JPH04289868A - Electrophotographic carrier - Google Patents
Electrophotographic carrierInfo
- Publication number
- JPH04289868A JPH04289868A JP3077145A JP7714591A JPH04289868A JP H04289868 A JPH04289868 A JP H04289868A JP 3077145 A JP3077145 A JP 3077145A JP 7714591 A JP7714591 A JP 7714591A JP H04289868 A JPH04289868 A JP H04289868A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- toner
- polymer
- group
- pendant
- 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 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000004793 Polystyrene Substances 0.000 claims abstract description 8
- 229920002223 polystyrene Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 33
- 239000011347 resin Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 32
- 150000002357 guanidines Chemical class 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000011162 core material Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- ABPSJVSWZJJPOQ-UHFFFAOYSA-N 3,4-ditert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C(O)=C1C(C)(C)C ABPSJVSWZJJPOQ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HFXVXHPSVLHXCC-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC1=CC=CC=C1 HFXVXHPSVLHXCC-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- NSIWGZFZGMIPEC-UHFFFAOYSA-N 2-propoxyethyl 2-methylprop-2-enoate Chemical compound CCCOCCOC(=O)C(C)=C NSIWGZFZGMIPEC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- -1 Chlormethyl Chemical group 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、トナーと共に静電荷像
現像剤を構成する電子写真用キャリアに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic carrier which constitutes an electrostatic image developer together with a toner.
【０００２】0002
【従来の技術】従来、電子写真法としては米国特許第２
２９７６９１号公報、特公昭４２−２３９１０号公報及
び特公昭４３−２４７４８号公報等に、種々の方法が記
載されている。それらは、光導電性絶縁体層上に一様な
静電荷を与え、該絶縁体層に光像を照射することによっ
て静電潜像を形成し、次いで該潜像を当該技術分野でト
ナーと呼ばれている微粉末によって現像可視化し、必要
に応じて紙等に粉像を転写した後、加熱、加圧、或は溶
剤蒸気等によって定着を行うものである。[Prior Art] Conventionally, as an electrophotographic method, US Pat.
Various methods are described in Japanese Patent Publication No. 297691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc. They impart a uniform electrostatic charge onto a photoconductive insulator layer, form an electrostatic latent image by irradiating the insulator layer with a light image, and then convert the latent image into a toner as known in the art. The image is developed and visualized using a so-called fine powder, and if necessary, the powder image is transferred to paper or the like, and then fixed by heating, pressure, solvent vapor, or the like.
【０００３】これらの電子写真法等に適用される現像方
法としては、大別して乾式現像法と湿式現像法がある。
乾式現像法は、更に、トナーを搬送するキャリアを含有
する二成分系現像剤を用いる方法と、これを用いない一
成分系現像剤を用いる方法とに二分される。又、二成分
系現像方法に属するものには、トナーを搬送するキャリ
アの種類により、鉄粉キャリアを用いるマグネットブラ
シ法、ビーズ・キャリアを用いるカスケード法、ファー
を用いるファーブラシ法等がある。一方、一成分系現像
方法に属するものには、トナー粒子を噴霧状態にして用
いるパウダークラウド法、トナー粒子を直接的に静電潜
像面に接触させて現像する接触現像法（コンタクト現像
又はトナー現像ともいう）、トナー粒子を静電潜像面に
直接接触させずにトナー粒子を荷電して静電潜像の有す
る電界により該潜像面に向けて飛行させるジャピング現
像法、磁性の導電性トナーを静電潜像面に接触させて現
像するマグネドライ法等がある。The developing methods applied to these electrophotographic methods are broadly divided into dry developing methods and wet developing methods. Dry developing methods are further divided into methods using a two-component developer containing a carrier for transporting the toner, and methods using a one-component developer without such a carrier. Further, the two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner. On the other hand, methods belonging to one-component development methods include the powder cloud method, in which toner particles are sprayed, and the contact development method (contact development or toner development method, in which toner particles are brought into direct contact with the electrostatic latent image surface for development). japing development method, in which toner particles are charged and flown toward the latent image surface by the electric field of the electrostatic latent image without directly contacting the electrostatic latent image surface; magnetic conductivity; There is the MagneDry method, which develops by bringing toner into contact with the electrostatic latent image surface.
【０００４】これらの種々の現像法に適用するトナーと
しては、従来、天然樹脂或は合成樹脂中に染料、顔料を
分散した微粉末が使用されている。例えば、ポリスチレ
ン等の結着樹脂中に着色剤を分散させたものを、１〜３
０μｍ程度の粒子に微粉砕したものがトナーとして用い
れらている。又、磁性トナーとしては、更にマグネタイ
ト等の磁性体粒子を結着樹脂中に含有せしめたものが用
いられている。上記の二成分系現像剤を用いる方式の場
合には、これらのトナーが通常ガラスビーズ、鉄粉等の
キャリア粒子と混合されて用いられる。[0004] As toners applied to these various developing methods, fine powders in which dyes and pigments are dispersed in natural resins or synthetic resins have conventionally been used. For example, if a colorant is dispersed in a binder resin such as polystyrene, 1 to 3
Finely pulverized particles of approximately 0 μm are used as toner. Further, as the magnetic toner, one in which magnetic particles such as magnetite are further contained in a binder resin is used. In the case of the method using the above two-component developer, these toners are usually mixed with carrier particles such as glass beads and iron powder.
