JPH01167852A - Electrostatic charge image developing carrier - Google Patents
Electrostatic charge image developing carrierInfo
- Publication number
- JPH01167852A JPH01167852A JP62325393A JP32539387A JPH01167852A JP H01167852 A JPH01167852 A JP H01167852A JP 62325393 A JP62325393 A JP 62325393A JP 32539387 A JP32539387 A JP 32539387A JP H01167852 A JPH01167852 A JP H01167852A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- toner
- acid
- copolymer
- image
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011162 core material Substances 0.000 abstract description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- -1 rare earths Substances 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N methyl ethyl ketone Substances CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BJQFWAQRPATHTR-UHFFFAOYSA-N 1,2-dichloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1Cl BJQFWAQRPATHTR-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-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
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- LCNAQVGAHQVWIN-UHFFFAOYSA-N 1-ethenyl-4-hexylbenzene Chemical compound CCCCCCC1=CC=C(C=C)C=C1 LCNAQVGAHQVWIN-UHFFFAOYSA-N 0.000 description 1
- LUWBJDCKJAZYKZ-UHFFFAOYSA-N 1-ethenyl-4-nonylbenzene Chemical compound CCCCCCCCCC1=CC=C(C=C)C=C1 LUWBJDCKJAZYKZ-UHFFFAOYSA-N 0.000 description 1
- HLRQDIVVLOCZPH-UHFFFAOYSA-N 1-ethenyl-4-octylbenzene Chemical compound CCCCCCCCC1=CC=C(C=C)C=C1 HLRQDIVVLOCZPH-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- GMGLYSIINJPYLI-UHFFFAOYSA-N butan-2-one;propan-2-one Chemical compound CC(C)=O.CCC(C)=O GMGLYSIINJPYLI-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 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
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-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
- 239000007788 liquid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-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
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はトナーとともに静電荷像現像剤を構成するキャ
リアに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a carrier that constitutes an electrostatic image developer together with a toner.
［従来技術］
電子写真法として米国特許第２，２９７，６９１号明細
書、特公昭４２−２３９１０号公報及び特公昭４３−２
４７４８号公報等に種々の方法が記載されているが、こ
れらの方法は、いずれも光導電層に原稿に応じた光像を
照射することにより静電潜像を形成し、次いで該静電潜
像上にこれとは反対の極性を有するトナーと呼ばれる着
色微粉末を付着させて該静電潜像を現像し、必要に応じ
て紙等の転写材にトナー画像を転写した後、熱、圧力あ
るいは溶剤蒸気等により定着し複写物を得るものである
。[Prior art] As an electrophotographic method, US Pat.
Various methods are described in Publication No. 4748, etc., but in all of these methods, an electrostatic latent image is formed by irradiating a photoconductive layer with a light image corresponding to the document, and then the electrostatic latent image is The electrostatic latent image is developed by attaching colored fine powder called toner having the opposite polarity onto the image, and if necessary, after transferring the toner image to a transfer material such as paper, heat or pressure is applied. Alternatively, copies can be obtained by fixing with solvent vapor or the like.
該静電潜像を現像する工程は、潜像とは反対の極性に帯
電せしめたトナー粒子を静電引力により吸引せしめて静
電潜像上に付着させるものであるが、一般にかかる静電
潜像をトナーを用いて現像する方法としては大別してト
ナーをキャリアと呼ばれる媒体に少量分散させたいわゆ
る二成分系現像剤を用いる方法と、キャリアを用いるこ
となくトナー単独使用のいわゆる一成分系現像剤を用い
る方法とがある。The process of developing the electrostatic latent image involves attracting toner particles charged with a polarity opposite to that of the latent image by electrostatic attraction and making them adhere to the electrostatic latent image. Methods for developing images using toner can be roughly divided into two types: two-component developers in which a small amount of toner is dispersed in a medium called a carrier, and one-component developers in which toner is used alone without using a carrier. There is a method using
一般にがかる二成分系現像剤を構成するキャリアは導電
性キャリアと絶縁性キャリアとに大別される。Generally, carriers constituting such two-component developers are broadly classified into conductive carriers and insulating carriers.
