JPH10104877A - Binder resin and toner for toner - Google Patents
Binder resin and toner for tonerInfo
- Publication number
- JPH10104877A JPH10104877A JP25949096A JP25949096A JPH10104877A JP H10104877 A JPH10104877 A JP H10104877A JP 25949096 A JP25949096 A JP 25949096A JP 25949096 A JP25949096 A JP 25949096A JP H10104877 A JPH10104877 A JP H10104877A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- molecular weight
- less
- particle diameter
- weight
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 90
- 239000011347 resin Substances 0.000 title claims abstract description 90
- 239000011230 binding agent Substances 0.000 title claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 176
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 229920006158 high molecular weight polymer Polymers 0.000 claims abstract description 29
- 230000005484 gravity Effects 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 8
- 230000002542 deteriorative effect Effects 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 22
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- -1 pn-dodecyl styrene Chemical compound 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000001993 wax Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920006026 co-polymeric resin Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010558 suspension polymerization method Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007870 radical polymerization 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
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 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
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CKSAKVMRQYOFBC-UHFFFAOYSA-N 2-cyanopropan-2-yliminourea Chemical compound N#CC(C)(C)N=NC(N)=O CKSAKVMRQYOFBC-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-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
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-M 3,5,5-trimethylhexanoate Chemical compound [O-]C(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-M 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-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
- OPPHXULEHGYZRW-UHFFFAOYSA-N 4-methoxy-2,4-dimethyl-2-phenyldiazenylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC1=CC=CC=C1 OPPHXULEHGYZRW-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- YCUVUDODLRLVIC-UHFFFAOYSA-N Sudan black B Chemical compound C1=CC(=C23)NC(C)(C)NC2=CC=CC3=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 YCUVUDODLRLVIC-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 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
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-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
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 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
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-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
- 230000002688 persistence Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
(57)【要約】
【課題】 取扱い性に優れ、作業環境を悪化させること
なく、定着性および非オフセット性のバランスのとれた
トナ−を提供する。
【解決手段】 テトラヒドロフラン不溶解分が０．５重
量％以下であり、テトラヒドロフラン可溶分のゲルパー
ミエーションクロマトグラフィーによる分子量分布にお
いて、分子量１×１０5 〜５×１０5 の領域にメインピ
ークを有する高分子量重合体成分と、４×１０3 〜３×
１０4 の領域にメインピークを有する低分子量重合体成
分とから構成され、長径（ＲL ）と短径（ＲS ）の比
（ＲL ／ＲS）が０．９以上である実質的に球形で、平
均粒子径が１００〜５００μｍ、粒子径１０００μｍ以
上の成分が１０％以下、粒子径７５μｍ未満の成分が１
０％以下で、嵩比重が０．３５ｇ／ｍｌ以上であるビニ
ル系重合体粒子からなるトナー用バインダー樹脂。PROBLEM TO BE SOLVED: To provide a toner which is excellent in handleability and has a well-balanced fixing property and non-offset property without deteriorating a working environment. SOLUTION: The tetrahydrofuran-insoluble content is 0.5% by weight or less and has a main peak in a molecular weight region of 1 × 10 5 to 5 × 10 5 in the molecular weight distribution by gel permeation chromatography of the tetrahydrofuran-soluble content. High molecular weight polymer component, 4 × 10 3 to 3 ×
And a low molecular weight polymer component having a main peak in the region of 10 4 , wherein the ratio (R L / R S ) of the major axis (R L ) to the minor axis (R S ) is substantially 0.9 or more. Spherical, with an average particle diameter of 100 to 500 μm, a component having a particle diameter of 1000 μm or more is 10% or less, and a component having a particle diameter of less than 75 μm is 1%.
A binder resin for toner comprising vinyl polymer particles having a bulk specific gravity of 0% or less and a specific gravity of 0.35 g / ml or more.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子写真法、静電
記録法、静電印刷法等において、静電荷像または磁気潜
像の現像に用いられるトナー用バインダー樹脂およびト
ナーに関するものであり、さらに詳しくは、定着性と非
オフセット性とのバランスに優れ、作業性の良いトナー
用バインダー樹脂およびそれを用いたトナーに関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner binder resin and a toner used for developing an electrostatic image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, the present invention relates to a toner binder resin having an excellent balance between fixing property and non-offset property and excellent workability, and a toner using the same.
【０００２】[0002]
【従来の技術】電子写真法、静電印刷法による代表的な
画像形成工程は、光電導性絶縁層を一様に帯電させ、そ
の絶縁層を露光させた後、露光された部分上の電荷を消
散させることによって電気的な潜像を形成し、該潜像に
電荷を持った微粉末のトナーを付着させることにより可
視化させる現像工程、得られた可視像を転写紙等の転写
材に転写させる転写工程、加熱あるいは加圧により永久
定着させる定着工程からなる。2. Description of the Related Art In a typical image forming process by an electrophotographic method or an electrostatic printing method, a photoconductive insulating layer is uniformly charged, the insulating layer is exposed, and then a charge on an exposed portion is obtained. To form an electric latent image by dissipating the toner, and a developing step of visualizing the latent image by adhering a finely charged toner to the latent image, and transferring the obtained visible image to a transfer material such as transfer paper. It comprises a transfer step of transferring and a fixing step of permanently fixing by heating or pressing.
【０００３】このような電子写真法あるいは静電印刷法
に使用されるトナーおよびトナー用バインダー樹脂とし
ては、上記各工程において様々な性能が要求される。例
えば、現像工程においては、電気的な潜像にトナーを付
着させるために、トナーおよびトナー用バインダー樹脂
は温度、湿度等の周囲の環境に影響されることなくコピ
ー機に適した帯電量を保持しなくてはならない。また、
熱ローラー定着方式による定着工程においては、熱ロー
ラーに付着しない非オフセット性、紙への定着性が良好
でなくてはならない。さらに、コピー機内での保存中に
トナーがブロッキングしない耐ブロッキング性も要求さ
れる。Various performances are required for the toner and the binder resin for the toner used in the electrophotographic method or the electrostatic printing method in each of the above steps. For example, in the development process, the toner and the binder resin for the toner maintain a charge amount suitable for a copying machine without being affected by the surrounding environment such as temperature and humidity in order to attach the toner to the electric latent image. I have to do it. Also,
In the fixing step by the heat roller fixing method, the non-offset property that does not adhere to the heat roller and the fixability to paper must be good. Further, it is required to have a blocking resistance so that the toner does not block during storage in a copying machine.
【０００４】従来、トナー用バインダー樹脂としては、
スチレン−アクリル系共重合体が多用されており、線状
タイプ（非架橋タイプ）の樹脂と架橋タイプの樹脂が使
用されている。架橋タイプのトナー用バインダー樹脂で
は、樹脂を架橋することによって分子量分布を広くし
て、トナーとしての定着性、非オフセット性を改良する
ことが試みられている。また、線状タイプのトナー用バ
インダー樹脂では、特公昭６３−３２１８０号公報等に
開示されているように高分子量重合体成分と低分子量重
合体成分とを混合して、両成分のガラス転移温度や分子
量をコントロールしたり、特公昭５５−６８９５号に開
示されているように樹脂全体の分子量分布（Ｍｗ／Ｍ
ｎ）をコントロールすることによって、トナーの定着性
や非オフセット性等を改良しようとする試みが行われて
いる。Conventionally, binder resins for toners include:
Styrene-acrylic copolymers are frequently used, and linear (non-crosslinked) resins and crosslinked resins are used. In a cross-linking type binder resin for a toner, attempts have been made to improve the fixability and the non-offset property as a toner by broadening the molecular weight distribution by cross-linking the resin. Further, in a linear type toner binder resin, a high molecular weight polymer component and a low molecular weight polymer component are mixed as disclosed in JP-B-63-32180, etc., and the glass transition temperature of both components is mixed. And the molecular weight distribution (Mw / M) of the entire resin as disclosed in JP-B-55-6895.
Attempts have been made to improve the fixing property and non-offset property of the toner by controlling n).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、架橋タ
イプのトナー用バインダー樹脂では、樹脂を単に架橋さ
せただけでは、トナーとしての定着性と非オフセット性
とのバランスに劣り、十分な定着特性を有するトナーを
得ることは困難であった。また、顔料等の分散性が悪い
ために高いせん断力によって分散させる必要があり、そ
の結果、架橋構造が切断させて非オフセット性が低下す
るという問題点も有していた。一方、線状タイプのトナ
ー用バインダー樹脂を用いたトナーは、顔料等の分散性
は良好ではあるが、例えば、定着性を改善すると、トナ
ー用バインダー樹脂の溶融粘度が低下しトナ−の非オフ
セット性が低下してしまい、両者のバランスの良いトナ
−を得ることは困難であった。However, in the case of a crosslinked type binder resin for a toner, simply cross-linking the resin is inferior in the balance between the fixing property and the non-offset property as a toner and has a sufficient fixing property. It was difficult to obtain a toner. In addition, since the dispersibility of the pigment or the like is poor, it is necessary to disperse the pigment by a high shear force. As a result, there is a problem that the crosslinked structure is cut and the non-offset property is reduced. On the other hand, a toner using a linear-type toner binder resin has good dispersibility of pigments and the like, but, for example, when the fixing property is improved, the melt viscosity of the toner binder resin is reduced, and the toner is not offset. Therefore, it was difficult to obtain toner having a good balance between the two.
