JP4196528B2 - Negatively chargeable magenta toner - Google Patents
Negatively chargeable magenta toner Download PDFInfo
- Publication number
- JP4196528B2 JP4196528B2 JP2000250763A JP2000250763A JP4196528B2 JP 4196528 B2 JP4196528 B2 JP 4196528B2 JP 2000250763 A JP2000250763 A JP 2000250763A JP 2000250763 A JP2000250763 A JP 2000250763A JP 4196528 B2 JP4196528 B2 JP 4196528B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- toner
- resin fine
- group
- dispersion
- 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
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- 239000002245 particle Substances 0.000 claims description 101
- 239000010419 fine particle Substances 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 59
- 239000003086 colorant Substances 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 40
- 239000011164 primary particle Substances 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000002776 aggregation Effects 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 238000004220 aggregation Methods 0.000 claims description 7
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000004931 aggregating effect Effects 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 239000001993 wax Substances 0.000 description 46
- 239000003795 chemical substances by application Substances 0.000 description 28
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- -1 polyethylene Polymers 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 239000003505 polymerization initiator Substances 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 5
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- 125000000217 alkyl group Chemical group 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910000859 α-Fe Inorganic materials 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass 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
- 239000000463 material Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- IEZDTNCUMWPRTD-UHFFFAOYSA-N 346704-04-9 Chemical compound [O-][N+](=O)C1=CC=C(N2CCNCC2)C=C1N1CCCCC1 IEZDTNCUMWPRTD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PBWGCNFJKNQDGV-UHFFFAOYSA-N 6-phenylimidazo[2,1-b][1,3]thiazol-5-amine Chemical compound N1=C2SC=CN2C(N)=C1C1=CC=CC=C1 PBWGCNFJKNQDGV-UHFFFAOYSA-N 0.000 description 1
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- 235000021357 Behenic acid Nutrition 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical class C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 description 1
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
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- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- KCNOEZOXGYXXQU-UHFFFAOYSA-N heptatriacontan-19-one Chemical group CCCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCCC KCNOEZOXGYXXQU-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Developing Agents For Electrophotography (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電子写真方式の複写機及びプリンターに用いられる負帯電性マゼンタトナーに関する。さらに詳しくは、定着性、耐ホットオフセット性、帯電性に優れた負帯電性マゼンタトナーに関する。
【０００２】
【従来の技術】
電子写真法において従来一般に広く用いられてきた静電荷像現像用トナーは、スチレン／アクリレート系共重合体やポリエステルのようなバインダー樹脂に、カーボンブラックや顔料のような着色剤、帯電制御剤及び／または磁性体を含む混合物を押出機により溶融混練し、ついで粉砕・分級することによって製造されてきた。しかし、上記のような溶融混練／粉砕法で得られる従来のトナーは、トナーの粒径制御に限界があり、実質的に１０μｍ以下、特に８μｍ以下の平均粒径のトナーを歩留まり良く製造することが困難であり、今後電子写真に要求される高解像度化を達成するためには十分なものとは言えなかった。
【０００３】
また、低温定着性を達成するために、混練時に低軟化点のワックスをトナー中にブレンドする方法が提案されているが、混練／粉砕法に於いては５％程度のブレンドが限界であり、十分な低温定着性能のトナーを得ることができなかった。特開昭６３−１８６２５３号公報には、粒径制御の問題を克服し、高解像度を達成するために乳化重合／凝集法によるトナーの製造方法が提案されている。しかしながら、この方法に於いても凝集工程で導入できるワックスの量に限界があり、低温定着性に関しては必ずしも十分な改良効果は得られていない。
【０００４】
特開平１０−２６８４２号公報には、乳化重合により得られた重合体一次粒子を凝集し、得られた凝集粒子の表面に樹脂微粒子を固着してなる、所謂カプセルトナーが開示されており、必ずしも常に十分な性能が得られるとは言えないが、低温定着性と高解像度化が図られている。
一方、近年カラープリンターの普及に伴い、カラー着色剤を有するトナーも種々のものが開発されているが、着色剤によっては、その化合物の物性等により帯電性の制御が困難なものがある。
【０００５】
例えば、特開２０００−１９７８２号公報には、特定の化合物を含有する正帯電性トナーが開示されており、該化合物は正帯電性が強く、赤色トナー用の着色剤として使用する他に、黒色トナーの添加物（正帯電性を付与する物質）として使用可能であることが示されている。同公報に開示された色素は、マゼンタ顔料として使用した場合、分光反射特性、分光透過特性が理想的なマゼンタ色に近く、ＯＨＰ用シート上の画像透明性に優れていることが知られており、マゼンタトナー用着色剤として好適である。しかしながら、これら色素を用いた場合でも、製造法によっては、上記のように解像性や低温定着性が不十分になり、また特に、負帯電性トナーとして使用する場合に帯電量の制御が困難であり、結果としてかぶりが出たり、画像濃度の調整が困難な場合があった。
【０００６】
【発明が解決しようとする課題】
本発明は、従来用いられていた負帯電性マゼンタトナーの欠点を克服し、正帯電性の強い化合物を着色剤として含有していても十分な負帯電量を持ち、さらに高解像度、低温定着性、耐ホットオフセット性を満足させる負帯電性のマゼンタトナーを提供することを目的とする。
【課題を解決するための手段】
本発明の要旨は、下記一般式（Ｉ）で表される化合物の正帯電性着色剤一次粒子及び重合体一次粒子を分散させてなる分散液中で粒子凝集体を形成し、該粒子凝集体の分散液中に、下記一般式（Ｉ）で表わされる化合物を始めとする正帯電性着色剤を含有しない樹脂微粒子を分散させてなる微粒子分散液を混合して凝集処理することにより、前記粒子凝集体に前記樹脂微粒子を付着又は固着せしめることを特徴とする負帯電性マゼンタトナーの製造方法に存する。
【０００７】
【化５】
（一般式（Ｉ）において、Ａ、Ｂは置換基を有していても良い芳香環を表す。Ｒ1は、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数５以下の炭化水素基、炭素数５以下のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基を表す。）
【０００９】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明のマゼンタトナーは、マゼンタ着色剤を含有する樹脂粒子に、着色剤を含まない樹脂微粒子を付着または固着してなるものであり、トナー中には必要に応じて、ワックス、帯電制御剤、及び流動化剤その他の添加剤を含むものである。また、本発明のマゼンタトナーは負帯電性を有する。
本発明のマゼンタトナーに用いられるマゼンタ着色剤を含有する樹脂粒子は、粉砕法によって得られたものであっても良いし、重合法によって得られたものであっても良いが、トナーの離型性を高めるために離型剤（ワックス）を用いる場合、ワックスの含有量を多くできることから、重合法によって得られた樹脂粒子を用いるのが好ましい。
【００１０】