導電性キャリアとしては通常酸化または未酸化の鉄粉が
用いられているが、この鉄粉キャリアを成分とする現像
剤においてはトナーに対する摩擦帯電性が不安定であり
、また現像剤により形成される可視像にカブリが発生す
る欠点がある。すなわち現像剤の使用に伴い、鉄粉キャ
リア粒子の表面にトナー粒子が付着するためキャリア粒
子の電気抵抗が増大してバイアス電流が低下し、しかも
摩擦帯電性が不安定となり、この結果形成される可視像
の画像濃度が低下しカブリが増大する。Oxidized or unoxidized iron powder is usually used as a conductive carrier, but in a developer containing this iron powder carrier, the triboelectricity of the toner is unstable, and the toner is formed by the developer. There is a drawback that fog occurs in the visible image. In other words, as the developer is used, toner particles adhere to the surface of the iron powder carrier particles, which increases the electrical resistance of the carrier particles, lowers the bias current, and makes triboelectric charging unstable, resulting in the formation of toner particles. The image density of the visible image decreases and fog increases.
また絶縁性キャリアとしては一般に鉄、ニッケル、フェ
ライト等の強磁性体より成るキャリア芯材の表面を絶縁
性樹脂により均一に被覆したキャリアが代表的なもので
ある。このキャリアを用いた現像剤においては、キャリ
ア表面にトナー粒子が融着することが導電性キャリアの
場合に比べて著しく少なく、耐久性に優れ、使用寿命が
長い点で特に高速の電子複写機に好適であるという利点
がある。しかしながら、この絶縁性キャリアにおいては
、キャリア電荷のリークがないため低湿下では繰り返し
の現像でトナーとキャリアとの摩擦帯電性を制御するこ
とが困難であり、本発明者らが鋭意研究した結果、キャ
リア自身の電荷の蓄積過多に起因することが判明した。Further, typical insulating carriers are carriers in which the surface of a carrier core material made of a ferromagnetic material such as iron, nickel, or ferrite is uniformly coated with an insulating resin. Developers using this carrier have significantly fewer toner particles fused onto the carrier surface than conductive carriers, and are particularly suitable for high-speed electronic copying machines due to their excellent durability and long service life. It has the advantage of being suitable. However, in this insulating carrier, since there is no carrier charge leakage, it is difficult to control the triboelectricity between the toner and the carrier during repeated development under low humidity.As a result of intensive research by the present inventors, It turns out that this is caused by excessive accumulation of charge on the carrier itself.
従来、かかる欠点を解決する技術として、キャリアに導
電性微粒子を添加させる方法やトナーの結着樹脂に酸価
を持たせるという方法が提案されているが、前者は耐久
が進むにつれてキャリアに添加された導電性微粉が消費
されるためにキャリアの耐久性に欠ける。また後者はト
ナーからキャリアの電荷をリークさせる効果を期待した
ものであるが、本発明者らの実験からはこの様な効果は
確認できなかった。また高湿下でトナーが吸湿しやすく
なり、流動性の低下のためにキャリアとトナーが十分に
混合されにくく、それと同時に吸湿による電荷のリーク
によりトナーの摩擦帯電量が低下しカブリやすい傾向に
ある。Techniques to solve this problem have been proposed in the past, such as adding conductive particles to the carrier and adding an acid value to the binder resin of the toner. The carrier lacks durability because the conductive fine powder is consumed. Furthermore, although the latter is expected to have the effect of leaking the charge of the carrier from the toner, such an effect could not be confirmed through experiments conducted by the present inventors. In addition, toner tends to absorb moisture in high humidity environments, which reduces fluidity and makes it difficult to mix the carrier and toner sufficiently.At the same time, due to charge leakage due to moisture absorption, the toner's triboelectric charge level decreases, making it more likely to fog. .
［発明が解決すべき問題点］
本発明の目的は、環境の変動においても極めて安定した
画像を提供し、かつ現像効率が極めて高い現像剤を提供
することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a developer that provides extremely stable images even under environmental changes and has extremely high development efficiency.
［問題点を解決するための手段および作用］上記の問題
点を解決できる本発明の静電荷像現像用キャリアはスチ
レン系単量体、アクリル酸もしくはメタクリル酸エステ
ル系単量体、酸基を含むビニル系単量体を構成単位とす
る共重合体で、その酸価が０．１〜２０である樹脂を被
覆することを特徴とする。[Means and effects for solving the problems] The electrostatic image developing carrier of the present invention which can solve the above problems contains a styrene monomer, an acrylic acid or methacrylic acid ester monomer, and an acid group. It is characterized by coating a resin whose acid value is 0.1 to 20 with a copolymer having a vinyl monomer as a constituent unit.