【０００６】また、トナー化の際にバインダー樹脂と混
合する顔料、帯電制御剤、離型剤、磁性体等の添加剤と
の混合性を改良する目的で、特開平１−２１９７７０号
公報、特開平１−２１９７５９号公報、特開平１−２１
９７６５号公報、特開平１−２１９７６８号公報、特開
平１−２１９７５８号公報、特開平１−２１９７６６号
公報等に記載されているように、バインダー樹脂の粒子
径や粒子形状を特定のものとする提案もなされている
が、バインダー樹脂の取り扱いにおいて樹脂微粒子が飛
散しやすいため作業性に劣るとともに、作業環境の悪化
を招くという問題点を有していた。そこで、本発明の目
的は、トナ−としての定着性および非オフセット性のバ
ランスに優れ、作業性の良好なトナ−用バインダ−樹脂
を提供することにある。[0006] Further, in order to improve the mixing property with additives such as a pigment, a charge controlling agent, a releasing agent, and a magnetic material mixed with a binder resin at the time of forming a toner, Japanese Patent Application Laid-Open No. 1-219770 discloses a method. Japanese Unexamined Patent Publication No. 1-219759, Japanese Unexamined Patent Publication No. 1-221
No. 9765, Japanese Patent Application Laid-Open No. 1-219768, Japanese Patent Application Laid-Open No. 1-219758, Japanese Patent Application Laid-Open No. 1-219766, and the like, the particle diameter and the particle shape of the binder resin are specified. Although proposals have been made, there has been a problem that workability is deteriorated because resin fine particles are easily scattered in handling the binder resin, and that the work environment is deteriorated. SUMMARY OF THE INVENTION An object of the present invention is to provide a binder resin for toner which is excellent in balance between fixing property and non-offset property as toner and has good workability.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、このよう
な状況に鑑み、トナー用バインダー樹脂について鋭意検
討した結果、バインダー樹脂の分子量を制御するととも
に、その粒子形状、粒子径および嵩比重を特定の範囲と
することによって、トナ−としての定着性および非オフ
セット性のバランスに優れるとともに、作業性の良好な
トナ−用バインダ−樹脂が得られることを見出し、本発
明に到達したものである。すなわち、本発明のトナー用
バインダー樹脂は、テトラヒドロフラン不溶解分が０．
５重量％以下であり、テトラヒドロフラン可溶分のゲル
パーミエーションクロマトグラフィーによる分子量分布
において、分子量１×１０5 〜５×１０5の領域にメイ
ンピークを有する高分子量重合体成分と、４×１０3 〜
３×１０4の領域にメインピークを有する低分子量重合
体成分とから構成され、長径（ＲL）と短径（ＲS ）の
比（ＲL ／ＲS ）が０．９以上である実質的に球形で、
平均粒子径が１００〜５００μｍ、粒子径１０００μｍ
以上の成分が１０％以下、粒子径７５μｍ未満の成分が
１０％以下で、嵩比重が０．３５ｇ／ｍｌ以上であるビ
ニル系重合体粒子からなることを特徴とするものであ
る。また、本発明のトナーは、上記のようなバインダー
樹脂を含有することを特徴とするものである。Means for Solving the Problems In view of such a situation, the present inventors have conducted intensive studies on a binder resin for toner, and as a result, while controlling the molecular weight of the binder resin, the particle shape, particle diameter and bulk specific gravity of the binder resin have been controlled. Is in a specific range, it is possible to obtain a binder resin for toner excellent in workability as well as excellent balance of fixing property and non-offset property as toner, and has reached the present invention. is there. That is, the binder resin for toner of the present invention has a tetrahydrofuran insoluble content of 0.1.
A high-molecular-weight polymer component having a main peak in a molecular weight region of 1 × 10 5 to 5 × 10 5 in a molecular weight distribution by gel permeation chromatography of a tetrahydrofuran-soluble portion of 4 × 10 3 or less; ~
Configured to 3 × 10 4 region of a low molecular weight polymer component having a main peak, the major axis (R L) and minor axis (R S) of the ratio (R L / R S) is 0.9 or more substantially Is spherical,
Average particle diameter 100-500 μm, particle diameter 1000 μm
It is characterized by comprising vinyl polymer particles having 10% or less of the above components, 10% or less of components having a particle diameter of less than 75 μm, and a bulk specific gravity of 0.35 g / ml or more. Further, the toner of the present invention contains the binder resin as described above.
【０００８】[0008]
【発明の実施の形態】本発明のトナー用バインダー樹脂
は、高分子量重合体成分と低分子量重合体成分とからな
り、いずれの重合体もスチレン系単量体および他の共重
合可能なビニル系単量体からなるスチレン−アクリル系
共重合体からなる。本発明において、高分子量重合体成
分および低分子量重合体成分の重合のために使用される
スチレン系単量体としては、スチレン、ｏ−メチルスチ
レン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−
メチルスチレン、ｐ−エチルスチレン、２，４−ジメチ
ルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−
ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−
オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−
デンシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−フ
ェニルスチレン、３，４−ジシクロシルスチレン等が挙
げられ、中でも、スチレンが好ましい。これらのスチレ
ン系単量体は、単独でまたは２種以上組み合わせて使用
することができる。BEST MODE FOR CARRYING OUT THE INVENTION The binder resin for a toner of the present invention comprises a high molecular weight polymer component and a low molecular weight polymer component, and each polymer is composed of a styrene monomer and another copolymerizable vinyl resin. It is composed of a styrene-acrylic copolymer composed of monomers. In the present invention, the styrene monomer used for the polymerization of the high molecular weight polymer component and the low molecular weight polymer component includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-
Methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-
Butylstyrene, pn-hexylstyrene, pn-
Octylstyrene, pn-nonylstyrene, pn-
Densyl styrene, pn-dodecyl styrene, p-phenyl styrene, 3,4-dicyclosyl styrene and the like can be mentioned, among which styrene is preferable. These styrene monomers can be used alone or in combination of two or more.
【０００９】また、他の共重合可能なビニル系単量体と
しては、アクリル酸エチル、アクリル酸メチル、アクリ
ル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸プ
ロピル、アクリル酸２−エチルヘキシル、アクリル酸ス
テアリル、メタアクリル酸、メタアクリル酸エチル、メ
タアクリル酸メチル、メタアクリル酸ｎ−ブチル、メタ
アクリル酸イソブチル、メタアクリル酸プロピル、メタ
アクリル酸２−エチルヘキシル、メタアクリル酸ステア
リル等の不飽和モノカルボン酸エステル、マレイン酸ジ
メチル、マレイン酸ジエチル、マレイン酸ブチル、フマ
ル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル等
の不飽和ジカルボン酸ジエステル等が挙げられる。さら
に、アクリル酸、メタクリル酸、ケイヒ酸等の不飽和モ
ノカルボン酸、マレイン酸、フマル酸、イタコン酸等の
不飽和ジカルボン酸、マレイン酸モノメチル、マレイン
酸モノエチル、マレイン酸モノブチル、フマル酸モノメ
チル、フマル酸モノエチル、フマル酸モノブチル等の不
飽和モノカルボン酸モノエステル等のカルボン酸含基ビ
ニル単量体を併用することもできる。Other copolymerizable vinyl monomers include ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate And unsaturated monocarboxylic acids such as methacrylic acid, ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate And unsaturated dicarboxylic acid diesters such as esters, dimethyl maleate, diethyl maleate, butyl maleate, dimethyl fumarate, diethyl fumarate and dibutyl fumarate. Further, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, fumarate Carboxylic acid-containing vinyl monomers such as unsaturated monocarboxylic acid monoesters such as monoethyl acrylate and monobutyl fumarate can also be used in combination.
【００１０】これらの単量体の共重合比率は特に限定さ
れるものではないが、得られるトナー用バインダー樹脂
のガラス転移温度が４５〜８０℃の範囲となるよう選定
することが好ましい。これは、トナー用バインダー樹脂
のガラス転移温度が４５℃未満であると、トナーのブロ
ッキング発生温度が低下し、保存安定性が極端に低下す
る傾向にあるためであり、８０℃を超えると軟化温度が
高くなりトナーの定着性が低下する傾向にあるためであ
り、さらに好ましくは５０〜７０℃の範囲で、より好ま
しくは５０〜６５℃の範囲である。本発明のトナー用バ
インダー樹脂は、高分子量重合体成分と低分子量重合体
成分とから構成され、高分子量重合体成分の含有割合は
２０〜７０重量％の範囲であることが好ましい。これ
は、高分子量重合体成分が２０重量％未満であると、ト
ナーとしての非オフセット性が劣る傾向にあるためであ
り、逆に７０重量％を超えるとトナーとしての定着性が
劣る傾向にあるためであり、さらに好ましくは２０〜６
０重量％の範囲である。The copolymerization ratio of these monomers is not particularly limited, but is preferably selected so that the glass transition temperature of the obtained binder resin for toner is in the range of 45 to 80 ° C. This is because if the glass transition temperature of the binder resin for the toner is less than 45 ° C., the blocking occurrence temperature of the toner tends to decrease, and the storage stability tends to extremely decrease. , And the fixability of the toner tends to decrease. The temperature is more preferably in the range of 50 to 70 ° C, and more preferably in the range of 50 to 65 ° C. The binder resin for a toner of the present invention is composed of a high molecular weight polymer component and a low molecular weight polymer component, and the content ratio of the high molecular weight polymer component is preferably in the range of 20 to 70% by weight. This is because if the high molecular weight polymer component is less than 20% by weight, the non-offset properties as a toner tend to be inferior, and if it exceeds 70% by weight, the fixability as a toner tends to be inferior. And more preferably 20 to 6
The range is 0% by weight.
【００１１】本発明においては、トナー用バインダー樹
脂を構成する高分子量重合体成分と低分子量重合体成分
の分子量分布を制御することによって、定着性と非オフ
セット性とのバランスのとれたトナーを提供できるもの
である。すなわち、トナー用バインダー樹脂のテトラヒ
ドロフラン可溶分のゲルパーミェーションクロマトグラ
フィーによる分子量分布において、高分子量重合体成分
が分子量１×１０5 〜５×１０5 の領域にメインピーク
を有し、低分子量重合体成分が４×１０3 〜３×１０4
の領域にメインピークを有するものである。In the present invention, by controlling the molecular weight distribution of a high molecular weight polymer component and a low molecular weight polymer component constituting a binder resin for a toner, a toner having a good balance between fixing property and non-offset property is provided. You can do it. That is, in the molecular weight distribution by gel permeation chromatography of the tetrahydrofuran soluble portion of the binder resin for the toner, the high molecular weight polymer component has a main peak in a region of a molecular weight of 1 × 10 5 to 5 × 10 5 , The molecular weight polymer component is 4 × 10 3 to 3 × 10 4
Has a main peak in the region of.
