JPH01200270A - Positive-chargeable color toner - Google Patents
Positive-chargeable color tonerInfo
- Publication number
- JPH01200270A JPH01200270A JP63024510A JP2451088A JPH01200270A JP H01200270 A JPH01200270 A JP H01200270A JP 63024510 A JP63024510 A JP 63024510A JP 2451088 A JP2451088 A JP 2451088A JP H01200270 A JPH01200270 A JP H01200270A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- toner
- acrylate
- vinyl polymer
- molecular 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
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 46
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 17
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 239000012933 diacyl peroxide Substances 0.000 claims abstract description 7
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 30
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 11
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 62
- -1 tetrahydrofurfuryl Chemical group 0.000 description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229920006163 vinyl copolymer Polymers 0.000 description 4
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle 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
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001106557 Papaver argemone Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000012508 resin bead Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- GPWQZTBXIQVBRB-UHFFFAOYSA-N 2,3-bis(2-sulfanylpropanoyloxy)propyl 2-sulfanylpropanoate Chemical compound CC(S)C(=O)OCC(OC(=O)C(C)S)COC(=O)C(C)S GPWQZTBXIQVBRB-UHFFFAOYSA-N 0.000 description 1
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- 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
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TVFJLSWPPLFHKR-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCC(O)OC1=CC=CC=C1 TVFJLSWPPLFHKR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- ACHWNFGWACZQHU-UHFFFAOYSA-N 2-propoxyethyl prop-2-enoate Chemical compound CCCOCCOC(=O)C=C ACHWNFGWACZQHU-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WPIYAXQPRQYXCN-UHFFFAOYSA-N 3,3,5-trimethylhexanoyl 3,3,5-trimethylhexaneperoxoate Chemical compound CC(C)CC(C)(C)CC(=O)OOC(=O)CC(C)(C)CC(C)C WPIYAXQPRQYXCN-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
- LVOJOIBIVGEQBP-UHFFFAOYSA-N 4-[[2-chloro-4-[3-chloro-4-[(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-methyl-2-phenylpyrazol-3-ol Chemical compound CC1=NN(C(O)=C1N=NC1=CC=C(C=C1Cl)C1=CC(Cl)=C(C=C1)N=NC1=C(O)N(N=C1C)C1=CC=CC=C1)C1=CC=CC=C1 LVOJOIBIVGEQBP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- REEFSLKDEDEWAO-UHFFFAOYSA-N Chloraniformethan Chemical compound ClC1=CC=C(NC(NC=O)C(Cl)(Cl)Cl)C=C1Cl REEFSLKDEDEWAO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- LTGPFZWZZNUIIK-LURJTMIESA-N Lysol Chemical compound NCCCC[C@H](N)CO LTGPFZWZZNUIIK-LURJTMIESA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100040160 Rabankyrin-5 Human genes 0.000 description 1
- 101710086049 Rabankyrin-5 Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- HEQCHSSPWMWXBH-UHFFFAOYSA-L barium(2+) 1-[(2-carboxyphenyl)diazenyl]naphthalen-2-olate Chemical compound [Ba++].Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O.Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O HEQCHSSPWMWXBH-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- HTUDBOWEKWIOCZ-UHFFFAOYSA-N cadmium(2+) mercury(1+) sulfide Chemical compound [S-2].[Cd+2].[Hg+] HTUDBOWEKWIOCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- HBHZKFOUIUMKHV-UHFFFAOYSA-N chembl1982121 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HBHZKFOUIUMKHV-UHFFFAOYSA-N 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- YOCIQNIEQYCORH-UHFFFAOYSA-M chembl2028361 Chemical compound [Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=CC=C1 YOCIQNIEQYCORH-UHFFFAOYSA-M 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- JYWJULGYGOLCGW-UHFFFAOYSA-N chloromethyl chloroformate Chemical compound ClCOC(Cl)=O JYWJULGYGOLCGW-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HTENFZMEHKCNMD-UHFFFAOYSA-N helio brilliant orange rk Chemical compound C1=CC=C2C(=O)C(C=C3Br)=C4C5=C2C1=C(Br)C=C5C(=O)C1=CC=CC3=C14 HTENFZMEHKCNMD-UHFFFAOYSA-N 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- SNWKNPMDQONHKK-UHFFFAOYSA-N methyl 2-sulfanylpropanoate Chemical compound COC(=O)C(C)S SNWKNPMDQONHKK-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VENDXQNWODZJGB-UHFFFAOYSA-N n-(4-amino-5-methoxy-2-methylphenyl)benzamide Chemical compound C1=C(N)C(OC)=CC(NC(=O)C=2C=CC=CC=2)=C1C VENDXQNWODZJGB-UHFFFAOYSA-N 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 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
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08726—Polymers of unsaturated acids or derivatives thereof
- G03G9/08728—Polymers of esters
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (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、静電潜像の現像に使用されるト・ナーに関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to toners used for developing electrostatic latent images.
〔従来の技術および発明が解決しようとする課題〕静電
潜像の現像は、種々の方式で感光体上に形成された正ま
たは負の電荷を有する静電潜像に対し、正または負に摩
擦帯電されたトナーを静電的に吸着させることにより行
なわれ、次いで転写紙上にトナー画像を転写し、定着さ
せることにより現像画像の定着が行なわれる。このトナ
ーは、カブリ等のない鮮明な現像画像を得るために適正
な帯電量を有することがまず要求される。更に、帯電量
に経時変化がなく、環境変化1例えば湿度変化等により
、著しい帯電量の減衰や固化等の変化を生じないことも
要求されている。これは帯電量が最初に設定された値か
ら減衰して小さくなると、トナー飛散が多くなり地肌カ
ブリや白紙部分へのトナー飛散、また現像装置周辺にト
ナー汚れが生ずる等の問題が発生するからである。[Prior Art and Problems to be Solved by the Invention] Development of an electrostatic latent image is carried out by applying a positive or negative charge to an electrostatic latent image having a positive or negative charge formed on a photoreceptor using various methods. This is done by electrostatically adhering the triboelectrically charged toner, and then the developed image is fixed by transferring and fixing the toner image onto the transfer paper. This toner is first required to have an appropriate amount of charge in order to obtain a clear developed image without fogging or the like. Furthermore, it is also required that the amount of charge does not change over time, and that changes such as significant attenuation or solidification of the amount of charge do not occur due to environmental changes 1, such as changes in humidity. This is because when the amount of charge attenuates from the initially set value and becomes smaller, toner scattering increases, causing problems such as background fog, toner scattering on blank areas, and toner stains around the developing device. be.
上記要求に応えるため、トナー製造に際し通常1F電制
御剤が添加される。帯電制御剤は一般に製糸:1または
紫等の濃い着色を有しており、黒色のトナーには用いる
ことができるものの、カラートナーに用いると色のにご
りが激しく、使用に附えない。従って、カラートナーに
は無色の帯電制御剤が要求される。In order to meet the above requirements, a 1F electrical control agent is usually added during toner production. The charge control agent generally has a deep color such as Silk 1 or purple, and can be used for black toner, but when used for color toner, the color becomes too muddy and cannot be used. Therefore, color toners require a colorless charge control agent.
負の電荷を付与する負帯電制御剤には無色、白色または
薄い黄色のものが市販され、効果も高い。Negative charge control agents that impart a negative charge are commercially available in colorless, white, or pale yellow colors, and are highly effective.
実用上これらの帯電制御剤を用いることに特に制限はな
い。ところが、正帯電用のカラートナー用には今のとこ
ろ有効な帯電制御剤が無く、顔料の帯電性を利用したり
、或いは用いる樹脂の帯電性をできるだけ正帯電性のも
のを使用したりすることにより製造されている。There are no particular restrictions on the use of these charge control agents in practice. However, there is currently no effective charge control agent for positively charged color toners, and it is necessary to utilize the chargeability of pigments or to use a resin that is as positively chargeable as possible. Manufactured by.
例えば、特開昭59−195662号公報、特開昭61
−172155号公報等に記載されるようにアミン含有
のポリマーを添加したり、第四級アンモニウム塩等を単
独又は併用で含有させることが知られているが、ポリエ
ステル樹脂等を用いた1〜ナーでは、その負帯電性の為
に容易に正帯電性を与えることができないばかりか、ア
ミン含有ポリマーの量を多くして正帯電性を与えても帯
電量分布が広くなる為に、トナーの飛散が大きくなり、
使用に耐えない。このように、負帯電性のカラートナー
に比べると帯電の安定性に乏しく、比較的経時変化の大
きいトナーしか得られなかった。また、極性の大きい樹
脂を用いるために、トナーの吸湿性が高く、流動性が悪
くなったり、帯電量の減衰が大きく、トナーの飛散が生
じたりする等の問題点が種々あった。For example, JP-A-59-195662, JP-A-61
It is known to add an amine-containing polymer or to contain a quaternary ammonium salt, etc. alone or in combination, as described in Japanese Patent No. 172155, etc.; Because of its negative chargeability, it is not easy to impart positive chargeability, and even if positive chargeability is imparted by increasing the amount of amine-containing polymer, the charge amount distribution becomes wide, resulting in toner scattering. becomes larger,
It cannot withstand use. As described above, compared to negatively chargeable color toners, only toners with poor charging stability and relatively large changes over time could be obtained. Furthermore, since a highly polar resin is used, there are various problems such as high hygroscopicity of the toner, poor fluidity, large attenuation of charge amount, and scattering of the toner.
そこで、メイン樹脂として、スチレン系、スチレン、ア
クリル系等のビニル系共重合体が多用されており、この
ビニル系共重合体の製造方法として、塊状重合、溶液重
合、S濁重合、乳化重合等の方法があるが、本発明者ら
は、この中でも懸濁重合により製造したビニル系共重合
体が正帯電性カラートナーに最適であることを見出した
。Therefore, vinyl copolymers such as styrene, styrene, and acrylic are often used as the main resin, and methods for producing these vinyl copolymers include bulk polymerization, solution polymerization, S-turbid polymerization, and emulsion polymerization. Among these methods, the present inventors have found that vinyl copolymers produced by suspension polymerization are most suitable for positively chargeable color toners.
懸濁重合により得られるビニル系共重合体が何故、正帯
電性トナーに適しているのかについては充分解明されて
はいないが、低分子量ビニル系重合体の製造に用いたジ
アシルパーオキサイド系の重合開始剤の分解残渣である
カルボン酸類、高分子量ビニル系重合体の製造に用いた
パーオキシケタール系の重合開始剤の分解残渣であるケ
トン類などがトナー中に僅かに残存し、これが正帯電性
を安定化させていることによるものと考えられる。Although it is not fully understood why vinyl copolymers obtained by suspension polymerization are suitable for positively chargeable toners, the polymerization of diacyl peroxide used to produce low molecular weight vinyl polymers is not fully understood. A small amount of carboxylic acids, which are the decomposition residues of the initiator, and ketones, which are the decomposition residues of the peroxyketal polymerization initiator used in the production of high molecular weight vinyl polymers, remain in the toner, and these are responsible for positively charging. This is thought to be due to the stabilization of the
すなわち、本発明は、
(A) ジアシルパーオキサイド系の重合開始剤を用
いて懸濁重合で得られた低分子量ビニル系重合体及びパ
ーオキシケタール系の重合開始剤を用いて懸濁重合で得
られた高分子量ビニル系重合体を含むビニル系重合体混
合物、
(B) スチレン−アミノ(メタ)アクリル系共重合
体及び/又はアミノ(メタ)アクリル系重合体、
(C) 第四級アンモニウム塩
並びに
(D) 着色剤
を含有し、かつ、重合開始剤の分解残渣であるカルボン
酸類及びケトン類を夫々0.1〜1 重量%含有してな
る正帯電性カラートナーに関する。That is, the present invention provides (A) a low molecular weight vinyl polymer obtained by suspension polymerization using a diacyl peroxide polymerization initiator and a low molecular weight vinyl polymer obtained by suspension polymerization using a peroxyketal polymerization initiator. (B) a styrene-amino(meth)acrylic copolymer and/or an amino(meth)acrylic polymer; (C) a quaternary ammonium salt; and (D) a positively chargeable color toner containing a colorant and 0.1 to 1% by weight of each of carboxylic acids and ketones, which are decomposition residues of a polymerization initiator.
(A)成分のビニル系重合体混合物の各々の重合体の原
料となるビニル系単量体としては、スチレン、α−メチ
ルスチレン、P−メチルスチレン(ビニルトルエン)、
p−t−ブチルスチレン、ρ−タロルスチレン等のスチ
レン系単量体、(メタ)アクリル酸(アクリル酸又はメ
タアクリル酸を意味する。以下、全て同様である。)、
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル
、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブ
チル、(メタ)アクリル酸ペンチル、(メタ)アクリル
酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)ア
クリル酸オクチル、(メタ)アクリル酸ノニル、(メタ
)アクリル酸デシル、(メタ)アクリル酸ウンデシル、
(メタ)アクリル酸ドデシル、(メタ)アクリル酸グリ
シジル、(メタ)アクリル酸メトキシエチル、(メタ)
アクリル酸プロポキシエチル、(メタ)アクリル酸ブト
キシエチル、(メタ)アクリル酸メトキシジエチレング
リコール、(メタ)アクリル酸メトキシエチレングリコ
ール、(メタ)アクリル酸ブトキシトリエチレングリコ
ール、(メタ)アクリル酸メトキシジプロピレングリコ
ール、(メタ)アクリル酸フェノキシエチル、(メタ)
アクリル酸フェノキシジエチレングリコール、(メタ)
アクリル酸フェノキシテトラエチレングリコール、(メ
タ)アクリル酸ベンジル、(メタ)アクリル酸シクロヘ
キシル、(メタ)アクリル酸テトラヒドロフルフリル、
(メタ)アクリル酸ジシクロペンテニル、(メタ)アク
リル酸ジシクロペンテニルオキシエチル、(メタ)アク
リル酸N−ビニル−2−ピロリドン、(メタ)アクリロ
ニトリル、(メタ)アクリルアミド、N−メチロール(
メタ)アクリルアミド、(メタ)アクリル酸2−ヒドロ
キシエチル、(メタ)アクリル酸ヒドロキシプロピル。The vinyl monomers used as raw materials for each polymer in the vinyl polymer mixture of component (A) include styrene, α-methylstyrene, P-methylstyrene (vinyltoluene),
Styrenic monomers such as pt-butylstyrene and ρ-thalolstyrene, (meth)acrylic acid (means acrylic acid or methacrylic acid. The same applies hereinafter),
Methyl (meth)acrylate, Ethyl (meth)acrylate, Propyl (meth)acrylate, Butyl (meth)acrylate, Pentyl (meth)acrylate, Hexyl (meth)acrylate, Heptyl (meth)acrylate, ( Octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate,
(meth)dodecyl acrylate, (meth)glycidyl acrylate, (meth)methoxyethyl acrylate, (meth)acrylate
Propoxyethyl acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, butoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, (meth)phenoxyethyl acrylate, (meth)
Phenoxydiethylene glycol acrylate, (meth)
Phenoxytetraethylene glycol acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,
Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, N-vinyl-2-pyrrolidone (meth)acrylate, (meth)acrylonitrile, (meth)acrylamide, N-methylol (
meth)acrylamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate.
(メタ)アクリル酸ヒドロキシブチル、 (メタ)アク
リル酸2−ヒドロキシ−3−フェニルオキシプロピル、
ジアセトン(メタ)アクリルアミド等の(メタ)アクリ
ル系単量体、ビニルピリジン等の単官能性ビニル系単量
体の1種又は2種以上が挙げられる。その他、ジビニル
ベンゼン、グリコールとメタクリル酸或いはアクリル酸
との反応生成物、例えば、エチレングリコールジ(メタ
)アクリレート、1,3−プチレンゲリコールジ(メタ
)アクリレート、1,4−ブタンジオールジ(メタ)ア
クリレート、1,5−ペンタンジオールジ(メタ)アク
リレート、1,6−ヘキサンシオールジ(メタ)アクリ
レート、ネオペンチルグリコールジ(メタ)アクリレー
ト、ジエチレングリコールジ(メタ)アクリレート、ト
リエチレングリコールジ(メタ)アクリレート、ポリエ
チレングリコールジ(メタ)アクリレート、トリプロピ
レングリコールジ(メタ)アクリレート、ヒドロキシビ
バリ酸ネオペンチルグリコールエステルジ(メタ)アク
リレート、トリメチロールエタントリ(メタ)アクリレ
ート、トリメチルロールプロパントリ(メタ)アクリレ
ート、ペンタエリトリットトリ(メタ)アクリレート、
ペンタエリトリットテトラ(メタ)アクリレート、トリ
ス(メタ)アクリロキシエチルホスフェート、゛ビス(
(メタ)アクリロイルオキシエチル)ヒドロキシエチル
イソシアヌレート、トリス((メタ)アクリロイルオキ
シエチル)イソシアヌレート)、メタアクリル酸グリシ
ジルとメタアクリル酸或いはアクリル酸のハーフエステ
ル化物、アクリル酸グリシジルとメタアクリル酸或いは
アクリル酸のハーフエステル化物等の1分子中に2個以
上のビニル基を有する多官能性ビニル系単量体を共重量
成分として単量体総量中好ましくは0〜2重量%の範囲
で併用することもできる。Hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate,
Examples include one or more of (meth)acrylic monomers such as diacetone (meth)acrylamide and monofunctional vinyl monomers such as vinylpyridine. In addition, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid, such as ethylene glycol di(meth)acrylate, 1,3-butylene gelicoldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, etc. ) acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate Acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxybivalic acid neopentyl glycol ester di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,
Pentaerythritol tetra(meth)acrylate, tris(meth)acryloxyethyl phosphate, bis(
(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, tris((meth)acryloyloxyethyl)isocyanurate), half ester of glycidyl methacrylate and methacrylic acid or acrylic acid, glycidyl acrylate and methacrylic acid or acrylic acid A polyfunctional vinyl monomer having two or more vinyl groups in one molecule, such as a half-esterified acid, is used as a co-weight component, preferably in the range of 0 to 2% by weight based on the total amount of monomers. You can also do it.
(A)成分において、低分子量ビニル系重合体の製造に
使用する重合開始剤は、ジアシルパーオキサイド系であ
る。ジアシルパーオキサイド系の重合開始剤としては、
ペンゾイルパーオ、キサイド、ラウロイルパーオキサイ
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、2,4−ジクロロベンゾイルパーオキサイド、
イソブチルパーオキサイド、3,3.5−トリメチルヘ
キサノイルパーオキサイド、アセチルパーオキサイド、
コハク酸パーオキサイド等が挙げられる。これらの重合
開始剤はビニル系単量体の総量に対し、0.5〜10重
量%用いるのが好ましい。In component (A), the polymerization initiator used for producing the low molecular weight vinyl polymer is a diacyl peroxide type. As a diacyl peroxide polymerization initiator,
Pennzoyl peroxide, oxide, lauroyl peroxide, octanoyl peroxide, decanoyl peroxide, 2,4-dichlorobenzoyl peroxide,
Isobutyl peroxide, 3,3.5-trimethylhexanoyl peroxide, acetyl peroxide,
Examples include succinic acid peroxide. These polymerization initiators are preferably used in an amount of 0.5 to 10% by weight based on the total amount of vinyl monomers.
また、高分子量ビニル系重合体の製造に使用する重合開
始剤は、パーオキシケタール系である。Further, the polymerization initiator used for producing the high molecular weight vinyl polymer is a peroxyketal type.
パーオキシケタール系の重合開始剤としては、3゜3.
5−トリメチルシクロへキサノンジターシャリブチルパ
ーオキシケタール、シクロへキサノンジターシャリブチ
ルパーオキシケタール、メチルエチルケトンジターシャ
リブチルパーオキシケタール、メチルへキシルケトンジ
ターシャリブチルパーオキシケタール等が挙げられる。As a peroxyketal polymerization initiator, 3°3.
Examples include 5-trimethylcyclohexanone ditertiary butyl peroxyketal, cyclohexanone ditertiary butyl peroxyketal, methyl ethyl ketone ditertiary butyl peroxyketal, methylhexyl ketone ditertiary butyl peroxyketal, and the like.
これらの重合開始剤は、ビニル系単量体の総量に対し、
0.1〜5重量%用いるのが好ましい。These polymerization initiators, based on the total amount of vinyl monomers,
It is preferable to use 0.1 to 5% by weight.
さらに、各ビニル系重合体の製造時に、ブチルメルカプ
タン、オクチルメルカプタン、ドデシルメルカプタン、
メチル2−メルカプトプロピオネート、エチル2−メル
カプトプロピオネート、ブチル2−メチルカプトプロピ
オネート、オクチル2−メルカプトプロピオネートペン
タエリトリットテトラ(2−メルカプトプロピオネート
)。Furthermore, during the production of each vinyl polymer, butyl mercaptan, octyl mercaptan, dodecyl mercaptan,
Methyl 2-mercaptopropionate, ethyl 2-mercaptopropionate, butyl 2-methylcaptopropionate, octyl 2-mercaptopropionate pentaerythritol tetra(2-mercaptopropionate).
エチレングリコールジ(2−メチルカプトプロピオネー
ト)、グリセリントリ(2−メルカプトプロピオネート
)等のメルカプタン類、クロロホルム、ブロモホルム、
四臭化炭素等のハロゲン化炭化水素などのラジカル重合
分子量3A整剤を使用することもできる。これらの分子
量調整剤は、ビニル系単量体の総量に対して0〜3重合
%使用されるのが好ましい。Mercaptans such as ethylene glycol di(2-methylcaptopropionate) and glycerin tri(2-mercaptopropionate), chloroform, bromoform,
Radical polymerization molecular weight 3A modifiers such as halogenated hydrocarbons such as carbon tetrabromide can also be used. These molecular weight regulators are preferably used in an amount of 0 to 3% by polymerization based on the total amount of vinyl monomers.
(A)成分の各ビニル系重合体は、以下に説明するよう
な懸濁重合によって得られる。Each vinyl polymer of component (A) is obtained by suspension polymerization as described below.
+i!lim重合を行う際には、部分ケン化ポリビニル
アルコール、アルキルセルロース、ヒドロキシアルキル
セルロース、カルボキシアルキルセルロース、ポリアク
リルアミド、ポリビニルピロリドン。+i! When performing lim polymerization, partially saponified polyvinyl alcohol, alkylcellulose, hydroxyalkylcellulose, carboxyalkylcellulose, polyacrylamide, polyvinylpyrrolidone.
ポリアクリル酸及びそのアルカリ金属塩、ポリメタクリ
ル酸及びそのアルカリ金属塩等の水溶性高分子分散剤、
リン酸カルシウム、ヒドロキシアパタイト、リン酸マグ
ネシウム、ピロリン酸マグネシウム、炭酸カルシウム、
硫酸バリウム、疎水性シリカ等の離溶性無機分散剤等の
分散剤が重合系に存在させられる。分散剤は、水溶性高
分子分散剤の場合は水性媒体に対して0.0001〜5
重量%使用されるのが好ましく、離溶性無機分散剤の場
合は水性媒体に対して0.01〜15重量%使用される
のが好ましい。分散剤が少なすぎると分散安定しにくく
なり、多すぎると分散効果が大きくなりすぎる。Water-soluble polymer dispersants such as polyacrylic acid and its alkali metal salts, polymethacrylic acid and its alkali metal salts,
Calcium phosphate, hydroxyapatite, magnesium phosphate, magnesium pyrophosphate, calcium carbonate,
A dispersant such as a dissolvable inorganic dispersant such as barium sulfate or hydrophobic silica is present in the polymerization system. In the case of a water-soluble polymer dispersant, the dispersant is 0.0001 to 5% relative to the aqueous medium.
It is preferably used in an amount of 0.01 to 15% by weight based on the aqueous medium in the case of a releasable inorganic dispersant. If the amount of dispersant is too small, it will be difficult to stabilize the dispersion, and if it is too large, the dispersion effect will be too large.
前記ビニル系単量体及び重合開始剤の混合物は、分散剤
の存在する水中に加え、撹拌して分散状態とし、昇温し
で重合反応させる。反応温度は、重合開始剤の10時時
間域温度より10〜20″C高い温度が最適である。な
お、重合開始剤は、重合反応の途中にその一部を加えて
もよい。反応終了後1通常の方法で、脱水、乾燥し、ビ
ニル系重合体を得ることができる。The mixture of the vinyl monomer and polymerization initiator is added to water containing a dispersant, stirred to form a dispersed state, and heated to cause a polymerization reaction. The optimum reaction temperature is 10 to 20"C higher than the 10 o'clock time range temperature of the polymerization initiator. A portion of the polymerization initiator may be added during the polymerization reaction. After the reaction is completed. 1. A vinyl polymer can be obtained by dehydration and drying using a conventional method.
(A)成分は、低分子量ビニル系重合体と、高分子量ビ
ニル系重合体を別々に製造し、予め又はトナー製造時に
混合する方法、一方のビニル系重合体を先に製造し、そ
の存在下でもう一方のビニル系重合体を製造する方法等
によって混合される。Component (A) can be produced by separately producing a low molecular weight vinyl polymer and a high molecular weight vinyl polymer and mixing them in advance or during toner production, or by producing one of the vinyl polymers first and placing them in the presence of the vinyl polymer. The other vinyl polymer is mixed using the same method as the other vinyl polymer.
これらの中で、先に低分子量ビニル系重合体を懸濁重合
によって得、その存在下に高分子量ビニル系重合体を懸
濁重合する方法は、両ビニル系重合体がより均一に混合
分散していると考えられ、トナーの画像特性がより優れ
るとともに製造工程が簡略化され、製造コスト面でも優
れるので好ましい。Among these methods, a method in which a low molecular weight vinyl polymer is first obtained by suspension polymerization and then a high molecular weight vinyl polymer is suspension polymerized in the presence of the polymer allows both vinyl polymers to be mixed and dispersed more uniformly. This is preferable because the image characteristics of the toner are better, the manufacturing process is simplified, and the manufacturing cost is also excellent.
(A)成分において、低分子量ビニル系重合体と、高分
子量ビニル系重合体は、前者/後者の重量比で5/95
〜9515の割合で混合されるのが好ましい。この重量
比が小さすぎると、トナーの定着性に劣る傾向にあり、
大きすぎると、トナーの耐オフセット性に劣る傾向にあ
る。In component (A), the low molecular weight vinyl polymer and the high molecular weight vinyl polymer have a weight ratio of 5/95 of the former/latter.
It is preferable to mix at a ratio of 9,515 to 9,515. If this weight ratio is too small, toner fixability tends to be poor.
If it is too large, the offset resistance of the toner tends to be poor.
(A)成分において、低分子量ビニル系重合体の重量平
均分子量(MW)は、 1,500〜100,000、
数平均分子量(Mn)は1 、 OOO〜20,000
ガラス転移点(T8)は55〜80℃に調整されるのが
好ましい。低分子量ビニル系重合体の重量平均分子量又
は数平均分子量が大きすぎると、定着性が低下しやすく
、小さすぎると、トナーカブリ等の現像をひき起こしや
すくなる。また、低分子量ビニル系本合体のガラス転移
点が、低すぎると耐ブロックキング性が低下しやすく、
高すぎると定着性が低下しやすい傾向にある。なお、本
発明において、重量平均分子量及び数平均分子量は、ゲ
ル・パーミェーション・クロマトグラフィー(GPC)
により、標準ポリスチレンの検量線を利用して求めたも
のを示し、ガラス転移点は、示差走査熱量計(DSC)
で測定した吸発熱挙動で、゛ガラス転移に伴なう吸熱が
最大になる温度を示す。In component (A), the weight average molecular weight (MW) of the low molecular weight vinyl polymer is 1,500 to 100,000,
Number average molecular weight (Mn) is 1, OOO~20,000
The glass transition point (T8) is preferably adjusted to 55 to 80°C. If the weight average molecular weight or number average molecular weight of the low molecular weight vinyl polymer is too large, fixing properties tend to deteriorate, and if it is too small, development such as toner fog is likely to occur. In addition, if the glass transition point of the low molecular weight vinyl-based polymer is too low, blocking resistance tends to decrease.
If it is too high, fixing properties tend to deteriorate. In the present invention, the weight average molecular weight and number average molecular weight are determined by gel permeation chromatography (GPC).
The glass transition point is determined using a standard polystyrene calibration curve.
The heat absorption and heat absorption behavior measured in ゛ indicates the temperature at which the heat absorption associated with the glass transition reaches its maximum.
また、低分子量ビニル系重合体及び高分子量ビニル系重
合体を含む(A)成分のビニル系重合体混合物は、トナ
ーの画像特性のバランスの面から。The vinyl polymer mixture of component (A) containing a low molecular weight vinyl polymer and a high molecular weight vinyl polymer is selected from the viewpoint of the balance of image characteristics of the toner.
重量平均分子量が、100,000〜500,000、
ガラス転移点が50〜75℃にfA整されるのが好まし
い。Weight average molecular weight is 100,000 to 500,000,
It is preferable that the glass transition point fA is adjusted to 50 to 75°C.
本発明の(B)成分としては、アミノ(メタ)アクリル
系モノマーの単独重合物またはスチレンとの共重合物が
挙げられる。アミノ(メタ)アクリル系モノマーは通常
以下の一般式(■):薯
CH2= CR2
1/
C0X−Q−N (I)\
〔式中、R□は水素またはメチル基、R2およびR1は
水素または炭素数1〜20のアルキル基、Xは酸素原子
または窒素原子、Qはアルキレン基またはアリーレン基
を示す。〕
で表わされる。アミノ(メタ)アクリル系モノマーの代
表例としてはN、N−ジメチルアミノメチル(メタ)ア
クリレート、N、N−ジエチルアミノメチル(メタ)ア
クリレート、N、N−ジメチルアミノエチル(メタ)ア
クリレート、N、N−ジエチルアミノエチル(メタ)ア
クリレート、N。Component (B) of the present invention includes a homopolymer of an amino(meth)acrylic monomer or a copolymer with styrene. Amino(meth)acrylic monomers usually have the following general formula (■): CH2=CR2 1/C0X-Q-N (I)\ [wherein, R□ is hydrogen or a methyl group, R2 and R1 are hydrogen or An alkyl group having 1 to 20 carbon atoms, X represents an oxygen atom or a nitrogen atom, and Q represents an alkylene group or an arylene group. ] It is expressed as . Representative examples of amino(meth)acrylic monomers include N,N-dimethylaminomethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N -diethylaminoethyl (meth)acrylate, N.
N−ジメチルアミノプロピル(メタ)アクリレート、N
、N−ジメチルアミノブチル(メタ)アクリレート、ρ
−N、N−ジメチルアミノフェニル(メタ)アクリレー
ト、P NUN−ジエチルアミノフェニル(メタ)ア
クリレート、p−N、 N−ジエチルアミノフェニル(
メタ)アクリレート、p−N、N−ジプロピルアミノフ
ェニル(メタ)アクリレート、p−N、N−ジブチルア
ミノフェニル(メタ)アクリレート、p−N−ラウリル
アミノフェニル(メタ)アクリレート、p−N−ステア
リルアミノフェニル(メタ)アクリレート、p−N、N
−ジメチルアミノベンジル(メタ)アクリレート、p
NUN−ジエチルアミノベンジル(メタ)アクリレート
、p−N、N−ジプロピルアミノベンジル(メタ)アク
リレート、p−N。N-dimethylaminopropyl (meth)acrylate, N
, N-dimethylaminobutyl (meth)acrylate, ρ
-N, N-dimethylaminophenyl (meth)acrylate, P NUN-diethylaminophenyl (meth)acrylate, p-N, N-diethylaminophenyl (
meth)acrylate, p-N,N-dipropylaminophenyl (meth)acrylate, p-N,N-dibutylaminophenyl (meth)acrylate, p-N-laurylaminophenyl (meth)acrylate, p-N-stearyl Aminophenyl (meth)acrylate, p-N, N
-dimethylaminobenzyl (meth)acrylate, p
NUN-diethylaminobenzyl (meth)acrylate, p-N, N-dipropylaminobenzyl (meth)acrylate, p-N.
N−ジブチルアミノベンジル(メタ)アクリレート、P
−N−ラウリルアミノベンジル(メタ)アクリレート、
rl−N−ステアリルアミノベンジル(メタ)アクリレ
ート等が例示される。さらに、N、N−ジメチルアミノ
エチル(メタ)アクリルアミド、N、N−ジエチルアミ
ノエチル(メタ)アクリルアミド、N、N−ジメチルア
ミノプロピル(メタ)アクリルアミド、N、N−ジエチ
ルアミノプロピル(メタ)アクリルアミド、P NT
N−ジメチルアミノフェニル(メタ)アクリルアミド、
p−N、N−ジエチルアミノフェニル(メタ)アクリル
アミド、p−N、N−ジプロピルアミノフェニル(メタ
)アクリルアミド、P NTN−ジブチルアミノフェ
ニル(メタ)アクリルアミド、p−N−ラウリルアミノ
フェニル(メタ)アクリルアミド、p−N−ステアリル
アミノフェニル(メタ)アクリルアミド、p−N、N−
ジメチルアミノベンジル(メタ)アクリルアミド、p−
N、N−ジエチルアミノベンジル(メタ)アクリルアミ
ド、p−N、N−ジプロピルアミノベンジル(メタ)ア
クリルアミド、p−N、N−ジブチルアミノベンジル(
メタ)アクリルアミド、p−N−ラウリルアミノベンジ
ル(メタ)アクリルアミド、p−N−ステアリルアミノ
ベンジル(メタ)アクリルアミド等が例示される。N-dibutylaminobenzyl (meth)acrylate, P
-N-Laurylaminobenzyl (meth)acrylate,
Examples include rl-N-stearylaminobenzyl (meth)acrylate. Furthermore, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, P NT
N-dimethylaminophenyl (meth)acrylamide,
p-N, N-diethylaminophenyl (meth)acrylamide, p-N, N-dipropylaminophenyl (meth)acrylamide, P NTN-dibutylaminophenyl (meth)acrylamide, p-N-laurylaminophenyl (meth)acrylamide , p-N-stearylaminophenyl (meth)acrylamide, p-N, N-
Dimethylaminobenzyl (meth)acrylamide, p-
N,N-diethylaminobenzyl (meth)acrylamide, p-N,N-dipropylaminobenzyl (meth)acrylamide, p-N,N-dibutylaminobenzyl (
Examples include meth)acrylamide, p-N-laurylaminobenzyl(meth)acrylamide, p-N-stearylaminobenzyl(meth)acrylamide, and the like.
正帯電制御剤として使用できる前記共重合体に関しては
、アミノ(メタ)アクリル系モノマーとスチレンとの共
重合割合はとくに制限されるものではない。トナーに所
望の正帯電特性を付与するにはアミノ(メタ)アクリル
系モノマーの共重合割合が大きい程、正15電制御剤の
使用量を減少しうるが、前記(A)成分と粉砕混合する
に当たっては、粉砕時の作業性、得られるトナーの耐熱
性などを考慮し、ある程度のガラス転移点(通常50℃
以上)を有することが望ましく、スチレン含有量の異な
る重合体(B)の選択、及びその使用量によりこれを調
節できる。いずれにしても重合体(B)の組成は、該制
御剤の使用量および粉砕作業性などを考慮して適宜決定
すればよく、重合体(B)は前記−飲代(I)のモノマ
ーとスチレンとの重合割合が100:O〜1:99(モ
ル比)、より好ましくは70 : 30〜5:90(モ
ル比)とするのがよい。Regarding the copolymer that can be used as a positive charge control agent, the copolymerization ratio of the amino(meth)acrylic monomer and styrene is not particularly limited. In order to impart the desired positive charging characteristics to the toner, the larger the copolymerization ratio of the amino(meth)acrylic monomer, the smaller the amount of the positive charge control agent used. In this process, we consider workability during crushing, heat resistance of the resulting toner, etc., and set the glass transition temperature to a certain level (usually 50°C
It is desirable to have the above), and this can be adjusted by selecting polymers (B) having different styrene contents and the amount used thereof. In any case, the composition of the polymer (B) may be appropriately determined by taking into account the amount of the control agent used and the pulverization workability, etc. The polymerization ratio with styrene is preferably 100:0 to 1:99 (molar ratio), more preferably 70:30 to 5:90 (molar ratio).
前記重合体(B)の製造については、特に制限されるこ
となく、従来公知の溶液重合法、塊状重合法などをその
まま採用することができるが1重合時の発熱を容易に制
御しつる点で溶液重合法を採用するのがよい。この際、
用い得る溶剤としては、使用する各種モノマーに対し不
活性であれば特に制限はなく、例えばベンゼン、トルエ
ン、キシレンなどを例示できる。Regarding the production of the polymer (B), there are no particular restrictions, and conventionally known solution polymerization methods, bulk polymerization methods, etc. can be used as they are, but it is possible to easily control the heat generation during one polymerization. It is preferable to employ a solution polymerization method. On this occasion,
The solvent that can be used is not particularly limited as long as it is inert to the various monomers used, and examples include benzene, toluene, and xylene.
本発明に用いる第4級アンモニウム塩(C)は−飲代(
■):
〔但し1式中R1,R2,R3およびR4は同一または
異なるアルキル基、アリール基、またはいずれかの2個
が合してトy素環基を構成する基、Xはハロゲン、スル
ホン酸基、スルホン酸エステル基、硫酸エステル基また
はアルキル硫酸エステル基を示す〕で示される化合物で
あって、特に白色または無色のものである。The quaternary ammonium salt (C) used in the present invention is -drinking cost (
(2): [However, in formula 1, R1, R2, R3, and R4 are the same or different alkyl groups, aryl groups, or a group in which any two of them combine to form a toy ring group, and X is a halogen or sulfone. An acid group, a sulfonic acid ester group, a sulfuric ester group, or an alkyl sulfate group], and is particularly white or colorless.
上記第4級アンモニウム塩(C)は潮解性を持たず、か
つ水に対する溶解性や吸湿度の低いものから選定すれば
よく、融点(m、p)100℃以上で分解点が200
’C以上であるのが好ましい。The above-mentioned quaternary ammonium salt (C) may be selected from those that do not have deliquescent properties and have low water solubility and moisture absorption, and have a melting point (m, p) of 100°C or higher and a decomposition point of 200°C.
'C or higher is preferable.
第4級アンモニウム塩の配合量はその分子量にもよるが
、分散性及び環境安定性の点から通常、トナー全量の0
.1〜10重量%、より好ましくは0.5〜5重量%で
ある。The amount of quaternary ammonium salt blended depends on its molecular weight, but from the viewpoint of dispersibility and environmental stability, it is usually 0% of the total amount of toner.
.. It is 1 to 10% by weight, more preferably 0.5 to 5% by weight.
本発明に使用しうる着色剤(D)としては、具体的には
、黒色顔料では、
カーボンブラック、アセチレンブラック、ランプブラッ
ク、アニリンブラック等:
黄色顔料では、
黄鉛、亜鉛黄、カドミウム二ロー、黄色酸化鉄。Specifically, the colorant (D) that can be used in the present invention includes, for black pigments, carbon black, acetylene black, lamp black, aniline black, etc.; for yellow pigments, yellow lead, zinc yellow, cadmium diro, Yellow iron oxide.
ミネラルファストイエロー、ニッケルチタン二ロー、ネ
ーブルスエロー、ナフトールエローS。Mineral Fast Yellow, Nickel Titanium Niro, Navel Yellow, Naphthol Yellow S.
ハンザ−イエローG、ハンサーイエロー10G。Hansa Yellow G, Hansa Yellow 10G.
ベンジジンエローG、ベンジジンエロー〇R。Benzidine Yellow G, Benzidine Yellow R.
キノリンエローレーキ、パーマネント二ロー。Quinoline Yellow Rake, Permanent Niro.
NCG、タートラジンレーキ等がある。There are NCG, tartrazine lake, etc.
橙色顔料では、
赤口黄鉛、モリブデンオレンジ、パーマネントオレンジ
GTR,ピラゾロンオレンジ、パルカンオレンジ、イン
ダスレンブリリアントオレンジRK、ベンジジンオレン
ジG、インダンスレンブリリアントオレンジGK等:
赤色顔料では、
ベンガラ、カドミウムレッド、鉛丹、硫化水銀カドミウ
ム、パーマネントレッド4R,リソールレッド、ピラゾ
ロンレッド、ウオッチングレッド、カルシューム塩、レ
ーキレッドD、ブリリアントカーミン6B、エオシンレ
ーキ、ローダミンレーキB、アリザリンレーキ、ブリリ
アントカーミノ3B等:
紫色顔料では、
マンガン紫、ファストバイオレットB、メチルバイオレ
ットレーキ等:
青色顔料では、
紺青、コバルトブルー、アルカリブルーレーキ、ビクト
リアブル−レーキ、フタロシアニンブルー、無金属フタ
シアニンブルー、フタロシアニンブル一部分塩素化物、
フォーストスカイブルー、インダスレンブルーBC等が
ある。Orange pigments include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, palkan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK, etc.; red pigments include red iron, cadmium red, and lead. Red, mercury cadmium sulfide, Permanent Red 4R, Lysol Red, Pyrazolone Red, Watching Red, Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmino 3B, etc.: Purple pigments , Manganese Purple, Fast Violet B, Methyl Violet Lake, etc.: Blue pigments include navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue,
There are Forst Sky Blue, Indus Thread Blue BC, etc.
緑色顔料では、
クロムグリーン、酸化クロム、ピグメントグリーンB、
マラカイトグリーンレーキ、ファナルイエローグリーン
G等:
白色顔料では、
亜鉛華、酸化チタン、アンチモン白、硫化亜鉛がある。Green pigments include chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.: White pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
体質顔料では、 パライト粉、炭酸バリウム、クレー、シリカ。In extender pigments, Palite powder, barium carbonate, clay, silica.
ホワイトカーボン、タルク、アルミナホワイト等を挙げ
ることができ、1種または2種以上混合して使用しても
よく、いずれも無公害で高い着色力があれば有機、無機
を問わず、これらに限定されるものではない。Examples include white carbon, talc, alumina white, etc., and they may be used alone or in combination of two or more, regardless of whether they are organic or inorganic, as long as they are non-polluting and have high coloring power. It is not something that will be done.
黄色着色剤として、ベンチジンイエロー、ハンザイエロ
ー、クロモフタールイエロー等が挙げられる。Examples of the yellow colorant include benzidine yellow, Hansa yellow, cromophthal yellow, and the like.
なお、無機の顔料としては、白色ではチタンホワイトや
亜鉛華があるが、無公害で高い着色力があれば有機無機
を問わず、これらに限定されるものではない。また、本
発明のトナーを黒トナーとして使用する場合、前記顔料
としてチャンネルブラック、ファーネスブラック等のカ
ーボンブラックを使用してもよい。着色剤は、全トナー
成分中に2〜20重量%含まれるのが好ましい。Inorganic pigments include titanium white and zinc white for white, but are not limited to these, and may be organic or inorganic as long as they are non-polluting and have high coloring power. Further, when the toner of the present invention is used as a black toner, carbon black such as channel black and furnace black may be used as the pigment. Preferably, the colorant is contained in an amount of 2 to 20% by weight in the total toner components.
本発明のトナーには更に必要に応じて他の添加剤、例え
ばシリカ粉末、疎水性シリカ粉末、ポリオレフィン、脂
肪酸エステル、部分けん化脂肪酸エステル、脂肪酸金属
器ワックス類等を好ましくはトナー中に0〜10重量%
添加してもよいし、また、定着性の改善の為に、各種の
熱可塑性樹脂を本発明の効果を減少しない範囲内で用い
てもよい。The toner of the present invention may further contain other additives, such as silica powder, hydrophobic silica powder, polyolefin, fatty acid ester, partially saponified fatty acid ester, fatty acid metallurgy wax, etc., as necessary. weight%
It may be added, or various thermoplastic resins may be used in order to improve fixing properties within a range that does not reduce the effects of the present invention.
前記の材料を、例えば次の方法で混合し、正帯電性カラ
ートナーを製造する。The above materials are mixed, for example, by the following method to produce a positively chargeable color toner.
秤量した材料を、Wコーン、■ブレンダー、ヘンシェル
ミキサー等で予備混合した後、加圧ニーダ−、バンバリ
ーミキサ−9熱ロール、エクストルーダー等を用いて樹
脂が溶融する温度下で混練する。冷却後、フェザ−ミル
、ピンミル、バルベライザー、ハンマーミル等で粗F9
砕する。次いでアキュカット、アルピネ分級機等で篩分
して、好ましくは5〜30μmの;泣径に調整する。The weighed materials are premixed using a W cone, (1) blender, Henschel mixer, etc., and then kneaded using a pressure kneader, Banbury mixer 9 hot roll, extruder, etc. at a temperature at which the resin melts. After cooling, use a feather mill, pin mill, valberizer, hammer mill, etc. to obtain a rough F9
crush. Next, it is sieved using an Accucut, Alpine classifier, etc., and adjusted to a diameter of preferably 5 to 30 μm.
さらに、金属酸化物の超微粉末でトナーの表面処理が施
されてもよい。Furthermore, the surface of the toner may be treated with ultrafine metal oxide powder.
得られる本発明のトナーには、この中に残る重合開始剤
の分解残渣であるカルボン酸類及びケトン類が、夫々0
.1〜1 重量%となるように調整される。The resulting toner of the present invention contains 0 carboxylic acids and ketones, which are decomposition residues of the polymerization initiator, each remaining in the toner.
.. The amount is adjusted to 1 to 1% by weight.
前記カルボン酸類は、主に、(A)成分の低分子量ビニ
ル系重合体の製造に用いたジアシルパーオキサイド系の
重合開始剤の分解残渣であり、前記ケトン類は、主に、
(A)成分の高分子量ビニル系重合体の製造に用いたパ
ーオキシケタール系の重合開始剤の分離残渣である。こ
れらの(A)成分の製造時に用いた重合開始剤の他の分
解残液(t−ブタノール等のアルコール成分等)は、懸
濁重合後の脱水乾燥工程、トナー製造工程等で除去され
やすく、トナー中にはあまり残存していない。The carboxylic acids are mainly decomposition residues of the diacyl peroxide polymerization initiator used in the production of the low molecular weight vinyl polymer of component (A), and the ketones are mainly the following:
This is the separation residue of the peroxyketal polymerization initiator used in the production of the high molecular weight vinyl polymer of component (A). Other decomposition residual liquids (alcohol components such as t-butanol, etc.) of the polymerization initiator used in the production of component (A) are easily removed during the dehydration and drying process after suspension polymerization, the toner production process, etc. Not much remains in the toner.
なお、上記の重合開始剤の分解残渣であるカルボン酸類
及びケトン類の量は、上記の(A)成分の製造時に用い
た重合開始剤に起因するもの以外の、トナーに含有され
る他の重合体成分の重合に用いられた重合開始剤の分解
残渣としてトナーに残存しているものがあれば、それら
を含むものである。Note that the amount of carboxylic acids and ketones that are decomposition residues of the polymerization initiator mentioned above is based on other polymers contained in the toner other than those caused by the polymerization initiator used during the production of component (A) above. The toner contains any residual decomposition residue of the polymerization initiator used in the polymerization of the combined components, if any.
重合開始剤の分解残渣であるカルボン酸類及びケトン類
は、トナー中に夫々0.1〜1重量%含まれる。この量
であることが、本発明のトナーの良好な帯電特性に必要
である。夫々の分解残渣が0.1重量%よりも少ないと
良好な正帯電性が得られず、1重量%を超えるとこれら
の分解残渣が可塑剤として働き、耐熱性、保存安定性が
悪くなる。トナーに残る重合開始剤の分解残液であるカ
ルボン酸類及びケトン類の量は、重合時の条件。Carboxylic acids and ketones, which are decomposition residues of the polymerization initiator, are each contained in the toner in an amount of 0.1 to 1% by weight. This amount is necessary for good charging properties of the toner of the present invention. If each decomposition residue is less than 0.1% by weight, good positive chargeability cannot be obtained, and if it exceeds 1% by weight, these decomposition residues act as a plasticizer, resulting in poor heat resistance and storage stability. The amount of carboxylic acids and ketones, which are the decomposition residual liquid of the polymerization initiator that remains in the toner, depends on the conditions at the time of polymerization.
重合開始剤の使用量2重合体の水洗の程度、トナーの溶
融混線時間等によって調整することができる。The amount of polymerization initiator used can be adjusted by adjusting the degree of water washing of the polymer, the melting and mixing time of the toner, etc.
なお、トナー中に残存する重合開始剤の分解残渣の定量
は、ガスクロマトグラフィー等を用いて行うことができ
る。Note that the decomposition residue of the polymerization initiator remaining in the toner can be quantified using gas chromatography or the like.
本発明のトナーは、例えば適当なキャリアと配合して2
成分系現像剤とされ得る。キャリアとしては、カスケー
ド現像方式を実施する場合、樹脂コートしたガラスピー
ズ、スチール環等が、磁気ブラシ現像方式を実施する場
合、フェライト、微粉鉱、あるいは、いわゆるバインダ
型キャリア等が用いられる。また、本発明のトナー自体
をtab性磁性トナーとして製造し、これを1成分系現
像剤として用いて磁気ブラシ現像方式を実施してもよい
。The toner of the present invention can be formulated with a suitable carrier, for example.
It can be used as a component developer. As the carrier, when implementing the cascade development method, resin-coated glass beads, steel rings, etc. are used, and when implementing the magnetic brush development method, ferrite, fine ore, or a so-called binder type carrier, etc. are used. Further, the toner of the present invention itself may be manufactured as a tab magnetic toner, and a magnetic brush development method may be implemented using this as a one-component developer.
さらに、インプレッション現像方式やタッチダウン現像
方式を実施する場合のトナーとして使用してもよい。Furthermore, it may be used as a toner when performing an impression development method or a touchdown development method.
本発明の詳細な説明する。 The present invention will be described in detail.
1、合成例1〜8(ビニル系重合体混合物(A)の製造
)
3Qの円筒形セパラブルフラスコに、撹拌機。1. Synthesis Examples 1 to 8 (Production of vinyl polymer mixture (A)) A stirrer was placed in a 3Q cylindrical separable flask.
冷却管、ガス導入管及び温度計を取り付け、ここへイオ
ン交換水1200g、スーパータイト10(商標2日本
化学工業(株)製のヒドロキシアパタイトの水分散剤、
固型分10%)60g及び塩化ナトリウム60gを入れ
た。表1の低分子量成分の配合の欄に示す単量体2重合
開始剤及び必要に応して分子量調整剤の混合物を上記セ
パラブルフラスコに加えた。次に窒素ガスを導入し、室
温で30分間撹拌し、分散を安定させた後、約1時間か
けて90℃迄昇温し、3時間撹拌した後、続いて95°
Cで2時間保温して反応を終了させた。Attach a cooling pipe, a gas introduction pipe, and a thermometer, and add 1200 g of ion-exchanged water, Supertite 10 (trademark 2), a hydroxyapatite water dispersant manufactured by Nihon Kagaku Kogyo Co., Ltd.
60 g (solid content: 10%) and 60 g of sodium chloride were added. A mixture of a monomer 2 polymerization initiator and, if necessary, a molecular weight regulator, shown in the column of low molecular weight component formulation in Table 1 was added to the separable flask. Next, nitrogen gas was introduced and stirred at room temperature for 30 minutes to stabilize the dispersion, then the temperature was raised to 90°C over about 1 hour, stirred for 3 hours, and then heated to 90°C.
The reaction was completed by incubating at C for 2 hours.
なお、得られた低分子量重合体の重量平均分子量、数平
均分子量及びガラス転移点を測定し、表1に示した。The weight average molecular weight, number average molecular weight, and glass transition point of the obtained low molecular weight polymer were measured and shown in Table 1.
次いで、上記フラスコ内を50℃迄冷却した後、表1の
高分子量成分の配合の欄に示す単量体及び重合開始剤の
混合物を添加し、50℃で2時間撹拌した。その後スー
パータイト10を60g及びイオン交換水30gを追加
し、50℃で1時間撹拌し−C分散を安定させてから、
約30分かけて85°C迄昇温し、そのまま3時間撹拌
した。さらに90℃で1時間、95℃で2時間保温した
後、40’C迄冷却して反応を終了させた。Next, after cooling the inside of the flask to 50°C, a mixture of monomers and polymerization initiators shown in the column of high molecular weight component formulation in Table 1 was added, and the mixture was stirred at 50°C for 2 hours. After that, 60g of Supertite 10 and 30g of ion-exchanged water were added and stirred at 50°C for 1 hour to stabilize the -C dispersion.
The temperature was raised to 85°C over about 30 minutes, and the mixture was stirred for 3 hours. After further heating at 90°C for 1 hour and at 95°C for 2 hours, the reaction was completed by cooling to 40'C.
この水性懸濁状態の位脂ビーズに、1塩酸30mΩを加
えて水相のpHを2以下にした後、減圧濾過し、500
mQのイオン交換水で3回洗浄し、50℃の乾燥機中で
12時間乾燥し、樹脂ビーズを得た。30 mΩ of 1-hydrochloric acid was added to the lipid beads in the aqueous suspension to bring the pH of the aqueous phase to 2 or less, and then filtered under reduced pressure.
The beads were washed three times with mQ ion-exchanged water and dried in a dryer at 50° C. for 12 hours to obtain resin beads.
得られた樹脂ビーズ(ビニル系重合体混合物(A))の
重量平均分子量、数平均分子量、ガラ2、スチレン・ア
ミノアクリル系共重合体〔重合体(B)〕の製造:
3aの4つロコルベンに、スチレン624g。Weight average molecular weight and number average molecular weight of the obtained resin beads (vinyl polymer mixture (A)), Gala 2, Production of styrene/aminoacrylic copolymer [polymer (B)]: 4 Locolbens of 3a and 624g of styrene.
ジメチルアミノエチルメタクリレート632g、トルエ
ン1200gおよびアゾビスイソブチロニトリル5.4
g加え、溶解した後、窒素気流下で80′Cで6時間反
応させ、重合を行った。次に、トルエンを留去した後1
80〜190°Cで40〜5Q jIwn Hgに減圧
し、揮発分を完全に除去した。得られた重合物は、無色
透明の固体で、ガラス転移点(T8)は56°C、アミ
ン価は174であった。632 g of dimethylaminoethyl methacrylate, 1200 g of toluene and 5.4 g of azobisisobutyronitrile
g was added and dissolved, the reaction was carried out at 80'C for 6 hours under a nitrogen stream to carry out polymerization. Next, after distilling off toluene, 1
The pressure was reduced to 40-5QjIwn Hg at 80-190°C to completely remove volatile components. The obtained polymer was a colorless and transparent solid with a glass transition point (T8) of 56°C and an amine value of 174.
3、実施例1〜5及び比較例1〜3(トナーの製造)
重量部
(A)表1に示す合成例1〜8のいず 100れかで
得たビニル系重合体混合物
(B)2で得たスチレン・アミノアク 2リル系
樹脂
(C)第4級アンモニウム塩(オリエ 2ント化
学工業(株)製P−51)
(D)銅フタロシアニン顔イ斗(犬日清 5化製
(株)製、#4920)
(E)低分子量ポリプロピレン(三洋 3化成工
業(株)製、ビスコール
550P)
以上をボールミルで充分混合した後、二軸の押出1幾で
混練し、予め略5rrfn角以下の大きさに粗粉砕した
後、ジェット粉砕機で微粉砕し、回転風力式の分級機で
粗粉、微粉を分級し、平均粒径13.5μm の粒子を
得た。さらに疎水性シリカR−972(日本アエロジル
(株)製)をトナー中に0.2重量%添加して、正帯電
性カラートナーを得た。このトナー中に残る、重合開始
剤の分解残渣であるカルボン酸類及びケトン類をガスク
ロマトグラフィーによって定量し、表2に示した。3. Examples 1 to 5 and Comparative Examples 1 to 3 (manufacture of toner) Part by weight (A) Vinyl polymer mixture obtained in any one of Synthesis Examples 1 to 8 shown in Table 1 (B) 2 (C) Quaternary ammonium salt (P-51 manufactured by Orie 2nd Kagaku Kogyo Co., Ltd.) (D) Copper phthalocyanine kaito (manufactured by Inu Nissin 5 Ka Co., Ltd.) (manufactured by Sanyo 3 Kasei Kogyo Co., Ltd., Viscol 550P) (E) Low molecular weight polypropylene (manufactured by Sanyo 3 Kasei Kogyo Co., Ltd., Viscol 550P) After coarsely pulverizing the powder, it was finely pulverized using a jet pulverizer, and the coarse powder and fine powder were classified using a rotary air classifier to obtain particles with an average particle size of 13.5 μm. Further, 0.2% by weight of hydrophobic silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was added to the toner to obtain a positively chargeable color toner. The carboxylic acids and ketones remaining in this toner as decomposition residues of the polymerization initiator were determined by gas chromatography and are shown in Table 2.
4、マイクロキャリア1の製造
重量部
ブライオライドACL (グツドイヤー 100ケミカ
ル(株)製:スチレン・アクリ
ル系共重合樹脂)
マピコブランクBL−500(チタエ 200業(株)
製;マグネタイト)
カーボンブラックMAR84
(三菱化成工業(株)製)
以上をボールミルで良く混合した後、三本ロールで良く
混練し、予め、粗粉砕し1次にジェットミルで微粉砕し
た後、回転風力式の分級機で分級し平均社径が35μm
のバインダ型マイクロキャリア1を得た。4. Production weight part of Microcarrier 1 Briolide ACL (manufactured by Gutsdoyer 100 Chemical Co., Ltd.: styrene-acrylic copolymer resin) Mapico Blank BL-500 (Chitae 200 Co., Ltd.)
Carbon black MAR84 (manufactured by Mitsubishi Chemical Industries, Ltd.) After mixing the above ingredients well in a ball mill, kneading them well in a three-roll mill, first coarsely pulverizing, then finely pulverizing in a jet mill, and then rotating Classified using a wind-powered classifier, with an average diameter of 35 μm.
A binder type microcarrier 1 was obtained.
5、マイクロキャリア2の製造
重量部
ビスフェノール型ポリエステル 100(軟化点
:122℃、ガラス転移点;63℃)Zn 系フェラ
イト 500カーボンブラック M
A#8 4(三菱化成工業(株)製)
以上を、ヘンシェルミキサーで良く混合した後三本ロー
ルにて、良く混練し、予め粗粉砕し1次にジェットミル
にて微粉砕し、回転風力式の分級機で分級し平均径55
μmのバインダ型マイクロキャリア2を得た。5. Production of Microcarrier 2 Part by weight Bisphenol type polyester 100 (softening point: 122°C, glass transition point: 63°C) Zn-based ferrite 500 Carbon black M
A#8 4 (manufactured by Mitsubishi Chemical Industries, Ltd.) The above was mixed well with a Henschel mixer, then kneaded well with three rolls, coarsely pulverized first, then finely pulverized with a jet mill, and then pulverized with a rotary wind blower. Classified with a type classifier and has an average diameter of 55
A binder type microcarrier 2 of μm was obtained.
6、トナーの評価
■ 社を促
前記マイクロキャリア1,2に夫々上記で調製した1−
ナーを10重量%のトナー濃度にして加えて現像剤を調
整し、100ccのポリ瓶に60gを入れ、毎分12O
rpmの架台に乗せ、3分、10分、30分後の各々の
帯電量(Qf)を求めた。6. Toner evaluation
Adjust the developer by adding toner to a toner concentration of 10% by weight, put 60g into a 100cc plastic bottle, and generate 12O per minute.
The charge amount (Qf) was determined after 3 minutes, 10 minutes, and 30 minutes.
■ 飛数l朗定
また、トナー濃度を20重量%にしてキャリア2に加え
、3分混合後の飛散量を、下記の装置を使用して求めた
。(2) Determining the number of scatterings Further, the toner concentration was made to be 20% by weight and the toner was added to carrier 2, and the amount of scattering after mixing for 3 minutes was determined using the following apparatus.
マグネットとその回りにスリーブを有するマグネットロ
ーラーの上に、上記のトナー濃度20重量%の現像剤を
10gセットし、マグネットを毎分11000rpに回
転したとき、飛散するトナーを柴田化学(株)製デジタ
ル粉塵計を用いて1分間計測した値を記した。10g of the above-mentioned developer with a toner concentration of 20% by weight is set on a magnetic roller having a magnet and a sleeve around it, and when the magnet is rotated at 11,000 rpm, the scattered toner is removed using a digital camera manufactured by Shibata Chemical Co., Ltd. The values measured for 1 minute using a dust meter are recorded.
500cpm以下の場合実用的に使用可能な飛散量で実
用機の中にあっても、飛散によるトラブルはほとんど見
られないが、500c”pm以上、特に11000cp
を越えると、飛散がひどく。If the amount is less than 500cpm, it is a practically usable amount of scattering, and even if it is in a practical aircraft, there will be almost no trouble due to scattering, but if it is more than 500c"pm, especially 11000cp.
If it exceeds the limit, the scattering will be severe.
現像装置周辺を汚したり、カブリ発生のトラブルの原因
となる。This may stain the area around the developing device and cause problems such as fogging.
■ 耐湿経時t′の帯11. 量
帯電量を測定した(30分間混合撹拌した際の?!電量
:Qf (30分))現像剤を35℃。■ Moisture resistance over time t' band 11. The amount of charge was measured (the amount of charge when mixed and stirred for 30 minutes: Qf (30 minutes)).The developer was heated at 35°C.
85%の環境下に瓶の蓋を開いて、3日間放置した後の
帯電量(Qf (35℃−85%−5days) )を
測定し、下記の式で減衰量を求めた。The cap of the bottle was opened in an environment of 85%, and the amount of charge (Qf (35° C.-85%-5 days)) after being left for 3 days was measured, and the amount of attenuation was determined using the following formula.
■ 団蓋止
ガラスサンプル瓶(50cc)の中にトナー5gを入れ
、50°C±95℃のオーブンの中に24時間放置した
後、静かに取出し、室温まで放冷したあと、逆に倒立さ
せ、トナーが落下するかどうかを下記の基準で評価した
。■ Put 5g of toner in a round-topped glass sample bottle (50cc), leave it in an oven at 50°C ± 95°C for 24 hours, then gently take it out, let it cool to room temperature, and then turn it upside down. , whether or not the toner would fall was evaluated based on the following criteria.
ランク AO以上5秒未満の間に落下し、凝集なし。rank It fell in less than 5 seconds than AO, and there was no aggregation.
B 5以上〜15秒未満の間に落下し、凝集なし。B: Falling within 5 seconds or more and less than 15 seconds, no aggregation.
C15以上30秒未満の間に落下し軽く凝集しているが
良く振ると元のトナーにもどり実用上問題なし。The toner fell and slightly aggregated within 30 seconds of C15 or above, but when shaken well, it returns to the original toner and poses no practical problem.
D 30秒以上〜1分未満の間に落下し凝集の程度は
弱いが良くふっても解砕されず。D: The particles fell within 30 seconds or more and less than 1 minute, and although the degree of agglomeration was weak, it did not disintegrate even if shaken well.
E 1分以上たっても落下せず瓶の底に固化。E It solidified at the bottom of the bottle without falling even after more than 1 minute.
■ 完1ゴし元ス」−
上部ローラーにテフロン系の樹脂をコートした40φの
定着ローラーを、下部ローラーにLTVゴムローラーを
用い、両者を圧力80kgをかけて圧接した定着器を用
いて20 cm / secの速度で定着したときの高
温オフセット及び低温オフセットの発生温度並びに17
5℃で定着したときの画像濃度(ID)1.2 及びI
D0.6の定着強度を求めた。■Complete printing process - A fixing device with a 40φ fixing roller coated with Teflon resin for the upper roller and an LTV rubber roller for the lower roller, and a 20 cm fixing device that presses both together by applying a pressure of 80 kg. Temperature at which high temperature offset and low temperature offset occur when fixing at a speed of / sec and 17
Image density (ID) 1.2 and I when fixed at 5°C
The fixing strength of D0.6 was determined.
定着強度は、コピーした画像を、砂ケシゴムの上に1k
gの荷重をのせた特製の装置でこすってトナー画像を消
す。このとき、砂ケシゴムでこする前後の反射濃度の比
を100分率で表わした。The fixing strength is 1k for the copied image on sand poppy rubber.
The toner image is erased by rubbing it with a specially made device carrying a load of 100 g. At this time, the ratio of the reflection density before and after rubbing with sand poppy rubber was expressed as a percentage.
■ 耐重し−とド
キャリア1と各トナーを夫々10重量%のトナー濃度に
なるように、IQのポリ瓶に入れ。■Pour the weight-resistant weight, carrier 1, and each toner into an IQ plastic bottle so that the toner concentration is 10% by weight.
ボールミル架台にのせ10時間120回転/分で現像剤
を調製する。A developer was prepared by placing it on a ball mill stand and rotating it at 120 revolutions/minute for 10 hours.
この現像剤をミノルタ(株)製EP450Z複写機に入
れ1万枚の耐刷テストをし下記の基準で評価した。This developer was put into an EP450Z copying machine manufactured by Minolta Co., Ltd., and subjected to a printing durability test of 10,000 sheets, and evaluated according to the following criteria.
ランク 5 カブリは全くなし。rank 5. No fogging at all.
4 カブリはわずかに認められる。4. Slight fogging is observed.
3 カブリ若干認められるが実用上問題なU)。3) Some fogging is observed, but it is a practical problem U).
2 カブリ多し。2. Lots of fog.
1 カブリ非常に多し。1. There is a lot of fog.
本発明に係る正帯電性カラートナーは、常に良好な正帯
電性を有するものであり、該トナーを用いた場合には、
カブリや飛散が少なく、耐熱性。The positively chargeable color toner according to the present invention always has good positive chargeability, and when the toner is used,
Heat resistant with little fogging or scattering.
Claims (1)
いて懸濁重合で得られた低分子量ビニル系重合体及びパ
ーオキシケタール系の重合開始剤を用いて懸濁重合で得
られた高分子量ビニル系重合体を含むビニル系重合体混
合物、 (B)スチレン−アミノ(メタ)アクリル系共重合体及
び/又はアミノ(メタ)アクリ ル系重合体、 (C)第四級アンモニウム塩並びに (D)着色剤 を含有し、かつ、重合開始剤の分解残渣であるカルボン
酸類及びケトン類を夫々0.1〜1重量%含有してなる
正帯電性カラートナー。 2、(A)成分が、懸濁重合で得られた低分子量ビニル
系重合体の存在下に、高分子量ビニル系重合体を懸濁重
合して得たものである請求項第1項記載の正帯電性カラ
ートナー。[Claims] 1. (A) A low molecular weight vinyl polymer obtained by suspension polymerization using a diacyl peroxide polymerization initiator and suspension polymerization using a peroxyketal polymerization initiator. (B) styrene-amino(meth)acrylic copolymer and/or amino(meth)acrylic polymer; (C) quaternary A positively chargeable color toner containing an ammonium salt and (D) a coloring agent, and 0.1 to 1% by weight of each of carboxylic acids and ketones, which are decomposition residues of a polymerization initiator. 2. Component (A) is obtained by suspension polymerization of a high molecular weight vinyl polymer in the presence of a low molecular weight vinyl polymer obtained by suspension polymerization. Positively chargeable color toner.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63024510A JP2591775B2 (en) | 1988-02-04 | 1988-02-04 | Positively chargeable color toner |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63024510A JP2591775B2 (en) | 1988-02-04 | 1988-02-04 | Positively chargeable color toner |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01200270A true JPH01200270A (en) | 1989-08-11 |
JP2591775B2 JP2591775B2 (en) | 1997-03-19 |
Family
ID=12140170
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63024510A Expired - Lifetime JP2591775B2 (en) | 1988-02-04 | 1988-02-04 | Positively chargeable color toner |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2591775B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01222268A (en) * | 1988-03-01 | 1989-09-05 | Sanyo Chem Ind Ltd | Toner binder |
JPH0627721A (en) * | 1992-03-27 | 1994-02-04 | Sanyo Chem Ind Ltd | Toner binder resin composition |
JPH0627733A (en) * | 1992-03-27 | 1994-02-04 | Sanyo Chem Ind Ltd | Toner binder resin composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60168701A (en) * | 1984-02-10 | 1985-09-02 | Hitachi Chem Co Ltd | Production of resin composition |
JPS61114245A (en) * | 1984-11-09 | 1986-05-31 | Sekisui Chem Co Ltd | Preparation of electrophotographic toner resin |
JPS61124958A (en) * | 1984-11-22 | 1986-06-12 | Konishiroku Photo Ind Co Ltd | Electrostatic charge image developing color toner |
JPS6221169A (en) * | 1985-07-20 | 1987-01-29 | Minolta Camera Co Ltd | Positively electrifiable toner |
-
1988
- 1988-02-04 JP JP63024510A patent/JP2591775B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60168701A (en) * | 1984-02-10 | 1985-09-02 | Hitachi Chem Co Ltd | Production of resin composition |
JPS61114245A (en) * | 1984-11-09 | 1986-05-31 | Sekisui Chem Co Ltd | Preparation of electrophotographic toner resin |
JPS61124958A (en) * | 1984-11-22 | 1986-06-12 | Konishiroku Photo Ind Co Ltd | Electrostatic charge image developing color toner |
JPS6221169A (en) * | 1985-07-20 | 1987-01-29 | Minolta Camera Co Ltd | Positively electrifiable toner |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01222268A (en) * | 1988-03-01 | 1989-09-05 | Sanyo Chem Ind Ltd | Toner binder |
JPH0627721A (en) * | 1992-03-27 | 1994-02-04 | Sanyo Chem Ind Ltd | Toner binder resin composition |
JPH0627733A (en) * | 1992-03-27 | 1994-02-04 | Sanyo Chem Ind Ltd | Toner binder resin composition |
Also Published As
Publication number | Publication date |
---|---|
JP2591775B2 (en) | 1997-03-19 |
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