JP5248996B2 - Method for producing toner for electrophotography - Google Patents
Method for producing toner for electrophotography Download PDFInfo
- Publication number
- JP5248996B2 JP5248996B2 JP2008294730A JP2008294730A JP5248996B2 JP 5248996 B2 JP5248996 B2 JP 5248996B2 JP 2008294730 A JP2008294730 A JP 2008294730A JP 2008294730 A JP2008294730 A JP 2008294730A JP 5248996 B2 JP5248996 B2 JP 5248996B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- particles
- weight
- particle dispersion
- aggregated
- 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.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 50
- 239000002245 particle Substances 0.000 claims description 317
- 239000011347 resin Substances 0.000 claims description 280
- 229920005989 resin Polymers 0.000 claims description 280
- 239000006185 dispersion Substances 0.000 claims description 177
- 239000010419 fine particle Substances 0.000 claims description 107
- 229920000728 polyester Polymers 0.000 claims description 49
- 230000004931 aggregating effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 description 57
- 238000007792 addition Methods 0.000 description 55
- 239000003795 chemical substances by application Substances 0.000 description 43
- 238000005538 encapsulation Methods 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- -1 polyoxypropylene-2 Chemical compound 0.000 description 32
- 230000009477 glass transition Effects 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 230000002776 aggregation Effects 0.000 description 21
- 238000009826 distribution Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- 239000012736 aqueous medium Substances 0.000 description 18
- 238000004220 aggregation Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000011362 coarse particle Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000004581 coalescence Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 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 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 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
- 239000002994 raw material Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001507 sample dispersion Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 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
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 150000004057 1,4-benzoquinones Chemical class 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical class O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- BURBNIPKSRJAIQ-UHFFFAOYSA-N 2-azaniumyl-3-[3-(trifluoromethyl)phenyl]propanoate Chemical compound OC(=O)C(N)CC1=CC=CC(C(F)(F)F)=C1 BURBNIPKSRJAIQ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- REEFSLKDEDEWAO-UHFFFAOYSA-N Chloraniformethan Chemical compound ClC1=CC=C(NC(NC=O)C(Cl)(Cl)Cl)C=C1Cl REEFSLKDEDEWAO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940063284 ammonium salicylate Drugs 0.000 description 1
- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Chemical class 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KGOGNDXXUVELIQ-UHFFFAOYSA-N dioctadecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC KGOGNDXXUVELIQ-UHFFFAOYSA-N 0.000 description 1
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Chemical class 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011592 zinc chloride Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Description
本発明は、電子写真法、静電記録法、静電印刷法などに用いられる電子写真用トナーの製造方法、及び該製造方法により得られる電子写真用トナーに関する。 The present invention relates to a method for producing an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner obtained by the production method.
電子写真用トナーの分野においては、電子写真システムの発展に伴い、高画質化および高速化に対応したトナーの開発が要求されている。特に、上記のようなトナーの性能を達成するために、トナーの機能分離技術が注目されており、このような技術の一つとしてカプセル化技術が知られている。
トナーのカプセル化技術としては、例えば、凝集粒子に樹脂微粒子を添加して行う方法があり、具体的には、特許文献１〜３に記載された技術が挙げられる。特許文献１は、スチレンアクリルを主体とした凝集粒子製造後、樹脂微粒子を添加し樹脂微粒子付着粒子を形成した後、系内を加熱してカプセル化を行なう技術を開示している。また、特許文献２は、付加重合系樹脂により凝集粒子を作成し、合一後に温度を高めながら、樹脂微粒子を添加する技術を開示している。さらに、特許文献３は、ポリエステルを主体とする凝集粒子製造後、樹脂微粒子を添加する際、凝集剤を添加する技術を開示している。
In the field of electrophotographic toner, with the development of an electrophotographic system, development of a toner corresponding to high image quality and high speed is required. In particular, in order to achieve the toner performance as described above, attention is paid to a toner function separation technique, and an encapsulation technique is known as one of such techniques.
As a toner encapsulation technique, for example, there is a method in which resin fine particles are added to aggregated particles, and specifically, techniques described in Patent Documents 1 to 3 can be mentioned. Patent Document 1 discloses a technique in which, after the production of aggregated particles mainly composed of styrene acrylic, resin fine particles are added to form resin fine particle-adhered particles, and then the inside of the system is heated for encapsulation. Patent Document 2 discloses a technique in which agglomerated particles are made from an addition polymerization resin and resin fine particles are added while raising the temperature after coalescence. Further, Patent Document 3 discloses a technique of adding an aggregating agent when adding resin fine particles after producing aggregated particles mainly composed of polyester.
しかしながら、ポリエステルを含むトナーは、定着性、耐久性に優れるが、上記特許文献１に開示された技術では、ポリエステルの場合、カプセル化が十分に行われないためポリエステルの特徴を発揮し得ない。また、特許文献２に記載の方法は重合反応させながら粒子を成長させるものであり、ポリエステルを結着樹脂として用いたトナーにおけるカプセル化への適用は困難である。さらに、特許文献３記載の技術は、カプセル化の際に凝集剤の添加を必須としており生産性に改善の余地を残している。 However, a toner containing polyester is excellent in fixability and durability. However, in the technique disclosed in Patent Document 1, in the case of polyester, since the encapsulation is not sufficiently performed, the characteristics of the polyester cannot be exhibited. The method described in Patent Document 2 grows particles while undergoing a polymerization reaction, and is difficult to apply to encapsulation in toner using polyester as a binder resin. Furthermore, the technique described in Patent Document 3 requires the addition of a flocculant during encapsulation, leaving room for improvement in productivity.
トナーの製造において、乳化凝集によりカプセル化する場合は、凝集性や安定性などの性質が異なるコア粒子をシェル粒子で効率よくカプセル化することが求められる。そのためにカプセル化時の製造系内の精密な凝集剤濃度制御などが必要となり、煩雑である一方で、実生産時には設備コストが懸念される。
本発明者らは、あらかじめ凝集させた粒子に、樹脂微粒子を添加してカプセル化を行う際に、従来は製造系内の凝集剤濃度の変化を抑えるため、凝集剤の追加添加が必要であったところ、凝集剤を添加することなく、特定の方法で製造系内の温度を上げることで、効率よくカプセル化を行うことが可能となることを見出した。
すなわち、本発明は、カプセル化の際に、凝集剤を添加することなく効率よくカプセル化を行うことができる電子写真用トナーの製造方法、及び該製造方法により得られる電子写真用トナーを提供することを課題とする。
In the production of toner, when encapsulating by emulsion aggregation, it is required to efficiently encapsulate core particles having different properties such as aggregation and stability with shell particles. For this reason, precise control of the concentration of the flocculant in the production system at the time of encapsulation is required, which is complicated, but there is a concern about equipment costs during actual production.
The inventors of the present invention have conventionally required additional addition of a flocculant in order to suppress changes in the concentration of the flocculant in the production system when adding resin fine particles to the previously agglomerated particles for encapsulation. As a result, it has been found that the encapsulation can be efficiently performed by increasing the temperature in the production system by a specific method without adding a flocculant.
That is, the present invention provides a method for producing an electrophotographic toner that can be efficiently encapsulated without adding a flocculant during encapsulation, and an electrophotographic toner obtained by the production method. This is the issue.
本発明は、
［１］（１）ポリエステルを含む樹脂粒子分散液中の樹脂粒子を、凝集剤を添加して凝集させて、凝集粒子の分散液を得る工程、及び（２）工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を連続的に添加する工程を含む電子写真用トナー製造方法であって、前記工程（２）を、凝集粒子１００重量部に対して、工程（２）で添加する樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で凝集粒子分散液を含む系内を昇温させながら行う、電子写真用トナーの製造方法、及び、
［２］上記［１］記載の製造方法により得られる電子写真用トナー、
に関する。
The present invention
[1] (1) A step of obtaining a dispersion of aggregated particles by adding a flocculant to agglomerate resin particles in a resin particle dispersion containing polyester, and (2) obtained in step (1). An electrophotographic toner manufacturing method comprising a step of continuously adding a dispersion of resin fine particles to an aggregated particle dispersion, wherein the step (2) is performed with respect to 100 parts by weight of the aggregated particles. A method for producing an electrophotographic toner, which is carried out while raising the temperature of the system containing the aggregated particle dispersion at a ratio of 0.05 to 0.25 ° C. per 1 part by weight of the resin fine particles added in
[2] An electrophotographic toner obtained by the production method according to [1] above,
About.
本発明により、カプセル化の際に、凝集剤を添加することなく効率よくカプセル化を行うことができる電子写真用トナーの製造方法、及び該製造方法により得られる電子写真用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 method for producing an electrophotographic toner that can be efficiently encapsulated without adding a flocculant during encapsulation, and an electrophotographic toner obtained by the production method. it can
凝集剤を添加して製造された凝集粒子をカプセル化するカプセル化トナーの製造においては、樹脂微粒子を、例えば凝集粒子分散液に添加することで、凝集剤濃度低下が起こるため、従来は凝集剤の濃度低下を防止するために同時に凝集剤の添加を行っていた。しかしながら、本発明においては、凝集剤を添加せず、樹脂微粒子の添加に伴う凝集剤濃度の低下に合わせて、系内の温度を上昇させることで、凝集剤を滴下するのと同様の効果が得られる。すなわち、本発明は、凝集剤を添加するのと同様の効果を、凝集粒子分散液を含む系内の温度を上昇させることで、具体的には、樹脂微粒子の添加量に応じた適切な温度上昇範囲で昇温させることで得ることができることを見出したものである。
以上のように、本発明は、ポリエステルを用いたカプセル化トナーの製造において、カプセル化の際に凝集剤等を追加添加することなく、効率よくカプセル化を行うことができる電子写真用トナーの製造方法に関するものであり、カプセル化の際に、樹脂微粒子を連続的に添加すると同時に、系内の温度を樹脂微粒子の添加量に応じて上昇させるものである。このような方法により、系内の温度と凝集剤濃度が適正化されることで、凝集粒子分散液を含む反応系の粒子の安定性を適正化させることができるために、上記効果が得られるものと考えられる。
In the production of an encapsulated toner that encapsulates aggregated particles produced by adding an aggregating agent, the concentration of the aggregating agent is lowered by adding resin fine particles to, for example, an aggregated particle dispersion. At the same time, a flocculant was added in order to prevent a decrease in the concentration. However, in the present invention, the same effect as dripping the flocculant can be obtained by increasing the temperature in the system in accordance with the decrease in the flocculant concentration accompanying the addition of the resin fine particles without adding the flocculant. can get. That is, the present invention has an effect similar to that of adding an aggregating agent, and by raising the temperature in the system containing the aggregated particle dispersion, specifically, an appropriate temperature corresponding to the amount of resin fine particles added. It has been found that it can be obtained by raising the temperature in the rising range.
As described above, according to the present invention, in the production of an encapsulated toner using polyester, the electrophotographic toner can be efficiently encapsulated without adding an aggregating agent or the like at the time of encapsulation. The present invention relates to a method, in which resin fine particles are continuously added during encapsulation, and at the same time, the temperature in the system is increased according to the amount of resin fine particles added. By such a method, the temperature in the system and the concentration of the flocculant are optimized, whereby the stability of the reaction system particles including the aggregated particle dispersion can be optimized, and thus the above-described effect can be obtained. It is considered a thing.
＜電子写真用トナーの製造方法＞
本発明の電子写真用トナーの製造方法は、（１）ポリエステルを含む樹脂粒子散液中の樹脂粒子を、凝集剤を添加して凝集させて、凝集粒子の分散液を得る工程、及び（２）工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を連続的に添加する工程を含む電子写真用トナー製造方法であって、前記工程（２）を、凝集粒子１００重量部に対して、工程（２）で添加する樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で凝集粒子分散液を含む系内を昇温させながら行うものである。
<Method for producing electrophotographic toner>
The method for producing an electrophotographic toner of the present invention includes (1) a step of adding a flocculant to agglomerate resin particles in a resin particle dispersion containing polyester to obtain a dispersion of aggregated particles, and (2 ) A method for producing a toner for electrophotography, which comprises a step of continuously adding a dispersion of resin fine particles to the aggregated particle dispersion obtained in step (1), wherein the step (2) is performed by adding 100 weights of aggregated particles. Part of the resin fine particles to be added in the step (2) with respect to the part, while raising the temperature in the system containing the aggregated particle dispersion at a ratio of 0.05 to 0.25 ° C.
［工程（１）］
工程（１）は、ポリエステルを含む樹脂粒子分散液中の樹脂粒子を、凝集剤を添加して凝集させて、凝集粒子の分散液を得る工程である。
（ポリエステルを含む樹脂粒子分散液）
本発明における樹脂粒子分散液中の樹脂粒子は、トナーの定着性及び耐久性の観点からポリエステルを含む。ポリエステルの含有量は、同様の観点から、樹脂中、６０重量％以上が好ましく、７０重量％以上がより好ましく、８０重量％以上がさらに好ましく、実質１００重量％であることがさらにより好ましい。樹脂粒子を構成する樹脂としては、ポリエステルとともに、トナーに用いられる公知の樹脂、例えば、ポリエステル、スチレンアクリル共重合体、エポキシ、ポリカーボネート、ポリウレタン等を含有することもできる。
[Step (1)]
Step (1) is a step of adding a flocculant to agglomerate the resin particles in the resin particle dispersion containing polyester to obtain a dispersion of aggregated particles.
(Resin particle dispersion containing polyester)
The resin particles in the resin particle dispersion in the present invention contain polyester from the viewpoint of toner fixability and durability. From the same viewpoint, the polyester content is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and still more preferably 100% by weight. As the resin constituting the resin particles, a known resin used in the toner, for example, polyester, styrene acrylic copolymer, epoxy, polycarbonate, polyurethane and the like can be contained together with polyester.
ポリエステルの原料モノマーは、特に限定されないが、公知のアルコール成分と、カルボン酸、カルボン酸無水物、カルボン酸エステル等の公知のカルボン酸成分が用いられる。
カルボン酸としては、フタル酸、イソフタル酸、テレフタル酸、フマル酸、マレイン酸、アジピン酸、コハク酸等のジカルボン酸、ドデセニルコハク酸、オクテニルコハク酸等の炭素数１〜２０のアルキル基又は炭素数２〜２０のアルケニル基で置換されたコハク酸等の２価のカルボン酸、トリメリット酸、ピロメリット酸等の３価以上の多価カルボン酸、それらの酸の無水物及びそれらの酸のアルキル（炭素数１〜３）エステル等が挙げられる。
このカルボン酸成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The raw material monomer of the polyester is not particularly limited, and a known alcohol component and a known carboxylic acid component such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester are used.
Examples of the carboxylic acid include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid, and succinic acid, alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid, octenyl succinic acid, and 2 to 2 carbon atoms. Divalent carboxylic acids such as succinic acid substituted with 20 alkenyl groups, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides of these acids, and alkyls of these acids (carbon Formulas 1-3) Esters and the like can be mentioned.
This carboxylic acid component may be used individually by 1 type, and may be used in combination of 2 or more type.
