JPS63201670A - Image forming method and its device - Google Patents
Image forming method and its deviceInfo
- Publication number
- JPS63201670A JPS63201670A JP62036210A JP3621087A JPS63201670A JP S63201670 A JPS63201670 A JP S63201670A JP 62036210 A JP62036210 A JP 62036210A JP 3621087 A JP3621087 A JP 3621087A JP S63201670 A JPS63201670 A JP S63201670A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- toner
- intermediate transfer
- softening point
- parts
- 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
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
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- 239000005018 casein Substances 0.000 description 1
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- 235000021240 caseins Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 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
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect 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
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 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
- 230000009191 jumping Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-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
- 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
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-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
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960005480 sodium caprylate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- UDWXLZLRRVQONG-UHFFFAOYSA-M sodium hexanoate Chemical compound [Na+].CCCCCC([O-])=O UDWXLZLRRVQONG-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 description 1
- FIWQZURFGYXCEO-UHFFFAOYSA-M sodium;decanoate Chemical compound [Na+].CCCCCCCCCC([O-])=O FIWQZURFGYXCEO-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- SMECTXYFLVLAJE-UHFFFAOYSA-M sodium;pentadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCOS([O-])(=O)=O SMECTXYFLVLAJE-UHFFFAOYSA-M 0.000 description 1
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Fixing For Electrophotography (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子写真装置、同プリンタ等の静電的に画像を
形成する画像形成方法及び画像形成装置に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method and image forming apparatus for electrostatically forming images, such as electrophotographic devices and printers.
表面に光導電層を備えた感光体の、該光導電層を一様か
つ特定極性に帯電し、これに適時の画像信号書き込み手
段で光像を投射して静電潜像を形成し、ついで、これに
該潜像と反対極性に帯電した微粒状のトナーを静電的に
付与してトナー像を形成したのち、このトナー像を紙を
主とするシート状の転写材にトナーと反対極性の電荷を
印加して静電的にトナー像を転写材に転写し、さらにこ
の転写材を定着部位に移送して、圧力あるいは熱と圧力
をこれに加えてトナー像を転写材に定着固定する画像形
成方法およびそのように構成した画像形成装置は従来か
ら広範に実用されている。The photoconductive layer of a photoreceptor having a photoconductive layer on its surface is charged uniformly and to a specific polarity, a light image is projected thereon by a suitable image signal writing means to form an electrostatic latent image, and then an electrostatic latent image is formed. After electrostatically applying fine toner particles charged to the opposite polarity to the latent image to form a toner image, this toner image is transferred to a sheet-like transfer material mainly made of paper with a polarity opposite to that of the toner. The toner image is electrostatically transferred to the transfer material by applying a charge of 2. Description of the Related Art Image forming methods and image forming apparatuses configured in this manner have been widely used in the past.
このような画像形成装置はトナー像を静電的に転写材に
担持させているために転写後にも相当量のトナーが感光
体表面に残り（転写率は８０〜９０％程度）、画像濃度
が低（なることを免れなかった。In such an image forming apparatus, since the toner image is electrostatically supported on the transfer material, a considerable amount of toner remains on the surface of the photoreceptor even after transfer (transfer rate is about 80 to 90%), resulting in poor image density. Low (could not be avoided.
また、静電的にトナーを移動するためにトナーの飛散を
完全に阻止することが困難で、このため画像の鮮明さを
損なったり、装置内各部を汚損するおそれがあった。Furthermore, since the toner is moved electrostatically, it is difficult to completely prevent the toner from scattering, which may impair the clarity of the image or stain various parts within the apparatus.
このような問題点を回避するために、たとえば、特開昭
５５−１３４８７２号公報、あるいは米国特許第４１９
５９２７号明細書にみるように、圧力を用いた転写手段
が提案されている。In order to avoid such problems, for example, Japanese Patent Application Laid-Open No. 55-134872 or U.S. Pat. No. 419
As seen in the specification of No. 5927, a transfer means using pressure has been proposed.
しかしながらこの種のものは転写、定着を行うために２
００Ｋｇ／ｃｒｒ？程度の圧力を用いるので、感光体表
面のトナー像を直接転写材に転写することが困難で、中
間転写体たる誘電体層に一旦静電潜像を転写する必要が
あり、このために装置の大型化、機構の複雑化を招いた
り、また静電潜像の転写を行うために画像の解像度の低
下を生来するなどの不都合があった。However, this type of device requires two
00Kg/crr? Since a moderate amount of pressure is used, it is difficult to directly transfer the toner image on the surface of the photoreceptor to the transfer material, and it is necessary to transfer the electrostatic latent image to the dielectric layer that is the intermediate transfer member. There are disadvantages such as an increase in size and a complicated mechanism, and a reduction in image resolution due to the transfer of an electrostatic latent image.
また、米国特許第３５９１２７６号明細書、同第３６６
９７０６号明細書などにみるように、感光体に形成した
潜像を顕像化し、これをシリコンゴム層を有する中間転
写体に転写した後、この転写像を、熱を加えることによ
って転写材に転写するようなものが提案されている。Also, U.S. Patent Nos. 3,591,276 and 366
As seen in the specification of No. 9706, a latent image formed on a photoreceptor is visualized and transferred to an intermediate transfer member having a silicone rubber layer, and then this transferred image is transferred to a transfer material by applying heat. Something like transcription has been proposed.
ところが、このようなものは、トナーの融点近傍あるい
は以上となるように熱を加える必要があり、かつ、従来
から用いられているトナーが画像性を維持するため適当
な粒径に微粉砕が可能なものでなければならず、又ブロ
ッキングと呼ばれる凝固を発生しないようにするため必
然的にトナーのメイン樹脂は高融点のものにならざるを
えなかった。このため転写・定着時に多量の熱量が必要
となり、またこの熱が中間転写体を介して感光体を昇温
させるため、感光体の特性を損なうという問題点があっ
た。However, for such products, it is necessary to apply heat to bring the temperature near or above the toner's melting point, and the toners conventionally used can be finely pulverized to an appropriate particle size in order to maintain image quality. Moreover, in order to prevent the occurrence of coagulation called blocking, the main resin of the toner had to have a high melting point. For this reason, a large amount of heat is required during transfer and fixing, and this heat increases the temperature of the photoreceptor via the intermediate transfer member, resulting in a problem in that the characteristics of the photoreceptor are impaired.
本発明は以上のような事態に対処すべ（なされたもので
あって、高い転写効率と低い消費熱量を有し、長期にわ
たって良質の画像を安定的に得られるような画像形成方
法及び装置を提供することを目的とするものである。The present invention has been made to address the above-mentioned situation, and provides an image forming method and apparatus that have high transfer efficiency and low heat consumption, and that can stably obtain high-quality images over a long period of time. The purpose is to
〔課題を解決する技術手段とその作用〕上記の目的を達
成するために、本発明に於いては導電性基体上に光導電
層をもうけた感光体の該光導電層に形成した静電潜像を
粉体トナーで顕像とし、前記感光体に圧接する中間転写
体にこの顕像を転写し前記中間転写体と圧接している加
圧体との間を通過する転写材を、前記感光体と中間転写
体との圧接力よりも大きい圧接力で中間転写体に圧接す
る加圧体との前記感光体と前記中間転写体との接触面の
温度よりも高い温度で中間転写材上の間を通過させると
ともに、トナー像を前記転写材へ転写・定着を行うもの
で、かつ、該トナーが、懸濁重合法によって生成された
静電荷像現像用重合トナーであり、スチレン系重合体ま
たはスチレン系共重合体１００重量部、軟化点４０〜１
３０℃を有し、且つ、芳香族基を有する低軟化点化合物
Ａ３０〜１５００重量部、前記低軟化点化合物以外の軟
化点４０〜１３０℃を有する低軟化点化合物８２０〜１
５００重全部および着色剤を含有している重合トナーで
あり、該圧接力をトナーに加えることで熱流動性を増加
せしめ、前述転写・定着時の温度をより低下せしめたこ
とを特徴とするものである。[Technical means for solving the problem and their effects] In order to achieve the above object, the present invention uses an electrostatic latent layer formed on the photoconductive layer of a photoreceptor having a photoconductive layer on a conductive substrate. The image is visualized with powder toner, the developed image is transferred to an intermediate transfer member that is in pressure contact with the photoreceptor, and the transfer material that passes between the intermediate transfer member and the pressure member that is in pressure contact with the photoreceptor is transferred to the photoreceptor. The intermediate transfer material is heated at a temperature higher than the temperature of the contact surface between the photoreceptor and the intermediate transfer member, and the pressure member is pressed against the intermediate transfer member with a pressure greater than the pressure contact force between the intermediate transfer member and the intermediate transfer member. The toner image is transferred and fixed onto the transfer material, and the toner is a polymerized toner for developing an electrostatic image produced by a suspension polymerization method, and is made of a styrene polymer or 100 parts by weight of styrene copolymer, softening point 40-1
30 to 1500 parts by weight of a low softening point compound A having a temperature of 30°C and having an aromatic group, 820 to 1 of a low softening point compound having a softening point of 40 to 130°C other than the above low softening point compound
A polymerized toner containing 500 gb and a colorant, which is characterized by increasing thermal fluidity by applying the pressure to the toner, thereby further lowering the temperature during transfer and fixing as described above. It is.
第１図は本発明の実施例を示す画像形成装置の概略側面
図であって、表面に光導電層をもうけた感光体１は、不
図示の駆動源によって矢印Ａ方向に回転する。符号２は
、表面にウレタンゴム、フッ素ゴム、またはシリコンゴ
ムなどを成膜した鋼などの剛性材料で回転円筒上に構成
した中間転写体で、その軸受は端部に配したバネ（不図
示）など適宜の手段で前記感光体に圧接して従動回転す
る。FIG. 1 is a schematic side view of an image forming apparatus showing an embodiment of the present invention, in which a photoreceptor 1 having a photoconductive layer on its surface is rotated in the direction of arrow A by a driving source (not shown). Reference numeral 2 denotes an intermediate transfer body made of a rigid material such as steel with a film of urethane rubber, fluororubber, or silicone rubber formed on its surface, and constructed on a rotating cylinder, and its bearing is supported by a spring (not shown) placed at the end. The photoreceptor is pressed against the photoreceptor by an appropriate means and rotates as a result.
前記中間転写体２には、表面に適宜膜厚の樹脂をコーテ
ィングした剛性材料からなる回転円筒状の加圧体３が圧
接しており、これら両者の圧接力は、前述の感光体と中
間転写体との間のそれよりも大となっていて、さらに、
この加圧体内部にはこれを加熱するためのヒーター１２
が配されている。A rotary cylindrical pressure body 3 made of a rigid material whose surface is coated with a resin of an appropriate thickness is in pressure contact with the intermediate transfer body 2, and the pressure between these two is applied to the aforementioned photoreceptor and the intermediate transfer body. It is larger than that between the body and furthermore,
Inside this pressurized body is a heater 12 for heating it.
are arranged.
前記感光体ｌの表面にもうけた光導電層としては比較的
耐圧性の大きいアモルファスシリコン、有機半導体を用
いるのが好適であり、さらにその表面に表面エネルギー
が３５ダイン／ｃｍ以下の物質、たとえばシリコン樹脂
、フッ素構脂またはこれらの官能器を有するブロックポ
リマーなどを直接塗布するか混合して感光体を形成する
のが好適である。このとき形成される表面層の厚みは２
μｍ以下好ましくは１μｍで、表面粗さは０．５μｍ
ＲＭ Ｓ以上、好ましくは０．２μｍ ＲＭ Ｓ程度と
するのがよい。感光体の芯金はアルミニウム、アルミニ
ウム合金、銅合金などの導電性材料で形成し、その肉あ
つは中間転写体との接触圧に充分耐えられるようにする
。As the photoconductive layer formed on the surface of the photoreceptor 1, it is preferable to use amorphous silicon or an organic semiconductor having relatively high voltage resistance, and furthermore, a material having a surface energy of 35 dynes/cm or less, such as silicon, is preferably used. It is preferable to form the photoreceptor by directly applying or mixing a resin, a fluorine resin, or a block polymer having a functional organ thereof. The thickness of the surface layer formed at this time is 2
μm or less, preferably 1 μm, surface roughness 0.5 μm
RMS or more, preferably about 0.2 μm RMS. The core metal of the photoreceptor is made of a conductive material such as aluminum, aluminum alloy, copper alloy, etc., and its thickness is made so that it can sufficiently withstand the contact pressure with the intermediate transfer member.
中間転写体２は、鋼などの剛性材料からなる芯金の表面
をシリコンゴム、フッ素ゴムあるいはウレタンゴムなど
の樹脂で被覆し、被覆している樹脂の厚みは、圧接時の
圧力によって１〜５μｍの範囲内で適宜定めるものとす
る。The intermediate transfer body 2 has a core made of a rigid material such as steel, and the surface thereof is coated with a resin such as silicone rubber, fluororubber, or urethane rubber, and the thickness of the coated resin varies from 1 to 5 μm depending on the pressure at the time of pressure contact. shall be determined as appropriate within the scope of.
さらに、前記加圧体の内部に内装した熱源としては、ハ
ロゲンランプ、面状発熱体など適宜のものが使用でき、
不図示の制御手段によって加圧体の表面温度が使用され
るトナーの転写・定着に必要な温度になるべ（維持され
るようになっている。Further, as the heat source installed inside the pressurizing body, an appropriate one such as a halogen lamp or a sheet heating element can be used.
A control means (not shown) ensures that the surface temperature of the pressurizing body reaches (and maintains) the temperature necessary for transferring and fixing the toner used.
前記感光体ｌの周縁にはよく知られているように、光導
電層を一様に帯電させるための一次帯電器５、この帯電
面に画像情報を与えて静電潜像を形成させるための露光
部６、該潜像を顕像化するためにトナーを供給する現像
器７、転写後、感光体表面に残る残留トナーを除去する
クリーナー４、残留電荷を除去するイレーズランプ４ｂ
、除電帯電器４ａなどが配設されている。As is well known, on the periphery of the photoreceptor 1, there is a primary charger 5 for uniformly charging the photoconductive layer, and a primary charger 5 for imparting image information to the charged surface to form an electrostatic latent image. an exposure unit 6, a developer 7 that supplies toner to visualize the latent image, a cleaner 4 that removes residual toner remaining on the surface of the photoreceptor after transfer, and an erase lamp 4b that removes residual charges.
, a static eliminator charger 4a, etc. are provided.
このような構成の画像形成手段は従来がら周知であるの
で詳述はしないが、現像器７の位置で形成されたトナー
像は感光体ｌの回転にともなって中間転写体２との圧接
ニップ部Ｎ、に至る。Image forming means having such a configuration is conventionally well known and will not be described in detail, but as the photoreceptor l rotates, the toner image formed at the position of the developing device 7 is brought into pressure contact with the intermediate transfer member 2 at the nip. This leads to N.
この位置で感光体上のトナー像は中間転写体に圧力転写
される。At this position, the toner image on the photoreceptor is pressure-transferred onto the intermediate transfer member.
このようにして中間転写体に転移したトナー像は、該転
写体の回転にともなって、加圧体３との圧接ニップ部Ｎ
２に至る。As the transfer body rotates, the toner image transferred to the intermediate transfer body in this way is brought into contact with the pressure body 3 at the pressure nip N.
2.
一方、カセットなどのリザーバ９から取り出されて搬送
路１３に送出された転写紙は一旦レジストローラ１０の
位置で待機し、ついで中間転写体上を進行するトナー像
とタイミングを合せてニップ部Ｎ２に於いてトナー像に
接触し、圧力と熱の作用でトナー像を受容したのち、排
出ローラーを経て装置外に排出される。On the other hand, the transfer paper taken out from the reservoir 9 such as a cassette and sent to the conveyance path 13 temporarily waits at the position of the registration roller 10, and then reaches the nip portion N2 in synchronization with the toner image traveling on the intermediate transfer member. After coming into contact with the toner image and receiving the toner image under the action of pressure and heat, it is discharged from the apparatus via a discharge roller.
なお、図中、符号８は残留トナーを除去するためのクリ
ーナーである。Note that in the figure, reference numeral 8 is a cleaner for removing residual toner.
次に、ニップ部Ｎ、、Ｎ２の位置に於ける圧力について
述べると、Ｎ、に於ける圧力はＯ，１Ｋｇ／ｃｒｒｒ以
下にすると転写率が６０％以下になり実用的でない。ま
た、ｌｏＯＫｇ／ｃｒｒｒ以上では感光体の特性変化や
摩耗が大きくなって耐久性に欠けるので好ましくない。Next, regarding the pressure at the nip portions N, N2, if the pressure at N is less than 0.1 kg/crrr, the transfer rate will be less than 60%, which is not practical. Further, if it exceeds loOKg/crrr, it is not preferable because the change in characteristics and wear of the photoreceptor become large, resulting in a lack of durability.
好ましくはＩ Ｋ ｇ ／ ｃ ｒｄ以上３０Ｋｇ／ｃ
ｒｄ以下が良い。ニップ部Ｎ２に於ける圧力は高い程転
写率は向上するが、極端に高いと、たとえば３００Ｋｇ
／ｃｒｒｆ以上になると転写紙が透明化したり、光沢が
増して見にくくなり好ましくない。反面この圧力が１０
Ｋｇ／ｃｒ＋ｆ以下では転写率が６０％以下になり実用
的でない。また、ニップ部Ｎ１での転写圧がニップ部Ｎ
２におけるそれよりも高い場合ニップ部Ｎ２における転
写率が低下するため好ましくない。実用的にはニップ部
Ｎ、の転写圧はニップ部Ｎ２のそれよりも３０Ｋｇ／ｃ
ｒｒｆ以上低いことが好ましい。Preferably IKg/crd or more 30Kg/c
rd or less is better. The higher the pressure in the nip part N2, the better the transfer rate will be, but if it is extremely high, for example, 300 kg
/crrf or more is not preferable because the transfer paper becomes transparent or becomes glossy, making it difficult to see. On the other hand, this pressure is 10
If it is less than Kg/cr+f, the transfer rate will be less than 60%, which is not practical. Also, the transfer pressure at the nip portion N1 is
If it is higher than that in N2, the transfer rate at the nip portion N2 will decrease, which is not preferable. Practically speaking, the transfer pressure at nip part N is 30 kg/c higher than that at nip part N2.
It is preferable that it is lower than rrf.
さらにニップ部Ｎ、およびＮ２での温度範囲を示すと、
ニップ部Ｎ１では、中間体が高温で感光体に接触した場
合、半導体である感光体は暗抵抗が減少し、帯電位が減
少する傾向を示す。このため、ニップ部Ｎ、における温
度は３０℃〜５０℃に保つことが良（、好ましくは４０
±５℃である。このためにニップ部Ｎ２を中間体が通過
後不図示のファン等の冷却手段を取ることが好ましい。Furthermore, the temperature ranges at nip part N and N2 are shown as follows:
In the nip portion N1, when the intermediate contacts the photoreceptor at high temperature, the photoreceptor, which is a semiconductor, exhibits a tendency for dark resistance to decrease and charged potential to decrease. For this reason, it is recommended to maintain the temperature at the nip part N at 30°C to 50°C (preferably at 40°C).
±5℃. For this purpose, it is preferable to take cooling means such as a fan (not shown) after the intermediate passes through the nip portion N2.
さらにニップ部Ｎ２における温度は使用するトナーの内
部ワックスの軟化点温度迄昇温される条件であって、か
つ十分な圧力が加えられていれば十分な転写定着が可能
である。この条件は、転写定着時の中間転写体と加圧・
加熱ローラーの接触幅にツブ巾）と温度、中間転写体の
移動速度（プロセス速度）に依存している。すなわち、
内部ワックスの軟化点温度を６９℃とすると、ニップ部
の温度は６９℃以上必要であり、プロセス速度をたかだ
か６００ｍｍ／ｓｅｅとしニップ巾を３〜４ｍｍとすれ
ば最高で１６０℃あれば十分であり、好ましくは１７０
℃である。Further, if the temperature at the nip portion N2 is raised to the softening point temperature of the internal wax of the toner used, and if sufficient pressure is applied, sufficient transfer and fixation is possible. These conditions apply to the intermediate transfer body and pressure/pressure during transfer and fixing.
It depends on the contact width of the heating roller (width), temperature, and moving speed of the intermediate transfer body (process speed). That is,
If the softening point temperature of the internal wax is 69°C, the temperature at the nip part must be 69°C or higher, and if the process speed is at most 600 mm/see and the nip width is 3 to 4 mm, a maximum of 160°C is sufficient. , preferably 170
It is ℃.
第２図は本発明による画像形成装置の他の実施態様を模
式的に示したものであって、このものにおいては、中間
転写体がエンドレスベルト状に形成され、感光体ｌに当
接するローラ２ａと加圧体３に当接するローラ２ｂに捲
回されている。FIG. 2 schematically shows another embodiment of the image forming apparatus according to the present invention, in which the intermediate transfer member is formed in the shape of an endless belt, and a roller 2a in contact with the photoreceptor l is shown. and is wound around a roller 2b that comes into contact with the pressurizing body 3.
このようなものが前述の実施例のものと同様の作用を奏
することは直ちに理解できるところであろう。It will be readily understood that such a device has the same effect as that of the previous embodiment.
次に、本発明に於いて用いることのできるトナーについ
て詳述する。Next, toners that can be used in the present invention will be described in detail.
本発明に使用されるトナーは、懸濁重合法によって生成
された静電荷像現像用重合トナーであり、スチレン系重
合体またはスチレン系共重合体１００重量部、軟化点４
０〜１３０℃を有し且つ芳香族基を有する低軟化点化合
物Ａ５〜１５００重量部、前記低軟化点化合物以外の軟
化点４０〜１３０℃を有する低軟化点化合物８４５〜１
５００重量部および着色剤を含有している。The toner used in the present invention is a polymerized toner for developing an electrostatic image produced by a suspension polymerization method, containing 100 parts by weight of a styrene polymer or styrene copolymer, and a softening point of 4.
5 to 1500 parts by weight of a low softening point compound A having a temperature of 0 to 130°C and having an aromatic group, 845 to 1 of a low softening point compound having a softening point of 40 to 130°C other than the above low softening point compound
500 parts by weight and a colorant.
本発明に係る重合トナーは、現像に使用され、通常体積
平均粒径約０．１〜約３０μｍの粒径を有し懸濁重合に
よって重合性単量体から生成された重合体１００重量部
に対して軟化点４０−１３０℃の芳香族基を有する低軟
化点化合物Ａ３０−１５００重量部含有し、且つ芳香族
基を有していない軟化点４０〜１３０℃の低軟化点化合
物８２０〜１５００重量部を含有している。The polymerized toner according to the present invention is used for development and usually has a volume average particle size of about 0.1 to about 30 μm, and contains 100 parts by weight of a polymer produced from polymerizable monomers by suspension polymerization. Contains 30-1500 parts by weight of a low-softening point compound A having an aromatic group with a softening point of 40-130°C, and 820-1500 parts by weight of a low-softening point compound having a softening point of 40-130°C and not having an aromatic group. Contains parts.
本発明の重合トナーは、上述の如〈従来の重合トナーと
比較して低軟化点化合物を多量に含有しているにもかか
わらず耐ブロッキング性に優れている。これは、低軟化
点化合物が重合性単量体から重合された重合体に良好に
内包化されており、低軟化点化合物が重合トナー粒子表
面に表出していないためである。耐ブロックキング性は
、直径約５ｃｍの１００ｍ ｌ容器に試料１〜５ｇを入
れ温度５０℃、相対温度約６０±５％の環境下に一日放
置した後の２０メツシ篩（ティラーメツシュ）に残留す
る長粒径約１ｍｍ以上の凝集塊状物の有無によって測定
可能である。As mentioned above, the polymerized toner of the present invention has excellent blocking resistance even though it contains a large amount of a low softening point compound compared to conventional polymerized toners. This is because the low softening point compound is well encapsulated in the polymer obtained from the polymerizable monomer, and the low softening point compound is not exposed on the surface of the polymerized toner particles. Blocking resistance was determined by placing 1 to 5 g of the sample in a 100 ml container with a diameter of approximately 5 cm, leaving it for one day in an environment with a temperature of 50°C and a relative temperature of approximately 60 ± 5%, and then passing it through a 20 mesh sieve (tiller mesh). It can be measured by the presence or absence of residual aggregates having a long particle size of about 1 mm or more.
本発明の低軟化点化合物ＡおよびＢにおいては、複数の
低軟化点化合物を混合して使用しても良い。In the low softening point compounds A and B of the present invention, a plurality of low softening point compounds may be mixed and used.
使用する複数の低軟化点化合物の軟化点（４０−１３０
℃）および使用量をそれぞれ（ＴＩ、 Ｗｌ）、（Ｔ２
゜Ｗ ２ ） −（Ｔ ｎ −１、Ｗ ｎ −１）、（
Ｔｎ、 Ｗｎ）とした場合、下記条件を見足すことが好
ましい。Softening points of multiple low softening point compounds used (40-130
°C) and usage amount (TI, Wl), (T2
゜W 2 ) −(T n −1, W n −1), (
Tn, Wn), it is preferable to consider the following conditions.
尚、低軟化点化合物の使用量は、添加した重合性単量体
がほぼ１００％重合して重合体を生成した場合を仮定し
ての値であり、重合体１００重量部に対して５０≦Ｗ
１ ＋ Ｗ ２ ＋−・Ｗ ｎ −１＋ Ｗ ｎ≦１０
００の条件を満たしている。重合体１００重量部とは、
換言すれば重合トナーを形成する重合体を生成するため
に有効に使用される重合性単量体１００重量部を意味す
る。したがって、水性媒体に溶解するＩおよび未反応量
を考慮して、重合性単量体を１００重量部以上使用して
重合体１００重量部が生成される場合もある。The amount of the low softening point compound used is based on the assumption that the added polymerizable monomer is almost 100% polymerized to form a polymer, and is 50≦per 100 parts by weight of the polymer. W
1 + W 2 +-・W n -1+ W n≦10
00 conditions are met. 100 parts by weight of polymer is
In other words, it means 100 parts by weight of the polymerizable monomer that is effectively used to produce the polymer forming the polymerized toner. Therefore, 100 parts by weight of the polymer may be produced by using 100 parts by weight or more of the polymerizable monomer, taking into consideration the I dissolved in the aqueous medium and the unreacted amount.
上記条件からはずれて、０，０５以下の値となった場合
には低軟化点化合物の使用量が多すぎて、耐ブロッキン
グ性が低下し、重合トナーの機械的強度が不足する傾向
が高まる。反対に、０．８以上の値となる場合には低温
定着性および／又は低圧定着性の改善の程度が少なくな
る。If the value deviates from the above conditions and the value is 0.05 or less, the amount of the low softening point compound used is too large, resulting in a decrease in blocking resistance and an increased tendency for the polymerized toner to lack mechanical strength. On the other hand, if the value is 0.8 or more, the degree of improvement in low-temperature fixability and/or low-pressure fixability will be reduced.
本発明の重合トナーは、次の製造方法により生成するこ
とが出来る。The polymerized toner of the present invention can be produced by the following manufacturing method.
すなわち、少な（とも重合性単量体、低軟化点４０〜１
３０℃を有する芳香族基を有する低軟化点化合物Ａ、低
軟化点化合物Ｂおよび着色剤を含有する単量体組成物を
、高温に加温された水性媒体中で分散造粒し、造粒工程
が実質的に終了した後に、造粒された単量体組成物粒子
を含有する重合温度に調整された水性媒体中へ重合開始
剤を添加して、懸濁重合する方法である。この場合、水
性媒体の造粒工程時における液温は、低軟化点化合物の
軟化点よりも高温にする方が、造粒の容易さ及び粒度分
布をシャープにする点で好ましい。That is, a small amount (polymerizable monomer, low softening point 40-1
A monomer composition containing a low softening point compound A having an aromatic group having a temperature of 30°C, a low softening point compound B, and a coloring agent is dispersed and granulated in an aqueous medium heated to a high temperature, and granulated. After the process is substantially completed, a polymerization initiator is added to an aqueous medium containing granulated monomer composition particles and adjusted to a polymerization temperature, and suspension polymerization is carried out. In this case, it is preferable that the temperature of the aqueous medium during the granulation step be higher than the softening point of the low softening point compound in terms of ease of granulation and sharp particle size distribution.
上記製造方法においては、重合性単量体を重合するため
の重合開始剤が単量体組成物を造粒後に水性媒体中に添
加されている。そのため、単量体組成物の分散媒体であ
る水性媒体の温度を従来より高温にして造粒をおこなう
ことが可能である。さらに、造粒後に分級工程を設けて
所定粒度を有する単量体組成物粒子と規定外の粒度を有
する単量体組成物粒子とを分級し、その後に重合開始剤
を添加して重合をおこなうことが可能であり、一方分別
された規定外の粒度を有する単量体組成物粒子を重合工
程前に他の単量体組成物と混合し、再度分散造粒して再
利用することも可能である。また、造粒工程中は重合開
始剤の分解温度を考慮することな（、水性媒体の温度を
高温にすることが可能であるため、単量体組成物中に低
軟化点化合物を多量に添加して造粒することができ、多
量に添加されている場合でも高温で造粒することができ
るため、シャープな粒度分布を有する低温定着および／
又は低圧定着可能な省エネルギー用の重合トナーを製造
し得る。In the above production method, a polymerization initiator for polymerizing the polymerizable monomer is added to the aqueous medium after granulating the monomer composition. Therefore, it is possible to perform granulation by setting the temperature of the aqueous medium, which is the dispersion medium of the monomer composition, to a higher temperature than conventionally. Furthermore, a classification step is provided after granulation to classify the monomer composition particles having a predetermined particle size and the monomer composition particles having an unspecified particle size, and then a polymerization initiator is added to perform polymerization. On the other hand, it is also possible to mix the separated monomer composition particles with an unspecified particle size with other monomer compositions before the polymerization process, re-disperse and granulate them, and reuse them. It is. Also, during the granulation process, the decomposition temperature of the polymerization initiator should not be taken into account (because it is possible to raise the temperature of the aqueous medium to a high temperature, it is possible to add a large amount of low softening point compounds to the monomer composition). It can be granulated at high temperature even when a large amount is added, so it can be granulated at low temperature and/or with a sharp particle size distribution.
Alternatively, an energy-saving polymerized toner that can be fixed at low pressure can be produced.
本発明者らの知見によれば、水溶性の重合開始剤を使用
した場合、生成される重合トナーは耐湿性が低下し、高
温高湿時における現像特性および耐ブロッキング性が劣
化してしまうので、環境特性に優れた重合トナーを製造
するためには実質的に非水溶性の重合開始剤を使用する
ことが好ましい。実質的に非水溶性の重合開始剤を使用
する場合、従来の如（単量体組成物に予め溶解混合して
いる系では、各単量体組成物粒子に均等に重合開始剤が
分配されることが予想されるが、上記製造方法の如（水
性媒体中で単量体組成物を造粒後、実質的に非水溶性の
重合開始剤を添加する系においても、各粒子に良好に重
合反応が生ずるということは驚くべきことである。According to the findings of the present inventors, when a water-soluble polymerization initiator is used, the moisture resistance of the polymerized toner produced decreases, and the development characteristics and blocking resistance at high temperature and high humidity deteriorate. In order to produce a polymerized toner with excellent environmental properties, it is preferable to use a substantially water-insoluble polymerization initiator. When using a substantially water-insoluble polymerization initiator, the polymerization initiator is distributed evenly to each monomer composition particle in the conventional manner (in a system in which it is dissolved and mixed in the monomer composition in advance). However, even in the production method described above (in which a substantially water-insoluble polymerization initiator is added after granulating the monomer composition in an aqueous medium), each particle is It is surprising that a polymerization reaction occurs.
上記製造方法で使用される重合開始剤は、実質的に非水
溶性であることが上述の如く好ましい。本発明における
実質的に非水溶性の重合開始剤とは、室温にて水１００
ｇに対して１ｇ以下の溶解度を有するものであり、好ま
しくは水１００ｇに対して０．５ｇ以下、特に好ましく
は水１００ｇに対して０．２ｇ以下の低溶解度を有する
ものである。水１００ｇに対してｔｇ以上の溶解度を有
する場合には、重合終了後に重合トナー粒子表面に残存
する重合開始剤の分解生成物が、重合トナーの耐湿性を
低下させるので好ましくない。また、上記製造方法で使
用する重合開始剤は重合性単量体に可溶であり、通常使
用する量範囲（単量体１００重量部に対して重合開始剤
２〜５重量部）では良好に重合性単量体に溶解する特性
を有する。上記製造方法に使用可能な重合開始剤として
、２，２′−アゾビス−（２，４−ジメチルバレロニト
リルＬ２，２’ −アゾビスイソブチロコトリル、１．
１’ −アゾビス（シクロヘキサン−１−カルボニトリ
ル）、２，２′ −アゾビス−４−メトキシ−２，４−
ジメチルバレロニトリル、その他のアゾビスイソブチロ
ニトリル（ＡＩＢＮ）の如きアゾ系またはジアゾ系重合
開始剤；ベンゾイルパーオキサイド、メチルエチルケト
ンパーオキサイド、イソプロピルパーオキシカーボネー
ト、キュメンハイドロパーオキサイド、２，４−ジクロ
リルベンゾイルパーオキサイド、ラウロイルパーオキサ
イドの如き過酸化合物系重合開始剤が挙げられる。本発
明の製造方法において、重合開始剤は重合温度（通常５
０℃以上）と同等またはそれ以下の融点を有するものが
好ましい。また、重合体の分子量および分子量分布を調
節する目的でまたは反応時間を調節する目的等で二種類
またはそれ以上重合開発剤を混合して使用することも好
ましい。As mentioned above, the polymerization initiator used in the above production method is preferably substantially water-insoluble. In the present invention, the substantially water-insoluble polymerization initiator means 100 ml of water at room temperature.
It has a solubility of 1 g or less per 100 g of water, preferably 0.5 g or less per 100 g of water, particularly preferably 0.2 g or less per 100 g of water. When the solubility is tg or more in 100 g of water, it is not preferable because the decomposition products of the polymerization initiator remaining on the surface of the polymerized toner particles after the completion of polymerization deteriorate the moisture resistance of the polymerized toner. In addition, the polymerization initiator used in the above production method is soluble in the polymerizable monomer, and the amount range normally used (2 to 5 parts by weight of polymerization initiator per 100 parts by weight of monomer) is satisfactory. It has the property of being soluble in polymerizable monomers. Examples of polymerization initiators that can be used in the above production method include 2,2'-azobis-(2,4-dimethylvaleronitrile L2,2'-azobisisobutyrokotrile), 1.
1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-
Azo or diazo polymerization initiators such as dimethylvaleronitrile and other azobisisobutyronitrile (AIBN); benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichloryl Examples include peracid compound polymerization initiators such as benzoyl peroxide and lauroyl peroxide. In the production method of the present invention, the polymerization initiator is used at a polymerization temperature (usually 5
Those having a melting point equal to or lower than 0° C.) are preferred. It is also preferred to use a mixture of two or more polymerization developing agents for the purpose of adjusting the molecular weight and molecular weight distribution of the polymer or for the purpose of adjusting the reaction time.
その場合、す（な（とも１種は、重合時の水性媒体中の
液温に相当する温度またはそれ以下の温度の融点を有す
るものを使用することが好ましい。何故ならば、重合反
応時の液温で重合開始剤が油状化しているので、水性媒
体へ添加後に分散されている各単量体組成物粒子へ重合
開始剤または重合開始剤から生成するラジカルがより良
好に付与されるからである。ちなみに、後述の実施例で
使用している２、２′−アゾビス−（２，４−ジメチル
バレロニトリル）はメソ体（ｍ、ｐ、５’５〜５７℃）
と６１体（ｍ 、 ｐ 、 ７４〜７７℃）との混合物
であり、該混合物は約４５℃で融解を始め約７０℃で融
解が終了する。重合開始剤の使用量は、重合単量体１０
０重畳量部に対して０．１〜２０重量部、好ましくは１
〜ｌＯ重量部である。０．１重量部以下では、各単量体
組成物粒子へ均等に重合開始剤を付与することが困難で
あり、２０重量部以上では多過ぎて重合生成物の分子量
が低くなり過ぎるとともに重合反応が不均一に発生する
傾向が高まる。In that case, it is preferable to use one having a melting point at or below the temperature of the liquid in the aqueous medium during polymerization. Since the polymerization initiator is oily at the liquid temperature, the polymerization initiator or radicals generated from the polymerization initiator can be better imparted to each monomer composition particle dispersed after being added to the aqueous medium. By the way, 2,2'-azobis-(2,4-dimethylvaleronitrile) used in the examples below is the meso form (m, p, 5'5-57℃)
The mixture starts to melt at about 45°C and ends at about 70°C. The amount of polymerization initiator used is 10
0.1 to 20 parts by weight, preferably 1 part by weight
~lO parts by weight. If it is less than 0.1 part by weight, it is difficult to apply the polymerization initiator evenly to each monomer composition particle, and if it is more than 20 parts by weight, the molecular weight of the polymerization product becomes too low and the polymerization reaction is delayed. The tendency for this to occur unevenly increases.
懸濁重合反応は、通常重合温度５０℃以上でおこなわれ
、重合開始剤の分解速度を考慮して上限温度が設定され
る。設定重合温度が高すぎると、重合開始剤が急激に分
解されてしまうので好ましくない。上記製造方法におい
ては、懸濁造粒時には重合開始剤を単量体組成物中に存
在させる必要がないため、造粒時の水性媒体の液温を例
えば７５°Ｃ以上にして単量体組成物の溶融粘度を低下
させることにより、造粒を容易におこなうことが可能で
ある。The suspension polymerization reaction is usually carried out at a polymerization temperature of 50° C. or higher, and the upper limit temperature is set in consideration of the decomposition rate of the polymerization initiator. If the set polymerization temperature is too high, the polymerization initiator will be rapidly decomposed, which is not preferable. In the above production method, since it is not necessary to have a polymerization initiator in the monomer composition during suspension granulation, the temperature of the aqueous medium during granulation is set to 75°C or higher, for example, to obtain a monomer composition. By lowering the melt viscosity of the product, granulation can be easily performed.
形成された単量体組成物粒子が所定粒度を有しているこ
とを確認して後に、該粒子を含む水性媒体の液温を重合
温度（例えば５５〜７０℃）に下げて後に、重合開始剤
を添加する。水性媒体の液温を下げることにより、単量
体組成物粒子の保形酸も向上し、粒子同志の合一も抑制
される。重合反応時間は、重合開始剤の種類および重合
温度で変動するが、通常は２〜３０時間である。After confirming that the formed monomer composition particles have a predetermined particle size, the temperature of the aqueous medium containing the particles is lowered to the polymerization temperature (for example, 55 to 70°C), and then polymerization is started. Add agent. By lowering the liquid temperature of the aqueous medium, the shape retention acid of the monomer composition particles is also improved, and coalescence of particles is also suppressed. The polymerization reaction time varies depending on the type of polymerization initiator and the polymerization temperature, but is usually 2 to 30 hours.
上記の製造方法においては、高温での分散造粒が可能で
あるので、低軟化点化合物を単量体組成物に添加剤とし
て多量に加えてもトナーとして使用可能な重合生成物を
製造することが可能である。In the above production method, dispersion granulation at high temperatures is possible, so even if a large amount of a low softening point compound is added as an additive to the monomer composition, a polymerization product that can be used as a toner can be produced. is possible.
本発明の重合トナーにおいては、芳香族基を有する低軟
化点化合物Ａ及び低軟化点化合物Ｂは結着樹脂としての
役割をも有することが可能である。本発明における芳香
族基を有する低軟化点化合物Ａとは、環球法（ＪＩＳ
Ｋ ２５３１等参照）で測定した軟化点が４０〜１
３０℃、好ましくは５０〜１２０℃を有するものである
。軟化点が４０℃以下ではトナーの耐ブロッキング性及
び保形性が不充分であり、１３０℃以上では定着温度ま
たは定着圧力を低下させる効果が少ない。芳香族基を有
する低軟化点化合物へとしては、芳香族基を有する変性
ワックスを例示し得る。異なる低軟化点化合物を混合し
て用いても良い。具体的には、ベトロジン８０（三井石
油化学製）、ベトロジン１００（三井石油化学製）、ベ
トロジン１２０（三井石油化学製）、タックエースＡ−
１００（三井石油化学製）、タックエースＦ−１００（
三井石油化学製）、タックエースＢ−６０（三井石油化
学製）、変性ワックスＪＣ−１１４１（三井石油化学製
）、変性ワックスＪＣ−２１３０（三井石油化学製）、
変性ワックスＪＣ−４０２０（三井石油化学製）、変性
ワックスＪＣ−ｔ１４２（三井石油化学製）、変性ワッ
クスＪＣ−５０２０（三井石油化学製）等を挙げること
ができる。尚、低軟化点化合物が芳香族基を有している
か否かは、赤外線吸収スペクトル等から知見できる。In the polymerized toner of the present invention, the aromatic group-containing low softening point compound A and low softening point compound B can also have a role as a binder resin. In the present invention, the low softening point compound A having an aromatic group is defined by the ring and ball method (JIS
Softening point measured by K 2531 etc.) is 40-1
It has a temperature of 30°C, preferably 50 to 120°C. If the softening point is 40° C. or lower, the blocking resistance and shape retention of the toner will be insufficient, and if the softening point is 130° C. or higher, there will be little effect in lowering the fixing temperature or fixing pressure. An example of the low softening point compound having an aromatic group is a modified wax having an aromatic group. A mixture of different low softening point compounds may be used. Specifically, Vetrogin 80 (manufactured by Mitsui Petrochemicals), Vetrogin 100 (manufactured by Mitsui Petrochemicals), Vetrogin 120 (manufactured by Mitsui Petrochemicals), Tac Ace A-
100 (Mitsui Petrochemical), Tac Ace F-100 (
Mitsui Petrochemicals), Tac Ace B-60 (Mitsui Petrochemicals), modified wax JC-1141 (Mitsui Petrochemicals), modified wax JC-2130 (Mitsui Petrochemicals),
Examples include modified wax JC-4020 (manufactured by Mitsui Petrochemicals), modified wax JC-t142 (manufactured by Mitsui Petrochemicals), and modified wax JC-5020 (manufactured by Mitsui Petrochemicals). Note that whether or not a low softening point compound has an aromatic group can be determined from an infrared absorption spectrum or the like.
ハイレツツＴ−１００Ｘ（三井石油化学製）、ハイレツ
ツＴ−２００Ｘ （三井石油化学製）、ノｈイレツツＴ
−３００Ｘ （三井石油化学製）、密ロウ、カルナバワ
ックス、モンタンワックス等を挙げることができる。尚
、１００℃以上の軟化点の低軟化点化合物を使用する場
合には、加圧下で水性媒体の液温を１００℃以上にして
分散造粒するのが好ましい場合もある。Hiretsu T-100X (Mitsui Petrochemicals), Hiretsu T-200X (Mitsui Petrochemicals), Noh Iretsu T
-300X (manufactured by Mitsui Petrochemicals), beeswax, carnauba wax, montan wax, and the like. In addition, when using a low softening point compound having a softening point of 100° C. or higher, it may be preferable to carry out dispersion and granulation under pressure while raising the temperature of the aqueous medium to 100° C. or higher.
上記低軟化点化合物Ａ及びＢは、重合トナーの定着温度
および／又は定着圧を下げるためにスチレン系重合体ま
たはスチレン系共重合体１００重量部に対して、低軟化
点化合物Ａの場合は３０〜１５００重量部、好ましくは
５０〜８００重量部混合され、さらに低軟化点化合物Ｂ
の場合は２０〜１５００重量部、好ましくは３０〜８０
０重量部混合される。低軟化点化合物Ａが３０重量部以
下の場合は、定着時におけるスチレン系重合体又はスチ
レン系共重合体との融和が充分でな（、低軟化点化合物
ＡとＢとの総和が５０重量部以下では定着ローラの定着
温度または定着圧力を下げるには不充分である。一方、
低軟化点化合物ＡとＢの総和が３０００重量部以上では
、耐ブロッキング性および耐久性が低下する傾向が強ま
る。好ましくは低軟化点化合物Ａ及びＢの総和量が１０
００重量部以下が良い。スチレン系重合体またはスチレ
ン系共重合体との良好な融和性を得るには、低軟化点化
合物Ａ及びＢの総和量を基準にして、低軟化点化合物Ａ
が１０〜９０重量％含有されるのが好ましい。The above-mentioned low softening point compounds A and B are added to 100 parts by weight of the styrene polymer or styrene copolymer in order to lower the fixing temperature and/or fixing pressure of the polymerized toner, and in the case of low softening point compound A, 30 parts by weight of the styrene polymer or styrene copolymer is added. ~1500 parts by weight, preferably 50 to 800 parts by weight, and further low softening point compound B
20 to 1500 parts by weight, preferably 30 to 80 parts by weight
0 parts by weight are mixed. If the low softening point compound A is 30 parts by weight or less, the compatibility with the styrenic polymer or styrenic copolymer during fixing is insufficient (if the total of the low softening point compounds A and B is 50 parts by weight) Below is insufficient to lower the fusing temperature or fusing pressure of the fusing roller.On the other hand,
If the total amount of low softening point compounds A and B is 3000 parts by weight or more, blocking resistance and durability tend to decrease. Preferably, the total amount of low softening point compounds A and B is 10
00 parts by weight or less is preferable. In order to obtain good compatibility with the styrenic polymer or styrenic copolymer, low softening point compound A should be added based on the total amount of low softening point compounds A and B.
The content is preferably 10 to 90% by weight.
本発明に係る重合トナーを形成するために適用出来る重
合性単量体は、スチレンまたはスチレン誘導体であり、
スチレンまたはスチレン誘導体と共重合されるべき重合
性単量体は反応基としてＣＨ２＝Ｃく基を有するモノマ
ーである。例えば、スチレン、Ｏ−メチルスチレン、ｍ
−メチルスチレン、ｐ−メチルスチレン、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、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、ｐ
−ｔｅｒｔブチルスチレン、ｐ−ｎ−ヘキシルスチレン
、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン
、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン
等のスチレンおよびその誘導体；酢酸ビニル、プロピオ
ン酸ビニル、ベンジェ酸ビニルなどのビニルエステル類
；アクリル酸、メタクリ酸、マレイン酸、マレイン酸ハ
ーフエスレル；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−２−エチルヘキ
シル、メタクリル酸ステアリル、メタクリル酸フェニル
、メタクリル酸ジメチルアミノエチル、メタクリル酸ジ
エチルアミノエチルなどのα−メチレン脂肪族モノカル
ボン酸エステル類；アクリル酸メチル、アクリル酸エチ
ル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、ア
クリル酸プロピル、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、アクリル酸２−クロルエチル、アクリル
酸フェニルなどのアクリル酸エステル類；ビニルメチル
エーテル、ビニルエチルエーテル、ビニルイソブチルエ
ーテルなどのビニルエーテル類；ビニルメチルケトン、
ビニルへキシルケトン、メチルイソプロペニルケトンな
どのビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニル
カルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロ
リドンなどのＮ−ビニル化合物；ビニルナフタリン類；
アクリロニトリル、メタリル酸誘導体、アクリルアミド
などのアクリル酸もしくはメタリル酸誘導体などのビニ
ル基の如き反応性の二重結合を有する単量体がある。こ
れらを単独あるいは二種以上用いても良い。必要に応じ
て、架橋剤を使用しても良い。架橋剤として、ジビニル
ベンゼン、ジビニルナフタリン、ジエチレングリコール
ジメタクリレート、エチレングリコールジメタクリレー
ト等を例示し得る。架橋剤の添加世は、通常重合性単量
体１００重量部に対して０．１〜５重量部使用される。The polymerizable monomer that can be applied to form the polymerized toner according to the present invention is styrene or a styrene derivative,
The polymerizable monomer to be copolymerized with styrene or a styrene derivative is a monomer having a CH2═C group as a reactive group. For example, styrene, O-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3.4-dichlorostyrene, p-ethylstyrene, 2
．． 4-dimethylstyrene, p-n-butylstyrene, p
-Styrene and its derivatives such as tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene; vinyl acetate, propion Vinyl esters such as vinyl acid and vinyl benzoate; acrylic acid, methacrylic acid, maleic acid, half-ester maleate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, Acrylic acid esters such as n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone,
Vinyl ketones such as vinylhexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes;
There are monomers having reactive double bonds such as vinyl groups such as acrylonitrile, methacrylic acid derivatives, acrylic acid or methacrylic acid derivatives such as acrylamide. These may be used alone or in combination. A crosslinking agent may be used if necessary. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, diethylene glycol dimethacrylate, and ethylene glycol dimethacrylate. The amount of crosslinking agent added is usually 0.1 to 5 parts by weight per 100 parts by weight of the polymerizable monomer.
また、これらの重合性単量体の重合体を単量体組成物中
に少量添加しても良い。上記した単量体の中で、スチレ
ン、アルキル基の如き置換基を有するスチレン、または
スチレンとアクリル酸アルキルエステル及び／又はメタ
クリル酸アルキルエステル単量体との混合単量体から生
成された重合トナーは、現像性、耐久性を考慮した場合
好ましい。Further, a small amount of a polymer of these polymerizable monomers may be added to the monomer composition. Among the above-mentioned monomers, a polymerized toner produced from styrene, styrene having a substituent such as an alkyl group, or a mixed monomer of styrene and an acrylic acid alkyl ester and/or methacrylic acid alkyl ester monomer is preferable in consideration of developability and durability.
又、単量体の重合時に添加剤として極性基を有する極性
重合体、極性共重合体または環化ゴムを添加して重合性
単量体を重合すると好ましい重合トナーを得ることがで
きる。極性重合体、極性共重合体または環化ゴムは、重
合性単量体１００重量部に対して０．５〜５０重量部、
好ましくは１〜４０重量部を添加するのが良い。０．５
重量％以下では、充分な疑似カプセル構造をとることが
難しく、５０重量部以上では、重合性単量体の量が不足
して重合トナーとしての特性が低下する傾向が強（なる
。極性重合体、極性共重合体または環化ゴムを加えた重
合性単量体組成物を該極性重合体と逆荷電性の分散剤を
分散せしめた水性媒体の水相中に懸濁させ、重合させる
ことが好ましい。即ち、重合性単量体組成物中に含まれ
るカチオン性又はアニオン性重合体、カチオン性又はア
ニオン性共重合体またはアニオン性環化ゴムは水性媒体
中に分散している逆荷電性のアニオン性又はカチオン性
分散剤とトナーとからなる粒子表面で静電気的に引き合
い、粒子表面を分散剤が覆うことにより粒子同志の合一
を防ぎ、安定化せしめると共に、添加した極性重合体、
極性共重合体または環化ゴムがトナーとなる粒子表層部
に集まる為、一種の殻のような形態となり、得られた粒
子は疑似的なカプセルとなる。そして、粒子表層部に集
まった比較的高分子量の極性重合体、極性共重合体また
は環化ゴムは多量の芳香族基を有する低軟化点化合物Ａ
及び低軟化点化合物Ｂをトナー粒子内部に内包するので
、本発明の重合トナー粒子にブロッキング性、現像性、
耐摩耗性の優れた性質を付与する。本発明に使用し得る
極性重合体（極性共重合体及び環化ゴムを包含する）及
び逆荷重性分散剤を以下に例示する。尚、極性重合体は
ＧＰＣで測定した重量平均分子量が５，０００〜５００
，０００のものが重合性単量体に良好に溶解し、耐久性
も有するので好ましく使用される。Further, a preferable polymerized toner can be obtained by adding a polar polymer having a polar group, a polar copolymer, or a cyclized rubber as an additive during polymerization of the monomer to polymerize the polymerizable monomer. The polar polymer, polar copolymer or cyclized rubber is 0.5 to 50 parts by weight per 100 parts by weight of the polymerizable monomer,
It is preferable to add 1 to 40 parts by weight. 0.5
If it is less than 50 parts by weight, it is difficult to obtain a sufficient quasi-capsule structure, and if it is more than 50 parts by weight, the amount of polymerizable monomer is insufficient and the properties as a polymerized toner tend to deteriorate. , a polymerizable monomer composition to which a polar copolymer or cyclized rubber is added is suspended in an aqueous phase of an aqueous medium in which a dispersant having an opposite charge to the polar polymer is dispersed, and polymerization is carried out. Preferably, the cationic or anionic polymer, cationic or anionic copolymer, or anionic cyclized rubber contained in the polymerizable monomer composition is an oppositely charged polymer dispersed in the aqueous medium. The anionic or cationic dispersant and the toner are electrostatically attracted to each other on the surface of the particles, and the dispersant covers the particle surface, thereby preventing the particles from coalescing and stabilizing them.
Since the polar copolymer or cyclized rubber gathers on the surface layer of the toner particles, they form a kind of shell-like form, and the resulting particles become pseudo-capsules. The relatively high molecular weight polar polymer, polar copolymer or cyclized rubber gathered on the particle surface layer is a low softening point compound A having a large amount of aromatic groups.
and low softening point compound B are included inside the toner particles, so the polymerized toner particles of the present invention have blocking properties, developability,
Provides excellent wear resistance. Examples of polar polymers (including polar copolymers and cyclized rubbers) and counterloadable dispersants that can be used in the present invention are shown below. The polar polymer has a weight average molecular weight of 5,000 to 500 as measured by GPC.
,000 is preferably used because it dissolves well in the polymerizable monomer and has durability.
（ｉ） カチオン性重合体としては、ジメチルアミノ
エチルメタクリレート、ジエチルアミノエチルアクリコ
ート等含窒素単量体の重合体、スチレンと該含窒素単量
体との共重合体もしくはスチレン、不飽和カルボン酸エ
ステル等と該含窒素単量体との共重合体がある。(i) Examples of the cationic polymer include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl acrylate, copolymers of styrene and the nitrogen-containing monomer, or styrene and unsaturated carboxylic acid esters. There are also copolymers of these nitrogen-containing monomers.
（ｉｉ） アニオン性重合体としてはアクリロニトリ
ル等のニトリル系単量体、塩化ビニル等の含ハロゲン系
単量体、アクリル酸等の不飽和カルボン酸、不飽和二塩
基酸、不飽和二塩基酸の無水物の重合体またはスチレン
と該単量体との共重合体がある。(ii) Examples of anionic polymers include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid, unsaturated dibasic acids, and unsaturated dibasic acids. There are anhydride polymers or copolymers of styrene and the monomer.
分散剤としては、水性媒体中で単量体組成物粒子を分散
安定化する能力を有し、水に難溶性の無機微粉末が好ま
しい。水性媒体中への分散剤の添加量は水を基準として
００１〜５０重量％（好ましくは１〜２０重量％）添加
するのが良い。The dispersant is preferably an inorganic fine powder that has the ability to stabilize the dispersion of the monomer composition particles in an aqueous medium and is sparingly soluble in water. The amount of the dispersant added to the aqueous medium is preferably 0.01 to 50% by weight (preferably 1 to 20% by weight) based on water.
（ｉｉｉ） アニオン性分散剤としては、アエロジル
＃２００゜＃３００（日本アエロジル社製）等のコロイ
ダルシリカがある。(iii) Examples of anionic dispersants include colloidal silica such as Aerosil #200° and #300 (manufactured by Nippon Aerosil Co., Ltd.).
（ｉｖ） カチオン性分散剤としては酸化アルミニウ
ム、水酸化マグネシウム、カップリング剤処理によるア
ミノアルキル変性コロイダルシリカ等の親水性正帯電性
シリカ微粉末等がある。(iv) Examples of the cationic dispersant include aluminum oxide, magnesium hydroxide, and fine hydrophilic positively charged silica powder such as aminoalkyl-modified colloidal silica treated with a coupling agent.
上述の極性重合体または共重合体のかわりにアニオン性
を有する環化ゴムを使用しても良い。An anionic cyclized rubber may be used instead of the above-mentioned polar polymer or copolymer.
磁性重合トナーを生成するには、単量体組成物に磁性粒
子を添加する。この場合、磁性粒子は着色剤の役割をも
かねている。本発明に用い得る磁性粒子としては、磁場
の中に置かれて磁化される物質が用いられ、例えば鉄、
コバルト、ニッケルなどの強磁性金属の粉末もしくはマ
グネタイト、ヘマタイト、フェライトなどの合金や化合
物の粉末があげられる。粒径が０．０５μｍ〜５μｍ１
好ましくはｏ、ｔ−ｉμｍである磁性微粒子が用いれら
れる。To produce magnetic polymerized toners, magnetic particles are added to the monomer composition. In this case, the magnetic particles also serve as a coloring agent. The magnetic particles that can be used in the present invention include substances that are magnetized when placed in a magnetic field, such as iron,
Examples include powders of ferromagnetic metals such as cobalt and nickel, and powders of alloys and compounds such as magnetite, hematite, and ferrite. Particle size is 0.05μm~5μm1
Preferably, magnetic fine particles having a diameter of 0, t-i .mu.m are used.
この磁性粒子の含有量はトナー重量に対し、１０〜６０
重量％、好ましくは２０〜５０重量％が良い。又、これ
ら磁性微粒子はシランカップリング剤、チタンカップリ
ング剤等の処理剤あるいは適当な反応性の樹脂等で処理
されていても良い。この場合磁性徴粒子の表面積、表面
に存在する水酸基の密度にもよるが、５重量％以下（好
ましくは００１〜３重量％）の処理量で十分な重合性単
量体及び低軟化点化合物への分散性が得られ、トナー物
性に対しても悪影響を及ぼさない。重合トナーは着色剤
を含有しており、着色剤としては従来より知られている
染料、カーボンブラック、カーボンブラックの表面を樹
脂で被覆しているグラフト化カーボンブラックの如き顔
料が使用可能である。着色剤は、重合体および低軟化点
化合物を基準にして０．５〜３０重量％含有される。ト
ナー中には必要に応じて荷電制御剤、流動性改質剤を添
加（内添）しても良い。荷電制御剤および流動性改質剤
はトナー粒子と混合（外添）して用いても良い。荷電制
御剤としてはカルボキシル基又は含窒素基を有する有機
化合物の金属錯体、含金属染料、ニグロシン等がある。The content of these magnetic particles is 10 to 60% based on the weight of the toner.
% by weight, preferably 20 to 50% by weight. Further, these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent or a titanium coupling agent, or a suitable reactive resin. In this case, although it depends on the surface area of the magnetic particles and the density of hydroxyl groups present on the surface, a treatment amount of 5% by weight or less (preferably 001 to 3% by weight) is enough to obtain the polymerizable monomer and low softening point compound. The dispersibility of the toner is obtained, and the physical properties of the toner are not adversely affected. The polymerized toner contains a colorant, and as the colorant, conventionally known dyes, carbon black, and pigments such as grafted carbon black, which is the surface of carbon black coated with a resin, can be used. The colorant is contained in an amount of 0.5 to 30% by weight based on the polymer and low softening point compound. A charge control agent and a fluidity modifier may be added (internally added) to the toner as necessary. The charge control agent and the fluidity modifier may be used by being mixed (externally added) with the toner particles. Examples of charge control agents include metal complexes of organic compounds having carboxyl groups or nitrogen-containing groups, metal-containing dyes, and nigrosine.
流動性改質剤または潜像担持体（感光体）表面のクリー
ニング補助剤としてはコロイダルシリカ、脂肪酸金属塩
などがある。又、増量の目的で炭酸カルシウム、微粉状
シリカ等の充填剤を０．５〜２０重量％の範囲でトナー
中に配合してもよい。さらにトナー粒子相互の凝集を防
止して流動性を向上するために、テフロン微粉末または
ステアリン酸亜鉛粉末のような流動性向上剤を配合して
もよい。熱ロール定着時の離型性を良くするスチレンモ
ノマーをグラフト結合した低分子量炭化水素化合物（例
えば重量平均分子ｆ１５００〜５０００）を芳香族基を
有する低軟化点化合物Ａとした場合、炭化水素化合物は
疎水性であり、極性重合体、極性共重合体または環化ゴ
ムに比べ粒子表面には出にく（重合トナーの内部に押し
込まれる形となる。その結果、多量の芳香族基を有する
低軟化点化合物を含有していても、内包化されているた
め耐久性、耐ブロッキング性に優れる。そして加熱定着
時または加熱加圧定着時に内包されている芳香族基を有
する低軟化点化合物はスチレン系重合体または共重合体
を溶解または相溶するので低温・低圧定着性を顕著に改
善する。また、定着時にスチレン系重合体又は共重合体
が相溶することによって粘度が高くなるので定着ローラ
に対しての耐オフセット性が向上する。Examples of fluidity modifiers or cleaning aids for the surface of the latent image carrier (photoreceptor) include colloidal silica and fatty acid metal salts. Further, for the purpose of increasing the amount, a filler such as calcium carbonate or finely powdered silica may be added to the toner in an amount of 0.5 to 20% by weight. Further, in order to prevent toner particles from coagulating with each other and improve fluidity, a fluidity improver such as fine Teflon powder or zinc stearate powder may be added. When a low-molecular-weight hydrocarbon compound (e.g., weight average molecular f1500 to 5000) graft-bonded with a styrene monomer that improves mold releasability during hot roll fixing is used as a low softening point compound A having an aromatic group, the hydrocarbon compound is It is hydrophobic and does not appear on the particle surface compared to polar polymers, polar copolymers, or cyclized rubber (it is pushed into the interior of the polymerized toner. As a result, low softening particles with a large amount of aromatic groups Even if it contains a point compound, it has excellent durability and blocking resistance because it is encapsulated.In addition, during heat fixing or heat and pressure fixing, the low softening point compound with an aromatic group included is styrene-based. It dissolves or compatibilizes the polymer or copolymer, which significantly improves low-temperature/low-pressure fixing properties.In addition, the viscosity increases due to the compatibility of the styrene polymer or copolymer during fixing, so it is difficult to use on the fixing roller. This improves offset resistance.
本発明に係る重合トナーを二成分現像剤に適用する場合
、通常のトナーとキャリアーの配合比で適用可能であり
、例えばトナー１重量部に対してキャリアー１〜５００
重量部を混合して使用される。When the polymerized toner according to the present invention is applied to a two-component developer, it can be applied at a usual toner to carrier ratio, for example, 1 to 500 parts by weight of carrier to 1 part by weight of toner.
Used by mixing parts by weight.
懸濁方法は、着色剤（本発明においては磁性体も包含し
ている）、重合性単量体１００重量部に対して低軟化点
化合物５０〜１０００重量部および添加剤等を均一に溶
解、又は分散せしめた単量体組成物を、０．１〜５０重
量％懸濁安定剤（例えば、難溶解性分散剤）を含有する
水性媒体（例えば重合温度よりも５℃以上、好ましくは
１０℃〜３０℃以上の温度に加温されている）中に通常
の撹拌機又はホモミキサー、ホモジナイザ等により分散
せしめる。好ましくは溶融または軟化された単量体組成
物の粒子が所望のトナー粒子のサイズ、一般に３０μｍ
以下（例えば体積平均粒径０．１〜２０μｍ）の大きさ
を有する様に撹拌速度、時間および水性媒体の温度を調
整する。その後、分散安定剤の作用によりほぼその状態
が維持される様、撹拌を粒子の沈降が防止される程度に
行いながら、水性媒体の液温を重合温度まで下げる。重
合温度は５０℃以上、好ましくは５５〜８０℃、特に好
ましくは６０〜７５℃の温度に設定し、撹拌しながら実
質的に非水溶性の重合開始剤を添加し重合を行う。反応
終了後、生成したトナー粒子を洗浄、分散安定剤の除去
、濾過、デカンテーション、遠心等の如き適当な方法に
より回収し乾燥することにより本発明の重合トナーが得
られる。懸濁重合法においては、通常重合性単量体およ
び芳香族基を有する低軟化点化合物Ａおよび低軟化点化
合物Ｂの混合物１００重量部に対し水２００〜３０００
重量部を水性分散媒として使用する。The suspension method involves uniformly dissolving 50 to 1000 parts by weight of a low softening point compound, additives, etc. to 100 parts by weight of a colorant (the present invention also includes a magnetic material), and a polymerizable monomer. Alternatively, the dispersed monomer composition may be heated in an aqueous medium containing 0.1 to 50% by weight of a suspension stabilizer (e.g., a poorly soluble dispersant) (e.g., 5°C or higher than the polymerization temperature, preferably 10°C). (heated to a temperature of ~30°C or higher) using a conventional stirrer, homomixer, homogenizer, etc. Preferably, the particles of the fused or softened monomer composition have the desired toner particle size, typically 30 μm.
The stirring speed, time, and temperature of the aqueous medium are adjusted so that the particle size is as follows (for example, volume average particle size: 0.1 to 20 μm). Thereafter, the temperature of the aqueous medium is lowered to the polymerization temperature while stirring is performed to the extent that sedimentation of the particles is prevented, so that this state is substantially maintained by the action of the dispersion stabilizer. The polymerization temperature is set at 50° C. or higher, preferably 55 to 80° C., particularly preferably 60 to 75° C., and a substantially water-insoluble polymerization initiator is added while stirring to carry out the polymerization. After the reaction is completed, the produced toner particles are recovered by an appropriate method such as washing, removal of the dispersion stabilizer, filtration, decantation, centrifugation, etc., and dried to obtain the polymerized toner of the present invention. In the suspension polymerization method, 200 to 3000 parts of water is usually added to 100 parts by weight of a mixture of low softening point compound A and low softening point compound B having a polymerizable monomer and an aromatic group.
Parts by weight are used as aqueous dispersion medium.
また、適当な安定化剤、例えばポリビニルアルコール、
ゼラチン、メチルセルロース、メチルハイドロプロピル
セルロース、エチルセルロース、カルボキシメチルセル
ロースのナトリウム塩、ポリアクリル酸およびそれらの
塩、デンプン、ガムアルギン酸塩、ゼイン、カゼイン、
リン酸三カルシラム、タルク、硫酸バリウム、ベントナ
イト、水酸化アルミニウム、水酸化第二鉄、水酸化チタ
ン、水酸化ナトリウム等のいずれか１種または混合物を
水性媒体に本発明の製造方法に悪影響を与えない程度に
含有されたものも使用しても良い。Also suitable stabilizers, such as polyvinyl alcohol,
Gelatin, methylcellulose, methylhydropropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and their salts, starch, gum alginate, zein, casein,
Any one or a mixture of tricarcylam phosphate, talc, barium sulfate, bentonite, aluminum hydroxide, ferric hydroxide, titanium hydroxide, sodium hydroxide, etc., in an aqueous medium may adversely affect the production method of the present invention. It is also possible to use a substance containing only a small amount.
また、前記無機分散安定剤の均一な分散のために、界面
活性剤を本発明の製造方法に悪影響を与えない程度に使
用してもよい。これは上記分散安定剤の所期の作用を促
進するためのものであり、その具体例としては、ドデシ
ルベンゼンスルホン酸ナトリウム、テトラデシル硫酸ナ
トリウム、ペンタデシル硫酸ナトリウム、オクチル硫酸
ナトリウム、アリル−アルキル−ポリエーテルスルホン
酸ナトリウム、オレイン酸ナトリウム、ラウリン酸ナト
リウム、カプリン酸ナトリウム−、カプリル酸ナトリウ
ム、カプロン酸ナトリウム、ステアリン酸カリウム、オ
レイン酸カルシウム、３，３−ジスルホンジ、フェニル
尿素−４，４−ジアゾ−ビス−アミノ−８−ナフトール
−６−スルホン酸ナトリウム、オルト−カルボキシベン
ゼン−アゾ−ジメチルアニリン、２．２．５．５−テト
ラメチル−トリフェニルメタン−４，４−ジアゾ−ビス
−β−ナフトール−ジスルホン酸ナトリウム、その他を
挙げることができる。しかしながら、親水性の有機安定
剤または界面活性剤を使用した場合には重合トナーの耐
湿性が低下することに留意する必要がある。Further, for uniform dispersion of the inorganic dispersion stabilizer, a surfactant may be used to the extent that it does not adversely affect the production method of the present invention. This is to promote the intended action of the above-mentioned dispersion stabilizers, and specific examples thereof include sodium dodecylbenzenesulfonate, sodium tetradecylsulfate, sodium pentadecylsulfate, sodium octylsulfate, allyl-alkyl-polyether Sodium sulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, 3,3-disulfondi, phenylurea-4,4-diazo-bis- Sodium amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2.2.5.5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-disulfone sodium chloride, and others. However, it must be noted that when a hydrophilic organic stabilizer or surfactant is used, the moisture resistance of the polymerized toner decreases.
また、水に易溶性の重合単量体は水中で乳化重合を同時
におこし、できた懸濁重合物を小さな乳化重合粒子で汚
染するので水溶性の重合禁止剤、例えば金属塩等を加え
て水相での乳化重合を防ぐこともよい。また、水性媒体
の粘度をまして重合時の粒子の合一を防ぐために、水に
グリセリン、グリコールなどを添加することも可能であ
る。In addition, water-soluble polymerization monomers simultaneously cause emulsion polymerization in water, and the resulting suspension polymerization product is contaminated with small emulsion polymerization particles, so water-soluble polymerization inhibitors, such as metal salts, are added to It is also good to prevent emulsion polymerization in the phase. It is also possible to add glycerin, glycol, etc. to water in order to increase the viscosity of the aqueous medium and prevent coalescence of particles during polymerization.
また、易溶性重合性単量体の水への溶解度減少のために
ＮａＣｊ７、ＫＣＩ、Ｎａ ２ Ｓｏ ４などの塩類を
水性媒体に加えても良い。また単量体組成物中の極性重
合体または塩化ゴムの極性基のイオン化を高めるために
塩酸の如きブレンステッド酸を水性媒体へ添加すること
も可能である。特に、塩酸の如き、ブレンスレッド酸を
水性媒体中に添加することは、アニオン性重合体、アニ
オン性共重合体または環化ゴムの効果をより高める上で
有効である。Further, salts such as NaCj7, KCI, Na2So4, etc. may be added to the aqueous medium to reduce the solubility of the easily soluble polymerizable monomer in water. It is also possible to add a Brønsted acid such as hydrochloric acid to the aqueous medium to enhance the ionization of the polar groups of the polar polymer or chlorinated rubber in the monomer composition. In particular, it is effective to add a blended acid such as hydrochloric acid to the aqueous medium to further enhance the effects of the anionic polymer, anionic copolymer or cyclized rubber.
本発明に係る重合トナーは、公知の乾式静電荷像現像法
に適用できる。例えば、カスケード法、磁気ブラシ法、
マイクロトーニング法などの二成分現像法；導電性−成
分現像法、絶縁性−成分現像法、ジャンピング現像法な
どの磁硅トナーを使用する一成分現像法：粉末雲法およ
びファーブラシ法二トナー担持体上に静電気的力によっ
て保持されることによって現像部へ搬送され、現像され
る非磁性−成分現像法：電界カーテン法により現像部へ
搬送され現像される電界カーテン現像法などに適用可能
である。乾式現像法に特に好ましく適用できるが、場合
により湿式現像法のトナーとしても使用され得る。The polymerized toner according to the present invention can be applied to a known dry electrostatic image developing method. For example, cascade method, magnetic brush method,
Two-component development methods such as microtoning method; One-component development methods using magnetic silica toner such as conductive component development method, insulating component development method, and jumping development method: Powder cloud method and fur brush method Two toner support Non-magnetic component development method in which the component is transported to the developing section and developed by being held on the body by electrostatic force: Applicable to electric field curtain development method, etc. in which the component is transported to the developing section and developed by the electric field curtain method. . Although it is particularly preferably applicable to dry development, it can also be used as a toner for wet development in some cases.
以下、実施例に基づいて本発明の詳細な説明する。 Hereinafter, the present invention will be described in detail based on examples.
実施例１
上記成分をアトライターにより温度８０℃で４時間混合
してプレ単量体組成物を調製した。得られたプレ単量体
組成物２９８０重量部に芳香族基を有する低軟化点化合
物としてベンゼン環を有するベトロジン１００ （軟化
点１００℃、三井石油化学工業製）１０００重量部及び
パラフィンワックス１５５°Ｆ（軟化点６９℃） ２０
００重量部を加えて、さらに加熱混合した。調製した単
量体組成物のうちの２５０重量部を、アミノ変性シリカ
（アエロジル２００の１００ ｆｆｌｆｆｉ部をアミノ
プロピルトリエトキシシラン５重量部で処理したもの）
２０重量部および０．ＩＮ塩酸２５重量部を含有する８
５℃に加温された蒸留水１２００重量部の水性媒体へＴ
Ｋホモミキサーの撹拌下に投入し、投入後１５分間１０
．００Ｏｒｐｍで撹拌して、分散造粒した。Example 1 A premonomer composition was prepared by mixing the above components using an attritor at a temperature of 80° C. for 4 hours. 2980 parts by weight of the obtained premonomer composition, 1000 parts by weight of Vetrozine 100 (softening point 100°C, manufactured by Mitsui Petrochemical Industries) having a benzene ring as a low softening point compound having an aromatic group and paraffin wax 155°F. (Softening point 69℃) 20
00 parts by weight were added and further heated and mixed. 250 parts by weight of the prepared monomer composition was added to amino-modified silica (100 fflffi parts of Aerosil 200 treated with 5 parts by weight of aminopropyltriethoxysilane).
20 parts by weight and 0. 8 containing 25 parts by weight of IN hydrochloric acid
T into an aqueous medium containing 1200 parts by weight of distilled water heated to 5°C.
Add it to the K homo mixer while stirring, and let it stand for 15 minutes after adding it.
．． The mixture was dispersed and granulated by stirring at 0.00 rpm.
造粒後液温を６０℃に下げ、重合開始剤として２．２′
−アゾビス−（２，４−ジメチルバレロニトリル）３重
量部および２．２′ −アゾビスイソブチロニトリル１
．５重量部を水性媒体へ添加して、３０分間撹拌した。After granulation, the liquid temperature was lowered to 60°C, and 2.2' was added as a polymerization initiator.
-azobis-(2,4-dimethylvaleronitrile) 3 parts by weight and 2.2' -azobisisobutyronitrile 1 part
．． 5 parts by weight were added to the aqueous medium and stirred for 30 minutes.
さらに、撹拌をパドル刃撹拌に変えて６０℃で１０時間
撹拌し、重合を完結させた。Furthermore, the stirring was changed to paddle blade stirring, and the mixture was stirred at 60° C. for 10 hours to complete the polymerization.
得られた重合トナー含有の水性媒体を冷却し、脱水し、
水酸化ナトリウム溶液で洗浄してアミノ変性シリカを溶
解除去し、水洗し、脱水し、乾燥して（必要に応じて分
級して微粒子状の不用成分粒子を除去し）体積平均粒径
６．０μｍ（１００μｍのアパーチャーを使用してコー
ルタ−カウンターで測定）の重合トナーを得た。得られ
た重合トナーは、スチレン−メタクリル酸２−エチルヘ
キシル共重合体１００重量部に対してベトリジン約５０
重量部及びパラフィンワックス約１００重量部を含有し
ていた。また、得られたトナーは５０℃の環境に一日放
置してもブロッキングは発生しなかった。このことから
、ベトロジン及びパラフィンワックスは重合トナー粒子
内部に内包化していることが知見された。The obtained aqueous medium containing the polymerized toner is cooled and dehydrated,
Washing with sodium hydroxide solution to dissolve and remove the amino-modified silica, washing with water, dehydration, and drying (classifying as necessary to remove fine particulate unnecessary component particles) to a volume average particle size of 6.0 μm. A polymerized toner of (measured with a Coulter counter using a 100 μm aperture) was obtained. The obtained polymerized toner contains approximately 50 parts by weight of vetridine per 100 parts by weight of the styrene-2-ethylhexyl methacrylate copolymer.
parts by weight and about 100 parts by weight of paraffin wax. Further, even when the obtained toner was left in an environment of 50° C. for one day, no blocking occurred. From this, it was found that Vetrozin and paraffin wax were encapsulated inside the polymerized toner particles.
得られた重合トナー１０重量部、ステアリン酸亜鉛粉末
０．１重量部、疎水性シリカ（アエロジルＲ９７２゜日
本アエロジル社製）０．１重量部、および平均粒径４０
μｍの絶縁性キャリアー粒子（四三酸化鉄７５重量部と
エポキシ樹脂２５重量部から形成）９０重量部を混合し
て現像剤を調製し、下記条件で現像をおこなった。10 parts by weight of the obtained polymerized toner, 0.1 part by weight of zinc stearate powder, 0.1 part by weight of hydrophobic silica (Aerosil R972° manufactured by Nippon Aerosil Co., Ltd.), and an average particle size of 40
A developer was prepared by mixing 90 parts by weight of insulating carrier particles (formed from 75 parts by weight of triiron tetroxide and 25 parts by weight of an epoxy resin) of micrometer size, and development was carried out under the following conditions.
感光体 ・・・・・・・・・・・・・・・・・アモルフ
ァスシリコン感光体複写速度 ・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
２７０ｍｍ／ｓｅｃ静電潜像形成条件
暗電位 ・・・・・・・・・・・・・・・・・・・・・
・・・・・・−・・・・・・・・・・・・・・・・・・
・・ ＋４５０ｖスリーブ径 ・・・・・３２ｍｍ（周
速２７０ｍｍ／５ｅｃ）磁性体のＮ、 Ｓ磁極のスリ
ーブ表面の垂直方向の磁束密度 ・・・・・・・・・・
・・・・・１０００ガウス現像剤層の厚さ ・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・０．２ｍｍスリーブと感光体表面との距離・・・３
００μｍ現像バイアス ・・・・・・・・・・・・・・
・・・・・・・・＋２００ｖ （ＤＣ）３．０ＫＨｚ、
１．４ＫＶｐｐ （ＡＣ）転写条件（ドラムから中
間転写体）
中間転写体材質 ＲＴＶシリコンゴム（肉厚１ ｍ ｍ
）中間転写体表面粗さ ・・・・・・・・・・・・・
・・・・４μｍ ＲＭ Ｓ転写圧 ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・ＩＫｇ／ｃｒｒｒ中間転写体温度
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・５０ ’Ｃ転写・定着条
件（中間体転写体から転写紙）転写圧 ・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・３０Ｋｇ／ｃｒｒｆ加圧・加熱ロー
ラ温度 ・・・・・・・・・・・・・・・・・・・・・
・１１０ ’ＣＣニップ ・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・３ｍｍ結果を下記に示す。Photoconductor ・・・・・・・・・・・・・・・・・・Amorphous silicon photoconductor Copy speed ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
270mm/sec Electrostatic latent image forming conditions Dark potential ・・・・・・・・・・・・・・・・・・・・・
・・・・・・－・・・・・・・・・・・・・・・・・・
... +450v sleeve diameter ...32mm (peripheral speed 270mm/5ec) Magnetic flux density in the vertical direction of the sleeve surface of the magnetic N and S magnetic poles ......
...1000 Gauss Thickness of developer layer ...
・・・・・・・・・・・・・・・・・・・・・・・・
...Distance between 0.2mm sleeve and photoreceptor surface...3
00μm development bias ・・・・・・・・・・・・・・・
・・・・・・・・・+200v (DC) 3.0KHz,
1.4KVpp (AC) Transfer conditions (from drum to intermediate transfer body) Intermediate transfer body material RTV silicone rubber (thickness 1 mm)
) Intermediate transfer body surface roughness ・・・・・・・・・・・・・・・
・・・・・・4μm RM S transfer pressure ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・IKg/crrr Intermediate transfer body temperature ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・50'C Transfer/fixing conditions (from intermediate transfer body to transfer paper) Transfer pressure ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・30Kg/crrf Pressure/heating roller temperature ・・・・・・・・・・・・・・・・・・・・・
・110' CC nip ・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
......3mm results are shown below.
実施例２
ベトロジン１０００重量部及びパラフィン１５５°Ｆ２
゜０００重量部のかわりに、芳香族基含有変性ポリエチ
レンＴｌ１６３（三井石油化学工業■製）（軟化点９４
°Ｃ） １０００重量部およびパラフィン１５５°Ｆ（
軟化点６９℃） １，５００重量部を使用し、分散造粒
時の水性媒体の液温を８０℃にする以外は実施例１と同
様にして体積平均粒径５．８μｍの重合トナーを生成し
得られた重合トナーは、スチレン−メタクリル酸２−エ
チルヘキシル共重合体１００重量部に対して変性ポリエ
チレンＴｌ１６３約５０重量部及びパラフィン７５重量
部を含有していた。Example 2 Vetrozin 1000 parts by weight and paraffin 155°F2
Instead of ゜000 parts by weight, aromatic group-containing modified polyethylene Tl163 (manufactured by Mitsui Petrochemical Industries ■) (softening point 94
°C) 1000 parts by weight and paraffin 155 °F (
A polymerized toner with a volume average particle diameter of 5.8 μm was produced in the same manner as in Example 1, except that 1,500 parts by weight (softening point: 69°C) was used and the temperature of the aqueous medium during dispersion and granulation was set at 80°C. The resulting polymerized toner contained about 50 parts by weight of modified polyethylene Tl 163 and 75 parts by weight of paraffin based on 100 parts by weight of the styrene-2-ethylhexyl methacrylate copolymer.
実施例３
上記成分をアトライターで４時間混合して単量体組成物
を調製した。別途アミノ変性シリカ２０重量部、０．Ｉ
Ｎ塩酸２５重量部および蒸留水１２００重量部からなる
水性媒体を７５℃に加温し、ＴＫホモミキサーの撹拌下
で上記単量体組成物２７８重員部を水性媒体へ投入し、
投入後１０．００Ｏｒｐｍで３０分間撹拌し、造粒後水
性媒体を６０℃に冷却した。重合開始剤として、２．２
′−アゾビス−（２，４−ジメチルバ１）ロニトリル）
５重量部および２．２′アゾビスイソブチロニトリル２
重量部を添加後さらに３０分間撹拌した。その後、通常
の撹拌機により回転数１０Ｏｒｐｍで撹拌しながら６０
℃で１０時間反応させた。その後実施例１と同様にして
後処理したところ粒度分布のシャープな体積平均粒径７
．０μｍの重合トナーが得られた。得られた重合トナー
は、スチレン−メタクリル酸２−エチルヘキシル共重合
体１００重量部に対して変性ポリエチレンＴ１１８９を
１００重量部及びパラフィンを７５重量部を含有し比ｉ
ｆ殊１
上記成分をアトライターにより温度６０℃で４時間混合
して単量体組成物を調製した。Example 3 A monomer composition was prepared by mixing the above components in an attritor for 4 hours. Separately, 20 parts by weight of amino-modified silica, 0. I
An aqueous medium consisting of 25 parts by weight of N-hydrochloric acid and 1200 parts by weight of distilled water was heated to 75°C, and 278 parts by weight of the above monomer composition was added to the aqueous medium under stirring with a TK homomixer,
After the addition, the mixture was stirred at 10.00 rpm for 30 minutes, and after granulation, the aqueous medium was cooled to 60°C. As a polymerization initiator, 2.2
'-azobis-(2,4-dimethylba-1)lonitrile)
5 parts by weight and 2.2' azobisisobutyronitrile 2
After adding the parts by weight, the mixture was further stirred for 30 minutes. After that, while stirring with a regular stirrer at a rotation speed of 10 Orpm,
The reaction was carried out at ℃ for 10 hours. After that, it was post-treated in the same manner as in Example 1, and the volume average particle size was 7 with a sharp particle size distribution.
．． A polymerized toner of 0 μm was obtained. The obtained polymerized toner contained 100 parts by weight of modified polyethylene T1189 and 75 parts by weight of paraffin based on 100 parts by weight of styrene-2-ethylhexyl methacrylate copolymer.
fSpecial 1 A monomer composition was prepared by mixing the above components using an attritor at a temperature of 60° C. for 4 hours.
得られた単量体組成物２５４重量部に２．２’ −アゾ
ビス−（２，４−ジメチルバレロニトリル）を６重量部
及び２，２′ −アゾビスイソブチロニトリルを３重量
部添加し混合したものを、アミノ変性シリカ（アエロジ
ル２００の１００重量部をアミノプロピルトリ２エトキ
シシラン５重量部で処理したもの）２０重量部、および
０．ＩＮ塩酸２５重量部を含有する６０℃に加温された
蒸留水１２００重量部の水性媒体へＴＫホモミキサーの
撹拌下に投入し、投入後１５分間１０．００Ｏｒｐｍで
撹拌して、分散造粒した。6 parts by weight of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 3 parts by weight of 2,2'-azobisisobutyronitrile were added to 254 parts by weight of the obtained monomer composition. The mixture was mixed with 20 parts by weight of amino-modified silica (100 parts by weight of Aerosil 200 treated with 5 parts by weight of aminopropyl tri2-ethoxysilane), and 0. The mixture was added to an aqueous medium containing 25 parts by weight of IN hydrochloric acid and 1200 parts by weight of distilled water heated to 60°C under stirring using a TK homomixer, and after the addition, the mixture was stirred at 10.00 rpm for 15 minutes to perform dispersion and granulation. .
さらに、撹拌をパドル刃撹拌に変えて６０℃で１０時間
撹拌し、重合を完結させた。次いで、実施例１と同様に
して後処理して体積平均粒径５．３μｍの重合トナーを
得た。得られた重合トナーは、ポリスチレン１００重量
部に対してパラフィンワックス約２０重量部を含有して
いた。得られた重合トナー１０重量部、ステアリン酸亜
鉛粉末００１重量部、疎水性シリカ（アエロジルＲ９７
２，日本アエロジル社製） ０．１重量部および平均粒
径４０μｍのキャリアー粒子（実施例１と同様のもの）
９０重量部を混合して現像剤を調製した。調製した現像
剤を使用して実施例１と同様にして現像、転写、定着を
おこなったところ、定着温度１９０℃以上で実用に供し
得る定着画像が得られた。尚、定着ローラ温度１００’
Ｃ，１２０℃、１４０℃いずれの場合も、定着が不充分
であり、実用に供し得る定着画像は得られなかった。Furthermore, the stirring was changed to paddle blade stirring, and the mixture was stirred at 60° C. for 10 hours to complete the polymerization. Next, post-treatment was carried out in the same manner as in Example 1 to obtain a polymerized toner having a volume average particle diameter of 5.3 μm. The obtained polymerized toner contained about 20 parts by weight of paraffin wax based on 100 parts by weight of polystyrene. 10 parts by weight of the obtained polymerized toner, 0.01 parts by weight of zinc stearate powder, hydrophobic silica (Aerosil R97)
2, manufactured by Nippon Aerosil Co., Ltd.) 0.1 part by weight and carrier particles with an average particle size of 40 μm (same as in Example 1)
A developer was prepared by mixing 90 parts by weight. When development, transfer, and fixing were performed in the same manner as in Example 1 using the prepared developer, a fixed image that could be used for practical purposes was obtained at a fixing temperature of 190° C. or higher. Furthermore, the fixing roller temperature is 100'
C, 120° C., and 140° C., the fixing was insufficient and no fixed image usable for practical use was obtained.
比較例２
上記成分をアトライターにより温度６０℃で４時間混合
して単量体組成物を調製した。Comparative Example 2 A monomer composition was prepared by mixing the above components using an attritor at a temperature of 60° C. for 4 hours.
得られた単量体組成物２５４重量部に２．２′ −アゾ
ビス−（２，４−ジメチルバレロニトリル）を０゜５重
量部及び２，２′ −アゾビスイソブチロニトリルを
０．２重量部添加し混合したものを、アミノ変性シリカ
（アエロジル２００の１００重員部をアミノプロピルト
リエトキシシラン５重量部で処理したもの）２０重量部
および０．１Ｎ塩酸２５重量部を含有する６０℃に加温
された蒸留水１２００重量部の水性媒体へＴＫホモミキ
サーの撹拌下に投入し、投入後１５分間１０．００Ｏｒ
ｐｍで撹拌して、分散造粒した。0.5 parts by weight of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 0.2 parts by weight of 2,2'-azobisisobutyronitrile were added to 254 parts by weight of the obtained monomer composition. The mixture was added in parts by weight and mixed at 60°C containing 20 parts by weight of amino-modified silica (100 parts by weight of Aerosil 200 treated with 5 parts by weight of aminopropyltriethoxysilane) and 25 parts by weight of 0.1N hydrochloric acid. It was added to an aqueous medium containing 1200 parts by weight of distilled water heated to
The mixture was dispersed and granulated by stirring at pm.
さらに、撹拌をパドル刃撹拌に変えて６０℃で１０時間
撹拌し、重合をおこなった。次いで、実施例１と同様に
して後処理したところ粒径が１００μｍ以上の粒子が多
数あり、そのままでは静電荷像現像用トナーとして実用
に供し得なかった。そのため、分級して体積平均粒径約
８μｍの粒子を得たが、耐ブロッキング性が不充分であ
った。Furthermore, the stirring was changed to paddle blade stirring, and the mixture was stirred at 60° C. for 10 hours to carry out polymerization. Subsequently, when post-processing was carried out in the same manner as in Example 1, there were many particles with a particle size of 100 μm or more, so that the toner could not be put to practical use as a toner for developing electrostatic images as it was. Therefore, although particles having a volume average particle diameter of about 8 μm were obtained by classification, the blocking resistance was insufficient.
表
上記転写率は、トナー粒径に関する依存度もあるため、
トナーのオフセット性向上を行っても向上のパーセンテ
ージにバラツキが生じます。The transfer rate in the table above also depends on the toner particle size, so
Even if you try to improve the offset properties of toner, the percentage of improvement will vary.
本発明は以上のような装置と現像材を用いているから、
転写にあたって静電的な転写手段をとらないのでトナー
の転写材への付着力の弱さに基く画像の乱れや鮮明度の
低下を阻止でき、感光体に、転写時に過大な圧力がかか
ることを回避できるとともに、現像材が常圧時の融点よ
りもはるかに低い温度で転写並びに定着可能となるため
、感光体の昇温を充分に押えて特性の変化を生じにくく
するので、その寿命を大幅に増大せしめることが可能で
、長期に渡って良質の画像を安定的に得ることができる
。Since the present invention uses the above-described apparatus and developing material,
Since electrostatic transfer means are not used for transfer, it is possible to prevent image distortion and loss of clarity due to the weak adhesion of toner to the transfer material, and prevent excessive pressure from being applied to the photoreceptor during transfer. At the same time, it is possible to transfer and fix the developing material at a temperature far lower than its melting point under normal pressure, which sufficiently suppresses the rise in temperature of the photoreceptor and makes it difficult for changes in characteristics to occur, significantly extending its lifespan. It is possible to increase the number of images, and it is possible to stably obtain high-quality images over a long period of time.
第１図２は本発明の実施例たる画像形成装置を示す概略
側面図、
第２図は本発明の他の実施例を模式的に示す側面図であ
る。
ｌ ・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・曲間曲間感光体、３・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・曲間・曲・
・・・曲・・・曲間加圧体、２０・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・
・・曲・曲・・曲面中間転写体、Ｎ、、Ｎ２ ・・・・
・・・・・・・曲・曲間曲・曲間曲曲ニッフ部。FIG. 1 is a side view schematically showing an image forming apparatus according to an embodiment of the present invention, and FIG. 2 is a side view schematically showing another embodiment of the present invention. l ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・Photoconductor between songs, 3・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・Between songs・Songs・
... Song... Pressure body between songs, 20...
・・・・・・・・・・・・・・・・・・・・・・・・
...Song, song...Curved intermediate transfer body, N,,N2...
... Songs, inter-songs, and inter-song niff sections.
Claims (2)
してトナー画像を形成し、形成されたトナー画像を感光
体に圧接している中間転写体に圧力転写し、さらにこの
転写されたトナー画像を、該中間転写体と該中間転写体
に圧接している加圧体間を通過する転写材に転写かつ定
着させ定着画像を得る画像形成方法に於いて、該トナー
画像を形成するトナーが懸濁重合法によって生成された
静電荷像現像用重合トナーであり、スチレン系重合体ま
たはスチレン系共重合体１００重量部、軟化点４０〜１
３０℃を有し且つ芳香族基を有する低軟化点化合物Ａ３
０〜１５００重量部、前記低軟化点化合物以外の軟化点
４０〜１３０℃を有する低軟化点化合物Ｂ２０〜１５０
０重量部および着色剤を含有している重合トナーであり
、該中間転写体へ転写された画像を、該中間転写体と前
記加圧体間を通過する転写材に、前記感光体と前記中間
転写体との圧接力よりも大きい圧力と高い温度の条件下
で転写かつ定着することを特徴とする画像形成方法。(1) The electrostatic latent image formed on the photoreceptor is developed using a developer to form a toner image, the formed toner image is pressure-transferred to an intermediate transfer member that is in pressure contact with the photoreceptor, and then this In an image forming method for obtaining a fixed image by transferring and fixing the transferred toner image onto a transfer material passing between the intermediate transfer body and a pressure body that is in pressure contact with the intermediate transfer body, the toner image is The toner to be formed is a polymerized toner for electrostatic image development produced by a suspension polymerization method, containing 100 parts by weight of a styrene polymer or styrene copolymer, and a softening point of 40 to 1.
Low softening point compound A3 having a temperature of 30°C and having an aromatic group
0 to 1500 parts by weight, a low softening point compound B20 to 150 having a softening point of 40 to 130°C other than the above-mentioned low softening point compounds
The polymerized toner contains 0 parts by weight and a colorant, and the image transferred to the intermediate transfer member is transferred to a transfer material that passes between the intermediate transfer member and the pressurizing member, and is transferred to the photoreceptor and the intermediate transfer member. An image forming method characterized by transferring and fixing under conditions of pressure and temperature higher than the pressure in contact with a transfer member.
に形成されたトナー画像を圧力転写するための中間転写
体とを具備する画像形成装置において、懸濁重合法によ
って生成された静電荷像現像用重合トナーであり、スチ
レン系重合体またはスチレン系共重合体１００重量部、
軟化点４０〜１３０℃を有し且つ芳香族基を有する低軟
化点化合物Ａ３０〜１５００重量部、前記低軟化点化合
物以外の軟化点４０〜１３０℃を有する低軟化点化合物
Ｂ２０〜１５００重量部および着色剤を含有している重
合トナーから形成されている該中間転写体上のトナー画
像を通過する転写材へ転写するための該中間転写体に圧
接している加圧体が具備されており、該加圧体が該感光
体と該中間転写体との圧接力よりも大きい圧接力で該中
間転写体と圧接しており、且つ、トナーを加熱定着する
ための加熱手段を内包していることを特徴とする画像形
成装置。(2) In an image forming apparatus equipped with a photoreceptor for forming an electrostatic latent image and an intermediate transfer member for pressure-transferring a toner image formed on the surface of the photoreceptor, a toner image formed by a suspension polymerization method is used. 100 parts by weight of a styrene polymer or styrene copolymer,
30 to 1500 parts by weight of a low softening point compound A having a softening point of 40 to 130°C and having an aromatic group, 20 to 1500 parts by weight of a low softening point compound B having a softening point of 40 to 130°C other than the low softening point compound, and A pressure body is provided that is in pressure contact with the intermediate transfer body for transferring a toner image on the intermediate transfer body formed from a polymerized toner containing a colorant to a passing transfer material, The pressure body is in pressure contact with the intermediate transfer body with a pressure force greater than the pressure force between the photoreceptor and the intermediate transfer body, and includes a heating means for heating and fixing the toner. An image forming apparatus characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62036210A JP2614222B2 (en) | 1987-02-18 | 1987-02-18 | Image forming method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62036210A JP2614222B2 (en) | 1987-02-18 | 1987-02-18 | Image forming method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63201670A true JPS63201670A (en) | 1988-08-19 |
| JP2614222B2 JP2614222B2 (en) | 1997-05-28 |
Family
ID=12463388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62036210A Expired - Lifetime JP2614222B2 (en) | 1987-02-18 | 1987-02-18 | Image forming method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2614222B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6341207B1 (en) | 1992-06-16 | 2002-01-22 | Fujitsu Limited | Cleanerless image forming method and system therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134872A (en) * | 1979-04-06 | 1980-10-21 | Ricoh Co Ltd | Image recording method |
| JPS56146167A (en) * | 1980-04-15 | 1981-11-13 | Canon Inc | Developing method |
| JPS58142345A (en) * | 1982-02-17 | 1983-08-24 | Konishiroku Photo Ind Co Ltd | Image formation |
| JPS6128957A (en) * | 1984-07-20 | 1986-02-08 | Canon Inc | Toner and image forming method |
-
1987
- 1987-02-18 JP JP62036210A patent/JP2614222B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134872A (en) * | 1979-04-06 | 1980-10-21 | Ricoh Co Ltd | Image recording method |
| JPS56146167A (en) * | 1980-04-15 | 1981-11-13 | Canon Inc | Developing method |
| JPS58142345A (en) * | 1982-02-17 | 1983-08-24 | Konishiroku Photo Ind Co Ltd | Image formation |
| JPS6128957A (en) * | 1984-07-20 | 1986-02-08 | Canon Inc | Toner and image forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6341207B1 (en) | 1992-06-16 | 2002-01-22 | Fujitsu Limited | Cleanerless image forming method and system therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2614222B2 (en) | 1997-05-28 |
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