JP3211575B2 - Toner for developing electrostatic latent images - Google Patents
Toner for developing electrostatic latent imagesInfo
- Publication number
- JP3211575B2 JP3211575B2 JP18694794A JP18694794A JP3211575B2 JP 3211575 B2 JP3211575 B2 JP 3211575B2 JP 18694794 A JP18694794 A JP 18694794A JP 18694794 A JP18694794 A JP 18694794A JP 3211575 B2 JP3211575 B2 JP 3211575B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- resin
- calcium
- amount
- fine particles
- 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.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 50
- 239000003381 stabilizer Substances 0.000 claims description 43
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 34
- 229910052791 calcium Inorganic materials 0.000 claims description 34
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 17
- 238000005550 wet granulation Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 description 103
- 239000011347 resin Substances 0.000 description 103
- 239000002245 particle Substances 0.000 description 54
- 239000010419 fine particle Substances 0.000 description 49
- 239000000243 solution Substances 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 238000001914 filtration Methods 0.000 description 24
- 238000005406 washing Methods 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 19
- 239000000126 substance Substances 0.000 description 16
- 239000000725 suspension Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- -1 for example Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000003086 colorant Substances 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 11
- 239000008399 tap water Substances 0.000 description 11
- 235000020679 tap water Nutrition 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 10
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 238000004945 emulsification Methods 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000010558 suspension polymerization method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 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 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- YZQCRYHZKMFKDE-UHFFFAOYSA-N 1-octadecylperoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOOCCCCCCCCCCCCCCCCCC YZQCRYHZKMFKDE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- TZUBWGMDFVLGGT-UHFFFAOYSA-N 3,3-dichloroprop-1-enyl acetate Chemical compound CC(=O)OC=CC(Cl)Cl TZUBWGMDFVLGGT-UHFFFAOYSA-N 0.000 description 1
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- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
- LVOJOIBIVGEQBP-UHFFFAOYSA-N 4-[[2-chloro-4-[3-chloro-4-[(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-methyl-2-phenylpyrazol-3-ol Chemical compound CC1=NN(C(O)=C1N=NC1=CC=C(C=C1Cl)C1=CC(Cl)=C(C=C1)N=NC1=C(O)N(N=C1C)C1=CC=CC=C1)C1=CC=CC=C1 LVOJOIBIVGEQBP-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 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
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- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene 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
- 150000001412 amines Chemical class 0.000 description 1
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- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UHHXUPJJDHEMGX-UHFFFAOYSA-K azanium;manganese(3+);phosphonato phosphate Chemical compound [NH4+].[Mn+3].[O-]P([O-])(=O)OP([O-])([O-])=O UHHXUPJJDHEMGX-UHFFFAOYSA-K 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- HEQCHSSPWMWXBH-UHFFFAOYSA-L barium(2+) 1-[(2-carboxyphenyl)diazenyl]naphthalen-2-olate Chemical compound [Ba++].Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O.Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O HEQCHSSPWMWXBH-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical class C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- DFYKHEXCUQCPEB-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C(C)=C DFYKHEXCUQCPEB-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 235000019827 calcium polyphosphate Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- HBHZKFOUIUMKHV-UHFFFAOYSA-N chembl1982121 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HBHZKFOUIUMKHV-UHFFFAOYSA-N 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- YOCIQNIEQYCORH-UHFFFAOYSA-M chembl2028361 Chemical compound [Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=CC=C1 YOCIQNIEQYCORH-UHFFFAOYSA-M 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000005594 diketone group Chemical class 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- HTENFZMEHKCNMD-UHFFFAOYSA-N helio brilliant orange rk Chemical compound C1=CC=C2C(=O)C(C=C3Br)=C4C5=C2C1=C(Br)C=C5C(=O)C1=CC=CC3=C14 HTENFZMEHKCNMD-UHFFFAOYSA-N 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VENDXQNWODZJGB-UHFFFAOYSA-N n-(4-amino-5-methoxy-2-methylphenyl)benzamide Chemical compound C1=C(N)C(OC)=CC(NC(=O)C=2C=CC=CC=2)=C1C VENDXQNWODZJGB-UHFFFAOYSA-N 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 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 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- RBKBGHZMNFTKRE-UHFFFAOYSA-K trisodium 2-[(2-oxido-3-sulfo-6-sulfonatonaphthalen-1-yl)diazenyl]benzoate Chemical compound C1=CC=C(C(=C1)C(=O)[O-])N=NC2=C3C=CC(=CC3=CC(=C2[O-])S(=O)(=O)O)S(=O)(=O)[O-].[Na+].[Na+].[Na+] RBKBGHZMNFTKRE-UHFFFAOYSA-K 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電子写真、静電記録お
よび静電印刷等における静電潜像を現像するために用い
られる静電潜像現像用トナーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic latent image developing toner used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing and the like.
【０００２】[0002]
【従来の技術】従来より、電子写真、静電記録および静
電印刷等における静電潜像を現像するために用いられる
静電潜像現像用トナーは、カーボンブラック等の顔料を
熱可塑性樹脂中に混合溶融混練して一様な分散体にした
後、適当な微粉砕装置によってトナーとして必要な粒径
の粉末に粉砕する、いわゆる粉砕法により製造されてき
た。2. Description of the Related Art Conventionally, an electrostatic latent image developing toner used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like has a pigment such as carbon black in a thermoplastic resin. After the mixture is melt-kneaded to form a uniform dispersion, the mixture is pulverized by a suitable pulverizer into a powder having a particle size required as a toner.
【０００３】しかしながら、近年、製造コストの低減や
高画質化の観点から粉砕法に代わり、小粒径で比較的粒
径の揃った樹脂微粒子を得ることが可能な、懸濁重合
法、乳化分散法等に代表される湿式中での造粒法が注目
されている。[0003] However, in recent years, instead of the pulverization method from the viewpoint of reduction in production cost and high image quality, a suspension polymerization method, an emulsification and dispersion method, which can obtain resin fine particles having a relatively small particle size and a relatively uniform particle size, have been proposed. Attention has been paid to a granulation method in a wet method represented by a method.
【０００４】懸濁重合法は、重合性単量体、重合開始剤
および着色剤等を成分とする重合組成物を分散媒体中に
懸濁し重合することによって造粒を行うものである。ま
た、乳化分散法は、結着樹脂と着色剤とを適当な有機溶
媒に溶解ないしは分散させて着色樹脂溶液とし、これを
水性分散液に加えて激しく攪拌することにより、樹脂溶
液の液滴を形成させる。そして、加熱して液滴から有機
溶媒を除去することにより造粒を行うものである。In the suspension polymerization method, granulation is carried out by suspending and polymerizing a polymerization composition containing a polymerizable monomer, a polymerization initiator, a colorant and the like in a dispersion medium. In the emulsification dispersion method, a binder resin and a colorant are dissolved or dispersed in an appropriate organic solvent to form a colored resin solution, and the resulting solution is added to an aqueous dispersion and stirred vigorously to form droplets of the resin solution. Let it form. Then, granulation is performed by heating to remove the organic solvent from the droplets.
【０００５】湿式造粒法によれば、概して小粒径のトナ
ー粒子を形成することが容易であることから高画質化に
充分対応することが可能である。また、収率も良好であ
る。[0005] According to the wet granulation method, it is generally easy to form toner particles having a small particle diameter, so that it is possible to sufficiently cope with high image quality. Also, the yield is good.
【０００６】通常、このような湿式造粒法においては、
分散媒体中に分散した液滴の凝集を防止し、液滴の分散
状態を安定に保つため、分散媒体中に分散安定剤を添加
するようにしている。Usually, in such a wet granulation method,
In order to prevent aggregation of the droplets dispersed in the dispersion medium and to stably maintain the dispersion state of the droplets, a dispersion stabilizer is added to the dispersion medium.
【０００７】分散安定剤としては、種々のものが知られ
ているが、特に、分散安定性に優れていることおよび分
散安定剤の除去の容易性に優れていることなどから、リ
ン酸カルシウム等のカルシウム系の難溶性無機塩が好ま
しく用られる。[0007] Various dispersion stabilizers are known. In particular, calcium dispersions such as calcium phosphate are preferred because of their excellent dispersion stability and the ease of removal of the dispersion stabilizer. Insoluble inorganic salts of the system are preferably used.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上記の
カルシウム系難溶性無機塩を分散安定剤として使用する
湿式造粒法によって製造したトナーは、十分な帯電量を
示さなかったり、帯電不良トナーの量が多かったり、高
温高湿環境に放置すると帯電性が損なわれたり、耐刷時
に帯電量が低下するなどの問題を発生する虞のあること
が判明した。However, the toner produced by the wet granulation method using the above-mentioned calcium-based hardly soluble inorganic salt as a dispersion stabilizer does not show a sufficient charge amount or the amount of a poorly charged toner. It has been found that there is a possibility that problems such as deterioration of the chargeability when left in a high-temperature and high-humidity environment and a decrease in the charge amount during printing can occur.
【０００９】本発明は上記事情に鑑みなされたもので、
分散安定剤としてカルシウム系の難溶性無機塩を使用す
る湿式造粒法で製造されたトナーであっても、十分な帯
電量を有し、帯電不良トナー量が少なく、高温高湿環境
に放置しても帯電性が損なわれず、耐刷時にも帯電量が
低下しないトナーを提供することを目的とする。The present invention has been made in view of the above circumstances,
Even a toner manufactured by a wet granulation method using a calcium-based hardly soluble inorganic salt as a dispersion stabilizer, has a sufficient charge amount, has a small amount of poorly charged toner, and is allowed to stand in a high temperature and high humidity environment. It is an object of the present invention to provide a toner which does not lose its chargeability even when the printing is performed and the charge amount does not decrease even during printing.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するた
め、本発明は、カルシウム系の難溶性無機塩を分散安定
剤として使用する湿式造粒法により製造された静電潜像
現像用トナーにおいて、トナーに残存するカルシウム量
を０．２〜１０ｐｐｍとしたことを特徴とする。In order to achieve the above object, the present invention relates to a toner for developing an electrostatic latent image produced by a wet granulation method using a calcium-based hardly soluble inorganic salt as a dispersion stabilizer. And the amount of calcium remaining in the toner is set to 0.2 to 10 ppm.
【００１１】本発明者らは、種々検討した結果、トナー
に残存するカルシウムが上記問題の一因であることを見
出した。As a result of various studies, the present inventors have found that calcium remaining in the toner contributes to the above problem.