本発明は、低湿下でキャリアに蓄積される電荷をキャリ
ア自身から適当にリークさせ、かつ現像剤の流動性を低
下させない静電荷像現像用キャリアである。ただし、キ
ャリア被覆樹脂の酸価が２０、 を越える場合、高湿
下でキャリア電荷のリークが過多により、カブリやトナ
ー飛散が生じやすい欠点がある。The present invention is a carrier for developing electrostatic images that allows the charges accumulated in the carrier to appropriately leak from the carrier itself under low humidity conditions and does not reduce the fluidity of the developer. However, when the acid value of the carrier coating resin exceeds 20, there is a drawback that fogging and toner scattering are likely to occur due to excessive carrier charge leakage under high humidity.
本発明に使用されるキャリア芯材の材質としては、例え
ば表面酸化または未酸化の鉄、ニッケル、コバルト、マ
ンガン、クロム、希土類等の金属及びそれらの合金また
は酸化物などが使用できるが、好ましくはフェライト粒
子が使用できる。As the material of the carrier core material used in the present invention, for example, surface oxidized or unoxidized metals such as iron, nickel, cobalt, manganese, chromium, rare earths, and alloys or oxides thereof can be used, but preferably Ferrite particles can be used.
またその製造方法としては、特別な制約はない。Moreover, there are no special restrictions on the manufacturing method.
キャリアは一般に平均粒径が３０〜７０ｇｍ、好ましく
は３５〜６５鉢層である０粒子が３０ル■より小さいと
キャリアが潜像保持体上に現像されやすくなり、潜像保
持体やクリーニングブレードに傷つけ易くなる。一方、
粒径が７０Ｂｍより大きいとキャリアのトナー保持能が
低下し、ベタ画像の不均一さ、トナー飛散、カブリ等が
発生する。キャリア芯材は磁性材料のみから成るもので
も、磁性材料と非磁性材料との結合体でもよいし、２種
以上の磁性体の混合物でも良い。Generally, the carrier has an average particle size of 30 to 70 gm, preferably 35 to 65 gm. If the particle size is smaller than 30 gm, the carrier will be easily developed on the latent image carrier, and the carrier will be easily developed on the latent image carrier or cleaning blade. It becomes easier to get hurt. on the other hand,
If the particle size is larger than 70 Bm, the toner retention ability of the carrier will be reduced, resulting in uneven solid images, toner scattering, fogging, etc. The carrier core material may be made of only a magnetic material, a combination of a magnetic material and a non-magnetic material, or a mixture of two or more types of magnetic materials.
また上記キャリアの表面を樹脂で被覆する方法としては
、樹脂を溶剤中に溶解もしくは懸濁せしめて塗布し、磁
性粒子に付着せしめる方法が好ましい。Further, as a method for coating the surface of the carrier with a resin, a method is preferred in which the resin is dissolved or suspended in a solvent, applied, and then adhered to the magnetic particles.
本発明に使用されるキャリア被覆樹脂としての具体例と
しては、スチレンの他に例えばＯ−メチルスチレン、ｍ
−メチルスチレン、ｐ−メチルスチレン、α−メチルス
チレン、ｐ−エチルスチレン、２．４−ジメチルスチレ
ン、 ｐ−ｎ−ブチルスチレン。In addition to styrene, specific examples of the carrier coating resin used in the present invention include O-methylstyrene, m
-Methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene.
ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−へキシルスチ
レン、ｐ−ｎ−オクチルスチレン、 ｐ−ｎ−ノニルス
チレン、Ｐ−１１−７’シルスチレン、ｐ−ｎ−ドデシ
ルスチレン、ｐ−メトキシスチレン、Ｐ−フェニルスチ
レン、ｐ−クロルスチレン、３．４−ジクロルスチレン
などを挙げることができる。共重合体中にスチレン成分
が５重量％以上８０重量％以下が好ましい。p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, P-11-7'silstyrene, p-n-dodecylstyrene, p-methoxystyrene, P -Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like. The styrene component in the copolymer is preferably 5% by weight or more and 80% by weight or less.
本発明に用いられるアクリル酸もしくはメタクリル酸エ
ステル系単量体の具体例としては、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
ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ−オ
クチル、アクリル酸ドデシル、アクリル酸２−エチルヘ
キシル、アクリル酸ステアリル、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ｎ−ブチル、メタクリル酸イソブチル、メタクリル
酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸
ステアリルなどのアクリル酸またはメタクリル酸のアル
キルエステルを挙げることができ、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、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等が特に好ましく用いられる。Specific examples of the acrylic acid or methacrylic acid ester monomer used in the present invention include methyl acrylate,
Ethyl acrylate, acrylic, propyl acid, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate,
Mention may be made of alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, and stearyl methacrylate; ,
Propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate and the like are particularly preferably used.