また、アルコール成分としては、具体的には、ポリオキシプロピレン−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン−２，２−ビス（４−ヒドロキシフェニル）プロパン等のビスフェノールＡのアルキレン（炭素数２〜３）オキサイド（平均付加モル数１〜１６）付加物、水素添加ビスフェノールＡ、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、１，４−ブタンジオール、１，３−ブタンジオール、１，６−ヘキサンジオール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、ソルビトール、又はそれらのアルキレン（炭素数２〜４）オキサイド（平均付加モル数１〜１６）付加物等が挙げられる。上記アルコールは、２種以上を組み合わせて用いてもよい。 Further, as the alcohol component, specifically, bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, and the like. Alkylene (2 to 3 carbon atoms) oxide (average added mole number 1 to 16) adduct, hydrogenated bisphenol A, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, Examples include 1,6-hexanediol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, or an alkylene (2 to 4 carbon) oxide (average added mole number 1 to 16) adduct thereof. You may use the said alcohol in combination of 2 or more type.
ポリエステルは、例えば、アルコール成分とカルボン酸成分とを不活性ガス雰囲気中にて、必要に応じエステル化触媒を用いて、１８０〜２５０℃程度の温度で縮重合することにより製造することができる。
エステル化触媒としては、酸化ジブチル錫、ジオクチル酸錫等の錫化合物やチタンジイソプロピレートビストリエタノールアミネート等のチタン化合物等のエステル化触媒を使用することができる。エステル化触媒の使用量は、アルコール成分とカルボン酸成分の総量１００重量部に対して、０.０１〜１重量部が好ましく、０.１〜０.６重量部がより好ましい。
The polyester can be produced, for example, by subjecting an alcohol component and a carboxylic acid component to condensation polymerization at a temperature of about 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.
As the esterification catalyst, an esterification catalyst such as a tin compound such as dibutyltin oxide or tin dioctylate or a titanium compound such as titanium diisopropylate bistriethanolamate can be used. The amount of the esterification catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.
トナーの定着性と保存性の観点から、ポリエステルの軟化点は７０〜１６５℃が好ましく、９０〜１６５℃であることがより好ましく、ガラス転移点は５０〜８５℃が好ましく、５５〜８５℃であることがより好ましい。酸価は、製造性の観点から、６〜３５ｍｇＫＯＨ／ｇが好ましく、１０〜３５ｍｇＫＯＨ／ｇがより好ましく、１５〜３５ｍｇＫＯＨ／ｇがさらに好ましい。軟化点や酸価はアルコールとカルボン酸の仕込み比率、縮重合の温度、反応時間を調節することにより所望のものを得ることができる。 From the viewpoint of toner fixing property and storage stability, the softening point of the polyester is preferably 70 to 165 ° C, more preferably 90 to 165 ° C, and the glass transition point is preferably 50 to 85 ° C, preferably 55 to 85 ° C. More preferably. The acid value is preferably 6 to 35 mgKOH / g, more preferably 10 to 35 mgKOH / g, and still more preferably 15 to 35 mgKOH / g from the viewpoint of manufacturability. The desired softening point and acid value can be obtained by adjusting the charging ratio of alcohol and carboxylic acid, the temperature of condensation polymerization, and the reaction time.
尚、本発明において、ポリエステルには、未変性のポリエステルのみならず、実質的にその特性を損なわない程度に変性されたポリエステルも含まれる。変性されたポリエステルとしては、例えば、特開平１１−１３３６６８号公報、特開平１０−２３９９０３号公報、特開平８−２０６３６号公報等に記載の方法によりフェノール、ウレタン、エポキシ等によりグラフト化やブロック化したポリエステルや、ポリエステルユニットを含む２種以上の樹脂ユニットを有する複合樹脂が挙げられる。 In the present invention, the polyester includes not only unmodified polyester but also polyester modified to such an extent that the characteristics are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.
尚、樹脂粒子分散液中の樹脂粒子が複数の樹脂を含有する場合には、前記樹脂粒子を構成する樹脂の軟化点、ガラス転移点、及び酸価は、各樹脂の混合物としての軟化点、ガラス転移点、酸価を意味し、各々の値は上記ポリエステルの値と同様の値であることが好ましい。
さらに、上記樹脂は、トナーの定着性及び耐久性の観点から、軟化点が異なる２種類のポリエステルを含有することができ、一方のポリエステル（Ｉ）の軟化点は７０℃以上１１５℃未満が好ましく、他方のポリエステル（II）の軟化点のポリエステルの軟化点は１１５℃以上１６５℃以下が好ましい。ポリエステル（Ｉ）とポリエステル（II）の重量比（Ｉ／II）は、１０／９０〜９０／１０が好ましく、５０／５０〜９０／１０がより好ましい。
In the case where the resin particles in the resin particle dispersion contain a plurality of resins, the softening point of the resin constituting the resin particles, the glass transition point, and the acid value are the softening point as a mixture of the resins, It means a glass transition point and an acid value, and each value is preferably the same value as that of the polyester.
Furthermore, the above-mentioned resin can contain two types of polyesters having different softening points from the viewpoint of toner fixability and durability, and the softening point of one polyester (I) is preferably 70 ° C. or higher and lower than 115 ° C. The softening point of the other polyester (II) is preferably 115 ° C. or higher and 165 ° C. or lower. The weight ratio (I / II) between the polyester (I) and the polyester (II) is preferably 10/90 to 90/10, more preferably 50/50 to 90/10.
本発明においては、樹脂粒子を構成する樹脂を分散させるに際し、水系媒体中で行うことが好ましい。樹脂を分散させる水系媒体は水を主成分とするものである。環境性の観点から、水系媒体中の水の含有量は８０重量％以上が好ましく、９０重量％以上がより好ましく、１００重量％がさらに好ましい。
水以外の成分としては、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール系有機溶媒やアセトン、メチルエチルケトン、テトラヒドロフラン等の水に溶解する有機溶媒が挙げられる。これらのなかでは、トナーへの混入を防止する観点から、樹脂を溶解しない有機溶媒である、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール系有機溶媒が使用できる。本発明では、実質的に有機溶剤を用いることなく、水のみを用いて樹脂を微粒化させることが好ましい。
In the present invention, the resin constituting the resin particles is preferably dispersed in an aqueous medium. The aqueous medium in which the resin is dispersed is mainly composed of water. From the environmental viewpoint, the content of water in the aqueous medium is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 100% by weight.
Examples of components other than water include alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, and organic solvents that dissolve in water such as acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, can be used. In the present invention, it is preferable to atomize the resin using only water without substantially using an organic solvent.
樹脂を分散させて得られる樹脂分散液中には、前記樹脂とともに必要に応じて離型剤、着色剤などの添加剤を含有させることができる。
離型剤としては、例えば固形のパラフィンワックス、ライスワックス、脂肪酸アミド系ワックス、脂肪酸系ワックス、脂肪酸金属塩系ワックス、脂肪酸エステル系ワックス、シリコーンワニス、高級アルコール、カルナウバワックスなどを挙げることができる。また、低分子量ポリエチレン、ポリプロピレン等のポリオレフィンなども用いることができる。上記離型剤は、１種を単独で又は２種以上を組み合わせて使用することができる。
これら離型剤の融点は、トナーの定着性の観点から、６０〜９０℃であることが好ましく、６５〜９０℃がさらに好ましく、この中でもトナーの低温定着の観点からは融点が６０〜９０℃のパラフィンワックスが好ましく、ポリエステルとの相溶性の観点からは融点が６０〜９０℃のエステル系ワックスが好ましく、カルナウバワックスがさらに好ましい。
離型剤の含有量は、樹脂への分散性及びトナーの定着性の観点から、樹脂１００重量部に対して、好ましくは０．５〜２０重量部、より好ましくは１〜１８重量部、さらに好ましくは１．５〜１５重量部である。
In the resin dispersion obtained by dispersing the resin, additives such as a release agent and a colorant can be contained together with the resin as necessary.
Examples of the mold release agent include solid paraffin wax, rice wax, fatty acid amide wax, fatty acid wax, fatty acid metal salt wax, fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. . Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. The said mold release agent can be used individually by 1 type or in combination of 2 or more types.
The melting point of these release agents is preferably 60 to 90 ° C. from the viewpoint of toner fixability, more preferably 65 to 90 ° C. Among these, the melting point is 60 to 90 ° C. from the viewpoint of low temperature fixing of the toner. From the viewpoint of compatibility with polyester, an ester wax having a melting point of 60 to 90 ° C. is preferable, and carnauba wax is more preferable.
The content of the release agent is preferably 0.5 to 20 parts by weight, more preferably 1 to 18 parts by weight, and more preferably 1 to 18 parts by weight with respect to 100 parts by weight of the resin, from the viewpoint of dispersibility in the resin and toner fixability. Preferably it is 1.5-15 weight part.
着色剤としては、特に制限はなく公知の着色剤がいずれも使用できる。具体的には、カーボンブラック、無機系複合酸化物、クロムイエロー、ベンジジンイエロー、ピラゾロンオレンジ、バルカンオレンジ、ウオッチヤングレッド、ブリリアンカーミン３Ｂ、ブリリアンカーミン６Ｂ、レーキレッドＣ、ベンガル、フタロシアニンブルー、フタロシアニングリーン等の種々の顔料やアクリジン系、アゾ系、ベンゾキノン系、アジン系、アントラキノン系、インジコ系、フタロシアニン系、アニリンブラック系等の各種染料を１種を単独で又は２種以上を組み合わせて使用することができる。
着色剤の含有量は、樹脂１００重量部に対して、２０重量部以下が好ましく、０．０１〜１０重量部がより好ましい。
The colorant is not particularly limited, and any known colorant can be used. Specifically, carbon black, inorganic complex oxide, chrome yellow, benzidine yellow, pyrazolone orange, vulcan orange, watch young red, brilliantamine 3B, brilliantamine 6B, lake red C, bengal, phthalocyanine blue, phthalocyanine green, etc. Various pigments and various dyes such as acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indico series, phthalocyanine series, and aniline black series may be used alone or in combination of two or more. it can.
The content of the colorant is preferably 20 parts by weight or less, and more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin.
本発明においては、樹脂粒子分散液の製造に際して、樹脂の分散安定性の向上などの観点から、樹脂１００重量部に対して、好ましくは１０重量部以下、より好ましくは５重量部以下、より好ましくは０．１〜３重量部、さらに好ましくは０．５〜２重量部の界面活性剤を存在させることが好ましい。
界面活性剤としては、例えば、硫酸エステル系、スルホン酸塩系、せっけん系等のアニオン性界面活性剤；アミン塩型、４級アンモニウム塩型等のカチオン性界面活性剤；ポリエチレングリコール系、アルキルフェノールエチレンオキサイド付加物系、多価アルコール系等の非イオン性界面活性剤などが挙げられる。これらの中でも、アニオン性界面活性剤、カチオン性界面活性剤等のイオン性界面活性剤が好ましい。非イオン性界面活性剤は、アニオン性界面活性剤又はカチオン性界面活性剤と併用されるのが好ましい。前記界面活性剤は、１種を単独で用いてもよいが、２種以上を組み合わせて用いてもよい。
In the present invention, in the production of the resin particle dispersion, from the viewpoint of improving the dispersion stability of the resin, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, more preferably 100 parts by weight of the resin. Is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight of a surfactant.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type and alkylphenol ethylene Nonionic surfactants such as oxide adducts and polyhydric alcohols can be mentioned. Among these, ionic surfactants such as anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant. Although the said surfactant may be used individually by 1 type, you may use it in combination of 2 or more type.
前記アニオン性界面活性剤の具体例としては、ドデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム、アルキルエーテル硫酸ナトリウムなどが挙げられる。これらの中でもドデシルベンゼンスルホン酸ナトリウムが好ましい。
また、前記カチオン性界面活性剤の具体例としては、アルキルベンゼンジメチルアンモニウムクロライド、アルキルトリメチルアンモニウムクロライド、ジステアリルアンモニウムクロライドなどが挙げられる。
Specific examples of the anionic surfactant include dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium alkyl ether sulfate, and the like. Among these, sodium dodecylbenzenesulfonate is preferable.
Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
非イオン性界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルアリールエーテル類あるいはポリオキシエチレンアルキルエーテル類、ポリエチレングルコールモノラウレート、ポリチレングリコ−ルモノステアレート、ポリエチレングリコールモノオレエート等のポリオキシエチレン脂肪酸エステル類、オキシエチレン／オキシプロピレンブロックコポリマー等が挙げられる。 Nonionic surfactants include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers, polyethylene glycol mono Examples thereof include polyoxyethylene fatty acid esters such as laurate, polyethylene glycol monostearate, and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers.
上記樹脂粒子分散液の調製に際しては、樹脂にアルカリ水溶液を加え、樹脂及び必要に応じて用いられる添加剤を分散させることが好ましい。
前記アルカリ水溶液は１〜２０重量％の濃度のものが好ましく、１〜１０重量％の濃度のものがより好ましく、１．５〜７．５重量％の濃度のものがさらに好ましい。用いるアルカリについては、樹脂が塩になったときその界面活性能を高めるようなアルカリを用いることが好ましい。具体的には、水酸化カリウム、水酸化ナトリウムなどの１価のアルカリ金属の水酸化物などが挙げられる。
分散後、好ましくは樹脂のガラス転移点以上の温度で中和させた後、樹脂のガラス転移点以上の温度で水系媒体を添加することによって、乳化させる事により、樹脂粒子分散液を製造することができる。
In preparing the resin particle dispersion, it is preferable to add an aqueous alkali solution to the resin and disperse the resin and additives used as necessary.
The aqueous alkaline solution preferably has a concentration of 1 to 20% by weight, more preferably 1 to 10% by weight, and even more preferably 1.5 to 7.5% by weight. As the alkali to be used, it is preferable to use an alkali that enhances the surface activity when the resin becomes a salt. Specific examples thereof include monovalent alkali metal hydroxides such as potassium hydroxide and sodium hydroxide.
After dispersion, preferably after neutralizing at a temperature above the glass transition point of the resin, and then emulsifying by adding an aqueous medium at a temperature above the glass transition point of the resin to produce a resin particle dispersion. Can do.
上記水系媒体の添加速度は、乳化を効果的に実施し得る点から、樹脂１００ｇ当たり好ましくは０．１〜５０ｇ／分、より好ましくは０．５〜４０ｇ／分、さらに好ましくは１〜３０ｇ／分である。この添加速度は、一般にＯ／Ｗ型の乳化液を実質的に形成するまで維持すればよく、Ｏ／Ｗ型の樹脂粒子分散液を形成した後の水の添加速度に特に制限はない。
当該樹脂粒子分散液の製造に用いる水系媒体としては、前述の樹脂粒子を構成する樹脂の分散に用いられる水系媒体と同じものを挙げることができ、好ましくは、脱イオン水又は蒸留水である。
水系媒体の量は、後の凝集処理で均一な凝集粒子を得る観点から、樹脂１００重量部に対して１００〜２，０００重量部が好ましく、１５０〜１，５００重量部がより好ましい。得られる樹脂粒子分散液の安定性と取扱い性などの観点から、樹脂粒子分散液の固形分濃度は、好ましくは７〜５０重量％、より好ましくは７〜４０重量％、さらに好ましくは１０〜３５重量％になるように水系媒体の量を選定する。なお、固形分には樹脂、非イオン性界面活性剤などの不揮発性成分が含まれる。
The addition rate of the aqueous medium is preferably from 0.1 to 50 g / min, more preferably from 0.5 to 40 g / min, and even more preferably from 1 to 30 g / min per 100 g of resin from the viewpoint that emulsification can be effectively carried out. Minutes. This addition rate is generally maintained until an O / W type emulsion is substantially formed, and there is no particular limitation on the addition rate of water after forming the O / W type resin particle dispersion.
