity and reduction of fog and dust. Preferably, 2 to 8 parts by weight is more preferable.
〔樹脂の軟化点〕
フローテスター（島津製作所、CFT-500D）を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出す。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とする。
[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a 1.96 MPa load was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔樹脂のガラス転移点〕
示差走査熱量計(セイコー電子工業社製、DSC210)を用いて25℃から120℃まで昇温速度10℃／分で昇温し、吸熱の最高ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度とする。
[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature is increased from 25 ° C to 120 ° C at a rate of temperature increase of 10 ° C / min, and the baseline extension and peak rise below the maximum endothermic peak temperature. The temperature at the intersection with the tangent that indicates the maximum slope from the part to the peak apex.
〔樹脂の吸熱の最高ピーク温度及び融点〕
示差走査熱量計(ティー・エイ・インスツルメント・ジャパン社製、Q-100)を用いて、室温から降温速度10℃/分で0℃まで冷却した試料をそのまま１分間静止させ、その後昇温速度10℃/分で測定する。観測される吸熱ピークのうち、最も高温側にあるピークの温度を吸熱の最高ピーク温度とする。最高ピーク温度が軟化点と20℃以内の差であれば融点とし、軟化点との差が20℃を超えるピークはガラス転移に起因するピークとする。
[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., Q-100), the sample cooled from room temperature to 0 ° C at a temperature lowering rate of 10 ° C / min is left still for 1 minute, and then the temperature is raised Measure at a rate of 10 ° C / min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point is set, and the peak having a difference from the softening point exceeding 20 ° C. is a peak due to glass transition.
〔樹脂の酸価〕
JIS K0070の方法により測定する。但し、測定溶媒のみJIS K0070の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒(アセトン：トルエン＝1:1(容量比))に変更する。
[Acid value of the resin]
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
〔トナー母粒子の体積中位粒径（Ｄ50）〕
測定機：コールターマルチサイザーII（ベックマンコールター社製）
アパチャー径：50μm
解析ソフト：コールターマルチサイザーアキュコンプ バージョン 1.19（ベックマンコールター社製）
電解液：アイソトンII（ベックマンコールター社製）
分散液：エマルゲン109Ｐ（花王社製、ポリオキシエチレンラウリルエーテル、HLB：13.6）を5重量％の濃度となるよう前記電解液に溶解させて分散液を得る。
分散条件：前記分散液5mlに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mlを添加し、さらに、超音波分散機にて1分間分散させて、試料分散液を調製する。
測定条件：前記試料分散液を前記電解液100mlに加えることにより、3万個の粒子の粒径を20秒で測定できる濃度に調整した後、3万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ50）を求める。
[Volume Median Particle Size (D 50 ) of Toner Base Particles]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolytic solution to a concentration of 5% by weight to obtain a dispersion.
Dispersion conditions: 10 mg of a measurement sample is added to 5 ml of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 ml of an electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare a dispersion.
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 ml of the electrolyte solution, 30,000 particles are measured, Determine the volume median particle size (D 50 ).
〔ポリテトラフルオロエチレン粒子及び磁性粉の平均粒径〕
平均粒径とは、個数平均粒径のことである。
個数平均粒径は、走査型電子顕微鏡にて撮影倍率5000〜50000倍の適切な倍率で、粒径(長径と短径の平均値)を100個の粒子について測定し、それらの平均値を平均粒径とする。
[Average particle diameter of polytetrafluoroethylene particles and magnetic powder]
The average particle diameter is the number average particle diameter.
The number average particle size is measured with a scanning electron microscope at an appropriate magnification of 5000 to 50000 times, and the particle size (average value of major axis and minor axis) is measured for 100 particles, and the average value is averaged. The particle size.
非晶質ポリエステルの製造例１
ポリオキシプロピレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン2450g、ポリオキシエチレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン975g、テレフタル酸963g、ドデセニル無水コハク酸343ｇ、無水トリメリット酸289ｇ及びジブチル錫オキシド10gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃で反応率が90％に達するまで反応させた後、8.3kPaにて反応を行い、軟化点が150℃に達するまで反応させ、非晶質ポリエステル(樹脂Ａ)を得た。樹脂Ａの軟化点は150℃、吸熱の最高ピーク温度は72.1℃、(軟化点／吸熱の最高ピーク温度)比は2.08、ガラス転移点は64℃、酸価7.8mgKOH/gであった。なお、反応率とは、反応水量(mol)/理論生成水量(mol)×100の値をいう。
Production Example 1 of Amorphous Polyester
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2450 g, Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 975 g, terephthalic acid 963 g, dodecenyl succinic anhydride 343 g, trimellitic anhydride 289 g and dibutyltin oxide 10 g are put into a 10 liter four-necked flask equipped with a nitrogen inlet tube, dehydrating tube, stirrer and thermocouple, and the reaction rate is 230 ° C under a nitrogen atmosphere. After reacting until it reached 90%, the reaction was performed at 8.3 kPa, and the reaction was continued until the softening point reached 150 ° C. to obtain an amorphous polyester (resin A). Resin A had a softening point of 150 ° C., a maximum endothermic peak temperature of 72.1 ° C., a (softening point / maximum endothermic peak temperature) ratio of 2.08, a glass transition point of 64 ° C., and an acid value of 7.8 mgKOH / g. The reaction rate is a value of reaction water amount (mol) / theoretical water generation amount (mol) × 100.
非晶質ポリエステルの製造例２
ポリオキシプロピレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン3812g、ポリオキシエチレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン35g、テレフタル酸546g、及びジブチル錫オキシド10g、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃で反応率が90％に達するまで反応させた後、8.3kPaにて1時間反応を行った。その後、185℃に冷却し、フマル酸826ｇ及びターシャリブチルカテコール2.4gを投入し、210℃まで常圧で4時間かけて反応させた後、8.3kPaにて反応を行い、軟化点が104℃に達するまで反応させ、非晶質ポリエステル(樹脂Ｂ)を得た。樹脂Ｂの軟化点は104℃、吸熱の最高ピーク温度は70.3℃、(軟化点／吸熱の最高ピーク温度)比は1.48、ガラス転移点は60℃、酸価は11.5mgKOH/gであった。
Production Example 2 of Amorphous Polyester
3812 g polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 35 g polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 546 g terephthalic acid, and dibutyltin oxide 10 g, put into a 10-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, react at 230 ° C. in a nitrogen atmosphere until the reaction rate reaches 90%, then 8.3 kPa The reaction was carried out for 1 hour. Thereafter, the mixture was cooled to 185 ° C., 826 g of fumaric acid and 2.4 g of tertiary butyl catechol were added, reacted at 210 ° C. under normal pressure for 4 hours, then reacted at 8.3 kPa, and the softening point was 104 ° C. Until an amorphous polyester (resin B) was obtained. Resin B had a softening point of 104 ° C., a maximum endothermic peak temperature of 70.3 ° C., a (softening point / maximum endothermic peak temperature) ratio of 1.48, a glass transition point of 60 ° C., and an acid value of 11.5 mgKOH / g.
結晶性ポリエステルの製造例１
1,6-ヘキサンジオール2407g(20.4モル)、フマル酸2320g(20モル)、ハイドロキノン2.5g、及びジブチル錫オキシド10gを窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、窒素雰囲気下、130℃から160℃まで4時間かけて反応させた後、ポリプロピレンワックス(ハイワックスNP-105、三井化学社製)400gを添加し、200℃まで3時間かけて昇温し、200℃にて30分反応させた後、さらに8.3kPaにて反応を行い、軟化点が116℃に達するまで反応させ、結晶性ポリエステル(樹脂ａ)を得た。樹脂ａの軟化点は116℃、吸熱の最高ピーク温度は111℃、(軟化点／吸熱の最高ピーク温度)比は1.05であった。
Production Example 1 of Crystalline Polyester
1,6-hexanediol 2407 g (20.4 mol), fumaric acid 2320 g (20 mol), hydroquinone 2.5 g, and dibutyltin oxide 10 g were placed in a 10 liter volume equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple. Put into a one-necked flask and react for 4 hours from 130 ° C to 160 ° C under a nitrogen atmosphere, then add 400 g of polypropylene wax (High Wax NP-105, Mitsui Chemicals) and take it to 200 ° C over 3 hours. The temperature was raised and reacted at 200 ° C. for 30 minutes, followed by further reaction at 8.3 kPa until the softening point reached 116 ° C. to obtain a crystalline polyester (resin a). Resin a had a softening point of 116 ° C., a maximum endothermic peak temperature of 111 ° C., and a (softening point / maximum endothermic peak temperature) ratio of 1.05.
実施例Ａ１〜Ａ１０及び比較例１〜６、８、９
樹脂Ａ 60重量部、樹脂Ｂ 35重量部、樹脂ａ 5重量部、カーボンブラック「Regal 330R」(キャボット社製)7重量部、正帯電性荷電制御剤「ボントロン N-04」(オリエント化学工業社製)2重量部、ポリプロピレンワックス「NP-055」(三井化学社製)1重量部及びカルナバワックス「カルナバワックス C1」(加藤洋行社製)1.5重量部、表１に示す量のポリテトラフルオロエチレン(PTFE)粒子(比較例８、９以外の実施例及び比較例)、磁性粉(比較例１〜３、５以外の実施例及び比較例)及び負帯電性荷電制御剤(負ＣＣＡ)(比較例２のみ)を、ヘンシェルミキサーを用いて1分間予備混合した後、二軸押出機「PCM-87」(池貝鉄工社製)を用いて、原料のフィード量を2.5kg/min、スクリュー混練部の回転数を180r/minに調整し、溶融混練した。得られた溶融混練物をドラムフレーカーにより冷却し、カッターミルで体積中位粒径(Ｄ50)1.5〜2.5mmに粗紛砕した後、ジェットミルで微粉砕し、気流分級機で分級を行い、体積中位粒径(Ｄ50)が10μｍのトナー母粒子を得た。
Examples A1 to A10 and Comparative Examples 1 to 6, 8, and 9
60 parts by weight of resin A, 35 parts by weight of resin B, 5 parts by weight of resin a, 7 parts by weight of carbon black “Regal 330R” (manufactured by Cabot Corporation), positively chargeable charge control agent “Bontron N-04” (Orient Chemical Co., Ltd.) 2 parts by weight, 1 part by weight of polypropylene wax “NP-055” (manufactured by Mitsui Chemicals) and 1.5 parts by weight of carnauba wax “carnauba wax C1” (manufactured by Kato Yoko), polytetrafluoroethylene in the amounts shown in Table 1 (PTFE) particles (Examples and Comparative Examples other than Comparative Examples 8 and 9), magnetic powder (Examples and Comparative Examples other than Comparative Examples 1 to 3 and 5), and negative charge control agent (negative CCA) (Comparison Example 2 only) was premixed for 1 minute using a Henschel mixer, and then the feed rate of the raw material was 2.5 kg / min using a twin screw extruder “PCM-87” (manufactured by Ikekai Tekko Co., Ltd.) Was adjusted to 180 r / min and melt-kneaded. Melt-kneaded product obtained was cooled by a drum flaker, was roughly Muller the cutter volume median particle size (D 50) in a mill 1.5 to 2.5 mm, and finely pulverized with a jet mill, and classified by an air classifier Thus, toner mother particles having a volume median particle size (D 50 ) of 10 μm were obtained.
得られたトナー母粒子100重量部と、シリカ「ＨＤＫ3050」(クラリアント社製)0.35重量部とシリカ「TS720」(キャボット社製)0.1重量部とをヘンシェルミキサーで、1500r/minで3分間混合して、トナーを得た。 100 parts by weight of the obtained toner base particles, 0.35 parts by weight of silica “HDK3050” (manufactured by Clariant) and 0.1 parts by weight of silica “TS720” (manufactured by Cabot) are mixed with a Henschel mixer at 1500 r / min for 3 minutes. The toner was obtained.
実施例Ｂ１〜Ｂ４及び比較例７
樹脂Ａ 60重量部、樹脂Ｂ 35重量部、樹脂ａ 5重量部、カーボンブラック「Regal 330R」(キャボット社製)7重量部、正帯電性荷電制御剤「ボントロン N-04」(オリエント化学工業社製)2重量部、ポリプロピレンワックス「NP-055」(三井化学社製)1重量部及びカルナバワックス「カルナバワックス C1」(加藤洋行社製)1.5重量部及び表１に示す量の磁性粉(実施例のみ)を、ヘンシェルミキサーを用いて1分間予備混合した後、二軸押出機「PCM-87」(池貝鉄工社製)を用いて、原料のフィード量を2.5kg/min、スクリュー混練部の回転数を180r/minに調整し、溶融混練した。得られた溶融混練物をドラムフレーカーにより冷却し、カッターミルで体積中位粒径(Ｄ50)1.5〜2.5mmに粗紛砕した後、ジェットミルで微粉砕し、気流分級機で分級を行い、体積中位粒径(Ｄ50)が10μｍのトナー母粒子を得た。
Examples B1 to B4 and Comparative Example 7
60 parts by weight of resin A, 35 parts by weight of resin B, 5 parts by weight of resin a, 7 parts by weight of carbon black “Regal 330R” (manufactured by Cabot Corporation), positively chargeable charge control agent “Bontron N-04” (Orient Chemical Co., Ltd.) 2 parts by weight, 1 part by weight of polypropylene wax “NP-055” (manufactured by Mitsui Chemicals) and 1.5 parts by weight of carnauba wax “Carnauba wax C1” (manufactured by Kato Yoko) and magnetic powder in the amount shown in Table 1 Example only), premixed for 1 minute using a Henschel mixer, then using a twin screw extruder `` PCM-87 '' (manufactured by Ikekai Tekko Co., Ltd.), using a raw material feed rate of 2.5 kg / min, The rotational speed was adjusted to 180 r / min, and melt kneading was performed. The obtained melt-kneaded product is cooled by a drum flaker, coarsely pulverized to a volume median particle size (D 50 ) of 1.5 to 2.5 mm by a cutter mill, finely pulverized by a jet mill, and classified by an airflow classifier. Thus, toner mother particles having a volume median particle size (D 50 ) of 10 μm were obtained.
得られたトナー母粒子100重量部と、シリカ「ＨＤＫ3050」(クラリアント社製)0.35重量部及びシリカ「TS720」(キャボット社製)0.1重量部と、及び表１に示す量のポリテトラフルオロエチレン(PTFE)粒子とをヘンシェルミキサーで、1500r/minで3分間混合して、トナーを得た。 100 parts by weight of the obtained toner base particles, 0.35 parts by weight of silica “HDK3050” (manufactured by Clariant) and 0.1 parts by weight of silica “TS720” (manufactured by Cabot), and polytetrafluoroethylene in an amount shown in Table 1 PTFE) particles were mixed with a Henschel mixer at 1500 r / min for 3 minutes to obtain a toner.
実施例及び比較例で得られたトナー39重量部と、キャリア1261重量部とをナウターミキサーで混合し、二成分現像剤を得た。なお、キャリアは、Infoprint4100用現像剤(P/N:17R7726)からトナーとキャリアを分離しキャリアのみを得た。 39 parts by weight of toner obtained in Examples and Comparative Examples and 1261 parts by weight of carrier were mixed with a Nauta mixer to obtain a two-component developer. As the carrier, only the carrier was obtained by separating the toner and the carrier from the developer for Infoprint 4100 (P / N: 17R7726).
試験例１〔耐刷後の帯電量〕
接触現像方式の「Infoprint4000IS1」(日本アイビーエム株式会社：線速1066mm/sec、解像度240dpi、現像システム：3本マグネットロール、セレン感光体、反転現像)に、二成分現像剤を実装し、2.5cm四方のベタ画像を含む、黒化率が8％のプリントパターンを11×18インチの連続紙に、常温常湿(24℃・50RH％)の環境下で3000枚印刷した。3000枚印刷後の現像剤の帯電量を測定し、このときの帯電量を3000枚の帯電量とした。
Test Example 1 [Charge amount after printing]
A two-component developer is mounted on the contact development system "Infoprint4000IS1" (Japan IBM Co., Ltd .: linear speed 1066mm / sec, resolution 240dpi, development system: 3 magnet rolls, selenium photoreceptor, reversal development), 2.5cm square A print pattern containing a solid image of 8% black was printed on 11 × 18 inch continuous paper in an environment of normal temperature and humidity (24 ° C, 50RH%). The charge amount of the developer after printing 3000 sheets was measured, and the charge amount at this time was defined as the charge amount of 3000 sheets.
その後、Driver Routineで現像ロールのモーターのみ20時間回転させた後、2.5cm四方のベタ画像を含む、黒化率が8％のプリントパターンを11×18インチの連続紙に、常温常湿(24℃・50RH％)の環境下で3000枚印刷した。このときの帯電量を6000枚の帯電量とした。同様に、さらに３回繰り返して、15,000枚まで帯電量測定を繰り返した。帯電量と印刷枚数との関係を図１〜５に示す。 Then, after rotating only the developing roll motor for 20 hours with Driver Routine, a print pattern containing a solid image of 2.5 cm square and a blackening rate of 8% was printed on 11 x 18 inch continuous paper at room temperature and normal humidity (24 3000 sheets were printed in an environment of 50 ° C. The charge amount at this time was 6000 sheets. Similarly, the charge amount measurement was repeated up to 15,000 sheets by repeating three more times. The relationship between the charge amount and the number of printed sheets is shown in FIGS.
なお、帯電量の測定は、以下の方法により、実施例Ａ１〜Ａ１０、実施例Ｂ１〜Ｂ４、比較例１〜３、５〜７のトナーを用いた二成分現像剤について行った。 The charge amount was measured for the two-component developers using the toners of Examples A1 to A10, Examples B1 to B4, and Comparative Examples 1 to 3 and 5 to 7 by the following method.
〔帯電量の測定〕
Q/Mメーター(エッピング社製)を用いて測定する。
Q/Mメーター付属のセルに規定量の現像剤を投入し、目開き32μｍのメッシュ(ステンレス製、綾織、線径0.0035ｍｍ)を通してトナーのみを90秒間吸引する。そのとき発生するキャリア上の電圧変化をモニターし、90秒後の総電気量(μC)／吸引されたトナー量(g)の値を帯電量(μC/g)として算出する。
[Measurement of charge amount]
Measure using a Q / M meter (Epping).
A specified amount of developer is put into the cell attached to the Q / M meter, and only the toner is sucked through a mesh having a mesh size of 32 μm (stainless steel, twill weave, wire diameter 0.0035 mm) for 90 seconds. The voltage change on the carrier generated at that time is monitored, and the value of the total amount of electricity (μC) / the amount of attracted toner (g) after 90 seconds is calculated as the charge amount (μC / g).
かかる結果より、磁性粉を0.5重量部以上含有する実施例Ａ１〜Ａ１０及び実施例Ｂ１〜Ｂ４のトナーは、磁性粉を含まない比較例１、３、５、７のトナーや磁性粉を0.5重量部以上含まない比較例６のトナーに比べ、耐刷時の帯電量の安定性に優れていることが分かる。磁性粉の代わりに、負帯電性荷電制御剤を含有する比較例２のトナーでは、耐刷時の帯電量が安定していない。また、ポリテトラフルオロエチレン粒子を内添した実施例Ａ１〜Ａ１０のトナーの方が、ポリテトラフルオロエチレン粒子を外添した実施例Ｂ１〜Ｂ４のトナーよりも、耐刷時の帯電量の安定性に優れている。 From these results, the toners of Examples A1 to A10 and Examples B1 to B4 containing 0.5 parts by weight or more of magnetic powder are 0.5 weights of the toners and magnetic powders of Comparative Examples 1, 3, 5, and 7 that do not contain magnetic powder. It can be seen that the charge amount stability at the time of printing durability is excellent as compared with the toner of Comparative Example 6 which does not contain more than one part. In the toner of Comparative Example 2 containing a negatively chargeable charge control agent instead of magnetic powder, the charge amount at the time of printing durability is not stable. Further, the toners of Examples A1 to A10 in which polytetrafluoroethylene particles were internally added were more stable in charge amount during printing durability than the toners of Examples B1 to B4 in which polytetrafluoroethylene particles were externally added. Is excellent.
試験例２〔耐刷後の画像濃度〕
試験例１において、実施例Ａ１〜Ａ１０、実施例Ｂ１〜Ｂ４、比較例１〜３、５〜７のトナーを用いた二成分現像剤を用いて得られた3000枚目と9,000枚目の印字物の画像濃度を測定し、3,000枚目の印字物の画像濃度と9,000枚目の印字物の画像濃度を比較した。結果を表２Ａ、２Ｂに示す。なお、画像濃度は以下の方法で測定した。
Test Example 2 [Image density after printing]
In Test Example 1, the 3000th and 9,000th prints obtained using the two-component developers using the toners of Examples A1 to A10, Examples B1 to B4, and Comparative Examples 1 to 3 and 5 to 7 The image density of the printed matter was measured, and the image density of the 3,000th printed matter was compared with the image density of the 9,000th printed matter. The results are shown in Tables 2A and 2B. The image density was measured by the following method.
〔画像濃度の測定〕
「GretagSPM50」(Gretag社、絶対白キャリブレイション；Polフィルタ、観測視野：2℃、照明タイプ：＋、Wbase：Abs、Dstd：DIN NB、Sampleモード)を用いて4個の2.5cm四方黒ベタ部に対して、1個につき、5箇所の画像濃度を測定し、合計20箇所の画像濃度の測定した後、その平均値を画像濃度とする。
(Measurement of image density)
Four 2.5cm square black solid parts using "GretagSPM50" (Gretag, absolute white calibration; Pol filter, observation field: 2 ° C, illumination type: +, Wbase: Abs, Dstd: DIN NB, Sample mode) On the other hand, after measuring the image density at 5 locations for each image and measuring the image density at a total of 20 locations, the average value is taken as the image density.
以上の結果より、磁性粉を0.5重量部以上含有する実施例Ａ１〜Ａ１０、実施例Ｂ１〜Ｂ４のトナーは、磁性粉を含まない比較例１〜３、５、７のトナーや、磁性粉を0.5重量部以上含まない比較例６のトナーに比べ、耐刷時の画像濃度の安定性に優れていることが分かる。 From the above results, the toners of Examples A1 to A10 and Examples B1 to B4 containing 0.5 parts by weight or more of magnetic powder are the same as the toners of Comparative Examples 1 to 3, 5, and 7 that do not contain magnetic powder, and magnetic powder. It can be seen that the image density stability during printing durability is superior to the toner of Comparative Example 6 which does not contain 0.5 parts by weight or more.
試験例３〔擦り定着性〕
実施例Ａ１〜Ａ１０、実施例Ｂ１〜Ｂ４、比較例４、８、９のトナーを用いた二成分現像剤を用い、試験例１と同様にして3000枚の耐刷を行った。得られた3000枚目の印刷物を、金属ブレードを備えた擦り試験機にセットした。印刷用紙との接触面に日本アイ・ビー・エム株式会社製の高品質レーザー・プリンター専用連続用紙(HSP用紙 G 18×11インチ(連量55kg))の白紙を巻きつけ、3kgの荷重をかけた金属ブレードにより、黒ベタ部を20往復擦った。擦り前後の白紙の白色度を、「Gretag SPM50」(GretagMacbet社、絶対白キャリブレーション；Pol フィルタ、観察視野2℃、照明タイプ；＋、Wbase；Abs、Dstd；DIN NB、Sampleモード)を用いて測定し、その差(擦り後の白紙の白色度−擦り前の白紙の白色度)を定着強度の指標として算出し、擦り定着性を評価した。結果を表３に示す。
Test Example 3 [Rubbing Fixability]
Using two-component developers using the toners of Examples A1 to A10, Examples B1 to B4, and Comparative Examples 4, 8, and 9, 3000 sheets were printed in the same manner as in Test Example 1. The 3000th printed matter obtained was set in a rubbing tester equipped with a metal blade. Wrap a white paper of high quality laser printer-made continuous paper manufactured by IBM Japan Ltd. (HSP paper G 18 x 11 inches (55 kg)) on the contact surface with the printing paper and apply a load of 3 kg The black solid part was rubbed 20 times with a metal blade. Using “Gretag SPM50” (GretagMacbet, absolute white calibration; Pol filter, observation field of view 2 ° C., illumination type; +, Wbase; Abs, Dstd; DIN NB, Sample mode) The difference (whiteness of white paper after rubbing−whiteness of white paper before rubbing) was calculated as an index of fixing strength, and the rubbing fixability was evaluated. The results are shown in Table 3.
以上の結果から、ポリテトラフルオロエチレン粒子を内添した実施例Ａ１〜Ａ１０のトナーは、ポリテトラフルオロエチレン粒子を含まない比較例８、９のトナーや、ポリテトラフルオロエチレン粒子を含むが15重量部を超える磁性粉を含有する比較例４のトナーに比べ、擦り定着性に優れていることが分かる。また、ポリテトラフルオロエチレン粒子を外添した実施例Ｂ１〜Ｂ４のトナーも、ポリテトラフルオロエチレン粒子を含まない比較例８、９のトナーに比べ、擦り定着性に優れていることが分かる。 From the above results, the toners of Examples A1 to A10 in which polytetrafluoroethylene particles were internally added included the toners of Comparative Examples 8 and 9 that did not contain polytetrafluoroethylene particles, and the polytetrafluoroethylene particles contained 15% by weight. It can be seen that the rubbing and fixing properties are excellent as compared with the toner of Comparative Example 4 containing more than part of the magnetic powder. In addition, it can be seen that the toners of Examples B1 to B4, to which polytetrafluoroethylene particles are externally added, are superior in the rubbing fixability as compared with the toners of Comparative Examples 8 and 9 that do not contain polytetrafluoroethylene particles.
本発明の非磁性トナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に好適に用いられる。 The nonmagnetic toner of the present invention is suitably used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012220883A (en) * | 2011-04-13 | 2012-11-12 | Casio Electronics Co Ltd | Negatively chargeable decoloring electrophotographic toner and method for manufacturing the same |
| JP2015099351A (en) * | 2013-10-18 | 2015-05-28 | 花王株式会社 | Manufacturing method of positively-charged toner |
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| JPH07271090A (en) * | 1994-03-25 | 1995-10-20 | Matsushita Electric Ind Co Ltd | Magnetic toner, its production and electrophotographic method |
| JP2006235256A (en) * | 2005-02-25 | 2006-09-07 | Tomoegawa Paper Co Ltd | Toner for electrophotography and its manufacturing method |
| JP2007293242A (en) * | 2006-03-31 | 2007-11-08 | Tomoegawa Paper Co Ltd | Toner and two-component developer |
| JP2008139851A (en) * | 2006-11-02 | 2008-06-19 | Kao Corp | Electrophotographic toner |
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| JPS60166957A (en) * | 1983-10-07 | 1985-08-30 | Hitachi Metals Ltd | Developer of electrostatic charge image |
| JPH07271090A (en) * | 1994-03-25 | 1995-10-20 | Matsushita Electric Ind Co Ltd | Magnetic toner, its production and electrophotographic method |
| JP2006235256A (en) * | 2005-02-25 | 2006-09-07 | Tomoegawa Paper Co Ltd | Toner for electrophotography and its manufacturing method |
| JP2007293242A (en) * | 2006-03-31 | 2007-11-08 | Tomoegawa Paper Co Ltd | Toner and two-component developer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012220883A (en) * | 2011-04-13 | 2012-11-12 | Casio Electronics Co Ltd | Negatively chargeable decoloring electrophotographic toner and method for manufacturing the same |
| JP2015099351A (en) * | 2013-10-18 | 2015-05-28 | 花王株式会社 | Manufacturing method of positively-charged toner |
| US9470991B2 (en) | 2013-10-18 | 2016-10-18 | Kao Corporation | Method for producing positively chargeable toner |
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