【００１２】高分子量重合体成分は、トナーとしての非
オフセット性や強度に寄与する成分であり、そのメイン
ピークが１×１０5 未満の領域であると、トナーとして
の非オフセット性が低下するとともに、トナーの強度が
低下して定着した画像が擦れたり折り曲げられたりする
ことによって容易に欠落する。逆に、メインピークが５
×１０5 を超える領域にあると軟化温度が高くなりトナ
ーとしての定着性が低下するとともに、粉砕性が損なわ
れたり、低分子量重合体成分との分散性が損なわれるた
めであり、好ましくは１．３×１０5 〜３×１０5 の領
域であり、さらに好ましくは１．５×１０5 〜２×１０
5 の領域である。The high molecular weight polymer component is a component that contributes to the non-offset property and strength of the toner. If the main peak is in a region of less than 1 × 10 5 , the non-offset property of the toner is reduced. In addition, the fixed image is easily lost due to rubbing or bending of the fixed image due to a decrease in toner strength. Conversely, the main peak is 5
When it is in a region exceeding × 10 5 , the softening temperature is increased, the fixing property as a toner is reduced, the pulverizability is impaired, and the dispersibility with a low molecular weight polymer component is impaired. 3 × 10 5 to 3 × 10 5 , more preferably 1.5 × 10 5 to 2 × 10 5
This is area 5 .
【００１３】低分子量重合体成分は、トナーとしての定
着性に寄与する成分であり、そのメインピークが４×１
０3 未満の領域であると、トナーとしての耐ブロッキン
グ性が低下するとともに、バインダー樹脂の機械的強度
が低下し、帯電発生工程でトナーが過粉砕状態となり、
画像にカブリが発生しやすくなるためである。逆に、３
×１０4 を超える領域にメインピークがあると、トナー
としての定着性が低下するためであり、好ましくは５×
１０3 〜２×１０5 の領域であり、さらに好ましくは７
×１０3 〜１．５×１０4 の領域である。The low molecular weight polymer component is a component that contributes to fixability as a toner, and its main peak is 4 × 1
If it is 0 3 less than in the region, along with the blocking resistance of the toner is reduced, decreased mechanical strength of the binder resin, the toner in the charging generator process becomes excessively pulverized state,
This is because fogging easily occurs in the image. Conversely, 3
If the main peak is in a region exceeding × 10 4 , the fixability as a toner is reduced, and it is preferably 5 × 4.
10 3 to 2 × 10 5 , more preferably 7
It is an area of × 10 3 to 1.5 × 10 4 .
【００１４】本発明のトナー用バインダー樹脂は、テト
ラヒドロフランの不溶解分が０．５重量％以下である。
これは、テトラヒドロフラン不溶解分が０．５重量％を
超えると、トナー化の際に添加される顔料、帯電制御
剤、離型剤等との混合性が低下するためである。また、
本発明において、トナ用バインダー樹脂は、長径（Ｒ
L ）と短径（ＲS）の比（ＲL ／ＲS ）が０．９以上で
ある実質的に球形である重合体粒子であることが必要で
ある。これは、長径（ＲL ）と短径（ＲS ）の比（ＲL
／ＲS ）が０．９未満であり、エッジ部を有するような
形状の重合体粒子であると、トナー化の際の予備混合や
混練工程時にフィーダー部での流動性が低下しするとと
もに、樹脂の輸送時等に樹脂粒子が微粉化する傾向にあ
るためである。The binder resin for toner of the present invention has an insoluble content of tetrahydrofuran of 0.5% by weight or less.
This is because if the tetrahydrofuran insoluble content exceeds 0.5% by weight, the miscibility with a pigment, a charge controlling agent, a release agent, etc., added at the time of forming the toner is reduced. Also,
In the present invention, the binder resin for the toner is a long diameter (R
It is necessary that the particles are substantially spherical polymer particles having a ratio (R L / R S ) of L ) to the minor axis (R S ) of 0.9 or more. This is the ratio (R L ) of the major axis (R L ) to the minor axis (R S ).
/ R s ) is less than 0.9 and the polymer particles have a shape having an edge portion, and the fluidity in the feeder portion during the pre-mixing and kneading steps at the time of forming the toner decreases, and This is because the resin particles tend to be pulverized during transportation of the resin.
【００１５】さらに、本発明のトナー用バインダー樹脂
は、平均粒子径が１００〜５００μｍ、好ましくは２０
０〜４００μｍ、粒子径１０００μｍ以上の成分が１０
％以下、好ましくは７％以下、粒子径７５μｍ未満の成
分が１０％以下、好ましくは７％以下で、嵩比重が０．
３５ｇ／ｍｌ以上、好ましくは０．４ｇ／ｍｌ以上の重
合体粒子から構成される。これは、粒子の平均粒子径が
１００μｍ未満であると、トナー化の際の予備混合や混
練工程時にフィーダー部での流動性が低下するととも
に、樹脂粒子が飛散しやすくなり取扱い性が低下し、作
業環境を悪化させるためである。逆に、粒子の平均粒子
径が５００μｍを超えると、トナー化の際に添加される
顔料、帯電制御剤、離型剤等との混合性が低下し、トナ
ーの画像濃度が低下するためである。また、粒子径１０
００μｍ以上の成分が１０％を超えて含まれていると、
トナー化の際に添加される顔料、帯電制御剤、離型剤等
との混合性が低下し、トナーの画像濃度が低下するため
でり、粒子径７５μｍ未満の成分が１０％を超えて含ま
れていると、トナー化の際の予備混合や混練工程時にフ
ィーダー部での流動性が低下するとともに、樹脂粒子が
飛散しやすくなり取扱い性が低下し、作業環境を悪化さ
せるためである。粒子の嵩比重が０．３５ｇ／ｍｌ未満
であると、トナー化の際の予備混合や混練工程時にフィ
ーダー部での流動性が低下しするとともに、樹脂の輸送
時等に樹脂粒子が微粉化する傾向にあるためである。好
ましくは、平均粒子径が２００〜４００μｍ、粒子径１
０００μｍ以上の成分が７％以下、粒子径７５μｍ未満
の成分が７％以下で、嵩比重が０．４ｇ／ｍｌ以上の重
合体粒子である。Further, the binder resin for a toner of the present invention has an average particle diameter of 100 to 500 μm, preferably 20 to 500 μm.
0 to 400 μm, and a component having a particle diameter of 1000 μm or more
% Or less, preferably 7% or less, and a component having a particle diameter of less than 75 μm is 10% or less, preferably 7% or less, and the bulk specific gravity is 0.1% or less.
It is composed of polymer particles of 35 g / ml or more, preferably 0.4 g / ml or more. This is because if the average particle diameter of the particles is less than 100 μm, the fluidity in the feeder portion during the pre-mixing and kneading steps during toner formation is reduced, and the resin particles are liable to be scattered, and the handleability is reduced, This is for deteriorating the work environment. Conversely, if the average particle diameter of the particles exceeds 500 μm, the miscibility with a pigment, a charge controlling agent, a release agent, etc., which is added during the formation of the toner, is reduced, and the image density of the toner is reduced. . In addition, particle diameter 10
When a component of 00 μm or more is contained in more than 10%,
This is because the miscibility with a pigment, a charge controlling agent, a release agent, etc., which is added at the time of forming the toner is reduced, and the image density of the toner is reduced. If it is used, the fluidity in the feeder portion during the pre-mixing or kneading step in forming the toner is reduced, and the resin particles are liable to be scattered, the handleability is reduced, and the working environment is deteriorated. When the bulk specific gravity of the particles is less than 0.35 g / ml, the fluidity in the feeder portion is reduced during the pre-mixing and kneading steps in forming the toner, and the resin particles are pulverized during transportation of the resin. This is because there is a tendency. Preferably, the average particle diameter is 200 to 400 μm, and the particle diameter is 1
The polymer particles have a bulk specific gravity of 0.4 g / ml or more, in which components having a particle size of 000 μm or more are 7% or less, components having a particle diameter of less than 75 μm are 7% or less.
【００１６】本発明のトナー用バインダー樹脂は、上記
の重合性モノマーの混合物を懸濁重合法によって重合す
ることによって製造することができる。懸濁重合法は、
残存溶剤による臭気の問題がないとともに、発熱の制御
の容易であり、分散剤の使用量も少なく耐湿性を損なう
こともない点で好ましい。特に、得られたトナー用バイ
ンダー樹脂が、均一に混合された高分子量重合体成分と
低分子量重合体成分とから構成されていることが好まし
く、高分子量重合体成分の懸濁重合を行い、次いで高分
子重合体成分の懸濁粒子の存在下で低分子量重合体成分
の懸濁重合する２段懸濁重合法等の重合方法によって重
合を行うことが好ましい。以下、２段懸濁重合法による
本発明のトナー用バインダー樹脂の製造方法ついて、具
体的に説明する。高分子量重合体成分の懸濁重合は、特
に限定されるものではなく、一般的な懸濁重合法に従っ
て行うことができ、上記のような単量体とともに、懸濁
重合において一般的に使用される分散剤、重合開始剤、
分子量調整剤等を使用することができ、温度９５〜１５
０℃、圧力０．５〜７ｋｇ／ｃｍ2の条件下で行うこと
が好ましい。The binder resin for a toner of the present invention can be produced by polymerizing a mixture of the above polymerizable monomers by a suspension polymerization method. The suspension polymerization method is
This is preferable because there is no problem of odor due to the residual solvent, the control of heat generation is easy, the amount of the dispersant used is small, and the moisture resistance is not impaired. In particular, the obtained toner binder resin is preferably composed of a uniformly mixed high molecular weight polymer component and low molecular weight polymer component, and suspension polymerization of the high molecular weight polymer component is performed. It is preferable to carry out polymerization by a polymerization method such as a two-stage suspension polymerization method in which suspension polymerization of a low molecular weight polymer component is carried out in the presence of suspended particles of a high molecular weight polymer component. Hereinafter, a method for producing the toner binder resin of the present invention by a two-stage suspension polymerization method will be specifically described. The suspension polymerization of the high molecular weight polymer component is not particularly limited, and can be performed according to a general suspension polymerization method, and is commonly used in the suspension polymerization together with the above-mentioned monomers. Dispersant, polymerization initiator,
A molecular weight modifier or the like can be used.
It is preferable to carry out the reaction at 0 ° C. under a pressure of 0.5 to 7 kg / cm 2 .
【００１７】高分子量重合体成分の懸濁重合に使用され
る重合開始剤としては、１分子内に３個以上のｔ−ブチ
ルパ−オキサイド基を有する化合物あるいは１０時間半
減期温度が９０〜１４０℃の１分子中の官能基が１個で
あるラジカル重合開始剤等を使用することができる。本
発明においては、重合開始剤として１分子内に３個以上
のｔ−ブチルパ−オキサイド基を有する化合物を使用す
るとともに、高分子量重合体成分を９５℃以上、好まし
くは９５〜１４０℃、さらに好ましくは１１０〜１４０
℃の高温下で、懸濁重合によって重合することによっ
て、重合開始剤が効率よく消費され、重量平均分子量が
１×１０5 以上の分子量の高い高分子量重合体成分を１
〜３時間程度の短時間で得ることができることから好ま
しい。As a polymerization initiator used for suspension polymerization of a high molecular weight polymer component, a compound having three or more t-butyl peroxide groups in one molecule or a 10-hour half-life temperature of 90 to 140 ° C. A radical polymerization initiator having one functional group per molecule can be used. In the present invention, a compound having three or more t-butyl peroxide groups in one molecule is used as a polymerization initiator, and a high molecular weight polymer component is 95 ° C or higher, preferably 95 to 140 ° C, more preferably. Is 110-140
Polymerization is carried out by suspension polymerization at a high temperature of 100 ° C., whereby the polymerization initiator is efficiently consumed, and a high-molecular-weight polymer component having a weight-average molecular weight of 1 × 10 5 or more is removed.
It is preferable because it can be obtained in a short time of about 3 hours.
【００１８】１分子内に３個以上のｔ−ブチルパ−オキ
サイド基を有する化合物としては、２，２−ビス（４，
４−ジ−ｔ−ブチルパ−オキシシクロヘキシル）プロパ
ン等が挙げられる。また、１０時間半減期温度が９０〜
１４０℃の１分子中の官能基が１個であるラジカル重合
開始剤としては、ｔ−ブチルパーオキシラウレート、ｔ
−ブチルパーオキシ３，５，５−トリメチルヘキサノエ
ート、シクロヘキサノンパーオキシド、ｔ−ブチルパー
オキシイソプロピルカーボネート、ｔ−ブチルパーオキ
シアセテート、ｔ−ブチルパーオキシベンゾエート、ジ
クミルパーオキシド、ｔ−ブチルクミルパーオキシド、
ジイソプロピルベンゼンハイドロパーオキシド、ジ−ｔ
−ブチルパーオキシド、ｐ−メタンハイドロパーオキシ
ド、２−（カルバモイルアゾ）イソブチロニトリル、
２，２−アゾビス（２，４，４−トリメチルペンタ
ン）、２−フェニルアゾ−２，４−ジメチル−４−メト
キシバレロニトリル等の有機過酸化物あるいはアゾ化合
物等が挙げられる。これら重合開始剤は、単独あるいは
２種以上を組み合わせて使用することができる。重合開
始剤の使用量としては、従来の懸濁重合での重合開始剤
の使用量と比較して非常に少量でよく、全単量体１００
重量部に対して０．００１〜０．５重量部の範囲で使用
することが好ましく、さらに好ましくは０．００２〜
０．０５重量部の範囲である。Compounds having three or more t-butyl peroxide groups in one molecule include 2,2-bis (4,4
4-di-t-butylper-oxycyclohexyl) propane and the like. The 10-hour half-life temperature is 90-
Examples of the radical polymerization initiator having one functional group in one molecule at 140 ° C. include t-butylperoxylaurate and t-butylperoxylaurate.
-Butylperoxy 3,5,5-trimethylhexanoate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcum Luperoxide,
Diisopropylbenzene hydroperoxide, di-t
-Butyl peroxide, p-methane hydroperoxide, 2- (carbamoylazo) isobutyronitrile,
Organic peroxides such as 2,2-azobis (2,4,4-trimethylpentane) and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile or azo compounds are exemplified. These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used may be very small compared to the amount of the polymerization initiator used in the conventional suspension polymerization.
It is preferably used in the range of 0.001 to 0.5 part by weight, more preferably 0.002 to 0.5 part by weight.
It is in the range of 0.05 parts by weight.
【００１９】次いで、懸濁重合した高分子量重合体懸濁
粒子の存在下で、懸濁重合によって低分子量重合体成分
の重合を行う。懸濁重合は、特に限定されるものではな
く、一般的な懸濁重合法に従って行うことができ、例え
ば、高分子量重合体の重合反応率が１０〜９０％程度に
なった時点で、低分子量重合体用の重合開始剤を水また
は低分子量重合体用単量体に溶解して添加することによ
って重合を開始することが好ましい。Next, the low-molecular-weight polymer component is polymerized by suspension polymerization in the presence of suspension particles of the high-molecular-weight polymer obtained by suspension polymerization. The suspension polymerization is not particularly limited, and can be carried out according to a general suspension polymerization method. For example, when the polymerization reaction rate of a high molecular weight polymer becomes about 10 to 90%, a low molecular weight It is preferable to start the polymerization by dissolving and adding the polymerization initiator for the polymer to water or the monomer for the low molecular weight polymer.
【００２０】低分子量重合体成分を懸濁重合に使用され
る重合開始剤としては、特に限定されるものではなく、
通常使用されるラジカル重合性を有する過酸化物やアゾ
系化合物等が使用でき、例えば、ジ−ｔ−ブチルパーオ
キシド、ｔ−ブチルクミルパーオキシド、ジクミルパー
オキシド、アセチルパーオキシド、イソブチリルパーオ
キシド、オクタノニルパーオキシド、デカノニルパーオ
キシド、ラウロイルパーオキシド、３，５，５−トリメ
チルヘキサノイルパーオキシド、ベンゾイルパーオキシ
ド、ｍ−トルオイルパーオキシド、ｔ−ブチルパーオキ
シアセテート、ｔ−ブチルパーオキシイソブチレート、
ｔ−ブチルパーオキシピパレート、ｔ−ブチルパーオキ
シネオデカノエート、クミルパーオキシネオデカノエー
ト、ｔ−ブチルパーオキシ２−エチルヘキサノエート、
ｔ−ブチルパーオキ３，５，５−トリメチルヘキサノエ
ート、ｔ−ブチルパオキシライレート、ｔ−ブチルパー
オキシベンゾエート、ｔ−ブチルパーオキシイソプロピ
ルカオーボネート、アゾビスイソブチルニトリル、２，
２−アゾビス−（２，４−ジメチルバレロニトリル）等
が挙げられるが、中でも、単量体に対する重合活性の持
続性や比較的短時間で重合が完了する点から、オクタノ
ニルパーオキシド、デカノニルパーオキシド、ラウロイ
ルパーオキシド、ベンゾイルパーオキシド、ｍ−トリオ
イルパーオキシドが好ましい。これら重合開始剤は、単
独または２種以上を組み合わせて使用することができ、
単量体１００重量部に対して０．１〜１０重量部の範囲
で使用することが好ましく、さらに好ましくは０．５〜
１０重量部の範囲である。The polymerization initiator used for suspension polymerization of the low molecular weight polymer component is not particularly limited,
Usually used peroxides and azo compounds having radical polymerizability can be used. For example, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, acetyl peroxide, isobutyryl peroxide Oxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluoyl peroxide, t-butylperoxyacetate, t-butylperoxide Oxyisobutyrate,
t-butyl peroxypiparate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate,
t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylylate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, azobisisobutyl nitrile, 2,
Examples thereof include 2-azobis- (2,4-dimethylvaleronitrile). Among them, octonyl peroxide, decanonyl, and the like, from the viewpoint of the persistence of the polymerization activity for the monomer and the completion of the polymerization in a relatively short time. Peroxide, lauroyl peroxide, benzoyl peroxide and m-trioil peroxide are preferred. These polymerization initiators can be used alone or in combination of two or more,
It is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomer.
The range is 10 parts by weight.
【００２１】懸濁重合は、単量体に対して好ましくは１
〜１０倍、さらに好ましくは２〜４倍程度の水ととも
に、分散剤、重合開始剤、必要に応じて分散助剤あるい
は連鎖移動剤等を添加して、所定の重合温度まで昇温し
て、所定の重合率となるまで加温を続けることによって
行われる。懸濁重合で使用される分散剤としては、ポリ
ビニルアルコール、（メタ）アクリル酸の単独重合体あ
るいは共重合体のアルカリ金属塩、カルボキシチルセル
ロース、ゼラチン、デンプン、硫酸バリウム、硫酸カル
シウム、炭酸カルシウム、炭酸マグネシウム、リン酸カ
ルシウム等のが挙げられ、中でも、ポリビニルアルコー
ルが好ましく、特に好ましくは、酢酸基と水酸基がブロ
ック的に存在する部分鹸化ポリビニルアルコールであ
る。これら分散剤は、水１００重量部に対して、０．０
１〜５重量部の範囲で使用することが好ましい。これ
は、分散剤の使用量が０．０１重量部未満であると、懸
濁重合の安定性が低下して生成粒子の凝集によって重合
体が固化する傾向にあり、逆に５重量部を超えるとトナ
ーの環境依存性、特に耐湿性が低下する傾向にあるため
であり、さらに好ましくは０．０５〜２重量部の範囲で
ある。また、必要に応じて、これら分散剤とともに、塩
化ナトリウム、塩化カリウム、硫酸ナトリウム、硫酸カ
リウム等の分散助剤を併用することもできる。さらに、
分子量を調整するために、必要に応じて、ｎ−オクチル
メルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシ
ルメルカプタン、チオグリコール酸２−エチルヘクシ
ル、α−メチルスチレンダイマー等の連鎖移動剤を使用
してもよい。Suspension polymerization is preferably carried out on one monomer.