As an aqueous medium used for manufacture of the said resin particle dispersion liquid, the same thing as the aqueous medium used for dispersion | distribution of the resin which comprises the above-mentioned resin particle can be mentioned, Preferably it is deionized water or distilled water.
The amount of the aqueous medium is preferably from 100 to 2,000 parts by weight, more preferably from 150 to 1,500 parts by weight, based on 100 parts by weight of the resin, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation treatment. From the viewpoint of the stability and handleability of the obtained resin particle dispersion, the solid content concentration of the resin particle dispersion is preferably 7 to 50% by weight, more preferably 7 to 40% by weight, and still more preferably 10 to 35%. The amount of the aqueous medium is selected so as to be weight%. In addition, non-volatile components, such as resin and a nonionic surfactant, are contained in solid content.
また、この際の温度は、微細な樹脂粒子分散液を調製する観点から、樹脂のガラス転移点以上かつ軟化点以下の範囲であることが好ましい。前記範囲の温度で行うことにより、乳化がスムーズに行われ、また加熱に特別の装置を必要としない。この点から、上記温度は、（樹脂のガラス転移点＋１０℃）（「ガラス転移点より１０℃高い温度」を意味する、以下同様の表記は同様に解する）以上であることが好ましく、また、（樹脂の軟化点−５℃）以下であることが好ましい。
このようにして得られた樹脂粒子分散液中の樹脂粒子の体積中位粒径（Ｄ５０）は、後の凝集処理での均一な凝集を行うために、好ましくは０．０２〜２μｍ、より好ましくは０．０５〜１μｍ、さらに好ましくは０．０５〜０．６μｍである。ここで「体積中位粒径（Ｄ５０）」とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して５０％になる粒径を意味する。
Moreover, it is preferable that the temperature in this case is the range above the glass transition point of a resin and below a softening point from a viewpoint of preparing a fine resin particle dispersion. By carrying out at a temperature within the above range, emulsification is carried out smoothly and no special apparatus is required for heating. From this point, the above temperature is preferably (glass transition point of the resin + 10 ° C.) (which means “temperature higher by 10 ° C. than the glass transition point”, hereinafter the same notation is similarly understood), , (Resin softening point −5 ° C.) or less.
The volume median particle size (D50) of the resin particles in the resin particle dispersion thus obtained is preferably 0.02 to 2 μm, more preferably for uniform aggregation in the subsequent aggregation treatment. Is 0.05-1 μm, more preferably 0.05-0.6 μm. Here, “volume median particle size (D50)” means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.
樹脂粒子分散液を得る他の方法としては、例えば、まず、目的とする樹脂粒子原料として重縮合性単量体を水系媒体中に例えば機械的シェアや超音波などにより乳化分散させる方法が挙げられる。この際、必要に応じて、重縮合触媒、界面活性剤などの添加剤も水溶性媒体に添加する。そして、この溶液に対して例えば加熱などを施すことで、重縮合を進行させる。樹脂がポリエステルである場合は、前述のポリエステルの重縮合性単量体、重縮合触媒が使用でき、界面活性剤としては前述のものが同様に使用できる。
通常、重縮合樹脂は重合時に脱水を伴うために原理的に水系媒体中では進行しない。しかしながら、例えば、水系媒体中にミセルを形成せしめるような界面活性剤とともに重縮合性単量体を水系媒体中に乳化せしめた場合、単量体がミセル中のミクロな疎水場に置かれることによって、脱水作用が生じ、生成した水はミセル外の水系媒体中に排出せしめ重合を進行させることができる。このようにして、低エネルギーで、水系媒体に重縮合樹脂の樹脂粒子が分散した樹脂粒子分散液が得られる。
Examples of other methods for obtaining a resin particle dispersion include, for example, a method in which a polycondensable monomer is first emulsified and dispersed in an aqueous medium by, for example, mechanical shearing or ultrasonic waves as a target resin particle raw material. . At this time, if necessary, additives such as a polycondensation catalyst and a surfactant are also added to the water-soluble medium. And polycondensation is advanced by, for example, heating the solution. When the resin is polyester, the above-mentioned polyester polycondensable monomer and polycondensation catalyst can be used, and the above-mentioned surfactants can be used in the same manner.
Usually, polycondensation resins do not proceed in an aqueous medium in principle because they are dehydrated during polymerization. However, for example, when a polycondensable monomer is emulsified in an aqueous medium together with a surfactant that causes micelles to form in the aqueous medium, the monomer is placed in a micro hydrophobic field in the micelle. Then, dehydration occurs, and the generated water can be discharged into an aqueous medium outside the micelles to allow polymerization to proceed. In this way, a resin particle dispersion in which the resin particles of the polycondensation resin are dispersed in an aqueous medium with low energy is obtained.
（凝集粒子分散液）
工程（１）においては、上記得られたポリエステルを含む樹脂粒子分散液中の樹脂粒子を、凝集剤を添加して凝集させて、凝集粒子の分散液を得る。
凝集剤として、有機系の凝集剤では、ポリエチレンイミン等、無機系の凝集剤では、無機金属塩、無機アンモニウム塩、２価以上の金属錯体等が用いられる。有機塩としては、酢酸ナトリウム、酢酸アンモニウムが、無機金属塩としては、例えば、硫酸ナトリウム、塩化ナトリウム、塩化カルシウム、塩化マグネシウム、塩化亜鉛、塩化アルミニウム、硫酸アルミニウム等の金属塩、及びポリ塩化アルミニウム等の無機金属塩重合体が挙げられる。無機アンモニウム塩としては、例えば硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウムなどが挙げられる。
(Aggregated particle dispersion)
In step (1), the resin particles in the resin particle dispersion containing the polyester obtained above are aggregated by adding an aggregating agent to obtain a dispersion of aggregated particles.
As an aggregating agent, an organic aggregating agent includes polyethyleneimine and the like, and an inorganic aggregating agent includes an inorganic metal salt, an inorganic ammonium salt, a divalent or higher metal complex, and the like. Examples of organic salts include sodium acetate and ammonium acetate. Examples of inorganic metal salts include sodium sulfate, sodium chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and other metal salts, and polyaluminum chloride. And inorganic metal salt polymers. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
本発明においては、凝集剤は、凝集粒子の粒径制御の観点から、有機塩及び無機塩から選ばれる少なくとも一種を、好ましくは９０重量％以上、より好ましくは９５重量％以上含有する。凝集剤として有機塩及び無機塩から選ばれる２種類以上を使用する場合、凝集粒子の粒径制御の観点から、これらは同一の価数であることが好ましい。また、高精度のトナーの粒径制御及びシャープな粒度分布を達成する観点から、上記凝集剤のうち、１価の塩を用いることが好ましい。ここで１価の塩とは、該塩を構成する金属イオン又は陽イオンの価数が１であることを意味する。１価の塩としては、無機金属塩、アンモニウム塩等の無機系凝集剤が用いられるが、本発明においては、分子量３５０以下の水溶性含窒素化合物が好ましく用いられる。 In the present invention, the flocculant contains at least one selected from organic salts and inorganic salts from the viewpoint of controlling the particle size of the aggregated particles, preferably 90% by weight or more, more preferably 95% by weight or more. When using 2 or more types chosen from organic salt and inorganic salt as an aggregating agent, it is preferable that these are the same valence from a viewpoint of the particle size control of an aggregated particle. Further, from the viewpoint of achieving highly accurate toner particle size control and sharp particle size distribution, it is preferable to use a monovalent salt among the above-mentioned flocculants. Here, the monovalent salt means that the valence of the metal ion or cation constituting the salt is 1. As the monovalent salt, an inorganic flocculant such as an inorganic metal salt or ammonium salt is used. In the present invention, a water-soluble nitrogen-containing compound having a molecular weight of 350 or less is preferably used.
分子量３５０以下の水溶性含窒素化合物は、一次粒子を速やかに凝集させる観点から、酸性を示す化合物であることが好ましく、その１０重量％水溶液の２５℃でのｐＨ値が４〜６であるものが好ましく、４．２〜６のものがより好ましい。また、高温高湿におけるトナーの帯電性等の観点から、その分子量が３５０以下のものが好ましく、３００以下のものがより好ましい。このような水溶性含窒素化合物としては、例えば、ハロゲン化アンモニウム、硫酸アンモニウム、酢酸アンモニウム、サリチル酸アンモニウム等のアンモニウム塩、テトラアルキルアンモニウムハライド等の４級アンモニウム塩等が挙げられるが、生産性の点から、硫酸アンモニウム（１０重量％水溶液の２５℃でのｐＨ値、以下ｐＨ値という：５．４）、塩化アンモニウム（ｐＨ値：４．６）、臭化テトラエチルアンモニウム（ｐＨ値：５．６）、臭化テトラブチルアンモニウム（ｐＨ値：５．８）が好ましく挙げられる。 The water-soluble nitrogen-containing compound having a molecular weight of 350 or less is preferably a compound exhibiting acidity from the viewpoint of rapidly agglomerating primary particles, and a 10% by weight aqueous solution having a pH value of 4 to 6 at 25 ° C. Are preferable, and 4.2 to 6 are more preferable. Further, from the viewpoint of chargeability of the toner at high temperature and high humidity, the molecular weight is preferably 350 or less, more preferably 300 or less. Examples of such water-soluble nitrogen-containing compounds include ammonium salts such as ammonium halide, ammonium sulfate, ammonium acetate, and ammonium salicylate, and quaternary ammonium salts such as tetraalkylammonium halides. , Ammonium sulfate (pH value of a 10% by weight aqueous solution at 25 ° C., hereinafter referred to as pH value: 5.4), ammonium chloride (pH value: 4.6), tetraethylammonium bromide (pH value: 5.6), odor Preferred is tetrabutylammonium bromide (pH value: 5.8).
凝集剤の使用量は、凝集剤の価数により異なるが、一般に、凝集剤の濃度を０.０００１〜１０モル／Ｌとする量であればよい。一般に、トナーの帯電性、特に高温高湿環境の帯電特性の観点から、樹脂１００重量部に対して、５０重量部以下が好ましく、４０重量部以下がより好ましく、３０重量部以下がさらに好ましい。また、凝集性の観点から、樹脂１００重量部に対して１重量部以上が好ましく、３重量部以上がより好ましく、５重量部以上がさらに好ましい。以上の点を考慮して、凝集剤の使用量は、樹脂１００重量部に対して１〜５０重量部が好ましく、３〜４０重量部がより好ましく、５〜３０重量部がさらに好ましい。 The amount of the flocculant used varies depending on the valence of the flocculant, but in general, it may be an amount that makes the concentration of the flocculant 0.0001 to 10 mol / L. In general, from the viewpoint of toner charging properties, particularly charging characteristics in a high-temperature and high-humidity environment, 50 parts by weight or less is preferable, 40 parts by weight or less is more preferable, and 30 parts by weight or less is more preferable. Moreover, from a cohesive viewpoint, 1 weight part or more is preferable with respect to 100 weight part of resin, 3 weight part or more is more preferable, and 5 weight part or more is further more preferable. Considering the above points, the amount of the flocculant used is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, and even more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the resin.
凝集工程においては、凝集性及び凝集粒子の粒度分布制御の観点から、上記凝集系内の温度を（樹脂粒子を構成する樹脂のガラス転移点＋２５）℃以下の温度とすることが好ましく、粗大粒子の抑制の観点から、より好ましくは（ガラス転移点−３０）℃〜（ガラス転移点＋２５℃）、より好ましくは２５℃〜（ガラス転移点＋２５）℃、さらに好ましくは２５℃〜（ガラス転移点＋１５）℃、さらにより好ましくは３５℃〜（ガラス転移点＋５）℃、さらに好ましくは４０℃〜（ガラス転移点−５）℃の範囲である。
本発明においては、トナーの低温定着性及び保存性の観点から、離型剤を水系媒体中に分散した離型剤分散液を、樹脂粒子分散液と混合し、凝集剤を添加し凝集させることが望ましい。離型剤としては、前述の樹脂粒子分散液の調製に用いたものと同様のものを使用することができる。離型剤分散液の調製においては、離型剤を水系媒体中に界面活性剤の存在下で分散し、離型剤の融点以上に加熱しながら、ホモジナイザーや超音波分散機等で微粒子に分散し、体積中位粒径（Ｄ５０）が好ましくは1μｍ以下の離型剤粒子の分散液とする。
In the agglomeration step, from the viewpoint of agglomeration and particle size distribution control of the agglomerated particles, the temperature in the agglomerated system is preferably (temperature of the glass transition point of the resin constituting the resin particles +25) ° C. or less, and the coarse particles From the viewpoint of suppression, it is more preferably (glass transition point-30) ° C. to (glass transition point + 25 ° C.), more preferably 25 ° C. to (glass transition point + 25) ° C., more preferably 25 ° C. to (glass transition point). +15) ° C., even more preferably 35 ° C. to (glass transition point + 5) ° C., still more preferably 40 ° C. to (glass transition point−5) ° C.
In the present invention, from the viewpoint of low-temperature fixability and storage stability of the toner, a release agent dispersion in which a release agent is dispersed in an aqueous medium is mixed with a resin particle dispersion, and an aggregating agent is added to cause aggregation. Is desirable. As the release agent, the same ones used for the preparation of the resin particle dispersion described above can be used. In the preparation of the release agent dispersion, the release agent is dispersed in an aqueous medium in the presence of a surfactant and dispersed into fine particles with a homogenizer or an ultrasonic disperser while being heated above the melting point of the release agent. The volume median particle size (D50) is preferably a dispersion of release agent particles having a particle size of 1 μm or less.
また、本発明においては、トナーの帯電性の観点から、荷電制御剤を樹脂粒子分散液と混合し、凝集剤を添加し凝集させることも望ましい方法である。荷電制御剤としては、例えば安息香酸の金属塩、サリチル酸の金属塩、アルキルサリチル酸の金属塩、カテコールの金属塩、含金属ビスアゾ染料、第四級アンモニウム塩などが挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
荷電制御剤の含有量は、樹脂１００重量部に対して、１０重量部以下が好ましく、０．０１〜５重量部がより好ましい。
In the present invention, from the viewpoint of chargeability of the toner, it is also desirable to mix a charge control agent with a resin particle dispersion and add a flocculant to cause aggregation. Examples of the charge control agent include a metal salt of benzoic acid, a metal salt of salicylic acid, a metal salt of alkyl salicylic acid, a metal salt of catechol, a metal-containing bisazo dye, and a quaternary ammonium salt. These may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the charge control agent is preferably 10 parts by weight or less, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin.