本発明に用いられるマゼンタ着色剤を含有する樹脂粒子を、重合法によって得る場合、トナーの製造における重合の種類としては典型的には、懸濁重合法と乳化重合凝集法があり、いずれの方法も用いることができる。
懸濁重合も乳化重合も、モノマーを液中に分散して重合を行うが、懸濁重合においては、通常、モノマーと共に着色剤を分散液中に存在させる。そして重合開始剤として油溶性のものを用い、液中のモノマー等からなる油滴の大きさ（３〜１５μｍ）がほぼ維持された重合体となり、これを着色剤を含有する樹脂粒子として用いる。
【００１１】
一方、乳化重合においては、通常、重合開始剤として水溶性のものを用い、０．１〜２μｍの重合体一次粒子が形成される。この重合体一次粒子を凝集させて３〜１５μｍの粒子凝集体とし、これを着色剤を含有する樹脂粒子として用いるが、粒子凝集体に着色剤を含有させる方法としては、重合体一次粒子と共に、着色剤一次粒子を凝集させる方法、着色剤一次粒子をシードとして重合体一次粒子を製造する方法、及びこれらの併用がある。
トナーの形状を変化させることが容易な点では乳化重合凝集法によるものが有効である。
以下、好ましい実施態様として、乳化重合凝集法によって着色剤を含有する樹脂粒子を製造する場合を例により説明する。
【００１２】
本発明で用いられるワックスは、公知のワックス類の任意のものを使用することができるが、具体的には低分子量ポリエチレン、低分子量ポリプロピレン、共重合ポリエチレン等のオレフィン系ワックス、パラフィンワックス、ベヘン酸ベヘニル、モンタン酸エステル、ステアリン酸ステアリル等の長鎖脂肪族基を有するエステル系ワックス、水添ひまし油カルナバワックス等の植物系ワックス、ジステアリルケトン等の長鎖アルキル基を有するケトン、アルキル基を有するシリコーン、ステアリン酸等の高級脂肪酸、長鎖脂肪酸アルコール、ペンタエリスリトール等の長鎖脂肪酸多価アルコール、及びその部分エステル体、オレイン酸アミド、ステアリン酸アミド等の高級脂肪酸アミド、等が例示される。
【００１３】
これらのワックスの中で定着性を改善するためにより好ましいのは、融点が１００℃以下のワックスであり、更に好ましいワックスの融点は４０〜９０℃の範囲、特に好ましいのは５０〜８０℃の範囲である。融点が１００℃を越えると低温定着化の効果が乏しくなる。
また更に、長鎖脂肪族基を有するエステル系ワックスが好ましく、エステル系ワックスの中でも炭素数が２０〜６０のものが更に好ましい。
これらワックスは単独で使用するのみならず、混合して用いても良く、特にエステル系ワックスを用いる場合には、炭素数の異なる複数種のエステルを混合して用いるのが好ましい。
【００１４】
上記ワックスは、バインダー樹脂１００重量部に対して通常１〜４０重量部で用いられ、好ましくは５〜３５重量部、更に好ましくは１０〜３０重量部で用いられる。ワックスのトナー中における存在状態は特に限定されず、着色剤一次粒子や重合体一次粒子と共に凝集粒子を形成するワックス一次粒子として用いても良く、また、重合体一次粒子、着色剤一次粒子、あるいは帯電制御剤一次粒子中に包含される形で用いても良いが、好ましくは、ワックスは重合体一次粒子の内部に包含された構造を持つことであり、更に好ましくはワックス微粒子を樹脂のシード重合に供し、ワックスをシードとして重合体一次粒子中に含むものである。本発明で用いるワックス微粒子は、上記ワックスを公知のカチオン界面活性剤、アニオン界面活性剤、ノニオン界面活性剤の中から選ばれる少なくともひとつの乳化剤の存在下で乳化して得られる。これらの界面活性剤は２種以上を併用してもよい。
【００１５】
カチオン界面活性剤の具体例としては、ドデシルアンモニウムクロライド、ドデシルアンモニウムブロマイド、ドデシルトリメチルアンモニウムブロマイド、ドデシルピリジニウムクロライド、ドデシルピリジニウムブロマイド、ヘキサデシルトリメチルアンモニウムブロマイド、等があげられる。
【００１６】
また、アニオン界面活性剤の具体例としては、ステアリン酸ナトリウム、ドデカン酸ナトリウム、等の脂肪酸石けん、硫酸ドデシルナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等があげられる。
【００１７】
さらに、ノニオン界面活性剤の具体例としては、ポリオキシエチレンドデシルエーテル、ポリオキシエチレンヘキサデシルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンソルビタンモノオレアートエーテル、モノデカノイルショ糖、等があげられる。
【００１８】
ワックス微粒子をシードとして用いる場合、ワックスの平均粒径は、０．０１〜３μｍが好ましく、さらに好ましくは０．０３〜１μｍ、特に０．０５〜０．８μｍのものが好適に用いられる。なお、平均粒径は、例えば日機装社製マイクロトラックＵＰＡを用いて測定することができる。ワックス微粒子の平均粒径が３μｍよりも大きい場合にはシード重合して得られる重合体一次粒子の平均粒径が大きくなり、その結果、それを用いて粒度分布のそろった小粒径トナーを製造することが困難になるので、トナーとして高解像度を要求される用途には不適当である。また、ワックス微粒子の平均粒径が０．０１μｍよりも小さい場合には、シード重合後の重合体一次粒子中のワックス含有量が低くなりすぎるためワックスの効果が低くなる。
【００１９】
乳化重合をするに当たっては、逐次、ブレンステッド酸性基（以下、単に酸性基と称することがある）を有するモノマーもしくはブレンステッド塩基性基（以下、単に塩基性基と称することがある）を有するモノマー、及び、ブレンステッド酸性基及びブレンステッド塩基性基をいずれも有さないモノマー（以下、その他のモノマーと称することがある）とを添加する事により、重合を進行させる。この際、モノマー同士は別々に加えても良いし、予め複数のモノマー混合しておいて添加しても良い。更に、モノマー添加中にモノマー組成を変更することも可能である。また、モノマーはそのまま添加しても良いし、予め水や界面活性剤などと混合、調整した乳化液として添加することもできる。界面活性剤としては、前記の界面活性剤から１種又は２種以上の併用系が選択される。
シード乳化重合を進行するにあたっては、界面活性剤を一定量ワックスエマルションに添加してもかまわない。
【００２０】
本発明に用いられるブレンステッド酸性基を有するモノマーとしては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ケイ皮酸、等のカルボキシル基を有するモノマー、スルホン化スチレン等のスルホン酸基を有するモノマー、ベンゼンスルホンアミド等のスルホンアミド基を有するモノマー等があげられる。
【００２１】
また、ブレンステッド塩基性基を有するモノマーとしては、アミノスチレン等のアミノ基を有する芳香族ビニル化合物、ビニルピリジン、ビニルピロリドン、等の窒素含有複素環含有モノマー、ジメチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、等のアミノ基を有する（メタ）アクリル酸エステル、等が挙げられる。
また、これら酸性基を有するモノマー及び塩基性基を有するモノマーは、それぞれ対イオンを伴って塩として存在していても良い。
【００２２】
その他のモノマーとしては、スチレン、メチルスチレン、クロロスチレン、ジクロロスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｎ−ノニルスチレン、等のスチレン類、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ｎ−ブチル、アクリル酸イソブチル、アクリル酸ヒドロキシエチル、アクリル酸エチルヘキシル、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ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ヒドロキシエチル、メタクリル酸エチルヘキシル、等の（メタ）アクリル酸エステル、ジビニルベンゼン、１、６−ヘキサンジオールジアクリレート、等の架橋剤、を挙げることができる。
【００２３】
これらのモノマーは単独、または混合して用いられるが、その際、重合体のガラス転移温度が４０〜８０℃となることが好ましい。ガラス転移温度が８０℃を越えると定着温度が高くなりすぎたり、ＯＨＰ透明性の悪化が問題となることがあり、一方重合体のガラス転移温度が４０℃未満の場合は、トナーの保存安定性が悪くなりすぎて問題を生じる。本発明では、酸性極性基を持つモノマーとしてアクリル酸が、その他のモノマーとしてスチレン、アクリル酸エステル、及びメタクリル酸エステルが好適に使用される。
【００２４】
重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、等の過硫酸塩、及び、これら過硫酸塩を一成分として酸性亜硫酸ナトリウム等の還元剤を組み合わせたレドックス開始剤、過酸化水素、４，４‘−アゾビスシアノ吉草酸、ｔ−ブチルハイドロパーオキサイド、クメンハイドロペーオキサイド、等の水溶性重合開始剤、及び、これら水溶性重合性開始剤を一成分として第一鉄塩等の還元剤と組み合わせたレドックス開始剤系、過酸化ベンゾイル、２，２‘−アゾビス−イソブチロニトリル、等が用いられる。これら重合開始剤はモノマー添加前、添加と同時、添加後のいずれの時期に重合系に添加しても良く、必要に応じてこれらの添加方法を組み合わせても良い。
【００２５】
本発明では、必要に応じて公知の連鎖移動剤を使用することができるが、その様な連鎖移動剤の具体的な例としては、ｔ―ドデシルメルカプタン、２−メルカプトエタノール、ジイソプロピルキサントゲン、四塩化炭素、トリクロロブロモメタン、等があげられる。連鎖移動剤は単独または２種類以上の併用でもよく、重合性単量体に対して０〜５重量％用いられる。
【００２６】
重合体一次粒子の平均粒径は、通常０．０５〜３μｍの範囲であり、好ましくは０．１〜１μｍ、更に好ましくは０．１〜０．５μｍである。なお、平均粒径は、例えばＵＰＡを用いて測定することができる。粒径が０．０５μｍより小さくなると凝集速度の制御が困難となり好ましくない。また、３μｍより大きいと凝集して得られるトナー粒径が大きくなりすぎるため、トナーとして高解像度を要求される用途には不適当である。
【００２７】
本発明では、重合体一次粒子を得る際に着色剤をシードとして用いたり、着色剤をモノマー又はワックスに溶解又は分散させて用いたりしても構わないが、重合体一次粒子と同時に着色剤一次粒子を凝集させて粒子凝集体を形成し、着色剤を含有する樹脂粒子とすることが好ましい。必要に応じて２種類以上の重合体一次粒子を用いても良い。
【００２８】
次に、本発明に用いられる着色剤一次粒子には、下記一般式（Ｉ）で表される化合物を含むことを特徴としている。一般式（Ｉ）で表される化合物は、マゼンタ着色剤として公知のものであり、これら化合物が、正帯電性の傾向にあることは、特開２０００−１９７８２号公報に記載されている。
【００２９】
【化６】
（一般式（Ｉ）において、Ａ、Ｂは置換基を有していても良い芳香環を表す。Ｒ1は、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数５以下の炭化水素基、炭素数５以下のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基を表す。）
一般式（Ｉ）において、Ａ、Ｂはベンゼン環、ナフタレン環、アントラセン環、フェナントレン環等の芳香環を表すが、これらの内、ベンゼン環又はナフタレン環が好ましく、更にＢがベンゼン環であり、Ａがナフタレン環であるのが好ましい。
また、一般式（Ｉ）において、置換基を有していても良い芳香環（Ａ、Ｂ）における置換基としては、ハロゲン原子、ニトロ基、シアノ基、炭化水素基、アルコキシ基、アルキルチオ基、アミノ基、窒素原子上が置換されていても良いアミノ基、窒素原子上が置換されていても良いアミノカルボニル基、窒素原子上が置換されていても良いアミノスルホニル基、アルキルスルホニル基、アルコキシスルホニル基等、通常の安定な置換基が挙げられるが、好ましくは、置換基の式量が１２〜３００のものが好ましい。
【００３１】
これらの置換基の内、ハロゲン原子、ニトロ基、シアノ基、炭素数５以下の炭化水素基、炭素数５以下のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基が更に好ましい。
より具体的には、下記一般式（ＩＩ）で表される化合物を好ましく用いることが出来る。これらの化合物は色目及び製造上有利であ。
【００３２】
【化７】
（一般式（ＩＩ）において、Ｒ1〜Ｒ4は各々独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数５以下の炭化水素基、炭素数５以下のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基を表す。）
【００３４】
ここで、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基における窒素上の置換基としては、フェニル基、トリル基等のアリール基、メチル基、エチル基、１−プロピル基、１−ブチル基等のアルキル基、ベンジル基等のアラルキル基、ハロゲン原子あるいはアルコキシ基で置換されたアリール基、ハロゲン原子あるいはアルコキシ基で置換されたアルキル基等が挙げられる。
【００３５】
さらには一般式（ＩＩ）において、Ｒ1が水素原子であり、Ｒ2がメトキシ基でありＲ3が水素原子であり、Ｒ4が塩素原子である化合物を用いることが、分光反射特性、重合性単量体中への分散性、着色剤分散液への加工性の点で好ましい。
【００３６】
上記の一般式（Ｉ）で表される化合物を乳化剤の存在下で水中に乳化させエマルションの状態で用いる場合、平均粒径としては、０．０１〜３μｍのものを用いるのが好ましい。
上記一般式（Ｉ）で表される化合物と、他のマゼンタ着色剤とを混合して用いても良い。その場合、一般式（Ｉ）で表される化合物の割合は、マゼンタ着色剤全体に対し、通常３０％以上であり、好ましくは５０％以上であり、更に好ましくは７０％以上である。
【００３７】
帯電制御剤としては、負帯電性とカラートナーへの適応性（帯電制御剤自体が無色ないしは淡色でトナーへの色調障害がないこと）を勘案すると、サリチル酸もしくはアルキルサリチル酸のクロム、亜鉛、アルミニウムなどとの金属塩、金属錯体や、ベンジル酸の金属塩、金属錯体、アミド化合物、フェノール化合物、ナフトール化合物、フェノールアミド化合物、４，４’−メチレンビス〔２−〔Ｎ−（４−クロロフェニル）アミド〕−３−ヒドロキシナフタレン〕等のヒドロキシナフタレン化合物が好ましい。その使用量はトナーに所望の帯電量により決定すればよいが、通常はバインダー樹脂１００重量部に対し０．０１〜１０重量部用い、更に好ましくは０．１〜１０重量部用いる。
【００３８】
本発明では、トナー中に帯電制御剤を含有させる方法として、重合体一次粒子を得る際に、帯電制御剤をシードとして用いたり、帯電制御剤をモノマー又はワックスに溶解又は分散させて用いたり、重合体一次粒子と同時に帯電制御剤一次粒子を凝集させて粒子凝集体を形成し、着色剤を含有する樹脂粒子としても構わないが、着色剤を含まない樹脂微粒子を得る際に、帯電制御剤をシードとして用いたり、モノマーに溶解または分散させて用いるか、樹脂微粒子を付着または固着する工程の前または工程と同時にまたは工程の後に帯電制御剤一次粒子を付着又は固着することが好ましい。この場合帯電制御剤も水中で平均粒径０．０１〜３μｍのエマルション（帯電制御剤一次粒子）として使用する。
【００３９】
本発明のトナーの製造方法において、着色剤を含んだ樹脂粒子である粒子凝集体（トナー芯材）を得る好ましい一態様としては、ワックスをシードとした重合体一次粒子、及び着色剤一次粒子をエマルションとして混合し、凝集させて粒子凝集体を得るものである。
【００４０】
次に、本発明のマゼンタトナーは、上述の粒子凝集体に更に、樹脂微粒子を被覆（付着又は固着）してトナー粒子を形成するものである。樹脂微粒子としては、好ましくは体積平均粒径が０．０２〜２μｍ、更に好ましくは０．０５〜１．５μｍであって、前述の重合体一次粒子に用いられるモノマーと同様なモノマーを重合して得られたもの等を用いることができる。低温定着性と保存安定性を両立させるためには、重合体のガラス転移温度は、樹脂微粒子が前述の重合体一次粒子に比べ高くなるように設定するのが良い。樹脂微粒子は、乳化剤（前述の界面活性剤）により水または水を主体とする液中に分散してエマルションとして用いるが、乳化重合法によって得られた樹脂微粒子を用いることが好ましい。
また、粒子凝集体に樹脂微粒子を被覆するに先だって、重合体一次粒子のガラス転移点以上の温度で粒子凝集体を融着してもよい。また、粒子凝集体への樹脂微粒子の付着又は固着は、複数回に分けて行っても良い。
【００４１】
また、該樹脂微粒子としては、ワックスを含んでいても良く、上述のワックスをシードとして乳化重合を行ったものでもよい。但し、トナーの最外殻は、ワックスを含有しない方が好ましいので、粒子凝集体をワックスを含んだ樹脂微粒子を用いて被覆した場合は、更にその外側にワックスを含まない樹脂微粒子で被覆したものが好ましい。
【００４２】
また、負帯電性を向上させるためには、一般式（Ｉ）で表される化合物をトナーの最外殻には含まない必要があるので、粒子凝集体を１段の樹脂微粒子で被覆する場合には、通常、該樹脂微粒子には一般式（Ｉ）で表される化合物を含まないものを用いる。また、粒子凝集体を２段以上の樹脂微粒子で被覆する場合には、内側の樹脂微粒子には一般式（Ｉ）で表される化合物を含んでいてもよい。しかしながら、負帯電性を確実にするには、いずれの樹脂微粒子にも一般式（Ｉ）で表される化合物を含まないものが好ましい。
同様の理由から、粒子凝集体を樹脂微粒子で被覆する際に、樹脂微粒子と併せて、一般式（Ｉ）で表される化合物からなる着色剤微粒子を被覆材としては用いないことが好ましい。
従って、トナー外殻部にもマゼンタ着色剤が必要とされる場合は、着色剤としては一般式（Ｉ）で表される化合物以外のものを用いるのが好ましい。
【００４３】
また、本発明のトナーは、必要により流動化剤等の添加剤と共に用いることができ、そのような流動化剤としては、具体的には、疎水性シリカ、酸化チタン、酸化アルミニウム等の微粉末を挙げることができ、通常、バインダー樹脂１００重量部に対して、０．０１〜５重量部、好ましくは０．１〜３重量部用いられる。
【００４４】
さらに、本発明のトナーは、マグネタイト、フェライト、酸化セリウム、チタン酸ストロンチウム、導電性チタニア等の無機微粉末やスチレン樹脂、アクリル樹脂等の抵抗調節剤や滑剤などが内添剤又は外添剤として用いられる。これらの添加剤の使用量は所望する性能により適宜選定すれば良く、通常バインダー樹脂１００重量部に対し０．０５〜１０重量部程度が好適である。
【００４５】
本発明の負帯電性マゼンタトナーは２成分系現像剤又は非磁性１成分系現像剤のいずれの形態で用いてもよい。２成分系現像剤として用いる場合、キャリアとしては、鉄粉、マグネタイト粉、フェライト粉等の磁性物質またはそれらの表面に樹脂コーティングを施したものや磁性キャリア等公知のものを用いることができる。しかしながら、２成分系現像剤においては、キャリアを選択することによりトナーの負帯電性を確保することができる場合もあるので、本発明は、キャリアーを用いない１成分系現像剤への適用が効果的である。
また、磁性現像剤は、磁性粉を用いるためマゼンタトナーには適用困難であることから、非磁性現像剤への適用が好ましい。従って、本発明は、非磁性１成分系現像剤への適用が特に好ましい。
【００４６】
【実施例】
以下に実施例により本発明を具体的に説明する。
以下の例で「部」とあるのは「重量部」を意味する。また、重合体粒子の平均粒径、分子量、ガラス転移温度（Ｔｇ）、定着温度幅、及び帯電量は、それぞれ下記の方法により測定した。
【００４７】
平均粒径：日機装社製マイクロトラックＵＰＡ、またはコールター社製コールターカウンターマルチサイザーＩＩ型（コールターカウンターと略）により測定した。
重量平均分子量：ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。（溶媒：ＴＨＦ、検量線：標準ポリスチレン）
ガラス転移温度（Ｔｇ）：パーキンエルマー社製ＤＳＣ７により測定した。
【００４８】
定着温度幅：未定着のトナー像を担持した記録紙を用意し、加熱ローラの表面温度を１００℃から２２０℃まで変化させ、定着ニップ部に搬送し、排出されたときの定着状態を観察した。定着時に加熱ローラにトナーのオフセットが生じず、定着後の記録紙上のトナーが十分に記録紙に接着している温度領域を定着温度領域とした。定着機の加熱ローラは、離型層がＰＦＡ（テトラフルオロエチレンーパーフルオロアルキルビニルエーテル共重合体）でできており、シリコンオイルの塗布なしで、ニップ幅は４ｍｍで評価した。定着速度は１２０ｍｍ／ｓと３０ｍｍ／ｓで実施した。
【００４９】
１成分帯電量：トナーを非磁性１成分の現像槽（カシオ社製ＣｏｌｏｒＰａｇｅＰｒｅｓｔｏＮ４現像槽）に投入し、ローラーを一定数回転させた後、ローラー上のトナーを吸引し、帯電量と吸引したトナー重量から単位重量あたりの帯電量を求めた。
２成分帯電量：トナー４部とフェライトキャリア（アクリル系重合体による樹脂コート）９６部を１分間混合攪拌し、東芝製ブローオフ帯電量測定機を用いて帯電量を測定した。
【００５０】
・乳化重合凝集法による例
（ワックス分散液の作製）
ワックス分散液１００部として、ベヘン酸ベヘニル３０部をＮ−ドデシルベンゼンスルホン酸ナトリウム１．６７部の存在下に高圧剪断をかけて乳化し、エステルワックスの分散液を得た。得られた分散液の固形分濃度は３０％であり、ＵＰＡで測定した平均粒径は２２０ｎｍであった（これをワックス分散液Ａとする）。
【００５１】
（重合体一次粒子分散液の作製）
攪拌装置、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えたガラス製反応器にワックス分散液Ａ ３５部、脱塩水 ４００部を仕込み、窒素気流下で９０℃に昇温した。
その後、下記のモノマー類、乳化剤水溶液、開始剤を添加し、６．５時間乳化重合を行った。
【００５２】
【表１】
重合反応終了後冷却し、乳白色の重合体分散液を得た。得られた重合体の重量平均分子量は９８，０００、ＵＰＡで測定した平均粒子径は１９０ｎｍ、Ｔｇは５７℃であった。得られたエマルションの断面をＴＥＭで観察したところ、ワックスが樹脂で内包化されているのが観察された（これを重合体一次粒子分散液Ａとする）。
【００５４】
架橋剤ＨＤＤＡをジビニルベンゼン（ＤＶＢ、０．４部）に変える以外重合体一次粒子分散液Ａと同様に重合して、乳白色の重合体分散液を得た。得られた重合体の重量平均分子量は１５０，０００、ＵＰＡで測定した平均粒子径は１９０ｎｍ、Ｔｇは５７℃であった。得られたエマルションの断面をＴＥＭで観察したところ、ワックスが樹脂で内包化されているのが観察された（これを重合体一次粒子分散液Ｂとする）。
【００５５】
（樹脂微粒子分散液の作製）