【０００５】又、トナーは、現像される静電潜像の極性
に応じて正又は負の電荷がトナーに保有される様にする
。この際、トナーに電荷を保有させる手段としては、ト
ナーの主要成分である結着樹脂の摩擦帯電性のみを利用
して帯電させる方法があるが、この方法ではトナーの帯
電性が小さい為、現像により得られる画像はカブリ易く
、不鮮明なものとなるという問題がある。そこで、トナ
ーと摩擦帯電するキャリアの表面を、強い帯電付与能力
を有している材料で被覆することでトナーに良好な帯電
性を付与することが提案されている。この場合は、従来
の様にトナー中に帯電を制御する為の添加剤を含有させ
る必要が通常ない為、例えば、添加剤によるキャリアや
感光体等への汚染が生ずることがない。この為、耐久中
に帯電性が低下したり、潜像が乱れたりすることがない
。又、カラートナーを容易に帯電させることも出来る。[0005] Furthermore, the toner has a positive or negative charge depending on the polarity of the electrostatic latent image to be developed. At this time, there is a method of charging the toner using only the triboelectricity of the binder resin, which is the main component of the toner, but since the toner's chargeability is small, this method There is a problem that the image obtained by this method is easily fogged and becomes unclear. Therefore, it has been proposed to impart good chargeability to the toner by coating the surface of a carrier that is triboelectrically charged with the toner with a material having a strong charge imparting ability. In this case, unlike conventional toners, there is usually no need to include additives for controlling charging, so that, for example, contamination of carriers, photoreceptors, etc. by additives does not occur. Therefore, during durability, the charging property does not deteriorate and the latent image is not disturbed. Furthermore, color toner can be easily charged.
【０００６】トナーに電荷を保有せしめる為の別の方法
として、トナー自体に帯電を制御する為の荷電制御剤を
含有させる場合もあるが、この場合には、トナーに含有
せしめた荷電制御剤のみでは、帯電能力が温湿度の変化
に対して十分安定で、且つ十分に高い摩擦帯電能力を有
するトナーや、現像器内でのキャリアとの混合撹拌によ
り速やかに所定の帯電量にまで立ち上がり得るトナーを
実現することは困難である。更に、カラートナーに用い
ることを考えれば有色の荷電制御剤は使えないという様
な制約を受けるという問題もある。従って、トナー自体
に帯電制御剤を含有せしめる場合においても、上述した
トナーに対して帯電付与能力を有する材料で表面を被覆
したキャリアを用いることは有効である。Another method for making the toner retain electric charge is to include a charge control agent in the toner itself to control the charge, but in this case, only the charge control agent contained in the toner is used. Now, we need a toner whose charging ability is sufficiently stable against changes in temperature and humidity and a sufficiently high triboelectric charging ability, and a toner that can quickly rise to a predetermined amount of charge by mixing and stirring with carrier in a developing device. It is difficult to realize this. Furthermore, when considering use in color toners, there is a problem in that colored charge control agents cannot be used. Therefore, even when the toner itself contains a charge control agent, it is effective to use a carrier whose surface is coated with a material capable of imparting charge to the above-mentioned toner.
【０００７】[0007]
【発明が解決しようとする問題点】しかしながら、この
場合キャリアに良好な帯電付与性をもたせる為には、上
記の材料は強い帯電付与能力を有し、且つ、キャリアに
対し被覆可能な材料であるか、又は被覆材料中に分散可
能な化合物でなければならない。又、キャリアは一般に
長期間交換しないものである為、機械的又は耐久的にも
強いものでなければならない。[Problems to be Solved by the Invention] However, in order to give the carrier good chargeability, the above-mentioned material must have a strong chargeability and be able to coat the carrier. or it must be a compound that can be dispersed in the coating material. Furthermore, since the carrier is generally not replaced for a long period of time, it must be mechanically and durable as well.
【０００８】従って、本発明の目的は、上記の従来技術
の問題点を解決した新規な電子写真用キャリアを提供す
ることにある。即ち、本発明の目的は、トナーに適正な
負電荷を付与し得る新規なキャリアを提供することにあ
り、更に、温度、湿度等の環境変動に対し、トナーが十
分に高く安定した帯電量を有することの出来る新規キャ
リアを提供することにある。又、本発明の別の目的は、
現像器内での混合撹拌により、速やかにトナーが所望の
帯電量にまで立ち上がり得る新規キャリア、更には、長
期間の使用であっても性能の劣化のない新規キャリアを
提供することにある。更に、本発明の別の目的は、トナ
ーのカラー化に適した帯電付与能力が改善された新規キ
ャリアを提供することにある。[0008] Accordingly, an object of the present invention is to provide a new electrophotographic carrier that solves the problems of the prior art described above. That is, an object of the present invention is to provide a new carrier that can impart an appropriate negative charge to toner, and furthermore, to provide a new carrier that can provide a sufficiently high and stable charge amount to toner against environmental changes such as temperature and humidity. The goal is to provide new carriers that people can have. Moreover, another object of the present invention is to
It is an object of the present invention to provide a new carrier in which toner can quickly rise to a desired charge amount by mixing and stirring in a developing device, and further, a new carrier that does not deteriorate in performance even when used for a long period of time. Furthermore, another object of the present invention is to provide a new carrier with improved charge imparting ability suitable for colorizing toners.
【０００９】[0009]
【課題を解決するための手段】即ち、本発明は、少なく
とも下記一般式（化１）又は（化２）で示される化合物
をペンダント化したポリマーを含有することを特徴とす
る電子写真用キャリアである。[Means for Solving the Problems] That is, the present invention provides an electrophotographic carrier containing at least a polymer pendant with a compound represented by the following general formula (Formula 1) or (Formula 2). be.
【化３】[Chemical formula 3]
【化４】
（但し、ＸとＹで窒素原子を２個含む、置換基を有して
もよい複素５員環又は６員環を形成し、Ｒ１ 、Ｒ２
及びＲ３ はＨ又は置換基を有してもよいアルキル基、
アリール基又はアラルキル基を示す。）尚、本発明でい
う「ペンダント化」とは、上記化合物（化１）又は（化
２）を重合体主骨格、或は重合体主骨格に結合している
ペンダント基に結合させて重合体主骨格に結合するペン
ダント基にすることである。又、これらのグアニジン誘
導体がポリマーにペンダント化したかどうかの確認は、
得られたポリマーのＩＲ測定及び中和滴定法により行う
。embedded image (However, X and Y form a 5- or 6-membered hetero ring containing two nitrogen atoms and which may have a substituent, and R1, R2
and R3 is H or an alkyl group which may have a substituent,
Indicates an aryl group or an aralkyl group. ) In the present invention, "pendantization" means to form a polymer by bonding the above compound (Chem. 1) or (Chem. 2) to the main skeleton of the polymer or to a pendant group bonded to the main skeleton of the polymer. This is to make it a pendant group that is bonded to the main skeleton. In addition, to confirm whether these guanidine derivatives are pendant to the polymer,
This is carried out by IR measurement of the obtained polymer and neutralization titration method.