【００１２】一般に、難溶性無機塩を分散安定剤として
使用する湿式造粒法においては、懸濁液中で分散安定剤
である難溶性無機塩が液滴表面を覆うことにより、液滴
どうしの凝集を防いでいる。このため、造粒された樹脂
微粒子の表面にはこの難溶性無機塩が付着する。したが
って、通常は、造粒後に粒子表面に付着している難溶性
無機塩を、塩酸等により溶解しついで水洗浄することに
よって除去するようにしている。In general, in a wet granulation method using a hardly soluble inorganic salt as a dispersion stabilizer, the hardly soluble inorganic salt, which is a dispersion stabilizer, in a suspension covers the surface of the droplets, so that the droplets can be separated from each other. Prevents agglomeration. Therefore, the hardly soluble inorganic salt adheres to the surface of the granulated resin fine particles. Therefore, usually, the hardly soluble inorganic salt adhering to the particle surface after granulation is removed by dissolving with hydrochloric acid or the like and then washing with water.
【００１３】ところが、カルシウム系の難溶性無機塩を
分散安定剤として使用する場合、分散安定剤に含まれて
いたカルシウムが何らかの形で樹脂粒子表面に付着する
ものと考えられ、単に酸によって溶解し水洗しただけで
は、分散安定剤に含まれていたカルシウムを粒子表面か
ら十分に除去できないことが判明した。そして、トナー
表面に付着していると考えられるカルシウム含有成分が
上記問題の一因となることを見出した。However, when a calcium-based hardly soluble inorganic salt is used as a dispersion stabilizer, it is considered that calcium contained in the dispersion stabilizer adheres to the surface of the resin particles in some form. It was found that the calcium contained in the dispersion stabilizer could not be sufficiently removed from the particle surface only by washing with water. Then, they have found that a calcium-containing component considered to be attached to the toner surface contributes to the above problem.
【００１４】トナー表面に付着するカルシウム含有成分
が上記問題の一因となる理由は必ずしも明らかではない
が、このカルシウム含有成分自身がある程度の帯電性を
有しており、これがトナーの帯電性に影響を与えること
によるものと考えられる。Although the reason why the calcium-containing component adhering to the toner surface contributes to the above problem is not always clear, the calcium-containing component itself has a certain degree of chargeability, which affects the chargeability of the toner. It is thought that it is due to giving.
【００１５】本発明者らは、上記知見に基づいてさらに
検討を重ねた結果、湿式造粒法によって得た樹脂微粒子
を、分散安定剤の仕込量に応じた量の酸を使用して酸洗
浄し、ついで分散安定剤の仕込量に応じた水量で水洗浄
し、さらに乾燥する前の段階で分散安定剤の仕込量に応
じた水量の脱イオン水によって洗浄するなどの方法によ
り、樹脂微粒子表面に残存するカルシウムの量を所定の
範囲にまで減少させることによって、上記問題を解決す
ることが可能であることを見い出し、本発明に至ったも
のである。The present inventors have conducted further studies based on the above findings. As a result, the resin fine particles obtained by the wet granulation method were acid-washed using an acid in an amount corresponding to the charged amount of the dispersion stabilizer. Then, the resin fine particles are washed with water in an amount corresponding to the amount of the dispersion stabilizer, and then washed with deionized water in an amount of water in accordance with the amount of the dispersion stabilizer before drying. It has been found that the above problem can be solved by reducing the amount of calcium remaining in the above to a predetermined range, leading to the present invention.
【００１６】本発明においては、まず湿式中において造
粒を行う。湿式中におけるトナー粒子の造粒法として
は、例えば、乳化分散法がある。In the present invention, granulation is first performed in a wet system. As a method for granulating toner particles in a wet process, for example, there is an emulsification dispersion method.
【００１７】乳化分散法においては、結着樹脂と、着色
剤と、必要に応じてその他の添加物とを非水溶性有機溶
媒に溶解ないしは分散させて着色樹脂溶液とし、これを
水性分散媒液中に乳化分散させてＯ／Ｗ型エマルジョン
を形成し、その後Ｏ／Ｗ型エマルジョンから非水溶性有
機溶媒を除去することにより造粒を行う。なお、Ｏ／Ｗ
型エマルジョンとは、水性分散液中に油性液体が液滴と
なって分散している状態の懸濁液を指す。In the emulsification dispersion method, a binder resin, a colorant and, if necessary, other additives are dissolved or dispersed in a water-insoluble organic solvent to form a colored resin solution, which is then dispersed in an aqueous dispersion medium. The O / W emulsion is formed by emulsifying and dispersing therein, and then the water-insoluble organic solvent is removed from the O / W emulsion to perform granulation. O / W
The type emulsion refers to a suspension in which an oily liquid is dispersed as droplets in an aqueous dispersion.
【００１８】乳化分散法に用いられる結着樹脂として
は、後述する非水溶性有機溶媒に溶解可能でかつ水に不
溶性あるいは難溶性のものであれば特に限定されず、例
えば、スチレン系樹脂、（メタ）アクリル系樹脂、スチ
レン−（メタ）アクリル系共重合体樹脂、オレフィン系
樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリカ
ーボネート樹脂、ポリエーテル樹脂、ポリ酢酸ビニル系
樹脂、ポリスルフォン樹脂、エポキシ樹脂、ポリウレタ
ン樹脂、尿素樹脂などのような公知の各種の樹脂を単独
あるいは２種以上組み合わせて用いることができる。The binder resin used in the emulsification dispersion method is not particularly limited as long as it can be dissolved in a water-insoluble organic solvent described later and is insoluble or hardly soluble in water. (Meth) acrylic resin, styrene- (meth) acrylic copolymer resin, olefin resin, polyester resin, polyamide resin, polycarbonate resin, polyether resin, polyvinyl acetate resin, polysulfone resin, epoxy resin, Various known resins such as polyurethane resins and urea resins can be used alone or in combination of two or more.
【００１９】このような結着樹脂としては、ガラス転移
点（Ｔｇ）が５０〜７０℃、数平均分子量（Ｍｎ）が１
０００〜５００００、好ましくは３０００〜２０００
０、Ｍｎと重量平均分子量（Ｍｗ）との比で表わされる
分子量分布（Ｍｗ／Ｍｎ）が２〜６０であることが望ま
しい。Ｔｇが５０℃未満では最終的に得られるトナーの
耐熱性が低下し、Ｔｇが７０℃を越えるとトナーの定着
性が低下する。また、Ｍｎが１０００未満では高温オフ
セットが発生しやすくなり、５００００を越えるもので
あると逆に低温オフセットが発生しやすくなる。さら
に、Ｍｗ／Ｍｎが２未満であると非オフセット領域が狭
いものとなる虞があり、６０を越えるものであると低温
オフセットが発生しやすくなる。なお、本発明のトナー
をオイル塗布定着用トナーとする場合には、Ｍｗ／Ｍｎ
は２〜５とすることが望ましく、また、オイルレス定着
用トナーとする場合には、Ｍｗ／Ｍｎは２０〜５０とす
ることが望ましい。Such a binder resin has a glass transition point (Tg) of 50 to 70 ° C. and a number average molecular weight (Mn) of 1
000 to 50,000, preferably 3000 to 2000
It is preferable that the molecular weight distribution (Mw / Mn) represented by the ratio of 0, Mn to the weight average molecular weight (Mw) be 2 to 60. If the Tg is lower than 50 ° C., the heat resistance of the finally obtained toner is lowered, and if the Tg is higher than 70 ° C., the fixability of the toner is lowered. If Mn is less than 1,000, high-temperature offset is likely to occur, and if it exceeds 50,000, low-temperature offset is likely to occur. Furthermore, if Mw / Mn is less than 2, the non-offset region may be narrow, and if it exceeds 60, low-temperature offset tends to occur. In the case where the toner of the present invention is used as an oil application fixing toner, Mw / Mn
Is desirably 2 to 5, and Mw / Mn is desirably 20 to 50 when the oilless fixing toner is used.
【００２０】上記の結着樹脂を溶解するための有機溶媒
としては、水に不溶かあるいは難溶で、上記結着樹脂を
溶解するものであればよく、例えば、トルエン、キシレ
ン、ベンゼン、四塩化炭素、塩化メチレン、１，２−ジ
クロロエタン、１，１，２−トリクロロエタン、トリク
ロロエチレン、クロロホルム、モノクロロベンゼン、ジ
クロロエチリデン、酢酸メチル、酢酸エチル、メチルエ
チルケトン、メチルイソブチルケトン等を単独あるいは
２種以上組合せて用いることができる。特に、トルエ
ン、キシレン等の芳香族系溶媒および塩化メチレン、
１，２−ジクロロエタン、クロロホルム、四塩化炭素等
のハロゲン化炭化水素が好ましい。The organic solvent for dissolving the binder resin may be any solvent which is insoluble or hardly soluble in water and which dissolves the binder resin, for example, toluene, xylene, benzene, tetrachloride. Carbon, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. are used alone or in combination of two or more. be able to. In particular, aromatic solvents such as toluene and xylene and methylene chloride,
Halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred.
【００２１】トナーに含有される着色剤としては、以下
に示されるような有機ないしは無機の各種、各色の顔料
が使用可能である。As the colorant contained in the toner, various kinds of organic or inorganic pigments as shown below can be used.
【００２２】すなわち、黒色顔料としては、カーボンブ
ラック、酸化銅、二酸化マンガン、アニリン・ブラッ
ク、活性炭、非磁性フェライト、磁性フェライト、マグ
ネタイトなどがある。That is, examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, and magnetite.
【００２３】黄色顔料としては、黄鉛、亜鉛黄、カドミ
ウムイエロー、黄色酸化鉄、ミネラルファストイエロ
ー、ニッケルチタンイエロー、ネーブルイエロー、ナフ
トールイエローＳ、ハンザイエローＧ、ハンザイエロー
１０Ｇ、ベンジジンイエローＧ、ベンジジンイエローＧ
Ｒ、キノリンイエローレーキ、パーマネントイエローＮ
ＣＧ、タートラジンレーキなどがある。Examples of the yellow pigment include: lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hanza yellow G, Hanza yellow 10G, benzidine yellow G, benzidine yellow. G
R, quinoline yellow lake, permanent yellow N
There are CG and tartrazine lake.
【００２４】橙色顔料としては、赤色黄鉛、モリブデン
オレンジ、パーマネントオレンジＧＴＲ、ピラゾロンオ
レンジ、バルカンオレンジ、インダスレンブリリアント
オレンジＲＫ、ベンジジンオレンジＧ、インダスレンブ
リリアントオレンジＧＫなどがある。As the orange pigment, there are red lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indaslen brilliant orange RK, benzidine orange G, indaslen brilliant orange GK and the like.
【００２５】赤色顔料としては、ベンガラ、カドミウム
レッド、鉛丹、硫化水銀、カドミウム、パーマネントレ
ッド４Ｒ、リソールレッド、ピラゾロンレッド、ウオッ
チングレッド、カルシウム塩、レーキレッドＣ、レーキ
レッドＤ、ブリリアントカーミン６Ｂ、エオシンレー
キ、ローダミンレーキＢ、アリザリンレーキ、ブリリア
ントカーミン３Ｂなどがある。Examples of red pigments include red iron, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, lithol red, pyrazolone red, watching red, calcium salt, lake red C, lake red D, and brilliant carmine 6B. Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B and the like.
【００２６】紫色顔料としては、マンガン紫、ファスト
バイオレットＢ、メチルバイオレットレーキなどがあ
る。The violet pigment includes manganese violet, fast violet B, methyl violet lake and the like.
【００２７】青色顔料としては、紺青、コバルトブル
ー、アルカリブルーレーキ、ビクトリアブルーレーキ、
フタロシアニンブルー、無金属フタロシアニンブルー、
フタロシアニンブルー部分塩素化物、ファーストスカイ
ブルー、インダスレンブルーＢＣなどがある。Blue pigments include navy blue, cobalt blue, alkaline blue lake, Victoria blue lake,
Phthalocyanine blue, metal-free phthalocyanine blue,
Phthalocyanine blue partially chlorinated products, Fast Sky Blue, Indaslen Blue BC and the like.
【００２８】緑色顔料としては、クロムグリーン、酸化
クロム、ピグメントグリーンＢ、マイカライトグリーン
レーキ、ファイナルイエローグリーンＧなどがある。Green pigments include chrome green, chromium oxide, pigment green B, micalite green lake, final yellow green G, and the like.
【００２９】白色顔料としては、酸化亜鉛、酸化チタ
ン、酸化アンチモン、硫化亜鉛、炭酸カルシウム、酸化
スズなどがある。Examples of the white pigment include zinc oxide, titanium oxide, antimony oxide, zinc sulfide, calcium carbonate, tin oxide and the like.
【００３０】体質顔料としては、バライト粉、炭酸バリ
ウム、クレー、シリカ、ホワイトカーボン、タルク、ア
ルミナホワイトなどがある。The extender includes baryte powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.
【００３１】これらの着色剤は単独あるいは複数組合せ
て用いることができる。着色剤はトナーに含有される結
着樹脂１００重量部に対して、１〜２０重量部、好まし
くは２〜１５重量部使用する。着色剤が２０重量部より
多いとトナーの定着性が低下し、１重量部より少ないと
所望の画像濃度が得られない虞がある。These coloring agents can be used alone or in combination. The colorant is used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the binder resin contained in the toner. If the amount of the colorant is more than 20 parts by weight, the fixability of the toner is reduced. If the amount is less than 1 part by weight, a desired image density may not be obtained.
【００３２】本発明のトナー中には、上記したような結
着樹脂および着色剤以外にも、例えば、荷電制御剤、磁
性粉、オフセット防止剤などの成分を必要に応じて配合
することができる。In the toner of the present invention, for example, components such as a charge control agent, a magnetic powder, and an anti-offset agent can be added as required in addition to the binder resin and the colorant described above. .
【００３３】荷電制御剤としては、摩擦帯電により正ま
たは負の荷電を与え得る物質として各種のものがあり、
正荷電制御剤としては、例えば、ニグロシンベースＥＸ
（オリエント化学工業社製）などのニグロシン系染料、
Ｐ−５１（オリエント化学工業社製）、コピーチャージ
ＰＸ ＶＰ４３５（ヘキスト社製）などの第４級アン
モニウム塩、アルコキシ化アミン、アルキルアミド、モ
リブデン酸キレート顔料、およびＰＬＺ１００１（四国
化成工業社製）などのイミダゾール化合物等が挙げられ
る。As the charge control agent, there are various substances which can give a positive or negative charge by triboelectric charging.
As the positive charge control agent, for example, Nigrosine-based EX
Nigrosine dyes such as (manufactured by Orient Chemical Industries),
Quaternary ammonium salts such as P-51 (manufactured by Orient Chemical Industries), Copy Charge PX VP435 (manufactured by Hoechst), alkoxylated amines, alkylamides, molybdate chelate pigments, and PLZ1001 (manufactured by Shikoku Chemicals) And the like.
【００３４】負荷電制御剤としては、例えば、ボントロ
ンＳ−２２（オリエント化学工業社製）、ボントロンＳ
−３４（オリエント化学工業社製）、ボントロンＥ−８
１（オリエント化学工業社製）、ボントロンＥ−８４
（オリエント化学工業社製）、スピロンブラックＴＲＨ
（保土谷化学工業社製）などの金属錯体、チオインジゴ
系顔料、コピーチャージＮＸ ＶＰ４３４（ヘキスト社
製）などの第４級アンモニウム塩、ボントロンＥ−８９
（オリエント化学工業社製）などのカリックスアレーン
化合物、フッ化マグネシウム、フッ化カーボンなどのフ
ッ素化合物などが挙げられる。なお、負荷電制御剤とな
る金属錯体としては、上記に示したもの以外にもオキシ
カルボン酸金属錯体、ジカルボン酸金属錯体、アミノ酸
金属錯体、ジケトン金属錯体、ジアミン金属錯体、アゾ
基含有ベンゼン−ベンゼン誘導体骨格金属錯体、アゾ基
含有ベンゼン−ナフタレン誘導体骨格金属錯体などの各
種の構造を有したものであってもよい。Examples of the negative charge control agent include Bontron S-22 (manufactured by Orient Chemical Industries) and Bontron S
-34 (manufactured by Orient Chemical Industries), Bontron E-8
1 (manufactured by Orient Chemical Industries), Bontron E-84
(Manufactured by Orient Chemical Industries), Spiron Black TRH
Metal complexes such as (Hodogaya Chemical Industry Co., Ltd.), thioindigo pigments, quaternary ammonium salts such as Copy Charge NX VP434 (manufactured by Hoechst), Bontron E-89
(Orient Chemical Industry Co., Ltd.), and fluorine compounds such as magnesium fluoride and carbon fluoride. In addition, as the metal complex serving as the negative charge control agent, in addition to those described above, metal oxycarboxylates, metal complexes of dicarboxylic acids, metal complexes of amino acids, metal complexes of diketones, metal complexes of diamines, benzene-containing benzene-benzene complexes It may have various structures such as a derivative skeleton metal complex and an azo group-containing benzene-naphthalene derivative skeleton metal complex.
【００３５】これらの荷電制御剤は、その粒径が１０〜
１００ｍμｍ程度のものであることが、均一な分散を得
る上から望ましい。市販品等として供給される形態にお
いてその粒径が上記範囲の上限値も大きい場合には、ジ
ェットミル等により粉砕を行うなどの公知の方法により
適当な粒径に調整することが望ましい。These charge control agents have a particle size of 10 to 10.
A thickness of about 100 μm is desirable from the viewpoint of obtaining uniform dispersion. In the case where the particle size is large in the form supplied as a commercial product or the like and the upper limit of the above range is large, it is desirable to adjust the particle size to an appropriate value by a known method such as pulverization by a jet mill or the like.
【００３６】磁性粉としては、マグネタイト、γ−ヘマ
タイト、あるいは各種フェライト等がある。Examples of the magnetic powder include magnetite, γ-hematite, and various ferrites.
【００３７】オフセット防止剤としては、各種ワック
ス、特に、低分子量ポリプロピレン、ポリエチレン、あ
るいは、酸化型のポリプロピレン、ポリエチレン等のポ
リオレフィン系ワックスなどが挙げられる。Examples of the anti-offset agent include various waxes, in particular, polyolefin waxes such as low molecular weight polypropylene and polyethylene, or oxidized polypropylene and polyethylene.
【００３８】非水溶性有機溶媒に結着樹脂、着色剤、お
よびその他のトナー成分を溶解ないし分散させるには、
ボールミル、サンドミル、ホモミキサー、超音波ホモジ
ナイザーなどの装置を用いることができる。To dissolve or disperse a binder resin, a colorant, and other toner components in a water-insoluble organic solvent,
An apparatus such as a ball mill, a sand mill, a homomixer, and an ultrasonic homogenizer can be used.
【００３９】結着樹脂、着色剤、およびその他の添加剤
を非水溶性有機溶媒に溶解ないしは分散させて得た着色
樹脂溶液における固形分濃度は、この着色樹脂溶液を水
性分散液中に乳化分散させてなるＯ／Ｗ型エマルジョン
を加熱して液滴中より非水溶性有機溶媒を除去する際
に、液滴が容易に微粒子へと凝固できるように設定する
必要があり、５〜５０重量％、好ましくは１０〜４０重
量％とする。The solid content concentration in a colored resin solution obtained by dissolving or dispersing a binder resin, a coloring agent, and other additives in a water-insoluble organic solvent is determined by emulsifying and dispersing the colored resin solution in an aqueous dispersion. When the O / W emulsion is heated to remove the water-insoluble organic solvent from the droplets, it is necessary to set the droplets so that the droplets can be easily solidified into fine particles. , Preferably 10 to 40% by weight.
【００４０】Ｏ／Ｗ型エマルジョンを形成するために
は、ホモミキサーなどの撹拌装置を用いて、着色樹脂溶
液と水性分散液との混合系を十分に撹拌する方法を採用
することができる。なお、撹拌時間が短すぎるとシャー
プな粒径分布が得られないため、撹拌時間は１０分以上
であることが好ましい。In order to form the O / W emulsion, a method of sufficiently stirring the mixed system of the colored resin solution and the aqueous dispersion using a stirring device such as a homomixer can be adopted. Note that if the stirring time is too short, a sharp particle size distribution cannot be obtained, and therefore the stirring time is preferably 10 minutes or more.
【００４１】また、着色樹脂溶液の体積（Ｖｐ）と水性
分散液の体積（Ｖｗ）との比（Ｖｐ／Ｖｗ）は、Ｖｐ／
Ｖｗ≦１、好ましくは０．３≦Ｖｐ／Ｖｗ≦０．７とす
る。Ｖｐ／Ｖｗ＞１であると、安定なＯ／Ｗ型エマルジ
ョンが形成できず、途中で相転移が生じたり、Ｗ／Ｏ型
エマルジョンが形成されてしまう虞が大きい。The ratio (Vp / Vw) of the volume (Vp) of the colored resin solution to the volume (Vw) of the aqueous dispersion is Vp / Vp.
Vw ≦ 1, preferably 0.3 ≦ Vp / Vw ≦ 0.7. When Vp / Vw> 1, a stable O / W emulsion cannot be formed, and there is a high possibility that a phase transition occurs on the way or a W / O emulsion is formed.
【００４２】Ｏ／Ｗ型エマルジョンを形成するために使
用する水性分散液としては、水や、水にエマルジョンを
破壊しない程度の水溶性有機溶媒を含んだもの、例え
ば、水／メタノール混液（重量比５０／５０〜１００／
０）、水／エタノール混液（重量比５０／５０〜１００
／０）、水／アセトン混液（５０／５０〜１００／
０）、水／メチルエチルケトン混液（重量比７０／３０
〜１００／０）などが使用可能である。The aqueous dispersion used to form the O / W emulsion may be water or a water-soluble organic solvent that does not destroy the emulsion in water, for example, a water / methanol mixed solution (weight ratio). 50 / 50-100 /
0), water / ethanol mixture (weight ratio 50 / 50-100
/ 0), water / acetone mixture (50 / 50-100 /
0), water / methyl ethyl ketone mixed solution (weight ratio 70/30)
１００100/0) can be used.
【００４３】水性分散液には、カルシウム系の難溶性無
機塩を分散安定剤として添加する。カルシウム系の難溶
性無機塩としては、水に難溶性のリン酸カルシウム塩
や、硫酸カルシウム、炭酸カルシウム等が挙げられる。
水に難溶性のリン酸カルシウム塩としては、リン酸三カ
ルシウム、第二リン酸カルシウム、水酸化リン酸カルシ
ウム、ピロリン酸カルシウム、ポリリン酸カルシウムお
よび、これらの混晶や、フッ化カルシウムや塩化カルシ
ウムとの複塩の形態のものを挙げることができる。これ
らの分散安定剤は、単独あるいは２種以上組み合わせて
用いることができる。To the aqueous dispersion, a calcium-based hardly soluble inorganic salt is added as a dispersion stabilizer. Examples of the calcium-based hardly soluble inorganic salt include a calcium phosphate salt that is hardly soluble in water, calcium sulfate, and calcium carbonate.
Examples of the water-insoluble calcium phosphate salts include tricalcium phosphate, dibasic calcium phosphate, calcium hydroxide phosphate, calcium pyrophosphate, calcium polyphosphate, and mixed crystals thereof, and those in the form of double salts with calcium fluoride or calcium chloride. Can be mentioned. These dispersion stabilizers can be used alone or in combination of two or more.
【００４４】乳化分散法においてリン酸カルシウム塩を
分散安定剤として用いると、トナー表面に凹凸が形成さ
れ、不定形のトナーが得られる。そのため、ブレードク
リーニングを行う画像形成装置においては、良好なクリ
ーニング性を得ることができる。When a calcium phosphate salt is used as a dispersion stabilizer in the emulsification dispersion method, irregularities are formed on the surface of the toner, and an amorphous toner is obtained. Therefore, in an image forming apparatus that performs blade cleaning, good cleaning properties can be obtained.
【００４５】分散安定剤としてカルシウム系の難溶性無
機塩を含む水性分散液のｐＨは、カルシウム系難溶性無
機塩の安定性を考慮して、５〜１４、好ましくは６〜１
２に調整することが望ましい。水性分散液のｐＨを調整
するためには、水酸化カルシウム、水酸化ナトリウム等
のアルカリや、塩酸、リン酸等の酸を添加するなどの方
法を採用することができる。The pH of the aqueous dispersion containing the calcium-based hardly soluble inorganic salt as a dispersion stabilizer is 5 to 14, preferably 6 to 1, in consideration of the stability of the calcium-based hardly soluble inorganic salt.
It is desirable to adjust to 2. In order to adjust the pH of the aqueous dispersion, a method of adding an alkali such as calcium hydroxide or sodium hydroxide or an acid such as hydrochloric acid or phosphoric acid can be adopted.
【００４６】分散安定剤としてのカルシウム系の難溶性
無機塩の使用量は、使用する水性分散液の総量に対して
０．５〜１０重量％とする。分散安定剤が０．５重量％
未満であると液滴を十分安定な状態で分散させることが
できず、１０重量％を超えると、樹脂粒子中への分散安
定剤の取り込みが問題となる虞がある。The amount of the calcium-based hardly soluble inorganic salt used as a dispersion stabilizer is 0.5 to 10% by weight based on the total amount of the aqueous dispersion used. 0.5% by weight of dispersion stabilizer
If it is less than 10%, the droplets cannot be dispersed in a sufficiently stable state.
【００４７】また、着色樹脂溶液の水性分散液への分散
途中あるいは分散終了後に、分散安定剤を追加して添加
するようにしてもよい。このような分散安定剤の再添加
は、液滴あるいは析出した樹脂微粒子の凝集の防止に有
効である。Further, a dispersion stabilizer may be additionally added during or after the dispersion of the colored resin solution in the aqueous dispersion. Such re-addition of the dispersion stabilizer is effective for preventing aggregation of droplets or precipitated resin fine particles.
【００４８】液滴の分散安定性を向上させるため、分散
安定剤としてのカルシウム系の難溶性無機塩とともに、
分散安定補助剤を用いてもよい。分散安定補助剤として
は、サポニンなどの天然界面活性剤、アルキレンオキサ
イド系、グリセリン系、グリシドール系などのノニオン
系界面活性剤、カルボン酸、スルホン酸、リン酸、硫酸
エステル基、リン酸エステル基等の酸性基を含むアニオ
ン系界面活性剤などが挙げられる。特に、ドデシルベン
ゼンスルホン酸ナトリウムやラウリル硫酸ナトリウムな
どのアニオン系界面活性剤が好ましい。In order to improve the dispersion stability of droplets, together with a calcium-based hardly soluble inorganic salt as a dispersion stabilizer,
A dispersion stabilizing aid may be used. Examples of the dispersion stabilizing aid include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, carboxylic acid, sulfonic acid, phosphoric acid, sulfate group, and phosphate group. And an anionic surfactant containing an acidic group. In particular, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate are preferred.
【００４９】分散安定補助剤と分散安定剤との混合比率
は、１／１０００〜１０／１００、好ましくは２／１０
００〜８／１００とする。混合比率が１／１０００未満
では、十分な分散安定性を得ることができず、また、１
０／１００を超えると乳化が起こりすぎて液滴に凝集が
発生したり、造粒後に分散安定剤および分散安定補助剤
を十分に除去することが困難になるなどの虞がある。The mixing ratio of the dispersion stabilizer to the dispersion stabilizer is 1/1000 to 10/100, preferably 2/10.
00 to 8/100. If the mixing ratio is less than 1/1000, sufficient dispersion stability cannot be obtained.
If it exceeds 0/100, emulsification may occur too much to cause aggregation of droplets, or it may be difficult to sufficiently remove the dispersion stabilizer and the dispersion stabilizer after granulation.
【００５０】Ｏ／Ｗ型エマルジョンから非水溶性有機溶
媒を除去するためには、系全体を徐々に昇温して、液滴
中の非水溶性有機溶媒を完全に蒸発させる方法や、Ｏ／
Ｗ型エマルジョンを乾燥雰囲気中に噴霧し、液滴中の非
水溶性有機溶媒を完全に除去してトナー微粒子を形成し
合わせて水性分散液を蒸発除去する方法を用いることが
できる。In order to remove the water-insoluble organic solvent from the O / W emulsion, a method of gradually elevating the temperature of the whole system to completely evaporate the water-insoluble organic solvent in the droplets,
A method in which the W-type emulsion is sprayed in a dry atmosphere, the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersion is evaporated and removed.
【００５１】乳化分散法には、懸濁重合法などに比べて
使用可能な樹脂の種類が多いという特徴がある。The emulsification dispersion method is characterized in that there are many types of resins that can be used as compared with the suspension polymerization method and the like.
【００５２】湿式中におけるトナー粒子の造粒法として
は、この他に、重合過程を含む造粒法である、懸濁重合
法、乳化重合法、ソープフリー乳化重合法、マイクロカ
プセル法（界面重合法、ｉｎ−ｓｉｔｕ重合法等）、非
水分散重合法などが挙げられる。As the granulation method of the toner particles in the wet process, there are other granulation methods including a polymerization process, such as a suspension polymerization method, an emulsion polymerization method, a soap-free emulsion polymerization method, and a microcapsule method (interfacial weight). And a non-aqueous dispersion polymerization method.
【００５３】懸濁重合法においては、重合性単量体、重
合開始剤、着色剤、および必要に応じて添加される荷電
制御剤、磁性粉、オフセット防止剤などの添加物からな
る重合組成物を、分散媒体中に懸濁させて油滴分散粒子
を形成する。そして、加熱して重合させることにより造
粒を行う。In the suspension polymerization method, a polymerization composition comprising a polymerizable monomer, a polymerization initiator, a colorant, and additives such as a charge control agent, a magnetic powder, and an anti-offset agent which are added as needed. Is suspended in a dispersion medium to form oil-dispersed particles. Granulation is performed by heating and polymerizing.
【００５４】懸濁重合法に使用される重合性単量体とし
ては、例えば、スチレン、メチルスチレン、メトキシス
チレン、ブチルスチレン、フェニルスチレン、エチルス
チレン、クロルスチレン等のスチレン系モノマー、アク
リル酸メチル、アクリル酸エチル、アクリル酸プロピ
ル、アクリル酸ブチル、アクリル酸ドデシル、アクリル
酸ステアリル、アクリル酸エチルヘキシル、アクリルア
ミド、メタクリル酸メチル、メタクリル酸エチル、メタ
クリル酸プロピル、メタクリル酸ブチル、メタクリル酸
オクチル、メタクリル酸ドデシル、メタクリル酸エチル
ヘキシル、メタクリル酸ステアリル等のアクリル酸ある
いはメタクリル酸系モノマー、エチレン、プロピレン、
ブチレン、塩化ビニル、酢酸ビニル、アクリロニトリル
等が挙げられ、これらを単独あるいは複数組み合わせて
用いることができる。また、これらをプレポリマーの形
にしてから用いてもよい。Examples of the polymerizable monomer used in the suspension polymerization method include styrene monomers such as styrene, methyl styrene, methoxy styrene, butyl styrene, phenyl styrene, ethyl styrene, and chloro styrene; methyl acrylate; Ethyl acrylate, propyl acrylate, butyl acrylate, dodecyl acrylate, stearyl acrylate, ethylhexyl acrylate, acrylamide, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, Ethyl hexyl methacrylate, acrylic acid or methacrylic acid monomers such as stearyl methacrylate, ethylene, propylene,
Examples thereof include butylene, vinyl chloride, vinyl acetate, and acrylonitrile, and these can be used alone or in combination. These may be used after being made into a prepolymer.
【００５５】懸濁重合法に使用される重合開始剤として
は、例えば、ベンゾイルーオキサイド、ラウロイルパー
オキサイド、ステアリルパーオキサイドのようなパーオ
キサイド系開始剤や２，２’−アゾビスイソブチロニト
リル、２，２’−アゾビス−（２，４−ジメチルパレロ
ニトリル）のようなアゾビス系開始剤が挙げられる。Examples of the polymerization initiator used in the suspension polymerization method include peroxide initiators such as benzoyl oxide, lauroyl peroxide and stearyl peroxide, and 2,2'-azobisisobutyronitrile. And azobis-based initiators such as 2,2'-azobis- (2,4-dimethylpareronitrile).
【００５６】重合組成物を分散媒体中に懸濁させて油滴
分散粒子を形成するには、ホモミキサーやホモジナイザ
ー等の高速攪拌式の分散機を用いて激しく攪拌すればよ
い。In order to suspend the polymer composition in a dispersion medium to form oil-droplet-dispersed particles, the mixture may be vigorously stirred using a high-speed stirring type disperser such as a homomixer or a homogenizer.
【００５７】重合を行うためには、重合組成物の分散し
た溶液系を重合開始剤の分解温度以上の任意の温度にす
ればよいが、通常４０〜１５０℃とすることが好まし
い。In order to carry out the polymerization, the temperature of the solution system in which the polymerization composition is dispersed may be set to any temperature higher than the decomposition temperature of the polymerization initiator, but it is usually preferably 40 to 150 ° C.
【００５８】分散媒体中には、分散した液滴の凝集を防
ぐために分散安定剤を添加する。分散安定剤としては、
上記の乳化分散法に用いられるものと同様のものを用い
ることができる。A dispersion stabilizer is added to the dispersion medium in order to prevent aggregation of the dispersed droplets. As a dispersion stabilizer,
The same ones as those used in the above emulsification dispersion method can be used.
【００５９】懸濁重合法においては、樹脂微粒子内のモ
ノマーの残留を極力抑える必要がある。モノマーの残留
量が多いと、洗浄により分散安定剤を除去する際の凝集
の発生、トナーとなってからの臭い、帯電性の不安定
化、軟化温度のばらつき等の原因となる。モノマーの残
留を抑えるためには、反応の前半は低温で（４０〜８０
℃）重合を行い、反応の後半は高温（８０〜１５０℃）
で重合を行うなどの多段重合法を用いたり、プレポリマ
ーを用いたりすることが望ましい。In the suspension polymerization method, it is necessary to minimize the residual monomer in the resin fine particles. If the residual amount of the monomer is large, it causes aggregation when removing the dispersion stabilizer by washing, odor after becoming a toner, instability of charging property, variation in softening temperature, and the like. In order to suppress the residual monomer, the first half of the reaction is carried out at a low temperature (40 to 80).
℃) polymerization, the latter half of the reaction is high temperature (80-150 ℃)
It is desirable to use a multi-stage polymerization method such as performing polymerization at a temperature, or to use a prepolymer.
【００６０】また、重合中や重合終了後に分散安定剤を
追加して添加してもよい。このような分散安定剤の再添
加は、液滴の凝集や、造粒された樹脂微粒子の凝集の防
止に有効である。A dispersion stabilizer may be additionally added during or after the polymerization. Such re-addition of the dispersion stabilizer is effective for preventing aggregation of droplets and aggregation of granulated resin fine particles.
【００６１】本発明においては、こうして湿式中で製造
された樹脂微粒子を、酸洗浄し、ついで水洗浄し、さら
に乾燥する前の段階で脱イオン水によって洗浄するなど
の方法により、トナーに残存するカルシウム量を０．２
〜１０ｐｐｍとする。In the present invention, the resin fine particles thus produced in a wet process remain in the toner by a method such as acid washing, then water washing, and further washing with deionized water before drying. 0.2 calcium
-10 ppm.
【００６２】トナーに残存するカルシウムの量を測定す
るためには、たとえば、ＩＣＰ発光分光分析装置、Ｘ線
マイクロアナライザー、螢光Ｘ線分析装置等の公知の分
析装置を用いることができる。In order to measure the amount of calcium remaining in the toner, a known analyzer such as an ICP emission spectrometer, an X-ray microanalyzer, and a fluorescent X-ray analyzer can be used.
【００６３】酸洗浄の方法としては、例えば、樹脂微粒
子を形成させた後、この樹脂微粒子を含む溶液に、塩
酸、硝酸、硫酸などの酸を添加することにより樹脂微粒
子表面に付着している分散安定剤を溶解するなどの方法
が挙げられる。分散安定剤の溶解を完全なものとするた
め、溶液のｐＨを１〜２とし、３０分間以上攪拌するこ
とが好ましい。また、酸の添加により樹脂微粒子を含ん
だ溶液が発熱し、一旦溶解した分散安定剤が樹脂微粒子
中に取り込まれる虞があるので、樹脂微粒子を含む溶液
の温度を３０℃以下に保つことが好ましい。As a method of acid cleaning, for example, after resin fine particles are formed, an acid such as hydrochloric acid, nitric acid, sulfuric acid or the like is added to a solution containing the resin fine particles to disperse the resin particles on the surface of the resin fine particles. Examples of the method include dissolving a stabilizer. In order to completely dissolve the dispersion stabilizer, it is preferable to adjust the pH of the solution to 1 to 2 and stir for 30 minutes or more. Further, the temperature of the solution containing the resin fine particles is preferably maintained at 30 ° C. or less because the solution containing the resin fine particles may generate heat due to the addition of the acid, and the dispersion stabilizer once dissolved may be taken into the resin fine particles. .
【００６４】酸洗浄後、樹脂微粒子をろ別し、水洗浄を
行うことによって分散安定剤や分散安定補助剤を樹脂微
粒子表面から洗い流す。After the acid washing, the fine resin particles are separated by filtration and washed with water to wash off the dispersion stabilizer and the auxiliary dispersion stabilizing agent from the surface of the fine resin particles.
【００６５】水洗浄は、まず、ろ別した樹脂微粒子を水
道水等を用いて懸洗し、さらに、脱イオン水によって数
回洗浄するなどの方法により行う。こうして、樹脂微粒
子の乾燥を行う前に脱イオン水によって数回洗浄するこ
とにより、分散安定剤、分散安定補助剤、水洗浄に使用
した水道水等に含まれるハロゲンイオン等を十分減少さ
せることができる。脱イオン水としては、電導度が０．
５μＳ／ｃｍ以下であるものを使用すると、洗浄効率が
高く好ましい。The water washing is carried out by first washing the filtered fine resin particles with tap water or the like, and then washing them several times with deionized water. Thus, by washing several times with deionized water before drying the resin fine particles, it is possible to sufficiently reduce the dispersion stabilizer, the dispersion stabilization aid, the halogen ions and the like contained in the tap water used for water washing, and the like. it can. As deionized water, the conductivity is 0.1.
It is preferable to use one having a concentration of 5 μS / cm or less because the cleaning efficiency is high.
【００６６】なお、トナーに残存するカルシウム量を
０．２ｐｐｍ未満にすると、洗浄時に凝集して粒径分布
がブロードになったり、異形粒子が増えて飛散を引き起
こしたりする虞がある。If the amount of calcium remaining in the toner is less than 0.2 ppm , there is a possibility that the particles aggregate during washing and the particle size distribution becomes broad, or irregular particles increase to cause scattering.
【００６７】こうして洗浄された樹脂微粒子は乾燥され
た後、さらに、必要に応じて、分級等の工程を経ること
により、平均粒径が２〜１５μｍ、好ましくは４〜１０
μｍの静電潜像現像用トナーとすることができる。The resin fine particles thus washed are dried and, if necessary, subjected to a step such as classification, so that the average particle diameter is 2 to 15 μm, preferably 4 to 10 μm.
μm electrostatic latent image developing toner.
【００６８】[0068]
【実施例】以下、本発明を実施例によりさらに具体的に
説明する。なお、以下の部数は重量部である。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The following parts are parts by weight.
【００６９】＜実施例１＞ポリエステル樹脂（ＮＥ−３
８２：花王社製）１００部をトルエン４００部に溶解し
た。そして、フタロシアニン顔料６部および亜鉛金属錯
体（Ｅ−８４：オリエント化学工業社製）２部を添加
し、ボールミルに入れて３時間混合して分散させること
により着色樹脂溶液を調製した。<Example 1> Polyester resin (NE-3)
82: Kao Corporation) was dissolved in 400 parts of toluene. Then, 6 parts of a phthalocyanine pigment and 2 parts of a zinc metal complex (E-84: manufactured by Orient Chemical Industry Co., Ltd.) were added, mixed in a ball mill for 3 hours, and dispersed to prepare a colored resin solution.
【００７０】一方、分散安定剤として４重量％の水酸化
リン酸カルシウムを含有する水溶液１０００部に、ラウ
リル硫酸ナトリウム（和光純薬社製）０．１部を溶解さ
せることにより水性分散液を調製した。On the other hand, an aqueous dispersion was prepared by dissolving 0.1 part of sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1000 parts of an aqueous solution containing 4% by weight of calcium phosphate as a dispersion stabilizer.
【００７１】上記の着色樹脂溶液をＴＫオートホモミク
サー（特殊機化工業社製）を用いてこの水性分散液中に
懸濁させた。この際、ホモミクサーの回転数を調整し、
平均粒径３〜１２μｍの液滴を形成するようにした。The above colored resin solution was suspended in this aqueous dispersion using TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). At this time, adjust the rotation speed of the homomixer,
A droplet having an average particle size of 3 to 12 μm was formed.
【００７２】こうして得た樹脂懸濁液を、６０〜６５
℃、７０〜１４０ｍｍＨｇの条件で５時間放置すること
により、液滴からトルエンを除去し、樹脂微粒子を析出
させた。The resin suspension obtained in this way is used for 60-65.
By leaving the mixture at 70 ° C. and 70 to 140 mmHg for 5 hours, toluene was removed from the droplets to precipitate resin fine particles.
【００７３】そして、液温を３０℃以下に保ちながら溶
液のｐＨが１．６になるまで１Ｎの塩酸を徐々に添加し
て水酸化リン酸カルシウムを溶解した。さらに、３０分
間攪拌を続けた後、樹脂微粒子をろ別した。Then, while maintaining the solution temperature at 30 ° C. or lower, 1N hydrochloric acid was gradually added until the pH of the solution reached 1.6 to dissolve the calcium hydroxide phosphate. After further stirring for 30 minutes, the fine resin particles were separated by filtration.
【００７４】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を３回繰り返した。続
いて、５倍量の脱イオン水（電導度０．１μＳ／ｃｍ）
で３０分間懸洗し、ろ過する操作を３回繰り返した。Next, the operation of suspending the resin fine particles in a five-fold amount of tap water for 30 minutes and filtering was repeated three times. Subsequently, 5 times the volume of deionized water (conductivity: 0.1 μS / cm)
, And the operation of filtration was repeated three times.
【００７５】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー１を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 1 having an average particle diameter of 6 μm.
【００７６】＜実施例２＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、液温を３０
℃以下に保ちながら溶液のｐＨが１．２になるまで１Ｎ
の塩酸を徐々に添加して水酸化リン酸カルシウムを溶解
した。さらに、１時間攪拌を続けた後、樹脂微粒子をろ
別した。<Example 2> First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from the droplets in the resin suspension to precipitate resin fine particles. Then, the solution temperature is set to 30 with respect to the solution containing the resin fine particles.
1N until the pH of the solution reaches 1.2
Was slowly added to dissolve the calcium hydroxide phosphate. Further, after stirring was continued for 1 hour, the resin fine particles were separated by filtration.
【００７７】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を３回繰り返した。続
いて、５倍量の脱イオン水（電導度０．１μＳ／ｃｍ）
で３０分間懸洗し、ろ過する操作を５回繰り返した。Next, the operation of suspending and washing the resin fine particles in a five-fold amount of tap water for 30 minutes and filtering was repeated three times. Subsequently, 5 times the volume of deionized water (conductivity: 0.1 μS / cm)
, And the operation of filtering was repeated 5 times.
【００７８】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー２を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 2 having an average particle diameter of 6 μm.
【００７９】＜実施例３＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、液温を３０
℃以下に保ちながら溶液のｐＨが１．５になるまで４Ｎ
の塩酸を徐々に添加して水酸化リン酸カルシウムを溶解
した。さらに、１時間攪拌を続けた後、樹脂微粒子をろ
別した。<Example 3> First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from the droplets in the resin suspension to precipitate resin fine particles. Then, the solution temperature is set to 30 with respect to the solution containing the resin fine particles.
4N until the pH of the solution reaches 1.5
Was slowly added to dissolve the calcium hydroxide phosphate. Further, after stirring was continued for 1 hour, the resin fine particles were separated by filtration.
【００８０】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を２回繰り返した。続
いて、５倍量の脱イオン水（電導度０．１μＳ／ｃｍ）
で３０分間懸洗し、ろ過する操作を２回繰り返した。Next, the operation of washing the resin fine particles in 5 times volume of tap water for 30 minutes and filtering was repeated twice. Subsequently, 5 times the volume of deionized water (conductivity: 0.1 μS / cm)
, And the operation of filtering was repeated twice.
【００８１】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー３を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 3 having an average particle diameter of 6 μm.
【００８２】＜実施例４＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、液温を３０
℃以下に保ちながら溶液のｐＨが１．８になるまで２Ｎ
の塩酸を徐々に添加して水酸化リン酸カルシウムを溶解
した。さらに、４０分間攪拌を続けた後、樹脂微粒子を
ろ別した。Example 4 First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from droplets in the resin suspension to precipitate fine resin particles. Then, the solution temperature is set to 30 with respect to the solution containing the resin fine particles.
2N until the pH of the solution reaches 1.8
Was slowly added to dissolve the calcium hydroxide phosphate. After stirring was further continued for 40 minutes, the resin fine particles were separated by filtration.
【００８３】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗した後、ろ過した。続いて、５倍量の脱
イオン水（電導度０．１μＳ／ｃｍ）で３０分間懸洗
し、ろ過する操作を２回繰り返した。Next, the resin fine particles were suspended and washed in tap water of 5 times volume for 30 minutes, and then filtered. Subsequently, the operation of washing with 5 times the amount of deionized water (conductivity: 0.1 μS / cm) for 30 minutes and filtering was repeated twice.
【００８４】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー４を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 4 having an average particle diameter of 6 μm.
【００８５】＜実施例５＞スチレン−ブチルメタクリレ
ート樹脂（軟化点１２１℃、Ｔｇ６５℃、Ｍｎ＝２３０
０、Ｍｗ／Ｍｎ＝８．５）１００部をジクロルメタン４
００部に溶解した。そして、ジメチルキナクリドン顔料
６部および亜鉛金属錯体（Ｅ−８４：オリエント化学工
業社製）２部を添加し、ボールミルに入れて３時間混合
して分散させることにより着色樹脂溶液を調製した。Example 5 Styrene-butyl methacrylate resin (softening point: 121 ° C., Tg: 65 ° C., Mn = 230)
0, Mw / Mn = 8.5) 100 parts of dichloromethane 4
Dissolved in 00 parts. Then, 6 parts of a dimethylquinacridone pigment and 2 parts of a zinc metal complex (E-84: manufactured by Orient Chemical Industries) were added, and the mixture was placed in a ball mill, mixed for 3 hours and dispersed to prepare a colored resin solution.
【００８６】一方、分散安定剤として１．５重量％の水
酸化リン酸カルシウムを含有する水溶液１０００部に、
にラウリル硫酸ナトリウム（和光純薬社製）０．１部を
溶解させることにより水性分散液を調製した。On the other hand, 1000 parts of an aqueous solution containing 1.5% by weight of calcium hydroxide as a dispersion stabilizer was added to
An aqueous dispersion was prepared by dissolving 0.1 part of sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.).
【００８７】上記の着色樹脂溶液をＴＫオートホモミク
サー（特殊機化工業社製）を用いてこの水性分散液中に
懸濁させた。この際、ホモミクサーの回転数を調整し、
平均粒径３〜１２μｍの液滴を形成するようにした。The above colored resin solution was suspended in this aqueous dispersion using TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). At this time, adjust the rotation speed of the homomixer,
A droplet having an average particle size of 3 to 12 μm was formed.
【００８８】こうして得た樹脂懸濁液に対して、５重量
％の水酸化リン酸カルシウムを含む水溶液５００部を添
加した後、３５〜４０℃、常圧の条件下で５時間放置す
ることにより、液滴からジクロルメタンを除去し、樹脂
微粒子を析出させた。To the resin suspension thus obtained was added 500 parts of an aqueous solution containing 5% by weight of calcium hydroxide, and the mixture was allowed to stand at 35 to 40 ° C. under normal pressure for 5 hours to obtain a liquid. Dichloromethane was removed from the droplet to precipitate resin fine particles.
【００８９】そして、液温を３０℃以下に保ちながら溶
液のｐＨが２．０になるまで１Ｎの塩酸を徐々に添加し
て水酸化リン酸カルシウムを溶解した。さらに、３０分
間攪拌を続けた後、樹脂微粒子をろ別した。Then, while maintaining the solution temperature at 30 ° C. or lower, 1N hydrochloric acid was gradually added until the pH of the solution reached 2.0 to dissolve calcium hydroxide phosphate. After further stirring for 30 minutes, the fine resin particles were separated by filtration.
【００９０】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を３回繰り返した。続
いて、５倍量の脱イオン水（電導度０．３μＳ／ｃｍ）
で３０分間懸洗した後、ろ過した。Next, the operation of washing the resin fine particles in a 5-fold amount of tap water for 30 minutes and filtering was repeated three times. Subsequently, 5 times the amount of deionized water (conductivity: 0.3 μS / cm)
, And then filtered.
【００９１】その後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径７μｍのトナー５を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 5 having an average particle diameter of 7 μm.
【００９２】＜実施例６＞ ・スチレン １００部 ・ｎ−ブチルメタクリレート ３５部 ・メタクリル酸 ５部 ・２，２−アゾビスイソブチロニトリル ０．５部 ・カーボンブラック顔料（三菱化成工業社製） ８部 ・帯電制御剤（アイゼンスピロンブラックＴＲＨ：保土
ケ谷化学社製） ３部 ・低分子量ポリプロピレン（三洋化成工業社製） ３部 上記材料をサンドスターラーで混合することにより重合
組成物を調製した。この重合組成物を、水５００部、水
酸化リン酸カルシウム２０部、ドデシル硫酸ナトリウム
（和光純薬社製）０．１部を溶解させた水性分散液に投
入しＴＫホモミキサー（特殊機化工業社製）を用いて毎
分８０００回転で撹拌しながら、６０℃で５時間重合さ
せ、さらに温度を７５℃に昇温し１時間重合させて、樹
脂微粒子を析出させた。<Example 6> 100 parts of styrene 35 parts of n-butyl methacrylate 5 parts of methacrylic acid 0.5 part of 2,2-azobisisobutyronitrile 0.5 parts of carbon black pigment (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 8 parts ・ Charge control agent (Eizen Spiron Black TRH: manufactured by Hodogaya Chemical Co., Ltd.) 3 parts ・ Low molecular weight polypropylene (manufactured by Sanyo Chemical Industry Co., Ltd.) 3 parts A polymer composition was prepared by mixing the above materials with a sand stirrer. This polymer composition is added to an aqueous dispersion in which 500 parts of water, 20 parts of calcium hydroxide, and 0.1 part of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved, and TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) ), Polymerization was carried out at 60 ° C. for 5 hours while stirring at 8,000 revolutions per minute, and the temperature was further raised to 75 ° C. for 1 hour to precipitate resin fine particles.
【００９３】冷却後、液温を３０℃以下に保ちながら溶
液のｐＨが１．０になるまで２Ｎの塩酸を添加して水酸
化リン酸カルシウムを溶解した。さらに、１時間攪拌を
続けた後、樹脂微粒子をろ別した。After cooling, 2N hydrochloric acid was added until the pH of the solution reached 1.0 while maintaining the solution temperature at 30 ° C. or lower to dissolve the calcium hydroxide phosphate. Further, after stirring was continued for 1 hour, the resin fine particles were separated by filtration.
【００９４】そして、この樹脂微粒子を５倍量の水道水
中で３０分間懸洗し、ろ過する操作を３回繰り返した。
続いて、５倍量の脱イオン水（電導度０．２μＳ／ｃ
ｍ）で３０分間懸洗した後、ろ過した。Then, the operation of suspending the resin fine particles in a 5-fold amount of tap water for 30 minutes and filtering was repeated three times.
Subsequently, 5 times the amount of deionized water (conductivity: 0.2 μS / c)
m) for 30 minutes, followed by filtration.
【００９５】その後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径７μｍのトナー６を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 6 having an average particle diameter of 7 μm.
【００９６】＜比較例１＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、溶液のｐＨ
が２．５になるまで１Ｎの濃塩酸を添加して水酸化リン
酸カルシウムを溶解した後、樹脂微粒子をろ別した。Comparative Example 1 First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from the droplets in the resin suspension to precipitate resin fine particles. Then, for the solution containing the resin fine particles, the pH of the solution
After adding 1N concentrated hydrochloric acid to dissolve the calcium hydroxide phosphate until the value became 2.5, the resin fine particles were separated by filtration.
【００９７】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を３回繰り返した。Next, the operation of suspending the resin fine particles in a 5-fold amount of tap water for 30 minutes and filtering was repeated three times.
【００９８】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー７を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 7 having an average particle diameter of 6 μm.
【００９９】＜比較例２＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、溶液のｐＨ
が３．０になるまで濃塩酸を添加して水酸化リン酸カル
シウムを溶解した後、樹脂微粒子をろ別した。<Comparative Example 2> First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from droplets in the resin suspension to precipitate resin fine particles. Then, for the solution containing the resin fine particles, the pH of the solution
Was added to dissolve the calcium hydroxide phosphate until the pH became 3.0, and then the resin fine particles were separated by filtration.
【０１００】次に、この樹脂微粒子を５倍量の水道水中
で３０分間懸洗し、ろ過する操作を２回繰り返した。Next, the operation of suspending the resin fine particles in a 5-fold amount of tap water for 30 minutes and filtering was repeated twice.
【０１０１】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行い平均粒径６μｍのトナー８を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 8 having an average particle diameter of 6 μm.
【０１０２】＜比較例３＞まず、実施例１と同様の手順
により、樹脂懸濁液を調製し、次いで樹脂懸濁液中の液
滴からトルエンを除去し、樹脂微粒子を析出させた。そ
して、この樹脂微粒子を含む溶液に対して、液温を３０
℃以下に保ちながら溶液のｐＨが１．０になるまで１Ｎ
の塩酸を添加して水酸化リン酸カルシウムを溶解した。
さらに、３０分間攪拌を続けた後、樹脂微粒子をろ別し
た。Comparative Example 3 First, a resin suspension was prepared in the same procedure as in Example 1, and then toluene was removed from the droplets in the resin suspension to precipitate resin fine particles. Then, the solution temperature is set to 30 with respect to the solution containing the resin fine particles.
1N until the pH of the solution reaches 1.0
Was added to dissolve the calcium hydroxide phosphate.
After further stirring for 30 minutes, the fine resin particles were separated by filtration.
【０１０３】そして、この樹脂微粒子を１０倍量の水道
水中で３０分間懸洗し、ろ過する操作を１０回繰り返し
た。続いて、１０倍量の脱イオン水（電導度０．５μＳ
／ｃｍ）で３０分間懸洗し、ろ過する操作を４回繰り返
した。この水洗工程において樹脂微粒子の凝集が発生し
た。Then, the operation of suspending and washing the resin fine particles in a 10-fold amount of tap water for 30 minutes and filtering was repeated 10 times. Subsequently, 10 times the volume of deionized water (conductivity 0.5 μS
/ Cm) for 30 minutes, and filtration was repeated four times. In this washing step, aggregation of the resin fine particles occurred.
【０１０４】この後、スラリー乾燥装置（ディスパーコ
ート：日清エンジニアリング社製）により粒子の乾燥を
行いトナー９を得た。Thereafter, the particles were dried by a slurry drying apparatus (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain a toner 9.
【０１０５】＜キャリアの製造例＞スチレン、メチルメ
タクリレート、２−ヒドロキシエチルアクリレート、お
よび、メタクリル酸からなるスチレン−アクリル系共重
合体（１．５：７：１．０：０．５）８０部と、ブチル
化メラミン樹脂２０部とをトルエンで希釈することによ
り、固形分比２重量％のスチレン−アクリル樹脂溶液を
調製した。<Example of Carrier Production> 80 parts of a styrene-acrylic copolymer (1.5: 7: 1.0: 0.5) composed of styrene, methyl methacrylate, 2-hydroxyethyl acrylate and methacrylic acid And 20 parts of a butylated melamine resin were diluted with toluene to prepare a styrene-acrylic resin solution having a solid content ratio of 2% by weight.
【０１０６】芯材として焼成フェライト粉（Ｆ−３０
０：平均粒径５０μｍ、嵩密度２．５３ｇ／ｃｍ3 ：パ
ウダーテック社製）を用い、上記スチレン−アクリル樹
脂溶液をスピラーコーター（岡田精工社製）により塗布
し、乾燥した。得られたキャリアを熱風循環式オーブン
中にて１４０℃で２時間放置して焼成した。冷却後、フ
ェライト粉バルクを目開き２１０μｍと９０μｍのスク
リーンメッシュを取り付けたフルイ振盪器を用いて解砕
し、樹脂コートされたフェライト粉とした。この樹脂コ
ートフェライト粉に対して、塗布、焼成、解砕の各処理
をさらに３回繰り返して樹脂被覆キャリアを得た。As a core material, fired ferrite powder (F-30)
0: average particle diameter 50 μm, bulk density 2.53 g / cm 3 : manufactured by Powdertech Co., Ltd.), and the styrene-acrylic resin solution was applied by a spiral coater (manufactured by Okada Seiko Co., Ltd.) and dried. The obtained carrier was calcined in a hot-air circulation oven at 140 ° C. for 2 hours. After cooling, the ferrite powder bulk was crushed using a sieve with a screen mesh having openings of 210 μm and 90 μm to obtain a resin-coated ferrite powder. Each process of coating, baking and crushing was further repeated three times on this resin-coated ferrite powder to obtain a resin-coated carrier.
【０１０７】こうして得られたキャリアの平均粒径は５
２μｍ、電気抵抗は約３×１０10Ωｃｍであった。The average particle diameter of the carrier thus obtained is 5
2 μm, and the electric resistance was about 3 × 10 10 Ωcm.
【０１０８】＜諸特性の評価＞上記の実施例１〜６およ
び比較例１、２のトナーについて、以下のようにして諸
特性の評価を行った。 （１）トナー中のカルシウム量 約２ｍｇのトナー粒子をとり、精秤した後、濃硝酸５ｍ
ｌに溶解させ、乾固し、さらに残留物を濃硝酸５ｍｌに
溶解させ、加熱して約２ｍｌまで濃縮した。この液を純
水で１００ｍｌになるように希釈し、ついでろ過するこ
とにより測定用試料を得た。<Evaluation of Various Properties> Various properties of the toners of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated as follows. (1) The amount of calcium in the toner is about 2 mg.
and concentrated to dryness. The residue was dissolved in 5 ml of concentrated nitric acid, heated and concentrated to about 2 ml. This liquid was diluted to 100 ml with pure water, and then filtered to obtain a measurement sample.
【０１０９】こうして得た試料のカルシウム濃度を、Ｉ
ＣＰ発光分光分析装置（ＳＰＳ−７０００：セイコー電
子社製）により測定した。そして測定された濃度値か
ら、測定に供したトナー粒子中の全カルシウム量を算出
し、トナー重量に対するカルシウム重量の比を求めて、
トナー中の残存カルシウム量とした。なお、比較例３の
トナーについても同様にして測定を行ったところ、残存
カルシウム量は０．１ｐｐｍであった。The calcium concentration of the sample thus obtained was calculated as
It was measured by a CP emission spectrometer (SPS-7000: manufactured by Seiko Denshi). Then, from the measured concentration value, the total calcium amount in the toner particles subjected to the measurement is calculated, and the ratio of the calcium weight to the toner weight is obtained,
The amount of residual calcium in the toner was taken. In addition, the same measurement was performed on the toner of Comparative Example 3, and the amount of residual calcium was 0.1 ppm.
【０１１０】（２）帯電量 実施例１〜６および比較例１〜２において得られたトナ
ー１００部に対して、疎水性シリカ０．３部（Ｈ−２０
００：ワッカー社製）および疎水性酸化チタン（Ｔ−８
０５：日本アエロジル社製）０．５部を添加し、ヘンシ
ェルミキサー（三井三池化工機社製）にて１０００ｒｐ
ｍで１分間、後処理した。そして、この後処理を行った
トナーと上記のキャリアとを５：９５の重量比率で混合
することによって評価用の現像剤を調製した。(2) Charge Amount 100 parts of the toner obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were added to 0.3 part of hydrophobic silica (H-20).
00: manufactured by Wacker Inc.) and hydrophobic titanium oxide (T-8)
05: Nippon Aerosil Co., Ltd.) 0.5 part was added, and the mixture was mixed with a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 1000 rpm.
m for 1 minute. A developer for evaluation was prepared by mixing the post-processed toner and the above-described carrier at a weight ratio of 5:95.
【０１１１】この現像剤３０ｇを容量５０ｍｌのポリエ
チレン瓶にいれ、１２００ｒｐｍで９０分間回転するこ
とにより現像剤を攪拌した。そして、所定の帯電量に帯
電させたフィルムに接触させ、フィルムに付着するトナ
ー重量を測定することによりトナーの帯電量を求めた。
また、３０℃、湿度８５％の環境下で２４時間保管した
後、同様に現像剤を攪拌してその帯電量を測定した。な
お、帯電量は常温常湿環境（２５℃、湿度６０％）にお
いて測定した。30 g of this developer was put into a polyethylene bottle having a capacity of 50 ml, and the developer was stirred by rotating at 1200 rpm for 90 minutes. Then, the film was brought into contact with a film charged to a predetermined charge amount, and the weight of the toner adhering to the film was measured to determine the charge amount of the toner.
Further, after storing in an environment of 30 ° C. and a humidity of 85% for 24 hours, the developer was similarly stirred to measure the charge amount. The charge amount was measured in a normal temperature and normal humidity environment (25 ° C., humidity 60%).
【０１１２】（３）帯電不良トナー量 上記の帯電量の測定と同様の手順で調製、撹拌を行った
現像液３ｇを、直径３１０ｍｍのマグネットロール上に
載せた。次に、精秤した対向電極をセットし、トナー極
性と逆極性にバイアス電圧１ｋＶをかけ、マグネットロ
ールを１０００ｒｐｍで１分間回転させた。そして、対
向電極を再度精秤して初期値との差をとることにより対
向電極に付着した分離トナー、すなわち帯電不良トナー
の重量を算出した。こうして、測定に供した全トナー重
量に対する帯電不良トナー重量の割合を帯電不良トナー
量とした。また、３０℃、湿度８５％の環境下で２４時
間保管した後、同様の手順によりその帯電不良トナー量
を測定した。なお、測定は常温常湿環境（２５℃、湿度
６０％）において行った。(3) Amount of Insufficiently Charged Toner 3 g of a developer prepared and agitated in the same procedure as the measurement of the amount of charge was placed on a magnet roll having a diameter of 310 mm. Next, the precisely weighed counter electrode was set, a bias voltage of 1 kV was applied to the polarity opposite to the toner polarity, and the magnet roll was rotated at 1000 rpm for 1 minute. Then, the weight of the separated toner attached to the counter electrode, that is, the poorly charged toner was calculated by precisely weighing the counter electrode again and taking a difference from the initial value. Thus, the ratio of the weight of the poorly charged toner to the total weight of the toner subjected to the measurement was defined as the amount of the poorly charged toner. After storing for 24 hours in an environment of 30 ° C. and a humidity of 85%, the amount of poorly charged toner was measured by the same procedure. The measurement was performed in a normal temperature and normal humidity environment (25 ° C., humidity 60%).
【０１１３】（４）耐刷後の帯電量 上記の帯電量の測定と同様の手順で調製した現像剤を、
市販のカラー複写機（ＣＦ−８０：ミノルタカメラ社
製）の現像器にセットして、１０００枚の連続コピーを
行った。その後、現像器より現像剤を取り出し、上記の
帯電量の測定と同様の手順で帯電量を測定した。以上の
測定結果を表１にまとめて示した。(4) Charge Amount after Printing Durability The developer prepared in the same procedure as the above-mentioned measurement of the charge amount was used.
It was set in a developing unit of a commercially available color copying machine (CF-80: manufactured by Minolta Camera Co., Ltd.), and 1000 continuous copies were made. Thereafter, the developer was taken out from the developing device, and the charge amount was measured in the same procedure as the above-described measurement of the charge amount. The above measurement results are summarized in Table 1.
【０１１４】[0114]
【表１】 [Table 1]
【０１１５】表１に示したように、実施例１〜６のもの
は、充分な帯電量を発揮し、また帯電不良トナーの発生
も極めて少なく、高温高湿環境に放置した場合も帯電量
の低下や帯電不良トナー量の増大を招かず、連続コピー
をおこなった後の帯電量の落ち込みも少ないものであっ
た。これに対して、残存カルシウム量の多い比較例１〜
２のものでは充分な帯電量が得られず、帯電不良トナー
の発生も多く、特に、高温高湿環境に放置するとこれら
が顕著であった。また、連続コピーを行った時の帯電量
の落ち込みも大きく、実用上使用不可であった。また、
比較例３のものは洗浄時に粒子の凝集が発生し、所望の
粒径のトナーが得られなかった。As shown in Table 1, the toners of Examples 1 to 6 exhibited a sufficient charge amount, had very little occurrence of poorly charged toner, and had a low charge amount even when left in a high temperature and high humidity environment. It did not cause a decrease or an increase in the amount of poorly charged toner, and the amount of charge after continuous copying was small. On the other hand, Comparative Examples 1 to 3 having a large amount of residual calcium
In the case of No. 2, a sufficient amount of charge was not obtained, and the occurrence of poorly charged toner was large. Particularly, when the toner was left in a high temperature and high humidity environment, these were remarkable. In addition, the amount of charge in continuous copying was greatly reduced, and was not practically usable. Also,
In the case of Comparative Example 3, particles aggregated during washing, and a toner having a desired particle size could not be obtained.
【０１１６】[0116]
【発明の効果】以上説明したように、本発明のトナー
は、カルシウム系の難溶性無機塩を分散安定剤として使
用する湿式造粒法により製造された静電潜像現像用トナ
ーであって、トナーに残存するカルシウムを所定量まで
減少させたものであるので、充分な帯電量が確保でき、
帯電不良トナーの発生が極めて少なく、高温高湿環境に
放置した後も十分な帯電性を示し、帯電不良トナー量が
増大することがなく、耐刷後も十分な帯電量を発揮でき
る。As described above, the toner of the present invention is an electrostatic latent image developing toner manufactured by a wet granulation method using a calcium-based hardly soluble inorganic salt as a dispersion stabilizer, Since the amount of calcium remaining in the toner is reduced to a predetermined amount, a sufficient charge amount can be secured,
The occurrence of poorly charged toner is extremely small, and shows sufficient chargeability even after being left in a high-temperature, high-humidity environment. The amount of poorly charged toner does not increase, and a sufficient amount of charge can be exhibited even after printing.
【０１１７】また、本発明のトナーは、カルシウム系の
難溶性無機塩を分散安定剤として使用する湿式造粒法に
より製造された静電潜像現像用トナーであって、トナー
に微量のカルシウムを含有するようにしたものであるの
で、トナーの製造時であって樹脂微粒子を洗浄する際に
樹脂微粒子が凝集するのを防止できる。The toner of the present invention is an electrostatic latent image developing toner manufactured by a wet granulation method using a calcium-based hardly soluble inorganic salt as a dispersion stabilizer. Since the fine particles are contained, it is possible to prevent the fine resin particles from aggregating when the fine resin particles are washed during the production of the toner.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 谷上 行夫 大阪市中央区安土町二丁目３番13号 大 阪国際ビル ミノルタ株式会社内 審査官 淺野 美奈 (56)参考文献 特開 平２−64652（ＪＰ，Ａ) 特開 平７−333894（ＪＰ，Ａ) 特開 平７−333895（ＪＰ，Ａ) 特開 平５−88409（ＪＰ，Ａ) 特開 平２−2577（ＪＰ，Ａ) 特開 昭61−184554（ＪＰ，Ａ) 特開 昭63−53563（ＪＰ，Ａ) 特開 平７−219271（ＪＰ，Ａ) 特開 平７−271099（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03G 9/08 - 9/087 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yukio Tanigami 2-3-3 Azuchicho, Chuo-ku, Osaka City Osaka International Building Minolta Co., Ltd. Examiner Mina Asano (56) References JP-A-2-64652 (JP, A) JP-A-7-333894 (JP, A) JP-A-7-333895 (JP, A) JP-A-5-88409 (JP, A) JP-A-2-2577 (JP, A) JP-A-61-184554 (JP, A) JP-A-63-53563 (JP, A) JP-A-7-219271 (JP, A) JP-A-7-271099 (JP, A) (58) Int.Cl. 7 , DB name) G03G 9/08-9/087
Claims (1)
剤として使用する湿式造粒法により製造された静電潜像
現像用トナーにおいて、トナーに残存するカルシウム量
が０．２〜１０ｐｐｍであることを特徴とする静電潜像
現像用トナー。1. An electrostatic latent image developing toner produced by a wet granulation method using a calcium-based hardly soluble inorganic salt as a dispersion stabilizer, wherein the amount of calcium remaining in the toner is 0.2 to 10 ppm. A toner for developing an electrostatic latent image.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18694794A JP3211575B2 (en) | 1994-08-09 | 1994-08-09 | Toner for developing electrostatic latent images |
| US08/451,861 US5604067A (en) | 1994-05-27 | 1995-05-26 | Toner for electrostatic latent image developing and manufacturing method of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18694794A JP3211575B2 (en) | 1994-08-09 | 1994-08-09 | Toner for developing electrostatic latent images |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0850370A JPH0850370A (en) | 1996-02-20 |
| JP3211575B2 true JP3211575B2 (en) | 2001-09-25 |
Family
ID=16197515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18694794A Expired - Fee Related JP3211575B2 (en) | 1994-05-27 | 1994-08-09 | Toner for developing electrostatic latent images |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3211575B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3721915B2 (en) | 2000-02-02 | 2005-11-30 | 日本ゼオン株式会社 | Electrophotographic developer, process for producing the same, and image forming method using the developer |
| US6569589B2 (en) | 2000-07-28 | 2003-05-27 | Canon Kabushiki Kaisha | Toner, toner production process and image forming method |
| JP4175177B2 (en) * | 2002-05-31 | 2008-11-05 | コニカミノルタホールディングス株式会社 | Toner for developing electrostatic image, method for producing toner for developing electrostatic image, image forming method and image forming apparatus |
| JP2008191697A (en) * | 2008-05-15 | 2008-08-21 | Nippon Zeon Co Ltd | Polymerized toner for electrophotography |
| JP5077118B2 (en) * | 2008-07-17 | 2012-11-21 | コニカミノルタビジネステクノロジーズ株式会社 | Toner for electrostatic image development |
| JP2013200523A (en) * | 2012-03-26 | 2013-10-03 | Fuji Xerox Co Ltd | Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method |
| JP6020230B2 (en) * | 2013-02-13 | 2016-11-02 | 富士ゼロックス株式会社 | Toner for developing electrostatic image, developer for developing electrostatic image, toner cartridge, process cartridge, and image forming apparatus |
| JP6085230B2 (en) * | 2013-07-26 | 2017-02-22 | 株式会社沖データ | Toner manufacturing method, toner, developing device, and image forming apparatus |
-
1994
- 1994-08-09 JP JP18694794A patent/JP3211575B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0850370A (en) | 1996-02-20 |
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