攪拌装置、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えたガラス製反応器に１０％Ｓ−ＤＢＳ水溶液４．３部、脱塩水 ４００部を仕込み、窒素気流下で９０℃に昇温した。
その後、下記のモノマー類、乳化剤水溶液、開始剤を添加し、６．５時間乳化重合を行った。
【００５６】
【表２】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
トリクロロブロモメタン ０．５部
ＤＶＢ ０．４部
（乳化剤水溶液）
１０％Ｓ−ＤＢＳ水溶液 ２．２部
脱塩水 ２５部
（開始剤）
８％過酸化水素水溶液 １０．６部
８％アスコルビン酸水溶液 １０．６部
【００５７】
重合反応終了後冷却し、乳白色の重合体分散液を得た。得られた重合体の重量平均分子量は１１０，０００、ＵＰＡで測定した平均粒子径は１２０ｎｍ、Ｔｇは８６℃であった（これを樹脂微粒子分散液Ａとする）。
【００５８】
（着色剤微粒子分散液の作製）
着色剤微粒子分散液１００部として、ピグメントレッド２３８ ２０部を、アルキルベンゼンスルホン酸塩２．５部の存在下にサンドグラインダーミルで６時間分散処理し、着色剤微粒子分散液を得た。得られた分散液の固形分濃度は２０％であり、ＵＰＡで測定した平均粒径は１８０ｎｍであった（これを着色剤微粒子分散液Ａとする）。
【００５９】
（帯電制御剤微粒子分散液の作製）
帯電制御剤微粒子分散液１００部として、４，４’−メチレンビス〔２−〔Ｎ−（４−クロロフェニル）アミド〕−３−ヒドロキシナフタレン〕２０部をアルキルナフタレンスルフォン酸塩4部の存在下にサンドグラインダーミルにて分散し、帯電制御剤微粒子分散液を得た。得られた分散液の固形分濃度は２４％であり、ＵＰＡで測定した平均粒径は２００ｎｍであった（これを帯電制御剤微粒子分散液Ａとする）。
【００６０】
【表３】
[実施例−１]
（トナーの製造）
重合体一次粒子分散液Ａ ９０部（固形分として）
樹脂微粒子分散液Ａ １０部（固形分として）
着色剤微粒子分散液Ａ ６．７部（固形分として）
帯電制御剤微粒子分散液Ａ ２部（固形分として）
Ｓ−ＤＢＳ水溶液 ０．５部（固形分として）
【００６１】
上記の各成分を以下のような順序で混合した。
重合体一次粒子分散液ＡにＳ−ＤＢＳ水溶液を添加して、均一に混合してから着色剤微粒子分散液Ａを添加し、均一に混合した。
こうして得られた混合分散液をバッフル付きのアンカー翼で攪拌しながら３０℃で硫酸アルミニウム水溶液を添加した（固形分として０．６部）。硫酸アルミニウム水溶液添加後の混合分散液の平均粒径は２μｍであった。その後、攪拌しながら５５℃に昇温して１時間保持し、更に５８℃に昇温して１時間保持した。その後帯電制御剤微粒子分散液Ａ、樹脂微粒子分散液Ａ、硫酸アルミニウム水溶液（固形分として０．１部）の順に添加した。１時間半保持した後、１０％Ｓ−ＤＢＳ水溶液（固形分として３部）を添加してから９５℃に昇温し、４時間保持した。その後冷却し、桐山ロートで濾過、水洗し、凍結乾燥することによりトナーを得た（これをトナーＡとする）。
【００６２】
トナー１００部に対して、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナーを得た（これを現像用トナーＡとする）。
得られたトナーＡのコールターカウンターによる体積平均粒径は７．５μｍ、また、体積粒径の５μｍ以下の割合は１．５％、１５μｍ以上の割合は０．２％であり、体積平均粒径と数平均粒径の比は１．１１であり、粒径分布は非常に良好であった。
【００６３】
現像用トナーＡの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは２００〜２２０以上℃で定着し、定着速度３０ｍｍ／ｓでは１６０〜１９０℃で定着した。トナーＡの１成分帯電量は‐２０μＣ／ｇ、現像用トナーＡの１成分帯電量は‐２５μＣ／ｇ、現像用トナーＡの２成分帯電量は−２３μＣ／ｇであった。
【００６４】
【表４】
[比較例−１]
（トナーの製造）
重合体一次粒子分散液Ｂ １１０部（固形分として）
着色剤微粒子分散液Ａ ６．７部（固形分として）
帯電制御剤微粒子分散液Ａ ２部（固形分として）
Ｓ−ＤＢＳ水溶液 ０．６５部（固形分として）
【００６５】
上記の各成分を以下のような順序で混合した。
重合体一次粒子分散液ＢにＳ−ＤＢＳ水溶液を添加して、均一に混合してから着色剤微粒子分散液Ａを添加し、均一に混合した。
こうして得られた混合分散液をバッフル付きのアンカー翼で攪拌しながら２０℃で硫酸アルミニウム水溶液を添加した（固形分として０．５部）。その後、攪拌しながら５５℃に昇温して１時間保持し、更に５８℃に昇温して１時間保持した。その後帯電制御剤微粒子分散液Ａを添加し、更に１０分間保持した後、１０％Ｓ−ＤＢＳ水溶液（固形分として３部）を添加してから９５℃に昇温し、５時間保持した。その後冷却し、桐山ロートで濾過、水洗し、凍結乾燥することによりトナーを得た（これをトナーＢとする）。
【００６６】
トナー１００部に対して、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナーを得た（これを現像用トナーＢとする）。
得られたトナーＢのコールターカウンターによる体積平均粒径は６．２μｍ、また、体積粒径の５μｍ以下の割合は１．５％、体積平均粒径と数平均粒径の比は１．１６であった。
【００６７】
現像用トナーＢの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１５８〜２００℃以上で定着し、定着速度３０ｍｍ／ｓでは１２３〜１８２℃で定着した。トナーＢの１成分帯電量は＋１５μＣ／ｇ、現像用トナーＢの１成分帯電量は＋１１μＣ／ｇであった。
・懸濁重合法による例
（樹脂粒子の作製）
【００６８】
【表５】
スチレン ６０部
ブチルアクリレート ３９．６部
ジビニルベンゼン ０．４部
ピグメントレッド２３８ ４部
パラフィンワックス（日本精蝋製 ＬＵＶＡＸ−１２６６） ５部
分散剤（楠本化成製 ディスパロン）
重合開始剤（和光純薬製 Ｖ−６５）
上記組成を、常法により混合分散してモノマー混合物を調整する。別に、
【００６９】
【表６】
リン酸三カルシウム ２５部
ポリアクリル酸ナトリウム ０．０５部
塩化カルシウム ２００部
脱塩水 ３００部
の混合分散液を用意しておき、これにモノマー混合物を添加して懸濁液を調整し、常法により懸濁重合して、酸洗浄・濾過・水洗浄・乾燥をして、ＭＷ３．３万、Ｔｇ４０℃の着色剤を含む樹脂粒子を得た（樹脂粒子Ｃ）。
【００７０】
[実施例−２]
（トナーの製造）
樹脂粒子Ｃ １００部
樹脂微粒子分散液Ａ １０部（固形分として）
帯電制御剤微粒子分散液Ａ ２部（固形分として）
脱塩水 ６００部
樹脂微粒子分散液Ａに脱塩水を添加して、均一に混合してから樹脂粒子Ｃを徐々に添加し、均一に分散した。得られた混合分散液を攪拌下ｐＨを３．０に調製し、続いて４０℃に昇温して２時間保持した。その後冷却し、桐山ロートで濾過、水洗し、凍結乾燥することによりトナーを得た（これをトナーＣとする）。
トナー１００部に対して、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナーを得た（これを現像用トナーＣとする）。
得られたトナーＣのコールターカウンターによる体積平均粒径は７．５μｍ、また、体積粒径の５μｍ以下の割合は５％、体積平均粒径と数平均粒径の比は１．３であった。
【００７１】
現像用トナーＣの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１４０〜２００℃以上で定着し、定着速度３０ｍｍ／ｓでは１２０〜１７０℃で定着した。トナーＣの１成分帯電量は−２５μＣ／ｇ、現像用トナーＣの１成分帯電量は−２８μＣ／ｇであった。
【００７２】
【発明の効果】
本発明により、低温定着性、耐ホットオフセット性及び負帯電性に優れたマゼンタトナーを提供することができる。また、特に重合法により製造した場合には粒径が小さく、粒度分布がシャープであり、高解像度の画像形成に適している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a negatively chargeable magenta toner used in electrophotographic copying machines and printers. More specifically, the present invention relates to a negatively chargeable magenta toner excellent in fixability, hot offset resistance, and chargeability.
[0002]
[Prior art]
Toner for electrostatic image development that has been widely used in electrophotography in the past is a binder resin such as styrene / acrylate copolymer or polyester, a colorant such as carbon black or pigment, a charge control agent, and / or Alternatively, it has been produced by melting and kneading a mixture containing a magnetic substance with an extruder, and then pulverizing and classifying the mixture. However, the conventional toner obtained by the melt-kneading / pulverization method as described above has a limit in controlling the particle size of the toner, and substantially manufactures a toner having an average particle size of 10 μm or less, particularly 8 μm or less with a high yield. However, it was difficult to achieve the high resolution required for electrophotography in the future.
[0003]
Further, in order to achieve low-temperature fixability, a method of blending a wax having a low softening point into the toner during kneading has been proposed, but in the kneading / pulverization method, blending of about 5% is the limit, A toner having sufficient low-temperature fixing performance could not be obtained. Japanese Patent Laid-Open No. 63-186253 proposes a toner production method by emulsion polymerization / aggregation in order to overcome the problem of particle size control and achieve high resolution. However, even in this method, there is a limit to the amount of wax that can be introduced in the coagulation step, and a sufficient improvement effect is not necessarily obtained with respect to low-temperature fixability.
[0004]
JP-A-10-26842 discloses a so-called capsule toner in which polymer primary particles obtained by emulsion polymerization are aggregated, and resin fine particles are fixed to the surface of the obtained aggregated particles. Although sufficient performance cannot always be obtained, low-temperature fixability and high resolution have been achieved.
On the other hand, with the widespread use of color printers in recent years, various toners having a color colorant have been developed. However, depending on the colorant, it is difficult to control the chargeability due to the physical properties of the compound.
[0005]
For example, Japanese Patent Laid-Open No. 2000-19784GazetteDiscloses a positively chargeable toner containing a specific compound, and the compound has a strong positive chargeability. In addition to being used as a colorant for red toner, an additive for black toner (positive chargeability is disclosed). It is shown that it can be used as a substance to be applied). When used as a magenta pigment, the dye disclosed in the publication is known to have a spectral reflection characteristic and a spectral transmission characteristic that are close to an ideal magenta color and excellent in image transparency on an OHP sheet. Suitable as a colorant for magenta toner. However, even when these dyes are used, depending on the production method, the resolution and the low-temperature fixability are insufficient as described above, and it is particularly difficult to control the charge amount when used as a negatively chargeable toner. And as a result the foggingGo outIn some cases, it is difficult to adjust the image density.
[0006]
[Problems to be solved by the invention]
The present invention overcomes the disadvantages of negatively chargeable magenta toners that have been used in the past, has a sufficient negative charge amount even if it contains a highly positively charged compound as a colorant, and further has high resolution and low temperature fixability. An object of the present invention is to provide a negatively chargeable magenta toner satisfying hot offset resistance.
[Means for Solving the Problems]
The gist of the present invention is a compound represented by the following general formula (I)ofA compound represented by the following general formula (I) is formed in a dispersion obtained by dispersing primary particles of positively charged colorant and primary particles of a polymer, and dispersed in the dispersion of the particles.Starting withA negatively chargeable magenta characterized by adhering or fixing the resin fine particles to the particle aggregate by mixing and aggregating a fine particle dispersion in which resin fine particles not containing a positively chargeable colorant are dispersed. It exists in the manufacturing method of a toner.
[0007]
[Chemical formula 5]
(In general formula (I), A and B represent an aromatic ring which may have a substituent. R1Is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, an aminosulfonyl group that may be substituted on the nitrogen atom, or a nitrogen atom. The aminocarbonyl group which may be substituted is represented. )
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The magenta toner of the present invention is formed by adhering or fixing resin fine particles not containing a colorant to resin particles containing a magenta colorant. In the toner, a wax, a charge control agent, And fluidizing agents and other additives. Further, the magenta toner of the present invention has negative chargeability.
The resin particles containing the magenta colorant used in the magenta toner of the present invention may be obtained by a pulverization method or may be obtained by a polymerization method. When a release agent (wax) is used to enhance the properties, it is preferable to use resin particles obtained by a polymerization method because the wax content can be increased.
[0010]
When the resin particles containing the magenta colorant used in the present invention are obtained by a polymerization method, typically, there are a suspension polymerization method and an emulsion polymerization aggregation method as the type of polymerization in the production of the toner. Can also be used.
In both suspension polymerization and emulsion polymerization, a monomer is dispersed in a liquid for polymerization. In suspension polymerization, a colorant is usually present in the dispersion together with the monomer. And an oil-soluble thing is used as a polymerization initiator, it becomes a polymer by which the magnitude | size (3-15 micrometers) of the oil droplet which consists of a monomer etc. in a liquid is substantially maintained, and this is used as a resin particle containing a coloring agent.
[0011]
On the other hand, in emulsion polymerization, a water-soluble one is usually used as a polymerization initiator, and polymer primary particles of 0.1 to 2 μm are formed. The polymer primary particles are agglomerated into particle aggregates of 3 to 15 μm and used as resin particles containing a colorant. As a method of adding a colorant to the particle aggregates, together with the polymer primary particles, There are a method of aggregating the primary colorant particles, a method of producing polymer primary particles using the primary colorant particles as a seed, and a combination thereof.
The emulsion polymerization aggregation method is effective in that it is easy to change the shape of the toner.
Hereinafter, as a preferred embodiment, a case where resin particles containing a colorant are produced by an emulsion polymerization aggregation method will be described by way of example.
[0012]
As the wax used in the present invention, any of known waxes can be used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene, paraffin wax, and behenic acid are used. Ester waxes having long chain aliphatic groups such as behenyl, montanate ester, stearyl stearate, vegetable waxes such as hydrogenated castor oil carnauba wax, ketones having long chain alkyl groups such as distearyl ketone, having alkyl groups Examples thereof include higher fatty acids such as silicone and stearic acid, long chain fatty acid alcohols, long chain fatty acid polyhydric alcohols such as pentaerythritol, partial esters thereof, higher fatty acid amides such as oleic acid amide and stearic acid amide, and the like.
[0013]
Among these waxes, a wax having a melting point of 100 ° C. or lower is more preferable in order to improve fixability, and a more preferable wax has a melting point in the range of 40 to 90 ° C., particularly preferably in the range of 50 to 80 ° C. It is. When the melting point exceeds 100 ° C., the effect of fixing at low temperature becomes poor.
Furthermore, ester waxes having a long-chain aliphatic group are preferred, and ester waxes having 20 to 60 carbon atoms are more preferred.
These waxes may be used not only alone but also in combination. In particular, when an ester wax is used, it is preferable to use a mixture of a plurality of esters having different carbon numbers.
[0014]
The wax is usually based on 100 parts by weight of the binder resin.1-40Used in parts by weight, preferably5-35Parts by weight, more preferably10-30Used in parts by weight. The presence state of the wax in the toner is not particularly limited, and may be used as wax primary particles that form aggregated particles together with the primary colorant particles or the primary polymer particles, and the primary polymer particles, primary colorant particles, or The charge control agent may be used in the form of being included in the primary particles of the charge control agent, but preferably the wax has a structure included in the interior of the polymer primary particles, and more preferably, the wax fine particles are seed-polymerized with the resin. And containing the wax as a seed in the polymer primary particles. The wax fine particles used in the present invention are obtained by emulsifying the wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants, and nonionic surfactants. Two or more of these surfactants may be used in combination.
[0015]
Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.
[0016]
Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.
[0017]
Further, specific examples of nonionic surfactants include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl And sucrose.
[0018]
When wax fine particles are used as seeds, the average particle size of the wax is0.01 to 3μm is preferred, more preferably 0.03 to 1 μm, and particularly preferably 0.05 to 0.8 μm. The average particle diameter can be measured using, for example, Nikkiso Microtrac UPA. When the average particle size of the wax fine particles is larger than 3 μm, the average particle size of the polymer primary particles obtained by seed polymerization becomes large, and as a result, a small particle size toner having a uniform particle size distribution is produced using it. Therefore, the toner is not suitable for applications requiring high resolution as a toner. On the other hand, when the average particle size of the wax fine particles is smaller than 0.01 μm, the wax content in the polymer primary particles after the seed polymerization becomes too low, and the effect of the wax becomes low.
[0019]
In emulsion polymerization, a monomer having a Bronsted acidic group (hereinafter sometimes simply referred to as an acidic group) or a monomer having a Bronsted basic group (hereinafter sometimes simply referred to as a basic group). The polymerization proceeds by adding a monomer having neither a Bronsted acidic group nor a Bronsted basic group (hereinafter sometimes referred to as other monomer). At this time, the monomers may be added separately, or a plurality of monomers may be mixed and added in advance. Further, it is possible to change the monomer composition during the monomer addition. The monomer may be added as it is, or may be added as an emulsion mixed and adjusted in advance with water or a surfactant. As the surfactant, one or two or more combined systems are selected from the above surfactants.
In proceeding with seed emulsion polymerization, a certain amount of surfactant may be added to the wax emulsion.
[0020]
Examples of the monomer having a Bronsted acidic group used in the present invention include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, and monomers having a sulfonic acid group such as sulfonated styrene. And monomers having a sulfonamide group such as benzenesulfonamide.
[0021]
Examples of the monomer having a Bronsted basic group include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocycle-containing monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, (Meth) acrylic acid ester having an amino group such as
Moreover, the monomer which has these acidic groups, and the monomer which has a basic group may exist as a salt with a counter ion, respectively.
[0022]
Other monomers include styrenes such as styrene, methyl styrene, chlorostyrene, dichlorostyrene, p-tert-butyl styrene, pn-butyl styrene, pn-nonyl styrene, methyl acrylate, ethyl acrylate , Propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate And (meth) acrylic acid esters such as ethylhexyl methacrylate, divinylbenzene, 1,6-hexanediol diacrylate, and the like.
[0023]
These monomers are used alone or in combination, and in this case, the glass transition temperature of the polymer is preferably 40 to 80 ° C. If the glass transition temperature exceeds 80 ° C., the fixing temperature may become too high, or the deterioration of OHP transparency may be a problem. On the other hand, if the glass transition temperature of the polymer is less than 40 ° C., the storage stability of the toner Becomes too bad and causes problems. In the present invention, acrylic acid is suitably used as the monomer having an acidic polar group, and styrene, acrylic acid ester, and methacrylic acid ester are suitably used as the other monomers.
[0024]
Polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and redox initiators that combine these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide Water-soluble polymerization initiators such as 4,4′-azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, etc., and reduction of ferrous salts etc. using these water-soluble polymerizable initiators as one component Redox initiator systems in combination with agents, benzoyl peroxide, 2,2′-azobis-isobutyronitrile, and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.
[0025]
In the present invention, a known chain transfer agent can be used as necessary. Specific examples of such a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, tetrachloride. Carbon, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more, and is used in an amount of 0 to 5% by weight based on the polymerizable monomer.
[0026]
The average particle size of the polymer primary particles is usually0.05-3in the range of μm, preferably0.1-1μm, more preferably0.1-0.5μm. The average particle diameter can be measured using, for example, UPA. If the particle size is smaller than 0.05 μm, it is difficult to control the aggregation rate, which is not preferable. On the other hand, if the particle size is larger than 3 μm, the particle size of the toner obtained by agglomeration becomes too large, so that it is unsuitable for applications requiring high resolution as a toner.
[0027]
In the present invention, when obtaining the polymer primary particlesColorantIt may be used as a seed or dissolved or dispersed in a monomer or wax. However, the primary particles of the colorant are aggregated simultaneously with the primary particles of the polymer to form particle aggregates, It is preferable to make it the resin particle to contain. If necessary, two or more kinds of polymer primary particles may be used.
[0028]
Next, the colorant primary particles used in the present invention include a compound represented by the following general formula (I). The compounds represented by the general formula (I) are known as magenta colorants, and these compounds tend to be positively charged.JPNo. 2000-19882It is described in.
[0029]
[Chemical 6]
(In general formula (I), A and B represent an aromatic ring which may have a substituent. R1Is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, an aminosulfonyl group that may be substituted on the nitrogen atom, or a nitrogen atom. The aminocarbonyl group which may be substituted is represented. )
In general formula (I), A and B represent aromatic rings such as a benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring. Among these, a benzene ring or a naphthalene ring is preferable, and B is a benzene ring. A is preferably a naphthalene ring.
In the general formula (I), the substituent in the aromatic ring (A, B) which may have a substituent includes a halogen atom, a nitro group, a cyano group, a hydrocarbon group, an alkoxy group, an alkylthio group, Amino group, amino group optionally substituted on nitrogen atom, aminocarbonyl group optionally substituted on nitrogen atom, aminosulfonyl group optionally substituted on nitrogen atom, alkylsulfonyl group, alkoxysulfonyl Although usual stable substituents, such as a group, are mentioned, Preferably the thing whose formula weight of a substituent is 12-300 is preferable.
[0031]
Among these substituents, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, an aminosulfonyl group that may be substituted on the nitrogen atom, or a nitrogen atom More preferred is an aminocarbonyl group which may be substituted on the top.
More specifically, a compound represented by the following general formula (II) can be preferably used. These compounds are advantageous in terms of color and production.
[0032]
[Chemical 7]
(In the general formula (II), R1~ RFourAre each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, an aminosulfonyl group optionally substituted on the nitrogen atom, or It represents an aminocarbonyl group which may be substituted on the nitrogen atom. )
[0034]
Here, the aminosulfonyl group which may be substituted on the nitrogen atom, or the substituent on nitrogen in the aminocarbonyl group which may be substituted on the nitrogen atom includes an aryl group such as a phenyl group and a tolyl group, Alkyl groups such as methyl, ethyl, 1-propyl and 1-butyl groups, aralkyl groups such as benzyl, aryl groups substituted with halogen atoms or alkoxy groups, alkyl groups substituted with halogen atoms or alkoxy groups Etc.
[0035]
Furthermore, in the general formula (II), R1Is a hydrogen atom and R2Is a methoxy group and RThreeIs a hydrogen atom and RFourIs preferably a chlorine atom in view of spectral reflection characteristics, dispersibility in a polymerizable monomer, and processability to a colorant dispersion.
[0036]
When the compound represented by the general formula (I) is emulsified in water in the presence of an emulsifier and used in the form of an emulsion, an average particle size of 0.01 to 3 μm is preferably used.
You may mix and use the compound represented with the said general formula (I), and another magenta colorant. In that case, the ratio of the compound represented by the general formula (I) is usually 30% or more, preferably 50% or more, more preferably 70% or more with respect to the whole magenta colorant.
[0037]
As the charge control agent, considering the negative chargeability and adaptability to color toner (the charge control agent itself is colorless or light color and has no color tone trouble on the toner), salicylic acid or alkylsalicylic acid chromium, zinc, aluminum, etc. Metal salts, metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenolic compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- (4-chlorophenyl) amide] Hydroxylnaphthalene compounds such as -3-hydroxynaphthalene] are preferred. The amount used may be determined according to the desired charge amount for the toner, but is usually 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the binder resin.
[0038]
In the present invention, as a method of incorporating a charge control agent in the toner, when obtaining polymer primary particles, the charge control agent is used as a seed, or the charge control agent is dissolved or dispersed in a monomer or wax, The charge control agent primary particles may be aggregated simultaneously with the polymer primary particles to form particle aggregates, which may be resin particles containing a colorant. However, when obtaining resin fine particles not containing a colorant, the charge control agent Is preferably used as a seed, dissolved or dispersed in a monomer, or the charge control agent primary particles are attached or fixed before, simultaneously with, or after the step of attaching or fixing the resin fine particles. In this case, the charge control agent is also used as an emulsion (primary particles of the charge control agent) having an average particle size of 0.01 to 3 μm in water.
[0039]
In the method for producing a toner of the present invention, as a preferred embodiment for obtaining a particle aggregate (toner core material) which is a resin particle containing a colorant, polymer primary particles using wax as a seed, and colorant primary particles are used. It is mixed as an emulsion and aggregated to obtain particle aggregates.
[0040]
Next, in the magenta toner of the present invention, the above-mentioned particle aggregate is further coated (attached or fixed) with resin fine particles to form toner particles. The resin fine particles preferably have a volume average particle size of 0.02 to 2 μm, more preferably 0.05 to 1.5 μm, and are obtained by polymerizing a monomer similar to the monomer used for the aforementioned polymer primary particles. What was obtained can be used. In order to achieve both low-temperature fixability and storage stability, the glass transition temperature of the polymer is preferably set so that the resin fine particles are higher than the polymer primary particles described above. The resin fine particles are dispersed in water or a liquid mainly composed of water with an emulsifier (the above-mentioned surfactant) and used as an emulsion, but it is preferable to use resin fine particles obtained by an emulsion polymerization method.
Further, prior to coating the particle aggregate with resin fine particles, the particle aggregate may be fused at a temperature equal to or higher than the glass transition point of the polymer primary particles. Further, the adhesion or fixation of the resin fine particles to the particle aggregate may be performed in a plurality of times.
[0041]
The resin fine particles may contain a wax, or may be obtained by emulsion polymerization using the above wax as a seed. However, since it is preferable that the outermost shell of the toner does not contain wax, when the particle aggregate is coated with resin fine particles containing wax, it is further coated with resin fine particles not containing wax on the outside. Is preferred.
[0042]
Further, in order to improve the negative chargeability, it is necessary that the compound represented by the general formula (I) is not included in the outermost shell of the toner. Therefore, when the particle aggregate is coated with one-stage resin fine particles In general, the resin fine particles containing no compound represented by the general formula (I) are used. When the particle aggregate is coated with two or more stages of resin fine particles, the inner resin fine particles may contain a compound represented by the general formula (I). However, in order to ensure negative chargeability, it is preferable that none of the resin fine particles contain the compound represented by the general formula (I).
For the same reason, when the particle aggregate is coated with the resin fine particles, it is preferable not to use the colorant fine particles composed of the compound represented by the general formula (I) as the coating material together with the resin fine particles.
Therefore, when a magenta colorant is also required for the toner outer shell, it is preferable to use a colorant other than the compound represented by the general formula (I).
[0043]
Further, the toner of the present invention can be used together with additives such as a fluidizing agent, if necessary. Specific examples of such fluidizing agents include fine powders such as hydrophobic silica, titanium oxide, and aluminum oxide. Usually, 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight are used with respect to 100 parts by weight of the binder resin.
[0044]
Further, the toner of the present invention includes an inorganic fine powder such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania, a resistance adjuster such as styrene resin and acrylic resin, and a lubricant as an internal or external additive. Used. The amount of these additives to be used may be appropriately selected depending on the desired performance, and is usually about 0.05 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
[0045]
The negatively chargeable magenta toner of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder or ferrite powder, or a known material such as a resin coating on the surface thereof or a magnetic carrier. However, in the case of a two-component developer, since the negative chargeability of the toner may be ensured by selecting a carrier, the present invention is effective when applied to a one-component developer that does not use a carrier. Is.
In addition, since magnetic developer uses magnetic powder and is difficult to apply to magenta toner, application to non-magnetic developer is preferable. Therefore, the present invention is particularly preferably applied to a nonmagnetic one-component developer.
[0046]
【Example】
The present invention will be specifically described below with reference to examples.
In the following examples, “parts” means “parts by weight”. The average particle diameter, molecular weight, glass transition temperature (Tg), fixing temperature width, and charge amount of the polymer particles were measured by the following methods.
[0047]
Average particle diameter: measured by Nikkiso Microtrac UPA or Coulter Coulter Counter Multisizer II (abbreviated as Coulter Counter).
Weight average molecular weight: Measured by gel permeation chromatography (GPC). (Solvent: THF, calibration curve: standard polystyrene)
Glass transition temperature (Tg): Measured with DSC7 manufactured by PerkinElmer.
[0048]
Fixing temperature range: Recording paper carrying an unfixed toner image was prepared, the surface temperature of the heating roller was changed from 100 ° C. to 220 ° C., conveyed to the fixing nip, and the fixing state when discharged was observed. . The temperature range where the toner on the heating roller did not offset during fixing and the toner on the recording paper after fixing was sufficiently adhered to the recording paper was defined as the fixing temperature range. The heating roller of the fixing machine has a release layer made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) and was evaluated with a nip width of 4 mm without application of silicone oil. The fixing speed was 120 mm / s and 30 mm / s.
[0049]
One-component charge amount: The toner is put into a non-magnetic one-component developer tank (ColorPagePrestoN4 developer tank manufactured by Casio Co., Ltd.), the roller is rotated a certain number of times, the toner on the roller is sucked, the charge amount and the weight of the sucked toner From this, the charge amount per unit weight was determined.
Two-component charge amount: 4 parts of toner and 96 parts of ferrite carrier (resin coat with acrylic polymer) were mixed and stirred for 1 minute, and the charge amount was measured using a blow-off charge measuring device manufactured by Toshiba.
[0050]
・ Example by emulsion polymerization aggregation method
(Preparation of wax dispersion)
As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified by applying high-pressure shear in the presence of 1.67 parts of sodium N-dodecylbenzenesulfonate to obtain an ester wax dispersion. The resulting dispersion had a solid content concentration of 30%, and the average particle size measured by UPA was 220 nm (this is referred to as wax dispersion A).
[0051]
(Preparation of polymer primary particle dispersion)
35 parts of wax dispersion A and 400 parts of demineralized water were charged into a glass reactor equipped with a stirrer, heating / cooling device, concentrating device, and raw material / auxiliary charging device, and the temperature was raised to 90 ° C. under a nitrogen stream. .
Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.
[0052]
[Table 1]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight average molecular weight of the obtained polymer was 98,000, the average particle size measured by UPA was 190 nm, and Tg was 57 ° C. When the cross section of the obtained emulsion was observed with TEM, it was observed that the wax was encapsulated with the resin (this is referred to as polymer primary particle dispersion A).
[0054]
Polymerization was performed in the same manner as the polymer primary particle dispersion A except that the crosslinking agent HDDA was changed to divinylbenzene (DVB, 0.4 part) to obtain a milky white polymer dispersion. The obtained polymer had a weight average molecular weight of 150,000, an average particle size measured by UPA of 190 nm, and Tg of 57 ° C. When the cross section of the obtained emulsion was observed with TEM, it was observed that the wax was encapsulated with the resin (this is referred to as polymer primary particle dispersion B).
[0055]
(Preparation of resin fine particle dispersion)
A glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 4.3 parts of a 10% S-DBS aqueous solution and 400 parts of demineralized water, and 90 ° C. under a nitrogen stream. The temperature was raised to.
Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.
[0056]
[Table 2]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
0.5 parts of trichlorobromomethane
DVB 0.4 part
(Emulsifier aqueous solution)
10% S-DBS aqueous solution 2.2 parts
25 parts of demineralized water
(Initiator)
8% aqueous hydrogen peroxide solution 10.6 parts
10.6 parts of 8% ascorbic acid aqueous solution
[0057]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The obtained polymer had a weight average molecular weight of 110,000, an average particle size measured by UPA of 120 nm, and a Tg of 86 ° C. (this is referred to as resin fine particle dispersion A).
[0058]
(Preparation of colorant fine particle dispersion)
As 100 parts of the colorant fine particle dispersion, 20 parts of Pigment Red 238 was dispersed in a sand grinder mill for 6 hours in the presence of 2.5 parts of alkylbenzene sulfonate to obtain a colorant fine particle dispersion. The obtained dispersion had a solid content concentration of 20%, and the average particle size measured by UPA was 180 nm (this is called Colorant Fine Particle Dispersion A).
[0059]
(Preparation of charge control agent fine particle dispersion)
As 100 parts of the charge control agent fine particle dispersion, 20 parts of 4,4′-methylenebis [2- [N- (4-chlorophenyl) amido] -3-hydroxynaphthalene] was added in the presence of 4 parts of alkyl naphthalene sulfonate. Dispersion was performed with a grinder mill to obtain a charge control agent fine particle dispersion. The resulting dispersion had a solid content concentration of 24%, and the average particle size measured by UPA was 200 nm (this is referred to as charge control agent fine particle dispersion A).
[0060]
[Table 3]
[Example-1]
(Manufacture of toner)
Polymer primary particle dispersion A 90 parts (as solids)
Resin fine particle dispersion A 10 parts (as solid content)
Colorant fine particle dispersion A 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.5 part of S-DBS aqueous solution (as solid content)
[0061]
The above components were mixed in the following order.
The S-DBS aqueous solution was added to the polymer primary particle dispersion A and mixed uniformly, and then the colorant fine particle dispersion A was added and mixed uniformly.
While stirring the mixed dispersion thus obtained with an anchor blade with a baffle, an aqueous aluminum sulfate solution was added at 30 ° C. (0.6 parts as a solid content). The average particle diameter of the mixed dispersion after addition of the aqueous aluminum sulfate solution was 2 μm. Thereafter, the temperature was raised to 55 ° C. with stirring and held for 1 hour, and further heated to 58 ° C. and held for 1 hour. Thereafter, the charge control agent fine particle dispersion A, the resin fine particle dispersion A, and an aluminum sulfate aqueous solution (0.1 part as solid content) were added in this order. After holding for 1 hour and a half, 10% S-DBS aqueous solution (3 parts as a solid content) was added, and then the temperature was raised to 95 ° C. and kept for 4 hours. Thereafter, the mixture was cooled, filtered with a Kiriyama funnel, washed with water, and freeze-dried to obtain a toner (this toner is referred to as “toner A”).
[0062]
To 100 parts of toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is called developing toner A).
The volume average particle diameter of the obtained toner A by Coulter counter is 7.5 μm, the ratio of 5 μm or less of the volume particle diameter is 1.5%, and the ratio of 15 μm or more is 0.2%. The number average particle size ratio was 1.11 and the particle size distribution was very good.
[0063]
When the fixing property of the developing toner A was evaluated, it was fixed at 200 to 220 ° C. or higher at a fixing speed of 120 mm / s and fixed at 160 to 190 ° C. at a fixing speed of 30 mm / s. The one-component charge amount of toner A was −20 μC / g, the one-component charge amount of developing toner A was −25 μC / g, and the two-component charge amount of developing toner A was −23 μC / g.
[0064]
[Table 4]
[Comparative Example-1]
(Manufacture of toner)
110 parts of polymer primary particle dispersion B (as solids)
Colorant fine particle dispersion A 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.65 part of S-DBS aqueous solution (as solid content)
[0065]
The above components were mixed in the following order.
The S-DBS aqueous solution was added to the polymer primary particle dispersion B and mixed uniformly, and then the colorant fine particle dispersion A was added and mixed uniformly.
While stirring the mixed dispersion thus obtained with an anchor blade with a baffle, an aqueous aluminum sulfate solution was added at 20 ° C. (0.5 part as a solid content). Thereafter, the temperature was raised to 55 ° C. with stirring and held for 1 hour, and further heated to 58 ° C. and held for 1 hour. Thereafter, the charge control agent fine particle dispersion A was added and held for 10 minutes, and then a 10% S-DBS aqueous solution (3 parts as a solid content) was added, and then the temperature was raised to 95 ° C. and held for 5 hours. Thereafter, the mixture was cooled, filtered with a Kiriyama funnel, washed with water, and freeze-dried to obtain a toner (this toner is referred to as toner B).
[0066]
To 100 parts of the toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is called developing toner B).
The volume average particle diameter of the obtained toner B by Coulter counter is 6.2 μm, the ratio of the volume particle diameter of 5 μm or less is 1.5%, and the ratio of the volume average particle diameter to the number average particle diameter is 1.16. there were.
[0067]
When the fixing property of the developing toner B was evaluated, it was fixed at 158 to 200 ° C. or more at a fixing speed of 120 mm / s, and fixed at 123 to 182 ° C. at a fixing speed of 30 mm / s. The one-component charge amount of the toner B was +15 μC / g, and the one-component charge amount of the developing toner B was +11 μC / g.
・ Example by suspension polymerization
(Production of resin particles)
[0068]
[Table 5]
60 parts of styrene
Butyl acrylate 39.6 parts
0.4 parts of divinylbenzene
Pigment Red 238 4 parts
5 parts of paraffin wax (LUVAX-1266 made by Nippon Seiwa)
Dispersant (Disparon manufactured by Enomoto Kasei)
Polymerization initiator (Wako Pure Chemicals V-65)
The above composition is mixed and dispersed by a conventional method to prepare a monomer mixture. Apart from
[0069]
[Table 6]
Tricalcium phosphate 25 parts
Sodium polyacrylate 0.05 parts
200 parts of calcium chloride
300 parts of demineralized water
A mixed dispersion is prepared, a monomer mixture is added thereto to prepare a suspension, suspension polymerization is carried out by a conventional method, acid washing, filtration, water washing and drying are performed, and MW 3.3 is obtained. Resin particles containing a colorant having a Tg of 40 ° C. were obtained (resin particles C).
[0070]
[Example-2]
(Manufacture of toner)
Resin particle C 100 parts
Resin fine particle dispersion A 10 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
600 parts of demineralized water
Demineralized water was added to the resin fine particle dispersion A and mixed uniformly, and then the resin particles C were gradually added to uniformly disperse. The obtained dispersion mixture was adjusted to pH 3.0 with stirring, then heated to 40 ° C. and held for 2 hours. Thereafter, the mixture was cooled, filtered with a Kiriyama funnel, washed with water, and freeze-dried to obtain a toner (this toner is referred to as toner C).
To 100 parts of toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is called developing toner C).
The volume average particle diameter of the obtained toner C by Coulter counter was 7.5 μm, the ratio of the volume particle diameter of 5 μm or less was 5%, and the ratio of the volume average particle diameter to the number average particle diameter was 1.3. .
[0071]
When the fixing property of the developing toner C was evaluated, it was fixed at 140 to 200 ° C. or more at a fixing speed of 120 mm / s, and fixed at 120 to 170 ° C. at a fixing speed of 30 mm / s. The one-component charge amount of Toner C was −25 μC / g, and the one-component charge amount of Toner C for development was −28 μC / g.
[0072]
【The invention's effect】
According to the present invention, it is possible to provide a magenta toner excellent in low-temperature fixability, hot offset resistance and negative chargeability. In particular, when produced by a polymerization method, the particle size is small and the particle size distribution is sharp, which is suitable for high-resolution image formation.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000250763A JP4196528B2 (en) | 2000-08-22 | 2000-08-22 | Negatively chargeable magenta toner |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000250763A JP4196528B2 (en) | 2000-08-22 | 2000-08-22 | Negatively chargeable magenta toner |
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| Publication Number | Publication Date |
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