上記スチレン系単量体及びアクリル酸もしくはメタクリ
ル酸のエステル系単量体は、通常上記の共重合体中に８
０〜９９．５重量％程度含有される。The above styrene monomer and acrylic acid or methacrylic acid ester monomer are usually contained in the above copolymer.
It is contained in an amount of about 0 to 99.5% by weight.
本発明に用いられる酸基を含むビニル単量体の例として
は、アクリル酸、メタクリル酸、マレイン酸やヒドロキ
シル基を含有するアクリル酸系誘導体もしくはメタクリ
ル酸系誘導体とジカルボン酸とのエステル化反応によっ
て得られる構造の半エステル化合物が挙げられる。尚、
マレイン酸等のカルボン酸は酸無水物であっても良い、
そして上記半エステル化合物すなわちカルボキシル基含
有化合物は、例えばマロン酸、コハク酸、グルタル酸等
の脂肪族ジカルボン酸、もしくはフタル酸等の芳香族ジ
カルボン酸とヒドロキシル基を含有するアクリル酸、も
しくはメタクリル酸誘導体とのエステル化反応によって
得られる。Examples of vinyl monomers containing acid groups used in the present invention include acrylic acid, methacrylic acid, maleic acid, and esterification reactions between acrylic acid derivatives or methacrylic acid derivatives containing hydroxyl groups and dicarboxylic acids. A half-ester compound having the structure obtained can be mentioned. still,
Carboxylic acids such as maleic acid may be acid anhydrides,
The half-ester compound, that is, the carboxyl group-containing compound is, for example, an aliphatic dicarboxylic acid such as malonic acid, succinic acid, or glutaric acid, or an aromatic dicarboxylic acid such as phthalic acid, and an acrylic acid or methacrylic acid derivative containing a hydroxyl group. Obtained by esterification reaction with
上記のジカルボン酸はハロゲン族元素、低級アルコール
基、アルコキシ基等によって水素原、子が置換されてい
ても良く、また酸無水物でもよい。The dicarboxylic acids mentioned above may have hydrogen atoms or atoms substituted with halogen group elements, lower alcohol groups, alkoxy groups, etc., or may be acid anhydrides.
そして上記ヒドロキシル基含有アクリル酸もしくはメタ
クリル酸の誘導体としては、アクリル酸もしくはメタク
リル酸にエチレンオキシド、プロピレンオキサイド等の
フルキレンオキサイドを１モルまたは２モル以上付加せ
しめたものでも良く、或はアクリル酸、もしくはメタク
リル酸にプロピレンゲリコール等の２価アルコールをエ
ステル化反応させたヒドロキシアルキルエステルであっ
ても良い。The hydroxyl group-containing acrylic acid or methacrylic acid derivative may be one in which 1 or 2 moles or more of a fullylene oxide such as ethylene oxide or propylene oxide is added to acrylic acid or methacrylic acid, or acrylic acid or methacrylic acid. It may also be a hydroxyalkyl ester obtained by subjecting methacrylic acid to an esterification reaction with a dihydric alcohol such as propylene gellicol.
前記半エステル化合物は、例えば次の各構造式％式％
ｎはＯ〜８を表わす。）
（以下余白）
（２）、Ｒ３
（Ｒ３，ＲａはＨ又はＣＨ３、ｈは１〜１４、ＸはＨ，
ハロゲン族元素、低級アル
キル基、アルコキシ基を表わす、）
（３） Ｒｓ
瞭
ＣＨ２ツＣ
（Ｒ５はＨ又はＣＨ３、ｊは３〜６、
ｋはＯ〜８を表わす、）
（４） Ｒａ
（Ｒ６はＨ又はＣＨ３、！は３〜６、
ＹはＨ，ハロゲン族元素、低級アル
キル基又はアルコキシ基を表わす。）
そして半エステル化合物の好ましい具体例としては、コ
ハク酸モノ（メタ）アクリロイルオキシエチルエステル
、コハク酸七／（メタ）アクリロイルオキシエチルエス
テル、コハク酸モノ（メタ）アクリロイルオキシプロピ
ルエステル、グルタル酸モノ（メタ）アクリロイルオキ
シエチルエステル、フタル酸モノ（メタ）アクリロイル
オキシエチルエステル、フタル酸モノ（メタ）アクリロ
イルオキシプロピルエステル等が挙げられる。The half-ester compound may be represented by, for example, the following structural formula % where n represents O-8. ) (Left below) (2), R3 (R3, Ra is H or CH3, h is 1 to 14, X is H,
(represents a halogen group element, lower alkyl group, or alkoxy group) (3) Rs CH2C (R5 is H or CH3, j is 3 to 6, k is O to 8) (4) Ra (R6 represents H or CH3, ! represents 3 to 6, Y represents H, a halogen group element, a lower alkyl group, or an alkoxy group.) A preferred example of the half ester compound is succinic acid mono(meth)acryloyloxyethyl ester. , succinic acid hepta/(meth)acryloyloxyethyl ester, succinic acid mono(meth)acryloyloxypropyl ester, glutaric acid mono(meth)acryloyloxyethyl ester, phthalic acid mono(meth)acryloyloxyethyl ester, phthalic acid mono( Examples include meth)acryloyloxypropyl ester.
