JPH04215665A - Manufacture of organic fine grain deposited with insoluble polymer - Google Patents
Manufacture of organic fine grain deposited with insoluble polymerInfo
- Publication number
- JPH04215665A JPH04215665A JP2410831A JP41083190A JPH04215665A JP H04215665 A JPH04215665 A JP H04215665A JP 2410831 A JP2410831 A JP 2410831A JP 41083190 A JP41083190 A JP 41083190A JP H04215665 A JPH04215665 A JP H04215665A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- organic fine
- insoluble
- toner
- fine particles
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002612 dispersion medium Substances 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 24
- 125000003010 ionic group Chemical group 0.000 claims description 11
- 150000003839 salts Chemical group 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-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
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical group CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920003114 HPC-L Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000007875 V-40 Substances 0.000 description 1
- AVTLBBWTUPQRAY-BUHFOSPRSA-N V-59 Substances CCC(C)(C#N)\N=N\C(C)(CC)C#N AVTLBBWTUPQRAY-BUHFOSPRSA-N 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction 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
- 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
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-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
- 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
- 239000011146 organic particle Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【０００２】本発明は、不溶性ポリマーにより表面改質
した有機微粒子の製造法に関する。特に本発明は、電子
写真現像剤等に有用で、帯電制御剤としての不溶性イオ
ン性ポリマーが粒子表面に沈着したトナーの製造法に関
する。The present invention relates to a method for producing organic fine particles whose surface has been modified with an insoluble polymer. In particular, the present invention relates to a method for producing a toner useful in electrophotographic developers and the like, in which an insoluble ionic polymer as a charge control agent is deposited on the particle surface.
【０００３】従来、帯電制御剤は、４級アンモニウム塩
（特開昭６２−５３９４４号公報及び特開平２−１６１
４６８号公報）やサリチル酸錯体（特開昭６３−２８９
５５７号公報及び同６３−２０８８６５号公報）等の低
分子化合物を用いてトナー中に分散させて製造される。Conventionally, charge control agents include quaternary ammonium salts (JP-A-62-53944 and JP-A-2-161).
468) and salicylic acid complexes (JP-A-63-289)
557 and 63-208865) by dispersing it in a toner.
【０００４】しかし、これらの低分子化合物はトナー粒
子との担持力が弱くトナーの粒子表面から脱離等を起こ
し易く、トナーの寿命の低下をきたし易いという問題を
有する。又これらのトナーは、帯電制御剤である低分子
化合物をトナーのマトリックス樹脂組成物又はマトリッ
クス用モノマー組成物と混合して製造されるため、得ら
れるトナー粒子は帯電制御剤が粒子表面以外に粒子内部
にも存在するものである。そのためこれらのトナーは、
帯電制御剤の機能効率に乏しいという問題を有する。However, these low-molecular compounds have a problem in that they have a weak supporting force with toner particles and are easily detached from the toner particle surface, which tends to shorten the life of the toner. In addition, these toners are manufactured by mixing a low-molecular-weight compound as a charge control agent with the toner matrix resin composition or matrix monomer composition. It also exists inside. Therefore, these toners are
There is a problem in that the functional efficiency of the charge control agent is poor.
【０００５】本発明の目的の１つは、帯電制御剤の機能
効率を改善し電荷交換能を向上せしめることにより、帯
電量分布、環境依存性等を改善した長寿命の帯電制御剤
を沈着した有機微粒子を容易に製造出来る製造法を提供
することである。One of the objects of the present invention is to deposit a long-life charge control agent with improved charge distribution, environmental dependence, etc. by improving the functional efficiency of the charge control agent and improving the charge exchange ability. An object of the present invention is to provide a manufacturing method that allows easy production of organic fine particles.
【０００６】上記目的を達成するため、帯電制御剤とし
て高分子化合物を用いれば、有機微粒子からの帯電制御
剤の欠落を防ぐことが出来、得られたトナーの寿命を延
ばすことが出来ることを見出した。又有機微粒子を予め
製造しておき、これを分散媒中に分散し、この分散液系
中に於いて帯電制御剤を生成析出させれば、帯電制御剤
は粒子表面にのみ担持され粒子内部には担持されること
はないので、帯電制御剤の機能効率が著しく向上するこ
とを見出した。これらの発見より本発明を成すに至った
。In order to achieve the above object, it has been discovered that by using a polymer compound as a charge control agent, it is possible to prevent the charge control agent from being missing from organic fine particles, and the life of the obtained toner can be extended. Ta. In addition, if organic fine particles are produced in advance and dispersed in a dispersion medium, and a charge control agent is generated and precipitated in this dispersion system, the charge control agent is supported only on the particle surface and is not contained inside the particle. It has been found that the functional efficiency of the charge control agent is significantly improved because it is not supported. These discoveries led to the present invention.
【０００７】即ち本発明は、（Ａ）有機微粒子、（Ｂ）
４級塩イオン性基を含有する重量平均分子量２０００〜
２０００００のポリマー、及び（Ｃ）該有機微粒子（Ａ
）が不溶で且つ該ポリマー（Ｂ）が可溶の分散媒、を含
む分散液中に、（Ｄ）該ポリマー（Ｂ）中の４級塩イオ
ン性基とイオン交換して不溶性ポリマーを析出させる不
溶化剤、を加えることにより製造される不溶性ポリマー
が沈着した有機微粒子の製造法を提供する。That is, the present invention provides (A) organic fine particles, (B)
Weight average molecular weight containing quaternary salt ionic group 2000~
200,000 polymer, and (C) the organic fine particles (A
) is insoluble and the polymer (B) is soluble in a dispersion medium, (D) is ion-exchanged with the quaternary salt ionic group in the polymer (B) to precipitate an insoluble polymer. Provided is a method for producing organic fine particles on which an insoluble polymer is deposited, which is produced by adding an insolubilizing agent.
【０００８】本発明に用いられる有機微粒子（Ａ）とは
主にトナーを意味し、公知の着色剤（例えばカーボンブ
ラック、必要に応じて離型剤、磁性粉等を含む（尚本発
明は、着色剤等を含まない有機微粒子、たとえば乳化重
合粒子等にも適用することが可能であり、用途としても
トナーに限定されるものではない。）。有機微粒子（Ａ
）の製法としては特に制限はなく、公知の混練粉砕法、
懸濁重合法、分散重合法、界面重縮合法等であってよい
。[0008] The organic fine particles (A) used in the present invention mainly mean a toner, and include a known coloring agent (for example, carbon black, a release agent, magnetic powder, etc. as necessary) (in the present invention, It can also be applied to organic fine particles that do not contain colorants, such as emulsion polymerized particles, and the application is not limited to toner.) Organic fine particles (A
) There are no particular restrictions on the manufacturing method, and known kneading and grinding methods,
A suspension polymerization method, a dispersion polymerization method, an interfacial polycondensation method, etc. may be used.
【０００９】本発明で用いる有機微粒子（Ａ）のマトリ
ックス樹脂としては、ポリスチレン、ポリビニルトルエ
ンなどのスチレン及びその置換体の重合体、スチレン−
置換スチレン共重合体、スチレン−アクリル酸エステル
系の共重合体、スチレン−メタアクリル酸エステル系の
共重合体、スチレン−アクリロニトリル共重合体、ポリ
塩化ビニル系、ポリエチレン、シリコーン樹脂、ポリエ
ステル、ポリウレタン、ポリアミド、エポキシ樹脂、変
性ロジン、フェノール樹脂などがあげられる。有機微粒
子（Ａ）の重量平均粒子径は、０．１〜１００μｍ、特
にトナーとしては３〜１２μｍが好ましい。As the matrix resin of the organic fine particles (A) used in the present invention, polymers of styrene and its substituted products such as polystyrene and polyvinyltoluene, and styrene-
Substituted styrene copolymers, styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, styrene-acrylonitrile copolymers, polyvinyl chloride, polyethylene, silicone resins, polyesters, polyurethanes, Examples include polyamide, epoxy resin, modified rosin, and phenolic resin. The weight average particle diameter of the organic fine particles (A) is preferably 0.1 to 100 μm, particularly 3 to 12 μm for toner.
【００１０】本発明に用いるポリマー（Ｂ）は、４級塩
イオン性基を含有する。４級塩イオン性基としては、例
えば式The polymer (B) used in the present invention contains a quaternary salt ionic group. As the quaternary salt ionic group, for example, the formula
【００１１】[0011]
【化１】[Chemical formula 1]
【００１２】で表わされる４級アンモニウム塩基が挙げ
られ、これらの１種以上含有してよい。式（化１）にお
いてＲの具体例としては、メチル基、エチル基、プロピ
ル基、ブチル基、ペンチル基、ヘキシル基、オクチル基
、ノニル基、デシル基、ドデシル基、テトラデシル基、
ヘキサデシル基、オクタデシル基、ヘキシル基などのア
ルキル基；及びフェニル基、ナフチル基、トリル基、ベ
ンジル基、ｐ−クロルベンジル基、フェネチル基、アン
スリル基などの無置換若しくは置換フェニル基などがあ
げられる。Ａ−としては、例えば（Ｍｏ７Ｏ２４）６−
、（Ｈ２Ｗ１２Ｏ４２）１０−、及び（ＳｉＷ１２Ｏ４
０）４−、（ＢＷ１２Ｏ４０）５−、（ＢＭｏ１２Ｏ４
０）５−等のヘテロポリ酸アニオンが挙げられる。上記
４級塩イオン性基は、１分子中に２〜１００モル％有す
るのが好ましい。イオン性基が５モル％より少ないと帯
電制御能力に乏しくとなり、又９５モル％を超えると担
持処理中に粒子間凝集を起こし易い。ポリマーの重量平
均分子量は、２０００〜２０００００、特に１０，００
０〜１００，０００が好ましい。分子量が２０００未満
では効果に乏しく、２００，０００を超えると処理時に
粒子間凝集を起こし易いので好ましくない。そのような
ポリマー（Ｂ）は、４級塩イオン性基を含むビニル単量
体（以下、単に「４級塩ビニルモノマー」と云う。）と
その他のビニルモノマーとのコポリマーが好ましいが、
４級塩ビニルモノマーのみからなるホモポリマーであっ
てもよい。４級塩ビニルモノマーとしては、例えばＣＨ
２＝ＣＨ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｎ＋（ＣＨ３）
３・Ｃｌ−、ＣＨ２＝ＣＨ・ＣＯＮＨＣ３Ｈ６Ｎ＋（Ｃ
Ｈ３）３・Ｃｌ−等が挙げられ、これらの１種以上を使
用してよい。上記その他のビニルモノマーとしては、例
えばスチレン、メチルメタアクリレート、ｎ−ブチルメ
タアクリレート、２−エチルヘキシルアクリレート、エ
チルアクリレート等が挙げられ、これらの１種以上を使
用してよい。重合法は特に限定されないが、例えば通常
の乳化重合、溶液重合等であってよい。又共重合の場合
、例えば予め４級塩ビニルモノマーを単独重合して４級
塩イオン性基を含むプレポリマーとし、次いでその他の
ビニルモノマーを加えグラフト重合して調製してよい。
或るいは、４級塩ビニルモノマーとその他のビニルモノ
マーとを混合し共重合して調製してもよい。又３級アミ
ンビニルモノマーと他のモノマーとを共重合した後に４
級化してもよい。４級塩ビニルモノマーの使用量は、全
モノマーに対し２モル％以上、特に１０モル％以上が好
ましい。Examples include quaternary ammonium bases represented by the following, and one or more of these may be contained. Specific examples of R in formula (Chemical formula 1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group,
Examples thereof include alkyl groups such as hexadecyl, octadecyl, and hexyl; and unsubstituted or substituted phenyl groups such as phenyl, naphthyl, tolyl, benzyl, p-chlorobenzyl, phenethyl, and anthryl. As A-, for example, (Mo7O24)6-
, (H2W12O42)10-, and (SiW12O4
0)4-, (BW12O40)5-, (BMo12O4
Examples include heteropolyacid anions such as 0)5-. The quaternary salt ionic group is preferably present in an amount of 2 to 100 mol % in one molecule. If the ionic group content is less than 5 mol %, the charge control ability will be poor, and if it exceeds 95 mol %, interparticle aggregation is likely to occur during the loading process. The weight average molecular weight of the polymer is 2000 to 200000, especially 10,000
0 to 100,000 is preferred. If the molecular weight is less than 2,000, the effect is poor, and if it exceeds 200,000, interparticle aggregation tends to occur during processing, which is not preferred. Such a polymer (B) is preferably a copolymer of a vinyl monomer containing a quaternary salt ionic group (hereinafter simply referred to as "quaternary salt vinyl monomer") and another vinyl monomer,
A homopolymer consisting only of quaternary vinyl chloride monomers may also be used. As the quaternary vinyl chloride monomer, for example, CH
2=CH(CH3)COOCH2CH2N+(CH3)
3・Cl−, CH2=CH・CONHC3H6N+(C
Examples include H3)3.Cl-, and one or more of these may be used. Examples of the other vinyl monomers include styrene, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, and ethyl acrylate, and one or more of these may be used. The polymerization method is not particularly limited, but may be, for example, ordinary emulsion polymerization, solution polymerization, etc. In the case of copolymerization, for example, a quaternary salt vinyl monomer may be homopolymerized in advance to obtain a prepolymer containing a quaternary salt ionic group, and then other vinyl monomers may be added and graft polymerized to prepare the prepolymer. Alternatively, it may be prepared by mixing and copolymerizing a quaternary vinyl chloride monomer and other vinyl monomers. Also, after copolymerizing the tertiary amine vinyl monomer and other monomers, 4
May be graded. The amount of the quaternary vinyl chloride monomer used is preferably 2 mol% or more, particularly 10 mol% or more, based on the total monomers.
【００１３】本発明に使用する分散媒（Ｃ）は、前記有
機微粒子（Ａ）を溶解せず且つ上記ポリマー（Ｂ）を溶
解するものである。そのような分散媒（Ｃ）としては、
例えば水、アルコール類、セロソルブ類等が挙げられ、
これらの１種以上を使用してよい。具体的には、アルコ
ール類としては例えばメタノール、エタノール、イソプ
ロパノール、ｎ−ブタノール、イソブタノール等が挙げ
られる。又、セロソルブ類としては、例えばメチルセロ
ソルブ、エチルセロソルブ等が挙げられる。The dispersion medium (C) used in the present invention is one that does not dissolve the organic fine particles (A) but dissolves the polymer (B). As such a dispersion medium (C),
Examples include water, alcohols, cellosolves, etc.
One or more of these may be used. Specifically, examples of alcohols include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of cellosolves include methyl cellosolve and ethyl cellosolve.
【００１４】本発明に於いて分散液は、前記成分（Ａ）
及び（Ｂ）を分散媒（Ｃ）中に配合し撹拌混合すること
により調製されるが、分散液にはその他添加剤としてポ
リビニルアルコール、ヒドロキシプロピルセルロース、
ポリアクリル酸、ポリオキシエチレン等の保護コロイド
等を加えてもよい。[0014] In the present invention, the dispersion liquid contains the above component (A).
It is prepared by blending and (B) into a dispersion medium (C) and stirring and mixing, but the dispersion also contains polyvinyl alcohol, hydroxypropyl cellulose, and other additives.
Protective colloids such as polyacrylic acid and polyoxyethylene may also be added.
【００１５】本発明の不溶性ポリマーが沈着した有機微
粒子は、上記分散液中に不溶化剤（Ｄ）を加えることに
より、製造される。不溶化剤（Ｄ）は、前記ポリマー（
Ｂ）中に含まれる４級塩イオン性基とイオン交換して不
溶性のイオン性ポリマーを析出させるものである。化合
物（Ｄ）の具体例としては、例えばモリブデン酸塩［（
Ｍｏ７Ｏ２４）６−（ＮＨ４）６＋、（ＰＭｏ１２Ｏ４
０）３−（ＮＨ４）３＋等］、及び式The organic fine particles on which the insoluble polymer of the present invention is deposited are produced by adding an insolubilizing agent (D) to the above dispersion. The insolubilizing agent (D) is the polymer (
B) The insoluble ionic polymer is precipitated by ion exchange with the quaternary salt ionic group contained in B). Specific examples of compound (D) include molybdate [(
Mo7O24)6-(NH4)6+, (PMo12O4
0)3-(NH4)3+ etc.], and the formula
【００１６】[0016]
【化２】[Case 2]
【００１７】で表わされる化合物等が挙げられ、これら
の一種以上使用してよい。式（化２）に於いて、Ｒ１は
水素又はＣ１−Ｃ２２アルキル基である。Ｃ１−Ｃ２２
アルキル基としては、前記Ｒに於いて例示したアルキル
基等が挙げられる。式（化２）で表わされる化合物の具
体例としては、例えばテトラフェニルボレートナトリウ
ム、テトラトリルボレートナトリウム等が挙げられる。Examples include compounds represented by the following, and one or more of these may be used. In formula (Chemical formula 2), R1 is hydrogen or a C1-C22 alkyl group. C1-C22
Examples of the alkyl group include the alkyl groups exemplified for R above. Specific examples of the compound represented by formula (Chemical formula 2) include sodium tetraphenylborate, sodium tetratolylborate, and the like.
【００１８】本発明の配合組成に於いて、分散媒（Ｃ）
１００重量部に対し、有機微粒子（Ａ）は２〜８０重量
部、有機微粒子１００重量部に対しポリマー（Ｂ）は０
．０５〜２５重量部及び不溶化剤（Ｄ）は０．０２〜４
５重量部がそれぞれ好ましい。In the formulation of the present invention, the dispersion medium (C)
2 to 80 parts by weight of organic fine particles (A) per 100 parts by weight, and 0 parts of polymer (B) per 100 parts by weight of organic fine particles.
．． 05-25 parts by weight and insolubilizer (D) is 0.02-4
5 parts by weight each is preferred.
【００１９】上記のようにして、本発明の不溶性物質を
沈着した有機微粒子が得られるが、沈着・担持状態を確
実なものとするために担持処理後更に４０〜９０℃で熱
処理してもよい。熱処理は撹拌下に加熱するだけでよい
。４０℃未満では効果が少なく、９０℃を超えると有機
微粒子間で融着現象を生じるので好ましくない。[0019] As described above, organic fine particles having the insoluble substance of the present invention deposited thereon can be obtained, but in order to ensure the deposited and supported state, the particles may be further heat-treated at 40 to 90°C after the supporting treatment. . For heat treatment, simply heating while stirring is sufficient. If the temperature is lower than 40°C, the effect will be small, and if the temperature exceeds 90°C, a phenomenon of fusion will occur between the organic fine particles, which is not preferable.
【００２０】上記のようにして得られる本発明の有機微
粒子は、その表面上に不溶性ポリマー（即ち帯電制御剤
）が沈着・担持されたものである。The organic fine particles of the present invention obtained as described above have an insoluble polymer (ie, a charge control agent) deposited and supported on their surfaces.
【００２１】不溶性ポリマーの沈着・担持量は、粒子全
重量に対し、ポリマー（Ｂ）分で０．０５〜２５重量％
、特に０．１〜１０重量％が好ましい。２５重量％を超
えると、経済性に乏しいので好ましくない。The amount of the insoluble polymer deposited and supported is 0.05 to 25% by weight of the polymer (B) based on the total weight of the particles.
, particularly preferably 0.1 to 10% by weight. If it exceeds 25% by weight, it is not economical and therefore undesirable.
【００２２】[0022]
【発明の効果】本発明により、機能効率を改善した有機
微粒子、特に帯電制御効率を改善したトナーを容易に製
造することが出来る。又本発明によって製造される有機
微粒子は、その表面上に不溶性ポリマーが竪固に担持さ
れているので粒子の寿命が長く、更に不溶性ポリマーが
表面に被覆されることにより耐ブロッキング性、粉体流
動性が向上する。又本発明の製造法は、低温定着トナー
、圧力定着トナー等のマイクロカプセルトナー等へも応
用可能である。According to the present invention, organic fine particles with improved functional efficiency, particularly toner with improved charge control efficiency, can be easily produced. In addition, the organic fine particles produced by the present invention have a long lifetime because the insoluble polymer is solidly supported on the surface of the organic particles, and the coating of the insoluble polymer on the surface improves blocking resistance and powder flow. Improves sex. The manufacturing method of the present invention can also be applied to microcapsule toners such as low temperature fixing toners and pressure fixing toners.
【００２３】[0023]
【実施例】以下本発明を、実施例で具体的に説明する。
参考例（１）：懸濁重合法によるトナーの製造
（重量部） スチレンモ
ノマー
８５ ２−エチル
ヘキシルアクリレート
１５ Ｒｅｇａｌ３３０Ｒ（Ｃａ
ｂｏｔ）
１０ Ｓｏｌｓｐｅｒｃｅ＃
５０００
０．２ スチレン／
アクリエステルＰＡ（三菱レイヨン）
１０ ９０／１０共重合体
アクリル変性ワックス（三洋化成）
１７．５
ラウロイルパーオキシド
１．５
Ｖ−４０
１．５からなる分散液を、以下の組成の水溶液中に撹拌
下に投入し、９０℃で７時間重合した。[Examples] The present invention will be specifically explained below with reference to Examples. Reference example (1): Production of toner by suspension polymerization method
(Parts by weight) Styrene monomer
85 2-ethylhexyl acrylate
15 Regal330R (Ca
bot)
10 Solspace#
5000
0.2 Styrene/
Acryester PA (Mitsubishi Rayon)
10 90/10 copolymer acrylic modified wax (Sanyo Chemical)
17.5
lauroyl peroxide
1.5
V-40
A dispersion of 1.5 was added to an aqueous solution having the following composition under stirring, and polymerized at 90°C for 7 hours.
【００２４】
（重量部） イオン交換水
４５０ ヒドロキシエチル
セルロース（ダイセル）
１２ ポリエチレングリコールノニルフ
ェニルエーテル（花王） １．２ ヨ
ウ化カリウム
０．
０４５得られたトナーの粒子径は８．２μｍであり、３
回イオン交換水にて洗浄し、水分散状態で保存した。[0024]
(Parts by weight) Ion exchange water
450 Hydroxyethyl cellulose (Daicel)
12 Polyethylene glycol nonylphenyl ether (Kao) 1.2 Potassium iodide
0.
045 The particle size of the obtained toner was 8.2 μm, and 3
It was washed twice with ion-exchanged water and stored in an aqueous dispersion state.
【００２５】参考例（２）：分散重合法によるトナーの
製造
（重量部） スチレンモノマー
７０ ｎ−ブチルメタク
リレート
３０ Ｒｅｇａｌ３３０Ｒ
（Ｃａｂｏｔ）
１０ フタロシア
ニンブルー（大日精化）
０．５ ε−カプロラ
クトン１８量体の末端カルボン酸変性物
７．５ アクリル変性ワックス（三洋化成）
１７
．５ Ｖ−５９（和光）
３．０からなる分散液を、以下の組成の溶
液中に投入して、６５℃で２２時間重合した。Reference Example (2): Production of toner by dispersion polymerization method
(Parts by weight) Styrene monomer
70 n-butyl methacrylate
30 Regal330R
(Cabot)
10 Phthalocyanine Blue (Dainichiseika)
0.5 ε-caprolactone 18-mer modified with terminal carboxylic acid
7.5 Acrylic modified wax (Sanyo Chemical)
17
．． 5 V-59 (Wako)
A dispersion liquid consisting of 3.0 was added to a solution having the following composition and polymerized at 65° C. for 22 hours.
【００２６】
（
重量部） イソプロパノール
３２０
イオン交換水
８０
ＨＰＣ−Ｌ（日本曹達）
１０得られたトナーの
粒径は７．０μｍであり、イソプロパノール／イオン交
換水混合液（５０／５０）で３回洗浄しその後水置換し
て保存した。参考例（３）：分散重合法による低Ｔｇト
ナーの製造[0026]
(
parts by weight) isopropanol
320
ion exchange water
80
HPC-L (Nippon Soda)
10 The particle size of the obtained toner was 7.0 μm, and it was washed three times with an isopropanol/ion-exchanged water mixture (50/50), then replaced with water, and stored. Reference example (3): Production of low Tg toner by dispersion polymerization method
【００２７】参考例（２）において、ｎ−ブチルメタク
リレートを２エチルヘキシルアクリレートに替えた以外
は参考例（２）と同様にしてトナーを製造した。得られ
たトナーの粒子径は６．５μｍであった。参考例（４）
：ポリカチオンを含有する乳化重合ラテックスの製造
（重量部） イオン交換水
３６０ 分子鎖末端にＳＨ基を有す
る４級塩ポリマー ２０（重合
度約３００、モノマーはジメチルアミノプロピルメタク
リルアミド４級化物、クラレ（株）製）からなる水溶液
を７５℃まで加熱し、下記組成物を加えて３．５時間重
合した。A toner was produced in the same manner as in Reference Example (2) except that n-butyl methacrylate was replaced with 2-ethylhexyl acrylate. The particle size of the obtained toner was 6.5 μm. Reference example (4)
: Production of emulsion polymerization latex containing polycations
(Parts by weight) Ion exchange water
360 An aqueous solution consisting of quaternary salt polymer 20 (degree of polymerization: about 300, monomer is dimethylaminopropylmethacrylamide quaternized product, manufactured by Kuraray Co., Ltd.) having an SH group at the end of the molecular chain was heated to 75°C to form the following composition. was added and polymerized for 3.5 hours.
【００２８】
（重量部） イオン交換水
４０ Ｖ−５０（和光）
２．０ スチレンモ
ノマー
６０ メチルメタ
クリレート
４０これにより、ポリカチオ
ン基が化学的に吸着した粒子径１６０ｎｍのポリマーラ
テックスを得た。[0028]
(Parts by weight) Ion exchange water
40 V-50 (Wako)
2.0 Styrene monomer
60 Methyl methacrylate
40 As a result, a polymer latex with a particle size of 160 nm to which polycationic groups were chemically adsorbed was obtained.
【００２９】実施例（１）
参考例（１）のトナーの水分散物（トナー分１００ｇｒ
）に参考例（４）のラテックス（樹脂分２．０ｇｒ）加
えた後、モリブデン酸アンモニウム０．３４ｇｒを加え
て１０分間撹拌し、遠心分離後４０℃で熱風乾燥した。Example (1) Aqueous dispersion of the toner of Reference Example (1) (toner content: 100 gr
) was added to the latex of Reference Example (4) (resin content: 2.0 gr), and then 0.34 gr of ammonium molybdate was added, stirred for 10 minutes, centrifuged, and dried with hot air at 40°C.
【００３０】実施例（２）
参考例（２）のトナー水分散物（トナー分１００ｇｒ）
にカチオマー３００（三洋化成製）を０．５ｇｒ加えた
後、テトラフェニルボレートナトリウム塩を０．６５ｇ
ｒ加えて１０分間撹拌した。これを実施例（１）と同様
にして乾燥した。Example (2) Toner aqueous dispersion of Reference Example (2) (toner content: 100 gr)
After adding 0.5g of Cationomer 300 (manufactured by Sanyo Chemical) to the solution, 0.65g of tetraphenylborate sodium salt was added.
r and stirred for 10 minutes. This was dried in the same manner as in Example (1).
【００３１】実施例（３）
参考例（３）のトナーの水分散物（トナー分１００ｇｒ
）にカチオマー３００（三洋化成製）２．５ｇｒ及びセ
チルトリメチルアンモニウムクロライド０．５ｇｒを加
えた後、モリブデン酸アンモニウムを逐次添加してトナ
ー外殻層に新たにポリマー層を形成した。これを実施例
（１）と同様にして乾燥したがブロッキング等は生じな
かった。Example (3) An aqueous dispersion of the toner of Reference Example (3) (toner content: 100 gr
) were added with 2.5 gr of Catiomer 300 (manufactured by Sanyo Kasei) and 0.5 gr of cetyltrimethylammonium chloride, and then ammonium molybdate was successively added to form a new polymer layer on the toner outer shell layer. This was dried in the same manner as in Example (1), but no blocking or the like occurred.
【００３２】比較例（１）
参考例（２）のトナーを表面処理することなくそのまま
乾燥した。Comparative Example (1) The toner of Reference Example (2) was dried as it was without surface treatment.
【００３３】比較例（２）
参考例（３）のトナーを実施例（１）と同様に乾燥しよ
うとしたが、トナーのブロッキングが甚だしかった。Comparative Example (2) An attempt was made to dry the toner of Reference Example (3) in the same manner as in Example (1), but the blocking of the toner was severe.
【００３４】（画像評価試験）
実施例（１）〜（３）、比較例（１）の各トナーをキャ
リアーと混合し、シャープＳＦ８８００改造機にて画像
評価を行ったところ、実施例（１）〜（３）の各トナー
はかぶりのない鮮明な画像が得られたのに対し、比較例
（１）のトナーはかぶりが甚だしかった。又実施例（３
）のトナーはヒートロールの温度を１３５℃に下げても
充分な定着が可能であった。(Image evaluation test) Each of the toners of Examples (1) to (3) and Comparative Example (1) was mixed with a carrier, and image evaluation was performed using a modified Sharp SF8800 machine. The toners of Comparative Example (1) had severe fogging, whereas the toners of Comparative Example (1) produced clear images with no fog. Also, Example (3
) toner could be sufficiently fixed even when the temperature of the heat roll was lowered to 135°C.
Claims (1)
ン性基を含有する重量平均分子量２０００〜２００００
０のポリマー、及び（Ｃ）該有機微粒子（Ａ）が不溶で
且つ該ポリマー（Ｂ）が可溶の分散媒、を含む分散液中
に、（Ｄ）該ポリマー（Ｂ）中の４級塩イオン性基とイ
オン交換して不溶性ポリマーを析出させる不溶化剤、を
加えることにより製造される不溶性ポリマーが沈着した
有機微粒子の製造法。Claim 1: (A) organic fine particles, (B) quaternary salt containing an ionic group and having a weight average molecular weight of 2,000 to 20,000.
0 polymer, and (C) a dispersion medium in which the organic fine particles (A) are insoluble and the polymer (B) is soluble, (D) the quaternary salt in the polymer (B). A method for producing organic fine particles on which an insoluble polymer is deposited, which is produced by adding an insolubilizing agent that precipitates an insoluble polymer by ion exchange with an ionic group.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2410831A JPH04215665A (en) | 1990-12-14 | 1990-12-14 | Manufacture of organic fine grain deposited with insoluble polymer |
| CA002057126A CA2057126A1 (en) | 1990-12-07 | 1991-12-05 | Production of surface-modified organic particles |
| US07/803,418 US5190844A (en) | 1990-12-07 | 1991-12-06 | Production of surface-modified organic particles |
| EP91120999A EP0490300B1 (en) | 1990-12-07 | 1991-12-06 | Process for the production of surface-modified electrophotographic toner particles |
| DE69129144T DE69129144T2 (en) | 1990-12-07 | 1991-12-06 | Process for the production of surface-modified electrophotographic toner particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2410831A JPH04215665A (en) | 1990-12-14 | 1990-12-14 | Manufacture of organic fine grain deposited with insoluble polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04215665A true JPH04215665A (en) | 1992-08-06 |
Family
ID=18519928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2410831A Pending JPH04215665A (en) | 1990-12-07 | 1990-12-14 | Manufacture of organic fine grain deposited with insoluble polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04215665A (en) |
-
1990
- 1990-12-14 JP JP2410831A patent/JPH04215665A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1793281B1 (en) | Toner composition and method | |
| JPH05197203A (en) | Electrostatic charge image developing toner and electrostatic charge image developing two-component developer | |
| WO2007099693A1 (en) | Toner | |
| JPH04151671A (en) | Manufacture of toner | |
| JP3100392B2 (en) | Method for producing toner for developing electrostatic latent image and toner for developing electrostatic latent image | |
| US4758492A (en) | Weakly acidic crosslinked vinyl polymer particles and coating compositions and electrographic elements and developers containing such particles | |
| KR102014546B1 (en) | Powder coated carrier | |
| JPS5950449A (en) | Electrostatic image developing toner and its manufacture | |
| JPS603181B2 (en) | Method for manufacturing magnetic toner | |
| JP3531980B2 (en) | Binder resin for toner and positively chargeable toner containing the same | |
| JP2984540B2 (en) | Electrostatic image developing toner and method of manufacturing toner | |
| US5190844A (en) | Production of surface-modified organic particles | |
| JP3158713B2 (en) | Electrophotographic toner | |
| CN104185818B (en) | Toner for developing electrostatic latent image | |
| JPH08320593A (en) | Bonding resin and toner for developing electrostatic charge image containing same | |
| JPS58159546A (en) | Toner resin for developing electrostatic image | |
| JPH04215665A (en) | Manufacture of organic fine grain deposited with insoluble polymer | |
| US5334480A (en) | Capsule toner | |
| US5215851A (en) | Electrophotographic toner | |
| JPH05142863A (en) | Electrophotographic toner | |
| JPH0561251A (en) | Electrostatic charge image developing toner | |
| JPS63226661A (en) | Developer for electrostatic charge image | |
| JPS59127064A (en) | Electrophotographic dry type developer | |
| JPH04213464A (en) | Production of organic fine particles deposited with insoluble material | |
| JP2547011B2 (en) | Toner for electrostatic image development |