【００１０】0010
【作用】本発明の電子写真用キャリアで使用する上記の
キャリアに含有させる特定の電荷制御剤に類似ものとし
て、グアニジン誘導体を電荷制御剤としてキャリア表面
に含有させて用いることが特公平２−７０６０号公報等
で公知である。[Operation] Similar to the specific charge control agent contained in the above carrier used in the carrier for electrophotography of the present invention, it is possible to use a guanidine derivative as a charge control agent by incorporating it on the surface of the carrier according to Japanese Patent Publication No. 2-7060. It is publicly known in the publication No.
【００１１】しかし、本発明者らは、これに対し下記に
挙げた事項を知見して本発明を完成した。即ち、グアニ
ジン誘導体をポリスチレン等のポリマーにペンダント化
することで、上記の様にグアニジン誘導体をそのまま電
荷制御剤として用いた場合よりもトナーの帯電速度を向
上出来ること、更には、ポリマーにペンダント化するこ
とで摩擦帯電量を増加出来ることを見出した。又、グア
ニジン誘導体の特徴の一つとして、置換基の性質により
摩擦帯電量を制御することが可能であることが知られて
いるが、非常に高い摩擦帯電量の電荷制御剤を得ようと
すると構造が複雑化する傾向があり、電荷制御剤が高価
なものになり易いという問題があった。これに対しても
、本発明の様にグアニジン誘導体をポリマーにペンダン
ト化した場合は、摩擦帯電量が低い、しかも比較的単純
な構造のグアニジン誘導体を用いても高摩擦帯電性の電
荷制御剤が得られる為、高い摩擦帯電性が要求される場
合にも有利であることを見出した。しかも、一般的にペ
ンダント化に用いるグアニジン誘導体の量は、ポリマー
に対し２ｗｔ％程度で十分である為、同一帯電量の電荷
制御剤を製造する場合に価格的にも有利な場合が多いこ
とを見出した。However, the present inventors discovered the following matters and completed the present invention. That is, by making the guanidine derivative pendant in a polymer such as polystyrene, the charging speed of the toner can be improved compared to the case where the guanidine derivative is used as a charge control agent as described above, and furthermore, by making it pendant in the polymer. It was discovered that the amount of triboelectric charging could be increased by doing this. In addition, it is known that one of the characteristics of guanidine derivatives is that the amount of triboelectric charge can be controlled by the nature of the substituent, but when trying to obtain a charge control agent with a very high amount of triboelectric charge, There is a problem that the structure tends to be complicated and the charge control agent tends to be expensive. On the other hand, when a guanidine derivative is made pendant to a polymer as in the present invention, the amount of triboelectric charge is low, and even if a guanidine derivative with a relatively simple structure is used, a charge control agent with high triboelectricity can be obtained. It has been found that this is advantageous even in cases where high triboelectric charging properties are required. Moreover, the amount of guanidine derivative used for pendant formation is generally about 2 wt% of the polymer, so it is often advantageous in terms of cost when producing a charge control agent with the same charge amount. I found it.
【００１２】又、ペンダンド化することで、結着樹脂と
して用いるポリマーに対する分散性が極端に向上し、ペ
ンダンド化しない従来のグアニジン誘導体を用いる場合
と比較してキャリアの表面に非常に均一にグアニジン誘
導体が存在出来、その為トナーはキャリアと接触する際
に必ずグアニジン誘導体と接触することになり、現像器
内の軽度の混合撹拌でも速やかにトナーが所望の帯電量
となるという効果を十分発揮しうることを見出した。
又、温度、湿度等の環境変動に伴いトナーの帯電量が変
動することに対しても、環境特性に優れた本発明の電子
写真用キャリアによれば、トナー帯電量の変動を補うこ
とが出来、結果として環境変動の少ない現像剤が得られ
ることを見出した。又、本発明は、グアニジン誘導体そ
のものをキャリア被覆樹脂に分散させるわけではなく、
グアニジン誘導体によりペンダント化したポリマーをキ
ャリア被覆するものである為、長期に渡る耐久によって
もキャリア表面に被覆された樹脂からグアニジン誘導体
が離脱することがなく、その結果キャリアの性能が劣化
することがないことを見出した。[0012] Furthermore, by forming pendants, the dispersibility in the polymer used as the binder resin is extremely improved, and the guanidine derivatives are distributed very uniformly on the surface of the carrier, compared to the case of using conventional guanidine derivatives that are not formed into pendants. Therefore, when the toner comes into contact with the carrier, it always comes into contact with the guanidine derivative, and even slight mixing and agitation in the developing device can sufficiently exhibit the effect that the toner quickly becomes the desired charge amount. I discovered that. Furthermore, the electrophotographic carrier of the present invention, which has excellent environmental characteristics, can compensate for fluctuations in the toner charge amount due to environmental changes such as temperature and humidity. It has been found that as a result, a developer with less environmental fluctuation can be obtained. Furthermore, the present invention does not involve dispersing the guanidine derivative itself in the carrier coating resin;
Since the polymer pendant with a guanidine derivative is coated with a carrier, the guanidine derivative will not separate from the resin coated on the carrier surface even after long-term durability, and as a result, the performance of the carrier will not deteriorate. I discovered that.
【００１３】[0013]
【好ましい実施態様】本発明の電子写真用キャリアで使
用するグアニジン誘導体をポリマー側鎖にペンダント化
した電荷制御剤は、公知の方法で合成出来る。即ち、ス
チレン樹脂或はスチレン−アクリル樹脂のスチレン部分
を常法によりクロロメチル化する。次いで、ジメチルホ
ルムアミドを溶媒として塩基触媒（例えば、ナトリウム
エトキシド等）下、グアニジン誘導体と反応させる。[Preferred Embodiment] The charge control agent having a guanidine derivative pendant on a polymer side chain used in the electrophotographic carrier of the present invention can be synthesized by a known method. That is, the styrene portion of the styrene resin or styrene-acrylic resin is chloromethylated by a conventional method. Next, it is reacted with a guanidine derivative under a base catalyst (eg, sodium ethoxide, etc.) using dimethylformamide as a solvent.
【００１４】この際、ペンダント化に使用するグアニジ
ン誘導体は、電荷制御剤として要求される摩擦帯電性に
より決定されるもので特に限定されるものではない。以
下に本発明で使用される代表的なグアニジン誘導体の具
体例を挙げるが、これは合成の容易さ等も考慮したもの
であり本発明を何ら限定するものではない。[0014] The guanidine derivative used for pendant formation is determined by the triboelectric charging properties required as a charge control agent and is not particularly limited. Specific examples of typical guanidine derivatives used in the present invention are listed below, but these are given in consideration of ease of synthesis, etc., and are not intended to limit the present invention in any way.
【化５】[C5]
【化６】[C6]
【化７】[C7]
【化８】[Chemical formula 8]
【化９】[Chemical formula 9]
【化１０】[Chemical formula 10]
【化１１】[Chemical formula 11]
【化１２】[Chemical formula 12]
【化１３】[Chemical formula 13]
【化１４】[Chemical formula 14]
【化１５】[Chemical formula 15]
【化１６】[Chemical formula 16]
【００１５】上記のグアニジン誘導体でペンダント化さ
れるポリマーとしては、コート被膜の強度、耐久性の点
からポリスチレン或はスチレン−アクリル系共重合体が
好ましく、一般のものの単独或は数種の共重合体が用い
られる。モノマーとしては、例えば、スチレン、α−メ
チルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブ
チルスチレン、ｐ−クロルスチレン等のスチレン誘導体
、メタクリル酸メチル、メタクリル酸エチル、メタクリ
ル酸プロピル、メタクリル酸ブチル、メタクリル酸ペン
チル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、
メタクリル酸オクチル、メタクリル酸ノニル、メタクリ
ル酸デシル、メタクリル酸ウンデシル、メタクリル酸ド
デシル、メタクリル酸グリシジル、メタクリル酸メトキ
シエチル、メタクリル酸プロポキシエチル、メタクリル
酸ブトキシエチル、アクリル酸メチル、アクリル酸エチ
ル、アクリル酸プロピル、アクリル酸ブチル、アクリル
酸ペンチル、アクリル酸ヘキシル、アクリル酸ヘプチル
、アクリル酸オクチル、アクリル酸ノニル、アクリル酸
デシル、アクリル酸ウンデシル、アクリル酸ドデシルの
様なものがあるが、特にフェライト芯材との接着性の良
好なものとして、ヒドロキシル基を含むアクリル樹脂を
共重合させることは有効である。ヒドロキシル基を含む
アクリル系樹脂モノマーとしては、アクリル酸−２−ヒ
ドロキシエチル、アクリル酸−２−ヒドロキシプロピル
、アクリル酸ヒドロキシブチル、アクリル酸−２−ヒド
ロキシ−３−フェニルオキシプロピル、メタクリル酸−
２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシ
プロピル、メタクリル酸ヒドロキシブチル、メタクリル
酸−２−ヒドロキシ−３−フェニルオキシプロピル等が
ある。これらのモノマーは共重合体のヒドロキシル価が
１〜１００（ＫＯＨｍｇ／ｇ）が好ましい。The polymer pendant with the above guanidine derivative is preferably polystyrene or a styrene-acrylic copolymer from the viewpoint of the strength and durability of the coating film, and general single or several types of copolymers may be used. Consolidation is used. Examples of monomers include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-chlorostyrene and other styrene derivatives, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Pentyl methacrylate, hexyl methacrylate, heptyl methacrylate,
Octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate , butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, and dodecyl acrylate. It is effective to copolymerize an acrylic resin containing a hydroxyl group as a material with good adhesive properties. Acrylic resin monomers containing hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, and methacrylate.
Examples include 2-hydroxyethyl, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, and 2-hydroxy-3-phenyloxypropyl methacrylate. The copolymer of these monomers preferably has a hydroxyl value of 1 to 100 (KOHmg/g).
【００１６】又、キャリア芯材にコートする樹脂には、
前述のグアニジン誘導体を上記のポリスチレン或いはス
チレン−アクリル共重合体にペンダント化したポリマー
のみをコート材として用いることも出来るし、従来から
一般的にキャリアコート用に用いられている樹脂との混
合物を用いることも出来る。この様な一般的なキャリア
コート用の樹脂としては、例えば、ポリスチレン、アク
リル系樹脂、ポリエステル樹脂、フッ素系樹脂、エポキ
シ樹脂、ポリウレタン樹脂、ポリアミド樹脂、フェノー
ル樹脂、シリコン樹脂等が挙げられる。本発明において
、上記の特定の被覆樹脂をキャリア芯材に塗布する方法
としては、該被覆樹脂を一般の溶剤中に溶解して被覆樹
脂溶液を作成し、スプレー法や流動床法等の一般的な塗
布装置を用いる方法によって塗布することが出来る。[0016] Furthermore, the resin coated on the carrier core material includes:
It is possible to use only a polymer in which the above-mentioned guanidine derivative is pendant to the above-mentioned polystyrene or styrene-acrylic copolymer as a coating material, or to use a mixture with a resin that has conventionally been generally used for carrier coating. You can also do that. Examples of such general carrier coat resins include polystyrene, acrylic resins, polyester resins, fluorine resins, epoxy resins, polyurethane resins, polyamide resins, phenol resins, and silicone resins. In the present invention, the above-mentioned specific coating resin is applied to the carrier core material by dissolving the coating resin in a common solvent to create a coating resin solution, and using a general method such as a spray method or a fluidized bed method. It can be coated by a method using a suitable coating device.
【００１７】本発明による被覆樹脂のキャリア芯材に対
する塗布量は、樹脂固形分が０．１ｗｔ％〜３０ｗｔ％
、好ましくは０．２ｗｔ％〜１０ｗｔ％である。０．１
ｗｔ％未満ではキャリア芯材の樹脂による被覆効果が十
分でなく、３０ｗｔ％を越える過剰な塗布は無意味であ
り、又、製造上からも過剰な樹脂が単独で存在する場合
も生じ好ましくない。本発明ではキャリア芯材として、
鉄粉、フェライト粉等の一般のものがすべて使用出来る
が、これも上記の被覆樹脂を用いることにより生じる一
つの大きな特徴である。又、用いるキャリア芯材の粒径
は１０〜２００μｍ、好ましくは２０〜１００μｍであ
る。[0017] The coating amount of the coating resin according to the present invention to the carrier core material is such that the resin solid content is 0.1 wt% to 30 wt%.
, preferably 0.2 wt% to 10 wt%. 0.1
If it is less than 30% by weight, the coating effect of the carrier core resin with the resin will not be sufficient, and if it exceeds 30% by weight, it is meaningless, and also from the viewpoint of manufacturing, the presence of an excessive amount of resin alone may be undesirable. In the present invention, as a carrier core material,
All common materials such as iron powder and ferrite powder can be used, and this is also one of the major features produced by using the above-mentioned coating resin. Further, the particle size of the carrier core material used is 10 to 200 μm, preferably 20 to 100 μm.
【００１８】ここで、本発明の電子写真キャリアの特性
を調べる為のトナーのキャリアに対する摩擦帯電量の測
定法を、図１の摩擦帯電量測定装置の説明図を用いて詳
述する。底に４００メッシュ（キャリア粒子の通過しな
い大きさに適宜変更可能）の導電性スクリーン３のある
金属製の測定容器２に、摩擦帯電量を測定しようとする
現像剤担持体上の磁気ブラシ（トナーと磁性粒子の混合
物）を入れ金属製のフタ４をする。このときの測定容器
２の全体の重量を秤り、Ｗ１ （ｇ）とする。次に、吸
引機（測定容器２と接する部分は少なくとも絶縁体で構
成、図示なし）において、吸引口７から吸引し風量調節
弁６を調整して真空計５の圧力を７０ｍｍＨｇとする。
この状態で充分（約１分間）吸引を行いトナーを吸引除
去する。このときの電位計９の電位をＶ（ボルト）とす
る。ここで８はコンデンサーであり容量をＣ（μＦ）と
する。又、吸引後の測定容器全体の重量を秤り、Ｗ２
（ｇ）とする。この結果、摩擦帯電量Ｑ（μＣ／ｇ）は
下式の如く計算され求められる。[0018] Here, a method for measuring the amount of triboelectric charge of toner on a carrier for investigating the characteristics of the electrophotographic carrier of the present invention will be described in detail with reference to an explanatory diagram of a triboelectricity measuring apparatus shown in FIG. A metal measuring container 2 with a conductive screen 3 of 400 mesh (can be changed to a size that does not allow carrier particles to pass through) at the bottom is equipped with a magnetic brush (toner) on the developer carrier whose triboelectric charge amount is to be measured. and a mixture of magnetic particles) and cover with a metal lid 4. At this time, the entire weight of the measuring container 2 is weighed and set as W1 (g). Next, in a suction device (at least the portion in contact with the measurement container 2 is made of an insulator, not shown), suction is performed through the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 70 mmHg. In this state, suction is applied sufficiently (for about 1 minute) to remove the toner. The potential of the electrometer 9 at this time is assumed to be V (volt). Here, 8 is a capacitor, and the capacitance is C (μF). Also, weigh the entire measurement container after suction, and
(g). As a result, the amount of triboelectric charge Q (μC/g) is calculated and obtained as shown in the following formula.
【式１】 但し、測定条件は２３℃、６０％ＲＨとする。[Formula 1] However, the measurement conditions are 23° C. and 60% RH.
【００１９】[0019]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、これは、本発明を何ら限定するものではない
。尚、以下の配合における部数は、全て重量部である。EXAMPLES The present invention will now be explained in more detail with reference to Examples, but these are not intended to limit the invention in any way. Note that all parts in the following formulations are parts by weight.
【００２０】実施例１
（キャリアの作製）スチレン−メタクリル酸−２−ヒド
ロキシエチル−メタクリル酸メチル共重合体（モノマー
組成比３５：１０：５５、ヒドロキシル価＝３０ ＫＯ
Ｈｍｇ／ｇ）のスチレン部を通常の方法でクロロメチル
化した後、化合物例１で示したグアニジン誘導体をナト
リウムエトキシドを触媒としてＤＭＦ中で作用させ、ペ
ンダント化した。この際の反応条件は、表１にまとめて
挙げた。以上の様にして得られたポリマーの２０ｗｔ％
トルエン溶液を作成した後、この被覆液を塗布機（岡田
精工社製、スピラコータ）で平均粒径４５μｍの球形フ
ェライト粒子に塗布した。次に、得られた塗布後のキャ
リアを６０℃で１時間乾燥して溶剤を除去した後、１４
０℃で１時間加熱して本発明の電子写真用キャリアを得
た。得られたキャリアの樹脂被覆量は、０．９２ｗｔ％
であり、電子顕微鏡による観察によれば、フェライトの
芯材が樹脂で均一に被覆されていることが確認された。Example 1 (Preparation of carrier) Styrene-2-hydroxyethyl methacrylate-methyl methacrylate copolymer (monomer composition ratio 35:10:55, hydroxyl number = 30 KO)
After chloromethylating the styrene moiety of Hmg/g) in a conventional manner, the guanidine derivative shown in Compound Example 1 was reacted with sodium ethoxide as a catalyst in DMF to form pendants. The reaction conditions at this time are summarized in Table 1. 20wt% of the polymer obtained as above
After preparing a toluene solution, this coating liquid was applied to spherical ferrite particles having an average particle size of 45 μm using a coating machine (Spira Coater, manufactured by Okada Seiko Co., Ltd.). Next, the obtained carrier after coating was dried at 60°C for 1 hour to remove the solvent, and then
The electrophotographic carrier of the present invention was obtained by heating at 0° C. for 1 hour. The resin coating amount of the obtained carrier was 0.92 wt%
According to observation using an electron microscope, it was confirmed that the ferrite core material was uniformly coated with resin.
【００２１】（トナーの作製）一方、下記の材料をヘン
シェルミキサーにより充分予備混合を行った後、３本ロ
ールミルで少なくとも２回以上溶融混練し、冷却後ハン
マーミルを用いて粒径約１〜２ｍｍ程度に粗粉砕した。
次いでエアージェット方式による微粉砕機で微粉砕した
た後、更に、得られた微粉砕物を分級して体積平均粒径
が７．３μｍであるシアン色の粉体を得た。上記着色粉
体１００重量部とヘキサメチルジシラザンで疎水化処理
したシリカ微粉体０．５重量部とを混合してシアントナ
ーとした。
・プロボキシ化ビスフェノールとフマル酸を縮合し
て得られたポリエステル 樹脂
１００重量部
・フタロシアニン顔料
５重量部 ・ジ−ターシャリーブチルサリチル酸のク
ロム錯塩 ４重量部(Preparation of toner) On the other hand, the following materials were sufficiently premixed using a Henschel mixer, then melted and kneaded at least twice using a three-roll mill, and after cooling, the materials were mixed using a hammer mill to a particle size of approximately 1 to 2 mm. It was roughly ground to a certain extent. After pulverizing with an air jet type pulverizer, the resulting pulverized product was further classified to obtain a cyan powder having a volume average particle size of 7.3 μm. A cyan toner was prepared by mixing 100 parts by weight of the colored powder and 0.5 parts by weight of fine silica powder treated with hexamethyldisilazane to make it hydrophobic.・Polyester resin obtained by condensing proboxylated bisphenol and fumaric acid
100 parts by weight
・Phthalocyanine pigment
5 parts by weight Chromium complex salt of di-tert-butylsalicylic acid 4 parts by weight
【００
２２】（試験用現像剤の作製）この様にして作製したシ
アントナーと、上記の本発明の電子写真用キャリアとを
Ｌ／Ｌ（２０℃／２０％）、Ｎ／Ｎ（２３℃／６０％）
、Ｈ／Ｈ（３０℃／８０％）の各環境に４日間放置した
。その後、トナー濃度５％で、Ｎ／Ｎ及びＨ／Ｈの環境
下のものは３０秒間、Ｌ／Ｌの環境下のものは１０、３
０及び６０秒間夫々混合して二成分系現像剤を作製し、
図１の装置により夫々について帯電量を測定した。又、
Ｎ／Ｎ環境下で、トナー濃度５％で混合して作製した二
成分系現像剤を用い、現像コントラストを３５０Ｖに固
定したキヤノン（株）製フルカラーレザー複写機ＣＬＣ
−５００で、前記した種々の環境下で夫々画像出しテス
トを行い評価した。00
22] (Preparation of test developer) The cyan toner thus prepared and the electrophotographic carrier of the present invention were mixed at L/L (20°C/20%) and N/N (23°C/60%). %)
, H/H (30°C/80%) for 4 days. After that, at a toner concentration of 5%, for 30 seconds in N/N and H/H environments, and for 10, 3 seconds in L/L environments.
A two-component developer was prepared by mixing for 0 and 60 seconds, respectively.
The amount of charge was measured for each using the apparatus shown in FIG. or,
Full-color leather copying machine CLC manufactured by Canon Inc., using a two-component developer prepared by mixing toner concentration 5% under N/N environment, with development contrast fixed at 350V.
-500, and image output tests were conducted and evaluated under the various environments described above.
【００２３】（評価）以上の結果、表２及び表３に示し
た様に、本発明の電子写真用キャリアを用いた現像剤は
耐久性に優れ、環境変動に対する変化の少ないことがわ
かる。更に、帯電量の立ち上がり速度も十分に速いこと
がわかる。一方、Ｎ／Ｎ環境下において、上記の二成分
系現像剤を現像器内で空回転２時間耐久し、トナーとキ
ャリアを分離してキャリアのみを回収した。この回収キ
ャリアを電子顕微鏡にて観察したところ、顕著なトナー
によるスペント化或いは樹脂被覆層のハクリは認められ
なかった。又、一連の画像出しテスト中、感光ドラム上
或いは紙上へのキャリア付着は極めて少なく良好な画質
の画像が得られた。(Evaluation) As shown in Tables 2 and 3, the above results show that the developer using the electrophotographic carrier of the present invention has excellent durability and is less susceptible to environmental changes. Furthermore, it can be seen that the rate of rise in the amount of charge is also sufficiently fast. On the other hand, under an N/N environment, the above-mentioned two-component developer was idle-rotated in a developing device for 2 hours, and the toner and carrier were separated and only the carrier was recovered. When this recovered carrier was observed under an electron microscope, no significant toner-induced spent or peeling of the resin coating layer was observed. Further, during a series of image printing tests, there was very little carrier adhesion on the photosensitive drum or paper, and images of good quality were obtained.
【００２４】比較例１
実施例１で用いたと同様のスチレン系共重合体の２０％
トルエン溶液１００部を用い、実施例１と同様のフェラ
イト粒子に実施例１と同様の方法で塗布して、キャリア
芯材の表面を樹脂被覆層で被覆した比較用のキャリアを
得た。このキャリアを用いて実施例１と同様に二成分系
現像剤を作成した後、実施例１と同様の測定或いはテス
トを行った結果を表２及び表３に示す。表１〜表３の結
果からわかる様に、グアニジン誘導体をペンダント化し
ない樹脂被覆層をキャリア芯材に被覆したキャリアにお
いては、本発明の電子写真用キャリアを用いた場合と異
なり、耐久性、耐トナースペント性には優れているもの
の、環境変動による帯電量の変動が大きくなり、その結
果、画像濃度の差が大きくなる。又、Ｌ／Ｌ環境下の帯
電量の立ち上がり速度も、実施例１に比べ劣る。Comparative Example 1 20% of the same styrenic copolymer used in Example 1
Using 100 parts of a toluene solution, the same ferrite particles as in Example 1 were coated in the same manner as in Example 1 to obtain a comparative carrier in which the surface of the carrier core material was coated with a resin coating layer. A two-component developer was prepared using this carrier in the same manner as in Example 1, and then the same measurements or tests as in Example 1 were conducted. The results are shown in Tables 2 and 3. As can be seen from the results in Tables 1 to 3, the carrier in which the carrier core material is coated with a resin coating layer that does not have a guanidine derivative pendant has superior durability and resistance, unlike the case in which the electrophotographic carrier of the present invention is used. Although the toner spend properties are excellent, the amount of charge varies greatly due to environmental changes, and as a result, the difference in image density becomes large. Furthermore, the rate of rise in the amount of charge under the L/L environment is also inferior to that in Example 1.
【００２５】実施例２〜４
実施例１において化合物例１の代わりに化合物例２〜４
を用いた他は（反応条件は表１に示す）、実施例１と同
様の方法で本発明の電子写真用キャリアを作製し、これ
を用いて二成分系現像剤を作製し、実施例１と同様の評
価を行った。この結果、実施例１と同様に表２及び表３
に示す様な良好な結果が得られた。Examples 2 to 4 In Example 1, Compound Examples 2 to 4 were used instead of Compound Example 1.
An electrophotographic carrier of the present invention was prepared in the same manner as in Example 1, except for using (reaction conditions are shown in Table 1), and a two-component developer was prepared using this. The same evaluation was conducted. As a result, as in Example 1, Tables 2 and 3
Good results were obtained as shown in .
【表１】
＊：クロルメチルポリスチレン ＊＊：ナトリウ
ムエトキシド[Table 1] *: Chlormethyl polystyrene **: Sodium ethoxide
【００２６】実施例５
スチレン−メタクリル酸メチル−２−エチルヘキシルア
クリレート共重合体（モノマー組成比＝４５：３５：２
０）のスチレン部を通常の方法でクロロメチル化した後
、化合物例１で示したグアニジン誘導体をナトリウムエ
トキシドを触媒としてＤＭＦ中で作用させ、ポリマーを
グアニジン誘導体でペンダント化した。この様にして得
られたポリマーの１５ｗｔ％キシレン溶液を作成し、こ
の被覆液を平均粒径４３μｍの球形フェライト粒子に実
施例１と同様の方法で塗布し、実施例１と同様の工程を
経て本発明の樹脂コートされた電子写真用キャリアを得
た。得られたキャリアの樹脂被覆量は０．８５ｗｔ％で
あり、電子顕微鏡による観察によればフェライトの芯材
が樹脂で均一に被覆されていることがわかった。一方、
実施例１で用いたトナーにおいて、ジ−ターシャリブチ
ルサリチル酸のクロム錯塩を除くこと以外は、実施例１
と全く同様の工程を経て体積平均粒径が７．５μｍであ
るシアントナーを得た。この様にして作製したトナーと
上記キャリアを用いて、実施例１と同様の方法で二成分
系現像剤を作成し、実施例１と同様の評価をしたところ
表２及び表３に示す様な良好な結果を得た。Example 5 Styrene-methyl methacrylate-2-ethylhexyl acrylate copolymer (monomer composition ratio = 45:35:2
After chloromethylating the styrene moiety of 0) in a conventional manner, the guanidine derivative shown in Compound Example 1 was reacted with sodium ethoxide as a catalyst in DMF to form a polymer pendant with the guanidine derivative. A 15 wt % xylene solution of the polymer thus obtained was prepared, and this coating liquid was applied to spherical ferrite particles with an average particle size of 43 μm in the same manner as in Example 1. A resin-coated electrophotographic carrier of the present invention was obtained. The resin coating amount of the obtained carrier was 0.85 wt%, and observation using an electron microscope revealed that the ferrite core material was uniformly coated with the resin. on the other hand,
Example 1 except that the chromium complex salt of di-tert-butylsalicylic acid was removed from the toner used in Example 1.
A cyan toner having a volume average particle size of 7.5 μm was obtained through the same process as above. Using the toner thus prepared and the carrier described above, a two-component developer was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Good results were obtained.
【００２７】実施例６
スチレン−メタクリル酸エチル−２−エチルヘキシルア
クリレート共重合体（モノマー組成比＝４５：３５：２
０）のスチレン部を通常の方法でクロロメチル化した後
、化合物例２で示したグアニジン誘導体をナトリウムエ
トキシドを触媒としてＤＭＦ中で作用させた。上記の様
にして得られたポリマーの１５ｗｔ％キシレン溶液を作
成し、この被覆液を平均粒径４３μｍの球形フェライト
粒子に実施例１と同様の方法で塗布し、実施例１と同様
の工程を経て本発明の樹脂コートした電子写真用キヤリ
アを得た。得られたキャリアの樹脂被覆量は０．８３％
であり、電子顕微鏡による観察によれば、フェライトの
芯材が樹脂で均一に被覆されていることがわかった。
このキャリアとキヤノン（株）製ＮＰ−５０００複写機
用トナー（結着樹脂：スチレン系共重合体及びパラフィ
ン類１００部、着色材：カーボンブラック９部、電荷制
御剤：負帯電性含金属錯体：３部）とをトナー濃度２ｗ
ｔ％で実施例１と同様の環境下で混合し、図１の方法に
より帯電量を測定した。又、上記トナーとキャリアをＮ
／Ｎ環境下でトナー濃度２ｗｔ％で混合し、作成した二
成分系現像剤を上記ＮＰ−５０００改造複写機によって
実施例１と同様の評価をしたところ、表２及び表３に示
す様な良好な結果を得た。Example 6 Styrene-ethyl methacrylate-2-ethylhexyl acrylate copolymer (monomer composition ratio = 45:35:2
After chloromethylating the styrene moiety of 0) in a conventional manner, the guanidine derivative shown in Compound Example 2 was allowed to act in DMF using sodium ethoxide as a catalyst. A 15 wt % xylene solution of the polymer obtained above was prepared, and this coating solution was applied to spherical ferrite particles with an average particle size of 43 μm in the same manner as in Example 1, and the same steps as in Example 1 were carried out. As a result, a resin-coated electrophotographic carrier of the present invention was obtained. The resin coating amount of the obtained carrier was 0.83%
According to observation using an electron microscope, it was found that the ferrite core material was uniformly coated with resin. This carrier and toner for NP-5000 copier manufactured by Canon Inc. (binder resin: 100 parts of styrene copolymer and paraffins, colorant: 9 parts of carbon black, charge control agent: negatively chargeable metal-containing complex: 3 parts) and toner density 2w
t% under the same environment as in Example 1, and the amount of charge was measured by the method shown in FIG. Also, the above toner and carrier are
/N environment at a toner concentration of 2 wt% and the prepared two-component developer was evaluated in the same manner as in Example 1 using the above-mentioned NP-5000 modified copying machine, and the results were good as shown in Tables 2 and 3. I got good results.
【表２】 表２[Table 2] Table 2
【表３
】 （表２の続き）
＊Ｌ／Ｌ環境下におけるトナーとキャリアとの混合時間
の違いによるトナーの帯電量[Table 3
] (Continued from Table 2) *Toner charge amount due to difference in mixing time of toner and carrier under L/L environment
【００２８】[0028]
【本発明の効果】以上の様に本発明の電子写真用キャリ
アを用いれば、トナーに適正な負電荷を付与し得ると共
に、温度、湿度等の環境変動に対して、トナーが十分に
高く安定した帯電量を有するものと出来る。又、現像器
内での本発明の電子写真用キャリアとトナーとの混合撹
拌により、速やかにトナーを所望の帯電量にまで立ち上
げることが出来る。又、本発明の電子写真用キャリアは
、長期間使用しても性能が劣化することがない。更に、
本発明の電子写真用キャリアは、カラートナーにも適用
することも出来る。[Effects of the present invention] As described above, by using the electrophotographic carrier of the present invention, it is possible to impart an appropriate negative charge to the toner, and the toner remains sufficiently high and stable against environmental changes such as temperature and humidity. It can be made to have a certain amount of charge. Further, by mixing and stirring the electrophotographic carrier of the present invention and the toner in the developing device, the toner can be quickly raised to a desired charge amount. Furthermore, the electrophotographic carrier of the present invention does not deteriorate in performance even after long-term use. Furthermore,
The electrophotographic carrier of the present invention can also be applied to color toners.
【図１】本発明を評価する為に用いる摩擦帯電量測定装
置の概略図である。FIG. 1 is a schematic diagram of a triboelectric charge measuring device used to evaluate the present invention.
２：測定容器 ３：導電性スクリーン ４：金属性フタ ７：吸引口 2: Measuring container 3: Conductive screen 4: Metal lid 7: Suction port
Claims (3)
化２）で示される化合物をペンダント化したポリマーを
含有することを特徴とする電子写真用キャリア。 【化１】 【化２】 （但し、ＸとＹで窒素原子を２個含む、置換基を有して
もよい複素５員環又は６員環を形成し、Ｒ１ 、Ｒ２
及びＲ３ はＨ又は置換基を有してもよいアルキル基、
アリール基又はアラルキル基を示す。）Claim 1: At least the following general formula (Chemical formula 1) or (
An electrophotographic carrier comprising a polymer having a pendant compound represented by formula 2). [Chemical 1] [Chemical 2] (However, X and Y form a 5- or 6-membered hetero ring containing two nitrogen atoms and which may have a substituent, and R1, R2
and R3 is H or an alkyl group which may have a substituent,
Indicates an aryl group or an aralkyl group. )
る化合物をペンダント化するポリマーがポリスチレン或
はスチレン−アクリル系共重合体である請求項１に記載
の電子写真用キャリア。2. The electrophotographic carrier according to claim 1, wherein the polymer on which the compound represented by formula (1) or (2) is pendant is polystyrene or a styrene-acrylic copolymer.
、Ｒ１ 及びＲ２ が電子供与性基を置換基として有す
るアリール基である請求項１に記載の電子写真用キャリ
ア。3. The carrier for electrophotography according to claim 1, wherein in the general formula (Formula 1) or (Formula 2), R1 and R2 are aryl groups having an electron-donating group as a substituent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3077145A JPH04289868A (en) | 1991-03-18 | 1991-03-18 | Electrophotographic carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3077145A JPH04289868A (en) | 1991-03-18 | 1991-03-18 | Electrophotographic carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04289868A true JPH04289868A (en) | 1992-10-14 |
Family
ID=13625632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3077145A Pending JPH04289868A (en) | 1991-03-18 | 1991-03-18 | Electrophotographic carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04289868A (en) |
-
1991
- 1991-03-18 JP JP3077145A patent/JPH04289868A/en active Pending
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