10 to 10 times, more preferably about 2 to 4 times with water, adding a dispersant, a polymerization initiator, a dispersing aid or a chain transfer agent if necessary, and raising the temperature to a predetermined polymerization temperature, This is performed by continuing to heat until a predetermined polymerization rate is reached. Examples of the dispersant used in the suspension polymerization include polyvinyl alcohol, an alkali metal salt of a homopolymer or copolymer of (meth) acrylic acid, carboxytyl cellulose, gelatin, starch, barium sulfate, calcium sulfate, calcium carbonate, Examples thereof include magnesium carbonate and calcium phosphate. Among them, polyvinyl alcohol is preferable, and particularly preferable is partially saponified polyvinyl alcohol having an acetic acid group and a hydroxyl group in a block manner. These dispersants are used in an amount of 0.0
It is preferable to use it in the range of 1 to 5 parts by weight. If the amount of the dispersant is less than 0.01 part by weight, the stability of the suspension polymerization is lowered, and the polymer tends to be solidified by aggregation of formed particles, and conversely, the amount exceeds 5 parts by weight. This is because the toner tends to have a lower environmental dependency, particularly the moisture resistance, and the content is more preferably in the range of 0.05 to 2 parts by weight. If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate and potassium sulfate can be used together with these dispersants. further,
In order to adjust the molecular weight, a chain transfer agent such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 2-ethylhexyl thioglycolate, α-methylstyrene dimer may be used, if necessary. .
【００２２】本発明においては、上記のようなバインダ
ー樹脂をトナー中に８０〜９７重量％の範囲で含有され
ることが好ましく、さらに好ましくは９０〜９５重量％
の範囲である。これは、バインダー樹脂の含有量が８０
重量％未満であると、トナーとしての非オフセット性が
低下する傾向にあり、逆に９７重量％を超えるとトナー
の帯電安定性に劣る傾向にあるためである。本発明のト
ナーは、バインダー樹脂とともにワックス、着色剤、顔
料、荷電制御剤、オフセット防止剤、磁性粉等の添加剤
を、例えば、二軸押出機やミキサー等の混練機を用い
て、バインダー樹脂の軟化温度よりも１５〜３０℃程度
高い温度で混練した後、微粉砕、分級を行いトナー化さ
れる。得られたトナー粒子は、平均粒径が５〜２０μｍ
程度、好ましくは８〜１５μｍ程度であり、粒径が５μ
ｍ以下の微粒子が３重量％未満であることが好ましい。In the present invention, the binder resin is preferably contained in the toner in the range of 80 to 97% by weight, more preferably 90 to 95% by weight.
Range. This is because the binder resin content is 80
When the amount is less than 100% by weight, the non-offset property of the toner tends to decrease, and when the amount is more than 97% by weight, the charging stability of the toner tends to deteriorate. The toner of the present invention comprises, together with a binder resin, additives such as a wax, a colorant, a pigment, a charge control agent, an anti-offset agent, and a magnetic powder, for example, by using a kneading machine such as a twin-screw extruder or a mixer. Is kneaded at a temperature about 15 to 30 ° C. higher than the softening temperature of the mixture, and then finely pulverized and classified to form a toner. The average particle diameter of the obtained toner particles is 5 to 20 μm.
Degree, preferably about 8 to 15 μm, and the particle size is 5 μm.
It is preferable that the number of fine particles having a particle size of m or less is less than 3% by weight.
【００２３】トナーに使用されるワックス、着色剤、顔
料、荷電制御剤、オフセット防止剤、磁性粉は、通常使
用されているものでよく、例えば、ポリプロピレンワッ
クス等の低分子量ポリオレフィンワックス等のワックス
（トナーに対して０．５〜５重量％の範囲で使用され
る。）、カーボンブラック、ニグロシン染料、ランプ
黒、スーダンブラックＳＭ、ネーブルイエロー、ミネラ
ルファーストイエロー、リソールレッド、パーマネント
オレンジ４Ｒ等の着色剤あるいは顔料、ニグロシン、ア
ルキル基含有アジン系染料、塩基性染料、モノアゾ染料
あるいはその金属錯体、サリチル酸あるいはその金属錯
体、アルキルサルチル酸あるいはその金属錯体、ナフト
エ酸あるいはその金属錯体等の荷電制御剤、ポリエチレ
ン、ポリプロピレン、エチレン−ポリプロピレン共重合
体等のオフセット防止剤、フェライト、マグネタイト等
の磁性粉が挙げられる。The wax, colorant, pigment, charge control agent, anti-offset agent, and magnetic powder used in the toner may be those commonly used, for example, waxes such as low molecular weight polyolefin wax such as polypropylene wax. Used in the range of 0.5 to 5% by weight based on the toner), carbon black, nigrosine dye, lamp black, Sudan black SM, navel yellow, mineral fast yellow, lithol red, permanent orange 4R, etc. Or charge control agents such as pigments, nigrosine, alkyl-containing azine dyes, basic dyes, monoazo dyes or their metal complexes, salicylic acid or its metal complexes, alkylsalicylic acids or their metal complexes, naphthoic acids or their metal complexes, polyethylene ,polypropylene, Styrene - polypropylene copolymer anti-offset agent such as ferrite, and a magnetic powder such as magnetite.
【００２４】[0024]
【実施例】以下、実施例を用いて本発明を具体的に説明
する。実施例において、樹脂の物性、トナー特性は、以
下の方法で行った。テトラヒドロフラン（ＴＨＦ）不溶解分 ：セライト５４
５（片山化学社製）を充填したガラスフィルター（１Ｇ
−３または２Ｇ−３）の重量（Ｗ１）を秤量し、このガ
ラスフィルターに０．５ｇの樹脂（Ｗ２）に５０ｍｌの
ＴＨＦを添加して、６０℃で３時間加熱処理した後に、
ＴＨＦ溶液を吸引濾過する。次いで、ガラスフィルター
上に残存したＴＨＦ不溶解分をアセトンで完全に洗い流
し、８０℃で３時間以上の真空乾燥を行った後、ガラス
フィルターの重量（Ｗ３）を秤量して、次の式（１）に
よって算出した。The present invention will be specifically described below with reference to examples. In the examples, the physical properties of the resin and the toner characteristics were measured by the following methods. Tetrahydrofuran (THF) insoluble : Celite 54
5 (Katayama Chemical Co., Ltd.) filled glass filter (1G
-3 or 2G-3) was weighed (W1), 0.5 g of resin (W2) was added to 50 ml of THF in the glass filter, and the mixture was heated at 60 ° C. for 3 hours.
The THF solution is suction filtered. Next, the THF-insoluble matter remaining on the glass filter was completely washed away with acetone, vacuum-dried at 80 ° C. for 3 hours or more, and the weight (W3) of the glass filter was weighed. ).
【００２５】[0025]
【数１】 ＴＨＦ不溶解分（％）＝｛（Ｗ３−Ｗ１）×１００｝／Ｗ２ ・・・（１）ゲルパーミェーションクロマトグラフィーによる分子量
分布 ：ＴＨＦを溶剤とした０．０４重量％の樹脂溶液を
ＰＴＦＥ膜（東ソー社製マイショリデイスクＨ−２５−
５）で濾過し、３本のカラム（東ソー社製ＴＳＫｇｅｌ
／ＧＭＨXLカラム）から構成されたゲルパーミエーショ
ンクロマトグラフィー（東ソー社製ＨＣＬ−８０２０）
によって温度３８℃で測定し、Ｆ２０００／Ｆ７００／
Ｆ２８８／Ｆ１２８／Ｆ８０／Ｆ４０／Ｆ２０／Ｆ２／
Ａ１０００（東ソー社製ポリスチレン）およびスチレン
モノマーを用いた検量線にて、ポリスチレン換算により
求めた。なお、測定温度は３８℃、検出器はＲＩにて行
った。## EQU1 ## THF-insoluble matter (%) = {(W3−W1) × 100} / W2 (1) Molecular weight by gel permeation chromatography
Distribution : A resin solution of 0.04% by weight using THF as a solvent is coated with a PTFE membrane (Mythodisc H-25 manufactured by Tosoh Corporation).
5), and filtered through three columns (TSKgel manufactured by Tosoh Corporation).
/ GMH XL column) and gel permeation chromatography (HCL-8020 manufactured by Tosoh Corporation)
Measured at a temperature of 38 ° C. by F2000 / F700 /
F288 / F128 / F80 / F40 / F20 / F2 /
It was determined in terms of polystyrene by a calibration curve using A1000 (polystyrene manufactured by Tosoh Corporation) and a styrene monomer. The measurement temperature was 38 ° C., and the detector was RI.
【００２６】ガラス転移温度：１００℃で試料を溶融し
急冷後のＤＳＣ測定におけるショルダー値を採用した。樹脂粒子の形状 ：走査型電子顕微鏡を用い、１００個の
樹脂粒子の形状を観察し、その平均の長径（ＲL ）と短
径（ＲS ）の比（ＲL ／ＲS ）を求めた。ＲL ／ＲS が
０．９以下であり、エッジ部のないものを実質的に球形
であるとした。 Glass transition temperature : A sample was melted at 100 ° C., and a shoulder value in DSC measurement after quenching was adopted. Shape of resin particles : The shape of 100 resin particles was observed using a scanning electron microscope, and the ratio ( RL / RS ) of the average major axis ( RL ) to minor axis ( RS ) was determined. . Those having R L / R S of 0.9 or less and having no edge portion were regarded as substantially spherical.
【００２７】平均粒子径：目開きが１０００μｍ、７１
０μｍ、５００μｍ、３５５μｍ、２５０μｍ、１５０
μｍ、７５μｍの篩いを、この順序で重ねて、振動機を
用いてサンプル量５００ｇで粒径分布を求め、これの累
積の５０重量％の値で示した。１０００μｍ以上の成分
割合は、目開き１０００μｍの篩い上に残ったものの質
量を測定して、その割合を求めた。また、７５μｍ未満
の成分割合は、目開き７５μｍの篩いを通過したものの
質量を測定し、その割合を求めた。 Average particle size : opening is 1000 μm, 71
0 μm, 500 μm, 355 μm, 250 μm, 150
The sieves of μm and 75 μm were stacked in this order, the particle size distribution was determined using a vibrator with a sample amount of 500 g, and the value was shown as a value of 50% by weight of the cumulative value. The component ratio of 1000 μm or more was determined by measuring the mass of what remained on the sieve having an opening of 1000 μm. In addition, for the component ratio of less than 75 μm, the mass of a component having passed through a sieve having an opening of 75 μm was measured, and the ratio was determined.
【００２８】嵩比重：ＪＩＳ Ｋ−５１０１に準じて測
定した。定着温度領域 ：市販の複写機（松下電器産業社製ＦＰ−
１５７０）を用いて得られた未定着画像を、ローラー温
度可変の定着試験機を用いて、定着速度３００ｍｍ／秒
で得られた定着画像を砂消しゴム（ＪＩＳ５１２）で９
回擦り、その前後での画像濃度をマクベス濃度計で測定
し、濃度の低下が２０％未満である最低温度と、ローラ
ーにトナーが移行する最低温度で表示した。 Bulk specific gravity : Measured according to JIS K-5101. Fixing temperature range : Commercial copying machine (FP-Made by Matsushita Electric Industrial Co., Ltd.)
1570), the unfixed image obtained at a fixing speed of 300 mm / sec was fixed with a sand eraser (JIS 512) using a fixing tester with a variable roller temperature.
The image density before and after the rubbing was measured with a Macbeth densitometer, and the result was indicated by the lowest temperature at which the decrease in density was less than 20% and the lowest temperature at which the toner transferred to the roller.
【００２９】画像濃度：市販の複写機（松下電器産業社
製ＦＰ−１５７０）を用いて得られた未定着画像の画像
濃度をマクベス濃度計で測定し、画像濃度が１．２以上
ものを良好、画像濃度が１．２未満ものを不良とした。樹脂の非飛散性 ：樹脂１００ｇを５００ｍｌのガラス製
ビーカーに入れ、１ｍの高さから樹脂を落とし、その飛
散状態を観察して評価した。粒径保持性 ：樹脂１ｋｇを生産日本社製チャック付きポ
リ袋に入れ、３ｍの高さから１０回落下させた後、粒径
分布の変化状況および７５μｍ未満の微粉の発生状況か
ら評価した。 Image density : The image density of an unfixed image obtained using a commercially available copying machine (FP-1570 manufactured by Matsushita Electric Industrial Co., Ltd.) was measured with a Macbeth densitometer. And those having an image density of less than 1.2 were regarded as defective. Non-scattering property of resin: 100 g of resin was put into a 500 ml glass beaker, the resin was dropped from a height of 1 m, and the scattering state was observed and evaluated. Particle size retention : 1 kg of resin was placed in a plastic bag with a zipper manufactured by Production Japan Co., Ltd., dropped 10 times from a height of 3 m, and evaluated based on the change in the particle size distribution and the generation of fine powder of less than 75 μm.
【００３０】合成例１ スチレン４０重量部とアクリル酸ｎ−ブチル１０重量部
からなる単量体混合物に、重合開始剤として２，２−ビ
ス（４，４−ジ−ｔ−ブチルパーオキシシクロヘキシ
ル）プロパン（化薬アクゾ社製「パーカドックス１
２」）０．０２４重量部を溶解し、脱イオン水２００重
量部と部分鹸化ポリビニルアルコ−ル（日本合成化学工
業社製「ゴ−セノ−ルＧＨ−２３」）０．２重量部との
混合物中に添加して撹拌する。次いで、１３０℃まで昇
温して２時間、高分子量重合体成分の懸濁重合を行っ
た。その後、４０℃まで冷却した高分子量重合体成分の
分散液中に、スチレン４０重量部とアクリル酸ｎ−ブチ
ル１０重量部からなる単量体混合物と、重合開始剤とし
てベンゾイルパーオキシド６重量部とｔ−ブチルパーオ
キシベンゾエート（日本油脂社製「パーブチルＺ」）１
重量部を添加し、１３０℃まで昇温して１．５時間、低
分子量重合体成分の懸濁重合を行った。その後、室温ま
で冷却し、十分に洗浄、脱水して、乾燥を行い、高分子
量重合体成分と低分子量重合体成分とが均一に混合した
スチレン−アクリル系共重合体（樹脂Ａ）を得た。得ら
れたスチレン−アクリル系共重合体（樹脂Ａ）は、ガラ
ス転移温度が５７℃、ＴＨＦ不溶解分が０．０２重量
％、ＴＨＦ可溶分のゲルパーミエーションクロマトグラ
フィーによる分子量分布で分子量１．８×１０5 と８×
１０3 にピークを有していた。また、重合体粒子は、Ｒ
L ／ＲS が０．９６でエッジ部のない実質的に球形であ
り、平均粒子径が３４３μｍで、１０００μｍ以上の成
分が１７％、７５μｍ未満の成分が１５％で、嵩比重が
０．６１ｇ／ｍｌであった。Synthesis Example 1 To a monomer mixture consisting of 40 parts by weight of styrene and 10 parts by weight of n-butyl acrylate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) was used as a polymerization initiator. Propane (Parkadox 1 manufactured by Kayaku Akzo)
2)) dissolving 0.024 parts by weight, mixing 200 parts by weight of deionized water with 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Add into the mixture and stir. Then, the temperature was raised to 130 ° C., and suspension polymerization of the high molecular weight polymer component was performed for 2 hours. Thereafter, a monomer mixture consisting of 40 parts by weight of styrene and 10 parts by weight of n-butyl acrylate, and 6 parts by weight of benzoyl peroxide as a polymerization initiator were added to the dispersion of the high molecular weight polymer component cooled to 40 ° C. t-butyl peroxybenzoate ("Perbutyl Z" manufactured by NOF Corporation) 1
By weight, the temperature was raised to 130 ° C., and suspension polymerization of the low molecular weight polymer component was performed for 1.5 hours. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer (resin A) in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. . The obtained styrene-acrylic copolymer (resin A) has a glass transition temperature of 57 ° C., a THF-insoluble content of 0.02% by weight, and a THF-soluble content of 1 wt. .8 × 10 5 and 8 ×
It had a peak at 10 3 . Further, the polymer particles are represented by R
L / R S is 0.96, is substantially spherical without edges, has an average particle diameter of 343 μm, 17% of components having a size of 1000 μm or more, 15% of components having a size of less than 75 μm, and has a bulk specific gravity of 0.61 g. / Ml.
【００３１】合成例２ スチレン３２重量部とアクリル酸ｎ−ブチル８重量部か
らなる単量体混合物をオートクレーブに投入し、窒素置
換を行った後に１２０℃に昇温し、１６時間塊状重合を
行った。さらに、キシレン５０重量部を加え、ジブチル
パーオキサイド０．０４重量部を溶解したエチルベンゼ
ン５０重量部を１３０℃に保持したオートクレーブ内に
８時間かけて連続投入し、その後２時間重合を継続し
た。次いで、２００℃に昇温し、スチレン４８重量部、
アクリル酸ｎ−ブチル１２重量部とキシレンとエチルベ
ンゼンの混合溶媒３０重量部からなる混合溶液に、スチ
レン１００モルに対して０．５モルのジ−ｔ−ブチルパ
ーオキサイドを溶解した溶液を、オートクレーブ内に３
時間かけて連続投入し、その後、１時間重合を継続して
反応を終了しスチレン−アクリル系共重合体を得た。得
られたスチレン−アクリル系共重合体を、２００℃、１
０ｍｍＨｇの真空系にフラッシュして溶剤を除去して、
室温に冷却した後にチョッパーミルを用いて粉砕してス
チレン−アクリル系共重合体（樹脂Ｂ）を得た。得られ
たスチレン−アクリル系共重合体（樹脂Ｂ）は、ガラス
転移温度が５５℃、ＴＨＦ不溶解分が０．０３重量％、
ＴＨＦ可溶分のゲルパーミエーションクロマトグラフィ
ーによる分子量分布で分子量４×１０5 と６×１０3 に
ピークを有していた。また、重合体粒子は、ＲL ／ＲS
が０．６５でエッジ部を有する形状であり、平均粒子径
が３３５μｍで、１０００μｍ以上の成分が０％、７５
μｍ未満の成分が３４％で、嵩比重が０．５７ｇ／ｍｌ
であった。Synthesis Example 2 A monomer mixture consisting of 32 parts by weight of styrene and 8 parts by weight of n-butyl acrylate was charged into an autoclave, purged with nitrogen, heated to 120 ° C., and subjected to bulk polymerization for 16 hours. Was. Further, 50 parts by weight of xylene was added, and 50 parts by weight of ethylbenzene in which 0.04 part by weight of dibutyl peroxide was dissolved was continuously charged into an autoclave maintained at 130 ° C. over 8 hours, and thereafter polymerization was continued for 2 hours. Then, the temperature was raised to 200 ° C., 48 parts by weight of styrene,
A solution obtained by dissolving 0.5 mol of di-t-butyl peroxide with respect to 100 mol of styrene in a mixed solution comprising 12 parts by weight of n-butyl acrylate and 30 parts by weight of a mixed solvent of xylene and ethylbenzene was placed in an autoclave. To 3
It was continuously charged over a period of time, and thereafter, the polymerization was continued for 1 hour to terminate the reaction, thereby obtaining a styrene-acrylic copolymer. The obtained styrene-acrylic copolymer was heated at 200 ° C.,
Flushing to 0 mmHg vacuum system to remove solvent,
After cooling to room temperature, the mixture was pulverized using a chopper mill to obtain a styrene-acrylic copolymer (resin B). The obtained styrene-acrylic copolymer (resin B) has a glass transition temperature of 55 ° C., a THF-insoluble content of 0.03% by weight,
The THF soluble portion had peaks at molecular weights of 4 × 10 5 and 6 × 10 3 in the molecular weight distribution by gel permeation chromatography. Further, the polymer particles are represented by R L / R S
Is 0.65 and has an edge portion, the average particle diameter is 335 μm, and the components of 1000 μm or more are 0%, 75%
34% of components less than μm and bulk specific gravity of 0.57 g / ml
Met.
【００３２】合成例３ スチレン２４重量部とアクリル酸ｎ−ブチル６重量部、
α−メチルスチレンダイマー０．１重量部からなる単量
体混合物に、脱イオン水２００重量部とドデシルベンゼ
ンスルフォン酸ソーダ０．１５重量部、ＫＰＳ０．０６
重量部との混合液を添加し、十分に窒素置換を行った後
に、９０℃まで昇温して３時間、高分子量重合体成分の
乳化重合を行った。その後、４０℃まで冷却した高分子
量重合体成分の乳化液中に、スチレン５６重量部とアク
リル酸ｎ−ブチル１４重量部からなる単量体混合物と、
ベンゾイルパーオキシド６重量部、ｔ−ブチルパーオキ
シベンゾエート（日本油脂社製「パーブチルＺ」）１重
量部、部分鹸化ポリビニルアルコ−ル（日本合成化学工
業社製「ゴ−セノ−ルＧＨ−２３」）０．３５量部を溶
解した脱イオン水１００重量部を添加し、１３０℃まで
昇温して１．５時間、低分子量重合体成分の懸濁重合を
行った。その後、室温まで冷却し、十分に洗浄、脱水し
て、乾燥を行い、高分子量重合体成分と低分子量重合体
成分とが均一に混合したスチレン−アクリル系共重合体
（樹脂Ｃ）を得た。得られたスチレン−アクリル系共重
合体（樹脂Ｃ）は、ガラス転移温度が５７℃、ＴＨＦ不
溶解分が０．０９重量％、ＴＨＦ可溶分のゲルパーミエ
ーションクロマトグラフィーによる分子量分布で分子量
２．３×１０5 と８×１０3 にピークを有していた。ま
た、重合体粒子は、ＲL ／ＲS が０．９４でエッジ部の
ない実質的に球形であり、平均粒子径が３６７μｍで、
１０００μｍ以上の成分が７％、７５μｍ未満の成分が
１５％で、嵩比重が０．３１ｇ／ｍｌであった。Synthesis Example 3 24 parts by weight of styrene and 6 parts by weight of n-butyl acrylate
To a monomer mixture consisting of 0.1 part by weight of α-methylstyrene dimer, 200 parts by weight of deionized water, 0.15 part by weight of sodium dodecylbenzenesulfonate and 0.06 part by weight of KPS
A mixed solution with the mixture was added and the mixture was sufficiently purged with nitrogen. Then, the temperature was raised to 90 ° C., and emulsion polymerization of the high molecular weight polymer component was performed for 3 hours. Thereafter, a monomer mixture consisting of 56 parts by weight of styrene and 14 parts by weight of n-butyl acrylate in an emulsion of the high molecular weight polymer component cooled to 40 ° C.,
6 parts by weight of benzoyl peroxide, 1 part by weight of t-butyl peroxybenzoate ("Perbutyl Z" manufactured by NOF Corporation), partially saponified polyvinyl alcohol ("Go-Senol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ) 100 parts by weight of deionized water in which 0.35 part by weight was dissolved was added, the temperature was raised to 130 ° C, and suspension polymerization of the low molecular weight polymer component was performed for 1.5 hours. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer (resin C) in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. . The obtained styrene-acrylic copolymer (resin C) has a glass transition temperature of 57 ° C., a THF insoluble content of 0.09% by weight, and a THF soluble content of molecular weight distribution by gel permeation chromatography of 2 and a molecular weight of 2 It had peaks at 3 × 10 5 and 8 × 10 3 . Further, the polymer particles had a R L / R S of 0.94, were substantially spherical without edges, had an average particle diameter of 367 μm,
The components having a size of 1000 μm or more were 7%, the components having a size of less than 75 μm were 15%, and the bulk specific gravity was 0.31 g / ml.
【００３３】実施例１ 樹脂Ａを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を完全に除去し、さらに目開き７
５μｍの篩を用いて７５μｍ未満の粒子径の粒子を完全
に除去した。得られた樹脂粒子の平均粒子径は３２０μ
ｍ、粒子径１０００μｍ以上の粒子は０％、粒子径７５
μｍ未満の粒子は０％で、嵩比重は０．６３ｇ／ｍｌで
あった。この樹脂粒子は、非飛散性、粒径保持性も良好
であり、粒径保持性試験前後での非飛散性に差は見られ
なかった。Example 1 Resin A was prepared by using a sieve having a mesh size of 1000 μm and
m or more, and particles having a particle size of
Particles having a particle diameter of less than 75 μm were completely removed using a 5 μm sieve. The average particle diameter of the obtained resin particles is 320 μm.
m, 0% of particles having a particle diameter of 1000 μm or more, particle diameter of 75%
The particles having a particle size of less than μm were 0%, and the bulk specific gravity was 0.63 g / ml. The resin particles had good non-scattering property and good particle size retention, and no difference was observed in non-scattering property before and after the particle size retention test.
【００３４】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まりはなく
良好な流動性を有していた。次いで、ジェットミル粉砕
機を用いて粉砕し、分級して平均粒子径１３μｍのトナ
ーを得た。得られたトナーの定着温度領域は１３５〜２
３０℃で実用レベルであり、画像濃度も良好であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei), and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, there was no clogging in the feeder portion, and the material had good fluidity. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. The fixing temperature range of the obtained toner is 135 to 2
It was at a practical level at 30 ° C., and the image density was good.
【００３５】実施例２ 樹脂Ａを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を除去し、さらに目開き７５μｍ
の篩を用いて７５μｍ未満の粒子径の粒子を除去した。
得られた樹脂粒子の平均粒子径は３２５μｍ、粒子径１
０００μｍ以上の粒子は５％、粒子径７５μｍ未満の粒
子は５％で、嵩比重は０．６３ｇ／ｍｌであった。この
樹脂粒子は、非飛散性、粒径保持性も良好であり、粒径
保持性試験前後での非飛散性に差は見られなかった。Example 2 Using a sieve having a mesh size of 1000 μm, resin A was
m or more and remove particles with a particle size of 75 μm or more.
The particles having a particle diameter of less than 75 μm were removed using a sieve.
The average particle size of the obtained resin particles is 325 μm, and the particle size is 1
5% of the particles had a particle size of 000 μm or more, 5% of the particles had a particle size of less than 75 μm, and had a bulk specific gravity of 0.63 g / ml. The resin particles had good non-scattering property and good particle size retention, and no difference was observed in non-scattering property before and after the particle size retention test.
【００３６】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まりはなく
良好な流動性を有していた。次いで、ジェットミル粉砕
機を用いて粉砕し、分級して平均粒子径１３μｍのトナ
ーを得た。得られたトナーの定着温度領域は１３５〜２
３０℃で実用レベルであり、画像濃度も良好であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, there was no clogging in the feeder portion, and the material had good fluidity. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. The fixing temperature range of the obtained toner is 135 to 2
It was at a practical level at 30 ° C., and the image density was good.
【００３７】実施例３ 樹脂Ａを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を除去し、さらに目開き７５μｍ
の篩を用いて７５μｍ未満の粒子径の粒子を除去した。
得られた樹脂粒子の平均粒子径は３２５μｍ、粒子径１
０００μｍ以上の粒子は１０％、粒子径７５μｍ未満の
粒子は１０％で、嵩比重は０．６２ｇ／ｍｌであった。
この樹脂粒子は、非飛散性はやや劣るものの実用上は問
題とならないレベルであり、粒径保持性は良好であり、
粒径保持性試験前後での非飛散性に差は見られなかっ
た。Example 3 Using a resin having a mesh size of 1000 μm,
m or more and remove particles with a particle size of 75 μm or more.
The particles having a particle diameter of less than 75 μm were removed using a sieve.
The average particle size of the obtained resin particles is 325 μm, and the particle size is 1
Particles having a particle size of 000 μm or more were 10%, particles having a particle size of less than 75 μm were 10%, and the bulk specific gravity was 0.62 g / ml.
Although the resin particles have a slightly inferior non-scattering property, they are at a level that does not pose a problem in practical use, and the particle size retention is good.
There was no difference in non-scattering property before and after the particle size retention test.
【００３８】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まりはなく
良好な流動性を有していた。次いで、ジェットミル粉砕
機を用いて粉砕し、分級して平均粒子径１３μｍのトナ
ーを得た。得られたトナーの定着温度領域は１３５〜２
３０℃で実用レベルであり、画像濃度も良好であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, there was no clogging in the feeder portion, and the material had good fluidity. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. The fixing temperature range of the obtained toner is 135 to 2
It was at a practical level at 30 ° C., and the image density was good.
【００３９】比較例１ 合成例１で得られた樹脂Ａを（平均粒子径は３４３μ
ｍ、粒子径１０００μｍ以上の粒子は１７％、粒子径７
５μｍ未満の粒子は１５％で、嵩比重は０．６１ｇ／ｍ
ｌ）を用いた。この樹脂粒子は、非飛散性は不良であっ
たが、粒径保持性は良好であり、粒径保持性試験前後で
の非飛散性に差は見られなかった。Comparative Example 1 Resin A obtained in Synthesis Example 1 (average particle diameter: 343 μm)
m, 17% of particles having a particle diameter of 1000 μm or more,
15% of particles smaller than 5 μm have a bulk specific gravity of 0.61 g / m 2
l) was used. Although the resin particles had poor non-scattering property, they had good particle size retention, and no difference was observed in the non-scattering property before and after the particle size retention test.
【００４０】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まりはなく
良好な流動性を有していた。次いで、ジェットミル粉砕
機を用いて粉砕し、分級して平均粒子径１３μｍのトナ
ーを得た。得られたトナーの定着温度領域は１３５〜２
３０℃で実用レベルであったが、画像濃度も不良であっ
た。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, there was no clogging in the feeder portion, and the material had good fluidity. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. The fixing temperature range of the obtained toner is 135 to 2
Although it was at a practical level at 30 ° C., the image density was also poor.
【００４１】比較例２ 樹脂Ａを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を完全に除去し、さらに目開き３
３５μｍの篩を用いて３３５μｍ未満の粒子径の粒子を
完全に除去した。得られた樹脂粒子の平均粒子径は６２
８μｍ、粒子径１０００μｍ以上の粒子は０％、粒子径
７５μｍ未満の粒子は０％で、嵩比重は０．５４ｇ／ｍ
ｌであった。この樹脂粒子は、非飛散性、粒径保持性も
良好であり、粒径保持性試験前後での非飛散性に差は見
られなかった。COMPARATIVE EXAMPLE 2 Resin A was prepared by using a sieve having a mesh size of 1000 μm.
m or more are completely removed, and the aperture 3
Particles having a particle size of less than 335 μm were completely removed using a 35 μm sieve. The average particle diameter of the obtained resin particles is 62.
8 μm, particles having a particle diameter of 1000 μm or more are 0%, particles having a particle diameter of less than 75 μm are 0%, and a bulk specific gravity is 0.54 g / m 2.
l. The resin particles had good non-scattering property and good particle size retention, and no difference was observed in non-scattering property before and after the particle size retention test.
【００４２】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まりはなく
良好な流動性を有していた。次いで、ジェットミル粉砕
機を用いて粉砕し、分級して平均粒子径１３μｍのトナ
ーを得た。得られたトナーの定着温度領域は１３５〜２
３０℃で実用レベルであったが、画像濃度は不良であっ
た。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, there was no clogging in the feeder portion, and the material had good fluidity. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. The fixing temperature range of the obtained toner is 135 to 2
Although it was at a practical level at 30 ° C., the image density was poor.
【００４３】比較例３ 樹脂Ａを目開き１００μｍの篩を用いて、１００μｍ以
上の粒子径の粒子を完全に除去し、さらに目開き７５μ
ｍの篩を用いて７５μｍ未満の粒子径の粒子を除去し
た。得られた樹脂粒子の平均粒子径は８２μｍ、粒子径
１０００μｍ以上の粒子は０％、粒子径７５μｍ未満の
粒子は５％で、嵩比重は０．６９ｇ／ｍｌであった。こ
の樹脂粒子は、非飛散性は不良であったが、粒径保持性
は良好であり、粒径保持性試験前後での非飛散性に差は
見られなかった。Comparative Example 3 Resin A was completely removed by using a sieve having an opening of 100 μm to completely remove particles having a particle diameter of 100 μm or more.
The particles having a particle diameter of less than 75 μm were removed using a sieve of m. The average particle diameter of the obtained resin particles was 82 μm, the particles having a particle diameter of 1000 μm or more were 0%, the particles having a particle diameter of less than 75 μm were 5%, and the bulk specific gravity was 0.69 g / ml. Although the resin particles had poor non-scattering property, they had good particle size retention, and no difference was observed in the non-scattering property before and after the particle size retention test.
【００４４】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まり流動性
は不良であった。次いで、ジェットミル粉砕機を用いて
粉砕し、分級して平均粒子径１３μｍのトナーを得た。
得られたトナーの定着温度領域は１３５〜２３０℃で実
用レベルであったが、画像濃度は不良であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, the clogging fluidity at the feeder portion was poor. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm.
The fixing temperature range of the obtained toner was a practical level at 135 to 230 ° C., but the image density was poor.
【００４５】比較例４ 樹脂Ｂを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を完全に除去し、さらに目開き７
５μｍの篩を用いて７５μｍ未満の粒子径の粒子を完全
に除去した。得られた樹脂粒子の平均粒子径は３７４μ
ｍ、粒子径１０００μｍ以上の粒子は０％、粒子径７５
μｍ未満の粒子は０％で、嵩比重は０．５０ｇ／ｍｌで
あった。この樹脂粒子は、非飛散性は良好であったが、
粒径保持性が不良であり、粒径保持性試験後の非飛散性
も不良であった。Comparative Example 4 Resin B was screened using a sieve having a mesh size of 1000 μm.
m or more, and particles having a particle size of
Particles having a particle diameter of less than 75 μm were completely removed using a 5 μm sieve. The average particle diameter of the obtained resin particles is 374 μm.
m, 0% of particles having a particle diameter of 1000 μm or more, particle diameter of 75%
The particles having a particle size of less than μm were 0%, and the bulk specific gravity was 0.50 g / ml. Although the resin particles had good non-scattering properties,
The particle size retention was poor, and the non-scattering property after the particle size retention test was also poor.
【００４６】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まり流動性
は不良であった。次いで、ジェットミル粉砕機を用いて
粉砕し、分級して平均粒子径１３μｍのトナーを得た。
得られたトナーの定着温度領域は１３５〜２３０℃で実
用レベルであったが、画像濃度は不良であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei), and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, the clogging fluidity at the feeder portion was poor. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm.
The fixing temperature range of the obtained toner was a practical level at 135 to 230 ° C., but the image density was poor.
【００４７】比較例５ 樹脂Ｃを目開き１０００μｍの篩を用いて、１０００μ
ｍ以上の粒子径の粒子を完全に除去し、さらに目開き７
５μｍの篩を用いて７５μｍ未満の粒子径の粒子を完全
に除去した。得られた樹脂粒子の平均粒子径は２０５μ
ｍ、粒子径１０００μｍ以上の粒子は０％、粒子径７５
μｍ未満の粒子は０％で、嵩比重は０．３３ｇ／ｍｌで
あった。この樹脂粒子は、非飛散性は良好であったが、
粒径保持性が不良であり、粒径保持性試験後の非飛散性
も不良であった。Comparative Example 5 Resin C was screened for 1000 μm using a sieve having an opening of 1000 μm.
m or more, and particles having a particle size of
Particles having a particle diameter of less than 75 μm were completely removed using a 5 μm sieve. The average particle diameter of the obtained resin particles is 205 μ
m, 0% of particles having a particle diameter of 1000 μm or more, particle diameter of 75%
The particles having a particle size of less than μm were 0%, and the bulk specific gravity was 0.33 g / ml. Although the resin particles had good non-scattering properties,
The particle size retention was poor, and the non-scattering property after the particle size retention test was also poor.
【００４８】得られたスチレン−アクリル系共重合体粒
子をバインダー樹脂として９３重量部に、カーボンブラ
ック（三菱化成社製＃４０）４重量部、荷電制御剤（オ
リエント化学工業社製「ボントロンＳ−３４」）１重量
部およびポリプロピレンワックス（三洋化成社製６６０
Ｐ）２重量部を配合し、２軸押出機を用いて１３５℃で
溶融混練した。この時、フィーダー部での詰まり流動性
は不良であった。次いで、ジェットミル粉砕機を用いて
粉砕し、分級して平均粒子径１３μｍのトナーを得た。
得られたトナーの定着温度領域は１３５〜２３０℃で実
用レベルであったが、画像濃度は不良であった。The obtained styrene-acrylic copolymer particles were used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei), and a charge control agent ("Bontron S-" manufactured by Orient Chemical Industries, Ltd.). 34 ") 1 part by weight and polypropylene wax (660 manufactured by Sanyo Chemical Industries, Ltd.)
P) 2 parts by weight were blended and melt-kneaded at 135 ° C. using a twin-screw extruder. At this time, the clogging fluidity at the feeder portion was poor. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm.
The fixing temperature range of the obtained toner was a practical level at 135 to 230 ° C., but the image density was poor.
【００４９】[0049]
【発明の効果】本発明は、バインダー樹脂を構成する高
分子量重合体成分と低分子量重合体成分の分子量分布を
制御することにより、トナーの定着性と非オフセット性
とのバランスをとり、バインダー樹脂の粒子形状、粒子
径を制御することによって、十分な画像濃度を有し、取
扱い性に優れ、作業環境を悪化させることのないトナー
用バインダー樹脂およびトナ−を提供できるものであ
る。According to the present invention, by controlling the molecular weight distribution of the high molecular weight polymer component and the low molecular weight polymer component constituting the binder resin, the balance between the fixing property and the non-offset property of the toner is improved. By controlling the particle shape and particle size of the toner, a toner binder resin and toner having a sufficient image density, excellent handleability and not deteriorating the working environment can be provided.
Claims (3)
量％以下であり、テトラヒドロフラン可溶分のゲルパー
ミエーションクロマトグラフィーによる分子量分布にお
いて、分子量１×１０5 〜５×１０5 の領域にメインピ
ークを有する高分子量重合体成分と、４×１０3 〜３×
１０4 の領域にメインピークを有する低分子量重合体成
分とから構成され、長径（ＲL ）と短径（ＲS ）の比
（ＲL ／ＲS ）が０．９以上である実質的に球形で、平
均粒子径が１００〜５００μｍ、粒子径１０００μｍ以
上の成分が１０％以下、粒子径７５μｍ未満の成分が１
０％以下で、嵩比重が０．３５ｇ／ｍｌ以上であるビニ
ル系重合体粒子からなることを特徴とするトナー用バイ
ンダー樹脂。1. A tetrahydrofuran-insoluble content of 0.5% by weight or less, and a main peak in a region of a molecular weight of 1 × 10 5 to 5 × 10 5 in a molecular weight distribution by gel permeation chromatography of a tetrahydrofuran-soluble content. Having a high molecular weight polymer component and 4 × 10 3 to 3 ×
And a low molecular weight polymer component having a main peak in the region of 10 4 , wherein the ratio (R L / R S ) of the major axis (R L ) to the minor axis (R S ) is substantially 0.9 or more. Spherical, with an average particle diameter of 100 to 500 μm, a component having a particle diameter of 1000 μm or more is 10% or less, and a component having a particle diameter of less than 75 μm is 1%.
A binder resin for a toner, comprising vinyl polymer particles having a bulk specific gravity of 0% or less and a bulk specific gravity of 0.35 g / ml or more.
上のｔ−ブチルパーオキシド基を有する重合開始剤を用
いた懸濁重合によって重合されることを特徴とする請求
項１記載のトナー用バインダー樹脂。2. The method according to claim 1, wherein the high molecular weight polymer component is polymerized by suspension polymerization using a polymerization initiator having three or more t-butyl peroxide groups in one molecule. Binder resin for toner.
ることを特徴とするトナー。3. A toner comprising the binder resin according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25949096A JPH10104877A (en) | 1996-09-30 | 1996-09-30 | Binder resin and toner for toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25949096A JPH10104877A (en) | 1996-09-30 | 1996-09-30 | Binder resin and toner for toner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10104877A true JPH10104877A (en) | 1998-04-24 |
Family
ID=17334823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25949096A Pending JPH10104877A (en) | 1996-09-30 | 1996-09-30 | Binder resin and toner for toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10104877A (en) |
-
1996
- 1996-09-30 JP JP25949096A patent/JPH10104877A/en active Pending
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