酸価０．１〜２０の共重合体の調整法は共重合体により
異なるが、アクリル酸やメタクリル酸等を含むビニル系
共重合体では従来より知られている塊状重合などの重合
法に従って行なえば良いが、モノマー比を変えることに
より、またエステル化の度合を変えることにより酸価を
調整できる。The method for preparing a copolymer with an acid value of 0.1 to 20 varies depending on the copolymer, but for vinyl copolymers containing acrylic acid, methacrylic acid, etc., it can be carried out according to conventionally known polymerization methods such as bulk polymerization. However, the acid value can be adjusted by changing the monomer ratio or by changing the degree of esterification.
本発明者等は、上述の酸基を含むビニル単量体を前記共
重合体中に導入することで酸価（試量Ｉｇを中和するに
要する水酸化カリウムのｍｇをもって表わされる数値）
を０．１〜２０の範囲でもたせることにより、現像効率
が極めて高く、環境の変動においても極めて安定した画
像を提供できる静電荷像現像用キャリア被覆樹脂を見い
出し、本発明を完成したものである。The present inventors have obtained an acid value (a value expressed in mg of potassium hydroxide required to neutralize a test amount of Ig) by introducing a vinyl monomer containing the above-mentioned acid group into the copolymer.
The present invention has been completed by discovering a carrier coating resin for electrostatic image development that has an extremely high development efficiency and can provide an extremely stable image even under environmental changes by having a .
上記のキャリア被覆樹脂としての共重合体はメラミンア
ルデヒド樹脂架橋あるいはイソシアネート架橋させても
よい、特に用いられるトナーを正の摩擦に呈するには上
記のキャリア被覆樹脂の他に、含フツ素ポリマー、例え
ばポリフッ化ビニル、ポリフッ化ビニリデン、ポリトリ
フルオロエチレン、ポリトリフルオロエチレン、ポリパ
ーフルオロプロピレン、フッ化ビニリデンとフッ化ビニ
ルとの共重合体、テトラフルオロエチレンとヘキサフル
オロプロピレンとの共重合体、フッ化ビニリデンとトリ
フルオロクロルエチレンとの共重合体、フッ化ビニリデ
ンとへキサフルオロプロピレンとの共重合体等を３０〜
７０重量％含有させることによりさらに良好な結果を得
ることができる。The above copolymer as the carrier coating resin may be crosslinked with melamine aldehyde resin or isocyanate crosslinking.In particular, in order to make the toner used have positive friction, in addition to the above carrier coating resin, fluorine-containing polymers such as Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytrifluoroethylene, polyperfluoropropylene, copolymer of vinylidene fluoride and vinyl fluoride, copolymer of tetrafluoroethylene and hexafluoropropylene, fluoride A copolymer of vinylidene fluoride and trifluorochloroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, etc.
Even better results can be obtained by containing 70% by weight.
本キャリアを用いる現像方法は、特に指定されるもので
はなく、一般の二成分系現像方法に適用されるが、現像
器と感光体間に交互電界を印加する現像方法（特開昭６
２−６３９７０号公報）において特に有効である。The developing method using this carrier is not particularly specified, and can be applied to general two-component developing methods.
2-63970) is particularly effective.
［実施例］ 以下、実施例により本発明の詳細な説明する。[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
例で示す部は全て重量部である。All parts shown in the examples are parts by weight.
実施例１
からなる平均粒径１２ｇ膿の青色微粉体に正帯電性コロ
イダルシリカ０．８重量％を添加しトナーとした。Example 1 A toner was prepared by adding 0.8% by weight of positively charged colloidal silica to blue fine powder with an average particle size of 12 g.
次にスチレン−アクリル酸ｎ−ブチル−コハク酸モノア
クリロイルオキシメチルエステル共重合体（６０： ２
０： ２０．酸価１Ｇ、０） ６ｇとフッ化ビニリデン
−テトラフルオロエチレン共重合体（７５： ２５）６
ｇをアセトン−メチルエチルケトン（１：ｌ’）混合溶
媒５００ｍＡ’に溶解して被覆液を調製し、この被覆液
により平均粒径５５μのフェライト粒子１ｋｇを流動化
ベット装置を用いて被覆し、キャリアＣ１とした。Next, styrene-n-butyl acrylate-monoacryloyloxymethyl succinate copolymer (60:2
0: 20. Acid value 1G, 0) 6g and vinylidene fluoride-tetrafluoroethylene copolymer (75: 25) 6
A coating solution was prepared by dissolving 500 mA' of acetone-methyl ethyl ketone (1:l') mixed solvent, and 1 kg of ferrite particles with an average particle size of 55 μm were coated with this coating solution using a fluidizing bed device. And so.
上記のトナーとキャリアを１５：８５の重量比率で混合
し、キャノン製複写機ＭＰ５５４Ｇに投入し。The above toner and carrier were mixed at a weight ratio of 15:85 and loaded into a Canon copier MP554G.
種々の環境で画像を出したところ画像反射濃度は２３℃
、６０％ＲＨで１．３０．１５℃、１０％Ｒ）Ｉで１．
３２゜３５℃、９０％ＲＨで１．２８と高く、カブリの
ない鮮やかな画像が得られた。When images were taken in various environments, the image reflection density was 23°C.
, 1.3 at 60% RH, 15°C, 10% R)I.
At 32°C and 35°C and 90% RH, the image quality was as high as 1.28, and a clear image without fogging was obtained.
この時のトナーの帯電量は各々の環境において、２３℃
、６０％ＲＨで＋２０１Ｌｃ／ｇ 、 １５℃、１０
％ＲＨテ＋ １９．５ｕＬｃ／ｇ 、 ３５℃、 ９０
％ＲＨで＋２１１Ｌｃ／ｇと環境差に依存せず安定して
いた。また各々の環境で複写枚数５０００枚後の画像に
おいても初期画像と同等な良好な結果が得られた。The amount of charge on the toner at this time is 23℃ in each environment.
, +201 Lc/g at 60% RH, 15°C, 10
%RH Te+ 19.5uLc/g, 35℃, 90
%RH was +211 Lc/g, which was stable regardless of environmental differences. Furthermore, in each environment, good results comparable to the initial images were obtained even after 5000 copies were made.
比較例１
酸価０．０３のスチレン−メタクリル酸メチル共重合体
（８５：１５）を実施例１と同様な方法で平均粒径５５
鉢閣のフェライト粒子に被覆し、キャリアＣ２を得た。Comparative Example 1 A styrene-methyl methacrylate copolymer (85:15) with an acid value of 0.03 was prepared in the same manner as in Example 1 to obtain an average particle size of 55.
The carrier C2 was obtained by coating Hachikaku ferrite particles.
実施例１で使用したトナーを１５：８５の重量比率で混
合し、実施例１と同様に画出しを行なったところ、低温
、低湿下で画像濃度低下が顕著でベタ黒部ががさついて
実用には適さなかった。このときのトナーの帯電量は＋
５１．５ ｕＬｃ／ｇであった。When the toners used in Example 1 were mixed at a weight ratio of 15:85 and image printing was carried out in the same manner as in Example 1, the image density decreased significantly at low temperatures and low humidity, and solid black areas were rough, making it unsuitable for practical use. It was not suitable for At this time, the amount of charge on the toner is +
It was 51.5 uLc/g.
比較例２
酸価４０のスチレン−アクリル酸ｎ−ブチルコハク酸モ
ノアクリロイルオキシエチルエステル共重合体（４０：
６０）と実施例１と同様な方法で平均粒径５５ｐｍのフ
ェライト粒子に被覆し、キャリアＣ３を得、実施例１で
使用したトナーを１５：８５の重量比率で混合し、実施
例１と同様に画出しを行ったところ、高温高湿下でカブ
リ、トナー飛散が顕著であった。このときのトナーの帯
電量は＋ ３．２ ｐ、 ｃ／ｇであった。Comparative Example 2 Styrene-acrylic acid n-butylsuccinic acid monoacryloyloxyethyl ester copolymer with an acid value of 40 (40:
60) was coated on ferrite particles with an average particle size of 55 pm in the same manner as in Example 1 to obtain carrier C3, and the toner used in Example 1 was mixed at a weight ratio of 15:85. When I printed the image, fogging and toner scattering were noticeable under high temperature and high humidity conditions. The charge amount of the toner at this time was +3.2 p, c/g.
（以下余白）
比較例３
からなる平均粒径１１．５ｐｍのＳ色微粉体に正電荷コ
ロイダルシリカ０．８重Ｑ［％を添加しトナーとした。(The following is a blank space) Comparative Example 3 0.8 weight Q% of positively charged colloidal silica was added to S color fine powder with an average particle size of 11.5 pm to prepare a toner.
次に比較例２で調製したキャリアＣ１と上記のトナーと
を１２：８８の重量比率で混合し、実施例１と同様に画
出しを行なったところ、低温低湿下で画像濃度の著しい
低下およびベタ黒部のがさつきが顕著であった。Next, carrier C1 prepared in Comparative Example 2 and the above toner were mixed at a weight ratio of 12:88, and image formation was performed in the same manner as in Example 1. The roughness of the solid black part was noticeable.
比較例４
比較例１のキャリアＣ２に導電性微粒子のＺｎ０（抵抗
値５０ｏｈｍｃｍｌ、−次粒子径０．５ μｔｓ ）
０．５ 重量部をＶ型混合機を用いて分散処理し、これ
をＤｌとする。実施例１のトナーとキャリアＤ１とを１
２：８８重量比率で混合し、実施例１と同様に画出しを
行ったところ、耐久５００枚目まで良好な画像が得られ
たが、５００枚以後低温低湿で画像濃度が著しく低下し
、比較例１と同様な画像になった。Comparative Example 4 Conductive fine particles of Zn0 (resistance value 50 ohm cml, -order particle size 0.5 μts) were added to the carrier C2 of Comparative Example 1.
0.5 parts by weight was dispersed using a V-type mixer, and this was designated as Dl. The toner of Example 1 and carrier D1 were combined into one
When they were mixed at a weight ratio of 2:88 and imaged in the same manner as in Example 1, a good image was obtained up to the 500th durability sheet, but after the 500th sheet, the image density decreased significantly at low temperature and low humidity. An image similar to that of Comparative Example 1 was obtained.
実施例２
からなる平均粒径１１．５川層の黒゛色微粉末に負帯電
性コロイダルシリカ１０重量％を添加しトナーとした。Example 2 A toner was prepared by adding 10% by weight of negatively chargeable colloidal silica to black fine powder with an average particle size of 11.5 mm.
次に酸価１２．３のスチレン−メチルメタクリレート共
重合体（７０： ３０） １５ｇを７セトンーメチルエ
チルケトンに溶解させ被覆液を調製し、この被覆液によ
り平均粒径５０Ｂｍのフェライト粒子１ｋｇを流動化ベ
ット装置を用いて被覆し、これをキャリアＣ４とする。Next, 15 g of styrene-methyl methacrylate copolymer (70:30) with an acid value of 12.3 was dissolved in 7 setone-methyl ethyl ketone to prepare a coating solution, and 1 kg of ferrite particles with an average particle size of 50 Bm was fluidized with this coating solution. The carrier C4 is coated using a bed device.
上記のトナーとキャリアＣ４とを１２：８８の重量比率
で混合し、静電荷像を形成できるように改造したキャノ
ン製複写機ＮＰ３５２５に没入し、実施例１と同様に画
出しを行ったところ。The above toner and carrier C4 were mixed at a weight ratio of 12:88, and the image was printed in the same manner as in Example 1 using a Canon copier NP3525 that had been modified to form an electrostatic image. .
実施例１と同様に良好な結果が得られた。この時のトナ
ーの帯電量は各々の環境において２３℃、６０％ＲＨで
−２２，７ｕＬｃ／ｇ 、 １５℃、 １０％ＲＨチ
ー２４．５ｐＣ／ｇ 、 ３５℃、９０％ＲＨで−２
１，８＃ＬＣ／ｇ で環境に依存せず安定していた。Similar to Example 1, good results were obtained. The charge amount of the toner at this time was -22.7 uLc/g at 23°C and 60% RH, 24.5 pC/g at 15°C and 10% RH, and -2 at 35°C and 90% RH in each environment.
It was stable at 1.8 #LC/g, independent of the environment.
比較例５
比較例２で調製したキャリアＣ３を実施例１で使用した
トナーと１２：８８の重量比率で混合し、実施例１と同
様に画出しを行なったところ、画像濃度が低く、特に低
温低湿ではｗＪ著であったが、画像レベルは比較例１よ
りやや良好であった。Comparative Example 5 When the carrier C3 prepared in Comparative Example 2 was mixed with the toner used in Example 1 at a weight ratio of 12:88 and an image was produced in the same manner as in Example 1, the image density was low, especially At low temperature and low humidity, wJ was outstanding, but the image level was slightly better than Comparative Example 1.
実施例３
フッ化ヒニリデンーテトラフルオロエチレン（７０：３
０）と酸価１２のスチレン−メチルメタクリレート共重
合体（６０：４０）の混合樹脂（１：２）１５ｇをメチ
ルエチルケトン溶媒５０ｈＪに溶解して被覆液を調製し
、この被覆液により平均粒径５８１Ｌ！ｌの表面酸化鉄
粉ｉｋｇを流動化ベット装置を用いて被覆し、これをキ
ャリアＣ５として、実施例１で使用したトナーを１０：
９０の重量比重で混合し、実施例１と同様に画出しを行
なったところ、トナーの帯電量は各々の環境において２
３℃、６０％ＲＨテ２５．３４ ｃ／ｇ 、 １５℃
、１０％ＲＨで＋’２４．２μｃ／ｇ 、 ３５℃、９
０％ＲＨで＋２６．７ｇｃ／ｇ と実施例１と比較して
各々の環境で高くなっているが、帯電量は耐久が進んで
も安定しており、実施例１と同様に良好な結果が得られ
た。Example 3 Hynylidene fluoride-tetrafluoroethylene (70:3
A coating liquid was prepared by dissolving 15 g of a mixed resin (1:2) of 0) and a styrene-methyl methacrylate copolymer (60:40) with an acid value of 12 in 50 hJ of methyl ethyl ketone solvent. ! The toner used in Example 1 was coated with 1 kg of surface oxidized iron powder using a fluidizing bed device, and this was used as carrier C5.
When the toner was mixed with a weight specific gravity of 90 and image formation was carried out in the same manner as in Example 1, the charge amount of the toner was 2 in each environment.
3℃, 60%RH 25.34 c/g, 15℃
, +'24.2 μc/g at 10% RH, 35°C, 9
Although it is +26.7gc/g at 0%RH, which is higher in each environment compared to Example 1, the amount of charge remains stable even as the durability progresses, and similar to Example 1, good results were obtained. It was done.
（以下余白）
［発明の効果］
以上のように本発明によれば現像効率が高く、かつ種々
の環境においても帯電特性が安定である現像剤が提供さ
れる。(Hereinafter in the margin) [Effects of the Invention] As described above, the present invention provides a developer that has high development efficiency and stable charging characteristics even in various environments.
Claims (1)
ステル系単量体、酸基を含むビニル系単量体を構成単位
とする共重合体でその酸価が０．１〜２０である樹脂を
被覆したことを特徴とする静電荷像現像用キャリア。A resin whose acid value is 0.1 to 20 is coated with a copolymer whose constituent units are a styrene monomer, an acrylic acid or methacrylic acid ester monomer, and a vinyl monomer containing an acid group. A carrier for developing electrostatic images characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325393A JP2598286B2 (en) | 1987-12-24 | 1987-12-24 | Carrier for developing electrostatic images |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325393A JP2598286B2 (en) | 1987-12-24 | 1987-12-24 | Carrier for developing electrostatic images |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01167852A true JPH01167852A (en) | 1989-07-03 |
| JP2598286B2 JP2598286B2 (en) | 1997-04-09 |
Family
ID=18176335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62325393A Expired - Lifetime JP2598286B2 (en) | 1987-12-24 | 1987-12-24 | Carrier for developing electrostatic images |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2598286B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354638A (en) * | 1989-12-11 | 1994-10-11 | Tdk Corporation | Magnetic carrier for use in electrophotographic development |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138859A (en) * | 1985-12-12 | 1987-06-22 | Hitachi Metals Ltd | Resin coated carrier |
| JPS62229159A (en) * | 1986-03-31 | 1987-10-07 | Ricoh Co Ltd | Electrostatic image developer |
-
1987
- 1987-12-24 JP JP62325393A patent/JP2598286B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138859A (en) * | 1985-12-12 | 1987-06-22 | Hitachi Metals Ltd | Resin coated carrier |
| JPS62229159A (en) * | 1986-03-31 | 1987-10-07 | Ricoh Co Ltd | Electrostatic image developer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354638A (en) * | 1989-12-11 | 1994-10-11 | Tdk Corporation | Magnetic carrier for use in electrophotographic development |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2598286B2 (en) | 1997-04-09 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |