JP2021092711A - Magenta toner - Google Patents
Magenta toner Download PDFInfo
- Publication number
- JP2021092711A JP2021092711A JP2019224182A JP2019224182A JP2021092711A JP 2021092711 A JP2021092711 A JP 2021092711A JP 2019224182 A JP2019224182 A JP 2019224182A JP 2019224182 A JP2019224182 A JP 2019224182A JP 2021092711 A JP2021092711 A JP 2021092711A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- mass
- resin
- less
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 claims abstract description 168
- 229920005989 resin Polymers 0.000 claims abstract description 147
- 239000011347 resin Substances 0.000 claims abstract description 147
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 64
- 239000006185 dispersion Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000005259 measurement Methods 0.000 claims description 24
- 238000004448 titration Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000004645 polyester resin Substances 0.000 claims description 12
- 229920001225 polyester resin Polymers 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002834 transmittance Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229920005792 styrene-acrylic resin Polymers 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 description 43
- 239000000203 mixture Substances 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 25
- 239000007788 liquid Substances 0.000 description 25
- 239000002904 solvent Substances 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- 239000000178 monomer Substances 0.000 description 19
- -1 pyrrolidone Chemical class 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000006082 mold release agent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 238000006149 azo coupling reaction Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000013480 data collection Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- ZDLVUKNLGUZMAS-UHFFFAOYSA-N dibutyl hydrogen phosphate;ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C.CCCCOP(O)(=O)OCCCC ZDLVUKNLGUZMAS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OYUWHGGWLCJJNP-UHFFFAOYSA-N 1,2-Dihydrophthalic acid Chemical compound OC(=O)C1C=CC=CC1C(O)=O OYUWHGGWLCJJNP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 229940084778 1,4-sorbitan Drugs 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- HYCNRDZKNBPHTC-UHFFFAOYSA-N 2-[2-[carboxy(hydroxy)methyl]phenyl]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1C(O)C(O)=O HYCNRDZKNBPHTC-UHFFFAOYSA-N 0.000 description 1
- YSUHBROHWRSYSF-UHFFFAOYSA-N 2-[3-[carboxy(hydroxy)methyl]phenyl]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=CC(C(O)C(O)=O)=C1 YSUHBROHWRSYSF-UHFFFAOYSA-N 0.000 description 1
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- FKLAJCGHOJXZRK-UHFFFAOYSA-N 2-[4-[carboxy(hydroxy)methyl]phenyl]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=C(C(O)C(O)=O)C=C1 FKLAJCGHOJXZRK-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- CIUBOFSKSMMQSG-UHFFFAOYSA-N 2-benzylperoxybenzoic acid Chemical group OC(=O)C1=CC=CC=C1OOCC1=CC=CC=C1 CIUBOFSKSMMQSG-UHFFFAOYSA-N 0.000 description 1
- PARCMDAOZHNXLU-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O PARCMDAOZHNXLU-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- XYHGSPUTABMVOC-UHFFFAOYSA-N 2-methylbutane-1,2,4-triol Chemical compound OCC(O)(C)CCO XYHGSPUTABMVOC-UHFFFAOYSA-N 0.000 description 1
- SZJXEIBPJWMWQR-UHFFFAOYSA-N 2-methylpropane-1,1,1-triol Chemical compound CC(C)C(O)(O)O SZJXEIBPJWMWQR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- UNRDNFBAJALSEY-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl benzoate Chemical class C=CC(=O)OCCOC(=O)C1=CC=CC=C1 UNRDNFBAJALSEY-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 1
- SYEOWUNSTUDKGM-YFKPBYRVSA-N 3-methyladipic acid Chemical compound OC(=O)C[C@@H](C)CCC(O)=O SYEOWUNSTUDKGM-YFKPBYRVSA-N 0.000 description 1
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DMEDOWYXHVUPMO-UHFFFAOYSA-N 4-(carboxymethyl)benzoic acid Chemical compound OC(=O)CC1=CC=C(C(O)=O)C=C1 DMEDOWYXHVUPMO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- SQAMZFDWYRVIMG-UHFFFAOYSA-N [3,5-bis(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC(CO)=CC(CO)=C1 SQAMZFDWYRVIMG-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical class C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical class C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BCJAMGWKHPTZEU-UHFFFAOYSA-N dibutyl hydrogen phosphate;ethyl prop-2-enoate Chemical class CCOC(=O)C=C.CCCCOP(O)(=O)OCCCC BCJAMGWKHPTZEU-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- VFAWCJZNIUIZOC-UHFFFAOYSA-N diethyl hydrogen phosphate;ethyl prop-2-enoate Chemical class CCOC(=O)C=C.CCOP(O)(=O)OCC VFAWCJZNIUIZOC-UHFFFAOYSA-N 0.000 description 1
- ZKHFUIIZFCSYQB-UHFFFAOYSA-N dimethyl hydrogen phosphate;ethyl prop-2-enoate Chemical class CCOC(=O)C=C.COP(O)(=O)OC ZKHFUIIZFCSYQB-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RLMXGBGAZRVYIX-UHFFFAOYSA-N hexane-1,2,3,6-tetrol Chemical compound OCCCC(O)C(O)CO RLMXGBGAZRVYIX-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- KSOCVFUBQIXVDC-FMQUCBEESA-N p-azophenyltrimethylammonium Chemical compound C1=CC([N+](C)(C)C)=CC=C1\N=N\C1=CC=C([N+](C)(C)C)C=C1 KSOCVFUBQIXVDC-FMQUCBEESA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- JEVOQXUAWFYIBD-UHFFFAOYSA-N pyrene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C2C(C(=O)O)=CC3=CC=CC4=CC=C1C2=C34 JEVOQXUAWFYIBD-UHFFFAOYSA-N 0.000 description 1
- LGZHPCIDRRUTMI-UHFFFAOYSA-N pyrene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C=CC3=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C4=CC=C1C2=C43 LGZHPCIDRRUTMI-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 208000022997 recurrent idiopathic neuroretinitis Diseases 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
本発明は、電子写真法、静電記録法、トナージェット法の如き画像形成方法における静電荷潜像を現像するためのマゼンタトナーに関する。 The present invention relates to a magenta toner for developing an electrostatically charged latent image in an image forming method such as an electrophotographic method, an electrostatic recording method, and a toner jet method.
近年、複合機やプリンターに於いては、さらなる高速化と高画質化が要求されており、トナーの性能改善が求められている。
高速化において高画質化を達成するためには、トナーの帯電特性を向上させる必要がある。特許文献１では、ベンジルオキシサリチル酸構造を有する樹脂を含有するトナーにおいて、帯電の立ち上がりが良好なトナーが提案されている。
また、高画質化を達成するためには、色再現範囲を広く、画像の着色力を向上させ、高画質・高品位のカラー画像を形成することが望まれている。特に、マゼンタトナーは、イエロートナーを加えて人間の視覚感度が高い赤色を再現するために重要であると同時に、例えば、複雑な色調を持つ人物像の肌色を再現する際には優れた現像性も要求される。また、シアントナーを加えてビジネスカラーとして使用頻度の高い青色の２次色再現を達成しなければならない。
これらの要求を満たすためには、高彩度なマゼンタトナーが必要である。そのためには、着色剤として顔料を用いる場合は、顔料を十分に微細化し、トナー中へ均一に分散させることが必要となる。そのため、特許文献２では、顔料との吸着率の低い極性樹脂と顔料分散剤とを用いたトナーが提案されている。
In recent years, in multifunction devices and printers, further speeding up and higher image quality have been required, and improvement of toner performance is required.
In order to achieve high image quality at high speed, it is necessary to improve the charging characteristics of the toner. Patent Document 1 proposes a toner containing a resin having a benzyloxysalicylic acid structure, which has a good rise in charging.
Further, in order to achieve high image quality, it is desired to widen the color reproduction range, improve the coloring power of the image, and form a high-quality, high-quality color image. In particular, magenta toner is important for reproducing red, which has high human visual sensitivity, by adding yellow toner, and at the same time, it has excellent developability when reproducing the skin color of a human image having a complicated color tone, for example. Is also required. In addition, cyan toner must be added to achieve secondary color reproduction of blue, which is frequently used as a business color.
Highly saturated magenta toner is required to meet these requirements. For that purpose, when a pigment is used as a colorant, it is necessary to make the pigment sufficiently fine and uniformly disperse it in the toner. Therefore, Patent Document 2 proposes a toner using a polar resin having a low adsorption rate with a pigment and a pigment dispersant.
特許文献１に記載されたトナーでは、帯電制御樹脂と顔料との吸着率が高く、顔料分散に改善の余地があった。特許文献２に記載されたトナーでは、顔料分散剤と顔料との吸着率の低い極性樹脂を使用することにより着色力と耐久性を両立している。しかしながら、特許文献２では顔料分散剤を使用することにより、色味が変化してしまう課題があった。また、顔料分散剤を使用するため材料コストがかかる課題があった。
本発明の目的は、顔料分散剤を用いることなく高彩度で帯電性に優れたマゼンタトナーを提供することである。
In the toner described in Patent Document 1, the adsorption rate between the charge control resin and the pigment is high, and there is room for improvement in pigment dispersion. In the toner described in Patent Document 2, both coloring power and durability are achieved by using a polar resin having a low adsorption rate between the pigment dispersant and the pigment. However, Patent Document 2 has a problem that the color taste is changed by using the pigment dispersant. Further, since the pigment dispersant is used, there is a problem that the material cost is high.
An object of the present invention is to provide a magenta toner having high saturation and excellent chargeability without using a pigment dispersant.
本発明は、結着樹脂、顔料、および極性樹脂を含有するトナー粒子を有するトナーであって、前記極性樹脂がカルボキシ基に由来する酸価を２．０ｍｇＫＯＨ／ｇ以上２０．０ｍｇＫＯＨ／ｇ以下有し、前記顔料に対する前記極性樹脂の吸着率が１０％以下であることを特徴とするマゼンタトナーに関する。 The present invention is a toner having toner particles containing a binder resin, a pigment, and a polar resin, and the polar resin has an acid value derived from a carboxy group of 2.0 mgKOH / g or more and 20.0 mgKOH / g or less. However, the present invention relates to a magenta toner characterized in that the adsorption rate of the polar resin with respect to the pigment is 10% or less.
本発明によれば、顔料分散剤を用いることなく高彩度で帯電性に優れたマゼンタトナーを提供することができる。 According to the present invention, it is possible to provide a magenta toner having high saturation and excellent chargeability without using a pigment dispersant.
本発明は、結着樹脂、顔料、および極性樹脂を含有するトナー粒子を有するトナーであって、前記極性樹脂がカルボキシ基に由来する酸価を２．０ｍｇＫＯＨ／ｇ以上２０．０ｍｇＫＯＨ／ｇ以下有し、前記顔料に対する前記極性樹脂の吸着率が１０％以下であることを特徴とするマゼンタトナーである。 The present invention is a toner having toner particles containing a binder resin, a pigment, and a polar resin, and the polar resin has an acid value derived from a carboxy group of 2.0 mgKOH / g or more and 20.0 mgKOH / g or less. However, the magenta toner is characterized in that the adsorption rate of the polar resin to the pigment is 10% or less.
上記の構成を有するトナーは、帯電性に優れ、かつ顔料分散剤を用いなくても彩度が高いマゼンタトナーを提供することができる。 The toner having the above structure can provide a magenta toner having excellent chargeability and high saturation without using a pigment dispersant.
トナーの帯電性を向上させるために極性樹脂を使用した場合、顔料に極性樹脂が吸着し、顔料を凝集させてしまい、高い彩度を維持することが難しい問題があった。また、顔料と極性樹脂が吸着することで、極性樹脂の帯電性能を顔料が阻害してしまう問題があった。ここで従来は、極性樹脂よりも顔料との吸着力の高い顔料分散剤を使用して解決を図ってきている。しかし、本発明者らが鋭意検討した結果、顔料に対する極性樹脂の吸着率を１０％以下に抑えることによりこの問題が解決することを見出した。 When a polar resin is used to improve the chargeability of the toner, there is a problem that the polar resin is adsorbed on the pigment and the pigment is agglomerated, making it difficult to maintain high saturation. Further, there is a problem that the pigment hinders the charging performance of the polar resin due to the adsorption of the pigment and the polar resin. Here, conventionally, a solution has been attempted by using a pigment dispersant having a higher adsorptive power with a pigment than a polar resin. However, as a result of diligent studies by the present inventors, it has been found that this problem can be solved by suppressing the adsorption rate of the polar resin to the pigment to 10% or less.
極性樹脂としては、カルボキシ基に由来する酸価を２．０ｍｇＫＯＨ／ｇ以上２０．０ｍｇＫＯＨ／ｇ以下有していることが必要である。カルボキシ基を有することで帯電特性の環境差を小さく抑えることが可能となる。また、酸価を２．０ｍｇＫＯＨ／ｇ以上２０．０ｍｇＫＯＨ／ｇ以下とすることで、かぶりとチャージアップ抑制の両立が可能となる。より好ましくは４．０ｍｇＫＯＨ／ｇ以上１５．０ｍｇＫＯＨ／ｇ以下である。 The polar resin needs to have an acid value derived from a carboxy group of 2.0 mgKOH / g or more and 20.0 mgKOH / g or less. Having a carboxy group makes it possible to keep the environmental difference in charging characteristics small. Further, by setting the acid value to 2.0 mgKOH / g or more and 20.0 mgKOH / g or less, it is possible to achieve both fog and charge-up suppression. More preferably, it is 4.0 mgKOH / g or more and 15.0 mgKOH / g or less.
ここでかぶりとは白画像を印字した際に感光体上にトナーが残る現象である。トナーの帯電性が低すぎる場合や、トナー表面に顔料が露出した際にトナー表面で逆極性の電荷が存在することによって引き起こされる現象だと考えている。また、チャージアップは、トナーの帯電性が高すぎる場合に引き起こされる現象であり、現像ローラ上でトナーが入れ替わらず摺擦されることでトナーが劣化し、各種部材に融着することで画像上にスジが発生すると考えている。 Here, fog is a phenomenon in which toner remains on the photoconductor when a white image is printed. It is considered to be a phenomenon caused by the presence of charge of opposite polarity on the toner surface when the chargeability of the toner is too low or when the pigment is exposed on the toner surface. In addition, charge-up is a phenomenon that occurs when the chargeability of the toner is too high. The toner is deteriorated by being rubbed on the developing roller without being replaced, and the toner is fused to various members to form an image. I think that streaks will occur on the top.
酸価が２．０ｍｇＫＯＨ／ｇ未満であるとかぶりが発生する懸念がある。また、２０．０ｍｇＫＯＨ／ｇを超えると、チャージアップを引き起こす懸念がある。 If the acid value is less than 2.0 mgKOH / g, there is a concern that fog may occur. Further, if it exceeds 20.0 mgKOH / g, there is a concern that charge-up may occur.
さらに、顔料に対する吸着率が１０％以下であることで、帯電性と顔料分散性の両立が図れ、彩度の高いマゼンタトナーを得ることができる。吸着率が１０％を超えると、顔料分散性が不十分となり、彩度が低下する懸念がある。極性基はカルボキシ基のみであることがさらに好ましい。カルボキシ基のみとすることでチャージアップをより効果的に抑制することができる。 Further, when the adsorption rate with respect to the pigment is 10% or less, both chargeability and pigment dispersibility can be achieved, and a highly saturated magenta toner can be obtained. If the adsorption rate exceeds 10%, the pigment dispersibility becomes insufficient, and there is a concern that the saturation may decrease. It is more preferable that the polar group is only a carboxy group. Charge-up can be suppressed more effectively by using only a carboxy group.
本発明において、極性樹脂は上記条件を満たすものであれば特に限定はなく、従来公知の極性樹脂を用いることができる。例えば、ポリエステル樹脂、スチレンアクリル樹脂、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、シリコーン樹脂などが挙げられる。中でもポリエステル樹脂又はスチレンアクリル樹脂であることが高温高湿下での保存や使用の観点から好ましい。 In the present invention, the polar resin is not particularly limited as long as it satisfies the above conditions, and conventionally known polar resins can be used. For example, polyester resin, styrene acrylic resin, polyamide resin, furan resin, epoxy resin, silicone resin and the like can be mentioned. Of these, polyester resin or styrene acrylic resin is preferable from the viewpoint of storage and use under high temperature and high humidity.
本発明に用いることができるマゼンタ顔料は、顔料に対する極性樹脂の吸着率が１０％以下であれば、キナクリドン系マゼンタ顔料、チオインジゴ系マゼンタ顔料、キサンテン系マゼンタ顔料、ペリレン系マゼンタ顔料、モノアゾ系マゼンタ顔料何れも選択できる。中でも、本発明に用いられるマゼンタ顔料は、モノアゾ系マゼンタ顔料が好ましい。 The magenta pigment that can be used in the present invention is a quinacridone-based magenta pigment, a thioindigo-based magenta pigment, a xanthene-based magenta pigment, a perylene-based magenta pigment, or a monoazo-based magenta pigment as long as the adsorption rate of the polar resin to the pigment is 10% or less. Either can be selected. Among them, the magenta pigment used in the present invention is preferably a monoazo magenta pigment.
中でも、下記式（５）で示されるモノアゾ系マゼンタ顔料である化合物Ｃが好ましい。 Of these, compound C, which is a monoazo-based magenta pigment represented by the following formula (5), is preferable.
上記アゾ系マゼンタ顔料の製造方法として、公知の方法を用いることができ、例えば、以下のようなアゾカップリングの方法によって製造することができる。 As a method for producing the azo-based magenta pigment, a known method can be used, and for example, the azo-based magenta pigment can be produced by the following azo coupling method.
先ず、メタノール等の溶剤、又は水中、下記式（６）で示される化合物Ｄを塩酸又は硫酸等の無機酸の存在下、亜硝酸ナトリウム、又はニトロシル硫酸等のジアゾ化剤と反応させて、対応するジアゾニウム化合物を製造する。更に、このジアゾニウム化合物と下記式（７）で示される化合物Ｅとカップリングさせて、化合物Ｃを製造することができる。 First, the compound D represented by the following formula (6) is reacted with a diazotizing agent such as sodium nitrite or nitrosylsulfuric acid in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in a solvent such as methanol or water. To produce a diazonium compound. Further, the compound C can be produced by coupling the diazonium compound with the compound E represented by the following formula (7).
本工程は無溶剤で行うことも可能であるが、反応の急激な進行を防ぐため溶剤の存在下で行うことが好ましい。溶剤としては、反応を阻害しないものであれば特に制限されるものではないが、例えば、メタノール、エタノール、及びプロパノール等のアルコール類、酢酸メチル、酢酸エチル、及び酢酸プロピル等のエステル類、ジエチルエーテル、テトラヒドロフラン、及びジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、ヘキサン、及びヘプタン等の炭化水素類、ジクロロメタン、ジクロロエタン、及びクロロホルム等の含ハロゲン炭化水素類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、Ｎ，及びＮ−ジメチルイミダゾリジノン等のアミド類、アセトニトリル、及びプロピオニトリル等のニトリル類、ギ酸、酢酸、及びプロピオン酸等の酸類、水等が挙げられる。また、上記溶剤は２種以上を混合して用いることができる。上記溶剤の使用量は、任意に定めることができるが、反応速度の点で、式（６）の化合物Ｄに対し５．０倍量以上５０．０倍量以下の範囲が好ましい。アゾカップリング反応は、−５℃〜３０℃の温度範囲で行われる。 Although this step can be carried out without a solvent, it is preferably carried out in the presence of a solvent in order to prevent a rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction, but for example, alcohols such as methanol, ethanol, and propanol, esters such as methyl acetate, ethyl acetate, and propyl acetate, and diethyl ether. , Tetrahydrofuran, and ethers such as dioxane, hydrocarbons such as benzene, toluene, xylene, hexane, and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane, and chloroform, N, N-dimethylformamide, N-methyl. Examples thereof include amides such as pyrrolidone, N and N-dimethylimidazolidinone, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid and propionic acid, water and the like. In addition, two or more kinds of the above solvents can be mixed and used. The amount of the solvent used can be arbitrarily determined, but in terms of reaction rate, it is preferably in the range of 5.0 times or more and 50.0 times or less the amount of the compound D of the formula (6). The azo coupling reaction is carried out in the temperature range of −5 ° C. to 30 ° C.
合成した化合物Ｃは水洗、乾燥後、アセトン濡れ性を制御することを目的として、溶媒での処理を行うことができる。所望のアセトン濡れ性に応じて、下記のような溶媒を選択することができる。例えば、アセトン、ＭＩＢＫなどケトン系溶媒、トルエン、キシレン等の芳香族炭化水素系溶媒、イソプロパノール、イソブタノール等のアルコール系溶媒、ヘキサンやヘプタンなどの脂肪族炭化水素系溶媒を用いることができる。溶媒処理の温度は１０〜５０℃が好ましく、処理時間は、３０分〜２４時間が好ましい。 After washing with water and drying, the synthesized compound C can be treated with a solvent for the purpose of controlling the wettability with acetone. The following solvents can be selected according to the desired acetone wettability. For example, a ketone solvent such as acetone or MIBK, an aromatic hydrocarbon solvent such as toluene or xylene, an alcohol solvent such as isopropanol or isobutanol, or an aliphatic hydrocarbon solvent such as hexane or heptane can be used. The temperature of the solvent treatment is preferably 10 to 50 ° C., and the treatment time is preferably 30 minutes to 24 hours.
この顔料を用いると、極性樹脂との吸着率を１０％以下に抑えることが可能となる。前記式（５）のモノアゾ系マゼンタ顔料は他のマゼンタ顔料と比較すると極性が低い。そのため、極性樹脂との相互作用が小さくなり吸着率を１０％以下に抑えることが可能である。詳細は明らかではないが、前記式（５）の顔料が粒子化される際、極性基が内側に存在するよう配向し、他のマゼンタ顔料と比較すると顔料粒子最表面は極性の低い結晶構造となっているのではないかと考えている。 When this pigment is used, the adsorption rate with the polar resin can be suppressed to 10% or less. The monoazo-based magenta pigment of the formula (5) has a lower polarity than other magenta pigments. Therefore, the interaction with the polar resin is reduced, and the adsorption rate can be suppressed to 10% or less. Although the details are not clear, when the pigment of the above formula (5) is granulated, the polar groups are oriented so as to be present inside, and the outermost surface of the pigment particles has a crystal structure having a low polarity as compared with other magenta pigments. I think it may be.
式（５）のモノアゾ系マゼンタ顔料の中でも、顔料が式（１）で示される化合物Ａと式（２）で示される化合物Ｂを含有していることが好ましい。化合物Ａと化合物Ｂを含有することで、顔料の一次粒径が従来のマゼンタ顔料よりも小さいものが得られる。 Among the monoazo magenta pigments of the formula (5), it is preferable that the pigment contains the compound A represented by the formula (1) and the compound B represented by the formula (2). By containing the compound A and the compound B, a pigment having a primary particle size smaller than that of the conventional magenta pigment can be obtained.
さらに、化合物Ａと化合物Ｂの質量比Ａ／Ｂが９５／５から５／９５であることが好ましい。Ａ／Ｂを上記範囲とすることでより一次粒径が小さい顔料が得られ、彩度の高いトナーが得られる。より好ましくは、Ａ／Ｂが８０／２０から６０／４０、もしくは４０／６０から２０／８０である。 Further, the mass ratio A / B of compound A to compound B is preferably 95/5 to 5/95. By setting A / B in the above range, a pigment having a smaller primary particle size can be obtained, and a toner having high saturation can be obtained. More preferably, the A / B is 80/20 to 60/40, or 40/60 to 20/80.
前記化合物Ａ１と前記化合物Ａ２を合わせた質量が、前記トナー粒子中の前記顔料の質量の９０％以上であることが好ましい。極性樹脂との吸着率を低い状態に保つためである。 The total mass of the compound A1 and the compound A2 is preferably 90% or more of the mass of the pigment in the toner particles. This is to keep the adsorption rate with the polar resin low.
また、前記極性樹脂の含有量が、前記結着樹脂の全質量に対して、１．０質量％以上３０．０質量％以下含有することが好ましい。前記範囲とすることで、トナーの帯電性能をより良い状態に制御することが可能となる。具体的には、１．０質量％以上とすることで、かぶりを抑制することが出来る。また、３０．０質量％以下とすることで、チャージアップを抑制することが出来る。 Further, the content of the polar resin is preferably 1.0% by mass or more and 30.0% by mass or less with respect to the total mass of the binder resin. Within the above range, it is possible to control the charging performance of the toner to a better state. Specifically, by setting it to 1.0% by mass or more, fog can be suppressed. Further, by setting the content to 30.0% by mass or less, charge-up can be suppressed.
さらに、トナー粒子を水に分散して得た分散物を滴定法により測定して得た酸価をＡＶＨ（ｍｇＫＯＨ／ｇ）としたとき、ＡＶＨが０．２０ｍｇＫＯＨ／ｇ以上１．００ｍｇＫＯＨ／ｇ以下であり、前記トナー粒子をエタノールに分散して得た分散物を滴定法により測定して得た酸価をＡＶＥ（ｍｇＫＯＨ／ｇ）としたとき、ＡＶＨ／ＡＶＥが０．１０以上０．２５以下であることが好ましい。 Further, when the acid value obtained by measuring the dispersion obtained by dispersing the toner particles in water by a titration method is AVH (mgKOH / g), the AVH is 0.20 mgKOH / g or more and 1.00 mgKOH / g or less. When the acid value obtained by measuring the dispersion obtained by dispersing the toner particles in ethanol by a titration method is AVE (mgKOH / g), AVH / AVE is 0.10 or more and 0.25 or less. Is preferable.
トナーの帯電性はトナー最表面の状態に強く影響される。本発明のトナーは、極性樹脂がその帯電制御機能を発現しており、トナーの最表面に存在していることが好ましい。トナー粒子を水に分散させた場合、トナー粒子は水には溶解しないため、得られた酸価ＡＶＨ（ｍｇＫＯＨ／ｇ）は、トナー粒子最表面のみの酸価を測定したことになる。ＡＶＨが０．２０ｍｇＫＯＨ／ｇ以上１．００ｍｇＫＯＨ／ｇ以下であると、かぶりとチャージアップを抑制することが可能となる。一方、トナー粒子をエタノールに分散させた場合、トナー粒子は溶解はしないもののエタノールとの僅かな親和性のために表面近傍が膨潤する。この状態で測定した酸価は、表面近傍の酸価を測定しており、表面近傍に極性樹脂がどの程度存在するかを表している。表面近傍に極性樹脂が存在することで、トナーの耐久性を高めることができる。ＡＶＨ／ＡＶＥが０．１０以上０．２５以下であると、帯電性能と耐久性が良好なトナーを得ることができる。 The chargeability of toner is strongly influenced by the state of the outermost surface of toner. In the toner of the present invention, it is preferable that the polar resin exhibits the charge control function and is present on the outermost surface of the toner. When the toner particles are dispersed in water, the toner particles are not dissolved in water, so that the obtained acid value AVH (mgKOH / g) is the acid value measured only on the outermost surface of the toner particles. When AVH is 0.20 mgKOH / g or more and 1.00 mgKOH / g or less, fog and charge-up can be suppressed. On the other hand, when the toner particles are dispersed in ethanol, the toner particles do not dissolve, but the vicinity of the surface swells due to a slight affinity with ethanol. The acid value measured in this state measures the acid value near the surface and indicates how much polar resin is present near the surface. The presence of the polar resin near the surface can enhance the durability of the toner. When AVH / AVE is 0.10 or more and 0.25 or less, a toner having good charging performance and durability can be obtained.
また、前記顔料は、アセトン／水混合溶媒に対する濡れ性試験において、波長７８０ｎｍの光の透過率が５０％のときのアセトン濃度が、５．５体積％以上１０．０体積％以下であり、前記結着樹脂の溶解度パラメータ（ＳＰ値）が９．８以上１１．０以下であることが好ましい。 Further, the pigment has an acetone concentration of 5.5% by volume or more and 10.0% by volume or less when the transmittance of light having a wavelength of 780 nm is 50% in a wettability test with an acetone / water mixed solvent. The solubility parameter (SP value) of the binder resin is preferably 9.8 or more and 11.0 or less.
本発明では、極性樹脂と顔料の吸着率を１０％以下とすることで良好な顔料分散状態を得ることが可能である。この吸着率を１０％以下に抑制するには、顔料の極性を低くすることが重要である。顔料は、溶媒やトナーの構成材料と溶解しない。したがって、吸着には顔料表面が作用している。そのため、顔料の極性としては顔料表面の極性を制御することが重要であり、極性を評価するには濡れ性試験が良い手段である。アセトン／水混合溶媒に対する濡れ性試験において、波長７８０ｎｍの光の透過率が５０％のときのアセトン濃度が、５．５体積％以上１０．０体積％以下であることが好ましい。この範囲にすることで、吸着率が低く、顔料分散性の良好なトナーを得ることができる。５．５体積％以上とすることで、極性樹脂との吸着率を低く抑えることができる。１０．０体積％以下とすることでトナー中での極性樹脂との親和性もある程度保つことができ、顔料分散性がより良好になる。また、この顔料と極性樹脂との親和性をある程度保つことで、定着時に極性樹脂と顔料とが反発し、凝集による彩度低下を抑制することができる。 In the present invention, it is possible to obtain a good pigment dispersion state by setting the adsorption rate of the polar resin and the pigment to 10% or less. In order to suppress this adsorption rate to 10% or less, it is important to lower the polarity of the pigment. Pigments do not dissolve in solvents or toner constituents. Therefore, the pigment surface acts on the adsorption. Therefore, it is important to control the polarity of the pigment surface as the polarity of the pigment, and the wettability test is a good means for evaluating the polarity. In the wettability test with respect to an acetone / water mixed solvent, the acetone concentration when the transmittance of light having a wavelength of 780 nm is 50% is preferably 5.5% by volume or more and 10.0% by volume or less. Within this range, a toner having a low adsorption rate and good pigment dispersibility can be obtained. By setting the volume to 5.5% by volume or more, the adsorption rate with the polar resin can be suppressed to a low level. By setting the content to 10.0% by volume or less, the affinity with the polar resin in the toner can be maintained to some extent, and the pigment dispersibility becomes better. Further, by maintaining the affinity between the pigment and the polar resin to some extent, the polar resin and the pigment repel each other at the time of fixing, and the decrease in saturation due to aggregation can be suppressed.
さらに、本発明では、前記結着樹脂のｆｅｄｏｒｓの式より求められる溶解度パラメータ（ＳＰ値）が９．８以上１１．０以下であることが好ましい。この範囲とすることで、前記顔料分散性を良好に保つばかりか、トナーの割れを抑制することができる。アセトン／水混合溶媒に対する濡れ性試験においては、顔料と極性樹脂の親和性を直接評価するのが難しいため、間接的に顔料と極性樹脂の親和性を試験するために行っている。顔料と極性樹脂の親和性をアセトンで疑似的に評価しており、実質アセトンと顔料との親和性を試験しているものである。アセトンのＳＰ値は、１０．０（「Ｅｃｙｃｌ．Ｐｏｌｙｍ．Ｓｃｉ．ｃｈｎｏｌ．、４２，７６（１９６５）」記載）である。アセトンと近いＳＰ値の結着樹脂を用いると、顔料／極性樹脂／結着樹脂の親和性のバランスがより良好に保たれ、トナーの割れも抑制できることが明らかとなった。結着樹脂のＳＰ値が９．８以上１１．０以下であるとトナー割れの抑制効果が良好である。この範囲とすることで、結着樹脂と顔料との界面での僅かなクラックから発生するトナー割れが抑制できるためであると考えている。 Further, in the present invention, the solubility parameter (SP value) obtained from the fedors formula of the binder resin is preferably 9.8 or more and 11.0 or less. Within this range, not only the pigment dispersibility can be kept good, but also the cracking of the toner can be suppressed. In the wettability test for an acetone / water mixed solvent, it is difficult to directly evaluate the affinity between the pigment and the polar resin, so the affinity between the pigment and the polar resin is indirectly tested. The affinity between the pigment and the polar resin is simulated with acetone, and the affinity between the real acetone and the pigment is tested. The SP value of acetone is 10.0 (described in "Ecycl. Polymer. Sci. Chnol., 42, 76 (1965)"). It was clarified that when a binder resin having an SP value close to that of acetone was used, the affinity balance of the pigment / polar resin / binder resin was better maintained and the cracking of the toner could be suppressed. When the SP value of the binder resin is 9.8 or more and 11.0 or less, the effect of suppressing toner cracking is good. It is considered that this is because the toner cracking generated from a slight crack at the interface between the binder resin and the pigment can be suppressed within this range.
上記のような顔料／極性樹脂／結着樹脂の親和性のバランスを保つため、結着樹脂の酸価は極性樹脂の酸価よりも小さいほうが好ましい。 In order to maintain the balance of affinity of the pigment / polar resin / binder resin as described above, the acid value of the binder resin is preferably smaller than the acid value of the polar resin.
さらに、結着樹脂の酸価をＡＶＢ、極性樹脂の酸価をＡＶＰとしたとき、ＡＶＢが５．０ｍｇＫＯＨ／ｇ以下であり、かつ、式（４）を満たすことがより好ましい。
式（４） ＡＶＢ＜ＡＶＰ−２
Further, when the acid value of the binder resin is ABB and the acid value of the polar resin is AVP, it is more preferable that the ABB is 5.0 mgKOH / g or less and the formula (4) is satisfied.
Equation (4) AVB <AVP-2
式（４）の条件を満たすことで、帯電性能がより良好な状態となる。 By satisfying the condition of the equation (4), the charging performance becomes better.
また、本発明は、顔料のＸＲＤ測定において、３°＜２θ＜６０°の範囲内の最大強度を有するピークにおいて算出される結晶子サイズＤが下記式（３）を満たすことが好ましい。
式（３） １．０ｎｍ≦Ｄ≦７．０ｎｍ
Further, in the present invention, it is preferable that the crystallite size D calculated at the peak having the maximum intensity within the range of 3 ° <2θ <60 ° satisfies the following formula (3) in the XRD measurement of the pigment.
Equation (3) 1.0 nm ≤ D ≤ 7.0 nm
結晶子サイズが１．０ｎｍ未満である場合、結晶性が低下し、耐光性が悪化する。また結晶子サイズが７．０ｎｍより大きい場合、散乱成分が増大し、彩度が低下する。結晶子サイズの制御方法としては、顔料の構造を変更する他、複数種の顔料骨格を用いて固溶体を形成する方法、顔料化工程での温度条件などを変更することによって制御することができる。 When the crystallinity size is less than 1.0 nm, the crystallinity is lowered and the light resistance is deteriorated. When the crystallite size is larger than 7.0 nm, the scattering component increases and the saturation decreases. As a method for controlling the crystallite size, in addition to changing the structure of the pigment, it can be controlled by changing a method of forming a solid solution using a plurality of types of pigment skeletons, a temperature condition in the pigmentation step, and the like.
本発明において、極性樹脂は結着樹脂１００質量部に対して１．０質量部以上１５．０質量部以下であることがより好ましい。また、顔料が前記結着樹脂１００質量部に対して１．０質量部以上１０．０質量部以下であることが好ましい。また、顔料が前記極性樹脂１００質量部に対して６．７質量部以上１０００質量部以下であることが好ましい。このような数値範囲とすることで、顔料分散性と帯電性能とがより良い状態となり、高彩度で高耐久なトナーを得ることができる。 In the present invention, the polar resin is more preferably 1.0 part by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin. Further, it is preferable that the pigment is 1.0 part by mass or more and 10.0 part by mass or less with respect to 100 parts by mass of the binder resin. Further, it is preferable that the pigment is 6.7 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the polar resin. By setting such a numerical range, the pigment dispersibility and the charging performance are improved, and a toner having high saturation and high durability can be obtained.
本発明の結着樹脂としては、ビニル系樹脂、マレイン酸共重合体、ポリエステル樹脂、エポキシ樹脂など公知の樹脂を用いることができる。この中でもビニル系樹脂とポリエステル樹脂が製造容易性の観点から好ましい。また、高温高湿下での保存や使用の観点からスチレンアクリル樹脂又はポリエステル樹脂がさらに好ましい。 As the binder resin of the present invention, known resins such as vinyl resins, maleic acid copolymers, polyester resins, and epoxy resins can be used. Of these, vinyl resins and polyester resins are preferable from the viewpoint of ease of manufacture. Further, a styrene acrylic resin or a polyester resin is more preferable from the viewpoint of storage and use under high temperature and high humidity.
ビニル系樹脂の製造に使用できるビニル系単量体としては、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、及びｐ−フェニルスチレンのようなスチレン誘導体類；
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、及び２−ベンゾイルオキシエチルアクリレートのようなアクリル系重合性単量体類；
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、ジエチルフォスフェートエチルメタクリレート、及びジブチルフォスフェートエチルメタクリレートなどのメタクリル系重合性単量体類；が挙げられる。
Examples of vinyl-based monomers that can be used in the production of vinyl-based resins include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and the like. pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p. -Styrene derivatives such as-methoxystyrene and p-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-ethylhexyl acrylate, n-octyl acrylate. , N-Nonyl acrylates, cyclohexyl acrylates, benzyl acrylates, dimethyl phosphate ethyl acrylates, diethyl phosphate ethyl acrylates, dibutyl phosphate ethyl acrylates, and acrylic polymerizable monomers such as 2-benzoyloxyethyl acrylates;
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, n-octyl methacrylate , Dibutyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate;
これらは単独あるいは二種以上組み合わせて使用することができる。 These can be used alone or in combination of two or more.
ポリエステル樹脂に使用できる縮重合単量体としては多価カルボン酸と多価アルコールが使用できる。 Polyvalent carboxylic acid and polyhydric alcohol can be used as the polycondensation monomer that can be used for the polyester resin.
多価カルボン酸としてはシュウ酸、グルタル酸、コハク酸、マレイン酸、アジピン酸、β−メチルアジピン酸、アゼライン酸、セバシン酸、ノナンジカルボン酸、デカンジカルボン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸、フマル酸、シトラコン酸、ジグリコール酸、シクロヘキサン−３，５−ジエン−１，２−ジカルボン酸、ヘキサヒドロテレフタル酸、マロン酸、ピメリン酸、フタル酸、イソフタル酸、テレフタル酸、テトラクロロフタル酸、クロロフタル酸、ニトロフタル酸、ｐ−カルボキシフェニル酢酸、ｐ−フェニレン二酢酸、ｍ−フェニレンジグリコール酸、ｐ−フェニレンジグリコール酸、ｏ−フェニレンジグリコール酸、ジフェニル酢酸、ジフェニル−ｐ，ｐ’−ジカルボン酸、ナフタレン−１，４−ジカルボン酸、ナフタレン−１，５−ジカルボン酸、ナフタレン−２，６−ジカルボン酸、アントラセンジカルボン酸、シクロヘキサンジカルボン酸等が挙げられる。また、ジカルボン酸以外の多価カルボン酸としては、例えば、トリメリット酸、ピロメリット酸、ナフタレントリカルボン酸、ナフタレンテトラカルボン酸、ピレントリカルボン酸、ピレンテトラカルボン酸等が挙げられる。 Examples of polyvalent carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, and fumal. Acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelliic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid Acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid , Naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. Examples of the polyvalent carboxylic acid other than the dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrentricarboxylic acid, pyrenetetracarboxylic acid and the like.
多価アルコールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，４−ブテンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタントリオール、グリセロール、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５−トリヒドロキシメチルベンゼン、ビスフェノールＡ、ビスフェノールＡエチレンオキサイド付加物、ビスフェノールＡプロピレンオキサイド付加物、水素化ビスフェノールＡ、水素化ビスフェノールＡエチレンオキサイド付加物、水素化ビスフェノールＡプロピレンオキサイド付加物などが挙げられる。 Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, and 1,5. -Pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1, 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4 -Butantriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydride bisphenol A, hydride bisphenol A ethylene Examples thereof include an oxide adduct and a hydride bisphenol A propylene oxide adduct.
本発明のトナーは、離型剤を含有しても良い。離型剤としては、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、パラフィンワックスの如き脂肪族炭化水素系ワックス；酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；脂肪族炭化水素系ワックスのブロック共重合物；カルナバワックス、サゾールワックス、モンタン酸エステルワックスの如き脂肪酸エステルを主成分とするワックス；及び脱酸カルナバワックスの如き脂肪酸エステルを一部又は全部を脱酸化したもの、ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂を水素添加することによって得られるヒドロキシ基を有するメチルエステル化合物が挙げられる。 The toner of the present invention may contain a mold release agent. As the release agent, fatty acid hydrocarbon-based waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystallin wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax; aliphatic hydrocarbon waxes. Block copolymer; wax containing fatty acid ester as a main component such as carnauba wax, sazole wax, montanic acid ester wax; and deoxidized fatty acid ester such as carnauba wax partially or completely deoxidized, behenic acid Partial esterifications of fatty acids and polyhydric alcohols such as monoglycerides; methyl ester compounds with hydroxy groups obtained by hydrogenating vegetable fats and oils.
離型剤の分子量分布としては、メインピークが分子量４００以上２４００以下の領域にあることが好ましく、４３０以上２０００以下の領域にあることがより好ましい。これによって、トナーに好ましい熱特性を付与することができる。離型剤の添加量は、結着樹脂１００質量部に対して総量で２．５０質量部以上４０．０質量部以下であることが好ましく、３．００質量部以上１５．０質量部以下であることがより好ましい。 As for the molecular weight distribution of the release agent, the main peak is preferably in the region having a molecular weight of 400 or more and 2400 or less, and more preferably in the region of 430 or more and 2000 or less. This makes it possible to impart favorable thermal properties to the toner. The total amount of the release agent added is preferably 2.50 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the binder resin, and is 3.00 parts by mass or more and 15.0 parts by mass or less. More preferably.
本発明のトナーの製造方法について説明する。本発明のトナーは従来公知の方法によって製造することができる。例えば、結着樹脂を得るための重合性単量体、顔料、極性樹脂及び必要に応じて離型剤等を含む重合性単量体組成物を水系媒体に懸濁・造粒し、重合性単量体組成物中の重合性単量体を重合する懸濁重合法；結着樹脂、顔料、極性樹脂及び必要に応じて離型剤等の各種トナー構成材料を混練、粉砕、分級する混練粉砕法；結着樹脂を乳化して分散した分散液と、顔料分散液と、極性樹脂を乳化して分散した分散液と必要に応じて離型剤等の分散液とを混合し、凝集、加熱融着させ、トナー粒子を得る乳化凝集法；結着樹脂を構成する重合性単量体を乳化重合させ、形成された分散液と、顔料分散液、極性樹脂を乳化、分散した極性樹脂分散液と、必要に応じて離型剤等の分散液とを混合し、凝集、加熱融着させ、トナー粒子を得る乳化重合凝集法；有機溶媒中に結着樹脂、顔料、極性樹脂及び必要に応じて離型剤等を含む有機溶媒分散液を水系媒体に懸濁させて造粒する溶解懸濁法；等が使用できる。 The method for producing the toner of the present invention will be described. The toner of the present invention can be produced by a conventionally known method. For example, a polymerizable monomer composition containing a polymerizable monomer, a pigment, a polar resin, and a mold release agent if necessary for obtaining a binder resin is suspended and granulated in an aqueous medium, and is polymerizable. Suspension polymerization method for polymerizing a polymerizable monomer in a monomer composition; kneading, crushing, and classifying various toner constituent materials such as a binder resin, a pigment, a polar resin, and a mold release agent as necessary. Grinding method: A dispersion liquid obtained by emulsifying and dispersing a binder resin, a pigment dispersion liquid, a dispersion liquid obtained by emulsifying and dispersing a polar resin, and a dispersion liquid such as a mold release agent are mixed and aggregated, if necessary. Emulsion aggregation method to obtain toner particles by heat fusion; Emulsion-polymerized polymerizable monomer constituting the binder resin, and emulsified and dispersed the dispersion liquid, the pigment dispersion liquid, and the polar resin. Emulsion polymerization aggregation method in which a liquid and a dispersion liquid such as a mold release agent are mixed as necessary, aggregated and heat-fused to obtain toner particles; a binder resin, a pigment, a polar resin and, if necessary, in an organic solvent. Therefore, a dissolution-suspension method in which an organic solvent dispersion containing a mold release agent or the like is suspended in an aqueous medium for granulation; or the like can be used.
本発明において、トナーの画質向上のために、外添剤がトナー粒子に外部添加されていてもよい。外添剤としては、シリカ微粉体、酸化チタン微粉体、または酸化アルミニウム微粉体のような無機微粉体が好適に用いられる。これら無機微粉体は、シランカップリング剤、シリコーンオイルまたはそれらの混合物の疎水化剤で疎水化処理されていることが好ましい。さらに、本発明のトナーは必要に応じて、前記以外の外添剤をトナー粒子に混合してもよい。無機微粉体の添加量は、トナー粒子１００質量部に対して、０．５質量部以上５．０質量部以下であることが好ましい。 In the present invention, an external additive may be externally added to the toner particles in order to improve the image quality of the toner. As the external additive, inorganic fine powder such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder is preferably used. These inorganic fine powders are preferably hydrophobized with a silane coupling agent, silicone oil or a hydrophobizing agent of a mixture thereof. Further, the toner of the present invention may be mixed with an external additive other than the above with the toner particles, if necessary. The amount of the inorganic fine powder added is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.
＜顔料に対する極性樹脂の吸着率の測定方法＞
吸着率は以下のように測定する。
顔料 １．０ｇ
極性樹脂 ０．１５ｇ
スチレン １６．０ｇ
ｎ−ブチルアクリレート ４．０ｇ
ガラスビーズ（直径０．８ｍｍ） ３０．０ｇ
上記材料を５０ｍｌの耐圧瓶に秤量する。その後ペイントシェイカー（東洋精機株式会社製）にて１０時間振とうする。
<Measurement method of adsorption rate of polar resin for pigment>
The adsorption rate is measured as follows.
Pigment 1.0g
Polar resin 0.15g
Styrene 16.0g
n-Butyl acrylate 4.0g
Glass beads (0.8 mm in diameter) 30.0 g
The above materials are weighed in a 50 ml pressure resistant bottle. Then shake with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 10 hours.
振とう後の分散液を遠心分離器（ｅｐｐｅｎｄｏｒｆ社製・ｍｉｎｉ ｓｐｉｎ ｐｌｕｓ：１４．５ｋｒｐｍ、３０分間）で分離し、上澄みを取る。 The dispersion after shaking is separated by a centrifuge (mini spin plus: 14.5 krpm, 30 minutes manufactured by eppendorf), and the supernatant is removed.
上澄みをマイレクス ＬＨ０．４５μｍ（日本ミリポア社製）でろ過し、ろ液をゲルパーミエーションクロマトグラフィー（ＧＰＣ）で分析する。得られたクロマトグラム（縦軸：濃度に依存した電気的強度、横軸：リテンションタイム）のピーク面積をＳ１とする。なお、縦軸は、濃度に依存した指標であればよく、特に限定されない。 The supernatant is filtered through Milex LH 0.45 μm (manufactured by Millipore, Japan), and the filtrate is analyzed by gel permeation chromatography (GPC). Let S1 be the peak area of the obtained chromatogram (vertical axis: electrical intensity depending on concentration, horizontal axis: retention time). The vertical axis may be an index depending on the concentration and is not particularly limited.
同様に、下記材料を混合した溶液をマイレクスでろ過し、ろ液をＧＰＣで分析する。
極性樹脂 ０．１５ｇ
スチレン １６．０ｇ
ｎ−ブチルアクリレート ４．０ｇ
Similarly, the solution mixed with the following materials is filtered by Milex, and the filtrate is analyzed by GPC.
Polar resin 0.15g
Styrene 16.0g
n-Butyl acrylate 4.0g
得られたクロマトグラムのピーク面積をＳ２とする。なお、以下でＳ１とＳ２との面積比と求めるため、ピーク面積Ｓ１およびＳ２を求めるクロマトグラムは、同じ縮尺度の縦軸及び横軸を用いたクロマトグラムを作成する。 Let the peak area of the obtained chromatogram be S2. In order to obtain the area ratio of S1 and S2 below, the chromatogram for obtaining the peak areas S1 and S2 prepares a chromatogram using the vertical axis and the horizontal axis of the same scale.
下記式に従って、顔料に対する顔料分散剤又は非晶性樹脂の吸着率を算出する。
吸着率（％）＝（１−Ｓ１／Ｓ２）×１００
The adsorption rate of the pigment dispersant or the amorphous resin with respect to the pigment is calculated according to the following formula.
Adsorption rate (%) = (1-S1 / S2) x 100
なお、ＧＰＣは、以下の条件で分析する。
装置：ＨＬＣ８１２０ ＧＰＣ（検出器：ＲＩ）（東ソー社製）
カラム：Ｓｈｏｄｅｘ ＫＦ−８０１、８０２、８０３、８０４、８０５、８０６、８０７の７連（昭和電工社製）
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍｌ／ｍｉｎ
オーブン温度：４０．０℃
試料注入量：０．１０ｍｌ
The GPC is analyzed under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
試料の分子量の算出にあたっては、標準ポリスチレン樹脂（商品名「ＴＳＫスタンダード ポリスチレン Ｆ−８５０、Ｆ−４５０、Ｆ−２８８、Ｆ−１２８、Ｆ−８０、Ｆ−４０、Ｆ−２０、Ｆ−１０、Ｆ−４、Ｆ−２、Ｆ−１、Ａ−５０００、Ａ−２５００、Ａ−１０００、Ａ−５００」、東ソ−社製）を用いて作成した分子量校正曲線を使用する。 In calculating the molecular weight of the sample, standard polystyrene resin (trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10," A molecular weight calibration curve prepared using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Toso Co., Ltd.) is used.
＜樹脂酸価の測定方法＞
酸価は試料１ｇに含まれる酸を中和するために必要な水酸化カリウムのｍｇ数である。本発明における酸価は、ＪＩＳ Ｋ ００７０−１９９２に準じて測定されるが、具体的には、以下の手順に従って測定する。
<Measuring method of resin acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
０．１モル／Ｌ水酸化カリウムエチルアルコール溶液（キシダ化学（株）製）を用いて滴定を行う。前記水酸化カリウムエチルアルコール溶液のファクターは、電位差滴定装置（京都電子工業（株）製 電位差滴定測定装置ＡＴ−５１０）を用いて求めることができる。０．１００モル／Ｌ塩酸１００ｍＬを２５０ｍＬトールビーカーに取り、前記水酸化カリウムエチルアルコール溶液で滴定し、中和に要した前記水酸化カリウムエチルアルコール溶液の量から求める。前記０．１００モル／Ｌ塩酸は、ＪＩＳ Ｋ ８００１−１９９８に準じて作製されたものを用いる。 Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titration device (potentiometric titration measuring device AT-510 manufactured by Kyoto Denshi Kogyo Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
下記に酸価測定の際の測定条件を示す。
滴定装置：電位差滴定装置ＡＴ−５１０（京都電子工業（株）製）
電極：複合ガラス電極ダブルジャンクション型（京都電子工業（株）製）
滴定装置用制御ソフトウエア：ＡＴ−ＷＩＮ
滴定解析ソフト：Ｔｖｉｅｗ
滴定時における滴定パラメーター並びに制御パラメーターは下記のように行う。
滴定パラメーター
滴定モード：ブランク滴定
滴定様式：全量滴定
最大滴定量：２０ｍＬ
滴定前の待ち時間：３０秒
滴定方向：自動
制御パラメーラー
終点判断電位：３０ｄＥ
終点判断電位値：５０ｄＥ／ｄｍＬ
終点検出判断：設定しない
制御速度モード：標準
ゲイン：１
データ採取電位：４ｍＶ
データ採取滴定量：０．１ｍＬ
The measurement conditions for acid value measurement are shown below.
Titration device: Potentiometric titration device AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Denshi Kogyo Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank Titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control Paramailer End point judgment potential: 30dE
End point judgment potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection Titration: 0.1 mL
本試験；
測定サンプル０．１００ｇを２５０ｍＬのトールビーカーに精秤し、トルエン／エタノール（３：１）の混合溶液１５０ｍＬを加え、１時間かけて溶解し、測定サンプルとした。前記電位差滴定装置を用い、前記水酸化カリウムエチルアルコール溶液を用いて滴定する。
Main test;
0.100 g of the measurement sample was precisely weighed in a 250 mL tall beaker, 150 mL of a mixed solution of toluene / ethanol (3: 1) was added, and the mixture was dissolved over 1 hour to prepare a measurement sample. Titration is performed using the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
空試験；
試料を用いない（すなわちトルエン／エタノール（３：１）の混合溶液のみとする）以外は、上記操作と同様の滴定を行う。
Blank test;
Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).
得られた結果を下記式に代入して、酸価を算出する。
Ａ＝［（Ｃ−Ｂ）×ｆ×５．６１１］／Ｓ
（式中、Ａ：酸価（ｍｇＫＯＨ／ｇ）、Ｂ：空試験の水酸化カリウムエチルアルコール溶液の添加量（ｍＬ）、Ｃ：本試験の水酸化カリウムエチルアルコール溶液の添加量（ｍＬ）、ｆ：水酸化カリウム溶液のファクター、Ｓ：試料（ｇ）である。）
The acid value is calculated by substituting the obtained result into the following formula.
A = [(CB) x f x 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide solution, S: Sample (g).)
＜樹脂分散液の個数平均粒径Ｄ１の測定＞
動的光散乱式マイクロトラック粒度分布測定装置［ＵＰＡ−１５０］（日機装（株））を用い、樹脂分散液の粒度分布を算出する。測定に用いる水系媒体と測定セル温度が同じになるように、セルの温調を行ないながら測定を行う。粒径測定は、温度２５℃で行う。
（１）セル内部にＲＯ水：３．０ｇを入れた後、Ｂａｃｋ ｇｒｏｕｎｄ ｃｈｅｃｋを行う。サンプルローディングが、０．００１０以下になるのを確認する。
（２）セル内部にＲＯ水：３．０ｇを入れた後、Ｓｅｔ Ｚｅｒｏを行う。Ｓｅｔ Ｚ
ｅｒｏの条件は、時間：６０秒で行う。
（３）以下の条件を入力する。
測定時間：３０ｓ、測定回数：２回
粒子条件：透過性、屈折率：１．６２、形状：非球形、密度：３．１７
溶媒条件：ＷＡＴＥＲを選択
屈折率：１．３３３
高温時粘度：０．７９７（３０℃）、低温時粘度：１．００２（２０℃）
表示設定：標準を選択
分布表示：体積を選択
（４）測定セルに乳化粒子を含有する水系媒体：３．０ｇを入れ、測定を開始する。
（５）測定データを装置付属の専用ソフトにて解析を行い、個数平均粒径（Ｄ１）を算出する。
<Measurement of number average particle size D1 of resin dispersion liquid>
The particle size distribution of the resin dispersion is calculated using a dynamic light scattering type microtrack particle size distribution measuring device [UPA-150] (Nikkiso Co., Ltd.). The measurement is performed while adjusting the temperature of the cell so that the temperature of the measurement cell is the same as that of the aqueous medium used for the measurement. The particle size is measured at a temperature of 25 ° C.
(1) After putting 3.0 g of RO water inside the cell, back ground check is performed. Confirm that the sample loading is 0.0010 or less.
(2) After putting 3.0 g of RO water inside the cell, Set Zero is performed. Set Z
The condition of ero is time: 60 seconds.
(3) Enter the following conditions.
Measurement time: 30s, Number of measurements: 2 Particle conditions: Transparency, Refractive index: 1.62, Shape: Non-spherical, Density: 3.17
Solvent condition: Select WATER Refractive index: 1.333
Viscosity at high temperature: 0.797 (30 ° C), Viscosity at low temperature: 1.002 (20 ° C)
Display setting: Select standard Distribution display: Select volume (4) Put 3.0 g of aqueous medium containing emulsified particles in the measurement cell and start measurement.
(5) The measurement data is analyzed by the dedicated software attached to the device, and the number average particle diameter (D1) is calculated.
＜顔料の結晶子サイズの測定方法＞
顔料の結晶子サイズは、Ｘ線回折（ＸＲＤ）を用いて、以下のような方法で測定した。
<Measuring method of pigment crystallite size>
The crystallite size of the pigment was measured by the following method using X-ray diffraction (XRD).
顔料は、下記装置および測定条件で測定を行った。
測定装置：ＲＩＮＲ−ＴＴＲＩＩ（リガク社製）
管球：Ｃｕ
開始角度：３°
終了角度：６０°
サンプリング幅：０．０２°
スキャンスピード：４．００°／ｍｉｎ
電圧：５０ｋＶ
電流：３００ｍＡ
平行ビーム光学系
発散スリット：開放
発散縦スリット：１０ｍｍ
散乱スリット：開放
受光スリット：開放
The pigment was measured with the following equipment and measurement conditions.
Measuring device: RINR-TTRII (manufactured by Rigaku)
Tube: Cu
Starting angle: 3 °
End angle: 60 °
Sampling width: 0.02 °
Scan speed: 4.00 ° / min
Voltage: 50kV
Current: 300mA
Parallel beam optical system divergence slit: open divergence vertical slit: 10 mm
Scattering slit: Open Light receiving slit: Open
上記測定条件により得られたスペクトルは以下のようにして波形処理を行い、計算スペクトルを算出した。 The spectrum obtained under the above measurement conditions was subjected to waveform processing as follows to calculate a calculated spectrum.
得られたスペクトルに対し、マニュアルでバックグラウンド処理を行った。その後、分割型疑Ｖｏｉｇｔ関数でフィッティングを行い、元のスペクトルとのピーク形状との乖離があれば、手動で計算スペクトルの調整を行った。 The obtained spectrum was manually subjected to background processing. After that, fitting was performed by the split type suspicious Voigt function, and if there was a deviation from the peak shape from the original spectrum, the calculated spectrum was manually adjusted.
上記操作にて得られた計算スペクトルのブラッグ角が３°から６０°（３°＜２θ＜６０°）の範囲内におけるピークの結晶子サイズの中で、最大積分強度を有するピークにおける結晶子サイズを結晶子サイズ（Ｄ）とした。 Among the crystallite sizes of peaks in which the Bragg angle of the calculated spectrum obtained by the above operation is in the range of 3 ° to 60 ° (3 ° <2θ <60 °), the crystallite size at the peak having the maximum integrated intensity. Was defined as the crystallite size (D).
＜ＡＶＨ／ＡＶＥの測定方法＞
（ＡＶＨ用試料作製）
トナー粒子０．５００ｇを１００ｍｌのビーカーに秤量し、和光純薬工業社製界面活性剤「コンタミノンＮ」０．１ｇと、イオン交換水４９．９ｇを加え、超音波分散器（シャープ製ＵＴ−３０５ＨＳ）で１分間分散させる。
<AVH / AVE measurement method>
(Preparation of sample for AVH)
Weigh 0.500 g of toner particles into a 100 ml beaker, add 0.1 g of Wako Pure Chemical Industries, Ltd. surfactant "Contaminone N" and 49.9 g of ion-exchanged water, and add an ultrasonic disperser (UT- made by Sharp). Disperse at 305HS) for 1 minute.
（ＡＶＥ試料作製）
トナー粒子０．５００ｇを１００ｍｌのビーカーに秤量し、エタノール５０ｇを加え、３０分間撹拌する。
(Preparation of AVE sample)
Weigh 0.500 g of toner particles into a 100 ml beaker, add 50 g of ethanol, and stir for 30 minutes.
上記樹脂酸価の測定方法の本試験において、測定サンプルをＡＶＨ試料とＡＶＥ試料にそれぞれ変更する以外は同様にして酸価を測定する。 In this test of the above method for measuring the resin acid value, the acid value is measured in the same manner except that the measurement sample is changed to an AVH sample and an AVE sample, respectively.
＜トナー粒子からの顔料の単離方法＞
本件顔料の結晶子サイズおよびアセトン濡れ性の測定においては、以下の方法でトナーから顔料を単離し、測定することができる。
<Method of isolating pigment from toner particles>
In the measurement of the crystallite size and the wettability of acetone of the Pigment, the pigment can be isolated from the toner and measured by the following method.
ＴＨＦ ５００ｇが入った１Ｌビーカー中にトナー５０ｇを投入し、マグネチックスターラーを用いて１００ｒｐｍの回転数で２４時間撹拌した。前記分散液を２４時間静置し、不溶分が沈降させた。次に顔料分散体を含んだＴＨＦ可溶分（上澄み）をデカンテーションによって回収した。回収した上澄み液を遠心分離に掛け、沈降した顔料を回収した。回収した顔料を蒸留水で３回水洗し、乾燥後、乳鉢で凝集した粗大粒子を砕いた。測定に要する顔料量に満たない場合は、前記操作を繰り返し行った。 50 g of toner was put into a 1 L beaker containing 500 g of THF, and the mixture was stirred at a rotation speed of 100 rpm for 24 hours using a magnetic stirrer. The dispersion was allowed to stand for 24 hours to allow the insoluble matter to settle. Next, the THF-soluble component (supernatant) containing the pigment dispersion was recovered by decantation. The recovered supernatant was centrifuged to recover the precipitated pigment. The recovered pigment was washed with distilled water three times, dried, and then the aggregated coarse particles were crushed in a mortar. When the amount of pigment required for the measurement was not enough, the above operation was repeated.
＜アセトン濡れ性の測定方法＞
顔料のアセトン濡れ性Ｗは粉体濡れ性試験機を用いて以下のような方法で測定を行った。
測定装置：ＷＥＴ１０１Ｐ（株式会社レスカ製）
<Acetone wettability measurement method>
The acetone wettability W of the pigment was measured by the following method using a powder wettability tester.
Measuring device: WET101P (manufactured by Reska Co., Ltd.)
顔料５０ｍｇを量り取り、蒸留水７０．０ｍｌを入れた２００ｍｌトールビーカーの上に静かに浮かべた。スターラーで上記液を撹拌しながら、アセトンを０．５ｍｌ／ｍｉｎの速度で水相に供給し、半導体レーザーによって透過率を測定した。測定において得られた透過率が５０％となった時の水−アセトン混合溶媒中におけるアセトンの体積分率をアセトン濡れ性とした。 50 mg of pigment was weighed and gently floated on a 200 ml tall beaker containing 70.0 ml of distilled water. Acetone was supplied to the aqueous phase at a rate of 0.5 ml / min while stirring the above liquid with a stirrer, and the transmittance was measured with a semiconductor laser. The volume fraction of acetone in the water-acetone mixture solvent when the transmittance obtained in the measurement was 50% was defined as the acetone wettability.
＜ＳＰ値の算出方法＞
結着樹脂のＳＰ値は、Ｆｅｄｏｒｓによって提案された算出方法に従い、以下のようにして求める。
<Calculation method of SP value>
The SP value of the binder resin is obtained as follows according to the calculation method proposed by Fedors.
各重合性単量体について、分子構造中の原子又は原子団に対して、「ｐｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，１４（２），１４７−１５４（１９７４）」に記載の表から蒸発エネルギー（Δｅｉ）（ｃａｌ／ｍｏｌ）及びモル体積（Δｖｉ）（ｃｍ3／ｍｏｌ）を求め、（ΣΔｅｉ／ΣΔｖｉ）をＳＰ値（ｃａｌ／ｃｍ3）とする。 For each polymerizable monomer, for atoms or atomic groups in the molecular structure, the evaporation energy (Δei) from the table described in “polym. Eng. Sci., 14 (2), 147-154 (1974)”. (Cal / mol) and molar volume (Δvi) (cm 3 / mol) are obtained, and (ΣΔei / ΣΔvi) is defined as the SP value (cal / cm 3 ).
重合体を構成する重合性単量体に由来するモノマーユニットの蒸発エネルギー（Δｅｉ）及びモル体積（Δｖｉ）をモノマーユニット毎に求め、各モノマーユニットのモル比（ｊ）との積をそれぞれ算出し、各モノマーユニットの蒸発エネルギーの総和をモル体積の総和で割ることによって求め、下記式（８）より算出する。
ＳＰ値＝｛（Σｊ×ΣΔｅｉ）／（Σｊ×ΣΔｖｉ）｝0.5 （８）
The evaporation energy (Δei) and molar volume (Δvi) of the monomer units derived from the polymerizable monomer constituting the polymer were obtained for each monomer unit, and the product with the molar ratio (j) of each monomer unit was calculated. , It is calculated by dividing the total evaporation energy of each monomer unit by the total molar volume, and is calculated by the following formula (8).
SP value = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 0.5 (8)
＜トナー粒子及びトナーの重量平均粒径（Ｄ４）の測定方法＞
トナー粒子及びトナーの重量平均粒径（Ｄ４）は、精密粒度分布測定装置「コールター・カウンター Ｍｕｌｔｉｓｉｚｅｒ ３」（登録商標、ベックマン・コールター社製）を用いて測定する。測定は下記条件で行う。
実効測定チャンネル数：２万５千チャンネル
コントロールモーター総個数：５００００個
アパチャー：１００μｍ
カレント：１６００μＡ
ゲイン；２
<Measuring method of toner particles and weight average particle size (D4) of toner>
The toner particles and the weight average particle diameter (D4) of the toner are measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). The measurement is performed under the following conditions.
Number of effective measurement channels: 25,000 channels Total number of control motors: 50,000 Aperture: 100 μm
Current: 1600 μA
Gain; 2
Ｋｄ値は「標準粒子１０．０μｍ」（ベックマン・コールター社製）を用いて得られた値で測定する。測定データを装置付属の専用ソフトにて解析を行ない、重量平均粒径（Ｄ４）を算出する。なお、前述の専用ソフトでグラフ／体積％と設定したときの、「分析／体積統計値（算術平均）」画面の「平均径」が重量平均粒径（Ｄ４）である。 The Kd value is measured with a value obtained using "standard particles 10.0 μm" (manufactured by Beckman Coulter). The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the above-mentioned dedicated software is the weight average particle diameter (D4).
本発明を以下に示す実施例により具体的に説明する。しかし、これは本発明をなんら限定するものではない。実施例及び比較例中の「部」は特に断りがない場合、全て質量基準である。 The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. Unless otherwise specified, all "parts" in Examples and Comparative Examples are based on mass.
＜極性樹脂１の製造例＞
原材料（酸成分およびアルコール成分）を表１に示す比率（ｍｏｌ％）で混合した混合物１００部と、触媒としての、ジ（２−エチルヘキサン酸）スズ０．５２部とを、窒素導入管、脱水管、撹拌機および熱電対を装備した６リットルの四つ口フラスコに入れ、窒素雰囲気下、２００℃で６時間かけて反応させた。さらに、２１０℃にて無水トリメリット酸を添加して、４０ｍｍＨｇの減圧下にて反応を行い、重量平均分子量（Ｍｗ）が１２０００になるまで反応を続けた。得られたポリエステル樹脂を極性樹脂１とする。また、得られた極性樹脂１の酸価は表１のようになった。
<Production example of polar resin 1>
100 parts of the mixture in which the raw materials (acid component and alcohol component) were mixed at the ratio (mol%) shown in Table 1 and 0.52 parts of di (2-ethylhexanoic acid) tin as a catalyst were placed in a nitrogen introduction tube. The flask was placed in a 6-liter four-necked flask equipped with a dehydration tube, a stirrer and a thermocouple, and reacted at 200 ° C. for 6 hours under a nitrogen atmosphere. Further, trimellitic anhydride was added at 210 ° C., and the reaction was carried out under a reduced pressure of 40 mmHg, and the reaction was continued until the weight average molecular weight (Mw) reached 12000. The obtained polyester resin is designated as polar resin 1. The acid value of the obtained polar resin 1 is as shown in Table 1.
＜極性樹脂２〜６の製造例＞
極性樹脂１の製造例において、原材料を表１に示す仕込み比率で混合する以外は極性樹脂１の製造例と同様にして極性樹脂２〜６を得た。得られた極性樹脂２〜６の酸価は表１に示す。
<Production example of polar resins 2 to 6>
In the production example of the polar resin 1, polar resins 2 to 6 were obtained in the same manner as in the production example of the polar resin 1 except that the raw materials were mixed at the charging ratio shown in Table 1. The acid values of the obtained polar resins 2 to 6 are shown in Table 1.
＜極性樹脂７の製造例＞
撹拌機、コンデンサー、温度計、窒素導入管を付した反応容器にキシレン２００部を仕込み、窒素気流下で還流した。
・２−アクリルアミド−２−メチルプロパンスルホン酸 ６．００部
・スチレン ７８．０部
・２−エチルヘキシルアクリレート １６．０部
・ジメチル−２，２’−アゾビス（２−メチルプロピオネート） ５．００部
を混合し、前記反応容器に撹拌しながら滴下し１０時間保持した。その後、蒸留を行って溶剤を留去し、減圧下４０℃で乾燥し極性樹脂７を得た。得られた極性樹脂７の酸価は表１に示す。
<Production example of polar resin 7>
200 parts of xylene was charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and refluxed under a nitrogen stream.
-2-acrylamide-2-methylpropanesulfonic acid 6.00 parts-Styrene 78.0 parts-2-ethylhexyl acrylate 16.0 parts-Dimethyl-2,2'-azobis (2-methylpropionate) 5.00 The parts were mixed, added dropwise to the reaction vessel with stirring, and held for 10 hours. Then, distillation was performed to distill off the solvent, and the mixture was dried under reduced pressure at 40 ° C. to obtain a polar resin 7. The acid value of the obtained polar resin 7 is shown in Table 1.
＜極性樹脂８の製造例＞
フラスコ内にキシレン３００部を投入し、撹拌しながら容器内を十分に窒素で置換した後、昇温して還流させる。
・スチレン ９２．５３部
・メタクリル酸メチル ２．５０部
・メタクリル酸２−ヒドロキシエチル ２．５０部
・メタクリル酸 ２．４８部
・パーブチルＤ（日本油脂製） ２．００部
上記混合液を添加した後、重合温度を１７５℃、圧力を０．１０ＭＰａとして５時間重合を行った。その後、減圧下にて脱溶剤工程を３時間行い、キシレンを除去して、粉砕することで極性樹脂８を得た。得られた極性樹脂８の酸価を表１に示す。
<Production example of polar resin 8>
300 parts of xylene is put into the flask, the inside of the container is sufficiently replaced with nitrogen while stirring, and then the temperature is raised to reflux.
-Styrene 92.53 parts-Methyl methacrylate 2.50 parts-2-Hydroxyethyl methacrylate 2.50 parts-Methacrylic acid 2.48 parts-Perbutyl D (manufactured by NOF Corporation) 2.00 parts The above mixture was added. After that, the polymerization was carried out for 5 hours at a polymerization temperature of 175 ° C. and a pressure of 0.10 MPa. Then, the solvent removal step was carried out under reduced pressure for 3 hours to remove xylene and pulverize the mixture to obtain a polar resin 8. The acid value of the obtained polar resin 8 is shown in Table 1.
＜極性樹脂９の製造例＞
極性樹脂８の製造例において、処方内容を以下のようにし、重合時の圧力を０．５０ＭＰａ変更することを除いて、極性樹脂８と同様にして製造し、極性樹脂９を得た。得られた極性樹脂９の酸価を表１に示す。
・スチレン ９１．３０部
・メタクリル酸メチル ２．５０部
・メタクリル酸２−ヒドロキシエチル １．２５部
・メタクリル酸 ４．９５部
・パーブチルＤ（日本油脂製） ２．００部
<Production example of polar resin 9>
In the production example of the polar resin 8, the formulation contents were as follows, and the polar resin 9 was produced in the same manner as the polar resin 8 except that the pressure at the time of polymerization was changed by 0.50 MPa. The acid value of the obtained polar resin 9 is shown in Table 1.
・ Styrene 91.30 parts ・ Methyl methacrylate 2.50 parts ・ 2-Hydroxyethyl methacrylate 1.25 parts ・ Methacrylic acid 4.95 parts ・ Perbutyl D (manufactured by NOF Corporation) 2.00 parts
＜極性樹脂１０の製造例＞
（工程１）
２，５−ジヒドロキシ安息香酸１００ｇと８０％硫酸１４４１ｇとを５０℃に加熱混合した。この分散液にｔｅｒｔ−ブチルアルコール１４４ｇを加えて５０℃で３０分間撹拌した。その後、この分散液にｔｅｒｔ−ブチルアルコール１４４ｇを加え３０分間撹拌する操作を３回行った。反応液を室温まで冷却し、氷水１ｋｇにゆっくり注いだ。析出物を濾過、水洗し、その後、ヘキサン洗浄した。この析出物をメタノール２００ｍＬに溶解させ、水３．６Ｌに再沈殿させた。濾過後、８０℃にて乾燥することで下記構造式（９）に示すサリチル酸中間体７４．９ｇを得た。
<Production example of polar resin 10>
(Step 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. 144 g of tert-butyl alcohol was added to this dispersion, and the mixture was stirred at 50 ° C. for 30 minutes. Then, 144 g of tert-butyl alcohol was added to the dispersion, and the mixture was stirred for 30 minutes three times. The reaction was cooled to room temperature and slowly poured into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following structural formula (9).
（工程２）
得られたサリチル酸中間体２５．０ｇをメタノール１５０ｍＬに溶解させ、炭酸カリウム３６．９ｇを加えて６５℃に加熱した。この反応液に４−（クロロメチル）スチレン１８．７ｇとメタノール１００ｍＬの混合液を滴下し、６５℃にて３時間反応させた。反応液を冷却後、濾過し、濾液を濃縮して粗生成物を得た。粗生成物をｐＨ＝２の水１．５Ｌに分散させ、酢酸エチルを加えて抽出した。その後、水洗し、硫酸マグネシウムで乾燥させ、減圧下、酢酸エチルを留去して析出物を得た。析出物をヘキサン洗浄後、トルエンと酢酸エチルにて再結晶することで精製し、下記構造式（１０）に示す重合性単量体を２０．１ｇ得た。
(Step 2)
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol, 36.9 g of potassium carbonate was added, and the mixture was heated to 65 ° C. A mixed solution of 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise to this reaction solution, and the mixture was reacted at 65 ° C. for 3 hours. The reaction mixture was cooled, filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water having a pH of 2, and ethyl acetate was added for extraction. Then, it was washed with water, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and then purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of a polymerizable monomer represented by the following structural formula (10).
式（１０）に示す重合性単量体 ５．９ｇ、２−エチルヘキシルアクリレート ７．８ｇ、スチレン ５６．４ｇをＤＭＦ４２．０ｍｌに溶解させ、窒素バブリングをしながら１時間撹拌した後、１１０℃まで加熱した。この反応液に、開始剤としてｔｅｒｔ−ブチルパーオキシイソプロピルモノカルボネート（日本油脂株式会社製、商品名パーブチルＩ）２．１ｇとトルエン４２ｍｌの混合液を滴下した。更に１１０℃にて４時間反応した。その後、冷却しメタノール１Ｌに滴下し、析出物を得た。得られた析出物をＴＨＦ１２０ｍｌに溶解後、メタノール１．８０Ｌに滴下し、白色析出物を析出させ、濾過し、減圧下９０℃にて乾燥させることで、極性樹脂１０を５７．６ｇ得た。得られた極性樹脂１０の酸価を表１に示す。 5.9 g of the polymerizable monomer represented by the formula (10), 7.8 g of 2-ethylhexyl acrylate, and 56.4 g of styrene were dissolved in 42.0 ml of DMF, stirred for 1 hour with nitrogen bubbling, and then heated to 110 ° C. did. A mixture of 2.1 g of tert-butylperoxyisopropyl monocarbonate (manufactured by NOF CORPORATION, trade name: Perbutyl I) and 42 ml of toluene was added dropwise to the reaction solution. The reaction was further carried out at 110 ° C. for 4 hours. Then, it was cooled and added dropwise to 1 L of methanol to obtain a precipitate. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure to obtain 57.6 g of polar resin 10. The acid value of the obtained polar resin 10 is shown in Table 1.
＜極性樹脂１１の製造例＞
極性樹脂１を３部と、極性樹脂７を２部とを撹拌機を備えた反応容器に入れ、キシレン１０部に溶解させた。溶解したのを確認後、減圧下にて脱溶剤を行い、キシレンを除去して、粉砕することで極性樹脂１１を得た。得られた極性樹脂１１の酸価を表１に示す。
<Production example of polar resin 11>
Three parts of the polar resin 1 and two parts of the polar resin 7 were placed in a reaction vessel equipped with a stirrer and dissolved in 10 parts of xylene. After confirming that it was dissolved, the solvent was removed under reduced pressure to remove xylene and pulverized to obtain a polar resin 11. The acid value of the obtained polar resin 11 is shown in Table 1.
＜極性樹脂１２の製造例＞
極性樹脂８の製造例において、処方内容を以下のように変更する以外は同様にして極性樹脂１２を得た。得られた極性樹脂１２の酸価を表１に示す。
・スチレン ９４．２５部
・メタクリル酸メチル ２．４２部
・メタクリル酸 ３．３３部
・パーブチルＤ（日本油脂製） ２．００部
<Production example of polar resin 12>
In the production example of the polar resin 8, the polar resin 12 was obtained in the same manner except that the formulation was changed as follows. The acid value of the obtained polar resin 12 is shown in Table 1.
・ Styrene 94.25 parts ・ Methyl methacrylate 2.42 parts ・ Methacrylic acid 3.33 parts ・ Perbutyl D (manufactured by NOF Corporation) 2.00 parts
＜極性樹脂１３の製造例＞
極性樹脂８の製造例において、処方内容を以下のように変更する以外は同様にして極性樹脂１３を得た。得られた極性樹脂１３の酸価を表１に示す。
・スチレン ９２．８７部
・メタクリル酸メチル ２．４６部
・メタクリル酸２−ヒドロキシエチル ４．３５部
・メタクリル酸 ３．２０部
・パーブチルＤ（日本油脂製） ２．００部
<Production example of polar resin 13>
In the production example of the polar resin 8, the polar resin 13 was obtained in the same manner except that the formulation was changed as follows. The acid value of the obtained polar resin 13 is shown in Table 1.
-Styrene 92.87 parts-Methyl methacrylate 2.46 parts-2-Hydroxyethyl methacrylate 4.35 parts-Methacrylic acid 3.20 parts-Perbutyl D (manufactured by NOF Corporation) 2.00 parts
マゼンタ顔料の製造例を示す。 An example of manufacturing a magenta pigment is shown.
＜マゼンタ顔料１の製造例＞ <Production example of magenta pigment 1>
アミン化合物（Ｄ１）９０ｇ（０．５００ｍｏｌ）を蒸留水１０００ｍＬに分散させ、溶液を２０℃にて撹拌させた。これを３℃にした後、１２Ｎの塩酸（キシダ化学（株）製）を１４０ｍＬ滴下し、塩酸塩を得た。これに亜硝酸ナトリウム水溶液（日産化学（株）製）を９０ｇ加え、１０℃で２０分撹拌し、ジアゾ化合物含有溶液を得た。 90 g (0.500 mol) of the amine compound (D1) was dispersed in 1000 mL of distilled water, and the solution was stirred at 20 ° C. After the temperature was adjusted to 3 ° C., 140 mL of 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added dropwise to obtain a hydrochloride. 90 g of an aqueous sodium nitrite solution (manufactured by Nissan Chemical Co., Ltd.) was added thereto, and the mixture was stirred at 10 ° C. for 20 minutes to obtain a diazo compound-containing solution.
＜カップリング反応水溶液の調製＞ <Preparation of coupling reaction aqueous solution>
別途、カップリング化合物（Ｅ１）９７ｇ（０．３５０ｍｏｌ）、カップリング化合物（Ｅ２）４７ｇ（０．１５０ｍｏｌ）を蒸留水１０００ｍＬに分散させ、９５℃に加熱した後、３３％の水酸化ナトリウム水溶液 １６５ｇを加えて、９５℃で２分間撹拌した。その後、７０℃に保持し、カップリング反応水溶液を得た。 Separately, 97 g (0.350 mol) of the coupling compound (E1) and 47 g (0.150 mol) of the coupling compound (E2) were dispersed in 1000 mL of distilled water, heated to 95 ° C., and then 165 g of a 33% aqueous sodium hydroxide solution. Was added, and the mixture was stirred at 95 ° C. for 2 minutes. Then, the temperature was maintained at 70 ° C. to obtain an aqueous coupling reaction solution.
（アゾカップリング反応によるマゼンタ顔料の製造）
ジアゾ化合物含有溶液に、１９ｇの酢酸ナトリウムを加えて、ｐＨを４．５にして、１０℃に冷却した。その後、カップリング反応水溶液を１時間かけて滴下し、反応液が１０℃以上に上がらないように冷却しながら反応させた。その際に、ｐＨが４．９に維持されるように、１２Ｎの塩酸（キシダ化学（株）製）を随時添加した。その後、２０℃で４時間反応させた。その後、固形分をろ過、水洗した後、化合物Ａと化合物Ｂを７０：３０で含有する未処理のマゼンタ顔料１のウェットケーキを得た。
(Manufacture of magenta pigment by azo coupling reaction)
To the diazo compound-containing solution, 19 g of sodium acetate was added to adjust the pH to 4.5, and the mixture was cooled to 10 ° C. Then, the coupling reaction aqueous solution was added dropwise over 1 hour, and the reaction was carried out while cooling so that the reaction solution did not rise above 10 ° C. At that time, 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added at any time so that the pH was maintained at 4.9. Then, it reacted at 20 degreeC for 4 hours. Then, after the solid content was filtered and washed with water, an untreated magenta pigment 1 wet cake containing compound A and compound B at 70:30 was obtained.
（溶媒加熱処理によるマゼンタ顔料表面特性調整）
マゼンタ顔料１のウェットケーキ ２００部をアセトンで３回洗った後、アセトン １０００部に懸濁させた。液温を６０℃に昇温した後、温度を保ったまま２４時間撹拌した。室温に降温した後、ろ別し、１００部の蒸留水によって洗浄した後乾燥し、マゼンタ顔料１を得た。得られたマゼンタ顔料１の物性を表２に示す。
(Adjustment of magenta pigment surface characteristics by solvent heat treatment)
200 parts of the magenta pigment 1 wet cake was washed 3 times with acetone and then suspended in 1000 parts of acetone. After raising the liquid temperature to 60 ° C., the mixture was stirred for 24 hours while maintaining the temperature. After the temperature was lowered to room temperature, the mixture was filtered off, washed with 100 parts of distilled water, and then dried to obtain magenta pigment 1. Table 2 shows the physical characteristics of the obtained magenta pigment 1.
＜マゼンタ顔料２〜８、１１、１２の製造例＞
アミド化合物（Ｅ１）、アミド化合物（Ｅ２）の添加量、溶媒加熱処理によるマゼンタ顔料表面特性調整に用いる溶媒を表２に記載の通りに変更する以外は、マゼンタ顔料１と同様の方法により、マゼンタ顔料２〜８、１１、１２を得た。得られたマゼンタ顔料２〜８、１１、１２の物性を表２に示す。
<Production examples of magenta pigments 2-8, 11 and 12>
Magenta by the same method as magenta pigment 1 except that the amount of the amide compound (E1) and the amide compound (E2) added and the solvent used for adjusting the surface characteristics of the magenta pigment by solvent heat treatment are changed as shown in Table 2. Pigments 2-8, 11 and 12 were obtained. Table 2 shows the physical characteristics of the obtained magenta pigments 2-8, 11 and 12.
＜マゼンタ顔料９の製造例＞
（ロジン処理によるマゼンタ顔料表面特性調整）
・蒸留水 １０００部
・マゼンタ顔料１ １００部
上記材料を撹拌・混合し、マゼンタ顔料１を水中に懸濁させた。その後、テトラヒドロアビエチン酸１５．０部、アビエチン酸５．０部および３３％濃度の水酸化ナトリウム水溶液３０部を添加した。液温を９８℃に昇温した後、温度を保ったまま１時間撹拌した。６５℃に降温した後、１２Ｎの塩酸（キシダ化学（株）製）を添加して樹脂を沈殿させた。沈殿した組成物をろ別し、蒸留水によって洗浄した後乾燥し、マゼンタ顔料９を得た。得られたマゼンタ顔料９の物性を表２に示す。
<Production example of magenta pigment 9>
(Adjustment of magenta pigment surface characteristics by rosin treatment)
-1000 parts of distilled water-100 parts of magenta pigment 1 The above materials were stirred and mixed, and magenta pigment 1 was suspended in water. Then, 15.0 parts of tetrahydroabietic acid, 5.0 parts of abietic acid and 30 parts of a 33% concentrated sodium hydroxide aqueous solution were added. After raising the liquid temperature to 98 ° C., the mixture was stirred for 1 hour while maintaining the temperature. After the temperature was lowered to 65 ° C., 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added to precipitate the resin. The precipitated composition was filtered off, washed with distilled water and then dried to obtain magenta pigment 9. Table 2 shows the physical characteristics of the obtained magenta pigment 9.
＜マゼンタ顔料１０の製造例＞
上記マゼンタ顔料９の製造例でテトラヒドロアビエチン酸を５．０部、アビエチン酸を１．７部に変更した以外は同様にしてマゼンタ顔料１０を得た。得られたマゼンタ顔料１０の物性を表２に示す。
<Production example of magenta pigment 10>
The magenta pigment 10 was obtained in the same manner except that the tetrahydroabietic acid was changed to 5.0 parts and the abietic acid was changed to 1.7 parts in the above-mentioned production example of the magenta pigment 9. Table 2 shows the physical characteristics of the obtained magenta pigment 10.
＜マゼンタ顔料１３＞
マゼンタ顔料１３としてＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ１２２を用いた。用いたＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ１２２の物性を表２に示す。
<Magenta Pigment 13>
As magenta pigment 13, C.I. I. PigmentRed122 was used. C. used. I. Table 2 shows the physical characteristics of PigmentRed122.
＜マゼンタ顔料１４＞
マゼンタ顔料１４としてＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２６９を用いた。用いたＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２６９の物性を表２に示す。
<Magenta pigment 14>
As magenta pigment 14, C.I. I. PigmentRed269 was used. C. used. I. Table 2 shows the physical characteristics of PigmentRed269.
＜マゼンタ顔料１５＞
マゼンタ顔料１５として、Ｃ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ１５０を用いた。用いたＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ１５０の物性を表２に示す。
<Magenta pigment 15>
As the magenta pigment 15, C.I. I. PigmentRed150 was used. C. used. I. Table 2 shows the physical characteristics of PigmentRed 150.
＜マゼンタ顔料１６の製造例＞
マゼンタ顔料９の製造例において、マゼンタ顔料１をＣ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２６９に変更する以外はマゼンタ顔料９の製造例と同様にしてマゼンタ顔料１６を得た。得られたマゼンタ顔料１６の物性を表２に示す。
<Production example of magenta pigment 16>
In the production example of the magenta pigment 9, the magenta pigment 1 was used as C.I. I. Magenta pigment 16 was obtained in the same manner as in the production example of magenta pigment 9 except that it was changed to PigmentRed269. Table 2 shows the physical characteristics of the obtained magenta pigment 16.
＜マゼンタ顔料１７＞
・メタノール １０００部
・マゼンタ顔料８ １００部
・Ｃ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２６９ １２部
上記材料を撹拌・混合し、メタノールに懸濁させた。液温を６０℃に昇温した後、温度を保ったまま２４時間撹拌した。室温に降温した後、ろ別し、１００部の蒸留水によって洗浄した後乾燥し、マゼンタ顔料１５を得た。得られたマゼンタ顔料１７の物性を表２に示す。
<Magenta pigment 17>
・ 1000 parts of methanol ・ 100 parts of magenta pigment 8 ・ C.I. I. PigmentRed269 12 parts The above materials were stirred and mixed and suspended in methanol. After raising the liquid temperature to 60 ° C., the mixture was stirred for 24 hours while maintaining the temperature. After the temperature was lowered to room temperature, the mixture was filtered off, washed with 100 parts of distilled water, and then dried to obtain a magenta pigment 15. Table 2 shows the physical characteristics of the obtained magenta pigment 17.
＜マゼンタ顔料１８＞
マゼンタ顔料１７の製造例において、Ｃ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２６９を１０部に変更する以外はマゼンタ顔料１７の製造例と同様にしてマゼンタ顔料１８を得た。得られたマゼンタ顔料１８の物性を表２に示す。
<Magenta pigment 18>
In the production example of the magenta pigment 17, C.I. I. A magenta pigment 18 was obtained in the same manner as in the production example of the magenta pigment 17 except that PigmentRed269 was changed to 10 parts. Table 2 shows the physical characteristics of the obtained magenta pigment 18.
トナーの製造例を示す。 An example of manufacturing toner is shown.
＜トナー１の製造例＞
・スチレン ８０．０部
・ｎ−ブチルアクリレート ２０．０部
・ジビニルベンゼン ０．２５部
・マゼンタ顔料１ ５．０部
・極性樹脂１ ５．０部
・パラフィンワックス １０．０部
（日本精蝋社製：ＨＮＰ−５１ 最大級熱ピーク：７４℃）
・トルエン １００．０部
からなる混合物を調製した。上記混合物をアトライター（日本コークス社製）に投入し、直径５ｍｍのジルコニアビーズを用いて、２００ｒｐｍで２時間分散することで原材料分散液を得た。
<Manufacturing example of toner 1>
・ Styrene 80.0 parts ・ n-butyl acrylate 20.0 parts ・ Divinylbenzene 0.25 parts ・ Magenta pigment 1 5.0 parts ・ Polar resin 1 5.0 parts ・ Paraffin wax 10.0 parts (Nippon Seiwa Co., Ltd.) Manufactured by: HNP-51 Maximum heat peak: 74 ° C)
A mixture consisting of 100.0 parts of toluene was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having a diameter of 5 mm to obtain a raw material dispersion.
一方、高速撹拌装置ホモミクサー（プライミクス社製）及び温度計を備えた容器に、イオン交換水７３５．０部とリン酸三ナトリウム（１２水和物）１６．０部を添加し、１２０００ｒｐｍで撹拌しながら６０℃に昇温した。そこに、イオン交換水６５．０部に塩化カルシウム（２水和物）９．０部を溶解した塩化カルシウム水溶液を投入し、６０℃を保持しながら１２０００ｒｐｍで３０分間撹拌した。そこに、１０％塩酸を加えてｐＨを５．５に調整し、ヒドロキシアパタイトを含む無機分散安定剤が水中に分散した水系媒体を得た。 On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix Corporation) and a thermometer, and the mixture was stirred at 12000 rpm. However, the temperature was raised to 60 ° C. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining 60 ° C. The pH was adjusted to 5.5 by adding 10% hydrochloric acid to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.
続いて、上記原材料分散液を撹拌装置及び温度計を備えた容器に移し、１００ｒｐｍで撹拌しながら６０℃に昇温した。そこに、重合開始剤として（１０時間半減期温度５４．６℃（日本油脂製））９．０部を添加して６０℃を保持しながら１００ｒｐｍで５分間撹拌した後、上記高速撹拌装置にて１２０００ｒｐｍで撹拌している水系媒体中に投入した。６０℃を保持しながら上記高速撹拌装置にて１２０００ｒｐｍで２０分間撹拌を継続し、造粒液を得た。 Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60 ° C. while stirring at 100 rpm. To this, 9.0 parts (10-hour half-life temperature 54.6 ° C. (manufactured by NOF CORPORATION)) was added as a polymerization initiator, and the mixture was stirred at 100 rpm for 5 minutes while maintaining 60 ° C. It was put into an aqueous medium that was stirred at 12000 rpm. Stirring was continued at 12000 rpm for 20 minutes with the above high-speed stirring device while maintaining 60 ° C. to obtain a granulated liquid.
上記造粒液を還流冷却管、撹拌機、温度計、窒素導入管を備えた反応容器に移し、窒素雰囲気下において１５０ｒｐｍで撹拌しながら７０℃に昇温した。７０℃を保持しながら１５０ｒｐｍで１０時間重合反応を行った。次に、イオン交換水を１００．０部添加して、還流管を取り外し、蒸留装置を取り付けた。容器内の温度が１００℃の蒸留を５時間行った。蒸留終了後、３０℃まで冷却し、容器内に希塩酸を添加してｐＨを１．５まで下げて、分散安定剤を溶解させた。さらに、濾別、洗浄、乾燥、分級をして、重量平均粒子径（Ｄ４）が６．５μｍのトナー粒子１を得た。 The granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 70 ° C. while stirring at 150 rpm in a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 10 hours while maintaining 70 ° C. Next, 100.0 parts of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the container was carried out for 5 hours. After completion of the distillation, the mixture was cooled to 30 ° C., dilute hydrochloric acid was added into the container to lower the pH to 1.5, and the dispersion stabilizer was dissolved. Further, the toner particles 1 were filtered, washed, dried, and classified to obtain toner particles 1 having a weight average particle diameter (D4) of 6.5 μm.
得られたトナー粒子１ １００．０部に対して、外部添加剤として、シリカ微粒子（ヘキサメチルジシラザンによる疎水化処理、１次粒子の個数平均粒径：１０ｎｍ、ＢＥＴ比表面積：１７０ｍ2／ｇ）２．０部を加えてヘンシェルミキサー（日本コークス社製）を用い、３０００ｒｐｍで１５分間混合してトナー１を得た。 With respect to 100.0 parts of the obtained toner particles 1, as an external additive, silica fine particles (hydrophobicization treatment with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) ) 2.0 parts were added and mixed using a Henshell mixer (manufactured by Nippon Coke Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 1.
＜トナー２〜１５、１８〜３０、比較トナー１〜１０の製造例＞
上記トナー１の製造例で各種トナー材料の種類および量を表３のように変更した以外はトナー１の製造例と同様にして、トナー２〜１５、１８〜３４、比較トナー１〜１０を得た。
<Manufacturing Examples of Toners 2 to 15, 18 to 30, and Comparative Toners 1 to 10>
Toners 2 to 15, 18 to 34, and comparative toners 1 to 10 are obtained in the same manner as in the production example of toner 1 except that the types and amounts of various toner materials are changed as shown in Table 3 in the production example of toner 1. It was.
得られたトナー１〜１５、１８〜３４、比較トナー１〜１０の物性を表４に示す。 Table 4 shows the physical properties of the obtained toners 1 to 15, 18 to 34 and the comparative toners 1 to 10.
＜トナー１６の製造例＞
（ポリエステル樹脂１の製造）
窒素導入管、脱水管、撹拌器および熱電対を装備した反応槽中に、表５に示す使用量のモノマーを入れた後、触媒としてジブチル錫をモノマー総量１００部に対して１．５部添加した。次いで、窒素雰囲気下にて常圧で１８０℃まで素早く昇温した後、１８０℃から２１０℃まで１０℃／時間の速度で加熱しながら水を留去して重縮合を行った。温度２１０℃に到達してから反応槽内を５ｋＰａ以下まで減圧し、温度２１０℃、５ｋＰａ以下の条件下にて重縮合を行い、ポリエステル樹脂１を得た。
<Manufacturing example of toner 16>
(Manufacturing of polyester resin 1)
After putting the amount of monomer shown in Table 5 into a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1.5 parts of dibutyltin was added as a catalyst to 100 parts of the total amount of monomer. did. Then, after rapidly raising the temperature to 180 ° C. under normal pressure under a nitrogen atmosphere, water was distilled off while heating at a rate of 10 ° C./hour from 180 ° C. to 210 ° C. to carry out polycondensation. After reaching the temperature of 210 ° C., the inside of the reaction vessel was depressurized to 5 kPa or less, and polycondensation was carried out under the conditions of a temperature of 210 ° C. and 5 kPa or less to obtain a polyester resin 1.
その際、得られるポリエステル樹脂Ｂ１の軟化点が１１５℃となるように重合時間を調整した。 At that time, the polymerization time was adjusted so that the softening point of the obtained polyester resin B1 was 115 ° C.
・ポリエステル樹脂１ ９０．０部
・極性樹脂１ １０．０部
・マゼンタ顔料１ ７．０部
・パラフィンワックス（ＤＳＣピーク温度：８０℃） ５．０部
上記材料をヘンシェルミキサー（ＦＭ−７５型、三井三池化工機（株）製）で混合した後、二軸混練機（池貝鉄工（株）製ＰＣＭ−３０型））にて回転数３．３ｓ-1、混練温度１２０℃の条件で混練した。得られた混練物を冷却し、ハンマーミルにて１ｍｍ以下に粗粉砕し、粗砕物を得た。得られた粗砕物を、機械式粉砕機（ターボ工業（株）製Ｔ−２５０）にて微粉砕した。さらに、得られた微粉砕粉末を、コアンダ効果を利用した多分割分級機を用いて分級し、重量平均粒径が７．０μｍのトナー粒子１６を得た。
・ Polyester resin 1 90.0 parts ・ Polar resin 1 10.0 parts ・ Magenta pigment 1 7.0 parts ・ Paraffin wax (DSC peak temperature: 80 ° C) 5.0 parts Henshell mixer (FM-75 type, FM-75 type, After mixing with Mitsui Miike Machinery Co., Ltd., kneading was performed with a twin-screw kneader (PCM-30 type manufactured by Ikekai Iron Works Co., Ltd.) under the conditions of a rotation speed of 3.3 s -1 and a kneading temperature of 120 ° C. .. The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to 1 mm or less to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250 manufactured by Turbo Industries, Ltd.). Further, the obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 16 having a weight average particle diameter of 7.0 μm.
得られたトナー粒子１６ １００．０部に対して、外部添加剤として、シリカ微粒子（ヘキサメチルジシラザンによる疎水化処理、１次粒子の個数平均粒径：１０ｎｍ、ＢＥＴ比表面積：１７０ｍ2／ｇ）２．０部を加えてヘンシェルミキサー（日本コークス社製）を用い、３０００ｒｐｍで１５分間混合してトナー１６を得た。トナー１６の物性を表４に示す。 With respect to 100.0 parts of the obtained toner particles 16, as an external additive, silica fine particles (hydrophobicization treatment with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) ) 2.0 parts were added and mixed using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 16. Table 4 shows the physical characteristics of the toner 16.
＜トナー１７の製造例＞
（結着樹脂微粒子の分散液の製造）
トルエン（和光純薬製）２００ｇにエチレン酢酸ビニル樹脂（東ソー製：ウルトラセン６８５）６０ｇを加え、９０℃まで加熱した後、３時間撹拌して溶解させた。エチレン酢酸ビニル樹脂が溶解したトルエン溶液に、アニオン界面活性剤（第一工業製薬製：ネオゲンＲＫ）６ｇおよびアニオン界面活性剤（日本油脂製：ノンサールＬＮ１）３ｇが溶解したイオン交換水１８０ｇを添加した。それから、超高速撹拌装置Ｔ．Ｋ．ロボミックス（（株）プライミクス製）を用いて４０００ｒｐｍで十分撹拌した。その後、高圧衝撃式分散機ナノマイザー（吉田機械興業製）を用いて約１時間分散した後、エバポレーターを用いて、トルエンを除去し、結着樹脂微粒子の分散液を得た。
<Manufacturing example of toner 17>
(Manufacturing of dispersion of binder resin fine particles)
60 g of ethylene vinyl acetate resin (manufactured by Tosoh: Ultrasen 685) was added to 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 90 ° C., and then stirred for 3 hours to dissolve. To a toluene solution in which an ethylene vinyl acetate resin was dissolved, 180 g of ion-exchanged water in which 6 g of an anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 3 g of an anionic surfactant (manufactured by Nippon Oil & Fats: Nonsar LN1) was added was added. .. Then, the ultra-high speed agitator T.I. K. Sufficient stirring was performed at 4000 rpm using Robomix (manufactured by Primix Corporation). Then, after dispersing for about 1 hour using a high-pressure impact disperser nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), toluene was removed using an evaporator to obtain a dispersion of binder resin fine particles.
（極性樹脂の分散液の製造）
上記結着樹脂微粒子の分散液の製造において、エチレン酢酸ビニル樹脂を極性樹脂１に変更する以外は結着樹脂微粒子の分散液の製造と同様にして、極性樹脂１の分散液を得た。
(Manufacturing of dispersion of polar resin)
In the production of the dispersion liquid of the binder resin fine particles, the dispersion liquid of the polar resin 1 was obtained in the same manner as in the production of the dispersion liquid of the binder resin fine particles except that the ethylene vinyl acetate resin was changed to the polar resin 1.
（離型剤微粒子の分散液の製造）
・離型剤（ＨＮＰ−５１、融点７８℃、日本精蝋製） ２０．０部
・アニオン性界面活性剤（第一工業製薬製：ネオゲンＲＫ） １．０部
・イオン交換水 ７９．０部
上記処方を撹拌装置付きの混合容器に投入した後、９０℃に加熱し、クレアミックスＷモーション（エム・テクニック製）へ循環しながらローター外径が３ｃｍ、クリアランスが０．３ｍｍの剪断撹拌部位にて、ローター回転数１９０００ｒ／ｍｉｎ、スクリーン回転数１９０００ｒ／ｍｉｎの条件にて撹拌し、６０分間分散処理した後、ローター回転数１０００ｒ／ｍｉｎ、スクリーン回転数０ｒ／ｍｉｎ、冷却速度１０℃／ｍｉｎの冷却処理条件にて４０℃まで冷却することで、離型剤微粒子の分散液を得た。
(Manufacturing of dispersion of mold release agent fine particles)
-Release agent (HNP-51, melting point 78 ° C, manufactured by Nippon Seiwa) 20.0 parts-Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part-Ion exchange water 79.0 parts After the above formulation is put into a mixing container equipped with a stirrer, it is heated to 90 ° C., and while circulating to Claremix W Motion (manufactured by M-Technique), the rotor outer diameter is 3 cm and the clearance is 0.3 mm. The mixture was stirred under the conditions of a rotor rotation speed of 19000 r / min and a screen rotation speed of 19000 r / min, and after dispersion treatment for 60 minutes, the rotor rotation speed was 1000 r / min, the screen rotation speed was 0 r / min, and the cooling speed was 10 ° C./min. By cooling to 40 ° C. under the cooling treatment conditions, a dispersion liquid of the release agent fine particles was obtained.
（顔料分散液の製造）
・マゼンタ顔料１ １０．０部
・イオン交換水 ７８．０部
・アニオン界面活性剤（第一工業製薬製：ネオゲンＲＫ） ２．０部
上記材料を混合した。その後、高圧衝撃式分散機ナノマイザー（吉田機械興業製）を用いて１時間分散し、マゼンタ顔料１の分散液を調製した。
(Manufacturing of pigment dispersion)
-Magenta pigment 1 10.0 parts-Ion-exchanged water 78.0 parts-Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 2.0 parts The above materials were mixed. Then, it was dispersed for 1 hour using a high-pressure impact disperser nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to prepare a dispersion liquid of magenta pigment 1.
・結着樹脂微粒子の分散液（固形分２５％） ３２０．０部
・マゼンタ顔料１の分散液（固形分１０％） ５０．０部
・離型剤微粒子の分散液（固形分２０％） ５０．０部
・極性樹脂１の分散液（固形分２５％） ４０．０部
上記の各材料を丸型ステンレス製フラスコに投入し、混合した。ここに、９８部のイオン交換水に対して硫酸マグネシウム８質量部を溶解させた水溶液を添加し、ホモジナイザー（ＩＫＡ社製：ウルトラタラックスＴ５０）を用いて５０００ｒ／ｍｉｎで１０分間分散した。その後、加熱用ウォーターバス中で撹拌翼を用いて、混合液が撹拌されるような回転数を適宜調節しながらで５０℃まで加熱した。５０℃で１時間保持した後、形成された凝集粒子の重量平均粒子径を測定した。その結果、重量平均粒子径が約６．０μｍである凝集粒子が形成されていることが確認された。
・ Dispersion liquid of binder resin fine particles (solid content 25%) 320.0 parts ・ Dispersion liquid of magenta pigment 1 (solid content 10%) 50.0 parts ・ Dispersion liquid of mold release agent fine particles (solid content 20%) 50 .0 parts ・ Dispersion liquid of polar resin 1 (solid content 25%) 40.0 parts Each of the above materials was put into a round stainless steel flask and mixed. An aqueous solution prepared by dissolving 8 parts by mass of magnesium sulfate in 98 parts of ion-exchanged water was added thereto, and the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer (manufactured by IKA: Ultratarax T50). Then, using a stirring blade in a water bath for heating, the mixture was heated to 50 ° C. while appropriately adjusting the rotation speed at which the mixture was stirred. After holding at 50 ° C. for 1 hour, the weight average particle size of the formed aggregated particles was measured. As a result, it was confirmed that agglomerated particles having a weight average particle diameter of about 6.0 μm were formed.
得られた凝集粒子の分散液に、３６０部のイオン交換水に対してエチレンジアミン四酢酸ナトリウム４０部を溶解させた水溶液を加え、更に、イオン交換水２８００部を添加した。撹拌を継続しながら８０℃まで加熱し、２時間密閉した状態で保持し、十分に融合した粒子を得た。その後、ろ過・固液分離した後、ろ物をイオン交換水で十分に洗浄し、真空乾燥機を用いて乾燥することにより、重量平均粒子径が５．４μｍのトナー粒子１７を得た。 An aqueous solution prepared by dissolving 40 parts of sodium ethylenediaminetetraacetate in 360 parts of ion-exchanged water was added to the obtained dispersion of agglomerated particles, and 2800 parts of ion-exchanged water was further added. The mixture was heated to 80 ° C. while continuing stirring and kept in a closed state for 2 hours to obtain fully fused particles. Then, after filtration and solid-liquid separation, the filtrate was thoroughly washed with ion-exchanged water and dried using a vacuum dryer to obtain toner particles 17 having a weight average particle diameter of 5.4 μm.
得られたトナー粒子１７ １００．０部に対して、外部添加剤として、シリカ微粒子（ヘキサメチルジシラザンによる疎水化処理、１次粒子の個数平均粒径：１０ｎｍ、ＢＥＴ比表面積：１７０ｍ2／ｇ）２．０部を加えてヘンシェルミキサー（日本コークス社製）を用い、３０００ｒｐｍで１５分間混合してトナー１７を得た。得られたトナー１７の物性を表４に示す。 With respect to 100.0 parts of the obtained toner particles 17, as an external additive, silica fine particles (hydrophobicization treatment with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) ) 2.0 parts were added and mixed using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 17. Table 4 shows the physical characteristics of the obtained toner 17.
〔実施例１〜３４、比較例１〜１０〕
上記トナー１〜３４、比較トナー１〜１０の各トナーに対し、下記に示す評価を行った。
[Examples 1 to 34, Comparative examples 1 to 10]
The following evaluations were performed on each of the toners 1 to 34 and the comparative toners 1 to 10.
＜画質の評価＞
カラーレーザープリンター（ＨＰ Ｃｏｌｏｒ ＬａｓｅｒＪｅｔ ３５２５ｄｎ、ＨＰ社製）を用意し、定着ユニットを取り外し可能にし、マゼンタステーションだけでプリント可能とした。
<Evaluation of image quality>
A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was prepared, the fixing unit was made removable, and printing was possible only at the magenta station.
このプリンター用のマゼンタトナーカートリッジに充填されているトナーを抜取り、代わりに評価するトナーを充填した。次いで、受像紙（ＧＦ−Ｃ０８１）上に、充填したトナーを用いて、縦２．０ｃｍ横１５．０ｃｍの未定着のトナー画像（０．４０ｍｇ／ｃｍ2）を、通紙方向に対し上端部から１．０ｃｍの部分に形成した。次いで、取り外した定着ユニットを定着温度とプロセススピードを調節できるように改造し、常温常湿環境下（２３℃、６０％ＲＨ）、プロセススピードを２３０ｍｍ／ｓに設定し、上記未定着画像を１００℃から１８０℃まで５℃ずつ変えて定着し、未定着画像の定着を行った。得られた定着画像は、反射濃度計ＳｐｅｃｔｒｏＬｉｎｏ（旧Ｇｒｅｔａｇ Ｍａｃｂｅｔｈ社製）にて、Ｌ＊ａ＊ｂ＊表色系における色度を測定した。得られた結果の彩度（Ｃ＊）および色相角（ｈ）の値を読み取った。測定を行った各定着温度における画像の中で、最も彩度（Ｃ＊）の高い画像を以下のような基準でランク付けし、Ｃランク以上を本発明において許容できる基準とした。色相角（ｈ）は、３００°≦ｈ≦３５５°の範囲外である場合、Ｃ＊の値にかかわらず、Ｄランクとした。結果を表６に示す。
［評価基準］
Ａ：Ｃ＊が７５．０以上、３００°≦ｈ≦３５５°
Ｂ：Ｃ＊が７２．０以上、３００°≦ｈ≦３５５°
Ｃ：Ｃ＊が６９．０以上、３００°≦ｈ≦３５５°
Ｄ：Ｃ＊が６９．０未満
The toner filled in the magenta toner cartridge for this printer was withdrawn and replaced with the toner to be evaluated. Next, on the image receiving paper (GF-C081), an unfixed toner image (0.40 mg / cm 2 ) having a length of 2.0 cm and a width of 15.0 cm is formed on the image receiving paper (GF-C081) by using the filled toner. It was formed in a portion of 1.0 cm from. Next, the removed fixing unit was modified so that the fixing temperature and process speed could be adjusted, the process speed was set to 230 mm / s in a normal temperature and humidity environment (23 ° C., 60% RH), and the above unfixed image was set to 100. The unfixed image was fixed by fixing at 5 ° C. from ° C. to 180 ° C. The obtained fixed image was measured for chromaticity in the L * a * b * color system with a reflection densitometer SpectroLino (formerly manufactured by Gretag Macbeth). The values of saturation (C *) and hue angle (h) of the obtained results were read. Among the measured images at each fixing temperature, the image having the highest saturation (C *) was ranked according to the following criteria, and C rank or higher was used as an acceptable criterion in the present invention. When the hue angle (h) was out of the range of 300 ° ≦ h ≦ 355 °, it was set as D rank regardless of the value of C *. The results are shown in Table 6.
[Evaluation criteria]
A: C * is 75.0 or more, 300 ° ≤ h ≤ 355 °
B: C * is 72.0 or more, 300 ° ≤ h ≤ 355 °
C: C * is 69.0 or more, 300 ° ≤ h ≤ 355 °
D: C * is less than 69.0
画質の評価で用いたプリンターと評価トナーを充填したカートリッジを使用し、１．０％の印字比率の画像を３，０００枚までプリントアウトして、初期と３，０００枚出力時（耐久後）のかぶり、及び、耐久性の評価を行った。 Using the printer used for the evaluation of image quality and the cartridge filled with the evaluation toner, print out up to 3,000 images with a print ratio of 1.0%, and output 3,000 sheets at the initial stage (after durability). The fog and durability were evaluated.
＜かぶりの評価＞
初期と３，０００枚印字後のベタ白画像を出力し、感光体上のかぶりトナーをマイラーテープでテーピングして剥ぎ取った。その後、該テープとテーピングしていないテープをＬＥＴＴＥＲサイズのＸＥＲＯＸ ４２００用紙（ＸＥＲＯＸ社製、７５ｇ／ｍ2）に貼り付けた。それぞれのテープの反射率（％）を「ＲＥＦＬＥＣＴＯＭＥＴＥＲ ＭＯＤＥＬＴＣ−６ＤＳ」（（有）東京電色製）で測定した。
<Evaluation of fog>
A solid white image was output at the initial stage and after printing 3,000 sheets, and the fog toner on the photoconductor was taped with Mylar tape and peeled off. Then, the tape and the tape not taped were attached to LETTER size XEROX 4200 paper (manufactured by XEROX, 75 g / m 2 ). The reflectance (%) of each tape was measured with "REFLECTOMETER MODELTC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.).
そしてテーピングしていないテープの反射率（％）からテーピングしたテープの反射率（％）を差し引いた数値（％）を用いて評価した。数値が小さいほど、かぶりが抑制されていることになる。結果を表６に示す。Ｃランク以上を実用上問題のないレベルと判断した。
（評価基準）
Ａ：反射率の差が２．０％未満
Ｂ：反射率の差が２．０％以上５．０％未満
Ｃ：反射率の差が５．０％以上１０．０％未満
Ｄ：反射率の差が１０．０％以上
Then, the evaluation was performed using a numerical value (%) obtained by subtracting the reflectance (%) of the taped tape from the reflectance (%) of the tape not taped. The smaller the value, the more the fog is suppressed. The results are shown in Table 6. C rank or higher was judged to be a level that would not cause any practical problems.
(Evaluation criteria)
A: Difference in reflectance is less than 2.0% B: Difference in reflectance is 2.0% or more and less than 5.0% C: Difference in reflectance is 5.0% or more and less than 10.0% D: Reflectance Difference is 10.0% or more
＜耐久性の評価＞
トナーの耐久性評価は、スジ画像の有無により判定を実施した。スジ画像は、外添剤による部材汚染やトナー劣化により発生する０．５ｍｍ程度の縦スジであり、全面ハーフトーン画像を出力した際に観察されやすい画像不良である。
<Evaluation of durability>
The durability of the toner was evaluated based on the presence or absence of a streak image. The streak image is a vertical streak of about 0.5 mm generated due to member contamination by an external additive or toner deterioration, and is an image defect that is easily observed when a full-face halftone image is output.
評価紙として、ＸＥＲＯＸ４２００用紙（ＸＥＲＯＸ社製７５ｇ／ｍ2）を用いた。３，０００印字後のカートリッジを用いて、全面ハーフトーン画像を出力し、スジの有無を観察した。以下の判定基準によって行った。評価結果を表６に示す。
［評価基準］
Ａ：スジやトナー塊が未発生。
Ｂ：斑点状のスジはないが、１〜３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、又は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、又は５個所以上小さなトナー塊若しくは明らかなトナー塊がある。
As the evaluation paper, XEROX4200 paper (75 g / m 2 manufactured by XEROX) was used. Using the cartridge after printing 3,000, a full-face halftone image was output and the presence or absence of streaks was observed. It was performed according to the following criteria. The evaluation results are shown in Table 6.
[Evaluation criteria]
A: No streaks or toner lumps have occurred.
B: There are no speckled streaks, but there are 1 to 3 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.
評価は、Ｃランク以上であれば良好な耐久性があると判断した。 The evaluation was judged to have good durability if it was C rank or higher.
＜顔料分散性の評価＞
トナーの顔料分散性を評価するため、ミクロトームによりトナーの超薄切片を作製し、透過型電子顕微鏡（ＴＥＭ）にて観察を行う。必要に応じて酸化ルテニウムまたはオスミウム酸などにより切片の染色を行う。評価基準としては、顔料が一次粒径として分散されているか、顔料の偏析やトナー表層への露出がないかを観察し、以下の基準でランク付けを行った。結果を表６に示す。
Ａ：顔料が１次粒径に分散し、トナー全体に均一に存在している。
Ｂ：顔料が凝集した部分が存在し、不均一に存在している。
Ｃ：顔料が凝集し、トナー表面に露出している顔料が多数観察される。
<Evaluation of pigment dispersibility>
In order to evaluate the pigment dispersibility of the toner, an ultrathin section of the toner is prepared by a microtome and observed with a transmission electron microscope (TEM). If necessary, the sections are stained with ruthenium oxide or osmium acid. As evaluation criteria, it was observed whether the pigment was dispersed as the primary particle size, and whether the pigment was segregated or exposed to the toner surface layer, and ranked according to the following criteria. The results are shown in Table 6.
A: The pigment is dispersed in the primary particle size and is uniformly present in the entire toner.
B: There is a portion where the pigment is agglomerated, and it is non-uniformly present.
C: Pigments are aggregated, and many pigments exposed on the toner surface are observed.
＜トナー割れの評価＞
トナー０．１０ｇとジルコニアビーズ０．３ｍｍ １０．０ｇを５０ｍＬの絶縁性のプラスチック容器に入れ、２００回／分の速度で３分間振とうさせた。その後、カーボンテープに振とう後のトナーを載せ、ＳＥＭにて観察を行った。２０００倍の画像１０枚から以下の式より割れ個数％を算出した。
割れ個数％＝割れや欠けの発生しているトナー粒子数／全トナー粒子数×１００
<Evaluation of toner cracking>
0.10 g of toner and 10.0 g of zirconia beads 0.3 mm were placed in a 50 mL insulating plastic container and shaken at a rate of 200 times / minute for 3 minutes. Then, the shaken toner was placed on the carbon tape, and the observation was performed by SEM. The number of cracks% was calculated from the following formula from 10 2000-fold images.
Number of cracks% = Number of toner particles with cracks or chips / Total number of toner particles x 100
以下の基準でランク付けを行った。Ｃランク以上が実用上問題のないレベルであると判断した。結果を表６に示す。
Ａ：割れ個数％が５％未満である。
Ｂ：割れ個数％が５％以上１０％未満である。
Ｃ：割れ個数％が１０％以上２０％未満である。
Ｄ：割れ個数％が２０％以上である。
The ranking was based on the following criteria. It was judged that C rank or higher is a level that does not cause any problem in practical use. The results are shown in Table 6.
A: The number of cracks% is less than 5%.
B: The number of cracks% is 5% or more and less than 10%.
C: The number of cracks% is 10% or more and less than 20%.
D: The number of cracks% is 20% or more.
Claims (11)
前記極性樹脂がカルボキシ基に由来する酸価を２．０ｍｇＫＯＨ／ｇ以上２０．０ｍｇＫＯＨ／ｇ以下有し、
前記顔料に対する前記極性樹脂の吸着率が１０％以下であることを特徴とするマゼンタトナー。 A toner having toner particles containing a binder resin, a pigment, and a polar resin.
The polar resin has an acid value derived from a carboxy group of 2.0 mgKOH / g or more and 20.0 mgKOH / g or less.
A magenta toner characterized in that the adsorption rate of the polar resin with respect to the pigment is 10% or less.
化合物Ａと化合物Ｂの質量比Ａ／Ｂが９５／５から５／９５である請求項１に記載のマゼンタトナー。
The magenta toner according to claim 1, wherein the mass ratio A / B of compound A to compound B is 95/5 to 5/95.
前記トナー粒子をエタノールに分散して得た分散物を滴定法により測定して得た酸価をＡＶＥ（ｍｇＫＯＨ／ｇ）としたとき、ＡＶＨ／ＡＶＥが０．１０以上０．２５以下である請求項１乃至４のいずれか１項に記載のマゼンタトナー。 When the acid value obtained by measuring the dispersion obtained by dispersing the toner particles in water by a titration method is AVH (mgKOH / g), the AVH is 0.20 mgKOH / g or more and 1.00 mgKOH / g or less. Yes,
A claim that AVH / AVE is 0.10 or more and 0.25 or less when the acid value obtained by measuring the dispersion obtained by dispersing the toner particles in ethanol by a titration method is defined as AVE (mgKOH / g). Item 2. The magenta toner according to any one of Items 1 to 4.
前記結着樹脂の溶解度パラメータ（ＳＰ値）が９．８以上１１．０以下である請求項１乃至５のいずれか１項に記載のマゼンタトナー。 The pigment has an acetone concentration of 5.5% by volume or more and 10.0% by volume or less when the transmittance of light having a wavelength of 780 nm is 50% in a wettability test with an acetone / water mixed solvent.
The magenta toner according to any one of claims 1 to 5, wherein the solubility parameter (SP value) of the binder resin is 9.8 or more and 11.0 or less.
式（３） １．０ｎｍ≦Ｄ≦７．０ｎｍ In any one of claims 1 to 6, the crystallite size D calculated at the peak having the maximum intensity within the range of 3 ° <2θ <60 ° in the XRD measurement of the pigment satisfies the following formula (3). The magenta toner described.
Equation (3) 1.0 nm ≤ D ≤ 7.0 nm
前記顔料が前記結着樹脂１００質量部に対して１．０質量部以上１０．０質量部以下であり、
前記顔料が前記極性樹脂１００質量部に対して６．７質量部以上１０００質量部以下である請求項１乃至８のいずれか１項に記載のマゼンタトナー。 The polar resin is 1.0 part by mass or more and 15.0 part by mass or less with respect to 100 parts by mass of the binder resin.
The pigment is 1.0 part by mass or more and 10.0 part by mass or less with respect to 100 parts by mass of the binder resin.
The magenta toner according to any one of claims 1 to 8, wherein the pigment is 6.7 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the polar resin.
式（４） ＡＶＢ＜ＡＶＰ−２ When the acid value of the binder resin is ABB and the acid value of the polar resin is AVP, the AVB is 5.0 mgKOH / g or less and any one of claims 1 to 9 satisfying the formula (4). The magenta toner described in the section.
Equation (4) AVB <AVP-2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019224182A JP7391649B2 (en) | 2019-12-12 | 2019-12-12 | magenta toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019224182A JP7391649B2 (en) | 2019-12-12 | 2019-12-12 | magenta toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021092711A true JP2021092711A (en) | 2021-06-17 |
| JP7391649B2 JP7391649B2 (en) | 2023-12-05 |
Family
ID=76312310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019224182A Active JP7391649B2 (en) | 2019-12-12 | 2019-12-12 | magenta toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7391649B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6748439B2 (en) | 2015-02-25 | 2020-09-02 | キヤノン株式会社 | Toner and toner manufacturing method |
| DE102015211827A1 (en) | 2015-06-25 | 2016-12-29 | Clariant International Ltd | New naphthol AS pigments |
| DE102015211829A1 (en) | 2015-06-25 | 2016-12-29 | Clariant International Ltd | Use of new Naphthol AS pigment mixtures in printing materials |
-
2019
- 2019-12-12 JP JP2019224182A patent/JP7391649B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP7391649B2 (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20180210361A1 (en) | Toner | |
| CN106468863B (en) | Toner and method for producing toner | |
| US9158216B2 (en) | Method for producing toner particles | |
| JP2017045042A (en) | Toner and method for manufacturing toner | |
| JP2017167473A (en) | Toner and method for manufacturing toner | |
| JP2018151431A (en) | toner | |
| JP2016224420A (en) | toner | |
| JP2019003082A (en) | toner | |
| JP5824721B2 (en) | Method for producing liquid developer | |
| JP2017173813A (en) | Toner and method for manufacturing toner | |
| JP2017102399A (en) | Toner and manufacturing method of toner | |
| JP2018072389A (en) | toner | |
| JP2017116807A (en) | toner | |
| CN104155857A (en) | Electrostatic latent image developer | |
| US20220365457A1 (en) | Toner and method for producing toner | |
| US11914325B2 (en) | Toner and method for producing toner | |
| JP7391649B2 (en) | magenta toner | |
| JP6460904B2 (en) | toner | |
| JP7350565B2 (en) | toner | |
| JP2018112688A (en) | toner | |
| JP2007114740A (en) | Toner for electrostatic image development and method for manufacturing same | |
| US10120297B2 (en) | Liquid developer | |
| JP7493963B2 (en) | Toner and method for producing the same | |
| JP2018136515A (en) | Toner, toner manufacturing method and polymer | |
| JP7187159B2 (en) | Toner and toner manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230817 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230822 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231006 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20231024 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20231122 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7391649 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |