JPH01219764A - Electrostatic charge image developing toner - Google Patents
Electrostatic charge image developing tonerInfo
- Publication number
- JPH01219764A JPH01219764A JP63044354A JP4435488A JPH01219764A JP H01219764 A JPH01219764 A JP H01219764A JP 63044354 A JP63044354 A JP 63044354A JP 4435488 A JP4435488 A JP 4435488A JP H01219764 A JPH01219764 A JP H01219764A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- molecular weight
- thf
- binder resin
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 32
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 32
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 62
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 31
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 40
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 34
- 239000004793 Polystyrene Substances 0.000 description 29
- 229920002223 polystyrene Polymers 0.000 description 29
- 238000005227 gel permeation chromatography Methods 0.000 description 26
- 239000011342 resin composition Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000011572 manganese Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- -1 polyethylene Polymers 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 230000007423 decrease Effects 0.000 description 14
- 108091008695 photoreceptors Proteins 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 230000004927 fusion Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 238000010557 suspension polymerization reaction Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 229920006158 high molecular weight polymer Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 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 1
- 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 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 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
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-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
- 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 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical group CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- LRRBANSQUYNJTH-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CC(C)(C)OOC(C)(C)C LRRBANSQUYNJTH-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
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- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006902 nitrogenation reaction Methods 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
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- ZAKVZVDDGSFVRG-UHFFFAOYSA-N prop-1-en-2-ylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 ZAKVZVDDGSFVRG-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- PRIFGVOVRHAALC-UHFFFAOYSA-N tert-butyl 3,3-dimethylbutaneperoxoate Chemical compound CC(C)(C)CC(=O)OOC(C)(C)C PRIFGVOVRHAALC-UHFFFAOYSA-N 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
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- MPCYPRXRVWZKGF-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C=C4C=C(C=C(C4=C3O)N)S([O-])(=O)=O)S([O-])(=O)=O)=C(O)C2=C1N MPCYPRXRVWZKGF-UHFFFAOYSA-J 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電子写真、静電記録、静電印刷などにおける
静電荷像を現像するためのトナーに関し、特に粉砕によ
る製造方法で得られた熱ローラ一定着に適する静電荷像
現像用トナーに関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a toner for developing electrostatic images suitable for constant fixation on a heated roller.
［従来の技術］
従来、電子写真法としては米国特許第２，２９７゜６９
１号明細書、特公昭４２−２３９１Ｏ号公報及び特公昭
４３−２４７４８号公報等に記載されている如く多数の
方法が知られているが、一般には光導電性物質を利用し
、種々の手段により感光体上に電気的潜像を形成し、次
いで該潜像をトナーを用いて現像し、必要に応じて紙等
の転写材にトナー画像を転写した後、加熱、圧力、加熱
加圧或いは溶剤蒸気などにより定着し複写物を得るもの
であり、そして感光体上に転写せず残ったトナーは種々
の方法でクリーニングされ、上述の工程が繰り返される
。[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297°69
Although many methods are known, such as those described in Japanese Patent Publication No. 42-2391O and Japanese Patent Publication No. 43-24748, etc., generally, photoconductive substances are used and various means are used. An electrical latent image is formed on the photoreceptor by a method, and then the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then heated, pressured, heated and pressed, or Copies are obtained by fixing with solvent vapor, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above-mentioned steps are repeated.
近年このような複写装置は、単なる一般にいうオリジナ
ル原稿を複写するための事務処理用複写機というだけで
なく、コンピューターの出力としてのプリンターあるい
は個人向けのパーソナルコピアという分野で使われ始め
た。In recent years, such copying devices have begun to be used not only as office copy machines for copying original manuscripts, but also as printers for computer output or as personal copiers for individuals.
そのため、より小型、より軽量そしてより高速、より高
信頼性が厳しく追究されてきており、機械は種々な点で
よりシンブルな要素で構成されるようになってきている
。その結果、トナーに要求される性鮨はより高度になり
、トナーの性能向上が達成できなければよりすぐれた機
械が成り立たなくなってきている。Therefore, smaller size, lighter weight, higher speed, and higher reliability are being strictly pursued, and machines are being constructed from simpler elements in various respects. As a result, the properties required of toner have become more sophisticated, and it has become impossible to create better machines unless the performance of toner can be improved.
例えばトナー像を紙などのシートに定着する工程に関し
て種々の方法や装置が開発されているが、現在最も一般
的な方法は熱ローラーによる圧着加熱方式である。For example, various methods and devices have been developed for the process of fixing a toner image on a sheet such as paper, but the most common method at present is a pressure-heating method using a heated roller.
加熱ローラーによる圧着加熱方式はトナーに対し離型性
を有する材料で表面を形成した熱ローラーの表面に被定
着シートのトナー像面を加圧下で接触しながら通過せし
めることにより定着を行なうものである。この方法は熱
ローラーの表面と被定着シートのトナー像とが加圧下で
接触するため、トナー像を被定着シート上に融着する際
の熱効率が極めて良好であり、迅速に定着を行うことが
でき、高速度電子写真複写機において非常に有効である
。しかしながら上記方法では、熱ローラー表面とトナー
像とが溶融状態で加圧下で接触するためにトナー像の一
部が定着ローラー表面に付着、転移し、次の被定着シー
トにこれが再転移して所謂オフセット現象を生じ、被定
着シートを汚すことがある。熱定着ローラー表面に対し
てトナーが付着しないようにすることが然ローラ一定着
方式の必須条件の１つとされている。The pressure heating method using a heated roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heated roller whose surface is made of a material that has releasability for toner. . In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in high-speed electrophotographic copying machines. However, in the above method, since the surface of the heat roller and the toner image contact each other under pressure in a molten state, a portion of the toner image adheres to and transfers to the surface of the fixing roller, and this is transferred again to the next sheet to be fixed, resulting in so-called This may cause an offset phenomenon and stain the fixing sheet. Preventing toner from adhering to the surface of the heat fixing roller is considered to be one of the essential conditions for the fixed roller fixing method.
従来、定着ローラー表面にトナーを付着させない目的で
、例えばローラー表面をトナーに対して離型性のすぐれ
た材料、シリコンゴムや弗素系樹脂などで形成し、さら
にその表面にオフセット防止及びローラー表面の疲労を
防止するためにシリコンオイルの如き離型性の良い液体
の薄膜でローラー表面を被覆することが行われている。Conventionally, in order to prevent toner from adhering to the fixing roller surface, for example, the roller surface was made of a material with excellent release properties for toner, such as silicone rubber or fluorine resin, and the surface was also coated with anti-offset and roller surface coatings. In order to prevent fatigue, the roller surface is coated with a thin film of a liquid with good mold releasability, such as silicone oil.
しかしながら、この方法はトナーのオフセットを防止す
る点では極めて有効であるが、オフセット防止用液体を
供給するための装置が必要なため、定着装置が複雑にな
ること等の問題点を有している。However, although this method is extremely effective in preventing toner offset, it requires a device to supply the offset prevention liquid, resulting in problems such as the complexity of the fixing device. .
これは小型化、軽量化と逆方向であり、しかもシリコン
オイルなどが熱により蒸発し、機内を汚染する場合があ
る。そこでシリコンオイルの供給装置などを用いないで
、かわりにトナー中から加熱時にオフセット防止液体を
供給しようという考えから、トナー中に低分子量ポリエ
チレン、低分子量ポリプロピレンなどのＭ型剤を添加す
る方法が提案されている。充分な効果を出すために多量
にこのような添加剤を加えると、感光体へのフィルミン
グやキャリアやスリーブなどのトナー担持体の表面を汚
染し、画像が劣化し実用上問題となる。そこで画像を劣
化させない程度に少量の離型剤をトナー中に添加し、若
干の離型性オイルの供給もしくはオフセットしたトナー
を巻きとり式の例えばウェブの如き部材を用いた装置で
クリーニングする装置を併用することが行われている。This is in the opposite direction to miniaturization and weight reduction, and what's more, silicone oil and other substances may evaporate due to heat and contaminate the interior of the aircraft. Therefore, instead of using a silicone oil supply device, we proposed a method of adding an M-type agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner, with the idea of supplying an anti-offset liquid from within the toner during heating. has been done. If a large amount of such additives is added in order to obtain a sufficient effect, it may cause filming on the photoreceptor or contaminate the surface of a toner carrier such as a carrier or sleeve, deteriorating the image and causing practical problems. Therefore, a small amount of release agent is added to the toner to the extent that the image does not deteriorate, and a device that cleans the toner by supplying a small amount of release oil or using a device such as a web to take up the offset toner. They are used together.
しかし最近の小型化、軽量化、高信頼性の要求を考慮す
るとこれらの補助的な装置すら除去することが必要であ
り好ましい、従ってトナーの定着、オフセットなどのさ
らなる性悌の向上がなければ対応しきれず、それはトナ
ーのバインダー樹脂のさらなる改良がなければ実現する
ことが困難である。トナーのバインダー樹脂の改良に関
する技術として、例えば特公昭５１−２３３５４号公報
に結着樹脂として架橋された重合体を用いたトナーが提
案されている。その方法に従えば耐オフセット性及び耐
まきつき性の改良には効果があるが、反面架橋度をます
と定着点が上昇してしまい、充分定着温度が低くて耐オ
フセット性及び酎まきつき性が良好で且つ十分な定着特
性のものは得られていない、一般的に定着性を向上させ
るためには、バインダー樹脂を低分子量化して軟化点を
低下させねばならず、耐オフセット性の改善処置とは相
反することになり、また低軟化点とするために必然的に
樹脂のガラス転移点が低下し保存中のトナーがブロッキ
ングするという好ましくない現象もおこる。However, considering the recent demands for miniaturization, weight reduction, and high reliability, it is necessary and desirable to eliminate even these auxiliary devices. Therefore, it is necessary to further improve performance such as toner fixing and offset. However, this is difficult to achieve without further improvement of the binder resin of the toner. As a technique for improving the binder resin of a toner, for example, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. If this method is followed, it will be effective in improving offset resistance and sticking resistance, but on the other hand, if the degree of crosslinking is increased, the fixing point will rise, and the fixing temperature will be sufficiently low, resulting in good offset resistance and sticking resistance. Generally speaking, in order to improve fixing properties, it is necessary to lower the softening point of the binder resin by lowering its molecular weight.What are the measures to improve offset resistance? This is contradictory, and in order to achieve a low softening point, the glass transition point of the resin inevitably decreases, resulting in an undesirable phenomenon of blocking of the toner during storage.
これに対して、特開昭５８−１５８３４０号公報に低分
子量重合体と高分子量重合体とよりなるトナーが提案さ
れているが、このバインダー樹脂は実際には架橋成分を
含有させることが難しく、より高性能に耐オフセット性
を向上させるためには、高分子量重合体の分子量を大き
くするか比率を増す必要がある。この方向は粉砕性を著
しく低下させる方法であり、実用上満足するものは得ら
れにくい、さらに低分子量重合体と架橋した重合体とを
ブレンドしたトナーに関し、例えば特開昭５８−８８５
５８号公報に低分子量重合体と不溶融性高分子量重合体
を主要樹脂成分とするトナーが提案されている。その方
法に従えば定着性及び粉砕性の改良は行われる傾向にあ
るが、低分子量重合体の重量平均分子量／数平均分子量
（Ｍｙ／Ｍｎ）が３．５以下と小さいこと及び不溶不融
性高分子量重合体の含有量が４０〜９０ｗｔ％と多量で
あることにより、耐オフセット性と粉砕性を共に高性能
で満足することが難しく、実際上はオフセット防止用液
体の供給装置をもつ定着器用でなければ定着性（特に高
速定着）、耐オフセット性、粉砕性を充分満足するトナ
ーを生成することは極めて困難である。On the other hand, JP-A-58-158340 proposes a toner made of a low molecular weight polymer and a high molecular weight polymer, but it is difficult to actually incorporate a crosslinking component into this binder resin. In order to improve offset resistance with higher performance, it is necessary to increase the molecular weight or ratio of the high molecular weight polymer. This approach is a method that significantly reduces the crushability, and it is difficult to obtain a product that is practically satisfactory.
No. 58 proposes a toner containing a low molecular weight polymer and an infusible high molecular weight polymer as main resin components. If this method is followed, fixing properties and crushability tend to be improved, but the weight average molecular weight/number average molecular weight (My/Mn) of the low molecular weight polymer is as small as 3.5 or less, and the insoluble and infusible Due to the large content of high molecular weight polymer, 40 to 90 wt%, it is difficult to satisfy both offset resistance and crushability with high performance. Otherwise, it is extremely difficult to produce a toner that fully satisfies fixing properties (especially high-speed fixing), anti-offset properties, and crushability.
さらに不溶不融性高分子量重合体が多くなると、トナー
作成時の熱混練で溶融粘度が非常に高くなるため通常よ
りはるかに高温で熱混練するか、あるいは高いシェアで
熱混練しなければならず、その結果前者は他の添加剤の
熱分解によるトナー特性の低下、後者はバインダー樹脂
の分子の過度な切断が起り、当初の耐オフセット性走が
出にくいという問題を有している。Furthermore, if there is a large amount of insoluble, infusible high molecular weight polymer, the melt viscosity will become extremely high during heat kneading during toner production, so it must be heat kneaded at a much higher temperature than usual, or heat kneaded at a high shear. As a result, the former has the problem of deterioration of toner properties due to thermal decomposition of other additives, and the latter has the problem that the molecules of the binder resin are excessively cut, making it difficult to achieve the initial offset resistance properties.
また特開昭８０−１６８！３５８号公報に、数平均分子
量（Ｍｎ）５００〜１．５００である低分子量のポリα
−メチルスチレンの存在下で重合して得られる樹脂組成
分からなるトナーが提案されている。Furthermore, in JP-A-80-168!358, a low molecular weight polyα having a number average molecular weight (Mn) of 500 to 1.500 is disclosed.
- A toner comprising a resin composition obtained by polymerization in the presence of methylstyrene has been proposed.
特に該公報では、数平均分子量（Ｍｎ）が９，０００〜
３０．０００の範囲が好ましいとあるが、耐オフセット
性をより向上させるためＭｎを大きくしていくと定着性
及びトナー製造時の粉砕性が実用上問題となり、故に高
性能に耐オフセット性と粉砕性を満足することは難しい
。このようにトナー製造時における粉砕性の悪いトナー
は、トナー製造時の生産効率が低下する他、トナー特性
として粗いトナーが混入しやすいため飛びちった画像と
なる場合があり好ましくない。In particular, in this publication, the number average molecular weight (Mn) is from 9,000 to
It is said that a range of 30.000 is preferable, but if Mn is increased in order to further improve offset resistance, fixing performance and pulverization during toner production become a practical problem. Sexual satisfaction is difficult. In this way, a toner with poor pulverizability during toner production is undesirable because not only does the production efficiency during toner production decrease, but also rough toner tends to be mixed into the toner, which may result in a scattered image.
また特開昭５８−１８１４４号公報にＧＰＣによる分子
量分布において、分子量１０３〜８ Ｘ １０’及び分
子量１０５〜２ Ｘ １０６のそれぞれの領域に少なく
とも１つの極大値をもつ結着樹脂成分を含有するトナー
が提案されている。この場合、粉砕性、耐オフセット性
、定着性、感光体へのフィルミングや融着２画像性など
すぐれているが、さらにトナーにおける耐オフセット性
及び定着性の向上が要望されている。特に定着性をより
向上させて他の種々の性能を保つか、あるいは向上させ
つつ今日の厳しい要求に対応するのは該樹脂ではむずか
しい。Further, JP-A-58-18144 discloses a toner containing a binder resin component having at least one maximum value in each of the molecular weight regions of 103 to 8 x 10' and 105 to 2 x 106 in molecular weight distribution by GPC. is proposed. In this case, the toner has excellent crushability, anti-offset properties, fixing properties, and filming and fusion two-image properties on photoreceptors, but there is a demand for further improvement in the anti-offset properties and fixing properties of the toner. In particular, it is difficult for such resins to meet today's strict demands while maintaining or improving various other properties by further improving fixing properties.
このように定着に関わる性能と粉砕性を共に高性能で実
現することは極めて困難である。特にトナー製造時にお
ける粉砕性は、複写画像の高品位化、高解像化、高細線
再現性の要望によりトナーの粒径をより小さくしていく
今日の方向に重要な因子であり、また粉砕工程はひじよ
うに大きなエネルギーを要するため粉砕性の向上は省エ
ネルギーの面からも重要である。In this way, it is extremely difficult to achieve both high performance related to fixing and crushability. In particular, pulverization during toner production is an important factor as the particle size of toner is becoming smaller in response to demands for higher quality, higher resolution, and fine line reproducibility of copied images. Since the process requires an enormous amount of energy, improving crushability is also important from the perspective of energy conservation.
また粉砕装置内壁へのトナーの融着現象も定着性能の良
いトナーに発生しやすく、そのため粉砕効率を悪くする
。さらに別な側面として他の複写工程において、転写後
の感光体上に残ったトナーをクリーニングする工程があ
る。今日、装置の小型化、軽量化、信頼性の面からブレ
ードによるクリーニング（ブレードクリーニング）が一
般的になっている。感光体の高寿命化と感光体ドラムな
どの小型化及びシステムの高速化に伴い、トナーに要求
される感光体に対する耐融着、耐フィルミング性などが
厳しくなっている。特に最近実用化されてきたアモルフ
ァスシリコン感光体はひじように高耐久性であり、また
ｏｐｃ （有機感光体）も寿命が延びてきており、そ
のためトナーに要求される諸性俺はより高度になってき
ている。In addition, toner fusion to the inner wall of the crushing device is more likely to occur with toner having good fixing performance, which impairs the crushing efficiency. As a further aspect, in another copying process, there is a process of cleaning the toner remaining on the photoreceptor after transfer. Nowadays, cleaning using a blade (blade cleaning) has become common in view of the miniaturization, weight reduction, and reliability of devices. With the increase in the lifespan of photoconductors, the miniaturization of photoconductor drums, and the increase in speed of systems, the requirements for toners such as fusion resistance and filming resistance with respect to photoconductors have become stricter. In particular, amorphous silicon photoreceptors that have recently been put into practical use have extremely high durability, and the lifespan of OPC (organic photoreceptors) is also getting longer, so the various properties required of toners are becoming more sophisticated. It's coming.
また小型化はせまい所に各要素をうまく納めていくこと
をしなければならない、そのため空気がうまくながれる
空間が少なくなる上、定着器や露光系の熱源がトナーホ
ッパーやクリーナーと非常に接近するため、トナーは高
温雰囲気にさらされる。そのため、より優れた耐ブロッ
キング性を有するトナーでないと実用化できなくなって
きた。In addition, miniaturization requires that each element be neatly housed in a narrow space, which reduces the space for air to flow properly, and the heat source of the fuser and exposure system is very close to the toner hopper and cleaner. , the toner is exposed to a high temperature atmosphere. Therefore, it has become impossible to put toners into practical use unless they have better anti-blocking properties.
添付の第７図に示すように、トナーに要求される諸性能
は相反する場合がほとんどであり、しかもそれらを共に
高性能に満足することがますます望まれ、研究されてい
るが、未だ充分なものがない。As shown in the attached Figure 7, the various performances required of toner are often contradictory, and although it is increasingly desired and researched to satisfy both of them with high performance, there is still insufficient performance. There's nothing.
［発明が解決しようとする課題］
一方現像性に関しては、前述の種々の定着特性を満足す
ることを前提として、長期にわたる連続複写でもカブリ
がなく鮮明で、しかも高画像濃度を維持し、環境変動に
影響されない高画質画像を与えるトナーが望まれている
。[Problems to be Solved by the Invention] On the other hand, regarding developability, on the premise that the various fixing characteristics described above are satisfied, it is possible to maintain a clear image without fogging even during continuous copying over a long period of time, maintain high image density, and maintain high image density. There is a need for a toner that provides high quality images that are not affected by.
特に複写スピードが中〜高速である複写機では、初期か
ら長期にわたってカブリがなく鮮明な高濃度の画像が安
定して得られる必要があり、さらに環境変化に影響され
ないことが必要である。In particular, in a copying machine whose copying speed is medium to high, it is necessary to stably obtain clear, high-density images without fog over a long period of time from the initial stage, and it is also necessary to be unaffected by environmental changes.
従来、耐オフセット、巻き付き、低温定着、耐ブロッキ
ングなどの一連の定着特性に優れ、また、粉砕性、添加
剤分散性にも優れたトナー用バインダーレジンを目的に
種々のレジンが提案そして改良されてきたが、トナーを
作成する際にある種の荷電制御剤をそのバインダーレジ
ンに組合わせると、長期にわたる複写のくり返しによっ
て、複写機の現像器のスリーブ（現像スリーブ）がトナ
ーに由来する物質によって汚染され、画像濃度が、初期
に比べて低下する現象が発生する。この現象は中〜ある
いは高速複写機に対応するトナーで特に問題となりその
解決が望まれている。Various resins have been proposed and improved in the past for the purpose of toner binder resins that have excellent fixing properties such as offset resistance, wrapping, low-temperature fixing, and blocking resistance, as well as excellent crushability and additive dispersibility. However, if a certain type of charge control agent is combined with the binder resin when making toner, the sleeve of the copier's developing device may become contaminated with substances derived from the toner over a long period of repeated copying. As a result, a phenomenon occurs in which the image density decreases compared to the initial state. This phenomenon is particularly problematic with toners compatible with medium to high speed copying machines, and a solution is desired.
さらに長期にわたる複写のくり返しによって画像濃度低
下が生じるトナーは、時として環境依存性があり、特に
高温、高湿環境下においてトナー自身の摩擦帯電能が低
下して、画像濃度低下が発生しその早期解決も望まれて
いる。Furthermore, toners that cause a decrease in image density due to repeated copying over a long period of time are sometimes environmentally dependent.Especially in high temperature and high humidity environments, the toner's own triboelectric charging ability decreases, causing a decrease in image density and its early stages. A solution is also desired.
本発明の目的は、上述の如き問題点を解決したトナーを
提供するものである。An object of the present invention is to provide a toner that solves the above-mentioned problems.
以下に本発明の目的を列挙する。The objects of the present invention are listed below.
本発明の目的は、オイルを塗布しない熱ロール定着方式
に適したトナーを提供することにある。An object of the present invention is to provide a toner suitable for a hot roll fixing method that does not apply oil.
本発明の目的は、ブレードを用いたクリーニング方式に
適したトナーを提供することにある。An object of the present invention is to provide a toner suitable for a cleaning method using a blade.
本発明の目的は、低い温度で定着し得、且つ耐オフセッ
ト性のすぐれたトナーを提供することにある。An object of the present invention is to provide a toner that can be fixed at a low temperature and has excellent offset resistance.
本発明の目的は、低い温度で定着し、感光体への融着、
フィルミングが高速システムにおいても、また長期間の
使用でも発生しないトナーを提供することにある。The purpose of the present invention is to fix at a low temperature, fuse to a photoreceptor,
It is an object of the present invention to provide a toner that does not cause filming even in high-speed systems and even after long-term use.
本発明の目的は、低い温度で定着し且つ耐ブロッキング
性がすぐれ、特に小型機の中の高温雰囲気中でも充分使
え得るトナーを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that can be fixed at low temperatures, has excellent anti-blocking properties, and can be used satisfactorily even in high-temperature atmospheres, especially in small machines.
本発明の目的は、低い温度で定着し且つトナーの製造時
における粉砕工程での装置の内壁へ粉砕物が融着しない
ため、効率よく連続で生産できるトナーを提供すること
にある。An object of the present invention is to provide a toner that can be efficiently and continuously produced because it is fixed at a low temperature and the pulverized material does not fuse to the inner wall of an apparatus during the pulverization process during toner production.
本発明の目的は、耐オフセット性がすぐれ且つ粉砕性が
すぐれているため、生産効率が良いトナーを提供するこ
とにある。An object of the present invention is to provide a toner that has excellent anti-offset properties and excellent pulverizability, and thus has good production efficiency.
本発明の目的は、耐オフセット性がすぐれ且つ粉砕性が
すぐれているため、生産効率が良いトナーを提供するこ
とにある。An object of the present invention is to provide a toner that has excellent anti-offset properties and excellent pulverizability, and thus has good production efficiency.
本発明の目的は、耐オフセット性がすぐれ、またテトラ
ヒドロフラン（ＴＨＦ）不溶分が必要以上に多くなく、
トナーの熱混練工程で変質、劣化しないトナーを提供す
ることにある。The purpose of the present invention is to have excellent offset resistance, and to have less tetrahydrofuran (THF) insoluble content than necessary.
An object of the present invention is to provide a toner that does not change in quality or deteriorate during a toner heat kneading process.
本発明の目的は、粉砕性が良いため粗粉などの発生が少
なく、そのため画像のまわりのとびちりが少なく、安定
した良好な現像画像を形成し得るトナーを提供すること
にある。An object of the present invention is to provide a toner that has good pulverizability, generates less coarse powder, and therefore has less scattering around the image, and can form a stable and good developed image.
本発明の目的は特に高速複写機において長期にわたる連
続複写に対して優れた耐久性をもち、カブリのない鮮明
な高画像濃度を維持するトナーを提供することにある。An object of the present invention is to provide a toner that has excellent durability for long-term continuous copying, especially in high-speed copying machines, and maintains clear, high image density without fogging.
本発明の目的は、環境変動に影響されにくいカブリのな
い鮮明な高画像濃度を安定して与えるトナーを提供する
ことにある。An object of the present invention is to provide a toner that stably provides a clear, high-density image without fog that is less susceptible to environmental changes.
［課題を解決するための手段］
すなわち本発明は、トナー中のバインダー樹脂のＴＨＦ
不溶分が１０〜８０ｗｔ％（バインダー樹脂を基準）で
あり、ＴＨＦ可溶分のＧＰＣによる分子量分布において
、重量平均分子量／数平均分子量（Ｍｗ／Ｍｎ）≧５で
あり、分子量２，０００〜１０，０００（７）領域に少
なくとも１つのピークを有し、分子量１５．０００〜１
００，０００領域にピーク又は肩を少なくとも１つ有し
、分子量１０，０００以下の成分の含有量が、へインダ
ー樹脂を基準にして１０〜５０ｗｔ％であるバインダー
樹脂と、含窒素荷電制御剤とを少なくとも含有し、且つ
安息香酸の含有量が５００９ｐ■以下であることを特徴
とする静電荷像現像用トナーに係るものである。[Means for Solving the Problem] That is, the present invention solves the problem by reducing THF of the binder resin in the toner.
The insoluble content is 10 to 80 wt% (based on the binder resin), the weight average molecular weight/number average molecular weight (Mw/Mn) is ≧5 in the molecular weight distribution of the THF soluble content by GPC, and the molecular weight is 2,000 to 10. ,000 (7) region and a molecular weight of 15.000 to 1
a binder resin having at least one peak or shoulder in the 00,000 region and a content of components having a molecular weight of 10,000 or less of 10 to 50 wt% based on the binder resin; and a nitrogen-containing charge control agent. The present invention relates to a toner for developing an electrostatic image, characterized in that the content of benzoic acid is 5009p or less.
本発明について以下に詳細に説明する。The present invention will be explained in detail below.
前記のような目的を同時に達成するため種々のバインダ
ー樹脂を用い、その構成と性悌についてさまざまの角度
から鋭意検討した。その結果バインダー樹脂のＴＨＦ不
溶分の割合と、ＴＨＦ可溶分の分子量分布の特定の構成
のときに達成できることを見出した。バインダー樹脂を
ＴＨＦなどの溶剤で溶かすと不溶分と可溶分に分離でき
、可溶分はＧＰＣで分子量分布を測定することができる
。 ＴＨＦ不溶分とＴＨＦ可溶分の分子量分布のピーク
の位置に着目すると、その位置と粉砕性の関係は第８図
に示すとおりである。これからＴＨＦ不溶分がないかま
たは少ない系は粉砕性においてひじように不利であり、
前述したように粉砕性を良化するためＴＨＦ可溶分の分
子量分布のピークの位置を単純に低分子量の位置に移行
させていく方向は耐オフセット性を悪化させ、耐オフセ
ット性と粉砕性をともに満足することが難しいというこ
とを裏付けている。In order to achieve the above objectives at the same time, various binder resins were used, and their composition and properties were carefully studied from various angles. As a result, it has been found that this can be achieved when the ratio of the THF-insoluble portion of the binder resin and the molecular weight distribution of the THF-soluble portion are in a specific configuration. When the binder resin is dissolved in a solvent such as THF, it can be separated into an insoluble component and a soluble component, and the molecular weight distribution of the soluble component can be measured by GPC. Focusing on the positions of the peaks in the molecular weight distribution of the THF-insoluble and THF-soluble components, the relationship between the positions and the crushability is as shown in FIG. Therefore, systems with no or only a small amount of THF-insoluble matter are extremely disadvantageous in terms of crushability.
As mentioned above, simply shifting the peak position of the molecular weight distribution of THF-soluble components to a lower molecular weight position in order to improve crushability will worsen offset resistance and reduce offset resistance and crushability. This proves that it is difficult to be satisfied with both.
この検討から、通常考えられているようにＴＨＦ不溶分
は耐オフセット性のためだけでなく、粉砕性を良化する
目的でも特定量含有させることはひじょうに有効である
ことが判明した。From this study, it has been found that it is very effective to contain a specific amount of THF-insoluble matter not only for the purpose of anti-offset properties, as is generally thought, but also for the purpose of improving crushability.
さらにＴＨＦ可溶分の分子量分布と定着可能温度が高い
か低いかという性質（以後、単に定着性という）、耐オ
フセット性、粉砕性、耐ブロッキング性について検討し
た。その結果、例えば第９図のようにＧＰＧ分子量分布
での分子量的１０，０００以下と約１０，０００以上の
分子量を有する成分の働きが異なることを見い出した。Furthermore, the molecular weight distribution of the THF-soluble content, the property of whether the fixable temperature is high or low (hereinafter simply referred to as fixability), offset resistance, crushability, and blocking resistance were investigated. As a result, it was found that components having a molecular weight of 10,000 or less and a component having a molecular weight of about 10,000 or more have different functions in the GPG molecular weight distribution, as shown in FIG. 9, for example.
すなわちバインダー樹脂全体に対する分子量１０，００
０以下の分子量を有する成分の含有割合は、通常言われ
ているように定着性あるいは耐オフセット性を強く左右
するのではなく、特定範囲ではどちらかというとほとん
ど関係せず、かわりに粉砕性に強く関係していることが
判明した。That is, the molecular weight of the entire binder resin is 10,00
The content ratio of components with a molecular weight of 0 or less does not strongly affect fixing properties or anti-offset properties as is usually said, but rather has little to do with it within a certain range, and instead affects crushability. It turned out that they are strongly related.
さらに他の検討などからバインダー樹脂は、基本的には
ＴＨＦ不溶分が主に耐オフセット性、まきつき性、粉砕
性に影響を与え、そしてＴＨＦ可溶分の分子量１０，０
００以下の成分が主に粉砕性、ブロッキング性、感光体
への融着性、フィルミング性そして粉砕装置内壁への融
着に影響を与え、さらにＴＨＦ可溶分の分子量ｉｏ、ｏ
ｏｏ以上の成分が主に定着性を左右していることが判明
した。そして分子量１０．０００以下の成分の割合は、
１０〜５０ｗｔ％が良く、好ましくは２０〜３９ｗｔ％
である。充分な性濠を出すためには、さらに分子量ｔｏ
、０００以下であり２，０００以上（好ましくは２．０
００〜８，０００ ）の領域にピークを有し、分子量１
５，０００〜１００，０００ （好ましくは２０．０
００〜７，０００ ）の領域にピークもしくは肩が必要
である。 ２，０００〜１０，０００にピークがなく分
子量２．０００以下にピークがあるが、分子量１０，０
００以下の成分の割合が５０ｗｔ％以上であると、耐ブ
ロッキング性、感光体への融着、フィルミング、粉砕装
置内壁への融着などがやや問題となる０分子量１０．０
００以下にピークがなく １０，０００以上にピークが
あるが、分子ｚ ｔｏ、ｏｏｏ以下の成分の割合が１０
ｗｔ％以下であると特に粉砕性が問題となり、粗粒子の
生成も問題となる。Furthermore, other studies have shown that the THF-insoluble content of binder resins mainly affects offset resistance, clinging properties, and crushability, and the THF-soluble content has a molecular weight of 10.0.
The components below 00 mainly affect the pulverizing properties, blocking properties, adhesion to the photoreceptor, filming properties, and adhesion to the inner wall of the grinding device, and furthermore, the molecular weight of the THF soluble component is io, o.
It has been found that components of oo or higher mainly affect fixing properties. And the proportion of components with a molecular weight of 10.000 or less is
10 to 50 wt% is good, preferably 20 to 39 wt%
It is. In order to produce a sufficient sexual moat, the molecular weight to
, 000 or less and 2,000 or more (preferably 2.0
It has a peak in the region of 00 to 8,000), and has a molecular weight of 1
5,000 to 100,000 (preferably 20.0
A peak or shoulder is required in the region of 00 to 7,000). There is no peak between 2,000 and 10,000, and there is a peak below molecular weight 2.000, but the molecular weight is 10.0
If the proportion of components with a molecular weight of 10.0 or less is 50 wt% or more, problems such as blocking resistance, adhesion to the photoreceptor, filming, and adhesion to the inner wall of the crushing device may occur.
There is no peak below 00, there is a peak above 10,000, but the proportion of components below molecule z to, ooo is 10
If it is less than wt%, pulverizability becomes a problem, and the formation of coarse particles also becomes a problem.
また分子量１５，０００以上の領域にピークもしくは肩
がなく、分子量１５，０００以下の領域のみにピークが
ある場合は耐オフセット性が問題となる０分子量１５，
０００〜１００，０００の領域にピークもしくは肩が゛
なく、かつ１００，０００以上にメインピークがあると
粉砕性が問題となる。Also, if there is no peak or shoulder in the region of molecular weight 15,000 or more, and there is a peak only in the region of molecular weight 15,000 or less, offset resistance becomes a problem.
If there is no peak or shoulder in the range of 000 to 100,000, and there is a main peak above 100,000, the crushability becomes a problem.
さらにＴＨＥ可溶分はＭｙ／Ｍｎ≧５であることが必要
であり、Ｍｙ／Ｍｎが５以下になると耐オフセット性が
低下する傾向が高まり問題となる。Furthermore, it is necessary that the THE soluble content satisfies My/Mn≧5, and if My/Mn becomes 5 or less, the offset resistance tends to decrease, which becomes a problem.
好ましくはＭｙ／Ｍｎが８０以下が良く、さらに好まし
くは１０≦Ｍｙ／Ｍｎ≦６０が良い。Preferably My/Mn is 80 or less, more preferably 10≦My/Mn≦60.
特にＭｗ／ＭｎがｌＯ≦Ｍｙ／Ｍｎ≦６０であると粉砕
性。In particular, when Mw/Mn satisfies lO≦My/Mn≦60, the crushability is improved.
定着性、耐オフセット性９画像性など種々の特性におい
て特にすぐれた性能を示す。It shows particularly excellent performance in various properties such as fixing properties, offset resistance, and image quality.
なおここでＭｙとは後述のＧＰＣによって測定された重
量平均分子量であり、Ｍｎとは同様の測定による数平均
分子量である。In addition, My here is the weight average molecular weight measured by GPC mentioned later, and Mn is the number average molecular weight measured by the same measurement.
そして、さらにトナーのバインダー樹脂の↑ＨＦ不溶分
は１０〜８０ｗｔ％が必要である。 ＴＨＦ不溶分が１
０ｗｔ％以下だと耐オフセット性が問題となり、８０ｗ
ｔ％以上だとトナー製造時の熱混練による分子鎖切断な
どの劣化の問題を生じる。好ましくはＴＨＥ不溶分の含
有量は１５〜４９ｗｔ％が粉砕性及び耐オフセット性の
点で良い。Further, the ↑HF-insoluble content of the binder resin of the toner is required to be 10 to 80 wt%. THF insoluble content is 1
If it is less than 0wt%, offset resistance becomes a problem, and 80w
If it exceeds t%, problems of deterioration such as molecular chain scission due to thermal kneading during toner production will occur. Preferably, the content of THE insoluble matter is 15 to 49 wt%, which is good in terms of crushability and offset resistance.
またＴＨＦ可溶分の分子量分布の１万以下の分子量分の
樹脂のガラス転移点Ｔｇｌ とトナー全体のガラス転移
点Ｔｇｔ を比較したとき、Ｔｇｌ≧Ｔｇｔ−５の関係
になると定着性、粉砕性、感光体への融着、フィルミン
グ性、粉砕装置内壁への融着性、耐ブロッキング性など
がより良好になる。Also, when comparing the glass transition point Tgl of the resin with a molecular weight of 10,000 or less in the molecular weight distribution of the THF soluble component and the glass transition point Tgt of the entire toner, if the relationship of Tgl≧Tgt-5 is established, the fixing property, crushability, The adhesion to the photoreceptor, the filming property, the adhesion to the inner wall of the crushing device, the blocking resistance, etc. are improved.
ここでいうＴｇｌ とは次の方法により測定されたもの
である。温度２５℃にてＴＨＦを毎分７＋ｓｆｌの流速
にて流し、トナーのＴＨＦ可溶成分の濃度的３■ｇ／ｒ
ａｉ！のＴＨＦ試料溶液を３ｍｊ）程度分子量分布測定
装置に柱入し、分子量１万以下の成分を分取する。分取
の後、溶媒を減圧留去し、さらに９０℃雰囲気中減圧で
２４ｆｆ８間乾燥する９分子量１万以下の成分が２０鳳
ｇ程度得られるまで上記操作を繰り返し行い、５０℃で
４８時間のアニーリングを行い、この後に示差走査熱量
測定法によりＴｇを測定し、この値をＴｇ、 とする
、この時の測定は、一般に知られているＡＳＴＭＤ３４
１８−８２法に準じ、行った。すなわち、ｌＯ℃／ｗｉ
ｎの昇温測定で１２０℃以上に昇温し、さらに約１０分
間保持し、これをＯ′Ｃに急冷し、そこで１０分間保持
後、１０℃／ｓｉｎで昇温し、吸熱カーブを得る。 Ｔ
ｇは、ベースラインの中間線と交曲線の交点をもって定
義される。Tgl here is measured by the following method. THF was flowed at a flow rate of 7+sfl/min at a temperature of 25°C, and the concentration of THF-soluble components in the toner was 3 g/r.
ai! A THF sample solution of approximately 3mj) is introduced into a molecular weight distribution measuring device, and components with a molecular weight of 10,000 or less are fractionated. After the fractionation, the solvent was distilled off under reduced pressure, and the above procedure was repeated until about 20 grams of components with a molecular weight of 10,000 or less were obtained. After annealing, Tg is measured by differential scanning calorimetry, and this value is defined as Tg. This measurement is performed using the generally known ASTM D34 method.
The procedure was carried out according to Method 18-82. That is, lO℃/wi
The temperature was increased to 120° C. or higher in the temperature increase measurement of n, held for further about 10 minutes, rapidly cooled to O'C, held there for 10 minutes, and then raised at a rate of 10° C./sin to obtain an endothermic curve. T
g is defined by the intersection of the median line of the baseline and the intersection line.
分取用カラムとしてはＴＳＫｇｅｌ Ｇ２０００Ｈ，Ｔ
ＳＫｇｅｌＧ２５００Ｈ，ＴＳＫｇｅｌ Ｇ３０００Ｈ
，ＴＳＫｇｅｌ Ｇ４０００）１ （共に東洋曹達工業
■）等が用いられるが、本発明ではＴＳＫｇｅｌ Ｇ２
０００ＨとＴＳＫｇｅｌ Ｇ３０００Ｈを組み合せて用
いた。As a preparative column, TSKgel G2000H,T
SKgel G2500H, TSKgel G3000H
, TSKgel G4000) 1 (both manufactured by Toyo Soda Kogyo ■), etc., but in the present invention, TSKgel G2
000H and TSKgel G3000H were used in combination.
またトナーのＴｇであるＴｇｔの値はトナーを５０℃、
４８時間アニーリングし、その後示差走査熱量測定法に
より求める。Also, the value of Tgt, which is the Tg of the toner, is when the toner is heated at 50°C.
Annealed for 48 hours and then determined by differential scanning calorimetry.
本発明の最も好ましい態様は、第１図に示すように、Ｔ
ＨＦ可溶分のＧＰＣ分子量分布において、分子量１５，
０００〜１００，０００の領域にある最も高いピークの
高さをｈ２、分子量２，０００〜１０，０００の領域に
ある最も高いピークの高さをｈｌとすると、ｂ＋／ｈ２
の比が０．４〜４．０／１を有するバインダー樹脂を
含有するトナーである。菫だ、さらにＴＨＦ可溶分の数
平均分子量について、２，０００≦Ｍｎ≦９，０００が
好ましい。Ｍｎ＜２，０００だとオフセット性などが問
題となり、９，０００ ＜Ｍｎだと粉砕性及び定着性が
問題となってくる。The most preferred embodiment of the present invention is as shown in FIG.
In the GPC molecular weight distribution of the HF soluble fraction, the molecular weight was 15,
If the height of the highest peak in the region of 000 to 100,000 is h2, and the height of the highest peak in the region of molecular weight 2,000 to 10,000 is hl, then b+/h2
The toner contains a binder resin having a ratio of 0.4 to 4.0/1. Furthermore, the number average molecular weight of the THF-soluble component is preferably 2,000≦Mn≦9,000. When Mn<2,000, offset properties become a problem, and when 9,000<Mn, pulverization properties and fixing properties become problems.
本発明でのＴＨＦ不溶分とは、トナー中の樹脂組成物中
のＴＨＦ溶媒に対して不溶性となったポリマー成分（実
質的に架橋ポリマー）の重量割合を示し、架橋成分を含
む樹脂組成物の架橋の程度を示すパラメーターとして使
うことができる。 ＴＨＦ不溶分とは、以下のように測
定された値をもって定義する。The THF-insoluble content in the present invention refers to the weight percentage of the polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent in the resin composition in the toner, and refers to the weight percentage of the polymer component (substantially crosslinked polymer) in the resin composition in the toner. It can be used as a parameter indicating the degree of crosslinking. The THF-insoluble content is defined by the value measured as follows.
すなわち、トナーサンプル０．５〜１．０ｇを秤量しく
Ｗａｇ） 、円筒鑓紙（例えば東洋症紙製Ｎｏ、 ８Ｓ
Ｒ）に入れてソックスレー抽出器にかけ、溶媒としてＴ
ＨＦ １００〜２００ｍｊ）を用いて６時間抽出し、溶
媒によって抽出された可溶成分をエバポレートした後、
１００℃で数時間真空乾燥し、ＴＨＦ可溶樹脂成分量を
秤量する（１１１２ｇ）。トナー中の磁性体あるいは顔
料の如き樹脂成分以外の成分の重量を（Ｗ３ｇ）とする
、 ＴＨＦ不溶分は、下記式から求められる。That is, weigh 0.5 to 1.0 g of toner sample (Wag), cylindrical paper (for example, No. 8S manufactured by Toyosho Paper Co., Ltd.)
R) and subjected to a Soxhlet extractor, using T as a solvent.
After extracting for 6 hours using HF 100-200 mj) and evaporating the soluble components extracted by the solvent,
Vacuum dry at 100° C. for several hours and weigh the amount of THF-soluble resin component (1112 g). The THF-insoluble content, where the weight of components other than resin components such as magnetic substances or pigments in the toner is (W3g), can be calculated from the following formula.
本発明において、ＧＰＣ： （ゲルパーミエーション
クロマトグラフィ）によるクロマトグラムのピーク又は
／およびショルダーの分子量は次の条件で測定される。In the present invention, the molecular weight of the peak and/or shoulder of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.
すなわち、４０℃のヒートチャンバー中でカラムを安定
化させ、この温度におけるカラムに、溶媒としてＴＨＦ
（テトラヒドロフラン）を毎分１層！の流速で流し
、試料濃度として０．０５〜０．６重量％に調整した樹
脂のＴＨＦ試料溶液を５０〜２００ｅｊ）注入して測定
する。試料の分子量測定にあたっては、試料の有する分
子量分布を数種の単分散ポリスチレン標準試料により作
製された検量線の対数値とカウント数との関係から算出
した。検量線作成用の標準ポリスチレン試料としては、
例えばＰｒｅｓｓｕｒｅＣｈｅｍｉｃａｌ Ｇｏ、製或
いは東洋ツーダニ業社製の分子量が６Ｘ１０２．２．ｌ
Ｘ１０３． ４Ｘ１０３．１．７５ Ｘ１０４゜５、Ｉ
Ｘ １０４．１．ＩＸ １０５．３．９Ｘ １０５．
８．８Ｘ １０５゜２ Ｘ １０６．４．４８ Ｘ １
０６のものを用い、少なくとも１０点程度の標準ポリス
チレン試料を用いるのが適当である。また検出器にはＲ
Ｉ（屈折率）検出器を用いる。That is, the column was stabilized in a heat chamber at 40°C, and THF was added to the column at this temperature as a solvent.
(Tetrahydrofuran) one layer per minute! Measurement is performed by injecting 50 to 200 ej) of a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6 wt%. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve,
For example, pressure chemical Go, or Toyo Tsudani Gyosha with a molecular weight of 6X102.2. l
X103. 4X103.1.75 X104゜5, I
X 104.1. IX 105.3.9X 105.
8.8X 105゜2 X 106.4.48 X 1
It is appropriate to use at least 10 standard polystyrene samples. Also, the detector has R
An I (refractive index) detector is used.
なお、カラムとしては１０３〜−ｊｘｌｏ６の分子量領
域を適確に測定するために、市収のポリスチレンゲルカ
ラムを複数組合せるのが良く、例えば、Ｗａｔｅｒｓ社
製のｇ−ｓｔ７ｒａｇｅｌ ５００． １０３． １０
’、 １０５の組み合せや、昭和電工社製の５ｈｏｄ
ｅｘ ＫＦ−８０Ｍや、ＫＦ−８０２，８０３，８０４
，８０５の組合せ、あるいは東洋曹達製のＴＳＫｇｅｌ
Ｇ１００ＯＨ，Ｇ２０００Ｈ，Ｇ２５００Ｈ。In addition, in order to accurately measure the molecular weight range of 103 to -jxlo6, it is recommended to use a combination of multiple commercially available polystyrene gel columns, such as g-st7ragel 500. manufactured by Waters. 103. 10
', 105 combination, 5hod manufactured by Showa Denko
ex KF-80M, KF-802, 803, 804
, 805 combination, or TSKgel manufactured by Toyo Soda
G100OH, G2000H, G2500H.
Ｇ３０００Ｈ，Ｇ４０００Ｈ，Ｇ５０００Ｈ，Ｇ３００
０Ｈ，Ｇ７００ＯＨ，ＣＭＨのうちの任意の組合せが好
ましい。G3000H, G4000H, G5000H, G300
Any combination of 0H, G700OH, and CMH is preferred.
本発明の分子量１０，０００以下のバインダー樹脂に対
する重量％はＧＰＣによるクロマトグラムの分子量１０
，０００以下を切りぬき、分子量１０，０００以上の切
りぬさとのｍｆｆ１比を計算し、前記のＴＨＦ不溶分の
重量％を使い、全体のバインダー樹脂に対する重量％を
算出する。The weight percent of the binder resin of the present invention having a molecular weight of 10,000 or less is the molecular weight of 10 in the chromatogram determined by GPC.
,000 or less, calculate the mff1 ratio with the cutout having a molecular weight of 10,000 or more, and use the weight % of the THF-insoluble content described above to calculate the weight % with respect to the entire binder resin.
本発明のトナーにおける樹脂組成物は、スチレン類、ア
クリル酸類、メタクリル酸類及びその誘導体から選ばれ
る１種以上のモノマーを重合して得られるものが現像特
性及び帯電特性等から好ましい、使用できる七ツマ−の
例としては、スチレン類としてスチレン、α−メチルス
チレン、ビニルトルエン、クロルスチレンなどがあげら
れる。The resin composition in the toner of the present invention is preferably one obtained by polymerizing one or more monomers selected from styrenes, acrylic acids, methacrylic acids, and derivatives thereof from the viewpoint of development characteristics and charging characteristics. Examples of - include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and the like.
アクリル酸類、メタクリル酸類及びその誘導体としては
、アクリル酸、アクリル酸メチル、アクリル酸エチル、
アクリル酸プロピル、アクリル酸ブチル、アクリル酸オ
クチル、アクリル酸２−エチルヘキシル、アクリル酸ｎ
−テトラデシル、アクリル酸ｎ−ヘキサデシル、アクリ
ル酸ラウリル、アクリル酸シクロヘキシル、アクリル酸
ジエチルアミノエチル、アクリル酸ジメチルアミノエチ
ルなどのアクリル酸エステル類があげられ、同様にメタ
クリル酸、メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸プロピル、メタクリル酸ブチル、メタクリ
ル酸アミル、メタクリル酸ヘキシル、メタクリル酸２−
エチルヘキシル、メタクリル酸オクチル、メタクリル酸
デシル、メタクリル酸ドデシル、メタクリル酸ラウリル
、メタクリル酸シクロヘキシル、メタクリル酸フェニル
、メタクリル酸２−ヒドロキシエチル、メタクリル酸２
−ヒドロキシプロピル、メタクリル酸ジメチルアミンエ
チル、メタクリル酸グリシジル、メタクリル酸ステアリ
ルなどのメタクリル酸エステル類があげられる。前述の
七ツマー以外に、本発明の目的を達成しうる範囲で少量
の他のモノマー、例えばアクリロニトリル、２−ビニル
ピリジン、４−ビニルピリジン、ビニルカルバソ゛−ル
、ビニルメチルエーテル、ブタジェン、イソプレン、無
水マレイン。Acrylic acids, methacrylic acids and their derivatives include acrylic acid, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n acrylate
- Acrylic acid esters such as -tetradecyl, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate, as well as methacrylic acid, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-methacrylate
Ethylhexyl, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methacrylate
Examples include methacrylic acid esters such as -hydroxypropyl, dimethylamine ethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate. In addition to the above-mentioned monomers, small amounts of other monomers can be used within the range that can achieve the purpose of the present invention, such as acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, vinyl carbazole, vinyl methyl ether, butadiene, isoprene, maleic anhydride. .
マレイン酸、マレイン酸モノエステル類、マレイン酸ジ
エステル類、酢酸ビニルなどが用いられても良い。Maleic acid, maleic monoesters, maleic diesters, vinyl acetate, etc. may also be used.
本発明のトナーに用いられる架橋剤としては、２官能の
架橋剤として、ジビニルベンゼン、ビス（４−アクリロ
キシポリエトキシフェニル）プロパン、エチレングリユ
ールジアクリレート、１，３−ブチレングリコールジア
クリレート、１．４−ブタンジオールジアクリレート、
１．５−ペンタンジオールジアクリレー）、１．８−ヘ
キサンジオールジアクリレート、ネオペンチルグリコー
ルジアクリレート、ジエチレングリコールジアクリレー
ト、トリエチレングリコールジアクリレート、テトラエ
チレンゲリコールジアクリレート、ポリエチレングリコ
ール＄２００．雲４００．８８００の各ジアクリレート
。Examples of crosslinking agents used in the toner of the present invention include divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and bifunctional crosslinking agents. .4-butanediol diacrylate,
1.5-pentanediol diacrylate), 1.8-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene gelicol diacrylate, polyethylene glycol $200. Cloud 400.8800 each diacrylate.
ジプロピレングリコールジアクリレート、ポリプロピレ
ングリコールジアクリレート、ポリエステル型ジアクリ
レー） （ＭＡＮＤＡ日本化薬）、及び以上のアクリレ
ートをメタクリレートにかえたものが挙げられる。Examples include dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and those in which the above acrylates are replaced with methacrylates.
多官能の架橋剤としてペンタエリスリトールトリアクリ
レート、トリメチロールエタントリアクリレート、トリ
メチロールプロパントリアクリレート、テトラメチロー
ルメタンテトラアクリレート、オリゴエステルアクリレ
ート及びそのメタクリレート、２，２−ビス（４−メタ
クリロキシ、ポリエトキシフェニル）プロパン、ジアリ
ルフタレート、トリアリルシアヌレート、トリアリルア
ンシアヌレート、トリアリルイソシアヌレート。As polyfunctional crosslinking agents, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxy, polyethoxyphenyl) Propane, diallyl phthalate, triallyl cyanurate, triallyl ancyanurate, triallyl isocyanurate.
トリアリルトリメリテート、−ジアリールクロレンデー
ト等があげられる。Examples include triallyl trimellitate, -diarylchlorendate, and the like.
本発明に係るバインダー樹脂の合成方法は、基本的に２
種以上の重合体を合成する方法が好ましい。The method for synthesizing the binder resin according to the present invention basically consists of two steps.
A method of synthesizing more than one type of polymer is preferred.
すなわち、ＴＨＦに可溶で且つ重合モノマーに可溶な第
１の重合体を重合モノマー中に溶解し、七ツマ−を重合
して樹脂組成物を得る方法である。That is, this is a method in which a first polymer that is soluble in THF and soluble in a polymerization monomer is dissolved in a polymerization monomer, and a 7-mer is polymerized to obtain a resin composition.
この場合、前者と後者の重合体が均一に混合している組
成物が形成される。In this case, a composition is formed in which the former and latter polymers are uniformly mixed.
ＴＨＦに可溶な第１の重合体は、溶液重合もしくはイオ
ン重合などが好ましく、ＴＨＦに不溶な成分を生成する
ための第２の重合体は、第１の重合体を溶解している条
件下で架橋性上ツマー存在下で懸濁重合もしくは塊状重
合で合成することが好ましい。第１の重合体は第２の重
合体を生成するための重合性単量体１００重量部に対し
て１０〜１２０（好ましくは、２０〜１００重量部）重
量部使用するのが好ましい。The first polymer soluble in THF is preferably subjected to solution polymerization or ionic polymerization, and the second polymer for producing a component insoluble in THF is prepared under the conditions in which the first polymer is dissolved. In view of crosslinking properties, it is preferable to synthesize by suspension polymerization or bulk polymerization in the presence of a polymer. The first polymer is preferably used in an amount of 10 to 120 (preferably 20 to 100 parts by weight) parts by weight based on 100 parts by weight of the polymerizable monomer for producing the second polymer.
添付図面の第２図は、後述の合成例１で得られた樹脂組
成物のＴＨＦ可溶分のＧＰＣのチャートを示している。FIG. 2 of the accompanying drawings shows a GPC chart of the THF soluble content of the resin composition obtained in Synthesis Example 1, which will be described later.
第３図は、第１の重合である溶液１合で調製されたポリ
スチレンのＧＰＣのチャートを示している。該ポリスチ
レンはＴＨＦに可溶であり、重合単量体であるスチレン
モノマー及びアクリル酸ｎ−ブチルモノマーに可溶であ
り、分子量３，５００にメインピークを有していた。第
４図は、該ポリスチレンを添加しない以外は同様の条件
で第２の重合で調製されるスチレン−アクリル酸ｎ−ブ
チル共重合体を懸濁重合で生成したもののＴＨＦ可溶分
のＧＰＣのチャートを示している。該スチレン−アクリ
ル酸ｎ−ブチル共重合体は、分子量４０，０００にメイ
ンピークを有していた。FIG. 3 shows a GPC chart of polystyrene prepared in Solution 1, the first polymerization. The polystyrene was soluble in THF, soluble in styrene monomer and n-butyl acrylate monomer as polymerization monomers, and had a main peak at a molecular weight of 3,500. Figure 4 is a GPC chart of the THF soluble content of a styrene-n-butyl acrylate copolymer produced by suspension polymerization, which was prepared in the second polymerization under the same conditions except that the polystyrene was not added. It shows. The styrene-n-butyl acrylate copolymer had a main peak at a molecular weight of 40,000.
第５図は、第３図のチャートと第４図のチャートを組み
合わせたものである。FIG. 5 is a combination of the chart in FIG. 3 and the chart in FIG. 4.
第６図は、第２図のチャートと第５図のチャート（実線
部分を破線で示した）を組み合わせて示したものである
。第６図からも明白な如く、本発明に係る合成例１で得
られた樹脂組成物は、別個に重合したポリスチレンとス
チレン−アクリル酸ｎ−ブチル共重合体を単に混合した
ものと異なるＧＰＣチャートを有していた。特に、高分
子量側に、スチレン−アクリル酸ｎ−ブチル共重合体単
独では生成していなかった高分子成分が生成しているこ
とが知見される。この高分子量成分は、第２段目の重合
である＠濁重合時に、第１段目の溶液重合で調製された
ポリスチレンが存在しているために、該ポリスチレンが
重合調整剤の如きｆ動きをし、その結果スチレン−アク
リル酸ｎ−ブチル共重合体のＴＨＦ不溶分とＴＨＦ可溶
分の合成が調整されたと考えられる０本発明に係る樹脂
組成物は、Ｔ）ＩＦ不溶分、ＴＨＦ可溶な高分子量成分
、ＴＨＦ可溶な中間分子量成分及びＴ）ＩＦ可溶な低分
子量成分が均一に混合されている。さらに本発明に係る
樹脂組成物は、トナー製造時の溶融混練工程による分子
鎖の切断により、分子量３０万以上（好ましくは５０万
以上）の領域に新たなピークを生成して、トナーの定着
性及び耐オフセット性を調製し得る能力を有する。FIG. 6 shows a combination of the chart in FIG. 2 and the chart in FIG. 5 (solid line portions are indicated by broken lines). As is clear from FIG. 6, the resin composition obtained in Synthesis Example 1 according to the present invention has a GPC chart different from that of a simple mixture of separately polymerized polystyrene and styrene-n-butyl acrylate copolymer. It had In particular, it was found that a high molecular component, which was not produced in the styrene-n-butyl acrylate copolymer alone, was produced on the high molecular weight side. This high molecular weight component is caused by the presence of the polystyrene prepared in the first stage solution polymerization during @turbidity polymerization, which is the second stage polymerization, so that the polystyrene exhibits f-movement like a polymerization regulator. As a result, it is thought that the synthesis of THF-insoluble and THF-soluble components of the styrene-n-butyl acrylate copolymer was adjusted. A high molecular weight component, a THF soluble intermediate molecular weight component, and a T)IF soluble low molecular weight component are uniformly mixed. Furthermore, the resin composition according to the present invention generates a new peak in the region of molecular weight of 300,000 or more (preferably 500,000 or more) by cutting molecular chains during the melt-kneading process during toner production, and improves toner fixability. and has the ability to adjust offset resistance.
さらに本発明において、トナーのＴ）ＩＦ可溶分のＧＰ
Ｃにおいて分子量３０万以上の成分がバインダー樹脂を
基準として５〜３０重量％（好ましくは１０〜３０１ｆ
Ｌ量％）含有しているものが良い、また、ドナーのＴＨ
Ｆ可溶分のＧＰＣにおいて、分子量３０万以上（好まし
くは５０万以上）に明確なピークを有するものがより耐
オフセット性及び耐巻き付性の改良という点で好ましい
。Furthermore, in the present invention, GP of the T)IF soluble portion of the toner
In C, the component having a molecular weight of 300,000 or more is 5 to 30% by weight (preferably 10 to 301f) based on the binder resin.
L content (%) is good, and donor TH
In GPC of the F-soluble fraction, those having a clear peak at a molecular weight of 300,000 or more (preferably 500,000 or more) are more preferable from the standpoint of improving offset resistance and wrapping resistance.
以下余白
以上のことから、本クレームに記すところの粉砕性、低
温定着性さらにトナー用の種々の添加剤の分散性に有効
な低分子量重合体の存在下で、モノマー、架橋剤を重合
させて、耐オフセット性。From the following margin, it is clear that monomers and crosslinking agents are polymerized in the presence of a low molecular weight polymer that is effective for crushability, low-temperature fixing properties, and dispersibility of various additives for toner as stated in this claim. , offset resistance.
粉砕性にすぐれた架橋成分を含む低分子量域から弱架橋
域まで均一に混在しているバインダー樹脂は、現像特性
、定着特性の観点から非常に有効である。A binder resin containing a crosslinked component with excellent pulverizability and uniformly mixed in a range from a low molecular weight range to a weakly crosslinked range is very effective from the viewpoint of developing properties and fixing properties.
この／゛＜イングー樹脂は、通常のポジトナー、ネガト
ナー用バインダー樹脂として非常に優れているが、トナ
ー用荷電制御剤として含窒素荷電制御剤を用い、レジン
中に、重合開始剤分解残存物である安息香酸がある程度
存在している場合に限ってトナーの現像特性、特に長期
にわたる連続複写において若干の画像濃度低下をおこす
場合がある。This /゛<Ingu resin is very excellent as a binder resin for ordinary positive toners and negative toners, but it uses a nitrogen-containing charge control agent as a charge control agent for toners, and contains polymerization initiator decomposition residues in the resin. Only when benzoic acid is present to a certain extent, the development characteristics of the toner, particularly in continuous copying over a long period of time, may cause a slight decrease in image density.
具体的に述べると、本発明に用いる樹脂組成物は、低分
子量域を架橋マトリックス中にもっているため、トナー
とする時に用いられる含窒素荷電制御剤の分散性にすぐ
れ、分散不良による画像濃度低下はほとんどおこり得な
いが、中〜高速複写機での長期にわたる連続複写では、
時として若干の画像濃度低下をおこすことがある。Specifically, since the resin composition used in the present invention has a low molecular weight region in the crosslinked matrix, it has excellent dispersibility of the nitrogen-containing charge control agent used when making toner, and reduces image density due to poor dispersion. However, during continuous copying over a long period of time with a medium to high speed copying machine,
Sometimes, a slight decrease in image density may occur.
これは、高速複写での長期連続耐久では含窒素荷電制御
剤と樹脂組成物の一部が、複写機の現像スリーブ表面に
、少量物理付着あるいは吸着されてスリーブを汚染する
ことによる。This is because, during long-term continuous durability during high-speed copying, a small amount of the nitrogen-containing charge control agent and the resin composition physically adhere or are adsorbed onto the surface of the developing sleeve of the copying machine, contaminating the sleeve.
このスリーブ汚染は、検討の結果、含窒素荷電制御剤と
樹脂組成物中の安息香酸の存在によって特異的に発生し
易いことから、含窒素荷電制御剤と安息香酸とのインタ
ーラクションによって、含窒素荷電制御剤を含んだ樹脂
組成物の一部がスリーブ表面に物理付着あるいは吸着さ
れることで発生すると推測される。As a result of study, it was found that this sleeve contamination is likely to occur specifically due to the presence of the nitrogen-containing charge control agent and benzoic acid in the resin composition. It is presumed that this occurs due to physical adhesion or adsorption of a part of the resin composition containing the charge control agent to the sleeve surface.
またこの様な含窒素荷電制御剤と安息香酸とのインター
ラクションは、一種の塩形成と考えられ、トナー中にこ
の様な状態が存在することは、トナーの環境特性におい
て好ましくなく、高温。In addition, such interaction between the nitrogen-containing charge control agent and benzoic acid is considered to be a type of salt formation, and the presence of such a state in the toner is unfavorable in terms of the environmental characteristics of the toner, and the high temperature.
高湿環境下における画像濃度低下、あるいは画質低下の
原因となる。This causes a decrease in image density or image quality in a high humidity environment.
上記の樹脂組成物中の安息香酸とは、重合開始剤の分解
残存物であり、樹脂中の安息香酸量が５００９Ｐ醜以上
では、スリーブ汚染による画像濃度低下がおこり易く、
５００Ｐｐ脂以下ではおこりにくく、さらに好ましくは
３００ｐｐｍ以下であり、安息香酸量ＯＰＰ■が最も好
ましい、なお、この安息香酸量は、トナーに使用する樹
脂組成物の酸価とも対応しており、酸価０．５以上では
スリーブ汚染による画像濃度低下がおこり易く、酸価０
．５以下ではおこりにくく、好ましくは０．３以下であ
り、酸価０が最も好ましい、なお、樹脂の酸価に関して
は特開昭５８−１９８０４９号公報、同５５−１３４８
８１号公報に酸価５〜１００などの記載があるが、本発
明とは発想が全く異なるものである。The benzoic acid in the above resin composition is a decomposition residue of the polymerization initiator, and if the amount of benzoic acid in the resin is 5009P or more, image density is likely to decrease due to sleeve contamination.
It is difficult to cause this when the amount is less than 500 ppm, more preferably 300 ppm or less, and the benzoic acid amount OPP■ is the most preferable.The amount of benzoic acid also corresponds to the acid value of the resin composition used in the toner, and the acid value If the acid value is 0.5 or more, a decrease in image density is likely to occur due to sleeve contamination, and the acid value is 0.
．． If the acid value is 5 or less, this is unlikely to occur, and the acid value is preferably 0.3 or less, and the acid value of 0 is most preferable.
No. 81 describes an acid value of 5 to 100, but the idea is completely different from the present invention.
安息香酸量を５００ｐｐｍ以下にする方法としては種々
の方法が考えられるが、例えば分解残存物として安息香
酸を与える重合開始剤であるベンゾイルパーオキサイド
の使用量を通常より減らす方法、通常の懸濁重合法で得
られた樹脂組成物を再び溶媒に膨潤させて、溶液重合法
のごとく分解残存物を溶媒と共に減圧留去する方法、さ
らには開始剤として分解残存物が安息香酸として樹脂中
に残らない重合開始剤、たとえば一般に下記の基本構造
式で示される重合開始剤が好ましく、具体的には、２．
２′−アゾビス（２，４−ジメチルバレロニトリル）、
ジメチル２，２′−７ゾビスイソブチレート、２．２′
−アゾビス（４−メトキシ−２，４−ジメチルバレロニ
トリル）等を用いて低分子量重合体及び架橋剤の存在下
で七ツマ−を懸濁重合させる方法などがさらに好ましい
。Various methods can be considered to reduce the amount of benzoic acid to 500 ppm or less. A method in which the legally obtained resin composition is swollen in a solvent again and the decomposition residue is distilled off under reduced pressure along with the solvent as in the solution polymerization method, and furthermore, the decomposition residue is used as an initiator so that the decomposition residue does not remain in the resin as benzoic acid. A polymerization initiator, for example, a polymerization initiator generally represented by the following basic structural formula is preferable, and specifically, 2.
2'-azobis(2,4-dimethylvaleronitrile),
Dimethyl 2,2'-7zobisisobutyrate, 2,2'
More preferred is a method in which a hexamer is subjected to suspension polymerization using -azobis(4-methoxy-2,4-dimethylvaleronitrile) or the like in the presence of a low molecular weight polymer and a crosslinking agent.
ＲＩ Ｒ６
（式中Ｒ１〜Ｒ６はメチル基、エチル基、七−ブチル基
、ネオペンチル基、などのアルキル基、シクロヘキシル
基、シクロペンチルなどの如き環状アルキル基、フェニ
ル基、ナフチル基の如きアリール基、ベンジル基、フェ
ニルエチル基などのアラルキル基、アセチル基、ベンゾ
イル基の如きアシル基、メトキシ基、エトキシ基、シア
ノ基、エステル基の中から単独あるいは複数に選択され
組み合わされる。さらにそれらは、上述した置換基で一
部置換されていても良い、）
本発明に用いられる重合開始剤としては、従来公知の過
酸化物系開始剤やアゾ系開始剤が用いられる。過酸化物
系開始剤としてはアセチルシグロへキシルスルフォニル
パーオキサイド、ｉ−ブチルパーオキサイド、クミルパ
ーオキシネオデカノエート、ジーイソプロピルパーオキ
シジカルポネート、ジーアリルパーオキシジカルポネー
ト、ジーｎ−プロビルパーオキシジカルポネート、ジー
ミリスチルーパーオキシジカルポネート、クミルパーオ
キシネオヘキサノエート、ジ（２−エトキシエチル）パ
ーオキシジカルポネート、ジ（メトキシイソプロピル）
パーオキシジカルポネート、ジ（２−エチルヘキシル）
バーオキシジカルポネート、ｔ−ヘキシルバーオギシネ
オデカノエート、ジ（３−メチル−３−メトキシブチル
）パーオキシジカーボネート、ｔ−ブチルパーオキシネ
オデカノエート、ｔ−ヘキシルパーオキシネオヘキサノ
エート、ｔ−ブチルパーオキシネオヘキサノエート、２
．４−ジクロロベンゾイルパーオキサイド、ｔ−ヘキシ
ルパーオキシピバレート、ｔ−ブチルパーオキシピバレ
ート、３，５．５− ）リメチルヘキサノイルパーオキ
サイド、オクタノイルパーオキサイド、デカノイルパー
オキサイド、ラウロイルパーオキサイド、クミルパーオ
キシオクトエート、スクシニックアシドパーオキサイド
、アセチルパーオキサイド、ｔ−ブチルパーオキシ（２
−エチルヘキサノエート）、■−トルオイルパーオキサ
イド、ベンゾイルパーオキサイド、ｔ−ブチルパーオキ
シミーブチレート、１．１−ビス（ｔ−ブチルパーオキ
シ）−３，３，５−トリメチルシクロヘキサン、１．１
−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｔ−
ブチルパーオキシマレイックアシド、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−
）リメチルヘキサノエート、シクロヘキサノンパーオキ
サイド、ｔ−ブチルパーオキシアリルカーボネート、ｔ
−プチルパーオキシイソプロビルカーポネート、２，５
−ジメチル−２，５′−ジ（ベンゾイルパーオキシ）へ
キサン、２，２−ビス（ｔ−ブチルパーオキシ）オクタ
ン、ｔ−ブチルパーオキシアセテート、２，２−ビス（
ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルパーオキシ
ベンゾエート、ｎ−ブチル−４，４−ビス（ｔ−ブチル
パーオキシ）バレレート、ジ−ｔ−ブチルシバ−オキシ
イソフタレート、メチルエチルケトンパーオキサイド、
ジ−クミルパーオキサイド、２，５−ジメチル−２，５
−ジ（ｔ−ブチルパーオキシ）ヘキサン、α、α′−ビ
ス（ｔ−プチルパーオキシーーーイソブロビル）ベンゼ
ン、ｔ−ブチルクミルパーオキサイド、ジ−イソプロピ
ルベンゼンハイドロパーオキサイド、ジ−ｔ−ブチルパ
ーオキサイド、ｐ−メンタンハイドロパーオキサイド、
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキシン−３，１，１，３，３−テトラメチルブチル
ハイドロパーオキサイド、２．５−ジメチルヘキサン−
２，５−シバイドロバ−オキサイド、クメンハイドロパ
ーオキサ・イド、ｔ−ブチルハイドロパーオキサイド等
があげられる。RI R6 (wherein R1 to R6 are alkyl groups such as methyl group, ethyl group, 7-butyl group, neopentyl group, cyclic alkyl group such as cyclohexyl group, cyclopentyl group, aryl group such as phenyl group, naphthyl group, benzyl group) A group, an aralkyl group such as a phenylethyl group, an acetyl group, an acyl group such as a benzoyl group, a methoxy group, an ethoxy group, a cyano group, and an ester group. As the polymerization initiator used in the present invention, conventionally known peroxide-based initiators and azo-based initiators are used. Peroxide initiators include acetyl cyclohexyl sulfonyl peroxide, i-butyl peroxide, cumyl peroxy neodecanoate, diisopropyl peroxy dicarponate, diallyl peroxy dicarponate, di-n-pro Vilperoxydicarponate, dimyristyl peroxydicarponate, cumylperoxyneohexanoate, di(2-ethoxyethyl)peroxydicarponate, di(methoxyisopropyl)
Peroxydicarponate, di(2-ethylhexyl)
Peroxydicarponate, t-hexyl oxyneodecanoate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-hexyl peroxyneohexano ate, t-butylperoxyneohexanoate, 2
．． 4-dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5.5-)limethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide , cumyl peroxyoctoate, succinic acid peroxide, acetyl peroxide, t-butyl peroxide (2
-ethylhexanoate), ■-toluoyl peroxide, benzoyl peroxide, t-butylperoxime butyrate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1 .1
-bis(t-butylperoxy)cyclohexane, t-
Butyl peroxymaleic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-
) Limethylhexanoate, cyclohexanone peroxide, t-butyl peroxyallyl carbonate, t
-butyl peroxyisopropyl carbonate, 2,5
-dimethyl-2,5'-di(benzoylperoxy)hexane, 2,2-bis(t-butylperoxy)octane, t-butylperoxyacetate, 2,2-bis(
t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylshiba-oxyisophthalate, methyl ethyl ketone peroxide,
Dicumyl peroxide, 2,5-dimethyl-2,5
-di(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy-isobrobyl)benzene, t-butylcumyl peroxide, di-isopropylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1,3,3-tetramethylbutylhydroperoxide, 2,5-dimethylhexane-
Examples include 2,5-sibide lobar oxide, cumene hydroperoxaide, t-butyl hydroperoxide, and the like.
アゾ系開始剤としては、２．２′−アゾビス（４−メト
キシ−２，４−ジメチルバレロニトリル） 、 ２．２
′−アゾビス（２，４−ジメチルバレロニトリル）、（
１−フェニルエチル）アゾジ−フェニルメタン、２，２
′−アゾビスイソブチロニトリル、ジメチル２．２′−
アゾビスイソブチレート、２，２′−アゾビス（２メチ
ルブチロニトリル） 、 １．１’−アゾビス（１−シ
クロヘキサンカルボニトリル）、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、２，２′
−アゾビス（２メチルプロパン） 、 ２．２’−アゾ
ビス（Ｎ、Ｎ’−ジメチレンイソブチルアミジン）ジハ
イドロクロライト、２，２′−アゾビス（２−アミジノ
プロパン）ジハイドロクロライド、２，２′−アゾビス
（Ｎ、Ｎ’−ジメチレンインブチルアミジン） 、 ４
．４’−アゾビス（４−シアノペンタノイックアシド）
、等があげられる。As the azo initiator, 2.2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2.2
'-Azobis(2,4-dimethylvaleronitrile), (
1-phenylethyl)azodi-phenylmethane, 2,2
'-Azobisisobutyronitrile, dimethyl 2.2'-
Azobisisobutyrate, 2,2'-azobis(2methylbutyronitrile), 1.1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)-isobutyronitrile, 2.2' -Azobis (2,
4,4-trimethylpentane), 2-phenylazo-2
, 4-dimethyl 4-methoxyvaleronitrile, 2,2'
-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochlorite, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-Azobis(N,N'-dimethyleneinbutyramidine), 4
．． 4'-Azobis (4-cyanopentanoic acid)
, etc.
本発明における安息香酸量は、ジフェニルエーテルを内
部標準としてガスタロマドグラフィーを用いて測定する
ことができる。The amount of benzoic acid in the present invention can be measured using gastalomadography using diphenyl ether as an internal standard.
具体的には、樹脂組成物１．２ｇおよび１．２−ジクロ
ロエタン（ＥＤＣ：） ２５＋ｓｊ）を秤取し、室温下
、３時間攪 ′拌させてサンプルを膨潤させ、安息香
酸をＥＤＣ中に抽出し、内部標準としてジフェニルエー
テルの１％ＥＤＣ溶液を約０．２ｇ精科してこれに添加
し、さらにアセトン２５重βを加えて、サンプル溶液と
する。サンプル溶液は、ガスクロマトグラフ装置（ＧＣ
−９Ａ 、島津製作所製）に注入してクロマトグラムを
得る。一方、同様にして、サンプル溶液のかわりに市販
の安息香酸試薬（和光紬薬製、１級）を用いて測定し、
作成したジフェニルエーテル−安息香酸の検量線に基づ
いて測定サンプル中の安息香酸含量を求めることができ
る。なお測定条件としては、使用カラム： ＮＰＧＳ充
填ガラスカラム（３ｍ／＋ｓφＸ２ｍ）、カラム温度：
１９０℃、インジェクション温度：２１０℃、キャリア
ガス（Ｎ２）流量：５０脂！／ｗｉｎ、が選ばれる（第
１Ｏ図及び第１１図のクロマトグラム参照）。Specifically, 1.2 g of the resin composition and 1,2-dichloroethane (EDC: 25+sj) were weighed out, stirred at room temperature for 3 hours to swell the sample, and benzoic acid was extracted into the EDC. Approximately 0.2 g of a 1% EDC solution of diphenyl ether is added as an internal standard, and 25 times β of acetone is further added to prepare a sample solution. The sample solution was collected using a gas chromatograph (GC).
-9A, manufactured by Shimadzu Corporation) to obtain a chromatogram. On the other hand, in the same manner, a commercially available benzoic acid reagent (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., grade 1) was used instead of the sample solution for measurement.
The benzoic acid content in the measurement sample can be determined based on the prepared diphenyl ether-benzoic acid calibration curve. The measurement conditions were as follows: Column used: NPGS packed glass column (3m/+sφX2m), column temperature:
190℃, injection temperature: 210℃, carrier gas (N2) flow rate: 50 fat! /win is selected (see chromatograms in Figures 1O and 11).
本発明における含窒素荷電制御剤としては従来公知の荷
電制御剤から選ばれる。含窒素荷電制御剤としては、一
般にニグロシン、炭素数２〜１６ノアルキル基を含むア
ジン系染料（特公昭４２−ＩＥｉ２７号）、塩基性染料
（例えばＣ，１，Ｂａ５ｉｃ Ｙｅｌｌｏｗ ２（Ｃ，
１，４１０００）、Ｃ−１，Ｂａ５ｉｃ Ｙｅｌｌｏｗ
３、Ｃ，１，Ｂａ５ｉｃＲｅｄ １ （Ｃ，１，４５
１８０）、Ｃ，１，Ｂａ５ｉｃ Ｒｅｄ Ｓ （Ｃ，１
゜４２５００）、Ｃ，１，Ｂａ５ｉｃ Ｖｉｏｌｅｔ
１（Ｃ，１，４２５３５）、Ｃ，Ｉ。The nitrogen-containing charge control agent in the present invention is selected from conventionally known charge control agents. Examples of nitrogen-containing charge control agents include nigrosine, azine dyes containing a noalkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-IEi27), and basic dyes (for example, C,1,Ba5ic Yellow 2 (C,
1,41000), C-1, Ba5ic Yellow
3, C, 1, Ba5icRed 1 (C, 1, 45
180), C,1,Ba5ic Red S (C,1
゜42500), C, 1, Ba5ic Violet
1 (C, 1, 42535), C, I.
Ｂａ５ｉｃ Ｖｉｏｌｅｔ ３ （Ｃ：、１．４２５５
５）、Ｃ，１，Ｂａ５ｉｃＶｉｏｌｅｔ １０ （Ｃ，
１，４５１７０）、Ｃ，１，Ｂａ５ｉｃ Ｖｉｏｌｅｔ
１４（Ｃ；、１．４２５１０）、Ｃ，１，Ｂａ５ｉｃ
Ｂｌｕｅ ｌ （１１１：、１．４２０２５）、Ｃ，
１，Ｂａ５ｉｃ Ｂｌｕｅ ３ （Ｃ：、１．５１００
５）、Ｃ，１，Ｂａ５ｉｃＢｌｕｅ ５ （Ｃ，１，４
２１４０）、Ｃ，１，Ｂａ５ｉｃ Ｂｌｕｅ ７ （Ｇ
、Ｉ。Ba5ic Violet 3 (C:, 1.4255
5), C,1,Ba5icViolet 10 (C,
1,45170), C,1,Ba5ic Violet
14(C;, 1.42510), C,1,Ba5ic
Blue l (111:, 1.42025), C,
1, Ba5ic Blue 3 (C:, 1.5100
5), C,1,Ba5icBlue 5 (C,1,4
2140), C,1, Ba5ic Blue 7 (G
,I.
４２５９５）、Ｃ，１，Ｂａ５ｉｃ Ｂｌｕｅ ９ （
Ｃ，１，５２０１５）、Ｃ：、Ｉ。42595), C,1,Ba5ic Blue 9 (
C,1,52015),C:,I.
Ｂａ５ｉｃ Ｂｌｕｅ ２４ （Ｃ，１，５２０３０）
、Ｃ，１，Ｂａ５ｉｃ Ｂｌｕｅ２５ （Ｃ，１，５２
０２５）、Ｃ，ｉ Ｂａ５ｉｃ Ｂｌｕｅ ２Ｂ （Ｃ
，１゜４４０２５）、Ｃ，１，Ｂａ５ｉｃ Ｇｒｅｅｎ
Ｇｒｅｅｎ １ （Ｇ、１．４２０４０）、Ｃ，１，
Ｅａｓｉｃ Ｇｒｅｅｎ ４ （Ｃ：、１．４２０００
）など、これらの塩基性染料のレーキ顔料（レーキ化剤
としては、りんタングステン酸、りんモリブデン酸、り
んタングステンモリブデン酸、タンニン酸、ラウリン酸
、没食子酸、フェリシアン化物、フェロシアン化物など
） 、 Ｃ，１，５ｏｖｅｎｔ Ｂｌａｃｋ ３ （Ｃ
，１，２８１５０）。Ba5ic Blue 24 (C, 1, 52030)
,C,1,Ba5ic Blue25 (C,1,52
025), C,i Ba5ic Blue 2B (C
,1゜44025),C,1,Ba5ic Green
Green 1 (G, 1.42040), C, 1,
Easic Green 4 (C:, 1.42000
), lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C, 1, 5 ovent Black 3 (C
, 1, 28150).
ハンザイエローＧ （Ｃ，１，１１ＨＯ）、Ｃ，１，
ＭｏｒｄｌａｎｔＢｌａｃｋ １１． Ｃ，１，Ｐｉｇ
ｍｅｎｔ Ｂｌａｃｋ １等。Hansa Yellow G (C,1,11HO), C,1,
MordlantBlack 11. C,1,Pig
ment Black 1st prize.
または、例えばベンシルメチル−ヘキサデシルアンモニ
ウムクロライド、デシル−トリメチルアンモニウムクロ
ライドなどの四級アンモニウム塩あるいはアミン基を含
有するビニル系ポリマー。Alternatively, vinyl polymers containing quaternary ammonium salts or amine groups, such as benzylmethyl-hexadecyl ammonium chloride and decyl-trimethyl ammonium chloride.
アミン基を含有する縮合系ポリマー等のポリアミン樹脂
等があげられ、好ましくはニグロシン。Examples include polyamine resins such as condensation polymers containing amine groups, and nigrosine is preferred.
四級アンモニウム塩、トリフェニルメタン系含窒素化合
物、ポリアミンなどがあげられる。Examples include quaternary ammonium salts, triphenylmethane-based nitrogen-containing compounds, and polyamines.
本発明のトナーは、必要に応じて添加剤を混合しても良
い、添加剤としては、例えばテフロン。The toner of the present invention may contain additives, if necessary. Examples of additives include Teflon.
ステアリン酸亜鉛、ポリ弗化ビニリデンの如き滑剤、中
でもポリ弗化ビニリデンが好ましい、あるいは酸化セリ
ウム、炭化ケイ素、チタン酸ストロンチウム等の研磨剤
、中でもチタン酸ストロンチウムが好ましい、あるいは
例えばコロイダルシリカ、酸化アルミニウム等の流動性
付与剤、中でも特に疎水性コロイダルシリカが好ましい
、ケーキング防止剤、あるいは例えばカーボンブラック
。A lubricant such as zinc stearate, polyvinylidene fluoride, preferably polyvinylidene fluoride, or an abrasive such as cerium oxide, silicon carbide, strontium titanate, preferably strontium titanate, or, for example, colloidal silica, aluminum oxide, etc. flow agents, especially preferably hydrophobic colloidal silica, anti-caking agents, or e.g. carbon black.
酸化亜鉛、酸化アンチモン、酸化スズ等の導電性付与剤
、あるいは低分子量ポリエチレン、低分子量ポリプロピ
レン、各種ワックス類などの定着助剤等または耐オフセ
ツト剤がある。また逆極性の白色微粒子及び黒色微粒子
を現像性向上剤として少量用いることもできる。Examples include conductivity imparting agents such as zinc oxide, antimony oxide, and tin oxide, fixing aids such as low molecular weight polyethylene, low molecular weight polypropylene, various waxes, and anti-offset agents. Further, a small amount of white fine particles and black fine particles of opposite polarity can be used as a developing property improving agent.
さらに本発明のトナーは、二成分系現像剤として用いる
場合にはキャリヤー粉と混合して用いられる。この場合
には、トナーとキャリヤー粉との混合比はトナー濃度と
して０．１〜５０重量％、好ましくは０．５〜ｌＯ重量
％、さらに好ましくは３〜５重量％が望ましい。Further, when the toner of the present invention is used as a two-component developer, it is used in combination with a carrier powder. In this case, the mixing ratio of toner and carrier powder is desirably 0.1 to 50% by weight, preferably 0.5 to 10% by weight, and more preferably 3 to 5% by weight in terms of toner concentration.
本発明に使用しうるキャリヤーとしては公知のものが使
用可能であり、例えば鉄粉、フェライト粉、ニッケル粉
の如き磁性を有する粉体、ガラスピーズ等及びこれらの
表面をフッ素系樹脂またはシリコン系樹脂等で表面処理
したものなどがあげられる。Known carriers can be used in the present invention, such as magnetic powders such as iron powder, ferrite powder, nickel powder, glass beads, etc., and their surfaces coated with fluorine-based resin or silicone-based resin. Examples include those whose surface has been treated with, etc.
さらに本発明のトナーは更に磁性材料を含有させ磁性ト
ナーとしても使用しうる。この場合、磁性材料は着色剤
の役割をかねている０本発明の磁性トナー中に含まれる
磁性材料としては、マグネタイト、ヘマタイト、フェラ
イト等の酸化鉄又は二価金属と酸化鉄との化合物；鉄、
コバルト。Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material also serves as a colorant. Examples of magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, or compounds of divalent metals and iron oxides;
cobalt.
ニッケルのような金属或いはこれらの金属とアルミニウ
ム、コバルト、銅、鉛、マグネシウム、スズ、亜鉛、ア
ンチモン、ベリリウム、ビスマス。Metals such as nickel or these metals with aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth.
カドミウム、カルシウム、マンガン、セレン、チタン、
タングステン、バナジウムのような金属の合金およびそ
の混合物等が挙げられる。cadmium, calcium, manganese, selenium, titanium,
Examples include alloys of metals such as tungsten and vanadium, and mixtures thereof.
これらの強磁性体は平均粒子が０．１〜２終履、好まし
くは０．１〜０．５編■程度のものが好ましく、特に球
形のものは好ましい、トナー中に含有させる量としては
樹脂成分１００重量部に対し約２０〜２００重量部、特
に好ましくは樹脂成分１００重量部に対し４０〜１８０
重量部が良い。These ferromagnetic materials preferably have an average particle size of 0.1 to 2, preferably 0.1 to 0.5, and are particularly preferably spherical. About 20 to 200 parts by weight per 100 parts by weight of the component, particularly preferably 40 to 180 parts by weight per 100 parts by weight of the resin component.
Good weight section.
さらに本発明のトナーには必要に応じて着色剤を添加し
ても良い。Furthermore, a coloring agent may be added to the toner of the present invention if necessary.
本発明のトナーに使用する着色剤としては、任意の適当
な顔料または染料が使用される。トナー着色剤は周知で
あって、例えば顔料としてカーボンブラック、アニリン
ブラック、アセチレンブラック、ナフトールイエロー、
ハンザイエロー。Any suitable pigment or dye can be used as the colorant used in the toner of the present invention. Toner colorants are well known and include pigments such as carbon black, aniline black, acetylene black, naphthol yellow,
Hansa yellow.
ローダミンレーキ、アリザリンレーキ、ベンガラ、フタ
ロシアニンブルー、インダンスレンブル−等がある。こ
れらは定着画像の光学濃度を維持するのに必要充分な量
が用いられ、樹脂１００重量部に対し０．１〜２０重量
部、好ましくは２〜ｌＯ重量部の添加量が良い、また同
様の目的で、さらに染料が用いられる０例えばアゾ系染
料、アントラキノン系染料、キサンチン系染料、メチン
系染料等があり樹脂１００重量部に対し０．１〜２０重
量部、好ましくは０．３〜３重量部の添加量が良い。Examples include rhodamine lake, alizarin lake, red iron, phthalocyanine blue, and indan strenblue. These are used in a necessary and sufficient amount to maintain the optical density of the fixed image, and the addition amount is preferably 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the resin. For this purpose, dyes are further used, such as azo dyes, anthraquinone dyes, xanthine dyes, methine dyes, etc., and are 0.1 to 20 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the resin. The amount of addition is good.
本発明に係る静電荷像現像用トナーを作成するには前記
本発明に係る樹脂組成物及び荷電制御剤、必要に応じて
磁性材料及び着色剤としての顔料又は染料、添加剤等を
ボールミルその他の混合機により充分混合してから加熱
ロール、ニーダ−、エクストルーダー等の熱混練機を用
いて溶融、捏和及び゛練肉して樹脂類を互いに相溶せし
めた中に顔料又は染料を分散又は溶解せしめ、冷却固化
後粉砕及び分級して平均粒径３〜２０ＩＬｍのトナーを
得ることができる。To prepare the toner for developing an electrostatic image according to the present invention, the resin composition and charge control agent according to the present invention, if necessary, a magnetic material, a pigment or dye as a coloring agent, additives, etc. are mixed in a ball mill or other machine. Pigments or dyes are dispersed or mixed into the mixture by thoroughly mixing with a mixer and then melting, kneading, and kneading using a heat kneading machine such as a heated roll, kneader, or extruder to make the resins compatible with each other. A toner having an average particle size of 3 to 20 ILm can be obtained by dissolving, cooling and solidifying, and then pulverizing and classifying.
［実施例］ 以下の配合における部数は全て重量部である。[Example] All parts in the following formulations are parts by weight.
合成例１
反応器にクメン２００部を入れ、還流温度まで昇温した
。これにスチレンモノマー１００部及びジーｔｅｒｔ−
ブチルパーオキサイド８部の混合物をクメン還流下で４
時間かけて滴下した。さらにクメン還流下（１４６℃〜
１５８℃）で溶液重合を完了し、クメンを除去した。得
られたポリスチレンはＴＨＦｉ、：可溶テアリ、Ｍｗ＝
３，７００． Ｍｗ／Ｍｎ＝ ２．６４、ＧＰＣのメ
インピークの位置する分子量は３，５００゜Ｔｇ＝５７
℃であった。この樹脂の安息香酸含量は０ＰＰＩＩであ
った。該ポリスチレンのＧＰＣチャートを第３図に示す
。Synthesis Example 1 200 parts of cumene was placed in a reactor, and the temperature was raised to reflux temperature. To this was added 100 parts of styrene monomer and
A mixture of 8 parts of butyl peroxide was added to 4 parts of cumene under reflux.
It dripped over time. Furthermore, under cumene reflux (146℃ ~
Solution polymerization was completed at 158° C.) and cumene was removed. The obtained polystyrene is THFi, :Soluble Teari, Mw=
3,700. Mw/Mn = 2.64, the molecular weight where the main peak of GPC is located is 3,500°Tg = 57
It was ℃. The benzoic acid content of this resin was 0PPII. A GPC chart of the polystyrene is shown in FIG.
上記ポリスチレン３０部を下記単量体混合物に溶解し、
混合溶液とした。Dissolve 30 parts of the above polystyrene in the following monomer mixture,
A mixed solution was prepared.
上記混合溶液にポリビニルアルコール部分ケン化物０．
１部を溶解した水１７０部を加え懸濁分散液とした。水
１５部を入れ窒素置換した反応器に上記懸濁分散液を添
加し、反応温度７０〜３５℃で６時間懸濁重合反応させ
た９反応終了後に炉別し、脱水、乾燥し、ポリスチレン
とスチレン−アクリル酸ｎ−ブチル共重合体の組成物を
得た。該組成物は、ＴＨＦ不溶分とＴＨＦ可溶分が均一
に混合しており、且つポリスチレンとスチレン−アクリ
ル酸ｎ−ブチル共重合体が均一に混合していた。得られ
た樹脂組成物のＴＨＦ不溶分（２４メツシユパス。Add 0% of the partially saponified polyvinyl alcohol to the above mixed solution.
170 parts of water in which 1 part was dissolved was added to form a suspension dispersion. The above suspension dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and suspension polymerization was carried out at a reaction temperature of 70 to 35°C for 6 hours. A composition of styrene-n-butyl acrylate copolymer was obtained. In the composition, THF-insoluble and THF-soluble components were uniformly mixed, and polystyrene and styrene-n-butyl acrylate copolymer were uniformly mixed. THF-insoluble portion of the obtained resin composition (24 mesh passes).
６０メツシユオンの粉体で測定）は、４２ｗｔ％以下で
あった。またＴＨＦ可溶分の分子量分布を測定したとこ
ろＧＰＣのチャートにおいて約０．４万、約３．３万の
位置にピークを有し、Ｍｎ＝ ０．５４万、 Ｍｖ＝１
３万、 Ｍｗ／Ｍｎ ＝ ２４ 、分子量１万以下が２
２ｗｔ％であった。さらに樹脂のＴｇは、５９℃であり
、ＧＰＣにより分取された１万以下の成分のガラス転移
点Ｔｇ＋ は５７℃であった。また安息香酸含量はＯｐ
ｐｍであった。さらに酸価はＯであった。(measured using 60 mesh powder) was 42 wt% or less. In addition, when the molecular weight distribution of the THF-soluble component was measured, there were peaks at approximately 4,000 and 33,000 positions on the GPC chart, Mn = 0,540,000, Mv = 1.
30,000, Mw/Mn = 24, molecular weight 10,000 or less is 2
It was 2wt%. Furthermore, the Tg of the resin was 59°C, and the glass transition point Tg+ of the components of 10,000 or less separated by GPC was 57°C. In addition, the benzoic acid content is Op.
It was pm. Furthermore, the acid value was O.
ＴＨＦ可溶分のＧＰＣクロマトグラムを第２図に示す。A GPC chromatogram of the THF-soluble fraction is shown in FIG.
尚、各樹脂及び樹脂組成物の分子量に関わる特性は下記
方法で測定した。In addition, the characteristics related to the molecular weight of each resin and resin composition were measured by the following method.
ＧＰＣＪｌｌ定用カラムとして５ｈｏｄｅｘ ＫＦ−８
０Ｍを用い、ＧＰＣ測定装置（ウォーターズ社製１５０
０ ＡＬＣ／ＧＰＣ）の４０℃のヒートチャンバーに組
み込みＴＨＦ流速１ ＠４／ｗｉｎ 、検出器はＲ１の
条件下、試料（ＴＨＦ可溶分の濃度的０．１重量％）を
２００μｐ注入することでＧＰＣを測定した。分子量測
定の検量線としては分子量０．５ Ｘ１０３．２．３５
Ｘ１０３．１０．２ Ｘ１０３゜３５Ｘ １０３ 、
ｌｌ０Ｘ １０３ 、２００Ｘ １０３ 、４７０Ｘ
１０３．１２００Ｘ１０３、２７００ Ｘ １０３．
８４２０ Ｘ １０３の１０点の単分散ポリスチレン基
準物質（ウォーターズ社製）のＴＨＦ溶液を用いた。5hodex KF-8 as GPCJll standard column
0M using a GPC measurement device (Waters 150
By injecting 200 μp of the sample (concentration of THF soluble content: 0.1% by weight) under the conditions of THF flow rate 1 @ 4/win and detector R1. GPC was measured. The calibration curve for molecular weight measurement is molecular weight 0.5 x 103.2.35.
X103.10.2 X103゜35X 103,
ll0X 103, 200X 103, 470X
103.1200X103, 2700X103.
A THF solution of a 10-point monodisperse polystyrene reference material (manufactured by Waters) measuring 8420 x 103 was used.
比較合成例１
合成例１中で得られたポリスチレン３０部を下記単量体
混合物に溶解し、混合溶液とした。Comparative Synthesis Example 1 30 parts of the polystyrene obtained in Synthesis Example 1 was dissolved in the following monomer mixture to prepare a mixed solution.
上記混合物を合成例１と同様にして懸濁重合を行い、ポ
リスチレンとスチレン−アクリル酸ｎ−ブチル共重合体
の組成物を得た。この樹脂組成物のＴＨＦ不溶分は７５
重量％であり、多量のＴＨＦ不溶分を含有していた。ま
たこの樹脂の安息香酸含量は１５８０ｐｐｍだった。ま
た酸価は０．７であった。The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. The THF-insoluble content of this resin composition is 75
% by weight, and contained a large amount of THF-insoluble matter. Moreover, the benzoic acid content of this resin was 1580 ppm. Moreover, the acid value was 0.7.
比較合成例２
合成例１中で得られたポリスチレン３０部を下記単量体
混合物に溶解し、混合溶液とした。Comparative Synthesis Example 2 30 parts of the polystyrene obtained in Synthesis Example 1 was dissolved in the following monomer mixture to prepare a mixed solution.
上記混合物を合成例１と同様にして懸濁重合を行い、ポ
リスチレンとスチレン−アクリル酸ｎ−ブチル共重合体
の組成物を得た。この組成物のＴＨＦ可溶成分のＧＰＣ
において、分子量的４，０００と分子３９１５万の位置
にピークがあった。またこの樹脂の安息香酸含量はＯｐ
ｐｍであった。The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. GPC of THF soluble components of this composition
There were peaks at molecular weights of 4,000 and 39.15 million molecules. Also, the benzoic acid content of this resin is Op.
It was pm.
比較合成例３
反応器にキシレン１５０部を入れ、還流温度まで昇温す
る。これにスチレンモノマー１００ ｍ 、 ｔｅｒｔ
−ブチルパーオキシベンゾエート２部、ジーｔｅｒｔブ
チルパーオキシサイド１部の混合物を、キシレン還流下
で４時間かけて滴下した。さらにキシレン還流下（１３
８〜１４４℃）で溶液重合を完了し、キシレンを除去し
た。Comparative Synthesis Example 3 150 parts of xylene is placed in a reactor and the temperature is raised to reflux temperature. To this, 100 m of styrene monomer, tert.
A mixture of 2 parts of -butyl peroxybenzoate and 1 part of di-tert butyl peroxide was added dropwise over 4 hours under refluxing xylene. Furthermore, under reflux of xylene (13
Solution polymerization was completed at 8-144°C) and xylene was removed.
得られたポリスチレンはＴＨＦに可溶であり、Ｍｗ＝
１０，０００、Ｍｗ／＞Ｉｎ ＝ ３．２２、分子量１
１，０００の位置にメインピークがあり、Ｔｇ＝ ８２
℃であった。またこの樹脂の安息香酸含量は６２０ｐｐ
ｍだった。The obtained polystyrene is soluble in THF and Mw=
10,000, Mw/>In = 3.22, molecular weight 1
There is a main peak at the 1,000 position, Tg = 82
It was ℃. The benzoic acid content of this resin is 620pp.
It was m.
上記ポリスチレン３０部を下記単量体混合物に溶解し、
混合溶液とした。Dissolve 30 parts of the above polystyrene in the following monomer mixture,
A mixed solution was prepared.
上記混合物を合成例１と同様にして懸濁重合を行い、ポ
リスチレンとスチレン−アクリル酸ｎ−ブチル共重合体
の組成物を得た。この組成物のＴＨＦ可溶成分のＧＰＣ
において、分子−量的１０，０００以下に実質的にピー
クを有していなかった。また、この樹脂の安息香酸含量
は１８４０ｐｐ■だった。The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. GPC of THF soluble components of this composition
There was virtually no peak at a molecular weight of 10,000 or less. Further, the benzoic acid content of this resin was 1840 pp■.
比較合成例４
下記単量体混合物に、ポリビニルアルコール部分ケン化
物０．１部を溶解した水１７０部を加え、懸濁分散液と
した。Comparative Synthesis Example 4 170 parts of water in which 0.1 part of partially saponified polyvinyl alcohol was dissolved was added to the following monomer mixture to prepare a suspension dispersion.
水１５部を入れ窒素置換した反応器に上記分散液を添加
し、反応温度７０〜９５℃で６時間懸濁重合反応させた
０反応終了後、炉別、脱水、乾燥し、スチレン−アクリ
ル酸ｎ−ブチル共重合体を得た。The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and the suspension polymerization reaction was carried out at a reaction temperature of 70 to 95°C for 6 hours. An n-butyl copolymer was obtained.
この共重合体は、メインピークが分子量的１７．０００
の位置にあり、分子量１万以下には実質的にピークはな
かった。またこの樹脂の安息香酸含量は３８７０ｐｐｍ
であった。This copolymer has a main peak with a molecular weight of 17.000.
There was virtually no peak at a molecular weight of 10,000 or less. Also, the benzoic acid content of this resin is 3870 ppm.
Met.
合成例２
反応器にクメン２００部を入れ、還流温度まで昇温した
。下記混合物をクメン還流下で４時間かけて滴下した。Synthesis Example 2 200 parts of cumene was placed in a reactor, and the temperature was raised to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.
さらにクメン還流下（１４６〜１５Ｅｉ℃）で重合を完
了し、クメンを除去した。得られたポリスチレンは、Ｍ
ｗ＝ ３，７００、Ｍｗ／Ｍｎ＝ ２．８４、分子量３
，５００にメインピークを有し、Ｔｇ＝５７℃であった
。また得られた樹脂の安息香酸含量はＯＰＰ■であった
。上記ポリスチレン３０部を下記単量体混合物に溶解し
、混合物とした。Further, the polymerization was completed under cumene reflux (146 to 15 Ei° C.), and cumene was removed. The obtained polystyrene was M
w= 3,700, Mw/Mn= 2.84, molecular weight 3
, 500, and Tg=57°C. Moreover, the benzoic acid content of the obtained resin was OPP■. 30 parts of the above polystyrene was dissolved in the following monomer mixture to form a mixture.
上記混合物にポリビニルアルコール部分ケン化物０．１
部を溶解した水１７０部を加え懸濁分散液とした。Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion.
水１５部を入れ窒素置換した反応器に上記分散液を添加
し、反応温度７０〜９５°Ｃで６時間反応させた０反応
終了後、炉別、脱水、乾燥し、ポリスチレンとスチレン
−アクリル酸２−エチルヘキシル共重合体の組成物を得
た。得られた樹脂組成物の安息香酸含量はＯｐｐｍだっ
た。The above dispersion was added to a reactor filled with 15 parts of water and purged with nitrogen, and reacted for 6 hours at a reaction temperature of 70 to 95°C. After the reaction was completed, it was separated in a furnace, dehydrated, dried, and mixed with polystyrene and styrene-acrylic acid. A composition of 2-ethylhexyl copolymer was obtained. The benzoic acid content of the obtained resin composition was Oppm.
合成例３
反応器にクメン２００部を入れ、還流温度まで昇温した
。下記混合物をクメン還流下で４時間かけて滴下した９
ざらにクメン還流下（１４６〜１５６℃）で重合を完了
し、クメンを除去した。得られたスチレン−α−メチル
スチレンはＭｗ＝ ４，５００、Ｍｙ／Ｍｎ＝ ２．８
、分子量４，４００の位置にメインピークを有し、Ｔｇ
＝６３℃であった。得られた樹脂の安息香酸含量はＯｐ
ｐｍであった。Synthesis Example 3 200 parts of cumene was placed in a reactor, and the temperature was raised to reflux temperature. The following mixture was added dropwise over 4 hours under refluxing cumene. Polymerization was completed under refluxing cumene (146-156°C), and cumene was removed. The obtained styrene-α-methylstyrene had Mw=4,500 and My/Mn=2.8.
, has a main peak at a molecular weight of 4,400, and has a Tg
=63°C. The benzoic acid content of the obtained resin is Op.
It was pm.
上記スチレン−α−メチルスチレン共重合体３０部を下
記単量体混合物に溶解し、混合物とした。30 parts of the above styrene-α-methylstyrene copolymer was dissolved in the following monomer mixture to form a mixture.
上記混合物にポリビニルアルコール部分ケン化物０．１
部を溶解した水１７０部を加え懸濁分散液とした。水１
５部を入れ窒素置換した反応器に上記分散液を添加し、
反応温度７０〜９５℃で６時間反応させた０反応終了後
、炉別、脱水、乾燥し、スチレン−α−メチルスチレン
共重合体とスチレン−アクリル酸ｎ−ブチル共重合体の
組成物を得た。この樹脂の安息香酸含量は３３０ｐｐ層
であった。Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion. water 1
The above dispersion was added to a reactor containing 5 parts and purged with nitrogen,
After the reaction was completed for 6 hours at a reaction temperature of 70 to 95°C, the mixture was separated in a furnace, dehydrated, and dried to obtain a composition of styrene-α-methylstyrene copolymer and styrene-n-butyl acrylate copolymer. Ta. The benzoic acid content of this resin was 330 pp layer.
比較合成例５
反応器にクメン２００部を入れ、還流温度まで昇温する
。下記混合物をクメン還流下で４時間かけて滴下した。Comparative Synthesis Example 5 200 parts of cumene was placed in a reactor and heated to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.
さらにクメン還流下（１４６〜１５８℃）で重合を完了
し、クメンを除去した。得られたポリスチレンは、Ｍｗ
＝ ３，７００、Ｍｙ／Ｍｎ＝ ２．８４、分子量３．
５００の位置にメインピークを有し、Ｔｇ＝ ５７℃で
あった。Further, polymerization was completed under cumene reflux (146 to 158°C), and cumene was removed. The obtained polystyrene has Mw
= 3,700, My/Mn = 2.84, molecular weight 3.
It had a main peak at position 500, and Tg = 57°C.
この樹脂の安息香酸含量はＯｐｐｍであった。The benzoic acid content of this resin was Oppm.
上記ポリスチレン３０部を下記単量体混合物に溶解し、
混合物とした。Dissolve 30 parts of the above polystyrene in the following monomer mixture,
It was made into a mixture.
上記混合物にポリビニルアルコール部分ケン化物０．１
部を溶解した水１７０部を加え分散液とした。水１５部
を入れ窒素置換した反応器に上記分散液を添加し、反応
温度７０〜Ｓ５°Ｃで６時間反応させた０反応終了後、
炉別、脱水、乾燥し、ポリスチレンとスチレン−アクリ
ル酸ｎ−ブチル共重合体の組成物を得た。この組成物の
ＴＨＦ不溶分は約３重量％であり、少量のＴＨＦ不溶分
しか含有していなかった。またこの樹脂の安息香酸含量
は２１７０ｐｐｍだった。Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a dispersion. The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and the reaction was carried out for 6 hours at a reaction temperature of 70 to 5°C. After completion of the reaction,
The mixture was separated in a furnace, dehydrated, and dried to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. The THF-insoluble content of this composition was approximately 3% by weight, and contained only a small amount of THF-insoluble content. Moreover, the benzoic acid content of this resin was 2170 ppm.
実施例１
上記材料をヘンシェルミキサーで前混合した後、１５０
℃に熱した２本ロールミルで２０分間混練した。混練物
を放冷後、カッターミルで粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて粉砕し、さらに風力分級機を
用いて分級し、体積平均粒径１１ 、５ＩＬｍの黒色微
粉体を得た。該黒色微粉体のＴＨＦ可溶分のＧＰＣチャ
ートを第１図に示す。Example 1 After premixing the above materials in a Henschel mixer, 150
The mixture was kneaded for 20 minutes in a two-roll mill heated to .degree. After cooling the kneaded material, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a black fine powder with a volume average particle size of 11.5 ILm. I got it. A GPC chart of the THF soluble content of the black fine powder is shown in FIG.
該黒色微粉体１００部に対してコロイダルシリカ微粉体
０．４部を乾式混合し、現像剤（トナー）を得た。0.4 parts of colloidal silica fine powder was dry mixed with 100 parts of the black fine powder to obtain a developer (toner).
トナーの粉砕性は、単位時間当りに粉砕できるトナーの
処理量で表わすことができ、このトナーの場合、エアー
圧５．５ｋｇ／ｃｍ２ テ１５ｋｇ／ｈｒ テあり、ひ
じょうに良かった。また粉砕機内に融着など起らなかっ
た。The pulverizability of the toner can be expressed by the amount of toner that can be pulverized per unit time, and in the case of this toner, the air pressure was 5.5 kg/cm2 and 15 kg/hr, which was very good. Furthermore, no fusion occurred inside the crusher.
また、ブロッキング性は、約１０ｇのトナーを１００ｃ
ｃのポリコツプに入れ、５０℃で１日放置した時の凝集
度の変化で調べた。凝集度は、紙用ミクロン製のパウダ
ーテスターにより測定した。室温放置品と５０℃１日放
置品とでは１０重量％と１２重量％でほぼ同じ値を示し
、差（ΔＧ）が２％であることから実質的にブロッキン
グしていないことを確認した。In addition, the blocking property is as follows: Approximately 10g of toner is
The samples were placed in a polyethylene cup (C) and left at 50°C for one day, and the change in aggregation degree was examined. The degree of aggregation was measured using a paper micron powder tester. The product left at room temperature and the product left at 50°C for one day showed almost the same values at 10% by weight and 12% by weight, and the difference (ΔG) was 2%, confirming that there was no substantial blocking.
定着性とオフセット性９巻き付き性及び画像性、耐久性
については、キャノン製高速複写機。Fixing properties and offset properties 9 Regarding wrapping properties, image quality, and durability, Canon high-speed copying machine.
ＮＰ−５５４０（毎分４０枚、 １００Ｖ） ヲ用イテ
調ヘタ。NP-5540 (40 sheets per minute, 100V) It's not suitable for use.
特にオフセット性は、定着ローラのクリーニング機構を
取りはずし、何枚の複写で画像が汚れるかあるいはロー
ラが汚れるかということを耐複写枚数で評価した。In particular, the offset property was evaluated by removing the cleaning mechanism of the fixing roller and determining the number of copies it took to stain the image or stain the roller.
定着器の設定温度を５°Ｃ下げテストした。定着性は、
画像をシルポンＣ紙で往復ｌＯ回約１００ｇ荷重でこす
り、画像のはがれを反射濃度の低下率（％）で表わした
。評価画像は連続２００枚とった時の２００枚目で見た
。A test was conducted by lowering the set temperature of the fixing device by 5°C. Fixability is
The image was rubbed with Silpon C paper back and forth 10 times under a load of about 100 g, and the peeling of the image was expressed as a percentage decrease in reflection density (%). The evaluation image was viewed at the 200th image out of 200 consecutive images.
巻き付き性は、全面黒画像を３枚出し、その時画像上に
つく定着ローラのはく敲用のツメの跡の様子で、ツメに
どの位頼っているかで判断した。The wrapping property was determined by printing three completely black images and checking the appearance of the marks left on the images by the fusing tabs of the fixing roller, and by how much the film relied on the tabs.
その結果、定着性は低下率３％でひじょうに良く、オフ
セット性は７０，０００枚時でも画像上ローラの汚れな
どなく良好であり、巻き付き性も画像上にツメに頼った
跡がわずかに付くが、ひじょうに良好であった。As a result, the fixing performance was very good with a decrease rate of 3%, the offset performance was good with no roller stains on the image even after printing 70,000 sheets, and the wrapping performance was also good, although there were slight marks on the image due to the claws. , was very good.
また、画像面積率約５％の画像を用いて約７０．０００
枚の耐久テストを行なったが、画像濃度１．２〜１．３
で、カブリのない高解像力の鮮明な画像が得られ、感光
体などへの融着、フィルミングなども発生しなかった。Also, using an image with an image area ratio of approximately 5%, approximately 70,000
I did a durability test on the sheet, and the image density was 1.2 to 1.3.
Clear, high-resolution images with no fog were obtained, and no fusion or filming occurred on the photoreceptor.
またスリーブ汚染による画像濃度の評価は、複写開始時
の画像濃度と、連続５０．０００枚複写後の画像濃度（
ΔＤｉ万枚）及び連続７０，０００枚複写後の画像濠度
差（ΔＤ５万枚）との両方を比較することで判断した。In addition, the evaluation of image density due to sleeve contamination is based on the image density at the start of copying and the image density after continuous copying of 50,000 sheets (
The judgment was made by comparing both ΔDi (10,000 sheets) and the image roughness difference after 70,000 continuous copies (ΔD 50,000 sheets).
それによればΔＤ５万枚＝±０．０３、ΔＤ７万枚＝±
０．０３であり、スリーブ汚染は問題がなかった。さら
に３０℃、相対湿度９０％の環境下での連続複写では、
画像濃度１．３と安定で、ガブリのない鮮明な画像が得
られ、耐高温特性に優れていた。According to that, ΔD50,000 sheets = ±0.03, ΔD70,000 sheets = ±
0.03, and there was no problem with sleeve contamination. Furthermore, in continuous copying in an environment of 30°C and 90% relative humidity,
A stable image density of 1.3 was obtained, a clear image with no blurring was obtained, and the high temperature resistance was excellent.
比較例１〜５
実施例１の樹脂組成物のかわりに比較合成例１〜５で調
製された樹脂組成物を用いて、実施例１と同様にトナー
を作り、そのトナーを比較例１〜５とした。Comparative Examples 1 to 5 Toners were made in the same manner as in Example 1 using the resin compositions prepared in Comparative Synthesis Examples 1 to 5 instead of the resin composition of Example 1, and the toners were used as Comparative Examples 1 to 5. And so.
比較例のトナーの評価を実施例１と同様に行い表１に示
した。The toner of the comparative example was evaluated in the same manner as in Example 1 and is shown in Table 1.
実施例２
上記混合物を実施例１と同様にしてトナーを調製した０
体植平均粒度は１１ 、７１Ｌｍであった。コロイダル
シリカ微粉体は、アミノ変性シリコンオイル処理したも
のを用いた。トナーの粉砕性は、処理ｉ１５．５ｋｇ／
ｈｒでひじょうに良かった。また粉砕機内の融着などは
なかった。ブロッキング性はΔＧ＝２％で全く問題なか
った。キャノン製高速複写機ＮＰ−５５４０定着器を用
いて、定着の設定温度を１０℃下げ、また定着器のクリ
ーニング機構をはずして定着性、オフセット性１巻き付
き性を検討したところ、定着性は低下率約３％で非常に
良好であり、オフセット、巻き付きについても全く問題
なかった。また現像性にわいては、ＭＰ−５５４０複写
機を用いて７０，０００枚の耐久テストを行なったが、
初期から画像濃度１．２〜１．３のカブリのない高解像
力の鮮明な画像が得られ、感光体などへの融着、フィル
ミングも発生しなかった。さらにスリーブ汚染に関して
はΔＤ５万枚＝±０．０３、ΔＤ７万枚＝±０．０５で
あり、全く問題がなかった。また３０°Ｃ１相対湿度９
０％の環境下での連続複写では、画像濃度１．２５〜１
．３５と安定で、カブリのない鮮明な画像が得られ、耐
高湿特性に優れていた。Example 2 A toner was prepared using the above mixture in the same manner as in Example 1.
The average grain size of the plant was 11.71 Lm. The colloidal silica fine powder treated with amino-modified silicone oil was used. The crushability of the toner was determined by treatment i15.5kg/
It was very good for hr. Furthermore, there was no fusion within the crusher. The blocking property was ΔG=2%, and there was no problem at all. Using a Canon high-speed copier NP-5540 fuser, we lowered the fixing temperature by 10 degrees Celsius, removed the fuser's cleaning mechanism, and examined the fixing performance, offset, and one-wrap property. It was about 3%, which was very good, and there were no problems with offset or winding. Regarding developability, we conducted a durability test of 70,000 sheets using an MP-5540 copying machine.
Clear, fog-free, high-resolution images with an image density of 1.2 to 1.3 were obtained from the initial stage, and no fusion or filming occurred on the photoreceptor. Furthermore, regarding sleeve contamination, ΔD of 50,000 sheets = ±0.03 and ΔD of 70,000 sheets = ±0.05, so there was no problem at all. Also 30°C1 relative humidity9
In continuous copying under a 0% environment, the image density is 1.25 to 1.
．． 35, a clear image without fogging was obtained, and it had excellent high humidity resistance.
実施例３
上記混合物を実施例１の方法でトナーを調製し、該トナ
ーを２００メツシユ〜３００メツシユの粒度の鉄粉に約
１０重量％混合し、現像剤とした。また補充剤としては
トナーのみを用いた。Example 3 A toner was prepared from the above mixture by the method of Example 1, and about 10% by weight of the toner was mixed with iron powder having a particle size of 200 to 300 meshes to prepare a developer. Further, only toner was used as a replenisher.
このトナーの粉砕性は、処理量１５．５ｋｇ／ｈｒでひ
じょうに良好であった。また粉砕機内の融着などもなか
った。ブロッキング性は、ΔＧ＝５％でまったく問題な
かった。The crushability of this toner was very good at a throughput of 15.5 kg/hr. Furthermore, there was no fusion within the crusher. The blocking property was ΔG=5%, and there was no problem at all.
またキャノン製超高速複写機ＮＰ−８５００スーパー機
で画像性、定着性を評価した。その結果、画像は良好で
、７０，０００枚耐久を行ったが安定した画像が得られ
た。またドラムへのフィルミング、融着などなかった。Further, image quality and fixing performance were evaluated using a super high speed copying machine manufactured by Canon NP-8500. As a result, the image was good and stable after 70,000 sheets. Also, there was no filming or fusion on the drum.
また長期連続複写によるスリーブ汚染に関しては、ΔＤ
５万枚＝±０．０８、ΔＤ７万枚＝±０．０８と、良好
なレベルであり、さらに３０℃、相対湿度８０％での連
続複写では、画像濃度１．１５〜１．２５と安定で、カ
ブリのない鮮明な画像が得られ、耐湿特性として満足で
きるレベルであった。Regarding sleeve contamination due to long-term continuous copying, ΔD
50,000 sheets = ±0.08, ΔD 70,000 sheets = ±0.08, which is a good level, and the image density is stable at 1.15 to 1.25 during continuous copying at 30°C and 80% relative humidity. A clear image without fogging was obtained, and the moisture resistance was at a satisfactory level.
トナーの特性について表−２に示した。Table 2 shows the characteristics of the toner.
以下余白
［発明の効果］
以上から明らかなように、本発明のトナーは低い温度で
定着し、感光体への融着、フィルミングが高速システム
においても、また長期間の使用でも発生することがない
ものである。Margin below [Effects of the Invention] As is clear from the above, the toner of the present invention is fixed at a low temperature, and fusion and filming on the photoreceptor do not occur even in high-speed systems and even after long-term use. It's something that doesn't exist.
また、低い温度で定着し且つ耐ブロッキング性がすぐれ
、特に小型機の中の高温雰囲気中でも充分使え得るもの
である。Furthermore, it can be fixed at low temperatures and has excellent anti-blocking properties, so it can be used satisfactorily even in high-temperature atmospheres, especially in small machines.
更に、本発明のトナーは、特に高速複写機において長期
にわたる画像の連続複写に対して優れた耐久性をもち、
環境変動にも影響されにくい、カブリのない鮮明な高画
像濃度を与えるものである。Further, the toner of the present invention has excellent durability against continuous copying of images over a long period of time, especially in high-speed copying machines.
It provides clear, high-density images with no fog and is not easily affected by environmental changes.
第１図は実施例１で調製されたトナーのＴＨＦ可溶分の
ＧＰＣのチャートを示す、第２図は合成例１で調製され
た樹脂組成物のＴＨＦ可溶分のＧＰＣのチャートを示す
、第３図は合−成例１で使用したポリスチレンのＧＰＧ
のチャートを示し、第４図は合成例１で使用したスチレ
ン−アクリル酸ｎ−ブチル共重合体を単独で懸／ｆｌＪ
重合して得たもののＴＨＦ可溶分のＧＰＣのチャートを
示す。第５図は第３図と第４図のチャートを組み合せた
ものであり、第６図は第２図と第５図を比較説明するた
めのチャートを示す、第７図はトナーに要求される各特
性の相関関係を示す図であり、第８図はＴＨＦ不溶分の
含有量と粉砕性との関係を示すグラフであり、第９図は
分子量１０．ＯＱＱ以下の成分の含有量とトナー特性と
の相関関係に係わるグラフを示す図である。第１０図は
、安息香酸のガスクロマトグラムを示す図であり、第１
１図は、安息香酸とジフェニルエーテルとの検量線を示
すグラフであり、第１２図は安息香酸の含有量と画像濃
度低下量との関係を示すグラフである。FIG. 1 shows a GPC chart of the THF-soluble content of the toner prepared in Example 1, and FIG. 2 shows a GPC chart of the THF-soluble content of the resin composition prepared in Synthesis Example 1. Figure 3 shows the GPG of polystyrene used in Synthesis Example 1.
Figure 4 shows a chart of the styrene-n-butyl acrylate copolymer used in Synthesis Example 1, suspended/flJ.
A GPC chart of the THF soluble content of the polymerization product is shown. Figure 5 is a combination of the charts in Figures 3 and 4, Figure 6 is a chart for comparing and explaining Figures 2 and 5, Figure 7 is the required amount of toner. FIG. 8 is a graph showing the relationship between the content of THF-insoluble matter and crushability, and FIG. FIG. 3 is a diagram showing a graph relating to the correlation between the content of components below OQQ and toner characteristics. Figure 10 is a diagram showing a gas chromatogram of benzoic acid;
FIG. 1 is a graph showing a calibration curve between benzoic acid and diphenyl ether, and FIG. 12 is a graph showing the relationship between the content of benzoic acid and the amount of image density reduction.
Claims (1)
（バインダー樹脂基準）であり、ＴＨＦ可溶分のＧＰＣ
による分子量分布において、重量平均分子量／数平均分
子量（Ｍｗ／Ｍｎ）≧５であり、分子量２，０００〜１
０，０００の領域にピークを少なくとも１つ有し、且つ
分子量１５，０００〜１００，０００の領域にピーク又
は肩を少なくとも１つ有し、分子量１０，０００以下の
成分の含有量がバインダー樹脂に１０〜５０重量％であ
るバインダー樹脂と、含窒素荷電制御剤とを少なくとも
含有し、且つ安息香酸の含有量が５００ｐｐｍ以下であ
ることを特徴とする静電荷像現像用トナー。The THF-insoluble content of the binder resin is 10 to less than 60% by weight (based on binder resin), and the THF-soluble content is GPC
In the molecular weight distribution according to
0,000, and at least one peak or shoulder in the molecular weight region of 15,000 to 100,000, and the content of components with a molecular weight of 10,000 or less is in the binder resin. A toner for developing an electrostatic image, comprising at least 10 to 50% by weight of a binder resin and a nitrogen-containing charge control agent, and having a benzoic acid content of 500 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044354A JPH0625872B2 (en) | 1988-02-29 | 1988-02-29 | Toner for electrostatic charge image development for heat and pressure fixing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044354A JPH0625872B2 (en) | 1988-02-29 | 1988-02-29 | Toner for electrostatic charge image development for heat and pressure fixing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01219764A true JPH01219764A (en) | 1989-09-01 |
| JPH0625872B2 JPH0625872B2 (en) | 1994-04-06 |
Family
ID=12689178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63044354A Expired - Lifetime JPH0625872B2 (en) | 1988-02-29 | 1988-02-29 | Toner for electrostatic charge image development for heat and pressure fixing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625872B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391450A (en) * | 1990-07-31 | 1995-02-21 | Canon Kabushiki Kaisha | Toner image heat-fixing method |
| WO1999023533A1 (en) * | 1997-10-31 | 1999-05-14 | Mitsubishi Rayon Co., Ltd. | Binder resin for toners and process for preparing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57211157A (en) * | 1981-06-23 | 1982-12-24 | Mitsui Toatsu Chem Inc | Resin composition for electrophotographic toner |
| JPS603644A (en) * | 1983-06-22 | 1985-01-10 | Fuji Xerox Co Ltd | Toner composition |
-
1988
- 1988-02-29 JP JP63044354A patent/JPH0625872B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57211157A (en) * | 1981-06-23 | 1982-12-24 | Mitsui Toatsu Chem Inc | Resin composition for electrophotographic toner |
| JPS603644A (en) * | 1983-06-22 | 1985-01-10 | Fuji Xerox Co Ltd | Toner composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391450A (en) * | 1990-07-31 | 1995-02-21 | Canon Kabushiki Kaisha | Toner image heat-fixing method |
| WO1999023533A1 (en) * | 1997-10-31 | 1999-05-14 | Mitsubishi Rayon Co., Ltd. | Binder resin for toners and process for preparing the same |
| US6495648B1 (en) | 1997-10-31 | 2002-12-17 | Mitsubishi Rayon Co., Ltd. | Toner binder resin and process for the production thereof |
| KR100446572B1 (en) * | 1997-10-31 | 2004-09-04 | 미쯔비시 레이온 가부시끼가이샤 | Binder resin for toners and process for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0625872B2 (en) | 1994-04-06 |
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