凝集工程における系内の凝集剤濃度は、樹脂粒子の凝集性の観点から０.０００１〜１０モル／Ｌであることが好ましい。凝集剤量が少なすぎると粒子を凝集させることができず、樹脂粒子をトナー粒子に成長させることができない。一方、凝集剤の量が多すぎると凝集粒子の粒子径に制御ができず所望のトナーを得ることができない。凝集剤濃度Ｅａは用いる凝集剤の価数によって異なることがあるが、凝集剤の価数をｚとすると、「最新コロイド化学」(北原、古沢著、１９９０年、講談社サイエンティフィク発行)に記載されているように、樹脂粒子の凝集性は凝集剤の価数の６乗に比例することから、凝集剤濃度Ｅａ（モル／Ｌ）は、好ましくは
０.１×ｚ-6≦Ｅａ≦１０×ｚ-6
の範囲内となるように、より好ましくは、
０.１×ｚ-6≦Ｅａ≦１×ｚ-6
の範囲内となるように凝集剤濃度を調整すればよい。1価の凝集剤の場合には、凝集剤濃度は０.１〜１０モル／Ｌが好ましく、より好ましくは０.１〜１モル／Ｌである。
The concentration of the coagulant in the system in the coagulation step is preferably 0.0001 to 10 mol / L from the viewpoint of the cohesiveness of the resin particles. If the amount of the aggregating agent is too small, the particles cannot be aggregated and the resin particles cannot be grown into toner particles. On the other hand, if the amount of the aggregating agent is too large, the particle diameter of the agglomerated particles cannot be controlled and a desired toner cannot be obtained. The flocculant concentration Ea may vary depending on the valency of the flocculant used. If the valency of the flocculant is z, it is described in “Latest Colloid Chemistry” (Kitahara, Furuzawa, 1990, published by Kodansha Scientific). As described above, the cohesiveness of the resin particles is proportional to the sixth power of the valence of the coagulant. Therefore, the coagulant concentration Ea (mol / L) is preferably 0.1 × z −6 ≦ Ea ≦ 10. × z -6
More preferably, within the range of
0.1 × z −6 ≦ Ea ≦ 1 × z −6
The flocculant concentration may be adjusted so as to be within the range of. In the case of a monovalent flocculant, the flocculant concentration is preferably 0.1 to 10 mol / L, more preferably 0.1 to 1 mol / L.
凝集剤の添加は、均一な凝集を行うために、前記温度で行うのが望ましい。また、凝集剤は水系媒体溶液にして添加することができる。凝集剤は、一時に添加しても良いし、連続的あるいは断続的に添加してもよい。また、分割して添加することもできる。凝集剤の添加時及び添加終了後には十分な攪拌をすることが好ましい。
工程（１）で得られる凝集粒子の分散液中における固形分濃度は、凝集粒子分散液の生産性及び凝集制御の観点から、５〜５０重量％であることが好ましく、より好ましくは５〜４０重量％である。
The addition of the flocculant is desirably performed at the above temperature in order to perform uniform agglomeration. The flocculant can be added as an aqueous medium solution. The flocculant may be added at once, or may be added continuously or intermittently. Moreover, it can also be divided and added. It is preferable to sufficiently stir at the time of adding the flocculant and after completion of the addition.
The solid content concentration in the dispersion liquid of the aggregated particles obtained in the step (1) is preferably 5 to 50% by weight, more preferably 5 to 40% from the viewpoint of productivity of the aggregated particle dispersion liquid and aggregation control. % By weight.
このようにして、樹脂粒子分散液中の樹脂粒子を凝集させることにより、凝集粒子分散液を調製する。
この凝集粒子分散液に含まれる凝集粒子は、得られるトナーの小粒径化の観点から、その体積中位粒径（Ｄ５０）が１〜１０μｍ、より好ましくは２〜９μｍ、さらに好ましくは２〜５μｍの範囲にあることが好ましい。また粒度分布の変動係数（ＣＶ値）は３０％以下であることが好ましく、より好ましくは２８％以下、さらに好ましくは２５％以下である。なお、粒度分布の変動係数（ＣＶ値）は、式
ＣＶ値（％）＝［粒度分布の標準偏差（μｍ）／体積中位粒径（μｍ）］×１００
で表される値である。
In this way, the aggregated particle dispersion is prepared by aggregating the resin particles in the resin particle dispersion.
The aggregated particles contained in this aggregated particle dispersion have a volume median particle size (D50) of 1 to 10 μm, more preferably 2 to 9 μm, and still more preferably 2 to 2 μm, from the viewpoint of reducing the particle size of the obtained toner. It is preferably in the range of 5 μm. The variation coefficient (CV value) of the particle size distribution is preferably 30% or less, more preferably 28% or less, and further preferably 25% or less. The coefficient of variation (CV value) of the particle size distribution is expressed by the formula CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100
It is a value represented by
本発明の製造方法は、工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を添加して樹脂微粒子付着凝集粒子を得る工程（以下、「カプセル化工程」ということがある）を有する。カプセル化工程は、工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を連続的に添加する工程である工程（２）を含む。
［工程（２）］
工程（２）は、工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を連続的に添加する工程であって、凝集粒子１００重量部に対して、工程（２）で添加する樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で凝集粒子分散液を含む系内を昇温させながら行う工程である。
The production method of the present invention is sometimes referred to as a step of obtaining resin fine particle-attached aggregated particles by adding a dispersion of resin fine particles to the aggregated particle dispersion obtained in step (1) (hereinafter referred to as “encapsulation step”). ). The encapsulation step includes step (2), which is a step of continuously adding a dispersion of resin fine particles to the aggregated particle dispersion obtained in step (1).
[Step (2)]
The step (2) is a step of continuously adding the dispersion of resin fine particles to the aggregated particle dispersion obtained in the step (1), and in step (2) with respect to 100 parts by weight of the aggregated particles. This is a step performed while raising the temperature of the system containing the aggregated particle dispersion at a rate of 0.05 to 0.25 ° C. per 1 part by weight of the resin fine particles to be added.
このような工程により、カプセル化での凝集剤の新たな添加による系内の凝集剤濃度の調整の必要がなく、簡便に、効率よくカプセル化が可能となる。すなわち、本発明は、凝集剤を添加することなく、樹脂微粒子の添加に伴い、その量に応じて系内の温度を上昇させることで、凝集剤を滴下するのと同様の効果を得ることができること、及びその際の樹脂微粒子添加量に応じた適切な温度上昇範囲を見出したものである。 By such a process, it is not necessary to adjust the concentration of the flocculant in the system by newly adding the flocculant in the encapsulation, and the encapsulation can be simply and efficiently performed. That is, the present invention can obtain the same effect as dropping the flocculant by adding the resin fine particles and increasing the temperature in the system according to the amount without adding the flocculant. The present inventors have found an appropriate temperature increase range according to what can be done and the amount of resin fine particles added at that time.
工程（２）において用いられる樹脂微粒子を構成する樹脂は、前述の工程（１）における樹脂粒子を構成する樹脂と同様のものが使用できるが、分子量や軟化点、あるいはモノマー構成等の異なる樹脂を使用する際に、本発明の効果を効果的に奏することができる。すなわち、樹脂微粒子を構成する樹脂が樹脂粒子を構成する樹脂と異なる場合に、凝集粒子分散液の製造後に、系内の温度を調整することにより、樹脂微粒子が凝集粒子に容易に付着し、かつ粗大粒子を発生しない等の所望のカプセル化が行われるため、得られるトナーは機能分離し、かつ粒径が制御されたものとなる。ここで、「系内」とは、樹脂微粒子を添加する前にあっては工程（１）で得られた凝集粒子分散液を、樹脂微粒子の添加を開始した後にあっては前記凝集粒子分散液に樹脂微粒子が添加された分散液を意味する。また、本発明において、凝集粒子を得るために供される樹脂の粒子を「樹脂粒子」、カプセル化のために凝集粒子に供される樹脂の粒子を「樹脂微粒子」と呼ぶ。 The resin constituting the resin fine particles used in the step (2) can be the same as the resin constituting the resin particles in the above-mentioned step (1), but a resin having a different molecular weight, softening point, or monomer composition can be used. When used, the effects of the present invention can be effectively achieved. That is, when the resin constituting the resin fine particles is different from the resin constituting the resin particles, the resin fine particles easily adhere to the aggregated particles by adjusting the temperature in the system after the production of the aggregated particle dispersion, and Since desired encapsulation such as generation of coarse particles is performed, the obtained toner is functionally separated and the particle size is controlled. Here, “in-system” means that the aggregated particle dispersion obtained in the step (1) is added before the resin fine particles are added, and the aggregated particle dispersion is added after the start of the addition of the resin fine particles. It means a dispersion in which resin fine particles are added. In the present invention, the resin particles provided to obtain aggregated particles are referred to as “resin particles”, and the resin particles provided to the aggregated particles for encapsulation are referred to as “resin fine particles”.
凝集粒子分散液に添加する樹脂微粒子分散液は、前述の樹脂粒子分散液の調製方法と同様にして調製できる。
樹脂微粒子分散液の調整において、樹脂微粒子を構成する樹脂を分散させるに際しては、工程（１）における樹脂粒子分散液の調製方法と同様に界面活性剤を使用することが好ましく、好ましい界面活性剤の種類や量は、前記樹脂粒子分散液の調製方法における場合と同様である。
樹脂微粒子分散液中には、前記樹脂とともに必要に応じて着色剤、離型剤、荷電制御剤などの添加剤を含有することができる。これらは前記工程（１）の樹脂粒子分散液の調製工程で述べたものと同様のものを使用することができる。
The resin fine particle dispersion added to the aggregated particle dispersion can be prepared in the same manner as the method for preparing the resin particle dispersion described above.
In preparing the resin fine particle dispersion, when dispersing the resin constituting the resin fine particles, it is preferable to use a surfactant in the same manner as the method for preparing the resin particle dispersion in the step (1). The type and amount are the same as in the method for preparing the resin particle dispersion.
In the resin fine particle dispersion, additives such as a colorant, a release agent, and a charge control agent can be contained together with the resin as necessary. These can use the same thing as what was described in the preparation process of the resin particle dispersion liquid of the said process (1).
樹脂微粒子分散液中の固形分濃度は、分散液の安定性及び凝集粒子へ均一な付着をさせる観点から、好ましくは７〜５０重量％、より好ましくは８〜４０重量％、さらに好ましくは１０〜３０重量％である。
このようにして得られる樹脂微粒子の体積中位粒径（Ｄ５０）は、均一に凝集させる観点から、０．０２〜２μｍが好ましく、０，０５〜１μｍがより好ましく、０．０５〜０．６μｍがさらに好ましい。
樹脂微粒子分散液の樹脂粒子の、凝集粒子に対する添加割合は、凝集粒子中の樹脂１００重量部に対して、樹脂微粒子中の樹脂が、好ましくは５〜１００重量部、より好ましくは１０〜９０重量部、さらに好ましくは２０〜８０重量部である。
The solid content concentration in the resin fine particle dispersion is preferably 7 to 50% by weight, more preferably 8 to 40% by weight, and still more preferably 10 to 10% from the viewpoint of the stability of the dispersion and uniform adhesion to the aggregated particles. 30% by weight.
The volume median particle size (D50) of the resin fine particles thus obtained is preferably 0.02 to 2 μm, more preferably 0.05 to 1 μm, and 0.05 to 0.6 μm from the viewpoint of uniform aggregation. Is more preferable.
The addition ratio of the resin particles in the resin fine particle dispersion to the aggregated particles is preferably 5 to 100 parts by weight, more preferably 10 to 90 parts by weight of the resin in the resin fine particles with respect to 100 parts by weight of the resin in the aggregated particles. Parts, more preferably 20 to 80 parts by weight.
工程（２）においては、凝集粒子分散液に、前記樹脂微粒子の分散液を連続的に添加する。本発明において、「連続的に添加する」とは、樹脂微粒子分散液の所定量を、経時的かつ間断なく、連続して添加することをいい、樹脂微粒子の添加量に応じた温度制御が可能な添加形態をいう。このような添加形態を有していればその具体的形式は問わない。
本発明における前記カプセル化工程は、１回の上記工程（２）からなる場合のみならず、複数の工程（２）を含む場合も包含する。複数の工程（２）を含む場合、各々の工程（２）の間には、樹脂微粒子を添加しない時間、及び／又は工程（２）以外の添加形態での添加時間を設けることができる。
In step (2), the dispersion of resin fine particles is continuously added to the aggregated particle dispersion. In the present invention, “continuously added” means that a predetermined amount of the resin fine particle dispersion is continuously added without interruption, and the temperature can be controlled according to the amount of resin fine particles added. This refers to the added form. If it has such an addition form, the specific form will not ask | require.
The encapsulation step in the present invention includes not only the case of comprising the above step (2) but also the case of including a plurality of steps (2). When a plurality of steps (2) are included, a time during which resin fine particles are not added and / or an addition time in an addition form other than step (2) can be provided between each step (2).
具体的には、工程（２）における樹脂微粒子の添加時間は、凝集粒子１００重量部に対して、工程（２）で添加する樹脂微粒子１重量部につき、通常１５秒〜１５分であり、カプセル化が効率良く行われ、また良好な生産効率を達成する観点から、好ましくは１.５〜９分、より好ましくは、１．７〜８分、さらに好ましくは２〜７分の時間で、樹脂微粒子を添加する。
また、工程（２）における樹脂微粒子の添加速度は、カプセル化が効率良く行われる観点から、凝集粒子１００重量部に対して０．１〜２．０重量部／分であることが好ましく、０．１５〜１．５重量部／分であることがより好ましい。
Specifically, the addition time of the resin fine particles in the step (2) is usually 15 seconds to 15 minutes per 1 part by weight of the resin fine particles added in the step (2) with respect to 100 parts by weight of the aggregated particles. From the viewpoint of achieving high production efficiency and achieving good production efficiency, the resin is preferably 1.5 to 9 minutes, more preferably 1.7 to 8 minutes, and even more preferably 2 to 7 minutes. Add fine particles.
In addition, the addition rate of the resin fine particles in the step (2) is preferably 0.1 to 2.0 parts by weight / min with respect to 100 parts by weight of the aggregated particles from the viewpoint of efficient encapsulation. More preferably, it is 15 to 1.5 parts by weight / minute.
工程（２）は、凝集粒子１００重量部に対して添加する樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で昇温させながら行う。上記範囲を越える割合で温度を上げると、カプセル化は一部進行するものの、同時に凝集粒子分散液中の凝集粒子同士の凝集や樹脂粒子付着凝集粒子同士の凝集が進行してしまい、所望の粒径の樹脂粒子付着凝集粒子分散液が得られず、また粗大粒子も発生してしまう。また、この範囲より低い割合で昇温すると、温度を上げることによる本発明の効果が得られないため、カプセル化が進行しない。すなわち、上述の樹脂微粒子の連続的添加の添加量に応じて、系内の温度を昇温させることにより、本発明の効果が得られる。上記観点から、昇温は、凝集粒子１００重量部に対して添加する樹脂微粒子１重量部につき、好ましくは０.０６〜０.２４℃であり、より好ましくは０.０７〜０.２３℃の割合で行う。 Step (2) is performed while raising the temperature at a rate of 0.05 to 0.25 ° C. per 1 part by weight of the resin fine particles added to 100 parts by weight of the aggregated particles. When the temperature is increased at a rate exceeding the above range, the encapsulation proceeds partially, but at the same time, aggregation of the aggregated particles in the aggregated particle dispersion and aggregation of the resin particle-adhered aggregated particles proceed, resulting in desired particles. A resin particle-attached aggregated particle dispersion having a diameter cannot be obtained, and coarse particles are also generated. Further, when the temperature is raised at a rate lower than this range, the effect of the present invention by raising the temperature cannot be obtained, so that encapsulation does not proceed. That is, the effect of the present invention can be obtained by raising the temperature in the system in accordance with the amount of continuous addition of the resin fine particles described above. From the above viewpoint, the temperature rise is preferably 0.06 to 0.24 ° C., more preferably 0.07 to 0.23 ° C. per 1 part by weight of the resin fine particles added to 100 parts by weight of the aggregated particles. Do it in proportion.
工程（２）における連続的添加に伴う昇温は、効率よくカプセル化を行う観点から、樹脂微粒子の添加前と添加終了後の間で０．４〜１２℃昇温して行うことが好ましく、１．０〜１０℃昇温して行うことがより好ましい。なお、カプセル化工程が複数の工程（２）を含む場合は、「樹脂微粒子の添加前」とは、複数の工程（２）のうち最初の工程（２）で添加する樹脂微粒子の添加前を意味し、「樹脂微粒子の添加後」とは、複数の工程（２）のうち最後の工程（２）で添加する樹脂微粒子の添加後を意味する。 From the viewpoint of efficiently encapsulating, the temperature increase accompanying the continuous addition in the step (2) is preferably performed at a temperature of 0.4 to 12 ° C. before and after the addition of the resin fine particles, More preferably, the temperature is raised by 1.0 to 10 ° C. In addition, when the encapsulation process includes a plurality of steps (2), “before the addition of resin fine particles” means that before the addition of the resin fine particles added in the first step (2) among the plurality of steps (2). The meaning “after the addition of the resin fine particles” means after the addition of the resin fine particles added in the last step (2) among the plurality of steps (2).
工程（２）は、前述のように「樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で昇温させながら行う」が、本発明において「昇温させながら行う」とは、樹脂微粒子を添加するのと並行して、その添加量に応じて上記決定される昇温速度で昇温することをいい、樹脂微粒子の添加終了後に昇温を行う態様、昇温した後に樹脂微粒子を添加する態様、あるいはこれらの繰り返しにより昇温する態様のみからなる場合はいずれも包含しない趣旨である。 As described above, the step (2) is “performed while raising the temperature at a rate of 0.05 to 0.25 ° C. per 1 part by weight of resin fine particles”. In parallel with the addition of the resin fine particles, the temperature is increased at the temperature increase rate determined as above according to the amount of the resin fine particles added. In the case where it consists only of the aspect which adds temperature, or the aspect which heats up by repeating these, it is the meaning which does not include any.
［カプセル化工程］
工程（２）を含むカプセル化工程においては、樹脂微粒子分散液を１回又は複数回に分割して凝集粒子に添加することができる。本発明においては、カプセル化工程は、少なくとも前述の工程（２）の方法による添加を少なくとも１回行うことが必要であるが、樹脂微粒子の添加を２回以上の複数回に分割して行う場合、各添加を、工程（２）の方法で行うことが好ましく、その全ての添加を工程（２）の方法で行うことがより好ましい。
樹脂微粒子分散液を複数回に分割して添加する場合、各々の分散液に含まれる樹脂微粒子の量は同量であることが好ましい。また、その回数については特に制限はないが、形成される樹脂微粒子付着凝集粒子の粒度分布及びトナーの生産性などの観点から、２〜１０回が好ましく、２〜８回がより好ましい。
[Encapsulation process]
In the encapsulation step including the step (2), the resin fine particle dispersion can be divided into one time or a plurality of times and added to the aggregated particles. In the present invention, the encapsulation step needs to be performed at least once by the method of the above-mentioned step (2), but the addition of resin fine particles is performed in two or more divided portions. Each addition is preferably performed by the method of step (2), and all of the additions are more preferably performed by the method of step (2).
When the resin fine particle dispersion is added in multiple portions, the amount of resin fine particles contained in each dispersion is preferably the same. Further, the number of times is not particularly limited, but is preferably 2 to 10 times, more preferably 2 to 8 times, from the viewpoint of the particle size distribution of the formed resin fine particle-attached aggregated particles and the productivity of the toner.
カプセル化工程は、工程（２）を含むことが必要であるが、本発明の要旨を損なわない範囲において、樹脂微粒子の添加を、工程（２）以外の方法で行う添加する工程を有することも可能である。このような工程（２）以外の方法としては、工程（２）以外の連続添加、一括添加、断続的添加等が挙げられ特に制限はない。 The encapsulation step needs to include the step (2), but may have a step of adding the resin fine particles by a method other than the step (2) within a range not impairing the gist of the present invention. Is possible. Examples of methods other than step (2) include continuous addition, batch addition, and intermittent addition other than step (2), and are not particularly limited.
本発明においては、カプセル化を効率よく行う観点から、前記凝集粒子に添加する全樹脂微粒子のうち、５０重量％以上の樹脂微粒子を工程（２）の方法で添加することが好ましく、６５重量％以上を工程（２）の方法で添加することがより好ましく、８０重量％以上を工程（２）の方法で添加することがさらに好ましく、９０重量％以上を工程（２）の方法で添加することがよりさらに好ましい。
また、凝集性及び形成される樹脂微粒子付着凝集粒子の粒度分布などの観点から、複数回の樹脂微粒子分散液の添加において、添加の後５〜１５分間、さらには５〜３０分間、さらに５分〜２時間熟成させることが好ましく、複数回添加の全ての添加について、上記熟成時間を設けることがより好ましい。なお、上記熟成時間は、添加終了後、次の添加における樹脂微粒子分散液の添加開始迄の時間とする。
In the present invention, from the viewpoint of efficient encapsulation, it is preferable to add 50% by weight or more of resin fine particles among the total resin fine particles added to the aggregated particles by the method of step (2), and 65% by weight. The above is more preferably added by the method of step (2), more preferably 80% by weight or more is added by the method of step (2), and 90% by weight or more is added by the method of step (2). Is even more preferable.
In addition, from the viewpoint of aggregation properties and particle size distribution of the formed resin fine particle-attached aggregate particles, in the addition of the resin fine particle dispersion multiple times, 5 to 15 minutes after addition, further 5 to 30 minutes, and further 5 minutes It is preferable to age for 2 hours, and it is more preferable to provide the above-mentioned aging time for all the additions of multiple times. The aging time is the time from the end of addition until the start of addition of the resin fine particle dispersion in the next addition.
高画質化の観点から、樹脂微粒子付着凝集粒子の体積中位粒径（Ｄ５０）は１〜１０μｍであることが好ましく、２〜１０μｍがより好ましく、３〜９μｍがさらに好ましい。
上記樹脂微粒子添加終了後、さらなる不必要な凝集を防止する観点から、本発明においては、合一前に、凝集停止剤を添加することが好ましい。凝集停止剤として界面活性剤を用いることが好ましいが、アニオン性界面活性剤を用いることがより好ましい。アニオン性界面活性剤のうち、アルキルエーテル硫酸塩、アルキル硫酸塩、及び直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種を添加することがさらに好ましい。
上記アルキルエーテル硫酸塩、アルキル硫酸塩、又は直鎖アルキルベンゼンスルホン酸塩は、１種で用いてもよいが、２種以上組み合わせて使用することもできる。
From the viewpoint of high image quality, the volume median particle size (D50) of the resin fine particle-adhered and agglomerated particles is preferably 1 to 10 μm, more preferably 2 to 10 μm, and even more preferably 3 to 9 μm.
From the viewpoint of preventing further unnecessary aggregation after the addition of the resin fine particles, in the present invention, it is preferable to add an aggregation terminator before coalescence. A surfactant is preferably used as the aggregation terminator, but an anionic surfactant is more preferably used. Of the anionic surfactants, it is more preferable to add at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates.
The alkyl ether sulfate, alkyl sulfate, or linear alkyl benzene sulfonate may be used singly or in combination of two or more.
上記アルキルエーテル硫酸塩、アルキル硫酸塩、及び直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種の添加量は、凝集停止性およびトナーへの残留性の観点から、樹脂粒子付着凝集粒子を構成する樹脂（すなわち、凝集粒子を構成する樹脂及び樹脂微粒子を構成する樹脂の総量）１００重量部に対して、好ましくは０．１〜１５重量部、より好ましくは０．１〜１０重量部、さらに好ましくは０．１〜８重量部である。これらは、上記添加量であれば、いかなる形態で添加してもよいが、生産性の観点から、水溶液で添加することが好ましい。上記各塩は、一時に添加しても良いし、断続的あるいは連続的に添加してもよい。 The addition amount of at least one selected from the group consisting of the above alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates is such that the resin particle adhering aggregated particles are selected from the viewpoint of aggregation stoppage and persistence to the toner. Preferably, 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin constituting the resin (that is, the total amount of the resin constituting the aggregated particles and the resin fine particles), More preferably, it is 0.1-8 weight part. These may be added in any form as long as they are added as described above, but are preferably added in an aqueous solution from the viewpoint of productivity. Each of the above salts may be added at once, or may be added intermittently or continuously.
［合一工程］
本発明では、工程（２）を含むカプセル化工程の後に、得られた樹脂微粒子付着凝集粒子を合一させる工程（以下、「合一工程」ということがある）を有することが好ましい。
上記合一工程は、工程（２）を含むカプセル化工程で得られた樹脂微粒子付着凝集粒子分散液中の凝集粒子と樹脂微粒子とを融着させ、合一粒子を得る工程である。この工程では、樹脂微粒子付着凝集粒子を加熱して、樹微粒子付着凝集粒子の、凝集粒子部分を合一させると共に、樹脂微粒子を凝集粒子と融着させて合一粒子を得ることが好ましい。
[Joint process]
In this invention, it is preferable to have the process (henceforth a "merging process") which unites the obtained resin fine particle adhesion aggregation particle | grains after the encapsulation process including a process (2).
The coalescing step is a step of obtaining coalesced particles by fusing the agglomerated particles and resin fine particles in the resin fine particle-attached agglomerated particle dispersion obtained in the encapsulation step including step (2). In this step, it is preferable to heat the resin fine particle-attached aggregated particles to coalesce the aggregated particle portions of the tree fine particle-attached aggregated particles, and to fuse the resin fine particles with the aggregated particles to obtain coalesced particles.
すなわち、樹脂微粒子付着凝集粒子は、上記合一工程においては、凝集粒子中の樹脂粒子同士、樹脂微粒子付着凝集粒子中の樹脂微粒子同士、及び、樹脂微粒子付着凝集粒子中の凝集粒子と樹脂微粒子とが主として物理的に付着している状態であったものが、凝集粒子が一体となり合一されると共に、樹脂微粒子同士が、及びコア粒子と樹脂微粒子が融着されて一体となり、合一粒子となっていると推定される。
合一工程における加熱温度は、目的とするトナーの粒径、粒度分布、形状制御、及び樹脂微粒子付着凝集粒子の融着性の観点から、樹脂微粒子を構成する樹脂、すなわち、樹脂微粒子を構成する樹脂のガラス転移点以上、（軟化点＋２０℃）以下が好ましく、より好ましくは（ガラス転移点＋５℃）以上、（軟化点＋１５℃）以下であり、さらに好ましくは（ガラス転移点＋１０℃）以上、（軟化点＋１０℃）以下である。
That is, in the coalescing step, the resin fine particle-attached aggregated particles are the resin particles in the aggregated particles, the resin fine particles in the resin fine particle-attached aggregated particles, and the aggregated particles and the resin fine particles in the resin fine particle-attached aggregated particles. Are mainly physically attached, the aggregated particles are united and united, and the resin fine particles are fused together, and the core particle and resin microparticles are united to form the united particles. It is estimated that
The heating temperature in the coalescing step constitutes the resin constituting the resin fine particle, that is, the resin fine particle, from the viewpoint of the target toner particle size, particle size distribution, shape control, and the fusion property of the resin fine particle adhered aggregated particle. The glass transition point of the resin is preferably (softening point + 20 ° C.) or less, more preferably (glass transition point + 5 ° C.) or more, (softening point + 15 ° C.) or less, and still more preferably (glass transition point + 10 ° C.) or more. , (Softening point + 10 ° C.) or less.
得られた合一粒子は、ろ過などの固液分離工程、洗浄工程、乾燥工程を経て、トナー粒子となる。ここで、トナーとして十分な帯電特性及び信頼性を確保する目的から、洗浄工程においてトナー表面の金属イオンを除去するため酸で洗浄を行うことが好ましい。
また、乾燥工程では、振動型流動乾燥法、スプレードライ法、冷凍乾燥法、フラッシュジェット法等、任意の方法を採用することができる。トナー粒子の乾燥後の水分含量は、トナーの帯電性の観点から、好ましくは１．５重量％以下、さらには１．０重量％以下に調整することが好ましい。
トナーの高画質化の観点から、合一粒子の体積中位粒径（Ｄ５０）は１〜１０μｍであることが好ましく、２〜８μｍがより好ましく、３〜８μｍがさらに好ましい。
The obtained coalesced particles become toner particles through a solid-liquid separation process such as filtration, a washing process, and a drying process. Here, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to perform cleaning with an acid in order to remove metal ions on the toner surface in the cleaning step.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner particles is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of chargeability of the toner.
From the viewpoint of improving the image quality of the toner, the volume median particle size (D50) of the coalesced particles is preferably 1 to 10 μm, more preferably 2 to 8 μm, and even more preferably 3 to 8 μm.
＜電子写真用トナー＞
本発明の電子写真用トナーは、工程（１）及び工程（２）を有する前記製造方法により得られるものであり、粗大粒子の発生、粒度分布のブロード化等の問題を有しないものである。すなわち、（１）ポリエステルを含む樹脂粒子分散液中の樹脂粒子を、凝集剤を添加して凝集させて、凝集粒子の分散液を得る工程、及び（２）工程（１）で得られた凝集粒子分散液に、樹脂微粒子の分散液を連続的に添加する工程を含む電子写真用トナー製造方法であって、前記工程（２）を、凝集粒子１００重量部に対して、工程（２）で添加する樹脂微粒子１重量部につき、０.０５〜０.２５℃の割合で凝集粒子分散液を含む系内を昇温させながら行う、電子写真用トナーの製造方法、により得られるものである。上記、工程（１）及び工程（２）については、前述の通りである。
<Toner for electrophotography>
The toner for electrophotography of the present invention is obtained by the production method having the steps (1) and (2), and does not have problems such as generation of coarse particles and broadening of the particle size distribution. That is, (1) a step of adding a flocculant to agglomerate resin particles in a resin particle dispersion containing polyester to obtain a dispersion of aggregated particles, and (2) agglomeration obtained in step (1) An electrophotographic toner manufacturing method comprising a step of continuously adding a dispersion of resin fine particles to a particle dispersion, wherein the step (2) is performed in step (2) with respect to 100 parts by weight of aggregated particles. This is obtained by a method for producing an electrophotographic toner, which is carried out while raising the temperature of the system containing the aggregated particle dispersion at a rate of 0.05 to 0.25 ° C. per 1 part by weight of the resin fine particles to be added. The step (1) and the step (2) are as described above.
トナーの軟化点は、低温定着性の観点から、６０〜１４０℃であることが好ましく、より好ましくは６０〜１３０℃、さらに好ましくは６０〜１２０℃である。また、ガラス転移点は、トナーの耐久性の観点から、３０〜８０℃が好ましく、４０〜７０℃がより好ましい。なお、軟化点及びガラス転移点の測定方法は、樹脂におけるこれらの測定方法に準ずる。
離型剤、着色剤、及び荷電制御剤を含有する場合は、その含有量は、トナー中の結着樹脂１００重量部に対し、離型剤については、トナーの定着性の観点から好ましくは０．５〜２０重量部、より好ましくは１〜１８重量部、さらに好ましくは１．５〜１５重量部であるり、着色剤については、好ましくは２０重量部以下が、より好ましくは０．０１〜１０重量部であり、荷電制御剤については、好ましく好ましくは１０重量部以下が、より好ましくは０．０１〜５重量部である。
The softening point of the toner is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and still more preferably 60 to 120 ° C. from the viewpoint of low-temperature fixability. The glass transition point is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., from the viewpoint of toner durability. In addition, the measuring method of a softening point and a glass transition point is based on these measuring methods in resin.
When a release agent, a colorant, and a charge control agent are contained, the content thereof is preferably 0 with respect to 100 parts by weight of the binder resin in the toner, and the release agent is preferably 0 from the viewpoint of toner fixing properties. 0.5 to 20 parts by weight, more preferably 1 to 18 parts by weight, still more preferably 1.5 to 15 parts by weight, and the colorant is preferably 20 parts by weight or less, more preferably 0.01 to 10 parts by weight, and the charge control agent is preferably 10 parts by weight or less, more preferably 0.01 to 5 parts by weight.
本発明のトナーは、前記製造方法で得られたトナー粒子をそのままトナーとして使用してもよいし、外添剤として流動化剤等の助剤をトナー粒子表面に添加処理したものをトナーとして使用することができる。外添剤としては、表面を疎水化処理したシリカ微粒子、酸化チタン微粒子、アルミナ微粒子等の無機微粒子やポリメチルメタクリレート、シリコーン樹脂等のポリマー微粒子等、公知の微粒子が使用できる。
外添剤の配合量は、外添剤による処理前のトナー１００重量部に対して、１〜５重量部が好ましく、１．５〜３．５重量部がより好ましい。
In the toner of the present invention, the toner particles obtained by the above production method may be used as a toner as they are, or a toner obtained by adding an additive such as a fluidizing agent to the toner particle surface as an external additive is used as the toner. can do. As the external additive, known fine particles such as inorganic fine particles such as silica fine particles, titanium oxide fine particles, and alumina fine particles whose surface is hydrophobized, and polymer fine particles such as polymethyl methacrylate and silicone resin can be used.
The amount of the external additive is preferably 1 to 5 parts by weight and more preferably 1.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner before processing with the external additive.
高画質化の観点から、トナー粒子の体積中位粒径（Ｄ５０）は１〜１０μｍであることが好ましく、２〜８μｍがより好ましく、３〜８μｍがさらに好ましい。また、前述の合一粒子及びトナー粒子のＣＶ値は、いずれも３０％以下が好ましく、より好ましくは２５％以下である。トナー粒子の粒径及び粒度分布は、後述の方法で測定することができる。本発明により得られる電子写真用トナーは、一成分系現像剤として、又はキャリアと混合して二成分系現像剤として使用することができる。 From the viewpoint of high image quality, the volume median particle size (D50) of the toner particles is preferably 1 to 10 μm, more preferably 2 to 8 μm, and even more preferably 3 to 8 μm. Further, the CV value of the coalesced particles and toner particles described above is preferably 30% or less, and more preferably 25% or less. The particle size and particle size distribution of the toner particles can be measured by the method described later. The toner for electrophotography obtained by the present invention can be used as a one-component developer or as a two-component developer by mixing with a carrier.
以下の実施例等においては、各性状値は次の方法により測定、評価した。
［樹脂の酸価］
ＪＩＳ Ｋ００７０に従って測定する。但し、測定溶媒をアセトンとトルエンの混合溶媒(アセトン：トルエン＝１:１(容量比))とした。
In the following examples and the like, each property value was measured and evaluated by the following method.
[Acid value of resin]
Measured according to JIS K0070. However, the measurement solvent was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
［樹脂の軟化点及びガラス転移点］
（１）軟化点
フローテスター（島津製作所社製、「ＣＦＴ−５００Ｄ」）を用い、１ｇの試料を昇温速度６℃／分で加熱しながら、プランジャーにより１．９６ＭＰａの荷重を与え、直径１ｍｍ、長さ１ｍｍのノズルから押し出す。温度に対し、フローテスターのブランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とする。
[Softening point and glass transition point of resin]
(1) Softening point Using a flow tester (manufactured by Shimadzu Corporation, “CFT-500D”), a 1 g sample was heated at a heating rate of 6 ° C./min. Extrude from a nozzle with a length of 1 mm and a length of 1 mm. Plot the flow tester drop by the flow tester against the temperature, and let the softening point be the temperature at which half the sample flowed out.
（２）ガラス転移点
示差走査熱量計（Parkin Elmer社製、Pyris6 DSC）を用いて２００℃まで昇温し、その温度から降温速度１０℃／分で−１０℃まで冷却した試料を昇温速度１０℃／分で測定する。軟化点より２０℃以上低い温度でピークが観測される場合にはそのピークの温度を、また軟化点より２０℃以上低い温度でピークが観測されずに段差が観測されるときは該段差部分の曲線の最大傾斜を示す接線と該段差の高温側のベースラインの延長線との交点の温度を、ガラス転移点として読み取る。なお、ガラス転移点は、樹脂の非晶質部分に特有の物性であり、一般には非晶質ポリエステルで観測されるが、結晶性ポリエステルでも非晶質部分が存在する場合には観測されることがある。
(2) Glass transition point The temperature was raised to 200 ° C using a differential scanning calorimeter (manufactured by Parkin Elmer, Pyris6 DSC), and the sample cooled from that temperature to -10 ° C at a rate of temperature drop of 10 ° C / min was heated up. Measure at 10 ° C / min. When a peak is observed at a temperature 20 ° C. or more lower than the softening point, the peak temperature is measured. When a peak is not observed at a temperature 20 ° C. or higher lower than the softening point, a step is observed. The temperature at the intersection of the tangent line indicating the maximum slope of the curve and the extension line of the base line on the high temperature side of the step is read as the glass transition point. The glass transition point is a physical property peculiar to the amorphous part of the resin, and is generally observed in amorphous polyester, but is observed when amorphous part exists even in crystalline polyester. There is.
［樹脂粒子、樹脂微粒子及び離型剤粒子の粒径］
（１）測定装置：レーザー散乱型粒径測定機（堀場製作所製、ＬＡ−９２０）
（２）測定条件：測定用セルに蒸留水を加え、吸光度を適正範囲になる温度で体積中位粒径（Ｄ５０）を測定する。粒度分布は、ＣＶ値（粒度分布の標準偏差／体積中位粒径（Ｄ５０）×１００）で示す。
[Particle size of resin particles, resin particles and release agent particles]
(1) Measuring apparatus: Laser scattering type particle size measuring machine (LA-920, manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water is added to the measurement cell, and the volume-median particle size (D50) is measured at a temperature where the absorbance falls within an appropriate range. The particle size distribution is represented by a CV value (standard deviation of particle size distribution / volume median particle size (D50) × 100).
［分散液の固形分濃度］
赤外線水分計（ケット科学研究所社製：ＦＤ−２３０）を用いて、乳化液５ｇを乾燥温度１５０℃，測定モード９６（監視時間２．５分／変動幅０．０５％）にて、ウェットベースの水分％を測定する。固形分は下記の式に従って算出した。
固形分（％）＝１００−Ｍ
Ｍ：ウェットベース水分（％）＝［（Ｗ−Ｗ０）／Ｗ］×１００
Ｗ：測定前の試料重量（初期試料重量）
Ｗ０：測定後の試料重量（絶対乾燥重量）
[Solid concentration of dispersion]
Using an infrared moisture meter (Kett Science Laboratory Co., Ltd .: FD-230), 5 g of the emulsion was wet at a drying temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). Measure the moisture content of the base. The solid content was calculated according to the following formula.
Solid content (%) = 100-M
M: wet base moisture (%) = [(W−W0) / W] × 100
W: Sample weight before measurement (initial sample weight)
W0: Sample weight after measurement (absolute dry weight)
〔凝集粒子、樹脂微粒子付着凝集粒子の粒径〕
・測定機：コールターマルチサイザー III（ベックマンコールター社製）
・アパチャー径：５０μｍ
・解析ソフト： マルチサイザーIIIバージョン３．５１(ベックマンコールター社製)
・電解液：アイソトンII（ベックマンコールター社製）
測定条件：凝集粒子分散液、樹脂微粒子付着凝集粒子分散液および合一粒子分散液を前記電解液１００ｍＬに加えることにより、３万個の粒子の粒径を２０秒で測定できる濃度に調整した後、３万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ５０）を求める。
・粒度分布は、ＣＶ値（粒度分布の標準偏差／体積中位粒径（Ｄ５０）×１００）で示す。
[Agglomerated particles, particle diameter of resin fine particles adhered aggregated particles]
・ Measuring machine: Coulter Multisizer III (Beckman Coulter)
・ Aperture diameter: 50μm
-Analysis software: Multisizer III version 3.51 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the agglomerated particle dispersion, the resin particle adhering agglomerated particle dispersion, and the coalesced particle dispersion to 100 mL of the electrolytic solution. 30,000 particles are measured, and the volume median particle size (D50) is determined from the particle size distribution.
The particle size distribution is indicated by a CV value (standard deviation of particle size distribution / volume median particle size (D50) × 100).
［トナーの粒径］
・測定機：コールターマルチサイザーIII（ベックマンコールター社製）
・アパチャー径：５０μｍ
・解析ソフト：マルチサイザーIIIバージョン３．５１（ベックマンコールター社製）
・電解液：アイソトンII（ベックマンコールター社製）
・分散液：エマルゲン１０９Ｐ（花王社製、ポリオキシエチレンラウリルエーテル、ＨＬＢ：１３．６）を５重量％濃度となるように前記電解液に溶解させて分散液を得る。
・分散条件：前記分散液５ｍＬに測定試料１０ｍｇを添加し、超音波分散機にて１分間分散させ、その後、電解液２５ｍＬを添加し、さらに、超音波分散機にて１分間分散させて、試料分散液を作製する。
・測定条件：前記試料分散液を前記電解液１００ｍＬに加えることにより、３万個の粒子の粒径を２０秒で測定できる濃度に調整した後、３万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ５０）を求める。
・粒度分布は、ＣＶ値（粒度分布の標準偏差／体積中位粒径（Ｄ５０）×１００）（％）で示す。
[Toner particle size]
-Measuring machine: Coulter Multisizer III (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: Multisizer III version 3.51 (Beckman Coulter, Inc.)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by weight to obtain a dispersion.
-Dispersion condition: 10 mg of a measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of an electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion is prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. To determine the volume-median particle size (D50).
The particle size distribution is indicated by a CV value (standard deviation of particle size distribution / volume median particle size (D50) × 100) (%).
［カプセル化の評価］
（１）上澄みの評価：樹脂微粒子付着凝集剤分散液を２５℃で２４０分間静置し、その上澄み液の透明度を評価した。上澄み液が透明であればカプセルが進行したと認められる
（２）粗大粒子の有無 ：樹脂微粒子付着凝集粒子の体積基準で１０μｍ以上の粒子の存在量で評価した。
[Evaluation of encapsulation]
(1) Evaluation of the supernatant: The resin fine particle adhesion flocculant dispersion was allowed to stand at 25 ° C. for 240 minutes, and the transparency of the supernatant was evaluated. If the supernatant is transparent, it is recognized that the capsule has progressed. (2) Presence / absence of coarse particles: Evaluation was made based on the abundance of particles of 10 μm or more based on the volume of the resin fine particle-attached aggregated particles.
製造例１（ポリエステルＡの製造）
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン８，３２０ｇ、ポリオキシエチレン（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン８０ｇ、テレフタル酸１，５９２ｇ及び酸化ジブチル錫（エステル化触媒）３２ｇを窒素雰囲気下、常圧（１０１．３ｋＰａ）下２３０℃で５時間反応させ、さらに減圧（８．３ｋＰａ）下で反応させた。２１０℃に冷却し、フマル酸１，６７２ｇ、ハイドロキノン８ｇを加え、５時間反応させた後に、さらに減圧下で反応させて、ポリエステルＡを得た。ポリエステルＡの軟化点は１１０℃、ガラス転移点は６６℃、酸価は２４．４ｍｇＫＯＨ／ｇであった。
Production Example 1 (Production of polyester A)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 8,320 g, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane 80 g, terephthalic acid 1,592 g and 32 g of dibutyltin oxide (esterification catalyst) were reacted at 230 ° C. under normal pressure (101.3 kPa) for 5 hours under a nitrogen atmosphere, and further reacted under reduced pressure (8.3 kPa). After cooling to 210 ° C., 1,672 g of fumaric acid and 8 g of hydroquinone were added and reacted for 5 hours, and further reacted under reduced pressure to obtain polyester A. Polyester A had a softening point of 110 ° C., a glass transition point of 66 ° C., and an acid value of 24.4 mgKOH / g.
製造例２（ポリエステルＢの製造）
ポリオキシプロピレン（２．２）−２、２−ビス(４−ヒドロキシフェニル)プロパン４，１７６ｇ、ポリオキシエチレン（２．０）−２、２−ビス(４−ヒドロキシフェニル)プロパン３，８８１ｇ、テレフタル酸２，２５３ｇ、ドデセニルコハク酸無水物３２２ｇ、トリメリット酸無水物９４５ｇ及び酸化ジブチル錫１５ｇを窒素導入管、脱水管、攪拌器及び熱電対を装備した四つ口フラスコに入れ、窒素雰囲気下、２２０℃で攪拌し、ＡＳＴＭ Ｄ３６−８６に従って測定した軟化点が１２０℃に達するまで反応させて、ポリエステルＢを得た。ポリエステルＢの軟化点は１２１℃、ガラス転移点は６５℃、酸価は２１．０ｍｇＫＯＨ／ｇであった。
Production Example 2 (Production of polyester B)
Polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane 4,176 g, polyoxyethylene (2.0) -2, 2-bis (4-hydroxyphenyl) propane 3,881 g, 2,253 g of terephthalic acid, 322 g of dodecenyl succinic anhydride, 945 g of trimellitic anhydride and 15 g of dibutyltin oxide were placed in a four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple. The mixture was stirred at 220 ° C. and reacted until the softening point measured according to ASTM D36-86 reached 120 ° C. to obtain polyester B. Polyester B had a softening point of 121 ° C, a glass transition point of 65 ° C, and an acid value of 21.0 mgKOH / g.
製造例３（ポリエステルＣの製造）
ポリオキシプロピレン（２．２）−２，２−ビス(４−ヒドロキシフェニル)プロパン６，１６０ｇ、フマル酸２，１２５ｇ及び酸化ジブチル錫５ｇを窒素導入管、脱水管、攪拌器及び熱電対を装備した四つ口フラスコに入れ、窒素雰囲気下、２３０℃で攪拌し、ＡＳＴＭ Ｄ３６−８６に準拠して測定した軟化点が１００℃に達するまで反応させて、ポリエステルＣを得た。ポリエステルＣの軟化点は１０１℃、ガラス転移点は５７℃、酸価は２２.４ｍｇＫＯＨ／ｇであった。
Production Example 3 (Production of polyester C)
Equipped with 6,160 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 2,125 g of fumaric acid and 5 g of dibutyltin oxide, equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The resulting mixture was stirred at 230 ° C. in a nitrogen atmosphere and reacted until the softening point measured in accordance with ASTM D36-86 reached 100 ° C. to obtain polyester C. Polyester C had a softening point of 101 ° C, a glass transition point of 57 ° C, and an acid value of 22.4 mgKOH / g.
製造例４（樹脂粒子分散液Ａの製造）
２リットル容のステンレス釜で、ポリエステルＡ ３９０．０ｇ、ポリエステルＢ ２１０．０ｇ、銅フタロシアニン顔料（ＥＣＢ−３０１：大日精化工業社製）３０ｇ、及び、アニオン性界面活性剤（花王社製「ネオペレックスＧ−１５」ドデシルベンゼンスルホン酸ナトリウム１５重量％水溶液）２０．０ｇ、非イオン性界面活性剤「エマルゲン ４３０（花王社製）」ポリオキシエチレン（２６ｍｏｌ）オレイルエーテル（ＨＬＢ：１６．２）６．０ｇ、及び５重量％水酸化カリウム水溶液２９２.８ｇをカイ型の攪拌機で２００ｒ／ｍｉｎの攪拌下、９５℃で分散させた。カイ型の攪拌機で２００ｒ／ｍｉｎの攪拌下で２時間保持した。続いて、カイ型の攪拌機で２００ｒ／ｍｉｎの攪拌下、脱イオン水を６ｇ／分で滴下した。また、系の温度は９５℃に保持した。冷却後、２００メッシュ（目開き：１０５μｍ）の金網を通して、微粒化した樹脂粒子分散液Ａを得た。得られた樹脂粒子分散液Ａ中の樹脂粒子の体積中位粒径（Ｄ５０）は２３７ｎｍ、ＣＶ値は２４％、固形分濃度は３１重量％であり、金網上には樹脂成分は何も残らなかった。
Production Example 4 (Production of resin particle dispersion A)
In a 2-liter stainless steel kettle, 390.0 g of polyester A, 210.0 g of polyester B, 30 g of copper phthalocyanine pigment (ECB-301: manufactured by Dainichi Seika Kogyo Co., Ltd.), and an anionic surfactant (“Neo” manufactured by Kao Corporation) Perex G-15 “Sodium dodecylbenzenesulfonate 15 wt% aqueous solution) 20.0 g, nonionic surfactant“ Emulgen 430 (manufactured by Kao) ”polyoxyethylene (26 mol) oleyl ether (HLB: 16.2) 6 0.028 g and 52.8% by weight potassium hydroxide aqueous solution 292.8 g were dispersed at 95 ° C. with stirring at 200 r / min with a chi-type stirrer. The mixture was held for 2 hours under stirring at 200 r / min with a Kai-type stirrer. Subsequently, deionized water was added dropwise at a rate of 6 g / min while stirring at 200 r / min with a Kai-type stirrer. The system temperature was maintained at 95 ° C. After cooling, the resin particle dispersion A was atomized through a 200 mesh (mesh: 105 μm) wire mesh. The resin particles in the obtained resin particle dispersion A have a volume median particle size (D50) of 237 nm, a CV value of 24%, a solid content concentration of 31% by weight, and no resin component remains on the wire mesh. There wasn't.
製造例５（樹脂粒子分散液Ｂの製造）
製造例４においてポリエステルＡをポリエステルＣに変えた以外は同様にして、樹脂粒子分散液Ｂを得た。得られた樹脂粒子分散液Ｂ中の樹脂粒子の体積中位粒径（Ｄ５０）は１５４ｎｍ、ＣＶ値は２６％、固形分濃度は３０重量％であり、金網上には樹脂成分は何も残らなかった。
Production Example 5 (Production of resin particle dispersion B)
Resin particle dispersion B was obtained in the same manner except that Polyester A was changed to Polyester C in Production Example 4. The volume median particle size (D50) of the resin particles in the obtained resin particle dispersion B is 154 nm, the CV value is 26%, the solid content concentration is 30% by weight, and no resin component remains on the wire mesh. There wasn't.
製造例６（離型剤分散液Ａの製造）
１リットル容のビーカーで、脱イオン水４８０ｇにアルケニル（ヘキサデセニル基、オクタデセニル基の混合物）コハク酸ジカリウム水溶液「ラテムルＡＳＫ（花王社製）、有効濃度２８重量％」４．２９ｇを溶解させた後、カルナウバロウワックス（加藤洋行社製、融点８５℃、酸価５ｍｇＫＯＨ／ｇ）１２０ｇを分散させた。この分散液を９０〜９５℃に温度を保持しながら、「Ｕｌｔｒａｓｏｎｉｃ Ｈｏｍｏｇｅｎｉｚｅｒ ６００Ｗ」（日本精機社製）で３０分間分散処理を行った後に室温まで冷却した。離型剤分散液中の離型剤粒子の体積中位粒径（Ｄ５０）は０.４１９ｎｍ、粒度分布の変動係数（ＣＶ値）は３１％であった。ここにイオン交換水を加え、離型剤固形分２０重量％に調整し、離型剤分散液Ａを得た。
Production Example 6 (Production of release agent dispersion A)
In a 1 liter beaker, after dissolving 4.29 g of alkenyl (mixture of hexadecenyl group and octadecenyl group) dipotassium succinate aqueous solution “Latemul ASK (manufactured by Kao Corporation), effective concentration 28 wt%” in 480 g of deionized water, 120 g of carnauba wax (manufactured by Kato Yoko Co., Ltd., melting point 85 ° C., acid value 5 mg KOH / g) was dispersed. The dispersion was subjected to a dispersion treatment for 30 minutes with “Ultrasonic Homogenizer 600W” (manufactured by Nippon Seiki Co., Ltd.) while maintaining the temperature at 90 to 95 ° C., and then cooled to room temperature. The volume median particle size (D50) of the release agent particles in the release agent dispersion was 0.419 nm, and the variation coefficient (CV value) of the particle size distribution was 31%. Ion exchange water was added thereto to adjust the release agent solid content to 20% by weight to obtain a release agent dispersion A.
実施例1
〔工程１〕
樹脂粒子分散液Ａ ３００ｇと脱イオン水７４ｇと離型剤分散液Ａ ２４ｇを脱水管、攪拌機及び熱電対を装備した２リットル容４つ口フラスコに入れ、室温下（２５℃）で混合した。次に、カイ型の攪拌機で攪拌下、この混合物に硫酸アンモニウム１９.８ｇを２４３ｇの脱イオン水に溶解させた水溶液を室温下で１０分かけて滴下した。このとき系内のアンモニウムイオン濃度は０．５５ｍｏｌ／Ｌであった。
その後、混合溶液を４５℃まで昇温し、４５℃の温度を保持することで体積中位粒径（Ｄ５０）が４．１μｍの凝集粒子を含む固形分濃度１４重量％の凝集粒子分散液を得た。
Example 1
[Step 1]
300 g of resin particle dispersion A, 74 g of deionized water, and 24 g of release agent dispersion A were placed in a 2-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple, and mixed at room temperature (25 ° C.). Next, an aqueous solution in which 19.8 g of ammonium sulfate was dissolved in 243 g of deionized water was dropped into the mixture over 10 minutes while stirring with a Kai-type stirrer. At this time, the ammonium ion concentration in the system was 0.55 mol / L.
Thereafter, the mixed solution is heated to 45 ° C., and a temperature of 45 ° C. is maintained to obtain an agglomerated particle dispersion having a solid content concentration of 14% by weight and containing agglomerated particles having a volume median particle size (D50) of 4.1 μm. Obtained.
〔工程２〕
工程２-(1)
工程１で得られた、４５℃に維持された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で４６℃へと昇温し、５分間４６℃で保持した。
工程２-(2)
４６℃に保持された樹脂粒子が添加された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で４７℃へと昇温し、５分間４７℃で保持した。
工程２-(3)
４７℃に保持された樹脂粒子が添加された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で４９℃へと昇温し、５分間４９℃で保持した。
工程２-(4)
４９℃に保持された樹脂粒子が添加された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で５０℃へと昇温し、５分間５０℃で保持した。
工程２-(5)
５０℃に保持された樹脂粒子が添加された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で５２℃へと昇温した。このときの系内温度は５２℃、系内のイオン濃度は０．４４ｍｏｌ／Ｌであった。また得られた樹脂粒子付着凝集粒子の体積中位粒径（Ｄ５０）は５．２μｍであり、分散液中には１０μｍ以上の粗大粒子は０．４％であり、静置後の上澄み液は透明であったことから、カプセル化が進行したことを確認した（この際の樹脂微粒子分散液の添加、温度等の詳細を表１に示す）。
[Step 2]
Process 2- (1)
A mixed liquid obtained by mixing Step 30 obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water was continuously added at a constant addition rate to the aggregated particle dispersion maintained at 45 ° C. While dropping over 60 minutes, the temperature in the system was increased to 46 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion A added, and maintained at 46 ° C. for 5 minutes.
Process 2- (2)
A mixture obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion to which resin particles maintained at 46 ° C. were added. While dropping over a period of time, the temperature in the system was raised to 47 ° C. at a constant rate of temperature rise according to the amount of the resin particle dispersion A added, and maintained at 47 ° C. for 5 minutes.
Process 2- (3)
A mixture obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion to which resin particles maintained at 47 ° C. were added. While dropping dropwise over a period of time, the temperature in the system was raised to 49 ° C. at a constant rate of temperature rise according to the amount of the resin particle dispersion A added, and held at 49 ° C. for 5 minutes.
Process 2- (4)
A mixture obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion to which resin particles maintained at 49 ° C. were added. While dropping dropwise over a period of time, the temperature in the system was increased to 50 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion A added, and maintained at 50 ° C. for 5 minutes.
Process 2- (5)
A mixture obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion to which resin particles maintained at 50 ° C. were added. While dropping dropwise over a period of time, the temperature in the system was raised to 52 ° C. at a constant rate of temperature increase according to the amount of resin particle dispersion A added. The system temperature at this time was 52 ° C., and the ion concentration in the system was 0.44 mol / L. Moreover, the volume median particle size (D50) of the obtained resin particle-attached aggregated particles is 5.2 μm, the coarse particles of 10 μm or more are 0.4% in the dispersion, and the supernatant after standing is Since it was transparent, it was confirmed that the encapsulation proceeded (details such as addition of resin fine particle dispersion, temperature, etc. are shown in Table 1).
〔合一工程〕
工程２で得られた樹脂微粒子付着凝集粒子にドデシルエーテル硫酸ナトリウム(エマールＥ２７Ｃ、固形分：２８重量％)１９ｇを脱イオン水３６８ｇで希釈した水溶液を添加した後、８０℃まで３時間かけて昇温した。その後、１時間保持した後、室温（２５℃）まで冷却した。この間で、トナー形状が樹脂微粒子付着凝集粒子から合一粒子へ変化した。得られた合一粒子を、固液分離のためのろ過工程、乾燥工程、洗浄工程を経て、トナーとした。得られたトナーの体積中位粒径（Ｄ５０）及びＣＶ値を表１に示す。
[Joint process]
An aqueous solution obtained by diluting 19 g of sodium dodecyl ether sulfate (Emar E27C, solid content: 28% by weight) with 368 g of deionized water was added to the resin fine particle-attached aggregated particles obtained in step 2, and the temperature was increased to 80 ° C. over 3 hours. Warm up. Then, after hold | maintaining for 1 hour, it cooled to room temperature (25 degreeC). During this time, the toner shape changed from the resin fine particle adhered aggregated particles to the coalesced particles. The obtained coalesced particles were used as a toner through a filtration step, a drying step, and a washing step for solid-liquid separation. Table 1 shows the volume-median particle size (D50) and CV value of the obtained toner.
実施例２
〔工程１〕
樹脂粒子分散液Ａ ３００ｇと脱イオン水７４ｇと離型剤分散液Ａ ２４ｇを脱水管、攪拌機及び熱電対を装備した２リットル容４つ口フラスコに入れ、室温下（２５℃）で混合した。次に、カイ型の攪拌機で攪拌下、この混合物に硫酸アンモニウム１９.８ｇを２９８ｇの脱イオン水に溶解させた水溶液を室温下で１０分かけて滴下した。このとき系内のアンモニウムイオン濃度は０．５０ｍｏｌ／Ｌであった。その後、混合溶液を４８℃まで昇温し、温度保持することで体積中位粒径（Ｄ５０）が４．０μｍの凝集粒子を含む固形分濃度１３重量％の凝集粒子分散液を得た。
Example 2
[Step 1]
300 g of resin particle dispersion A, 74 g of deionized water, and 24 g of release agent dispersion A were placed in a 2-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple, and mixed at room temperature (25 ° C.). Next, an aqueous solution in which 19.8 g of ammonium sulfate was dissolved in 298 g of deionized water was dropped into the mixture over 10 minutes while stirring with a Kai-type stirrer. At this time, the ammonium ion concentration in the system was 0.50 mol / L. Thereafter, the mixed solution was heated to 48 ° C. and kept at a temperature to obtain an aggregated particle dispersion having a solid content concentration of 13% by weight containing aggregated particles having a volume median particle size (D50) of 4.0 μm.
〔工程２〕
工程１で得られた、４８℃に維持された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温速度で５０℃へと昇温し、５分間５０℃で保持した。この時系内のイオン濃度は０．４８ｍｏｌ／Ｌであった。次に、樹脂粒子分散液Ａ １２０ｇと脱イオン水２９．８ｇを混合した混合液を一定速度で連続的に２４０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温速度(０.１５℃／部)で５６℃へと昇温した。この際の樹脂微粒子分散液の添加、温度等の詳細を表１に示す。この後の系内温度は５６℃、系内のイオン濃度は０．４１ｍｏｌ／Ｌであった。また得られた樹脂微粒子付着凝集粒子の体積中位粒径（Ｄ５０）は５．２μｍであり、分散液中には１０μｍ以上の粗大粒子は０．５％であり、静置後の上澄み液は透明であったことから、カプセル化が進行したことを確認した。以降は、実施例１と同様に合一を行いトナーを得た。得られたトナーの体積中位粒径（Ｄ５０）及びＣＶ値を表１に示す。
[Step 2]
A liquid mixture obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion maintained at 48 ° C. obtained in step 1. While dropping over 60 minutes, the temperature in the system was increased to 50 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion A added, and maintained at 50 ° C. for 5 minutes. At this time, the ion concentration in the system was 0.48 mol / L. Next, the temperature inside the system is adjusted to the addition amount of the resin particle dispersion A while dropping a mixture of 120 g of the resin particle dispersion A and 29.8 g of deionized water continuously at a constant rate over 240 minutes. Accordingly, the temperature was raised to 56 ° C. at a constant rate of temperature rise (0.15 ° C./part). Details of the addition of the resin fine particle dispersion, the temperature, etc. are shown in Table 1. Thereafter, the system temperature was 56 ° C., and the ion concentration in the system was 0.41 mol / L. Moreover, the volume median particle size (D50) of the obtained resin fine particle-attached aggregated particles is 5.2 μm, the coarse particles of 10 μm or more are 0.5% in the dispersion, and the supernatant after standing is Since it was transparent, it was confirmed that the encapsulation proceeded. Thereafter, coalescence was performed in the same manner as in Example 1 to obtain a toner. Table 1 shows the volume-median particle size (D50) and CV value of the obtained toner.
実施例３
〔工程１〕
樹脂粒子分散液Ａ ３００ｇと脱イオン水７４ｇと離型剤分散液Ａ ２４ｇを脱水管、攪拌機及び熱電対を装備した２リットル容４つ口フラスコに入れ、室温下（２５℃）で混合した。次に、カイ型の攪拌機で攪拌下、この混合物に硫酸アンモニウム１９.８ｇを２９８ｇの脱イオン水に溶解させた水溶液を室温下で１０分かけて滴下した。このとき系内のアンモニウムイオン濃度は０．５０ｍｏｌ／Ｌであった。その後、混合溶液を４９℃まで昇温し、温度保持することで体積中位粒径（Ｄ５０）が４．１μｍの凝集粒子を含む固形分濃度１３重量％の凝集粒子分散液を得た。
Example 3
[Step 1]
300 g of resin particle dispersion A, 74 g of deionized water, and 24 g of release agent dispersion A were placed in a 2-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple, and mixed at room temperature (25 ° C.). Next, an aqueous solution in which 19.8 g of ammonium sulfate was dissolved in 298 g of deionized water was dropped into the mixture over 10 minutes while stirring with a Kai-type stirrer. At this time, the ammonium ion concentration in the system was 0.50 mol / L. Thereafter, the mixed solution was heated to 49 ° C. and maintained at a temperature to obtain an aggregated particle dispersion having a solid content concentration of 13% by weight containing aggregated particles having a volume median particle size (D50) of 4.1 μm.
〔工程２〕
工程１で得られた、４９℃に維持された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ｂ ３１ｇと脱イオン水６．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ｂの添加量に応じて一定昇温度速度で５０℃へと昇温し、５分間５０℃で保持した。た。この時系内のイオン濃度は０．４８ｍｏｌ／Ｌであった。次に、樹脂粒子分散液Ｂ １２４ｇと脱イオン水２５．８ｇを混合した混合液を一定添加速度で連続的に２４０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ｂの添加量に応じて一定昇温度速度で５５℃へと昇温した。この際の樹脂微粒子分散液の添加、温度等の詳細を表２に示す。この後の系内温度は５５℃、系内のイオン濃度は０．４１ｍｏｌ／Ｌであった。また得られた樹脂微粒子付着凝集粒子の体積中位粒径（Ｄ５０）は５．１μｍであり、分散液中には１０μｍ以上の粗大粒子は０．６％であり、静置後の上澄み液は透明であったことから、カプセル化が進行したことを確認した。以降は、実施例１と同様に合一を行いトナーを得た。得られたトナーの体積中位粒径（Ｄ５０）及びＣＶ値を表１に示す。
[Step 2]
A liquid mixture obtained by mixing 31 g of resin particle dispersion B and 6.4 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion maintained at 49 ° C. obtained in step 1. While dropping over 60 minutes, the temperature in the system was raised to 50 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion B added, and maintained at 50 ° C. for 5 minutes. It was. At this time, the ion concentration in the system was 0.48 mol / L. Next, the temperature in the system was added to the amount of the resin particle dispersion B added while continuously adding a mixture of 124 g of the resin particle dispersion B and 25.8 g of deionized water at a constant addition rate over 240 minutes. Accordingly, the temperature was raised to 55 ° C. at a constant temperature increase rate. Details of addition of resin fine particle dispersion, temperature, etc. at this time are shown in Table 2. Thereafter, the system temperature was 55 ° C., and the ion concentration in the system was 0.41 mol / L. Moreover, the volume median particle size (D50) of the obtained resin fine particle-attached aggregated particles is 5.1 μm, the coarse particles of 10 μm or more are 0.6% in the dispersion, and the supernatant after standing is Since it was transparent, it was confirmed that the encapsulation proceeded. Thereafter, coalescence was performed in the same manner as in Example 1 to obtain a toner. Table 1 shows the volume-median particle size (D50) and CV value of the obtained toner.
実施例４
〔工程１〕
樹脂粒子分散液Ｂ ３００ｇと脱イオン水６２ｇと離型剤分散液Ａ ２４ｇを脱水管、攪拌機及び熱電対を装備した２リットル容４つ口フラスコに入れ、室温下（２５℃）で混合した。次に、カイ型の攪拌機で攪拌下、この混合物に硫酸アンモニウム１９.２ｇを２８９ｇの脱イオン水に溶解させた水溶液を室温下で１０分かけて滴下した。このとき系内のアンモニウムイオン濃度は０．５０ｍｏｌ／Ｌであった。
その後、混合溶液を５０℃まで昇温し、５０℃の温度を保持することで体積中位粒径（Ｄ５０）が３．９μｍの凝集粒子を含む固形分濃度１３重量％の凝集粒子分散液を得た。
Example 4
[Step 1]
300 g of resin particle dispersion B, 62 g of deionized water, and 24 g of release agent dispersion A were placed in a 2-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple, and mixed at room temperature (25 ° C.). Next, an aqueous solution in which 19.2 g of ammonium sulfate was dissolved in 289 g of deionized water was added dropwise to the mixture over 10 minutes while stirring with a Kai-type stirrer. At this time, the ammonium ion concentration in the system was 0.50 mol / L.
Thereafter, the mixed solution is heated to 50 ° C., and the aggregated particle dispersion liquid having a solid content concentration of 13% by weight containing aggregated particles having a volume median particle size (D50) of 3.9 μm is maintained by maintaining the temperature at 50 ° C. Obtained.
〔工程２〕
工程１で得られた、５０℃に維持された凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ｂ ３０ｇと脱イオン水６．２ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ｂの添加量に応じて一定昇温度速度で５１℃へと昇温し、５分間５１℃で保持した。この操作を４回繰り返したが、この際の樹脂微粒子分散液の添加、温度等の詳細を表２に示す。上記操作を合計５回行った後の系内温度は５５℃、系内のイオン濃度は０．４１ｍｏｌ／Ｌであった。また得られた樹脂微粒子付着凝集粒子の体積中位粒径（Ｄ５０）は４．９μｍであり、分散液中には１０μｍ以上の粗大粒子は０．４％であり、静置後の上澄み液は透明であったことから、カプセル化が進行したことを確認した。以降は、実施例１と同様に合一を行い、トナーを得た。得られたトナーの体積中位粒径（Ｄ５０）及びＣＶ値を表１に示す。
[Step 2]
A mixture obtained by mixing 30 g of resin particle dispersion B and 6.2 g of deionized water as a resin fine particle dispersion was continuously added at a constant addition rate to the aggregated particle dispersion maintained at 50 ° C. obtained in step 1. While dropping over 60 minutes, the temperature in the system was raised to 51 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion B added, and maintained at 51 ° C. for 5 minutes. This operation was repeated four times. Details of addition of the resin fine particle dispersion, temperature, etc. are shown in Table 2. The system temperature after performing the above operation 5 times in total was 55 ° C., and the ion concentration in the system was 0.41 mol / L. Moreover, the volume median particle size (D50) of the obtained resin fine particle-attached aggregated particles is 4.9 μm, the coarse particles of 10 μm or more are 0.4% in the dispersion, and the supernatant after standing is Since it was transparent, it was confirmed that the encapsulation proceeded. Thereafter, coalescence was performed in the same manner as in Example 1 to obtain a toner. Table 1 shows the volume-median particle size (D50) and CV value of the obtained toner.
比較例１
〔工程１〕
実施例２と同様にして凝集粒子を形成させた。
〔工程２〕
工程１で得られた凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ １５０ｇと脱イオン水３７．２ｇを混合した混合液を一定添加速度で連続的に２４０分かけて滴下した。この際の樹脂微粒子分散液の添加、温度等の詳細を表１に示す。この後の系内温度は４８℃、系内のイオン濃度は０．４１ｍｏｌ／Ｌであった。また得られた樹脂微粒子付着凝集粒子の体積中位粒径（Ｄ５０）は４．５μｍであり、分散液中には１０μｍ以上の粗大粒子は０．４％であるが、静置後の上澄み液は濁っており、カプセル化が進行しなかった。
Comparative Example 1
[Step 1]
Aggregated particles were formed in the same manner as in Example 2.
[Step 2]
A liquid mixture obtained by mixing 150 g of resin particle dispersion A and 37.2 g of deionized water as a resin fine particle dispersion was dropped into the aggregated particle dispersion obtained in step 1 continuously over 240 minutes at a constant addition rate. Details of the addition of the resin fine particle dispersion, the temperature, etc. are shown in Table 1. Thereafter, the system temperature was 48 ° C., and the ion concentration in the system was 0.41 mol / L. Moreover, the volume median particle size (D50) of the obtained resin fine particle-attached aggregated particles is 4.5 μm, and the coarse particles of 10 μm or more are 0.4% in the dispersion liquid. Was cloudy and encapsulation did not proceed.
比較例２
〔工程１〕
実施例３と同様にして凝集粒子を形成させた。
〔工程２〕
工程１で得られた凝集粒子分散液に、樹脂微粒子分散液として樹脂粒子分散液Ａ ３０ｇと脱イオン水７．４ｇを混合した混合液を一定添加速度で連続的に６０分かけて滴下しつつ、系内の温度を樹脂粒子分散液Ａの添加量に応じて一定昇温度速度で６０℃へと昇温した。この際の樹脂微粒子分散液の添加、温度等の詳細を表１に示す。系内温度は６０℃、系内のイオン濃度は０．４８ｍｏｌ／Ｌであった。また得られた樹脂粒子付着凝集粒子の体積中位粒径（Ｄ５０）は６．４μｍであり、分散液の静置後の上澄み液は透明であったが、分散液中には１０μｍ以上の粗大粒子の存在量が５．５％であった。
Comparative Example 2
[Step 1]
Aggregated particles were formed in the same manner as in Example 3.
[Step 2]
While continuously adding a mixed liquid obtained by mixing 30 g of resin particle dispersion A and 7.4 g of deionized water as a resin fine particle dispersion to the aggregated particle dispersion obtained in step 1 at a constant addition rate over 60 minutes. The temperature in the system was raised to 60 ° C. at a constant temperature increase rate according to the amount of the resin particle dispersion A added. Details of the addition of the resin fine particle dispersion, the temperature, etc. are shown in Table 1. The system temperature was 60 ° C., and the ion concentration in the system was 0.48 mol / L. Further, the volume-median particle size (D50) of the obtained resin particle-attached aggregated particles was 6.4 μm, and the supernatant after standing of the dispersion was transparent, but the dispersion was coarser than 10 μm. The amount of particles present was 5.5%.
本発明の製造方法によれば、様々な用途に応じたトナーの設計が容易なことから、本発明のトナーは、電子写真法、静電記録法、静電印刷法などに使用される電子写真用トナーに好適に用いることができる。 According to the production method of the present invention, it is easy to design a toner according to various uses. Therefore, the toner of the present invention is used for electrophotography, electrostatic recording method, electrostatic printing method and the like. It can be suitably used for a toner.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008294730A JP5248996B2 (en) | 2008-11-18 | 2008-11-18 | Method for producing toner for electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008294730A JP5248996B2 (en) | 2008-11-18 | 2008-11-18 | Method for producing toner for electrophotography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010122389A JP2010122389A (en) | 2010-06-03 |
| JP5248996B2 true JP5248996B2 (en) | 2013-07-31 |
Family
ID=42323800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008294730A Active JP5248996B2 (en) | 2008-11-18 | 2008-11-18 | Method for producing toner for electrophotography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5248996B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10310396B2 (en) * | 2017-05-15 | 2019-06-04 | Canon Kabushiki Kaisha | Method of producing toner |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3429986B2 (en) * | 1996-10-14 | 2003-07-28 | 日本ゼオン株式会社 | Polymerized toner and method for producing the same |
| JP2003098727A (en) * | 2001-09-25 | 2003-04-04 | Ricoh Co Ltd | Dry toner |
| JP4033098B2 (en) * | 2003-09-22 | 2008-01-16 | コニカミノルタビジネステクノロジーズ株式会社 | Image forming method |
| JP4466404B2 (en) * | 2005-02-23 | 2010-05-26 | コニカミノルタビジネステクノロジーズ株式会社 | Toner for developing electrostatic image and method for producing the same |
| JP2007108555A (en) * | 2005-10-17 | 2007-04-26 | Canon Inc | Image forming method |
| JP2007133093A (en) * | 2005-11-09 | 2007-05-31 | Fuji Xerox Co Ltd | Toner for electrostatic latent image development and method for manufacturing the same, developer for electrostatic latent image development, and image forming method |
| JP2008158037A (en) * | 2006-12-21 | 2008-07-10 | Matsushita Electric Ind Co Ltd | Toner, method for manufacturing toner, and image forming apparatus |
| JP4935519B2 (en) * | 2007-06-11 | 2012-05-23 | 三菱化学株式会社 | Method for producing toner for developing electrostatic image |
-
2008
- 2008-11-18 JP JP2008294730A patent/JP5248996B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010122389A (en) | 2010-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5507628B2 (en) | Method for producing toner for electrophotography | |
| JP4599272B2 (en) | Toner production method | |
| JP5624473B2 (en) | Method for producing polyester particle dispersion | |
| JP5192158B2 (en) | Resin emulsion | |
| JP4668828B2 (en) | toner | |
| JP4963582B2 (en) | Toner for electrophotography | |
| JP5739656B2 (en) | Method for producing toner for electrophotography | |
| JP5513060B2 (en) | Method for producing toner for electrophotography | |
| JP5189787B2 (en) | Method for producing resin emulsion | |
| JP5552493B2 (en) | Toner production method | |
| JP5180459B2 (en) | Resin emulsion | |
| JP5111956B2 (en) | Resin emulsion | |
| JP4866721B2 (en) | Method for producing toner for electrophotography | |
| JP4832228B2 (en) | Method for producing resin emulsion for toner | |
| JP5248996B2 (en) | Method for producing toner for electrophotography | |
| JP4689477B2 (en) | Method for producing resin emulsified particles | |
| JP5438336B2 (en) | Method for producing toner for electrophotography | |
| JP5255351B2 (en) | Method for producing toner for electrophotography | |
| JP5552297B2 (en) | Method for producing toner for electrophotography | |
| JP5010338B2 (en) | Method for producing toner for electrophotography | |
| JP2009128434A (en) | Electrophotographic toner | |
| JP4832274B2 (en) | Resin emulsion for toner | |
| JP4942542B2 (en) | Method for producing toner for electrophotography | |
| JP5667312B2 (en) | Method for producing resin particle dispersion and method for producing toner for developing electrostatic image | |
| JP5080341B2 (en) | Method for producing resin particle dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110914 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130312 |
|
| 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: 20130402 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130411 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5248996 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160419 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |