JP2021047350A - toner - Google Patents
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- JP2021047350A JP2021047350A JP2019171059A JP2019171059A JP2021047350A JP 2021047350 A JP2021047350 A JP 2021047350A JP 2019171059 A JP2019171059 A JP 2019171059A JP 2019171059 A JP2019171059 A JP 2019171059A JP 2021047350 A JP2021047350 A JP 2021047350A
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- toner
- pigment
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- 239000002245 particle Substances 0.000 claims abstract description 163
- 239000000049 pigment Substances 0.000 claims abstract description 108
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000654 additive Substances 0.000 claims abstract description 54
- 230000000996 additive effect Effects 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 64
- 125000005647 linker group Chemical group 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000010419 fine particle Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004040 coloring Methods 0.000 abstract description 20
- 230000033228 biological regulation Effects 0.000 abstract description 11
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- -1 pn-dodecyl styrene Natural products 0.000 description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- 150000004665 fatty acids Chemical class 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 238000010558 suspension polymerization method Methods 0.000 description 5
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
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- 239000001294 propane Substances 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 239000001060 yellow colorant Substances 0.000 description 3
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 2
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- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
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- 150000005846 sugar alcohols Polymers 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical class C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、電子写真,静電荷像を顕像化するための画像形成方法に使用されるトナーに関する。 The present invention relates to toners used in image forming methods for visualizing electrophotographic and electrostatic charge images.
近年、電子写真法など静電潜像を経て画像情報を可視化する方法は、様々な分野で利用されており、さらなる高画質、高速といった性能面のみならず、複写機やプリンター、カートリッジの小型化や長寿命化といったユーザビリティの面での進化も求められている。
カートリッジの小型化や長寿命化のためのひとつの手段として、トナー一粒の着色力を向上させて、印刷時のトナー消費量を少なくする手法が考えられる。具体的には、トナーに含まれる顔料の量を増やす方法、トナー中の顔料分散を機械的に向上させる方法(特許文献1)、顔料分散剤などを用いトナー中の顔料分散を向上させる方法(特許文献2)などが報告されている。
一方、これらの手法を用いた場合、必然的にトナー表面近傍に存在する顔料の量が増えるため、トナー表面の帯電性均一性が損なわれ、カブリや規制不良といった画像不良が発生しやすくなるといった課題を抱えている。
In recent years, methods such as electrophotographic methods for visualizing image information via electrostatic latent images have been used in various fields, and not only in terms of performance such as higher image quality and higher speed, but also in miniaturization of copiers, printers, and cartridges. Evolution in terms of usability such as longevity and longevity is also required.
As one means for reducing the size and life of the cartridge, a method of improving the coloring power of a single toner grain to reduce the amount of toner consumed during printing can be considered. Specifically, a method of increasing the amount of pigment contained in the toner, a method of mechanically improving the pigment dispersion in the toner (Patent Document 1), and a method of improving the pigment dispersion in the toner by using a pigment dispersant or the like (Patent Document 1). Patent Document 2) and the like have been reported.
On the other hand, when these methods are used, the amount of pigment present in the vicinity of the toner surface inevitably increases, so that the uniformity of chargeability on the toner surface is impaired, and image defects such as fog and poor regulation are likely to occur. I have a problem.
上述の通り、従来の技術ではトナーの着色力を向上させた場合、カブリや規制不良がトレードオフとなり、両者の高次元での両立が達成できていなかった。
すなわち、本発明の目的は、カートリッジの小型化や長寿命化を指向し、着色力を向上させたトナーであっても、カブリや規制不良のない良好なトナー画像を形成し得るトナーを提供することである。
As described above, in the conventional technique, when the coloring power of the toner is improved, fog and improper regulation become trade-offs, and it has not been possible to achieve both at a high level.
That is, an object of the present invention is to provide a toner capable of forming a good toner image without fogging or improper regulation even if the toner has improved coloring power with the aim of reducing the size and extending the life of the cartridge. That is.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、以下のトナーにより解決することができることを見出した。
すなわち、本発明は、結着樹脂および顔料を含有するトナー粒子、及び外添剤Aを含有するトナーであって、
該トナー粒子は、透過型電子顕微鏡を用いた該トナーの断面観察において、該トナー粒子の表面から深さ0.1μmまでの表層領域における顔料の占める面積の割合をApsとしたとき、Apsが2.5%以上5.5%以下であり、
該外添剤Aは仕事関数Wsが5.70eV以下のシリカ粒子であり、
該トナー表面に対する、該外添剤Aの被覆率が1.0%以上15.0%以下であることを特徴とするトナーである。
As a result of diligent studies to solve the above problems, the present inventors have found that the following toners can be used.
That is, the present invention is a toner particle containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
The toner is characterized in that the coverage of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less.
本発明によれば、カートリッジの小型化や長寿命化を指向し着色力を向上させたトナーであっても、カブリや規制不良のない良好なトナー画像を形成し得るトナーを得ることができる。 According to the present invention, it is possible to obtain a toner capable of forming a good toner image without fogging or improper regulation even if the toner has improved coloring power with the aim of reducing the size and extending the life of the cartridge.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のトナーは、結着樹脂および顔料を含有するトナー粒子、及び外添剤Aを含有するトナーであって、
該トナー粒子は、透過型電子顕微鏡を用いた該トナーの断面観察において、該トナー粒子の表面から深さ0.1μmまでの表層領域における顔料の占める面積の割合をApsとしたとき、Apsが2.5%以上5.5%以下であり、
該外添剤Aは仕事関数Wsが5.70eV以下のシリカ粒子であり、
該トナー表面に対する、該外添剤Aの被覆率が1.0%以上15.0%以下であることを特徴とする。
The toner of the present invention is a toner particle containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
The coating ratio of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less.
本発明のトナーに用いられるトナー粒子は、高着色力化を指向し、顔料の添加量を増やす、顔料分散を強化するなどの手法が施されたトナー粒子である。 The toner particles used in the toner of the present invention are toner particles that have been subjected to techniques such as increasing the amount of pigment added and strengthening pigment dispersion in order to increase the coloring power.
トナー粒子中の顔料の存在状態を評価する一つの指標として、Apsが挙げられる。Apsとは、透過型電子顕微鏡を用いた該トナーの断面観察において、該トナー粒子の表面から深さ0.1μmまでの表層領域における顔料の占める面積の割合である。本発明のトナー粒子は、Apsが2.5%以上5.5%以下であることが必須である。Apsが上記の範囲内であることで、本発明の目的である着色力とカブリや規制不良が両立されたトナーを得ることができる。Apsが2.5%未満の場合、該トナー粒子中で顔料が凝集している、もしくは顔料が該トナー粒子中心部に偏在している、トナー表面に顔料の存在しないシェル層が存在していることを意味しており、いずれの場合でも着色力に劣る傾向にある。一方、Apsが5.5%よりも大きい場合は、該トナー粒子表面近傍に顔料が極度に偏在している、もしくは該トナー粒子中の顔料量が大過剰であることを意味しており、いずれの場合でも帯電均一性が著しく劣るため、本発明の如き外添剤による帯電均一化は困難である。 Aps can be mentioned as one index for evaluating the presence state of the pigment in the toner particles. Aps is the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm in the cross-sectional observation of the toner using a transmission electron microscope. It is essential that the toner particles of the present invention have an Aps of 2.5% or more and 5.5% or less. When Aps is within the above range, it is possible to obtain a toner in which the coloring power, which is the object of the present invention, and fog and improper regulation are compatible. When Aps is less than 2.5%, the pigment is agglomerated in the toner particles, or the pigment is unevenly distributed in the center of the toner particles, and a pigment-free shell layer is present on the toner surface. In any case, it tends to be inferior in coloring power. On the other hand, when Aps is larger than 5.5%, it means that the pigments are extremely unevenly distributed near the surface of the toner particles, or that the amount of pigments in the toner particles is excessive. Even in this case, the charge uniformity is remarkably inferior, so that it is difficult to make the charge uniform with an external additive as in the present invention.
より好ましいApsの範囲は、3.2%以上5.0%以下である。 A more preferable range of Aps is 3.2% or more and 5.0% or less.
本発明のトナーに用いられるトナー粒子は、上述のApsが2.5%以上5.5%以下であれば、粉砕法や乳化凝集法、溶解懸濁法、懸濁重合法などの公知の手法を用いて製造することができる。中でも、懸濁重合法、溶解懸濁重合法などの水系媒体中で造粒する工程を含む製造方法で製造することが、Aps制御が容易であることから好ましい。 The toner particles used in the toner of the present invention are known methods such as a pulverization method, an emulsion aggregation method, a dissolution suspension method, and a suspension polymerization method as long as the above-mentioned Aps is 2.5% or more and 5.5% or less. Can be manufactured using. Above all, it is preferable to produce by a production method including a step of granulating in an aqueous medium such as a suspension polymerization method and a dissolution suspension polymerization method because Aps control is easy.
懸濁重合法により製造される本発明のトナー粒子は、例えば下記のようにして製造される。着色剤組成物、重合性単量体、ワックス及び重合開始剤等を混合して重合性単量体組成物を調製する。次に、該重合性単量体組成物を水系媒体中に分散して重合性単量体組成物の粒子を造粒する。そして、水系媒体中にて重合性単量体組成物の粒子中の重合性単量体を重合させてトナー粒子を得る。 The toner particles of the present invention produced by the suspension polymerization method are produced, for example, as follows. A polymerizable monomer composition is prepared by mixing a colorant composition, a polymerizable monomer, a wax, a polymerization initiator and the like. Next, the polymerizable monomer composition is dispersed in an aqueous medium to granulate the particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.
重合性単量体としては、ラジカル重合が可能なビニル系重合性単量体が用いられる。ビニル系重合性単量体としては、単官能性重合性単量体或いは多官能性重合性単量体を使用することができる。単官能性重合性単量体としては、スチレン;α−メチルスチレン、β−メチルスチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、2,4−ジメチルスチレン、p−n−ブチルスチレン、p−tert−ブチルスチレン、p−n−ヘキシルスチレン、p−n−オクチルスチレン、p−n−ノニルスチレン、p−n−デシルスチレン、p−n−ドデシルスチレン、p−メトキシスチレン、p−フェニルスチレン等のスチレン誘導体;メチルアクリレート、エチルアクリレート、n−プロピルアクリレート、iso−プロピルアクリレート、n−ブチルアクリレート、iso−ブチルアクリレート、tert−ブチルアクリレート、n−アミルアクリレート、n−ヘキシルアクリレート、2−エチルヘキシルアクリレート、n−オクチルアクリレート、n−ノニルアクリレート、シクロヘキシルアクリレート、ベンジルアクリレート、ジメチルフォスフェートエチルアクリレート、ジエチルフォスフェートエチルアクリレート、ジブチルフォスフェートエチルアクリレート、2−ベンゾイルオキシエチルアクリレート等のアクリル系重合性単量体;メチルメタクリレート、エチルメタクリレート、n−プロピルメタクリレート、iso−プロピルメタクリレート、n−ブチルメタクリレート、iso−ブチルメタクリレート、tert−ブチルメタクリレート、n−アミルメタクリレート、n−ヘキシルメタクリレート、2−エチルヘキシルメタクリレート、n−オクチルメタクリレート、n−ノニルメタクリレート、ジエチルフォスフェートエチルメタクリレート、ジブチルフォスフェートエチルメタクリレート等のメタクリル系重合性単量体;メチレン脂肪族モノカルボン酸エステル;酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル、ギ酸ビニル等のビニルエステル;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エーテル;ビニルメチルケトン、ビニルヘキシルケトン、ビニルイソプロピルケトン等のビニルケトンなどが挙げられる。 As the polymerizable monomer, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p. Styrene derivatives such as −phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 Acrylic-based polymerizable properties such as -ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate. Monomer; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic polymerizable monomers such as n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, benzoate Vinyl esters such as vinyl acid acid and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone can be mentioned.
多官能性重合性単量体としては、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、1,6−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、2,2’−ビス(4−(アクリロキシ・ジエトキシ)フェニル)プロパン、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、1,3−ブチレングリコールジメタクリレート、1,6−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、2,2’−ビス(4−(メタクリロキシ・ジエトキシ)フェニル)プロパン、2,2’−ビス(4−(メタクリロキシ・ポリエトキシ)フェニル)プロパン、トリメチロールプロパントリメタクリレート、テトラメチロールメタンテトラメタクリレート、ジビニルベンゼン、ジビニルナフタリン、ジビニルエーテルなどが挙げられる。 Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol. Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxy diethoxy) phenyl) propane, trimethylpropan triacrylate, tetramethylolmethanetetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis ( 4- (methacryloxy diethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethyl propanetrimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalin, divinyl ether, etc. Can be mentioned.
単官能性重合性単量体は、単独で或いは2種以上組み合わせて、又は、多官能性重合性単量体と組み合わせて使用する。多官能性重合性単量体は架橋剤として使用することも可能である。 The monofunctional polymerizable monomer is used alone, in combination of two or more, or in combination with the polyfunctional polymerizable monomer. The polyfunctional polymerizable monomer can also be used as a cross-linking agent.
上記工程における重合性単量体組成物は、上記着色剤組成物を第1の重合性単量体に分散させた分散液を、第2の重合性単量体と混合して調製されたものであることが好ましい。即ち、上記着色剤組成物を第1の重合性単量体により十分に分散させた後で、他のトナー材料と共に第2の重合性単量体と混合することにより、顔料がより良好な分散状態でトナー粒子中に存在できる。 The polymerizable monomer composition in the above step is prepared by mixing a dispersion liquid in which the above-mentioned colorant composition is dispersed in a first polymerizable monomer with a second polymerizable monomer. Is preferable. That is, the pigment is better dispersed by sufficiently dispersing the colorant composition with the first polymerizable monomer and then mixing it with the second polymerizable monomer together with other toner materials. Can be present in the toner particles in the state.
重合性単量体の重合の際に用いられる重合開始剤としては、油溶性開始剤及び/又は水溶性開始剤が用いられる。油溶性開始剤としては、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−2,4−ジメチルバレロニトリル、1,1’−アゾビス(シクロヘキサン−1−カルボニトリル)、2,2’−アゾビス−4−メトキシ−2,4−ジメチルバレロニトリル等の顔料分散剤;アセチルシクロヘキシルスルホニルパーオキサイド、ジイソプロピルパーオキシカーボネート、デカノニルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、プロピオニルパーオキサイド、アセチルパーオキサイド、t−ブチルパーオキシ−2−エチルヘキサノエート、ベンゾイルパーオキサイド、t−ブチルパーオキシイソブチレート、シクロヘキサノンパーオキサイド、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド、t−ブチルヒドロパーオキサイド、ジ−t−ブチルパーオキサイド、クメンヒドロパーオキサイド等のパーオキサイド系開始剤が挙げられる。 As the polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator is used. Examples of the oil-soluble initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), and 2 , 2'-Azobis-4-methoxy-2,4-dimethylvaleronitrile and other pigment dispersants; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide , Acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide. , Di-t-butyl peroxide, cumene hydroperoxide and other peroxide-based initiators.
水溶性開始剤としては、過硫酸アンモニウム、過硫酸カリウム、2,2’−アゾビス(N,N’−ジメチレンイソブチロアミジン)塩酸塩、2,2’−アゾビス(2−アミノジノプロパン)塩酸塩、アゾビス(イソブチルアミジン)塩酸塩、2,2’−アゾビスイソブチロニトリルスルホン酸ナトリウム、硫酸第一鉄又は過酸化水素などが挙げられる。 Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, and 2,2'-azobis (2-aminodinopropane) hydrochloric acid. Examples thereof include salts, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.
また、重合性単量体の重合度を制御する為に、連鎖移動剤、重合禁止剤等を更に添加し用いることも可能である。 Further, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.
上記重合開始剤の濃度は、重合性単量体100質量部に対して0.1質量部以上20質量部以下の範囲である場合が好ましく、より好ましくは0.1質量部以上10質量部以下の範囲である場合である。上記重合性開始剤の種類は、重合法により若干異なるが、10時間半減温度を参考に、単独または混合して使用される。 The concentration of the polymerization initiator is preferably in the range of 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, and more preferably 0.1 parts by mass or more and 10 parts by mass or less. If it is in the range of. The type of the above-mentioned polymerizable initiator is slightly different depending on the polymerization method, but it is used alone or in combination with reference to the 10-hour half temperature.
更に、本発明においては、トナー粒子の耐ストレス性を高めると共に、上記粒子構成分子の分子量を制御するために、ビニル系重合体の合成時に架橋剤を用いることもできる。 Further, in the present invention, a cross-linking agent can be used at the time of synthesizing the vinyl polymer in order to enhance the stress resistance of the toner particles and control the molecular weight of the particle constituent molecules.
架橋剤としては、2個以上の重合可能な二重結合を有する化合物が用いられる。具体的には、ジビニルベンゼン、ジビニルナフタレンのような芳香族ジビニル化合物;エチレングリコールジアクリレート、エチレングリコールジメタクリレート、1,6−ヘキサンジオールジアクリルレート、1,3−ブタンジオールジメタクリレートのような二重結合を2個有するカルボン酸エステル;ジビニルアニリン、ジビニルエーテル、ジビニルスルフィド、ジビニルスルホン等のジビニル化合物;及び3個以上のビニル基を有する化合物が挙げられる。これらは単独もしくは混合物として用いられる。 As the cross-linking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylic rate, and dimethacrylate such as 1,3-butanediol dimethacrylate. Examples include carboxylic acid esters having two double bonds; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.
これらの架橋剤は、トナーの定着性、耐オフセット性の点で、上記単量体100質量部に対して、好ましくは0.05質量部以上10質量部以下の範囲、より好ましくは0.1質量部以上5質量部以下の範囲で用いることが良い。 In terms of toner fixability and offset resistance, these cross-linking agents preferably have a range of 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass, based on 100 parts by mass of the monomer. It is preferable to use in the range of mass part or more and 5 parts by mass or less.
重合性単量体や架橋剤は、単独、または理論ガラス転移温度(Tg)が、40℃以上75℃以下の範囲を示すように単量体を適宜混合して用いられる。理論ガラス転移温度が40℃以上の場合にはトナーの保存安定性や耐ストレス性の面から問題が生じ難く、一方75℃以下の場合はトナーのフルカラー画像形成の場合において透明性や低温定着性が低下しない。 The polymerizable monomer and the cross-linking agent are used alone or in an appropriate mixture so that the theoretical glass transition temperature (Tg) is in the range of 40 ° C. or higher and 75 ° C. or lower. When the theoretical glass transition temperature is 40 ° C or higher, problems are unlikely to occur in terms of toner storage stability and stress resistance, while when it is 75 ° C or lower, transparency and low-temperature fixability in the case of full-color image formation of toner. Does not decrease.
上記懸濁重合法で用いられる水系媒体は、分散安定化剤を含む水系媒体であることが好ましい。該分散安定化剤としては、公知の無機系及び有機系の分散安定化剤を用いることができる。無機系の分散安定化剤としては、例えば、リン酸カルシウム、リン酸マグネシウム、リン酸アルミニウム、リン酸亜鉛、炭酸マグネシウム、炭酸カルシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、メタケイ酸カルシウム、硫酸カルシウム、硫酸バリウム、ベントナイト、シリカ、アルミナ等が挙げられる。 The aqueous medium used in the suspension polymerization method is preferably an aqueous medium containing a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of the inorganic dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like.
有機系の分散安定化剤としては、例えば、ポリビニルアルコール、ゼラチン、メチルセルロース、メチルヒドロキシプロピルセルロース、エチルセルロース、カルボキシメチルセルロースのナトリウム塩、デンプン等が挙げられる。また、ノニオン性、アニオン性、カチオン性の界面活性剤の利用も可能である。例えば、ドデシル硫酸ナトリウム、テトラデシル硫酸ナトリウム、ペンタデシル硫酸ナトリウム、オクチル硫酸ナトリウム、オレイン酸ナトリウム、ラウリル酸ナトリウム、ステアリン酸カリウム、オレイン酸カルシウム等が挙げられる。 Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. It is also possible to use nonionic, anionic and cationic surfactants. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like can be mentioned.
上記分散安定化剤のうち、本発明においては、酸に対して可溶性のある難水溶性無機分散安定化剤を用いることが好ましい。また、本発明においては、難水溶性無機分散安定化剤を用い、水系分散媒体を調製する場合に、これらの分散安定化剤が重合性単量体100質量部に対して0.2質量部以上2.0質量部以下の範囲となるような割合で使用することが好ましい。このような範囲となる割合で使用することによって、重合性単量体組成物の水系媒体中での液滴安定性が向上するからである。また、本発明においては、重合性単量体組成物100質量部に対して300質量部以上3000質量部以下の範囲の水を用いて水系媒体を調製することが好ましい。 Among the above dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. Further, in the present invention, when a poorly water-soluble inorganic dispersion stabilizer is used to prepare an aqueous dispersion medium, these dispersion stabilizers are 0.2 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable to use at a ratio so as to be in the range of 2.0 parts by mass or less. This is because the use in a ratio within such a range improves the droplet stability of the polymerizable monomer composition in an aqueous medium. Further, in the present invention, it is preferable to prepare an aqueous medium using water in the range of 300 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer composition.
本発明において、上記難水溶性無機分散安定化剤が分散された水系媒体を調製する場合には、市販の分散安定化剤をそのまま用いて分散させても良い。しかし、細かい均一な粒度を有する分散安定化剤粒子を得るために、水中にて高速撹拌下に、上記難水溶性無機分散安定化剤を生成させて調製することが好ましい。例えば、リン酸カルシウムを分散安定化剤として使用する場合、高速撹拌下でリン酸ナトリウム水溶液と塩化カルシウム水溶液を混合してリン酸カルシウムの微粒子を形成することで、好ましい分散安定化剤を得ることができる。 In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is for dispersion. However, in order to obtain dispersion stabilizer particles having a fine and uniform particle size, it is preferable to prepare the above-mentioned poorly water-soluble inorganic dispersion stabilizer by producing it under high-speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring to form fine particles of calcium phosphate.
本発明のトナー粒子の着色剤としては、以下に示すブラック、イエロー、マゼンタ及びシアンの顔料を用いることができる。また必要に応じて染料を併せて用いることができる。 As the colorant for the toner particles of the present invention, the following black, yellow, magenta and cyan pigments can be used. In addition, a dye can be used together if necessary.
ブラック着色剤としては、公知のブラック着色剤を用いることができるが、中でもカーボンブラックが好ましい。 As the black colorant, a known black colorant can be used, but carbon black is particularly preferable.
カーボンブラックとしては、特に制限はないが、例えばサーマル法、アセチレン法、チャンネル法、ファーネス法、ランプブラック法等の製法により得られたカーボンブラックを用いることができる。 The carbon black is not particularly limited, and for example, carbon black obtained by a production method such as a thermal method, an acetylene method, a channel method, a furnace method, or a lamp black method can be used.
本発明に用いるカーボンブラックの平均一次粒径は、特に制限はないが、平均一次粒径が14nm以上80nm以下であることが好ましい。平均一次粒径が14nm以上の場合には、トナーは赤味を呈さず、フルカラー画像形成用のブラックとして好ましい。カーボンブラックの平均一次粒径が80nm以下の場合には、良好に分散しかつ着色力が低くなり過ぎず好ましい。 The average primary particle size of carbon black used in the present invention is not particularly limited, but it is preferable that the average primary particle size is 14 nm or more and 80 nm or less. When the average primary particle size is 14 nm or more, the toner does not exhibit redness and is preferable as black for forming a full-color image. When the average primary particle size of carbon black is 80 nm or less, it is preferable that the carbon black is well dispersed and the coloring power is not too low.
尚、カーボンブラックの平均一次粒径は、走査型電子顕微鏡で拡大した写真を撮影して測定することができる。 The average primary particle size of carbon black can be measured by taking an enlarged photograph with a scanning electron microscope.
上記カーボンブラックは単独で用いても良く、2種以上を混合しても良い。 The carbon black may be used alone or in combination of two or more.
これらは粗製顔料であっても良く、本発明の効果を著しく阻害するものでなければ調製された顔料組成物であっても良い。 These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly impair the effects of the present invention.
イエロー着色剤としては、公知のイエロー着色剤を用いることができる。 As the yellow colorant, a known yellow colorant can be used.
顔料系のイエロー着色剤としては、縮合多環系顔料、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に代表される化合物が用いられる。具体的には、C.I.Pigment Yellow3、7、10、12、13、14、15、17、23、24、60、62、74、75、83、93、94、95、99、100、101、104、108、109、110、111、117、123、128、129、138、139、147、148、150、155、166、168、169、177、179、180、181、183、185、191:1、191、192、193、199が挙げられる。 As the pigment-based yellow colorant, compounds typified by condensed polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azometal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 , 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193. 199 can be mentioned.
マゼンタ着色剤としては、公知のマゼンタ着色剤を用いることができる。 As the magenta colorant, a known magenta colorant can be used.
マゼンタ着色剤としては、縮合多環系顔料、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、ペリレン化合物が用いられる。具体的には、C.I.Pigment Red 2、3、5、6、7、23、48:2、48:3、48:4、57:1、81:1、122、146、150、166、169、177、184、185、202、206、220、221、238、254、269、C.I.Pigment Violet19が挙げられる。 As the magenta colorant, condensed polycyclic pigments, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 238, 254, 269, C.I. I. Pigment Violet19 can be mentioned.
シアン着色剤としては、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が用いられる。具体的には、C.I.Pigment Blue1、7、15、15:1、15:2、15:3、15:4、60、62、66が挙げられる。 As the cyan colorant, a phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
着色剤は、単独又は混合し更には固溶体の状態で用いることができる。 The colorant can be used alone or in a mixed state and further in a solid solution state.
顔料の添加量としては、該トナー粒子中の顔料の質量%が4.8質量%以上、Apsが5.5%以下になるように添加するのが着色力の観点から好ましい。 The amount of the pigment added is preferably such that the mass% of the pigment in the toner particles is 4.8% by mass or more and the Aps is 5.5% or less from the viewpoint of coloring power.
トナー中に顔料を分散させる手法としては、公知の顔料分散手法を用いることができ、これらの手法を単独あるいは組み合わせて用いることで、Apsを上述の範囲に制御することができる。 As a method for dispersing the pigment in the toner, a known pigment dispersion method can be used, and by using these methods alone or in combination, Aps can be controlled within the above range.
具体的には、前述の着色剤組成物を第1の重合性単量体に分散させる工程において分散の物理的な強度を上げる方法や、トナー構成材料に顔料分散剤を添加するなどの手法がある。 Specifically, a method of increasing the physical strength of the dispersion in the step of dispersing the above-mentioned colorant composition in the first polymerizable monomer, a method of adding a pigment dispersant to the toner constituent material, and the like are used. is there.
中でも、着色力向上並びにAps制御の観点から顔料分散剤を用いる方法が好ましい。使用できる顔料分散剤としては広く公知のものを使用でき、ポリマー成分と顔料に吸着する吸着成分を有し、前記吸着成分が下記一般式(1)で示される部分構造を有する顔料分散剤が、顔料への吸着効率およびトナー製造工程中での顔料再凝集抑制の観点からより好ましい。 Above all, a method using a pigment dispersant is preferable from the viewpoint of improving the coloring power and controlling Aps. As the pigment dispersant that can be used, a widely known pigment dispersant can be used, and a pigment dispersant having a polymer component and an adsorption component that adsorbs to the pigment, and the adsorption component has a partial structure represented by the following general formula (1) It is more preferable from the viewpoint of adsorption efficiency to the pigment and suppression of pigment reaggregation in the toner manufacturing process.
R4は、アルキル基、フェニル基、OR8基又はNR9R10基を表し、R8〜R10は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。R4がポリマー成分と結合する場合、単結合又は連結基を介して結合し、R4に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−O−、−NR6−及び−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R6は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
R5は、アルキル基、フェニル基、OR42基又はNR43R44基を表し、R42〜R44は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。R5がポリマー成分と結合する場合、連結基を介して結合し、R5に結合する連結基は、アルキレン基、フェニレン基、−O−、−NR11−、−NHCOC(CH3)2−及び−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R11は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Arは、アリール基を表し、Arがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Arに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−O−、−NR6−及び−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R6は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
前記単結合又は連結基が、R4、R5、又はArに結合する場合は、R4、R5、又はArの水素原子と置換して結合する。]
R 4 represents an alkyl group, a phenyl group, an OR 8 group or an NR 9 R 10 group, and R 8 to R 10 independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R 4 is bonded to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R 4 is an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, -O. It is a divalent linking group selected from the group consisting of −, −NR 6 − and −NHCH (CH 2 OH) −, and R 6 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
R 5 represents an alkyl group, a phenyl group, an OR 42 group or an NR 43 R 44 group, and R 42 to R 44 independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. If R 5 is bound to the polymer component, bonded through a linking group, the linking group attached to R 5 is an alkylene group, a phenylene group, -O -, - NR 11 - , - NHCOC (CH 3) 2 - It is a divalent linking group selected from the group consisting of −NHCH (CH 2 OH) −, and R 11 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to a polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, a divalent linking group selected from the group consisting of −O−, −NR 6− and −NHCH (CH 2 OH) −, where R 6 is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
The single bond or a linking group, R 4, R 5, or when attached to Ar is, R 4, R 5, or bonded substituted with Ar hydrogen atoms. ]
トナー粒子中の顔料分散状態を評価する指標として、クラーク・エバンス指数(CEI)が挙げられる。CEIは、該トナー粒子の断面観察において、全顔料粒子の最近接重心間距離の平均をr、ポアソン分布をしている顔料粒子の最近接重心間距離の期待値をE(r)としたとき、CEIは、CEI=r/E(r)と定義される。このCEIが1より小さい場合は集中分布(凝集度合いが大きい)、CEIが1に等しい場合はポアソン分布(ランダム分布)、CEIが1より大きい場合は規則分布(一定間隔に分布している)となる。CEIの限界値は2.1程度である。本発明のトナー粒子は、CEIが0.70以上1.30以下であることが好ましい。CEIが上記範囲であることで、着色力が良好なトナーを得ることができる。 The Clark Evans Index (CEI) is an index for evaluating the pigment dispersion state in the toner particles. CEI is when the average of the distances between the closest centers of gravity of all the pigment particles is r and the expected value of the distances between the closest centers of gravity of the pigment particles having a Poisson distribution is E (r) in the cross-sectional observation of the toner particles. , CEI is defined as CEI = r / E (r). When the CEI is less than 1, it is a concentrated distribution (the degree of aggregation is large), when the CEI is equal to 1, it is a Poisson distribution (random distribution), and when the CEI is larger than 1, it is a regular distribution (distributed at regular intervals). Become. The limit value of CEI is about 2.1. The toner particles of the present invention preferably have a CEI of 0.70 or more and 1.30 or less. When the CEI is in the above range, a toner having good coloring power can be obtained.
さらにトナー粒子中の顔料分散状態を評価する別の指標として、該トナー粒子中における分散顔料粒径が挙げられる。該トナー粒子の断面観察において、観察された顔料粒子のの円相当径(平均値)に対して4/πを乗じた数値が分散顔料粒径である。分散顔料粒径は、一次粒子だけではなく、凝集した顔料の塊を1つの粒径単位として算出している。よって一次粒子で良好に分散するほど、分散顔料粒径の数値は低くなる。本発明のトナー粒子は、分散顔料粒径が30nm以上130nm以下であることが好ましい。分散顔料粒径が上記範囲であることで、着色力が良好なトナーを得ることができる。 Further, as another index for evaluating the pigment dispersion state in the toner particles, the dispersed pigment particle size in the toner particles can be mentioned. In the cross-sectional observation of the toner particles, the value obtained by multiplying the observed circle-equivalent diameter (mean value) of the pigment particles by 4 / π is the dispersed pigment particle size. The dispersed pigment particle size is calculated not only for the primary particles but also for agglomerated pigment lumps as one particle size unit. Therefore, the better the dispersion in the primary particles, the lower the numerical value of the dispersed pigment particle size. The toner particles of the present invention preferably have a dispersed pigment particle size of 30 nm or more and 130 nm or less. When the dispersed pigment particle size is in the above range, a toner having good coloring power can be obtained.
本発明のトナー粒子は、一種以上のワックスを含有していることが好ましい。トナー中に含まれるワックスは総量で、トナー粒子100質量部中に2.5質量部以上25.0質量部以下含有されることが好ましい。また、トナー中に含まれるワックスの総量は、4.0質量部以上20質量部以下であることがより好ましく、6.0質量部以上18.0質量部以下であることがさらに好ましい。 The toner particles of the present invention preferably contain one or more waxes. The total amount of wax contained in the toner is preferably 2.5 parts by mass or more and 25.0 parts by mass or less in 100 parts by mass of the toner particles. The total amount of wax contained in the toner is more preferably 4.0 parts by mass or more and 20 parts by mass or less, and further preferably 6.0 parts by mass or more and 18.0 parts by mass or less.
ワックスとしては、以下のものが挙げられる。低分子量ポリエチレン、低分子量ポリプロピレン、マイクロクリスタリンワックス、フィッシャートロプッシュワックス、パラフィンワックスなどの脂肪族炭化水素系ワックス;酸化ポリエチレンワックスなどの脂肪族炭化水素系ワックスの酸化物、またはそれらのブロック共重合物;カルナバワックス、モンタン酸エステルワックスなどの脂肪酸エステルを主成分とするワックス類、及び脱酸カルナバワックスなどの脂肪酸エステル類を一部または全部を脱酸化したもの;パルミチン酸、ステアリン酸、モンタン酸などの飽和直鎖脂肪酸類;ブラシジン酸、エレオステアリン酸、パリナリン酸などの不飽和脂肪酸類;ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコールなどの飽和アルコール類;ソルビトールなどの多価アルコール類;リノール酸アミド、オレイン酸アミド、ラウリン酸アミドなどの脂肪酸アミド類;メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドなどの飽和脂肪酸ビスアミド類;エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、N,N’ジオレイルアジピン酸アミド、N,N’ジオレイルセバシン酸アミドなどの不飽和脂肪酸アミド類;m−キシレンビスステアリン酸アミド、N,N’ジステアリルイソフタル酸アミドなどの芳香族系ビスアミド類;ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムなどの脂肪族金属塩(一般に金属石けんといわれているもの);脂肪族炭化水素系ワックスにスチレンやアクリル酸などのビニル系モノマーを用いてグラフト化させたワックス類;ベヘニン酸モノグリセリドなどの脂肪酸と多価アルコールの部分エステル化物;植物性油脂の水素添加などによって得られるヒドロキシル基を有するメチルエステル化合物が挙げられる。 Examples of the wax include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystallin wax, Fishertropush wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax, or block copolymers thereof. Waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized fatty acid esters such as carnauba wax partially or wholly deoxidized; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brush diic acid, eleostearic acid, parinaphosphoric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melicyl alcohol; sorbitol Polyhydric alcohols such as; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide, etc. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'diorail adipic acid amide, N, N'diorail sebacic acid amide; m-xylene bisstea Aromatic bisamides such as acid amides, N, N'dystearyl isophthalic acid amides; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap); Waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; obtained by hydrogenation of vegetable fats and oils, etc. Examples thereof include methyl ester compounds having a hydroxyl group.
本発明のトナー粒子は、トナーの帯電性を環境によらず安定に保つために、荷電制御剤を用いてもよい。 For the toner particles of the present invention, a charge control agent may be used in order to keep the chargeability of the toner stable regardless of the environment.
負荷電性の荷電制御剤としては、以下のものが挙げられる。モノアゾ金属化合物、アセチルアセトン金属化合物、芳香族オキシカルボン酸、芳香族ダイカルボン酸、オキシカルボン酸及びダイカルボン酸系の金属化合物、芳香族オキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノール等のフェノール誘導体類、尿素誘導体、含金属サリチル酸系化合物、含金属ナフトエ酸系化合物、ホウ素化合物、4級アンモニウム塩、カリックスアレーン、樹脂系帯電制御剤が挙げられる。 Examples of the load-electric charge control agent include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, Examples thereof include phenol derivatives such as anhydrides, esters and bisphenols, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calix arene, and resin-based charge control agents.
正荷電性の荷電制御剤としては、以下のものが挙げられる。ニグロシン及び脂肪酸金属塩等によるニグロシン変性物;グアニジン化合物;イミダゾール化合物;トリブチルベンジルアンモニウム−1−ヒドロキシ−4−ナフトスルフォン酸塩、テトラブチルアンモニウムテトラフルオロボレート等の4級アンモニウム塩、及びこれらの類似体であるホスホニウム塩等のオニウム塩及びこれらのレーキ顔料;トリフェニルメタン染料及びこれらのレーキ顔料(レーキ化剤としては、りんタングステン酸、りんモリブデン酸、りんタングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フェリシアン化物、フェロシアン化物など);高級脂肪酸の金属塩;ジブチルスズオキサイド、ジオクチルスズオキサイド、ジシクロヘキシルスズオキサイド等のジオルガノスズオキサイド;ジブチルスズボレート、ジオクチルスズボレート、ジシクロヘキシルスズボレートの如きジオルガノスズボレート類;樹脂系帯電制御剤が挙げられる。 Examples of the positively charged charge control agent include the following. Nigrosine modified products with niglosin and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and their analogs. Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lake agents, phosphoric acid, phosphoric acid, phosphorus tungsten molybdic acid, tannic acid, lauric acid, galvanic acid) Acids, ferricyanides, ferrocyanides, etc.); Metal salts of higher fatty acids; Diorganosin oxides such as dibutyltin oxide, dioctylstinoxide, dicyclohexylstinoxide; Diorganosins such as dibutyltinborate, dioctylstinborate, dicyclohexylstinborate Borates; Resin-based charge control agents can be mentioned.
これらを単独で或いは2種類以上組み合わせて用いることができる。 These can be used alone or in combination of two or more.
中でも、樹脂系帯電制御剤以外の荷電制御剤としては、含金属サリチル酸系化合物が良く、特にその金属がアルミニウムもしくはジルコニウムのものが良い。特に好ましい制御剤は、サリチル酸アルミニウム化合物である。 Among them, as the charge control agent other than the resin-based charge control agent, a metal-containing salicylic acid-based compound is preferable, and a metal containing aluminum or zirconium is particularly preferable. A particularly preferred control agent is an aluminum salicylate compound.
樹脂系帯電制御剤としては、スルホン酸基、スルホン酸塩基又はスルホン酸エステル基、サリチル酸部位、安息香酸部位を有する重合体又は共重合体を用いることが好ましい。 As the resin-based charge control agent, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group, a salicylic acid moiety, and a benzoic acid moiety.
荷電制御剤の好ましい配合量は、重合性単量体100.00質量部に対して0.01質量部以上20.00質量部以下、より好ましくは0.05質量部以上10.00質量部以下である。 The preferable blending amount of the charge control agent is 0.01 part by mass or more and 20.00 parts by mass or less, more preferably 0.05 part by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the polymerizable monomer. Is.
本発明のトナー粒子は、上述の重合性単量体とは別に、種々の目的で樹脂を添加してもよい。添加できる樹脂として、以下に一例を挙げるがこれら以外のものでも構わない。例えば、ポリエステル樹脂、ポリカーボネート樹脂、フェノール樹脂、エポキシ樹脂、ポリアミド樹脂、セルロース樹脂などが挙げられる。 In the toner particles of the present invention, a resin may be added for various purposes in addition to the above-mentioned polymerizable monomer. Examples of the resin that can be added are described below, but other resins may be used. For example, polyester resin, polycarbonate resin, phenol resin, epoxy resin, polyamide resin, cellulose resin and the like can be mentioned.
本発明のトナーは上記トナー粒子に対して、外添剤Aを外添したトナーである。 The toner of the present invention is a toner obtained by externally adding an external additive A to the toner particles.
本発明のトナーに用いられる外添剤Aは、仕事関数Wsが5.70eV以下に制御されたシリカ粒子であることが必須である。Apsが制御されたトナー粒子に対して、該シリカ粒子を外添することで、本発明の目的である、着色力とカブリや規制不良の両立が達成できる。 The external additive A used in the toner of the present invention is essential to be silica particles having a work function Ws controlled to 5.70 eV or less. By externally adding the silica particles to the toner particles whose Aps are controlled, it is possible to achieve both the coloring power and the fog and poor regulation, which are the objects of the present invention.
本発明より得られるトナーに、このような効果が得られる詳細な理由は明確ではないが、本発明者らは次のように考えている。 Although the detailed reason why such an effect can be obtained with the toner obtained from the present invention is not clear, the present inventors consider as follows.
一般的に、トナーに用いられる顔料の仕事関数は、ポリエステルやスチレンアクリル樹脂といったトナーに好適に用いられる結着樹脂の仕事関数よりも小さい値である。そのため摩擦帯電した場合、表面近傍に顔料が存在する部位はよりポジに、表面近傍に顔料が存在しない部位はよりネガに帯電することとなり、一粒のトナー粒子内で帯電のムラが生じてしまう。そのため、前述のようにApsを高く制御し高着色力を狙ったトナーでは、カブリや規制不良に劣るといった傾向があった。 Generally, the work function of the pigment used for the toner is smaller than the work function of the binder resin preferably used for the toner such as polyester and styrene acrylic resin. Therefore, in the case of triboelectric charging, the portion where the pigment is present near the surface is more positively charged, and the portion where the pigment is not present near the surface is more negatively charged, resulting in uneven charging in one toner particle. .. Therefore, as described above, the toner with high control of Aps and aiming at high coloring power tends to be inferior in fog and improper regulation.
本発明によれば、このようなApsを高く制御し高着色力を狙ったトナーであっても、仕事関数を規定したシリカ粒子を外添することで、帯電のムラを均一化することが可能である。仕事関数Wsを5.70eV以下と低く制御した該シリカ粒子は、摩擦帯電した際、獲得した電荷を他の物質へと受け渡す能力を有する。該シリカ粒子を、Apsの高い該トナー粒子に外添したトナーは、該シリカ粒子から近接している表面近傍の顔料への電荷の受け渡しが起こる。それにより電荷を失った該シリカ粒子は、再び摩擦帯電する。その後、再帯電した該シリカ粒子から再び顔料への電荷の受け渡しが起こる。この電荷授受のプロセスがトナー粒子内の帯電のムラが均一化されるまで繰り返されるため、カブリや規制不良のない良好なトナー画像を形成し得るトナーを得ることができると筆者らは考えている。 According to the present invention, even with a toner aiming at high coloring power by controlling such Aps at a high level, it is possible to make uneven charging uniform by externally adding silica particles having a defined work function. Is. The silica particles whose work function Ws is controlled to be as low as 5.70 eV or less have an ability to transfer the acquired charge to another substance when it is triboelectrically charged. The toner in which the silica particles are externally attached to the toner particles having a high Aps causes an electric charge to be transferred from the silica particles to a pigment in the vicinity of the surface in the vicinity of the silica particles. The silica particles that have lost their charge as a result are triboelectrically charged again. After that, the electric charge is transferred from the recharged silica particles to the pigment again. Since this charge transfer process is repeated until the unevenness of charge in the toner particles is made uniform, the authors think that it is possible to obtain a toner capable of forming a good toner image without fogging or improper regulation. ..
該外添剤Aの仕事関数Wsが5.70eV超の場合には、該外添剤Aから顔料への電荷の受け渡しが起こらず、帯電のムラが均一化されず、本発明の効果が発現しない。 When the work function Ws of the external agent A exceeds 5.70 eV, the electric charge is not transferred from the external agent A to the pigment, the unevenness of the electric charge is not made uniform, and the effect of the present invention is exhibited. do not do.
該外添剤Aの仕事関数Wsのより好ましい範囲は、5.35eV以上5.70eV以下である。仕事関数が上記範囲であることで、最終的に該外添剤Aの保持する電荷量が大きくなるため、カブリなどの画像不良が起きにくくなる。 A more preferable range of the work function Ws of the external preparation A is 5.35 eV or more and 5.70 eV or less. When the work function is in the above range, the amount of electric charge held by the external additive A is finally increased, so that image defects such as fog are less likely to occur.
また、本発明のトナーに用いられる顔料の仕事関数をWpとしたとき、顔料と該外添剤Aの仕事関数の差 Ws−Wpは、0eV<Ws−Wp<1.0eVがより規制不良を抑制できるという観点から好ましい。0eV<Ws−Wpであることで、該外添剤Aから該顔料への電荷の受け渡しが過剰にならず、トナーの過帯電を抑制できる。Ws−Wp<1.0eVであることで、該顔料から該外添剤Aへの電荷の逆流が抑制でき帯電のムラがより改善される。 Further, when the work function of the pigment used in the toner of the present invention is Wp, the difference between the work function of the pigment and the external agent A Ws-Wp is 0 eV <Ws-Wp <1.0 eV, which is more regulated. It is preferable from the viewpoint that it can be suppressed. When 0 eV <Ws-Wp, the transfer of electric charge from the external additive A to the pigment is not excessive, and the overcharge of the toner can be suppressed. When Ws-Wp <1.0 eV, the backflow of electric charge from the pigment to the external preparation A can be suppressed, and the unevenness of electric charge is further improved.
本発明の効果を得るためには、該トナー表面に対する、該外添剤Aの被覆率が1.0%以上15.0%以下であることが必須である。被覆率が1.0%未満の場合には、該外添剤Aの量が少ないため、顔料と近接する確率が下がり、帯電のムラを均一化することができない。被覆率が15.0%より大きい場合には、外添剤による定着阻害が起きてしまう。 In order to obtain the effect of the present invention, it is essential that the coverage of the external additive A on the toner surface is 1.0% or more and 15.0% or less. When the coverage is less than 1.0%, the amount of the external additive A is small, so that the probability of being close to the pigment is reduced, and uneven charging cannot be made uniform. If the coverage is greater than 15.0%, fixation inhibition by the external additive will occur.
該外添剤Aとなるシリカ粒子としては、ゾルゲルシリカ粒子、水性コロイダルシリカ粒子、アルコール性シリカ粒子、気相法により得られるフュームドシリカ粒子、溶融シリカ粒子、爆燃シリカ粒子が挙げられる。その中でも、仕事関数制御の容易さからゾルゲルシリカ粒子が好ましい。ゾルゲルシリカ粒子の仕事関数は、該シリカ粒子の粒径制御、表面官能基量の制御によって調整できる。 Examples of the silica particles serving as the external additive A include solgel silica particles, aqueous colloidal silica particles, alcoholic silica particles, fumed silica particles obtained by the vapor phase method, molten silica particles, and explosive silica particles. Among them, sol-gel silica particles are preferable because of the ease of controlling the work function. The work function of the sol-gel silica particles can be adjusted by controlling the particle size of the silica particles and controlling the amount of surface functional groups.
該外添剤Aの表面は、疎水化処理が施されていることがよい。疎水化処理は、例えば疎水化処理剤に無機粒子を浸漬する等して行う。疎水化処理剤は特に制限されないが、例えば、アルキル基(例えばメチル基、エチル基、プロピル基、ブチル基等)を有する公知の有機珪素化合物が挙げられ、具体的には、例えば、シラザン化合物(例えば、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルクロロシラン、トリメチルメトキシシラン等のシラン化合物;ヘキサメチルジシラザン;テトラメチルジシラザン等)のシラン系カップリング剤が挙げられる。その中でも、ヘキサメチルジシラザンが好ましい。シリカ粒子の仕事関数は、この疎水化処理剤の処理量でも制御できる。 The surface of the external additive A is preferably hydrophobized. The hydrophobizing treatment is performed, for example, by immersing inorganic particles in a hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include known organic silicon compounds having an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). Examples thereof include silane coupling agents of silane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylchlorosilane and trimethylmethoxysilane; hexamethyldisilazane; tetramethyldisilazane and the like). Among them, hexamethyldisilazane is preferable. The work function of the silica particles can also be controlled by the treatment amount of this hydrophobizing agent.
該外添剤Aの疎水化度は40%以上65%以下であることが好ましい。該外添剤Aの疎水化度が上記範囲であることにより、規制不良抑制とカブリ抑制をより高いレベルで両立することができる。 The degree of hydrophobization of the external preparation A is preferably 40% or more and 65% or less. When the degree of hydrophobicity of the external additive A is within the above range, it is possible to achieve both suppression of poor regulation and suppression of fog at a higher level.
該外添剤Aの平均円相当径は10nm以上80nm以下であることが好ましい。該外添剤Aの平均円相当径が80nm以下であることにより、トナー表面における該外添剤Aの固着状態が均一となり本発明の効果をより効率的に得ることができる。 The average circle equivalent diameter of the external additive A is preferably 10 nm or more and 80 nm or less. When the average circle equivalent diameter of the external additive A is 80 nm or less, the adhered state of the external additive A on the toner surface becomes uniform, and the effect of the present invention can be obtained more efficiently.
該トナー粒子に外添剤Aを外添する手法は広く公知の方法を利用できる。 As a method of externally adding the external additive A to the toner particles, a widely known method can be used.
また、外添剤Aとは別に本発明を損なわない範囲で他の外添剤を外添してもよい。使用できる外添剤としては、酸化アルミニウム、酸化チタン、チタン酸ストロンチウム、酸化セリウム、酸化マグネシウム、酸化クロム、酸化錫、酸化亜鉛等の金属酸化物;窒化ケイ素等の窒化物;炭化物炭化ケイ素等の炭化物;硫酸カルシウム、硫酸バリウム、炭酸カルシウム等の無機金属塩;ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩;シリカなどが挙げられる。 Further, apart from the external additive A, another external additive may be externally added as long as the present invention is not impaired. Examples of the external additive that can be used include metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide; nitrides such as silicon nitride; carbides such as silicon carbide. Carbides; inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; silica and the like.
本発明のトナーの重量平均粒径(D4)は、4.0μm以上9.0μm以下であることが好ましい。より好ましくは5.0μm以上7.5μm以下である。 The weight average particle size (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less. More preferably, it is 5.0 μm or more and 7.5 μm or less.
トナーの重量平均粒径が4.0μm以上あると、トナーの流動性が良好であり、カブリや飛散、画像濃度薄等の弊害を引き起こし難くなる。また、感光体上や中間転写体上に残る転写残トナーのクリーニング性が良化し、感光体や中間転写体や帯電付与部材への汚染が生じ難い。また、9.0μm以下であると、微小文字等の細線再現性の悪化及び画像飛び散りの悪化を引き起こし難くなり、昨今望まれる高画質画像を供し得る。 When the weight average particle size of the toner is 4.0 μm or more, the fluidity of the toner is good, and it is difficult to cause adverse effects such as fog, scattering, and thin image density. In addition, the cleanability of the transfer residual toner remaining on the photoconductor and the intermediate transfer body is improved, and the photoconductor, the intermediate transfer body, and the charging member are less likely to be contaminated. Further, when it is 9.0 μm or less, it becomes difficult to cause deterioration of fine line reproducibility of fine characters and the like and deterioration of image scattering, and it is possible to provide a high-quality image which is desired these days.
以下、本発明に係る各種物性の測定方法について説明する。 Hereinafter, methods for measuring various physical properties according to the present invention will be described.
<Apsの測定>
トナー中の顔料分布状態は、トナー粒子の断面を透過型電子顕微鏡で観察し、顔料によって形成されたドメインの断面積からApsを算出し、任意に選択したトナー100個の平均値をもって評価する。
<Measurement of Aps>
The pigment distribution state in the toner is evaluated by observing the cross section of the toner particles with a transmission electron microscope, calculating Aps from the cross-sectional area of the domain formed by the pigment, and using the average value of 100 arbitrarily selected toners.
詳細には、トナーを可視光硬化性包埋樹脂(D−800、日新EM社製)で包埋し、超音波ウルトラミクロトーム(EM5、ライカ社製)により60nm厚に切削し、透過型電子顕微鏡(H7500、日立社製)により加速電圧120kVで観察を行う。観察するトナー断面は、重量平均粒子径から±2.0μm以内のものを100個選んで撮影を行う。得られた画像に画像処理ソフト(Photoshop 5.0、Adobe製)を用い、顔料のドメインと結着樹脂の領域の区別を明確化する。詳細には顔料のドメインは、以下のようにして区別することができる。画像処理ソフトにて、取りこんだTEM画像を明るさにより2値化する。このとき、トナーの顔料と光硬化性樹脂D800が明部になり、トナーの顔料以外が暗部となる。トナーの輪郭は、トナーと光硬化性樹脂の明暗で区別ができる。 Specifically, the toner is embedded in a visible light curable embedding resin (D-800, manufactured by Nissin EM), cut to a thickness of 60 nm by an ultrasonic ultramicrotome (EM5, manufactured by Leica), and a transmission electron electron is used. Observation is performed with a microscope (H7500, manufactured by Hitachi, Ltd.) at an acceleration voltage of 120 kV. Select 100 toner cross sections to be observed within ± 2.0 μm from the weight average particle size and take a picture. Image processing software (Photoshop 5.0, manufactured by Adobe) is used for the obtained image to clarify the distinction between the pigment domain and the binder resin region. In detail, the pigment domains can be distinguished as follows. The captured TEM image is binarized according to the brightness with image processing software. At this time, the toner pigment and the photocurable resin D800 are bright areas, and the areas other than the toner pigment are dark areas. The outline of the toner can be distinguished by the brightness of the toner and the light and darkness of the photocurable resin.
トナー粒子の断面における、トナー粒子表面(断面の輪郭)から深さ0.1μmまで(0。1μmの境界を含む)の表層領域を残しマスキングを行う。詳細には、トナー粒子断面の重心から、トナー粒子断面の輪郭上の点に対して線を引く。該線上において、輪郭から重心方向0.1μmの位置を特定する。そして、トナー粒子断面の輪郭に対して一周分、この操作を行い、トナー粒子断面の輪郭から0.1μmまでの表層領域を明示する。得られた表層領域の面積における顔料のドメインの占有面積百分率を算出し、これをApsとした。 Masking is performed on the cross section of the toner particles, leaving the surface layer region from the surface of the toner particles (outline of the cross section) to a depth of 0.1 μm (including the boundary of 0.1 μm). Specifically, a line is drawn from the center of gravity of the toner particle cross section with respect to a point on the contour of the toner particle cross section. On the line, a position 0.1 μm in the direction of the center of gravity is specified from the contour. Then, this operation is performed for one round of the contour of the toner particle cross section to clearly indicate the surface layer region from the contour of the toner particle cross section to 0.1 μm. The occupied area percentage of the pigment domain in the area of the obtained surface layer region was calculated and used as Aps.
<クラーク・エバンス指数(CEI)の測定>
上記Apsの測定方法において解析された画像より、全顔料粒子の最近接重心間距離の平均rを算出した。次にrより、ポアソン分布をした場合の顔料粒子の最近接重心間距離の期待値E(r)を算出した。CEI=r/E(r)の式より、CEIを算出した。
<Measurement of Clark Evans Index (CEI)>
The average r of the distances between the closest centers of gravity of all the pigment particles was calculated from the images analyzed by the above-mentioned measurement method of Aps. Next, from r, the expected value E (r) of the distance between the closest centers of gravity of the pigment particles in the case of Poisson distribution was calculated. The CEI was calculated from the formula CEI = r / E (r).
<分散顔料粒径の測定>
上記Apsの測定方法において解析された画像より、顔料の円相当径の平均値を算出した。この数値を4/πで乗じることにより分散顔料粒径を算出した。
<Measurement of dispersed pigment particle size>
The average value of the circle-equivalent diameters of the pigments was calculated from the images analyzed by the above-mentioned Aps measurement method. The dispersed pigment particle size was calculated by multiplying this value by 4 / π.
<外添剤の円相当径の測定>
シリカ粒子の一次粒子は以下のようにして算出した。
<Measurement of the equivalent circle diameter of the external additive>
The primary particles of the silica particles were calculated as follows.
日立超高分解能電界放出形走査電子顕微鏡S−4800((株)日立ハイテクノロジーズ)を用いてトナーを撮影する。続いて撮影されたトナー像を画像処理ソフト(Photoshop 5.0、Adobe製)に取り込み、一次粒子の画像解析によって粒子ごとの面積を測定し、この面積値から円相当径を算出する。この円相当径の算出をシリカ粒子100個について実施してその平均を平均円相当径とした。 Toner is photographed using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). Subsequently, the captured toner image is taken into image processing software (Photoshop 5.0, manufactured by Adobe), the area of each particle is measured by image analysis of the primary particles, and the equivalent circle diameter is calculated from this area value. This circle-equivalent diameter was calculated for 100 silica particles, and the average thereof was taken as the average circle-equivalent diameter.
<被覆率の測定>
トナー粒子表面における該外添剤Aの被覆率は、以下のようにして算出した。
<Measurement of coverage>
The coverage of the external additive A on the surface of the toner particles was calculated as follows.
まず、日立超高分解能電界放出形走査電子顕微鏡S−4800((株)日立ハイテクノロジーズ)を用いて、トナーを撮影する。続いて、撮影されたトナー表面画像を、画像解析ソフトImAge−Pro Plus ver.5.0((株)日本ローパー)を用いて解析し、被覆率を算出した。 First, the toner is photographed using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). Subsequently, the photographed toner surface image was obtained from the image analysis software ImAge-Pro Plus ver. Analysis was performed using 5.0 (Nippon Roper Co., Ltd.), and the coverage was calculated.
S−4800の画像撮影条件は以下のとおりである。 The image capturing conditions of S-4800 are as follows.
(1)試料作製
試料台(アルミニウム試料台15mm×6mm)に導電性ペーストを薄く塗り、その上にトナーを吹きつける。さらにエアブローして、余分なトナーを試料台から除去し十分乾燥させる。試料台を試料ホルダにセットし、試料高さゲージにより試料台高さを36mmに調節する。
(1) Sample preparation A thin layer of conductive paste is applied to a sample table (aluminum sample table 15 mm x 6 mm), and toner is sprayed onto the sample table. Further air blow to remove excess toner from the sample table and allow it to dry sufficiently. Set the sample table in the sample holder and adjust the sample table height to 36 mm with the sample height gauge.
(2)S−4800観察条件設定
固着率の測定に際して、予め、上述したエネルギー分散型X線分析(EDS)による元素分析を行い、トナー粒子表面の外添剤Aを区別した上で測定を行う。
(2) S-4800 Observation condition setting When measuring the adhesion rate, elemental analysis is performed in advance by the above-mentioned energy dispersive X-ray analysis (EDS), and the measurement is performed after distinguishing the external additive A on the surface of the toner particles. ..
S−4800の筺体に取り付けられているアンチコンタミネーショントラップに液体窒素を溢れるまで注入し、30分間置く。S−4800の「PC−SEM」を起動し、フラッシング(電子源であるFEチップの清浄化)を行う。画面上のコントロールパネルの加速電圧表示部分をクリックし、[フラッシング]ボタンを押し、フラッシング実行ダイアログを開く。フラッシング強度が2であることを確認し、実行する。フラッシングによるエミッション電流が20〜40μAであることを確認する。試料ホルダをS−4800筺体の試料室に挿入する。コントロールパネル上の[原点]を押し試料ホルダを観察位置に移動させる。 Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start up "PC-SEM" of S-4800 and perform flushing (cleaning of FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
加速電圧表示部をクリックしてHV設定ダイアログを開き、加速電圧を[1.1kV]、エミッション電流を[20μA]に設定する。オペレーションパネルの[基本]のタブ内にて、信号選択を[SE]に設置し、SE検出器を[上(U)]および[+BSE]を選択し、[+BSE]の右の選択ボックスで[L.A.100]を選択し、反射電子像で観察するモードにする。同じくオペレーションパネルの[基本]のタブ内にて、電子光学系条件ブロックのプローブ電流を[NormAl]に、焦点モードを[UHR]に、WDを[4.5mm]に設定する。コントロールパネルの加速電圧表示部の[ON]ボタンを押し、加速電圧を印加する。 Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box to the right of [+ BSE]. L. A. 100] is selected to set the mode for observing with a reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [NormAl], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.
(3)トナーの個数平均粒径(D1)算出
コントロールパネルの倍率表示部内をドラッグして、倍率を5000(5k)倍に設定する。操作パネルのフォーカスつまみ[COARSE]を回転させ、ある程度焦点が合ったところでアパーチャアライメントの調整を行う。コントロールパネルの[Align]をクリックし、アライメントダイアログを表示し、[ビーム]を選択する。操作パネルのSTIGMA/ALIGNMENTつまみ(X,Y)を回転し、表示されるビームを同心円の中心に移動させる。次に[アパーチャ]を選択し、STIGMA/ALIGNMENTつまみ(X,Y)を一つずつ回し、像の動きを止める又は最小の動きになるように合わせる。アパーチャダイアログを閉じ、オートフォーカスで、ピントを合わせる。この操作を更に2度繰り返し、ピントを合わせる。
(3) Calculation of Number of Toners Average Particle Size (D1) Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated twice more to focus.
その後、トナー300個について粒径を測定してトナーの個数平均粒径(D1)を求める。なお、個々の粒子の粒径は、トナーの粒子を観察した際の最大径とする。 Then, the particle size of 300 toners is measured to obtain the number average particle size (D1) of the toners. The particle size of each particle is the maximum diameter when the toner particles are observed.
(4)焦点調整
(3)で得た、トナーの個数平均粒径(D1)の±0.1μmの粒子について、最大径の中点を測定画面の中央に合わせた状態でコントロールパネルの倍率表示部内をドラッグして、倍率を10000(10k)倍に設定する。
(4) Focus adjustment For particles with an average particle size of toner (D1) of ± 0.1 μm obtained in (3), the magnification is displayed on the control panel with the midpoint of the maximum diameter aligned with the center of the measurement screen. Drag the inside of the part to set the magnification to 10000 (10k) times.
操作パネルのフォーカスつまみ[COARSE]を回転させ、ある程度焦点が合ったところでアパーチャアライメントの調整を行う。コントロールパネルの[Align]をクリックし、アライメントダイアログを表示し、[ビーム]を選択する。操作パネルのSTIGMA/ALIGNMENTつまみ(X,Y)を回転し、表示されるビームを同心円の中心に移動させる。 Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.
次に[アパーチャ]を選択し、STIGMA/ALIGNMENTつまみ(X,Y)を一つずつ回し、像の動きを止める又は最小の動きになるように合わせる。アパーチャダイアログを閉じ、オートフォーカスで、ピントを合わせる。その後、倍率を50,000(50k)倍に設定し、上記と同様にフォーカスつまみ、STIGMA/ALIGNMENTつまみを使用して焦点調整を行い、再度オートフォーカスでピントを合わせる。この操作を再度繰り返し、ピントを合わせる。 Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus.
ここで、観察面の傾斜角度が大きいと被覆率の測定精度が低くなりやすいので、ピント調整の際に観察面全体のピントが同時に合うものを選ぶことで、表面の傾斜が極力無いものを選択して解析する。 Here, if the inclination angle of the observation surface is large, the measurement accuracy of the coverage tends to be low, so by selecting the one that focuses on the entire observation surface at the same time when adjusting the focus, select the one with the least inclination of the surface. And analyze.
(5)画像保存
ABCモードで明るさ合わせを行い、サイズ640×480ピクセルで写真撮影して保存する。この画像ファイルを用いて下記の解析を行う。トナー一つに対して写真を1枚撮影し、トナー25粒子について画像を得る。
(5) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it. The following analysis is performed using this image file. One photograph is taken for each toner to obtain an image of 25 toner particles.
(6)画像解析
下記解析ソフトを用いて、上述した手法で得た画像を2値化処理することで固着率を算出する。このとき、上記一画面を正方形で12分割してそれぞれ解析する。
(6) Image analysis Using the following analysis software, the fixation rate is calculated by binarizing the image obtained by the above method. At this time, the above screen is divided into 12 squares and each is analyzed.
画像解析ソフトImAge−Pro Plus ver.5.0の解析条件は以下のとおりである。ただし、添加されている外添剤の個数平均粒径が不明なときは、下記のように粒径により測定対象を除外する。分割区画内に、粒径が10nm未満、及び、40nmを超えるシリカ粒子が入る場合はその区画では固着率の算出を行わないこととする。 Image analysis software ImAge-Pro Plus ver. The analysis conditions for 5.0 are as follows. However, when the average particle size of the added external additives is unknown, the measurement target is excluded according to the particle size as shown below. If silica particles having a particle size of less than 10 nm and more than 40 nm are contained in the divided compartment, the adhesion rate is not calculated in that compartment.
ツールバーの「測定」から「カウント/サイズ」、「オプション」の順に選択し、二値化条件を設定する。オブジェト抽出オプションの中で8連結を選択し、平滑化を0とする。その他、予め選別、穴を埋める、包括線は選択せず、「境界線を除外」は「なし」とする。ツールバーの「測定」から「測定項目」を選択し、面積の選別レンジに2〜107と入力する。 Select "Measurement"-"Count / Size"-"Options" on the toolbar and set the binarization conditions. Select 8 concatenations in the object extraction options and set the smoothing to 0. In addition, pre-selection, filling holes, and inclusive lines are not selected, and "exclude borders" is set to "none". Select "measurement items" from the "measurement" in the toolbar, type 2-10 7 to screen the range of the area.
固着率の計算は、正方形の領域を囲って行う。このとき、領域の面積(C)は24,000〜26,000ピクセルになるようにする。「処理」−2値化で自動2値化し、外添剤Aの無い領域の面積の総和(D)を算出する。 The sticking rate is calculated by enclosing a square area. At this time, the area (C) of the area is set to 24,000 to 26,000 pixels. "Treatment"-Automatically binarizes by binarization, and calculates the total area (D) of the area without the external additive A.
正方形の領域の面積C、外添剤Aの無い領域の面積の総和Dから下記式で外添剤Aが存在する領域が求められる。
外添剤Aによる被覆率(%)=100−(D/C×100)
From the total area D of the area C of the square area and the area without the external agent A, the area where the external agent A exists can be obtained by the following formula.
Coverage with external additive A (%) = 100- (D / C x 100)
得られた全データの算術平均値を被覆率とした。 The arithmetic mean value of all the obtained data was used as the coverage ratio.
<外添剤Aの分離>
トナーの表面から分離した外添剤Aを測定試料とする場合、外添剤Aのトナーからの分離は以下の手順で行う。
<Separation of external additive A>
When the external additive A separated from the surface of the toner is used as the measurement sample, the external additive A is separated from the toner according to the following procedure.
イオン交換水100mLにスクロース(キシダ化学製)160gを加え、湯せんをしながら溶解させて、ショ糖濃厚液を調製する。遠心分離用チューブに該ショ糖濃厚液31gと、6mLのコンタミノンN(非イオン界面活性剤、陰イオン界面活性剤、有機ビルダーからなるpH7の精密測定器洗浄用中性洗剤の10質量%水溶液、和光純薬工業社製)を入れ、分散液を作製する。この分散液にトナー1gを添加し、スパチュラなどでトナーのかたまりをほぐす。 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a sucrose concentrate. In a centrifuge tube, 31 g of the sucrose concentrate and 6 mL of Contaminone N (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) , Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
遠心分離用チューブを、いわき産業社製「KM ShAker」(model: V.SX)にセットし、1分当たり350往復の条件で20分間振とうする。振とう後、溶液をスイングローター用ガラスチューブ(50mL)に入れ替えて、遠心分離機にて、3500rpm、30分間の条件で遠心分離を行う。 The centrifuge tube is set in "KM ShAker" (model: VSX) manufactured by Iwaki Sangyo Co., Ltd., and shaken for 20 minutes under the condition of 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed with a centrifuge at 3500 rpm for 30 minutes.
遠心分離後のガラスチューブ内においては、最上層にはトナーが存在し、下層の水溶液側には外添剤が存在する。下層の水溶液を採取して、遠心分離を行い、ショ糖と、外添剤を分離する。必要に応じて、遠心分離を繰り返し行い、分離を十分に行った後、分散液を乾燥し、外添剤を採集する。 In the glass tube after centrifugation, the toner is present in the uppermost layer, and the external additive is present in the aqueous solution side of the lower layer. The aqueous solution of the lower layer is collected and centrifuged to separate sucrose and the external additive. If necessary, centrifuge is repeated, and after sufficient separation, the dispersion is dried and the external additive is collected.
この採集された外添剤から、遠心分離法を利用して外添剤Aと外添剤Bを選別する。外添剤A以外の外添剤が添加されている場合は、同様に遠心分離法によって選別する。 From this collected external additive, the external additive A and the external additive B are selected by using a centrifugation method. When an external additive other than the external additive A is added, the mixture is similarly sorted by the centrifugation method.
なお、外添前の外添剤Aを入手可能な場合は、外添剤単独で下記の方法により各種物性を測定・算出することもできる。 If the external preparation A before the external addition is available, various physical properties can be measured and calculated by the following method with the external addition alone.
<仕事関数の測定>
顔料および外添剤Aの仕事関数は、光電子分光装置(理研計器(株)製AC−2)を使用して測定した。サンプルを該装置測定用ホルダーに均一に広げて載置し、試料を励起するためのUV光源として重水素ランプを使用し、照射光量500mWに設定する。また分光器により単色光を選択し、スポットサイズ4mm角、エネルギー走査範囲3.4乃至6.2eV、測定時間10sec/1ポイントでサンプルに照射する。そして、サンプル表面から放出される光電子を検知し、仕事関数計ソフトを使用して演算処理され得られるものである。仕事関数に関しては、繰り返し精度(標準偏差)0.02eVで測定されるものである。
<Measurement of work function>
The work functions of the pigment and the external additive A were measured using a photoelectron spectrometer (AC-2 manufactured by RIKEN Keiki Co., Ltd.). The sample is uniformly spread and placed on the device measurement holder, a deuterium lamp is used as a UV light source for exciting the sample, and the irradiation light amount is set to 500 mW. In addition, monochromatic light is selected by a spectroscope, and the sample is irradiated with a spot size of 4 mm square, an energy scanning range of 3.4 to 6.2 eV, and a measurement time of 10 sec / 1 point. Then, the photoelectrons emitted from the sample surface are detected, and the work function meter software is used to perform arithmetic processing. The work function is measured with a repetition accuracy (standard deviation) of 0.02 eV.
<疎水化度の測定>
外添剤Aの疎水化度は、粉体濡れ性試験機「WET−100P」(レスカ社製)によって測定した。
<Measurement of hydrophobicity>
The degree of hydrophobization of the external additive A was measured by a powder wettability tester "WET-100P" (manufactured by Reska).
直径5cmおよび厚さ1.75mmの円筒型ガラス容器中に、フッ素樹脂コーティングされた長さ25mmおよび最大胴径8mmの紡錘型回転子を入れた。上記円筒型ガラス容器中にメタノール50体積%と水50体積%とからなる含水メタノール液70mlを入れた後、チタン酸金属微粒子0.5gを添加し、粉体濡れ性試験機にセットした。マグネティックスターラーを用いて、回転数3.3回/秒で撹拌しながら、上記粉体濡れ性試験機を通して、メタノールを0.8mL/分の速度で液中に添加した。波長780nmの光で透過率を測定し、透過率が50%に達した時のメタノールの体積百分率(=(メタノールの体積/混合物の体積)×100)により表される値を疎水化度とした。試料の疎水化度に応じて、最初のメタノールと水の体積比率は適宜調整する。 A fluororesin-coated spindle-shaped rotor having a length of 25 mm and a maximum body diameter of 8 mm was placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm. After putting 70 ml of a hydrous methanol solution consisting of 50% by volume of methanol and 50% by volume of water in the cylindrical glass container, 0.5 g of metal titanate fine particles were added and set in a powder wettability tester. Methanol was added to the liquid at a rate of 0.8 mL / min through the powder wettability tester while stirring at a rotation speed of 3.3 times / sec using a magnetic stirrer. The transmittance was measured with light having a wavelength of 780 nm, and the value represented by the volume percentage of methanol (= (volume of methanol / volume of mixture) × 100) when the transmittance reached 50% was defined as the degree of hydrophobicity. .. The volume ratio of initial methanol to water is adjusted as appropriate according to the degree of hydrophobization of the sample.
以下、本発明を実施例によりさらに具体的に説明する。本発明は、以下の実施例によって制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited by the following examples.
<顔料分散剤1の製造例>
(顔料分散剤のポリマー成分(P−1)の製造例)
プロピレングリコールモノメチルエーテル100質量部を窒素置換しながら加熱し液温120℃以上で還流させ、そこへ、スチレン156質量部、アクリル酸7.2質量部、アクリル酸ブチル9.6質量部、アクリル酸ステアリル48.7質量部(スチレン/アクリル酸/アクリル酸ブチル/アクリル酸ステアリル=60/4/30/6[mol比])、及びtert−ブチルパーオキシベンゾエート[有機過酸化物系重合開始剤、日油(株)製、商品名:パーブチルZ]1.25質量部を混合したものを3時間かけて滴下した。滴下終了後、溶液を3時間撹拌した後、液温170℃まで昇温しながら常圧蒸留し、液温170℃到達後は1hPAで減圧下1時間蒸留して脱溶剤し、樹脂固形物を得た。該固形物をテトラヒドロフランに溶解し、n−ヘキサンで再沈殿させて析出した固体を濾別することでポリマー成分(P−1)を得た。
<Production example of pigment dispersant 1>
(Production example of polymer component (P-1) of pigment dispersant)
100 parts by mass of propylene glycol monomethyl ether is heated while replacing with nitrogen and refluxed at a liquid temperature of 120 ° C. or higher, and 156 parts by mass of styrene, 7.2 parts by mass of acrylic acid, 9.6 parts by mass of butyl acrylate, and acrylic acid are added thereto. 48.7 parts by mass of stearyl (styrene / acrylic acid / butyl acrylate / stearyl acrylate = 60/4/30/6 [mol ratio]), and tert-butylperoxybenzoate [organic peroxide-based polymerization initiator, A mixture of 1.25 parts by mass of [Purbutyl Z] manufactured by Nichiyu Co., Ltd. was added dropwise over 3 hours. After completion of the dropping, the solution is stirred for 3 hours, distilled at atmospheric pressure while raising the liquid temperature to 170 ° C., and after the liquid temperature reaches 170 ° C., the solution is distilled at 1 hPA under reduced pressure for 1 hour to remove the solvent, and the resin solid is removed. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a polymer component (P-1).
(顔料吸着成分(B−1)の製造例)
続いて、一般式(1)に記載の顔料吸着成分(B−1)を、下記スキームに従い製造した。
(Production example of pigment adsorbing component (B-1))
Subsequently, the pigment adsorbing component (B-1) described in the general formula (1) was produced according to the following scheme.
まず、クロロホルム30質量部に4−ニトロアニリン(東京化成工業株式会社製)3.11質量部を加え、10℃以下に氷冷し、ジケテン(東京化成工業株式会社製)1.89質量部を加えた。その後、65℃で2時間撹拌した。反応終了後、クロロホルムで抽出し、濃縮して化合物(27)を得た。 First, 3.11 parts by mass of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 parts by mass of chloroform, and the mixture was ice-cooled to 10 ° C. or lower to add 1.89 parts by mass of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.). added. Then, the mixture was stirred at 65 ° C. for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain compound (27).
次に、2−アミノテレフタル酸ジメチル(メルク株式会社製)4.25質量部に、メタノール40.00質量部、濃塩酸5.29質量部を加えて10℃以下に氷冷した。この溶液に、亜硝酸ナトリウム2.10質量部を水6.00質量部に溶解させたもの加えて同温度で1時間反応させた。次いでスルファミン酸0.990質量部を加えて更に20分間撹拌した(ジアゾニウム塩溶液)。メタノール70.00質量部に、化合物(27)4.51質量部を加えて、10℃以下に氷冷し、前記ジアゾニウム塩溶液を加えた。その後、酢酸ナトリウム5.83質量部を水7.00質量部に溶解させたものを加えて、10℃以下で2時間反応させた。反応終了後、水300.00質量部を加えて30分間撹拌した後、固体を濾別し、N,N−ジメチルホルムアミドからの再結晶法により精製することで化合物(28)を得た。次に、N,N−ジメチルホルムアミド150.00質量部に化合物(28)8.58質量部及びパラジウム−活性炭素(パラジウム5%)0.40質量部を加えて、水素ガス雰囲気下(反応圧力0.1乃至0.4MPA)、40℃で3時間撹拌した。反応終了後、溶液を濾別し、濃縮して化合物(B−1)を得た。 Next, 40.00 parts by mass of methanol and 5.29 parts by mass of concentrated hydrochloric acid were added to 4.25 parts by mass of dimethyl 2-aminoterephthalate (manufactured by Merck Group), and the mixture was ice-cooled to 10 ° C. or lower. To this solution, 2.10 parts by mass of sodium nitrite dissolved in 6.00 parts by mass of water was added, and the mixture was reacted at the same temperature for 1 hour. Then, 0.990 parts by mass of sulfamic acid was added, and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts by mass of compound (27) was added to 70.00 parts by mass of methanol, ice-cooled to 10 ° C. or lower, and the diazonium salt solution was added. Then, 5.83 parts by mass of sodium acetate dissolved in 7.00 parts by mass of water was added, and the mixture was reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300.00 parts by mass of water was added and the mixture was stirred for 30 minutes, and then the solid was separated by filtration and purified by the recrystallization method from N, N-dimethylformamide to obtain compound (28). Next, 8.58 parts by mass of compound (28) and 0.40 parts by mass of palladium-activated carbon (palladium 5%) were added to 150.00 parts by mass of N, N-dimethylformamide under a hydrogen gas atmosphere (reaction pressure). 0.1 to 0.4 MPa), stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered off and concentrated to give compound (B-1).
(顔料分散剤1の製造例)
次に、アゾ骨格部分構造である化合物(B−1)のアミノ基とポリマー成分(P−1)のカルボキシル基をアミド化により結合して顔料分散剤1を下記スキームに従い、製造した。
(Production Example of Pigment Dispersant 1)
Next, the amino group of the compound (B-1) having an azo skeleton partial structure and the carboxyl group of the polymer component (P-1) were bonded by amidation to produce a pigment dispersant 1 according to the following scheme.
まず、テトラヒドロフラン500.00質量部に化合物(B−1)を1.98質量部加えて、80℃まで加熱し溶解した。溶解後50℃に温度を下げ、ポリマー成分(P−1)37.50質量部を加えて溶解し、1−エチル−3−(3−ジメチルアミノプロピル)カルボジイミド・塩酸塩(EDC・HCl)1.96質量部を加えて50℃で5時間撹拌した後、液温を徐々に室温に戻し、一晩撹拌することにより反応を完結させた。反応終了後、溶液を濾過して濃縮し、メタノールで再沈殿させることにより精製し、顔料分散剤1を得た。 First, 1.98 parts by mass of compound (B-1) was added to 500.00 parts by mass of tetrahydrofuran, and the mixture was heated to 80 ° C. and dissolved. After dissolution, the temperature is lowered to 50 ° C., 37.50 parts by mass of the polymer component (P-1) is added and dissolved, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide / hydrochloride (EDC / HCl) 1 After adding .96 parts by mass and stirring at 50 ° C. for 5 hours, the liquid temperature was gradually returned to room temperature, and the reaction was completed by stirring overnight. After completion of the reaction, the solution was filtered, concentrated, and purified by reprecipitation with methanol to obtain a pigment dispersant 1.
<ポリエステル樹脂Aの製造例>
撹拌器、温度計、流出用冷却機を備えた反応装置にプロピレンオキサイド変性ビスフェノールA(2モル付加物)20質量部、プロピレンオキサイド変性ビスフェノールA(3モル付加物)80質量部、テレフタル酸20質量部、イソフタル酸20質量部およびテトラブトキシチタン0.50質量部を入れ、190℃でエステル化反応を行った。その後、無水トリメリット酸(TMA)1質量部を加え、220℃に昇温すると共に系内を徐々に減圧し、150Paで重縮合反応を行い、ポリエステル樹脂Aを得た。ポリエステル樹脂Aの酸価は12mg/KOH、軟化点は110℃であった。
<Production example of polyester resin A>
20 parts by mass of propylene oxide-modified bisphenol A (2 mol adduct), 80 parts by mass of propylene oxide-modified bisphenol A (3 mol adduct), 20 parts by mass of terephthalic acid in a reactor equipped with a stirrer, a thermometer, and an outflow cooler. 20 parts by mass of isophthalic acid and 0.50 parts by mass of tetrabutoxytitanium were added, and the esterification reaction was carried out at 190 ° C. Then, 1 part by mass of trimellitic anhydride (TMA) was added, the temperature was raised to 220 ° C., the pressure inside the system was gradually reduced, and a polycondensation reaction was carried out at 150 Pa to obtain a polyester resin A. The acid value of the polyester resin A was 12 mg / KOH, and the softening point was 110 ° C.
<顔料>
顔料に関しては、表1に記載のものを用いた。
<Pigment>
As for the pigments, those shown in Table 1 were used.
<トナー粒子1の製造>
(水系媒体の調製)
・イオン交換水 1000.0質量部
・リン酸ナトリウム 14.0質量部
・10%塩酸 4.5質量部
上記材料を、T.K.ホモミクサー(特殊機化工業株式会社製)を用いて、12000rpmにて撹拌し混合物を得た。得られた混合物は窒素パージしながら65℃で60分間保温した。次に、イオン交換水10質量部に8質量部の塩化カルシウムを溶解した塩化カルシウム水溶液を該混合物に一括投入し、分散剤を含む水系媒体を調製した。調製された水系媒体のpHは5.5であった。
<Manufacturing of toner particles 1>
(Preparation of aqueous medium)
-Ion-exchanged water 1000.0 parts by mass-Sodium phosphate 14.0 parts by mass-10% hydrochloric acid 4.5 parts by mass K. A mixture was obtained by stirring at 12000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). The resulting mixture was kept warm at 65 ° C. for 60 minutes while purging with nitrogen. Next, an aqueous solution of calcium chloride in which 8 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was collectively added to the mixture to prepare an aqueous medium containing a dispersant. The pH of the prepared aqueous medium was 5.5.
(顔料分散液1の調製:顔料分散工程)
・スチレン 60.0質量部
・顔料1(カーボンブラック) 8.0質量部
・帯電制御剤(オリヱント化学工業社製:ボントロンE−88) 0.5質量部
・顔料分散剤1 0.8質量部
上記材料及び直径1.7mmのジルコニア粒子をアトライタ(三井三池化工機株式会社)に投入し、220rpmで5時間混合することで、スチレン中に着色剤及び帯電制御剤を分散した。分散後にジルコニア粒子を分離して顔料分散液1を作製した。
(Preparation of Pigment Dispersion Solution 1: Pigment Dispersion Step)
・ Styrene 60.0 parts by mass ・ Pigment 1 (carbon black) 8.0 parts by mass ・ Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 0.5 parts by mass ・ Pigment dispersant 1 0.8 parts by mass The above materials and zirconia particles having a mass of 1.7 mm were put into an attritor (Mitsui Miike Kakoki Co., Ltd.) and mixed at 220 rpm for 5 hours to disperse a colorant and a charge control agent in styrene. After the dispersion, the zirconia particles were separated to prepare a pigment dispersion liquid 1.
(重合性単量体組成物1の調製)
・スチレン 15.0質量部
・n−ブチルアクリレート(n−BA) 25.0質量部
・ポリエステル樹脂A 6.0質量部
上記材料を混合し、2時間撹拌して、ポリエステル樹脂Aを溶解し、重合性単量体組成物1を得た。
(Preparation of Polymerizable Monomer Composition 1)
15.0 parts by mass of styrene ・ 25.0 parts by mass of n-butyl acrylate (n-BA) ・ 6.0 parts by mass of polyester resin A The above materials were mixed and stirred for 2 hours to dissolve the polyester resin A. A polymerizable monomer composition 1 was obtained.
(重合性単量体組成物2の調製)
顔料分散液1及び重合性単量体組成物1を混合した後、下記材料を添加した。
・炭化水素ワックス(融点:77℃) 10.0質量部
・ジビニルベンゼン 0.02質量部
(Preparation of Polymerizable Monomer Composition 2)
After mixing the pigment dispersion 1 and the polymerizable monomer composition 1, the following materials were added.
-Hydrocarbon wax (melting point: 77 ° C) 10.0 parts by mass-Divinylbenzene 0.02 parts by mass
添加後、混合しながら、65℃に加温した。65℃で30分間、保温しながらT.K.ホモミクサー(特殊機化工業株式会社製)を用いて、500rpmにて均一に溶解して重合性単量体組成物2を得た。 After the addition, it was heated to 65 ° C. while mixing. While keeping warm at 65 ° C. for 30 minutes, T.I. K. A polymerizable monomer composition 2 was obtained by uniformly dissolving at 500 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).
(造粒/重合工程)
得られた重合性単量体組成物2を上記水系媒体中に投入した。次いで、重合開始剤t−ブチルパーオキシピバレート(25%トルエン溶液)10.0質量部を添加し、65℃、窒素パージ下において、T.K.ホモミクサー(特殊機化工業株式会社製)にて10000rpmで5分間撹拌し、pH5.5で造粒した。その後、パドル撹拌翼で撹拌しつつ70℃に昇温し、撹拌しながら5時間反応した。
(Granulation / polymerization process)
The obtained polymerizable monomer composition 2 was put into the above-mentioned aqueous medium. Next, 10.0 parts by mass of the polymerization initiator t-butylperoxypivalate (25% toluene solution) was added, and T.I. K. The mixture was stirred with a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) at 10000 rpm for 5 minutes, and granulated at pH 5.5. Then, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade, and the reaction was carried out for 5 hours while stirring.
(蒸留工程)
重合反応終了後、容器内の温度を100℃に昇温し、4時間蒸留させた。
(Distillation process)
After completion of the polymerization reaction, the temperature inside the container was raised to 100 ° C. and distilled for 4 hours.
(洗浄/乾燥/分級/外添工程)
蒸留工程終了後、5℃/分で30℃まで反応容器を冷却し、10%塩酸を加えpHを2とした状態で2時間撹拌しながら分散剤を溶解した。得られたエマルションを加圧濾過し、さらに2000質量部以上のイオン交換水で洗浄した。得られたケーキを再び、1000質量部のイオン交換水に戻し、10%塩酸を加えpHを1以下とした状態で2時間撹拌しながら、再洗浄した。
(Washing / drying / classification / external addition process)
After completion of the distillation step, the reaction vessel was cooled to 30 ° C. at 5 ° C./min, 10% hydrochloric acid was added, and the dispersant was dissolved with stirring for 2 hours at a pH of 2. The obtained emulsion was pressure-filtered and further washed with 2000 parts by mass or more of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water, added with 10% hydrochloric acid, and rewashed with stirring at a pH of 1 or less for 2 hours.
上記と同様に得られたエマルションを加圧濾過し、さらに2000質量部以上のイオン交換水で洗浄し、十分通気をした後、乾燥して風力分級し、重量平均粒径7.0μmのトナー粒子1を得た。 The emulsion obtained in the same manner as above is pressure-filtered, further washed with 2000 parts by mass or more of ion-exchanged water, sufficiently aerated, dried and wind-classified, and toner particles having a weight average particle size of 7.0 μm. I got 1.
<トナー粒子2〜15の製造>
表2に示すように変更する以外は、トナー粒子1と同様の製造方法でトナー粒子2〜15を得た。
<Manufacturing of toner particles 2 to 15>
Toner particles 2 to 15 were obtained by the same production method as that of toner particles 1 except for the changes as shown in Table 2.
<トナー粒子16の製造>
(樹脂微粒子分散液1の製造例)
撹拌機、コンデンサー、温度計、窒素導入管を備えた反応容器に、得られたポリエステル樹脂を100.0質量部とメチルエチルケトン45.0質量部、テトラヒドロフラン45.0質量部を仕込み、80℃に加熱して溶解した。
<Manufacturing of toner particles 16>
(Production example of resin fine particle dispersion liquid 1)
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100.0 parts by mass of the obtained polyester resin, 45.0 parts by mass of methyl ethyl ketone, and 45.0 parts by mass of tetrahydrofuran were charged and heated to 80 ° C. And dissolved.
次いで、撹拌下、80℃のイオン交換水300.0質量部を添加して水分散させた後、得られた水分散体を蒸留装置に移し、留分温度が100℃に達するまで蒸留を行った。 Next, under stirring, 300.0 parts by mass of ion-exchanged water at 80 ° C. was added and dispersed in water, and then the obtained aqueous dispersion was transferred to a distillation apparatus and distilled until the fraction temperature reached 100 ° C. It was.
冷却後、得られた水分散体にイオン交換水を加え、分散液中の樹脂濃度が20%になるように調整した。これを、樹脂微粒子分散液1とした。得られた樹脂粒子分散液1中のポリエステル樹脂Aの平均粒径は48nmであった。 After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the resin concentration in the dispersion to 20%. This was designated as the resin fine particle dispersion liquid 1. The average particle size of the polyester resin A in the obtained resin particle dispersion 1 was 48 nm.
トナー粒子1の製造方法において、蒸留終了後のエマルションに35質量部(固形分7質量部)の樹脂微粒子分散液1を添加し、該エマルションのpHが8.0になるよう7.0%の炭酸ナトリウム水溶液を加え、80℃で1時間保持した。 In the method for producing the toner particles 1, 35 parts by mass (7 parts by mass of solid content) of the resin fine particle dispersion liquid 1 is added to the emulsion after completion of distillation, and the pH of the emulsion is 7.0% so as to be 8.0. An aqueous sodium carbonate solution was added, and the mixture was kept at 80 ° C. for 1 hour.
その後、トナー粒子1の製造方法と同様に処理し、トナー粒子16を得た。 Then, the treatment was carried out in the same manner as in the method for producing the toner particles 1, to obtain the toner particles 16.
トナー粒子16の断面を透過型電子顕微鏡で観察したところ、ポリエステルAの樹脂微粒子がトナー粒子表面に固着したコアシェル構造であった。 When the cross section of the toner particles 16 was observed with a transmission electron microscope, it was found that the resin fine particles of polyester A had a core-shell structure in which the resin fine particles were adhered to the surface of the toner particles.
<トナー粒子17の製造>
(樹脂粒子分散液2の調製)
・ポリエステル樹脂A 200.0質量部
・帯電制御剤(オリヱント化学工業社製:ボントロンE−88) 1.0質量部
・イオン交換水 500.0質量部
上記材料をステンレス製の容器に入れ、温浴下95℃まで加熱溶融し、ホモジナイザー(IKA社製:ウルトラタラックスT50)を用いて7800rpmで十分撹拌しながら、0.1N炭酸水素ナトリウムを加えpHを7.0よりも大きくする。その後、ドデシルベンゼンスルホン酸ナトリウム3質量部とイオン交換水297質量部の混合溶液を徐々に滴下し乳化分散することで樹脂粒子分散液2を得た。このポリエステル樹脂粒子分散液2の粒度分布を、粒度測定装置(堀場製作所製、LA−920)を用いて測定したところ、含まれるポリエステル樹脂粒子分散液の個数平均粒径は、0.20μmであり、また1μmを超える粗大粒子は観察されなかった。
<Manufacturing of toner particles 17>
(Preparation of resin particle dispersion liquid 2)
-Polyester resin A 200.0 parts by mass-Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 1.0 parts by mass-Ion-exchanged water 500.0 parts by mass Put the above material in a stainless steel container and take a hot bath. Heat and melt to 95 ° C. below, and add 0.1N sodium hydrogen carbonate to make the pH higher than 7.0 while sufficiently stirring at 7800 rpm using a homogenizer (manufactured by IKA: Ultratarax T50). Then, a mixed solution of 3 parts by mass of sodium dodecylbenzenesulfonate and 297 parts by mass of ion-exchanged water was gradually added dropwise to emulsify and disperse the mixture to obtain a resin particle dispersion liquid 2. When the particle size distribution of the polyester resin particle dispersion 2 was measured using a particle size measuring device (LA-920, manufactured by Horiba Seisakusho), the average particle size of the contained polyester resin particle dispersion was 0.20 μm. Also, no coarse particles larger than 1 μm were observed.
(ワックス粒子分散液の調製)
・イオン交換水 500.0質量部
・炭化水素ワックス(融点:77℃) 250.0質量部
上記材料をステンレス製の容器に入れ、温浴下95℃まで加熱溶融し、ホモジナイザー(IKA社製:ウルトラタラックスT50)を用いて7800rpmで十分撹拌しながら、0.1N炭酸水素ナトリウムを加えpHを7.0よりも大きくする。その後、ドデシルベンゼンスルホン酸ナトリウム5質量部とイオン交換水245質量部の混合溶液を徐々に滴下し乳化分散を行った。このワックス粒子分散液に含まれるワックス粒子の粒度分布を、粒度測定装置(堀場製作所製、LA−920)を用いて測定したところ、含まれるワックス粒子の個数平均粒径は、0.35μmであり、また1μmを超える粗大粒子は観察されなかった。
(Preparation of wax particle dispersion)
-Ion-exchanged water 500.0 parts by mass-Hydrocarbon wax (melting point: 77 ° C) 250.0 parts by mass Put the above material in a stainless steel container, heat and melt to 95 ° C in a warm bath, and homogenizer (IKA: Ultra). While sufficiently stirring at 7800 rpm using Talux T50), 0.1 N sodium hydrogen carbonate is added to make the pH larger than 7.0. Then, a mixed solution of 5 parts by mass of sodium dodecylbenzenesulfonate and 245 parts by mass of ion-exchanged water was gradually added dropwise to emulsify and disperse. When the particle size distribution of the wax particles contained in this wax particle dispersion was measured using a particle size measuring device (LA-920 manufactured by Horiba Seisakusho), the average particle size of the number of wax particles contained was 0.35 μm. Also, no coarse particles larger than 1 μm were observed.
(着色剤粒子分散液1の調製)
・顔料1(カーボンブラック) 100質量部
・ドデシルベンゼンスルホン酸ナトリウム 5質量部
・イオン交換水 400質量部
以上を混合し、サンドグラインダーミルを用いて分散した。この着色剤粒子分散液に含まれる着色剤粒子の粒度分布を、粒度測定装置(堀場製作所製、LA−920)を用いて測定したところ、含まれる着色剤粒子の個数平均粒径は、0.2μmであり、また1μmを超える粗大粒子は観察されなかった。
(Preparation of Colorant Particle Dispersion Solution 1)
-Pigment 1 (carbon black) 100 parts by mass, sodium dodecylbenzenesulfonate 5 parts by mass, ion-exchanged water 400 parts by mass or more were mixed and dispersed using a sand grinder mill. When the particle size distribution of the colorant particles contained in the colorant particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba Seisakusho), the average particle size of the number of the colorant particles contained was 0. No coarse particles were observed that were 2 μm and greater than 1 μm.
(トナー粒子17の製造例)
・樹脂粒子分散液2 500質量部
・着色剤粒子分散液1 37.5質量部
・ワックス粒子分散液 30質量部
・ドデシルベンゼンスルホン酸ナトリウム 5質量部
反応器(容積1リットルフラスコ、バッフル付きアンカー翼)にポリエステル樹脂粒子分散液1、ワックス粒子分散液およびドデシルベンゼンスルホン酸ナトリウムを仕込み、均一に混合する。一方、500mLビーカーに着色剤粒子分散液を均一に混合しておき、これを撹拌しながら反応器に徐々に添加し混合分散液を得る。得られた混合分散液を撹拌しながら硫酸アルミニウム水溶液を固形分として0.5質量部、滴下し凝集粒子を形成させた。
(Production example of toner particles 17)
-Resin particle dispersion 2500 parts by mass-Colorant particle dispersion 1 37.5 parts-Wax particle dispersion 30 parts by mass-Sodium dodecylbenzene sulfonate 5 parts by mass Reactor (Volume 1 liter flask, anchor blade with baffle) ) Is charged with the polyester resin particle dispersion 1, the wax particle dispersion and sodium dodecylbenzene sulfonate, and the mixture is uniformly mixed. On the other hand, the colorant particle dispersion is uniformly mixed in a 500 mL beaker and gradually added to the reactor with stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, 0.5 parts by mass of an aqueous aluminum sulfate solution was added dropwise to form aggregated particles.
滴下終了後、窒素を用いて系内を置換し、50℃にて1時間、さらに55℃にて1時間保持した。 After completion of the dropping, the inside of the system was replaced with nitrogen, and the mixture was kept at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour.
その後昇温して90℃にて30分保持した。その後、63℃まで降温したのち3時間保持させ、融合粒子を形成させた。このときの反応は窒素雰囲気下で行った。所定時間終了後、毎分0.5℃の降温速度にて室温になるまで冷却を行った。 Then, the temperature was raised and the temperature was maintained at 90 ° C. for 30 minutes. Then, the temperature was lowered to 63 ° C. and then kept for 3 hours to form fused particles. The reaction at this time was carried out in a nitrogen atmosphere. After the end of the predetermined time, cooling was performed at a temperature lowering rate of 0.5 ° C. per minute until room temperature was reached.
冷却後、反応生成物を10L容量の加圧濾過器にて、0.4MPAの圧力下で固液分離を行い、トナーケーキを得た。その後、イオン交換水を加圧濾過器に満水になるまで加え、0.4MpAの圧力で洗浄した。さらに同様に洗浄して、計3回洗浄した。このトナーケーキを、0.15質量部の非イオン性界面活性剤1を溶解させたメタノール/水の50:50混合溶媒1Lに分散して、表面処理したトナー粒子分散物を得た。 After cooling, the reaction product was subjected to solid-liquid separation under a pressure of 0.4 MPa with a 10 L volume pressure filter to obtain a toner cake. Then, ion-exchanged water was added to the pressure filter until it was full, and the mixture was washed at a pressure of 0.4 MpA. Further, it was washed in the same manner, and was washed a total of 3 times. This toner cake was dispersed in 1 L of a 50:50 mixed solvent of methanol / water in which 0.15 parts by mass of the nonionic surfactant 1 was dissolved to obtain a surface-treated toner particle dispersion.
このトナー粒子分散物を加圧濾過器に注ぎ、さらにイオン交換水を5L加えた。その後0.4MPAの圧力下で固液分離をしたのち、45℃で流動層乾燥を行い、トナー粒子17を得た。 The toner particle dispersion was poured into a pressure filter, and 5 L of ion-exchanged water was further added. Then, after solid-liquid separation under a pressure of 0.4 MPa, the fluidized bed was dried at 45 ° C. to obtain toner particles 17.
<トナー粒子18の製造>
トナー粒子17の製造例において、90℃で30分保持する工程の後、35質量部(固形分7質量部)の樹脂微粒子分散液1を添加し、該エマルションのpHが8.0になるよう7.0%の炭酸ナトリウム水溶液を加え、80℃で1時間保持した。
<Manufacturing of toner particles 18>
In the production example of the toner particles 17, after the step of holding at 90 ° C. for 30 minutes, 35 parts by mass (7 parts by mass of solid content) of the resin fine particle dispersion liquid 1 is added so that the pH of the emulsion becomes 8.0. A 7.0% aqueous sodium carbonate solution was added, and the mixture was kept at 80 ° C. for 1 hour.
その後、トナー粒子17の製造方法と同様に処理し、トナー粒子18を得た。 Then, the treatment was carried out in the same manner as in the method for producing the toner particles 17, and the toner particles 18 were obtained.
<トナー粒子19の製造>
・ポリエステル樹脂A 100質量部
・帯電制御剤(オリヱント化学工業社製:ボントロンE−88) 0.5質量部
・炭化水素ワックス(融点:77℃) 10.0質量部
・顔料1(カーボンブラック) 7.5質量部
上記原材料をヘンシェルミキサーFM10C(三井三池化工機(株))で予備混合した後、回転数200rpmに設定した二軸混練押し出し機(PCM−30:池貝鉄工所社製)により、混練物の出口付近における直接温度が155℃となるように設定温度を調節し、混練した。得られた溶融混練物を冷却し、冷却された溶融混練物をカッターミルで粗粉砕した。その後、得られた粗粉砕物を、ターボミルT−250(ターボ工業社製)を用いて、フィード量を20kg/hrとし、排気温度が38℃になるようエアー温度を調整して微粉砕した。得られた微粉砕物に対してコアンダ効果を利用した多分割分級機を用いて分級して、重量平均粒径(D4)が7.3μmのトナー粒子19を得た。
<Manufacturing of toner particles 19>
-Polyester resin A 100 parts by mass-Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 0.5 parts by mass-Hydrocarbon wax (melting point: 77 ° C) 10.0 parts by mass-Pigment 1 (carbon black) 7.5 parts by mass After premixing the above raw materials with a Henshell mixer FM10C (Mitsui Miike Machinery Co., Ltd.), a twin-screw kneading extruder (PCM-30: manufactured by Ikekai Iron Works Co., Ltd.) set at a rotation speed of 200 rpm. The set temperature was adjusted so that the direct temperature near the outlet of the kneaded product was 155 ° C., and the kneaded product was kneaded. The obtained melt-kneaded product was cooled, and the cooled melt-kneaded product was roughly pulverized with a cutter mill. Then, the obtained coarsely pulverized product was finely pulverized using a turbo mill T-250 (manufactured by Turbo Industries, Ltd.) with a feed amount of 20 kg / hr and an air temperature adjusted so that the exhaust temperature became 38 ° C. The obtained finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 19 having a weight average particle diameter (D4) of 7.3 μm.
<シリカ粒子1の製造例>
撹拌機、滴下ノズル、温度計を具備した1.5Lのガラス製反応容器にメタノール500質量部、10質量%塩酸を用いてpHを5.4に調整した水70質量部を添加して混合し、触媒溶液を得た。この触媒溶液を30℃に調整した後、撹拌しながら、テトラメトキシシラン(TMOS)100質量部と8.0質量%アンモニア水20質量部とを同時に60分かけ滴下して、親水性のシリカ微粒子分散液を得た。
<Production example of silica particles 1>
To a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle, and a thermometer, 500 parts by mass of methanol was added and 70 parts by mass of water whose pH was adjusted to 5.4 with 10% by mass hydrochloric acid was added and mixed. , A catalytic solution was obtained. After adjusting this catalyst solution to 30 ° C., 100 parts by mass of tetramethoxysilane (TMS) and 20 parts by mass of 8.0% by mass ammonia water are simultaneously added dropwise over 60 minutes with stirring to make hydrophilic silica fine particles. A dispersion was obtained.
その後、得られたシリカ粒子分散液をロータリーフィルターR−ファイン(寿工業社製)で固形分濃度40質量%まで濃縮してシリカ微粒子分散液を得た。 Then, the obtained silica particle dispersion was concentrated to a solid content concentration of 40% by mass with a rotary filter R-fine (manufactured by Kotobuki Kogyo Co., Ltd.) to obtain a silica fine particle dispersion.
シリカ粒子分散液250質量部に、疎水化処理剤としてヘキサメチルジシラザン(HMDS)50質量部を添加し、130℃で2時間反応させ、冷却した後、噴霧乾燥により乾燥し、外添剤Aであるシリカ粒子1を得た。物性を表3に示す。 To 250 parts by mass of the silica particle dispersion, 50 parts by mass of hexamethyldisilazane (HMDS) was added as a hydrophobizing agent, reacted at 130 ° C. for 2 hours, cooled, and then dried by spray drying. Silica particles 1 were obtained. The physical characteristics are shown in Table 3.
<シリカ粒子2〜4、6〜9の製造>
表3に示すように変更する以外は、シリカ粒子1と同様の製造方法で、外添剤Aであるシリカ粒子2〜4、6〜9を得た。
<Manufacturing of silica particles 2-4, 6-9>
Silica particles 2 to 4, 6 to 9, which are external additives A, were obtained by the same production method as that of silica particles 1 except for the modification as shown in Table 3.
<シリカ粒子5の製造>
シリカ粒子1の製造例において、触媒溶液のpHをアンモニア水で8.2に調整し、かつ諸条件を表3に記載の方法に変更する以外はシリカ粒子1と同様の製造方法で、外添剤Aであるシリカ粒子5を得た。
<Manufacturing of silica particles 5>
In the production example of silica particles 1, the pH of the catalyst solution was adjusted to 8.2 with aqueous ammonia, and the conditions were changed to the methods shown in Table 3, but the same production method as for silica particles 1 was used. Silica particles 5 as agent A were obtained.
<トナー1の製造方法>
得られたトナー粒子1に対して、外添剤Aとしてシリカ粒子1を外添した。
・トナー粒子1 100.0質量部
・シリカ粒子1(外添剤A) 1.0質量部
・疎水性シリカ微粒子 1.5質量部
・疎水性酸化チタン微粒子 0.3質量部
を、ヘンシェルミキサ(三井三池化工機株式会社製)を用いて、3000rpmで15分間混合して、トナー1を得た。
<Manufacturing method of toner 1>
Silica particles 1 were externally added as an external additive A to the obtained toner particles 1.
・ Toner particles 1 100.0 parts by mass ・ Silica particles 1 (appendix A) 1.0 parts by mass ・ Hydrophobic silica fine particles 1.5 parts by mass ・ Hydrophobic titanium oxide fine particles 0.3 parts by mass Using Mitsui Miike Kakoki Co., Ltd.), mixing was performed at 3000 rpm for 15 minutes to obtain toner 1.
なお、疎水性シリカ微粒子は、シリカ微粒子に対して20質量%のジメチルシリコーンオイルで表面処理したものであり、1次粒子の個数平均粒径:7nm、BET比表面積が130m2/gである。また、疎水性酸化チタン微粒子は、酸化チタン微粒子に対して15.0質量%のイソブチルトリメトキシシランで表面処理したものであり、1次粒子の個数平均粒径:50nmである。 The hydrophobic silica fine particles were surface-treated with 20% by mass of dimethyl silicone oil with respect to the silica fine particles, and the number average particle size of the primary particles was 7 nm, and the BET specific surface area was 130 m 2 / g. The hydrophobic titanium oxide fine particles were surface-treated with 15.0% by mass of isobutyltrimethoxysilane with respect to the titanium oxide fine particles, and the number average particle size of the primary particles was 50 nm.
<トナー2〜30の製造方法>
表4に示すように変更する以外は、トナー1と同様の製造方法でトナー2〜30を得た。
<Manufacturing method of toners 2 to 30>
Toners 2 to 30 were obtained by the same manufacturing method as that of toner 1 except for the changes as shown in Table 4.
〔実施例1〜23〕
実施例1〜23では、トナーとして、トナー1〜23を用いて以下の評価を行った。
[Examples 1 to 23]
In Examples 1 to 23, the following evaluations were performed using toners 1 to 23 as the toner.
結果を表5に示す。 The results are shown in Table 5.
〔比較例1〜7〕
比較例1〜7では、トナーとして、トナー24〜30を用いて以下の評価を行った。
[Comparative Examples 1 to 7]
In Comparative Examples 1 to 7, the following evaluations were performed using toners 24 to 30 as the toner.
結果を表5に示す。 The results are shown in Table 5.
<画像評価>
画像評価は、市販のカラーレーザープリンタ(HP Color LAserJet Enterprise M855)を一部改造して評価を行った。改造は一色のトナーカートリッジとイメージングドラムを装着するだけでも作動するよう改良した。また、プロセススピードを60ppmになるよう改造した。更に、必要に応じてトナー画像が未定着の状態で印刷紙を取り出せるよう改造した。更に、定着器を任意の温度に変更できるように改造した。
<Image evaluation>
The image evaluation was carried out by partially modifying a commercially available color laser printer (HP Color LaserJet Enterprise M855). The modification was improved so that it would work just by installing a one-color toner cartridge and an imaging drum. In addition, the process speed was modified to 60 ppm. Furthermore, if necessary, the printing paper was modified so that the printing paper could be taken out with the toner image unfixed. Furthermore, the fuser was modified so that it could be changed to any temperature.
このカラーレーザープリンタに搭載されていたブラックトナー用のトナーカートリッジ及びイメージングドラムの中に入っているトナーを抜き取り、エアーブローにて内部を清掃した後、トナーカートリッジに各トナー(425g)を、イメージングドラムに各トナー(127g)を導入し、トナーを詰め替えたトナーカートリッジ及びイメージングドラムをカラーレーザープリンタに装着し、以下の画像評価を行った。具体的な画像評価項目は下記の通りである。 After removing the toner contained in the toner cartridge for black toner and the imaging drum mounted on this color laser printer and cleaning the inside with an air blow, each toner (425 g) is put into the toner cartridge and the imaging drum. Each toner (127 g) was introduced into the color laser printer, and the toner cartridge and the imaging drum refilled with the toner were attached to the color laser printer, and the following image evaluation was performed. The specific image evaluation items are as follows.
[カブリ]
高温高湿環境下(温度33℃/湿度85%RH)において、横線で1%の印字率の画像を30000枚プリントアウトする試験を行った。試験終了後、48時間放置してからさらにプリントアウトした画像の非画像部の反射率(%)を「REFLECTOMETER MODEL TC−6DS」(東京電色社製)で測定した。得られた反射率を、同様にして測定した未使用のプリントアウト用紙(標準紙)の反射率(%)から差し引いた数値(%)を用いて評価した。数値が小さい程、画像カブリが抑制されていることになる。評価は、グロス紙モードで、普通紙(HP Brochure PAper 200g,Glossy、HP社製、200g/m2)を用いて行った。
[Fog]
In a high temperature and high humidity environment (temperature 33 ° C./humidity 85% RH), a test was conducted in which 30,000 images with a printing rate of 1% were printed out as horizontal lines. After the test was completed, the reflectance (%) of the non-image portion of the image printed out after being left for 48 hours was measured with "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using a numerical value (%) obtained by subtracting the reflectance (%) of the unused printout paper (standard paper) measured in the same manner. The smaller the value, the more the image fog is suppressed. The evaluation was performed using plain paper (HP Brochure Paper 200 g, Glossy, manufactured by HP, 200 g / m 2) in the gloss paper mode.
(評価基準)
A:0.5%未満
B:0.5%以上1.5%未満
C:1.5%以上3.0%未満
D:3.0%以上
(Evaluation criteria)
A: Less than 0.5% B: 0.5% or more and less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more
[規制不良]
低温低湿環境下(15℃、10%RH)において、横線で1%の印字率の画像を30000枚、35000枚プリントアウト試験終了後、トナーの載り量が0.3mg/cm2であるハーフトーン画像上現れた斑点状スジ及びトナー塊の量で評価した。
A:未発生。
B:斑点状のスジはないが、2、3個所の小さなトナー塊がある。
C:端部に斑点状スジが若干ある、若しくは4、5個所の小さなトナー塊がある。
D:全面に斑点状のスジある、若しくは5個所以上小さなトナー塊又は明らかなトナー塊がある。
[Poor regulation]
In a low temperature and low humidity environment (15 ° C, 10% RH), after the printout test of 30,000 and 35,000 images with a print rate of 1% with horizontal lines is completed, the toner load is 0.3 mg / cm 2 halftone. The evaluation was made based on the amount of spotted streaks and toner lumps that appeared on the image.
A: Not occurred.
B: There are no speckled streaks, but there are a few small toner lumps.
C: There are some spotted streaks on the edges, or there are 4 or 5 small toner lumps.
D: There are spot-like streaks on the entire surface, or there are 5 or more small toner lumps or obvious toner lumps.
[着色力]
着色力は、画像濃度1.40時の紙上のトナーの載り量として評価した。
[Coloring power]
The coloring power was evaluated as the amount of toner loaded on the paper at an image density of 1.40.
画像濃度1.40時のトナー載り量が少ないほど着色力は高く、画像濃度1.40時のトナー載り量が多いほど着色力は低い。 The smaller the toner loading amount at an image density of 1.40, the higher the coloring power, and the larger the toner loading amount at an image density of 1.40, the lower the coloring power.
A4の普通紙(GF−C081A4:キヤノンマーケティングジャパン社製)の紙中心に濃度測定用の10mm×10mmのベタ画像を出力した。濃度測定用の10mm×10mmのベタ画像の、マクベス反射濃度計RD918(マクベス社製)にて測定される画像濃度が、1.40になるように現像コントラストを調整した。 A solid image of 10 mm × 10 mm for density measurement was output on the center of A4 plain paper (GF-C081A4: manufactured by Canon Marketing Japan Inc.). The development contrast of a 10 mm × 10 mm solid image for density measurement was adjusted so that the image density measured by the Macbeth reflection densitometer RD918 (manufactured by Macbeth) was 1.40.
上記設定における紙上の未定着トナーの載り量を測定し以下、ランク付けを行った。 The amount of unfixed toner loaded on the paper in the above settings was measured and ranked below.
(評価基準)
A:0.35mg/cm2未満。
B:0.35mg/cm2以上0.43mg/cm2未満。
C:0.43mg/cm2以上0.47mg/cm2未満。
D:0.47mg/cm2以上。
(Evaluation criteria)
A: Less than 0.35 mg / cm 2.
B: 0.35mg / cm 2 more than 0.43mg / cm less than 2.
C: 0.43 mg / cm 2 or more and less than 0.47 mg / cm 2.
D: 0.47 mg / cm 2 or more.
[定着性]
上記評価機を使用し、坪量105g/m2のbusiness4200(Xerox社製)を評価紙として用いて、130℃から220℃までの温度域で設定温調を5℃おきに変化させながら、各温度においてオリジナル画像を出力した。
[Fixability]
Using the above evaluation machine and using businesss 4200 (manufactured by Xerox) with a basis weight of 105 g / m 2 as evaluation paper, each temperature control is changed every 5 ° C. in the temperature range from 130 ° C. to 220 ° C. The original image was output at the temperature.
オリジナル画像は、10mm四方のベタパッチ画像(トナー載り量0.90mg/cm2)を、紙面を9分割した時のそれぞれ中央に配置した画像を出力した。 As the original image, a 10 mm square solid patch image (toner loading amount 0.90 mg / cm 2 ) was output in which the image was arranged in the center of each of the nine divisions of the paper surface.
続いて、各温度において出力した定着画像の耐摺擦試験を行うことで、最低定着可能温度を判断した。 Subsequently, the minimum fixable temperature was determined by performing a rubbing resistance test of the fixed image output at each temperature.
最低定着可能温度とは、各パッチにおいて、定着画像濃度と定着画像を50g/cm2の荷重をかけたシルボン紙で5回摺擦した後の画像濃度を測定し、求めた濃度低下率の平均値が10%以下を満たす定着状態と定義する。 The minimum fixable temperature is the average of the density reduction rates obtained by measuring the fixed image density and the image density after rubbing the fixed image with Sylbon paper loaded with a load of 50 g / cm 2 five times in each patch. It is defined as a fixing state in which the value satisfies 10% or less.
尚、濃度の測定には「マクベス反射濃度計 RD918」(マクベス社製)を用いた。
A:最低定着可能温度が170℃以下で、安定した定着画像が得られる。
B:最低定着可能温度が170℃より高く175℃以下で、安定した定着画像が得られる。
C:最低定着可能温度が175℃より高く180℃以下で、安定した定着画像が得られる。
D:最低定着可能温度が180℃より高い、又は定着可能温度を有さない。
A "Macbeth reflection densitometer RD918" (manufactured by Macbeth) was used for measuring the density.
A: A stable fixed image can be obtained when the minimum fixable temperature is 170 ° C or lower.
B: A stable fixing image can be obtained when the minimum fixable temperature is higher than 170 ° C and 175 ° C or lower.
C: A stable fixed image can be obtained when the minimum fixable temperature is higher than 175 ° C and 180 ° C or lower.
D: The minimum fixable temperature is higher than 180 ° C., or there is no fixable temperature.
Claims (11)
該トナー粒子は、透過型電子顕微鏡を用いた該トナーの断面観察において、該トナー粒子の表面から深さ0.1μmまでの表層領域における顔料の占める面積の割合をApsとしたとき、Apsが2.5%以上5.5%以下であり、
該外添剤Aは仕事関数Wsが5.70eV以下のシリカ粒子であり、
該トナー表面に対する、該外添剤Aの被覆率が1.0%以上15.0%以下であることを特徴とするトナー。 Toner particles containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
A toner characterized in that the coverage of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less.
0<Ws−Wp<1.0
である請求項1に記載のトナー。 When the toner particles have the work function of the pigment as Wp,
0 <Ws-Wp <1.0
The toner according to claim 1.
R4は、アルキル基、フェニル基、OR8基またはNR9R10基を示し、R8〜R10は、それぞれ独立して、水素原子、アルキル基、フェニル基またはアラルキル基を示す。R4がポリマー成分と結合する場合、単結合または連結基を介して結合し、R4に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−O−、−NR6−および−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R6は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。R5は、アルキル基、フェニル基、OR42基またはNR43R44基を示し、R42〜R44は、それぞれ独立して、水素原子、アルキル基、フェニル基またはアラルキル基を示す。
R5がポリマー成分と結合する場合、連結基を介して結合し、R5に結合する連結基は、アルキレン基、フェニレン基、−O−、−NR11−、−NHCOC(CH3)2−および−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R11は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。
Arは、アリール基を示し、Arがポリマー成分と結合する場合、単結合または連結基を介して結合し、Arに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−O−、−NR6−および−NHCH(CH2OH)−からなる群より選ばれる二価の連結基であり、R6は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。
前記単結合または連結基が、R4、R5、またはArに結合する場合は、R4、R5、またはArの水素原子と置換して結合する。] The toner according to claim 10, wherein the pigment dispersant has a polymer component and an adsorption component that adsorbs to the pigment, and the adsorption component of the pigment dispersant has a partial structure represented by the following general formula (1).
R 4 represents an alkyl group, a phenyl group, an OR 8 group or an NR 9 R 10 group, and R 8 to R 10 independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R 4 is bonded to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R 4 is an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, -O. It is a divalent linking group selected from the group consisting of −, −NR 6 − and −NHCH (CH 2 OH) −, where R 6 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. R 5 represents an alkyl group, a phenyl group, an OR 42 group or an NR 43 R 44 group, and R 42 to R 44 independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
If R 5 is bound to the polymer component, bonded through a linking group, the linking group attached to R 5 is an alkylene group, a phenylene group, -O -, - NR 11 - , - NHCOC (CH 3) 2 - It is a divalent linking group selected from the group consisting of and -NHCH (CH 2 OH) -, and R 11 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to a polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, a divalent linking group selected from the group consisting of −O−, −NR 6− and −NHCH (CH 2 OH) −, where R 6 is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Is shown.
The single bond or a linking group, when bound to R 4, R 5 or Ar, is bonded substituted with R 4, R 5 or Ar hydrogen atoms. ]
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