JPS62226162A - Dry toner for electrostatic photogrpaphy - Google Patents
Dry toner for electrostatic photogrpaphyInfo
- Publication number
- JPS62226162A JPS62226162A JP61068950A JP6895086A JPS62226162A JP S62226162 A JPS62226162 A JP S62226162A JP 61068950 A JP61068950 A JP 61068950A JP 6895086 A JP6895086 A JP 6895086A JP S62226162 A JPS62226162 A JP S62226162A
- Authority
- JP
- Japan
- Prior art keywords
- resin particles
- temperature
- particles
- toner
- thermoplastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002245 particle Substances 0.000 claims abstract description 101
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 235000010893 Bischofia javanica Nutrition 0.000 claims description 8
- 240000005220 Bischofia javanica Species 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000011859 microparticle Substances 0.000 abstract description 26
- 239000000843 powder Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 15
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000012546 transfer Methods 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 ethylene, propylene, styrene Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920002601 oligoester Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 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 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 150000007524 organic acids Chemical class 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
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002102 polyvinyl toluene 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000001681 protective effect Effects 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
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- G03G9/0802—Preparation methods
- G03G9/0808—Preparation methods by dry mixing the toner components in solid or softened state
-
- 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は静電写真用乾式トナーに関する。更に詳しくは
、流動性、帯電性、製造性に優れ且つ汚染度の低い静電
写真用乾式トナーに関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrostatographic dry toner. More specifically, the present invention relates to an electrostatic photographic dry toner that has excellent fluidity, chargeability, and manufacturability, and has a low degree of contamination.
（従来技術およびその問題点）
従来、静電写真用乾式トナーは熱可塑性樹脂中に着色剤
、および必要に応じて磁性体やその他添加剤を溶融分散
したのち、平均粒子径を５〜２０μの範囲に粉砕、分級
して製造される。このようにして得られたトナーは物理
的な摩擦により、電荷が付与される。トナーはこの帯電
性が高い程優れており、そのために通常電荷制御剤が添
加される。この場合、電荷制御剤として使用されるニグ
ロジンやオイルブラックなどの染料１、有機酸の金属錯
体を樹脂中に均一に溶融分散、−仕ることは困難で、粉
砕時に各トナー粒子表面に露出する電荷制御剤量は各粒
子間で不均一になり、帯電時の電荷量が不均一になるこ
とがさけられない。従って、感光体電荷潜像に対する忠
実な現像性に欠け、転写率が低くなり、長期連続複写に
於いて画質変化が大きくなる。また熱可塑性樹脂に被覆
された粒子内部の電荷制御剤は帯電時の電荷制御機能が
低下するため、所望の電荷を有する乾式トナーの製造時
、高価な制御剤を多口に添加する必要があり、経済性に
も欠ける。また、トナー相互間で凝集がおこり、トナー
流動性が悪（なる欠点も有する。(Prior art and its problems) Conventionally, dry toner for electrostatic photography is produced by melting and dispersing a colorant and, if necessary, a magnetic substance and other additives in a thermoplastic resin, and then adjusting the average particle size to 5 to 20μ. Manufactured by crushing and classifying. The toner thus obtained is given an electric charge by physical friction. The higher the chargeability of the toner, the better it is, and for this purpose, a charge control agent is usually added. In this case, it is difficult to uniformly melt and disperse dyes such as nigrosine and oil black, which are used as charge control agents, and organic acid metal complexes in the resin, and they are exposed on the surface of each toner particle when crushed. It is unavoidable that the amount of charge control agent becomes non-uniform among each particle, and the amount of charge during charging becomes non-uniform. Therefore, faithful development of the photoreceptor charge latent image is lacking, the transfer rate is low, and image quality changes greatly during long-term continuous copying. In addition, the charge control agent inside the particles coated with thermoplastic resin deteriorates the charge control function during charging, so it is necessary to add large amounts of expensive control agent when producing dry toner with the desired charge. , it also lacks economic efficiency. It also has the disadvantage that toner particles tend to aggregate with each other, resulting in poor toner fluidity.
（発明の目的）
本発明は粉体流動性に優れ、高画質、高転写率、長期連
続複写に於いても安定な静電写真用乾式トナーを経済的
に製造することを目的とする。(Objective of the Invention) An object of the present invention is to economically produce a dry toner for electrostatic photography that has excellent powder flowability, high image quality, high transfer rate, and is stable even during long-term continuous copying.
（発明の内容）
即ち、本発明は高化式フローテスターにおける流出開始
温度ｔ１（’ｃ）を有する粒径２〜３０μの着色熱可塑
性樹脂粒子（以下、着色粒子と云う）と前記ｔ１（℃）
より高い流出開始温度ｔ２℃を有する粒径１μ以下の微
小樹脂粒子（以下、微小粒子と云う）とを、ｔ１以上か
つｔ２未満の温度で加熱処理することにより着色熱可塑
性樹脂粒子表面に微小樹脂粒子を付着させた静電写真用
乾式トナーを提供する。(Contents of the invention) That is, the present invention provides colored thermoplastic resin particles (hereinafter referred to as colored particles) having a particle size of 2 to 30 μ and having an outflow start temperature t1 ('c) in a Koka type flow tester, and the above t1 (°C). )
Fine resin particles with a particle size of 1 μ or less (hereinafter referred to as microparticles) having a higher outflow start temperature t2°C are heat-treated at a temperature of t1 or more and less than t2 to form a fine resin on the surface of the colored thermoplastic resin particles. An electrostatographic dry toner having particles attached thereto is provided.
本発明を構成する高化式フローテスターにおける流出開
始温度がｔ１（’Ｃ）である着色粒子は溶融混練後の粉
砕による方法、および乳化重合あるいは懸濁重合の如き
造粒重合などにより得られる。溶融混線法による場合は
、熱可塑性樹脂中に着色剤および必要に応じて磁性体や
その他の添加剤を溶融分散したのち粉砕することにより
得られる。また、乳化重合による場合は、通常、イオン
交換水あるいは乳化剤を予め溶解したイオン交換水中に
重合性モノマーの一部と重合開始剤を添加して攪拌乳化
し、その後重合性モノマーの残部を徐々に滴下して０．
２〜１μの粒子を得、この粒子を種として、染顔料を溶
解または分散させた重合性モノマーを用いたシード重合
、あるいは着色剤を含有しない重合性モノマーでのシー
ド重合の後、染顔料の溶液または分散液で着色すること
により得られる。更に懸濁重合の場合は、保護コロイド
を含有するイオン交換水中に疎水性重合開始剤および染
顔料などの着色剤を含有した重合性モノマーを分散懸濁
して重合を行なうか、あるいは着色剤を含まない重合性
モノマーでの懸濁重合ののち染顔料の溶液または分散液
で着色することにより得られる。本発明でいう高化式フ
ローテスターによる流出開始温度とは、断面積１ ｃｍ
２のブラジャーを用い荷重２０ｋｇ、昇温速度６℃／分
においてサンプルの溶融流出が始まる温度である。着色
粒子の粒径は２〜３０μ、好ましくは５〜２０μである
。２μ以下では飛散しやすく、また３０μ以上では画質
の低下を招く。Colored particles having an outflow start temperature of t1 ('C) in the Koka type flow tester constituting the present invention can be obtained by melt-kneading followed by pulverization, or by granulation polymerization such as emulsion polymerization or suspension polymerization. In the case of the melt mixing method, it is obtained by melting and dispersing a coloring agent and, if necessary, a magnetic substance and other additives in a thermoplastic resin, and then pulverizing the mixture. In the case of emulsion polymerization, a part of the polymerizable monomer and a polymerization initiator are usually added to ion-exchanged water or ion-exchanged water in which an emulsifier has been dissolved in advance, and emulsified by stirring, and then the remaining part of the polymerizable monomer is gradually added. Drop 0.
After obtaining particles of 2 to 1 μm and using these particles as seeds, seed polymerization using a polymerizable monomer in which dyes and pigments are dissolved or dispersed, or seed polymerization using a polymerizable monomer that does not contain a colorant, is performed. Obtained by coloring with a solution or dispersion. Furthermore, in the case of suspension polymerization, polymerization is carried out by dispersing and suspending a hydrophobic polymerization initiator and a polymerizable monomer containing a coloring agent such as a dye or pigment in ion-exchanged water containing a protective colloid, or by dispersing and suspending a polymerizable monomer containing a hydrophobic polymerization initiator and a coloring agent such as a dye or pigment. It can be obtained by suspension polymerization with a polymerizable monomer, followed by coloring with a dye/pigment solution or dispersion. In the present invention, the outflow start temperature by the Koka type flow tester is defined as
This is the temperature at which melting and outflow of the sample begins using brassiere No. 2 with a load of 20 kg and a heating rate of 6° C./min. The particle size of the colored particles is 2 to 30 microns, preferably 5 to 20 microns. If it is less than 2μ, it will easily scatter, and if it is more than 30μ, the image quality will deteriorate.
着色粒子の製造には従来公知の種々の熱可塑性樹脂、重
合性モノマー、着色剤等の材料が使用できる。例えば熱
可塑性樹脂としてはポリスチレン、ポリビニルトルエン
、スチレン−ブタジェン共重合体、スチレン−アクリル
酸共重合体、スチレン−無水マレイン酸共重合体などの
スチレンまたはその置換体の重合体または共重合体、ア
クリル系樹脂、ポリエステル樹脂、エポキシ樹脂、キシ
レン樹脂、アイオノマー樹脂、ケトン樹脂、テルペン樹
脂、フェノール変性テルペン樹脂、ロジン、ロジン変性
樹脂、マレイン酸変性フェノール樹脂、石油系樹脂、ポ
リビニルアルコール、ポリビニルピロリドンなどが単独
もしくは混合して用いられる。In the production of colored particles, various conventionally known materials such as thermoplastic resins, polymerizable monomers, colorants, etc. can be used. For example, thermoplastic resins include polymers or copolymers of styrene or its substituted products, such as polystyrene, polyvinyltoluene, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer, and acrylic. type resins, polyester resins, epoxy resins, xylene resins, ionomer resins, ketone resins, terpene resins, phenol-modified terpene resins, rosin, rosin-modified resins, maleic acid-modified phenolic resins, petroleum-based resins, polyvinyl alcohol, polyvinylpyrrolidone, etc. Or used in combination.
重合性モノマーとしては重合可能なモノマーであれば任
意のものが適用可能であり、エチレン、プロピレン、ス
チレン、α−クロロスチレン、α−メチルスチレン、４
−フルオロスチレン、アクリル酸、メタクリル酸、アク
リロニトリル、アクリルアミド、メチルアクリレート、
メチルメタクリレート、エチルアクリレート、ブチルア
クリレート、ブチルメタクリレート、トリフルオロエチ
ルメタクリレート、酢酸ビニル、無水マレイン酸等が単
独もしくは混合して用いられる。Any polymerizable monomer can be used as the polymerizable monomer, including ethylene, propylene, styrene, α-chlorostyrene, α-methylstyrene,
-Fluorostyrene, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, methyl acrylate,
Methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, trifluoroethyl methacrylate, vinyl acetate, maleic anhydride, and the like are used alone or in combination.
着色剤としては、カーボンブラック、ニグロシン染料、
ランプブラック、アニリンブルー、カルコイルブルー、
ウルトラマリンブルー、フタロシアニンブルー、クロム
イエロー、キノリンイエロー、デュポンオイルレッド、
ローズベンガル、メチレンブルークロリド等が代表例と
して挙げられる。Colorants include carbon black, nigrosine dye,
lamp black, aniline blue, calcoil blue,
Ultramarine blue, phthalocyanine blue, chrome yellow, quinoline yellow, DuPont oil red,
Representative examples include rose bengal and methylene blue chloride.
更に他の材料群としては、重合開始剤として過酸化水素
、過酢酸、アゾビスイソブチロニトリル、ｔ−ブチルハ
イドロパーオキサイド、過硫酸アンモニウム、過硫酸カ
リウム等のフリーラジカル開始剤や過硫酸ナトリウム−
ホルムアルデヒドスルホキシレートナトリウム、過酸化
水素−アスコルビン酸等のレドックス系開始剤が、乳化
剤としては、アニオン活性剤、例えばステアリン酸カリ
ウム、オレイン酸カリウム、ドデシルスルホン酸ナトリ
ウム、オレイン酸カリウム、ドデシルスルホン酸ナトリ
ウム、ラウリル酸ナトリウム等：カチオン活性剤、例え
ば長鎖第４級アミン塩等があり、非イオン活性剤として
はリルイン酸、ラウリン酸のエチレンオキサイド縮合物
等が挙げられる。また、分散剤としては、メチルセルロ
ース、カルボキシメチルセルロース、アミノエチルセル
ロース、ゼラチン、デンプン、ポリビニルアルコール等
がある。Furthermore, other material groups include free radical initiators such as hydrogen peroxide, peracetic acid, azobisisobutyronitrile, t-butyl hydroperoxide, ammonium persulfate, potassium persulfate, and sodium persulfate as polymerization initiators.
Redox initiators such as sodium formaldehyde sulfoxylate and hydrogen peroxide-ascorbic acid are used as emulsifiers, and anionic activators such as potassium stearate, potassium oleate, sodium dodecylsulfonate, potassium oleate, and sodium dodecylsulfonate are used as emulsifiers. , sodium laurate, etc.: Cationic activators, such as long-chain quaternary amine salts, and nonionic activators include ethylene oxide condensates of rillic acid and lauric acid. Examples of dispersants include methylcellulose, carboxymethylcellulose, aminoethylcellulose, gelatin, starch, and polyvinyl alcohol.
本発明の高化式フローテスターにおける流出開始温度が
ｔｔ（℃）であり、かつ粒径が１μ以下の微小粒子の合
成および付着方法としては次のような方法が適用できる
：（１）着色粒子の分散液中に重合開始剤および重合性
モノマーの一部を添加したのち、重合性モノマーの残部
を徐々に滴下して微小粒子を生成させしめ、次いで、着
色粒子の流出開始温度（ｔｌ）以上かつ微小粒子の流出
開始温度（し、）未満の温度範囲内で噴霧乾燥等により
乾燥させて付着させる方法：（２）着色粒子の分散液中
に、予め合成した微小粒子を均一分散せしめたのち、前
記ｔ３以上かつｔ１未満の温度範囲内で噴霧乾燥等によ
り乾燥させて付着させる方法；（３）予め乾燥した着色
粒子と微小粒子をｔ１以ド、好ましくは５０℃以下で均
一混合したのち、前記ｔ１以上かつｔ１以上ｔ２未満の
温度範囲内で更に混合攪拌することにより付着させる方
法などが適用できる。The following method can be applied as a method for synthesizing and attaching microparticles having an outflow start temperature of tt (°C) and a particle size of 1 μ or less in the Koka type flow tester of the present invention: (1) Colored particles After adding a polymerization initiator and a part of the polymerizable monomer to the dispersion liquid, the remaining part of the polymerizable monomer is gradually added dropwise to form microparticles. A method of drying and adhering by spray drying etc. within a temperature range below the outflow start temperature of the microparticles: (2) After uniformly dispersing pre-synthesized microparticles in a dispersion of colored particles. , a method of drying and adhering by spray drying or the like within the temperature range of t3 or more and less than t1; (3) After uniformly mixing pre-dried colored particles and microparticles at a temperature of t1 or more, preferably 50° C. or less, A method of adhesion by further mixing and stirring within the temperature range of t1 or more and t1 or more and less than t2 can be applied.
前述の（２）、（３）の方法で使用される微小粒子は従
来公知の乳化剤、重合開始剤、重合性モノマー等を用い
た乳化重合により得ることができる。The microparticles used in methods (2) and (3) above can be obtained by emulsion polymerization using conventionally known emulsifiers, polymerization initiators, polymerizable monomers, and the like.
具体的な乳化剤、重合開始剤、重合性モノマーの例とし
ては前記着色粒子で挙げたものが用いられる。微小粒子
の粒径は１μ以下であることが゛好ましく、それ以上の
大きさでは表面積の減少による帯電量が不足する傾向に
ある。As specific examples of emulsifiers, polymerization initiators, and polymerizable monomers, those listed above for colored particles can be used. It is preferable that the particle size of the microparticles is 1 μm or less; if the particle size is larger than that, the amount of charge tends to be insufficient due to a decrease in surface area.
前述の３種の合成および付着方法のいずれによっても本
発明の目的は達成されるが、更に各方法の特徴を述べる
と、（１）の方法によれば、着色粒子表面全体が均一に
微小粒子により被覆されていわゆるカプセル構造となる
ため造粒重合により着色粒子を得る場合は該着色粒子を
構成する熱可塑性樹脂としては、高化式フローテスター
における流出開始温度の低いものが適用できることから
、定着温度の低い乾式トナーも得ることが可能である。The purpose of the present invention can be achieved by any of the three synthesis and attachment methods described above, but to further describe the characteristics of each method, according to method (1), the entire colored particle surface is uniformly coated with fine particles. When colored particles are obtained by granulation polymerization, it is possible to use a thermoplastic resin that has a low outflow start temperature in a Koka type flow tester. It is also possible to obtain dry toners with low temperatures.
また（２）の方法によれば微小粒子は別途合成するため
該微小粒子表面への着色、帯電性付与等の処理方法が巾
広く採用できることにより帯電性の制御が容易となり正
極性トナーおよび負極性トナーのいずれの極性のトナー
も得られる。更に（３）の方法によれば従来の溶融混練
、粉砕、分級の製造設備を用いて着色粒子を得る際に磁
性体の含有が可能となるため非磁性トナーのみならず磁
性トナーも得ることができる。In addition, according to the method (2), since the microparticles are synthesized separately, a wide range of treatment methods such as coloring the surface of the microparticles and imparting chargeability can be adopted, making it easy to control the chargeability. Either polarity of toner can be obtained. Furthermore, according to method (3), it is possible to contain a magnetic substance when obtaining colored particles using conventional production equipment for melt-kneading, pulverization, and classification, so that not only non-magnetic toner but also magnetic toner can be obtained. can.
上記加熱処理の時間は使用し得る樹脂の流出開始温度ｔ
、およびｔ８、加熱温度、その他の条件により特に限定
的ではないが、例えば着色粒子のＬｌが１００℃前後で
、微小粒子のｔ、が１００℃程度である場合、１１０℃
の加熱温度で１０〜３０分加熱するのが望ましい。加熱
時間が短いと微小粒子が十分に着色粒子表面に付着せず
、雨粒子の分離がおこり好ましくない。加熱時間が長す
ぎると、着色粒子表面上の微小粒子と付着していない微
小粒子の間の過度の摩擦により、付着した粒子の脱離を
起こすと云う欠点を有する。The above heat treatment time is the outflow start temperature t of the usable resin.
, and t8, heating temperature, and other conditions are not particularly limited, but for example, if Ll of colored particles is around 100°C and t of fine particles is around 100°C, 110°C
It is desirable to heat at a heating temperature of 10 to 30 minutes. If the heating time is too short, the fine particles will not adhere to the surface of the colored particles sufficiently, and separation of rain particles will occur, which is not preferable. If the heating time is too long, there is a drawback that the adhered particles may come off due to excessive friction between the fine particles on the surface of the colored particles and the fine particles not attached.
得られた表面に微小粒子の付着したトナーは、種々の方
法、例えばピンミルあるいは気流式粉砕機により軽く解
砕して使用される。従って、着色粒子と微小粒子の付着
の程度は、例えば、この気流式粉砕機による２ｋｇ／ｃ
ｍ’の粉砕空気圧を用いる気流解砕によっても雨粒子の
分離がおこらない程度が好ましい。The obtained toner having fine particles attached to its surface is used after being lightly crushed by various methods, such as a pin mill or an air flow type crusher. Therefore, the degree of adhesion of colored particles and microparticles is, for example, 2 kg/c by this air flow type crusher.
It is preferable that rain particles are not separated even by air flow disintegration using a crushing air pressure of m'.
本発明の着色粒子および微小粒子の流出開始温度１＋お
よびｔ、はトナーの定着温度、通常１３０〜２００℃よ
り小さくなくてはならない。従って、通常ｔ１は５０−
１５０℃で、ｔ、は１３０〜１７０℃程度が好ましい。The outflow start temperatures 1+ and t of the colored particles and fine particles of the present invention must be lower than the fixing temperature of the toner, usually 130 to 200°C. Therefore, normally t1 is 50-
At 150°C, t is preferably about 130 to 170°C.
（発明の作用・効果）
本発明により得られる静電写真用乾式トナーは、従来方
式によるトナーに比べて、表面の微小粒子の存在による
摺擦時の摩擦係数の増大および表面積増加により帯電制
御剤を添加せずν二、または少塁添加するのみで効率良
く必要量の電荷４．得ることができる。従って、長期連
続複写に於いても高画質、高転写率である。また微小粒
子が着色粒子表面を均一に覆うためトナー粒子側々は球
形粒子としての特性を有し、しかも隣接粒子との接触面
積が小さく、凝集がおこりにくく、粉体流動性にも優れ
ている。更には着色粒子表面の微小粒子による細かな凹
凸の光散乱効果により粉粒体状態では外観上の着色度が
低くなり、黒より白っぽく見え、取扱い時や飛散時の汚
れ具合が極端に少なくなるという効果も有する。(Actions and Effects of the Invention) Compared to toners produced by conventional methods, the dry toner for electrostatic photography obtained by the present invention has a charge control agent due to an increase in the coefficient of friction during rubbing due to the presence of fine particles on the surface and an increase in surface area. By simply adding ν2 or a small base without adding ν2, the required amount of charge 4. Obtainable. Therefore, even in long-term continuous copying, high image quality and high transfer rate are achieved. In addition, because the microparticles uniformly cover the surface of the colored particles, the sides of the toner particles have the characteristics of spherical particles, and the contact area with adjacent particles is small, making it difficult for agglomeration to occur, and the powder has excellent fluidity. . Furthermore, due to the light-scattering effect of the fine irregularities caused by the microscopic particles on the surface of the colored particles, the degree of coloring in the powdered form is lowered in appearance, making it look more whitish than black, and it is extremely less likely to get dirty when handled or scattered. It also has effects.
（実施例） 以下、実施例に基づいて本発明を説明する。(Example) Hereinafter, the present invention will be explained based on Examples.
実施例１
攪拌機、温度計、モノマー滴下ロート、還流冷却器、加
熱装置、窒素ガス導入管を有する重合反応容器にイオン
交換水１５０部を仕込み、８０℃でスチレンとアクリル
酸ｎ−ブチルの８０：２０の混合モノマー（Ａ）１部と
１０％の過硫酸アンモニウム水溶液１０部を加え、その
後上記混合上ツマ−（Ａ）９９部を３時間で滴下して種
ラテツクスを得た。該粒子を電子顕微鏡観察したところ
ほぼ単分散で、粒径は０．６μであった。Example 1 150 parts of ion-exchanged water was charged into a polymerization reaction vessel equipped with a stirrer, a thermometer, a monomer dropping funnel, a reflux condenser, a heating device, and a nitrogen gas introduction tube, and 80 parts of styrene and n-butyl acrylate were heated at 80°C. 1 part of the mixed monomer (A) of No. 20 and 10 parts of a 10% ammonium persulfate aqueous solution were added thereto, and then 99 parts of the above-mentioned mixed monomer (A) was added dropwise over 3 hours to obtain a seed latex. When the particles were observed under an electron microscope, they were found to be almost monodisperse, with a particle size of 0.6 μm.
次いで同様の装置を用い、種ラテックス０．２部をイオ
ン交換水２５０部に加え、８０℃で１０％過硫酸アンモ
ニウム水溶液ｌＯ部と混合モノマー（Ａ）１００部を８
時間かけて滴下するシード重合で大粒径ラテックス粒子
を作成した。電子顕微鏡による観察では該粒子は粒径が
６〜８μの範囲でほぼ真球であった。該ラテックス中に
黒色染料スミアクリルブラックＢ（住友化学社製塩基性
染料）の５％水溶液５０部を加え、１時間攪拌すること
でラテックス粒子表面に染料が吸着された着色粒子（Ｉ
）を得た。着色粒子（Ｉ）について高化式フローテスタ
ーにおける流出開始温度を測定したところ１４８℃であ
った。Next, using the same apparatus, 0.2 part of the seed latex was added to 250 parts of ion-exchanged water, and 10 parts of a 10% ammonium persulfate aqueous solution and 100 parts of mixed monomer (A) were added to 80 parts at 80°C.
Large-sized latex particles were created by seed polymerization, which was carried out dropwise over a period of time. When observed using an electron microscope, the particles were found to be almost perfectly spherical with a particle size in the range of 6 to 8 μm. 50 parts of a 5% aqueous solution of black dye Sumiacryl Black B (basic dye manufactured by Sumitomo Chemical Co., Ltd.) was added to the latex and stirred for 1 hour to form colored particles (I
) was obtained. The outflow start temperature of the colored particles (I) was measured using a Koka type flow tester and was found to be 148°C.
更に着色粒子（Ｉ）の水分散体４００部中にスチレン、
アクリル酸−ｎ−ブチル、パクリル酸−２−ヒドロキシ
エチルの８０ ： １０ ： １０ ：、）混合モノマ
ー（Ｂ）１部とｌθ％過硫酸アンモニウム水溶液５部を
加えたのち混合モノマー（Ｂ）９部を１時間かけて滴下
し、微小粒子含有ラテックス（Ｉ）を生成せしめた。こ
のラテックス（Ｉ）を入口温度１５０℃、出口温度８５
℃の条件下で噴霧乾燥したのち気流式粉砕機により粉砕
空気圧２ｋｇ／ｃｍ２で解砕してトナー（１）を得た。Furthermore, styrene,
After adding 1 part of mixed monomer (B) of n-butyl acrylate and 2-hydroxyethyl pacrylate (80:10:10:) and 5 parts of lθ% ammonium persulfate aqueous solution, 9 parts of mixed monomer (B) was added. The mixture was added dropwise over 1 hour to produce latex (I) containing microparticles. This latex (I) has an inlet temperature of 150℃ and an outlet temperature of 85℃.
After spray drying under the conditions of .degree. C., the mixture was pulverized using a pneumatic pulverizer at a pulverizing air pressure of 2 kg/cm.sup.2 to obtain toner (1).
該トナー粒子を電子顕微鏡により観察したところ着色粒
子の表面全体に粒径が０．１〜０．５μの微小粒子が均
一に且つ球形を保った状態で付着していることがわかっ
た。When the toner particles were observed using an electron microscope, it was found that fine particles having a diameter of 0.1 to 0.5 μm were uniformly adhered to the entire surface of the colored particles while maintaining a spherical shape.
第１図に付着粒子の電子顕微鏡写真を示す（着色粒子６
．５μ：微小粒子０．４μ−倍率 １０１００倍）。Figure 1 shows an electron micrograph of adhered particles (colored particles 6
．． 5μ: microparticle 0.4μ - magnification 10100 times).
該トナー（Ｉ）とキャリア鉄粉を４：９６の割合で混合
して現像剤（Ｉ）を得た。The toner (I) and carrier iron powder were mixed at a ratio of 4:96 to obtain a developer (I).
実施例２
実施例１と同様の反応装置を用い、イオン交換水９００
部に両性イオン型オリゴエステル化合物（重量平均分子
ｆｆ１１６００）を５部溶解させて乳化剤とし、８５℃
に於いて１０％過硫酸アンモニウム水溶液ＩＯ部を加え
たのち、混合モノマー（Ｂ）１００部を２時間かけて滴
下し、粒径が０．０５〜０．１μのラテックス粒子（１
１）を得た。Example 2 Using the same reaction apparatus as in Example 1, 900 ml of ion-exchanged water was used.
5 parts of a zwitterionic oligoester compound (weight average molecular weight FF 11600) was dissolved in 1 part to serve as an emulsifier, and the mixture was heated at 85°C.
After adding IO parts of a 10% aqueous ammonium persulfate solution, 100 parts of mixed monomer (B) was added dropwise over 2 hours to form latex particles (1
1) was obtained.
実施例１で得られた着色粒子（Ｉ）の水分散体４００部
中に前記ラテックス（■）５部を混合して３０分間攪拌
したのち、実施例１と同条件下で噴霧乾燥、気流粉砕し
てトナー（ＩＩ）を得た。かくして得られたトナー粒子
を電子顕微鏡により観察したところ、着色粒子の表面全
体に微小粒子が均−且つ球形を保った状態で付着してい
ることがわかった。5 parts of the latex (■) were mixed into 400 parts of the aqueous dispersion of colored particles (I) obtained in Example 1, stirred for 30 minutes, and then spray-dried and air-pulverized under the same conditions as in Example 1. Toner (II) was obtained. When the toner particles thus obtained were observed using an electron microscope, it was found that fine particles were adhered to the entire surface of the colored particles in a uniform and spherical state.
該トナー（ｎ）とキャリア鉄粉を４；９６の割合で混合
して現像剤（ｎ）を得た。The toner (n) and carrier iron powder were mixed in a ratio of 4:96 to obtain a developer (n).
実施例３
実施例１で得た着色粒子（１）、および実施例２で得た
ラテックス（ｎ）を各々単独で、入口温度１４０℃、出
口温度７０℃の条件下で噴霧乾燥後、２ ｋｇ／ ｃｍ
’の粉砕空気圧で気流粉砕を行なった。Example 3 The colored particles (1) obtained in Example 1 and the latex (n) obtained in Example 2 were each individually spray-dried under conditions of an inlet temperature of 140°C and an outlet temperature of 70°C, and then 2 kg / cm
Air flow milling was carried out using a milling air pressure of '.
次いで着色粒子（Ｉ）１００部とラテックス粒子（ｎ）
より得た微小粒子１部を自動乳鉢に仕込んだ後、２５〜
３０℃で１０分分間式混合したのち１５０〜１５５℃に
昇温し、更にｌＯ分間攪拌混合することによりトナー（
Ｉ［［）を得た。Next, 100 parts of colored particles (I) and latex particles (n)
After putting 1 part of the obtained microparticles into an automatic mortar,
The toner (
I[[) was obtained.
得られたトナー粒子を電子顕微鏡により観察したところ
、着色粒子のほぼ表面全体に微小粒子が球形を保った状
態で付着していることがわかった。When the obtained toner particles were observed using an electron microscope, it was found that microparticles were adhered to almost the entire surface of the colored particles while maintaining a spherical shape.
該トナー（ＩＩＩ）とキャリア鉄粉を４＝９６の割合で
混合して現像剤（Ｉ）を得た。The toner (III) and carrier iron powder were mixed in a ratio of 4=96 to obtain a developer (I).
実施例４
実施例１における混合モノマー（Ａ）をスチレンとアク
リル酸−ｎ−ブチルの５０：５０の混合モノマー（Ｃ）
に変更する以外は実施例１と同条件で着色粒子（ｎ）を
合成したのち該着色粒子の水分散体中で実施例１と同条
件で微小粒子を生成せしめた。Example 4 The mixed monomer (A) in Example 1 was replaced with a 50:50 mixed monomer (C) of styrene and n-butyl acrylate.
Colored particles (n) were synthesized under the same conditions as in Example 1 except for the following changes, and then microparticles were produced in an aqueous dispersion of the colored particles under the same conditions as in Example 1.
該ラテックスを入口温度１３０℃、出口温度７０℃の条
件下で噴霧乾燥したのち気流式粉砕機により粉砕空気圧
２ｋｇ／ｃｍ２で解砕してトナー（ＩＶ）を得た。該ト
ナー粒子を電子顕微鏡により観察したところ着色粒子の
表面全体に粒径がＯｌ〜０５μの微小粒子が均一にかつ
球形を保った状態で付着していることがわかった。The latex was spray-dried under conditions of an inlet temperature of 130°C and an outlet temperature of 70°C, and then crushed using a pneumatic crusher at a crushing air pressure of 2 kg/cm 2 to obtain toner (IV). When the toner particles were observed using an electron microscope, it was found that fine particles having a particle diameter of 01 to 05 μm were uniformly adhered to the entire surface of the colored particles while maintaining a spherical shape.
なお着色粒子（ｎ）について高化式フローテスターにお
ける流出開始温度を測定したところ６２６Ｃであった。The outflow start temperature of the colored particles (n) was measured using a Koka type flow tester and was found to be 626C.
該トナー（ＩＶ）とキャリア鉄粉を４＝９６の割合で混
合して現像剤（ＩＶ）を得た。The toner (IV) and carrier iron powder were mixed in a ratio of 4=96 to obtain a developer (IV).
実施例５
実施例１と同様の反応装置を用い、イオン交換水９００
部に両性イオン型オリゴエステル化合物（重量平均分子
量１６００）を５部溶解させて乳化剤とし、７０℃に於
いてｌＯ％水溶性アゾ化合物水溶液（和光純薬製Ｖ−５
０）２０部を添加したのち、混合モノマー（Ｂ）１００
部を２時間かけて滴下し粒径が０．０５〜０．１μのう
・；−ツクス粒子（ＩＩ［）を得た。Example 5 Using the same reaction apparatus as in Example 1, 900 ml of ion-exchanged water was used.
5 parts of a zwitterionic oligoester compound (weight average molecular weight 1600) was dissolved in 5 parts of the zwitterionic oligoester compound (weight average molecular weight: 1600) to serve as an emulsifier, and a 10% water-soluble azo compound aqueous solution (V-5 manufactured by Wako Pure Chemical Industries, Ltd.) was prepared at 70°C.
0) After adding 20 parts, 100 parts of mixed monomer (B)
was added dropwise over 2 hours to obtain U.;-Tx particles (II[) having a particle size of 0.05 to 0.1 μm.
次いで、実施例！で得られた着色粒子（Ｉ）の水分散体
４００部中に前記ラテックス（■）５部を混合して３０
分間攪拌したのち、実施例１と同条件下で噴霧乾燥、気
流粉砕しトナー（Ｖ）を得た。得られたトナー（Ｖ）粒
子を電子顕微鏡観察としたところ、着色粒子の表面全体
に微小粒子が均一に且つ球形を保って付着していること
がわかった。またこの複合粒子とキャリア鉄粉を重量比
４：９６で混合したブローオフによる帯電性を確認した
ところ＋２５μｃ／ｇの帯電量を示した。Next, examples! 5 parts of the latex (■) were mixed into 400 parts of the aqueous dispersion of the colored particles (I) obtained in 30
After stirring for a minute, the mixture was spray-dried and air-pulverized under the same conditions as in Example 1 to obtain toner (V). When the obtained toner (V) particles were observed under an electron microscope, it was found that microparticles were uniformly adhered to the entire surface of the colored particles while maintaining a spherical shape. Further, when the chargeability was confirmed by blow-off of a mixture of the composite particles and the carrier iron powder at a weight ratio of 4:96, the charge amount was +25 μc/g.
該トナー（Ｖ）とフェライト球形キャリアをｌ０＝９０
の割合で混合して現像剤（Ｖ）を得た。The toner (V) and the ferrite spherical carrier are l0=90
A developer (V) was obtained by mixing in the following ratio.
実施例６
スチレン樹脂５６重量部、カーボンブラック５重塁部、
ポリプロピレンワックス４重量部および磁性粉３５重量
部をボールミルで１２時時間式混合したのち、バレル温
度１２５°Ｃに設定した二軸押出機で溶融混練したのち
、ピンミルおよび気流粉砕機を用いて微粉砕し、気流分
級機で２０部以上粒子量が重量比１％以下、５μ以下粒
子量が重量比１％以下、平均粒径ｌＯμに分級した着色
粒子（ＩＩＩ）を得た。Example 6 56 parts by weight of styrene resin, 5 layers of carbon black,
4 parts by weight of polypropylene wax and 35 parts by weight of magnetic powder were mixed for 12 hours in a ball mill, then melted and kneaded in a twin-screw extruder set at a barrel temperature of 125°C, and then finely pulverized using a pin mill and an air flow pulverizer. Colored particles (III) were then classified using an air classifier to obtain colored particles (III) in which the amount of particles of 20 parts or more was 1% by weight or less, the amount of particles of 5 μ or less was 1% by weight or less, and the average particle size was 10 μ.
次いで、実施例５で得たラテックス（Ｉ）を入口温度１
５０℃、出口温度８５℃の条件下で噴霧乾燥機、２ｋｇ
／ｃｍ２の粉砕空気圧で気流粉砕して０゜０５〜０．１
μの微小粒子を得た。Next, the latex (I) obtained in Example 5 was heated to an inlet temperature of 1
Spray dryer under conditions of 50℃ and outlet temperature 85℃, 2kg
/cm2 of air flow crushing with a crushing air pressure of 0°05~0.1
Microparticles of μ were obtained.
かくして得られた着色粒子１００部と微小粒子１部を自
動乳鉢に仕込んだのち２５〜３０°Ｃて２０分間混合し
、更に乳鉢の温度を１１０〜１Ｉ５０Ｃとして２０分間
攪拌混合してトナー（Ｖ［）を得た。100 parts of the thus obtained colored particles and 1 part of the microparticles were placed in an automatic mortar and mixed at 25-30°C for 20 minutes, and then the temperature of the mortar was set at 110-1I50C and mixed with stirring for 20 minutes to obtain toner (V[ ) was obtained.
該トナー粒子を電子顕微鏡により観察したところ、着色
粒子の表面に微小粒子が球形を保った状態で付着してい
ることがわかった。When the toner particles were observed using an electron microscope, it was found that fine particles were adhered to the surface of the colored particles while maintaining a spherical shape.
比較例Ｉ
Ｄ−１５０にバーキュレス社製）
キャボット社製）
三洋化成製）
オリエント化学源） −
をボールミルで１２時間乾式混合したのち、バレル温度
１２５℃に設定した二軸押出機で加熱溶融混練したのち
、ビンミル及びジェットミルを用い微粉砕を行ない、気
流分級機で２０μ以上粒子量、重量比１％以下、５μ粒
子徽、重量比１％以下、平均粒子径１０μに分級したの
ち、通常のシリカ処理を施してトナー（■）を得た。Comparative Example I D-150 was dry mixed with D-150 (manufactured by Vercules)) (manufactured by Cabot)) (manufactured by Sanyo Kasei)) - in a ball mill for 12 hours, and then heated and melt-kneaded in a twin-screw extruder set at a barrel temperature of 125°C. Afterwards, it is finely pulverized using a bottle mill and a jet mill, and classified using an air classifier to have a particle amount of 20 μ or more, a weight ratio of 1% or less, a 5 μ particle size, a weight ratio of 1% or less, and an average particle size of 10 μ. After treatment, a toner (■) was obtained.
比較例２
実施例１で得た着色粒子（Ｉ）に通常のシリカ処理を施
してトナー（■）を得た。Comparative Example 2 The colored particles (I) obtained in Example 1 were subjected to a conventional silica treatment to obtain a toner (■).
該トナー（■）とキャリア鉄粉を４＝９６の割合で混合
して現像剤（■）を得た。The toner (■) and carrier iron powder were mixed in a ratio of 4=96 to obtain a developer (■).
なお、上述した８種のトナー（１〜■）について耐ブロ
ツキング性テストを行ったところ、トナー（Ｄ〜（ＶＴ
）は５５℃、２４時間でも何ら異常はなく、トナー（■
）は５０℃、２４時間でブロッキングし、トナー（■）
は５５℃、２４時間でブロッキングした。In addition, when we conducted a blocking resistance test on the above-mentioned eight types of toners (1 to ■), we found that the toners (D to (VT)
) showed no abnormalities even at 55℃ for 24 hours, and the toner (■
) is blocked at 50℃ for 24 hours, and toner (■)
was blocked at 55°C for 24 hours.
実施例１〜６および比較例１〜２で得られた８種のトナ
ー（■〜■）の特性を表１に示す。Table 1 shows the characteristics of the eight types of toners (■ to ■) obtained in Examples 1 to 6 and Comparative Examples 1 to 2.
（注）１．実施例１〜３および比較例１は松下電器社製
ＰＰＣ複写機ＦＰ−３０００、実施例５はミノルタ社製
ＰＰＣ複写機ＥＰ４５０Ｚ、実施例６は松下電器社製Ｐ
ＰＣ複写機ＦＰ−１，０００を各々用いて試験した。(Note) 1. Examples 1 to 3 and Comparative Example 1 are PPC copier FP-3000 manufactured by Matsushita Electric Co., Ltd.; Example 5 is PPC copier EP450Z manufactured by Minolta; and Example 6 is PPC copier manufactured by Matsushita Electric Co., Ltd.
The test was conducted using a PC copying machine FP-1,000.
２、実施例４は、松下電器社製ＰＰＣ複写機ＦＰ−３０
００により未定着画像を得たのち、一対の金属ロールに
る１３０℃、２００ｋｇ／ｃｍ”の加圧条件下で定着さ
せろことにより試験した。2. Example 4 is a PPC copier FP-30 manufactured by Matsushita Electric Co., Ltd.
After obtaining an unfixed image using 00, a test was carried out by fixing the image using a pair of metal rolls at 130° C. and under pressure of 200 kg/cm”.
ａ）測定方法：寿命試験前の各現像剤について、東芝ケ
ミカル社製ブローオフ粉末帯電量測定装置を使用して測
定した。なお、実施例６以外は、ファラデーゲージとし
て４００メツシユのステンレス網を、実施例６は５００
メツシユのステンレス網を用いて測定を行った。a) Measurement method: Each developer before the life test was measured using a blow-off powder charge measuring device manufactured by Toshiba Chemical. In addition, except for Example 6, a 400-mesh stainless steel mesh was used as a Faraday gauge, and Example 6 used a 500-mesh stainless steel mesh.
Measurements were carried out using mesh stainless steel mesh.
ｂ）試験１０枚目の画像濃度（初期画像濃度）および試
験１万枚目の画像濃度（試験後画像濃度）を反射濃度計
（マクベスＲＤ −９１４Ｓ；マクベス社製）を用いて
測定し、次式によより算出した。b) Measure the image density of the 10th test sheet (initial image density) and the image density of the 10,000th test sheet (post-test image density) using a reflection densitometer (Macbeth RD-914S; manufactured by Macbeth Co., Ltd.), and then It was calculated using the formula.
Ｃ）寿命試験後の帯電１をａ）と同じ方法により測定し
、次式により算出した。C) Charge 1 after the life test was measured by the same method as a) and calculated by the following formula.
ｄ）試験開始後１０００枚目までの転写率（初期転写率
）、９０００〜１０，０００枚目の転写率（最終転写率
）を各々、式（１）により算出し、次いで式（２）によ
り転写率変化を算出した。d) Calculate the transfer rate up to the 1000th sheet after the start of the test (initial transfer rate) and the transfer rate from 9000 to 10,000 sheets (final transfer rate) using formula (1), and then calculate using formula (2). Transfer rate changes were calculated.
変化率（％） 初期転写率 、−９−（
２）ｅ）微小粒子付着率は各トナーの電子顕微鏡写真上
で、トナー表面の任意箇所の５ｍ／ｍＸ５ｍ／ｍマスロ
内において微小粒子が完全に充填された場合の表面積と
該範囲内に付着している粒子の表面積の割合で示した。Rate of change (%) Initial transcription rate, -9-(
2) e) Microparticle adhesion rate is the surface area when microparticles are completely filled in a 5m/m x 5m/m mass flow at any location on the toner surface and the amount of adhesion within this range on an electron micrograph of each toner. It is expressed as a percentage of the surface area of the particles.
ｆ）セロテープの粘着面上に、各トナーを２５０メツン
ユの篩を用いて散布したのち、非粘着面からはたくこと
により付着しきれていないトナーを除去してコピー用紙
上に貼付し、非粘着面側から反射濃度計（マクベスＲＤ
−９１４Ｓ；マクベス社製）により濃度測定を行った。f) Spread each toner on the adhesive side of the cellophane tape using a 250 mt sieve, remove the toner that has not completely adhered by flicking it from the non-adhesive side, and paste it on copy paper to make it non-adhesive. Reflection densitometer from the surface side (Macbeth RD
-914S; manufactured by Macbeth), the concentration was measured.
第１図は実施例１で得られたトナーの粒子構造を示す１
０１００倍の電子顕微鏡写真である。
第１図Figure 1 shows the particle structure of the toner obtained in Example 1.
This is an electron micrograph at a magnification of 0.0100 times. Figure 1
Claims (1)
（℃）を有する粒径２〜３０μの着色熱可塑性樹脂粒子
と前記ｔ＿１（℃）より高い流出開始温度ｔ＿２℃を有
する粒径１μ以下の微小樹脂粒子とをｔ＿１以上かつｔ
＿２未満の温度で加熱処理することにより着色熱可塑性
樹脂粒子表面に微小樹脂粒子を付着させた静電写真用乾
式トナー。 ２、加熱処理が着色熱可塑性樹脂粒子の分散液中に重合
開始剤および重合性モノマーを滴下して微小球形樹脂粒
子を生成させた後に、ｔ＿１以上かつｔ＿２未満の温度
で乾燥させることにより行なわれる第１項記載の静電写
真用乾式トナー。 ３、加熱処理が着色熱可塑性樹脂粒子の分散液中に予め
合成した微小球形樹脂粒子を分散した後に、ｔ＿１以上
かつｔ＿２未満の温度で乾燥させることにより行なわれ
る第１項記載の静電写真用乾式トナ。 ４、加熱処理が予め乾燥された着色熱可塑性樹脂粒子と
微小樹脂粒子とをｔ＿１以下の温度で混合した後に、ｔ
＿１以上ｔ＿２未満の温度で加熱混合することにより行
なわれる第１項記載の静電写真用乾式トナー。[Claims] 1. Outflow start temperature t_1 in Koka type flow tester
Colored thermoplastic resin particles with a particle size of 2 to 30μ and having a temperature of t_1 or more and t
A dry toner for electrostatic photography in which fine resin particles are attached to the surface of colored thermoplastic resin particles by heat treatment at a temperature of less than _2. 2. Heat treatment is carried out by dropping a polymerization initiator and a polymerizable monomer into a dispersion of colored thermoplastic resin particles to generate microspherical resin particles, and then drying at a temperature of t_1 or more and less than t_2. The dry toner for electrostatic photography according to item 1. 3. For electrostatic photography according to item 1, wherein the heat treatment is performed by dispersing pre-synthesized microspherical resin particles in a dispersion of colored thermoplastic resin particles and then drying at a temperature of t_1 or more and less than t_2. Dry Tona. 4. After mixing the pre-dried colored thermoplastic resin particles and fine resin particles at a temperature of t_1 or less,
2. The dry toner for electrophotography according to item 1, which is produced by heating and mixing at a temperature of _1 or more and less than t_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068950A JPS62226162A (en) | 1986-03-26 | 1986-03-26 | Dry toner for electrostatic photogrpaphy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068950A JPS62226162A (en) | 1986-03-26 | 1986-03-26 | Dry toner for electrostatic photogrpaphy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62226162A true JPS62226162A (en) | 1987-10-05 |
Family
ID=13388452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61068950A Pending JPS62226162A (en) | 1986-03-26 | 1986-03-26 | Dry toner for electrostatic photogrpaphy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62226162A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6349766A (en) * | 1986-08-20 | 1988-03-02 | Toyo Ink Mfg Co Ltd | Insulating magnetic toner |
| US4980257A (en) * | 1988-01-29 | 1990-12-25 | Minolta Camera Kabushiki Kaisha | Electrostatic latent image developing toner and method for production thereof |
| US5079125A (en) * | 1989-04-28 | 1992-01-07 | Minolta Camera Kabushiki Kaisha | Three layered toner for electrophotography |
| US5204205A (en) * | 1989-04-28 | 1993-04-20 | Minolta Camera Kabushiki Kaisha | Three layered toner for electrophotography |
| WO1993023442A1 (en) * | 1992-05-11 | 1993-11-25 | Daikin Industries, Ltd. | Particulate covering material |
-
1986
- 1986-03-26 JP JP61068950A patent/JPS62226162A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6349766A (en) * | 1986-08-20 | 1988-03-02 | Toyo Ink Mfg Co Ltd | Insulating magnetic toner |
| US4980257A (en) * | 1988-01-29 | 1990-12-25 | Minolta Camera Kabushiki Kaisha | Electrostatic latent image developing toner and method for production thereof |
| US5079125A (en) * | 1989-04-28 | 1992-01-07 | Minolta Camera Kabushiki Kaisha | Three layered toner for electrophotography |
| US5204205A (en) * | 1989-04-28 | 1993-04-20 | Minolta Camera Kabushiki Kaisha | Three layered toner for electrophotography |
| WO1993023442A1 (en) * | 1992-05-11 | 1993-11-25 | Daikin Industries, Ltd. | Particulate covering material |
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