JPH0246469A - Electrophotographic toner and electrophotographic developing agent - Google Patents
Electrophotographic toner and electrophotographic developing agentInfo
- Publication number
- JPH0246469A JPH0246469A JP63197556A JP19755688A JPH0246469A JP H0246469 A JPH0246469 A JP H0246469A JP 63197556 A JP63197556 A JP 63197556A JP 19755688 A JP19755688 A JP 19755688A JP H0246469 A JPH0246469 A JP H0246469A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- toner
- electrophotographic
- fine particles
- component
- 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
- 239000002245 particle Substances 0.000 claims abstract description 128
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010419 fine particle Substances 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 230000002744 anti-aggregatory effect Effects 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 230000002776 aggregation Effects 0.000 abstract description 31
- 238000004220 aggregation Methods 0.000 abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003112 inhibitor Substances 0.000 abstract description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 3
- 239000000194 fatty acid Substances 0.000 abstract description 3
- 229930195729 fatty acid Natural products 0.000 abstract description 3
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 17
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000003086 colorant Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000001993 wax Substances 0.000 description 12
- 238000005054 agglomeration Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 108091008695 photoreceptors Proteins 0.000 description 11
- 239000006247 magnetic powder Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 8
- 239000003006 anti-agglomeration agent Substances 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005792 styrene-acrylic resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- REEFSLKDEDEWAO-UHFFFAOYSA-N Chloraniformethan Chemical compound ClC1=CC=C(NC(NC=O)C(Cl)(Cl)Cl)C=C1Cl REEFSLKDEDEWAO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019086 Mg-Cu Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09783—Organo-metallic compounds
- G03G9/09791—Metallic soaps of higher carboxylic acids
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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、電子写真において潜像を現像するための電子
写真用トナーおよび電子写真用現像剤に関し、特に、１
成分系電子写真用現像剤として用いられる電子写真用ト
ナーと、電子写真用トナーとキャリア粒子とを含有する
２成分系の電子写真用現像剤とに関する。Detailed Description of the Invention <Industrial Application Field> The present invention relates to an electrophotographic toner and an electrophotographic developer for developing a latent image in electrophotography, and in particular, to
The present invention relates to an electrophotographic toner used as a component-based electrophotographic developer, and a two-component electrophotographic developer containing an electrophotographic toner and carrier particles.
〈従来の技術〉
電子写真装置における静電荷像現像は、通常、下記のよ
うに行なわれる。<Prior Art> Electrostatic image development in an electrophotographic apparatus is usually performed as follows.
■感光体表面を正または負に帯電させる。■Charge the surface of the photoreceptor positively or negatively.
■感光体表面に原稿からの反射光を照射する。■Irradiates the surface of the photoconductor with reflected light from the original.
■感光体は光の照射により導電性を増すため、感光体表
面には原稿からの反射光の強弱に対応して帯電が消失す
る部分と帯電が残存する部分とが生じ、感光体表面に潜
像が形成されることになる。■The conductivity of the photoconductor increases when it is irradiated with light, so there are areas on the photoconductor surface where the charge disappears and other areas where the charge remains, depending on the strength of the light reflected from the document, and the surface of the photoconductor is latent. An image will be formed.
■感光体表面の帯電と逆極性に帯電した現像用トナーを
、静電引力によりトナー担持体等から感光体表面に付着
させて顕像な得る。(2) Development toner charged to the opposite polarity to that on the surface of the photoreceptor is made to adhere to the surface of the photoreceptor from a toner carrier or the like by electrostatic attraction, thereby obtaining an image.
■この顕像な転写紙表面に転写した後、加熱、圧着等に
より定着する。(2) After being transferred to the surface of this visible transfer paper, it is fixed by heating, pressure bonding, etc.
このような静電荷像現像において、上記■の現像用トナ
ーとしては、１成分系あるいは２成分系トナーが用いら
れている。In such electrostatic image development, a one-component toner or a two-component toner is used as the developing toner described in (2) above.
２成分系現像用トナーは、着色剤を含有する樹脂粉から
なるトナー粒子と、鉄あるいはフェライト等からなるキ
ャリア粒子とから構成される。A two-component developing toner is composed of toner particles made of resin powder containing a colorant and carrier particles made of iron, ferrite, or the like.
一方、１成分系現像用トナーはキャリア粒子を使用せず
、例えば、米国特許第３９０９２５８号明細書、同第４
］、 ２１９３１号明細書に示されるように、それ自
身着色剤である磁性粉を含有する磁性トナー粒子からな
る。On the other hand, one-component developing toner does not use carrier particles and is disclosed in, for example, US Pat. No. 3,909,258 and US Pat.
], 21931, consists of magnetic toner particles containing magnetic powder which is itself a colorant.
これら１成分系および２成分系現像用トナーは、トナー
粒子同士の凝集を防止するため、通常、シリカ粒子等の
流動化剤が凝集防止剤として添加されている。In these one-component and two-component developing toners, a fluidizing agent such as silica particles is usually added as an anti-aggregation agent in order to prevent toner particles from coagulating with each other.
〈発明が解決しようとする課題〉
上記１成分系および２成分系現像用トナーは、通常、以
下のようにして製造される。<Problems to be Solved by the Invention> The one-component and two-component developing toners described above are usually manufactured as follows.
樹脂・ワックス・顔料・荷電制御剤等を混合し、溶融混
線・冷却後、粉砕・分級したトナーに流動化剤を添加し
、ヘンシェルミキサー等で混合してトナー表面に流動化
剤を付着させる。Resin, wax, pigment, charge control agent, etc. are mixed, melted and mixed, and after cooling, a fluidizing agent is added to the crushed and classified toner, and the fluidizing agent is attached to the toner surface by mixing with a Henschel mixer or the like.
流動化剤としては、特開昭４６−５７８２号公報等に示
されるようなシリカ粒子が一般的であり、このようなシ
リカ粒子の平均粒径は０．０１〜５μｍ程度である。As the fluidizing agent, silica particles as shown in Japanese Patent Application Laid-Open No. 46-5782 are generally used, and the average particle diameter of such silica particles is about 0.01 to 5 μm.
このような製造方法により得られるトナーは個々の粒子
が一般に不定形であり粒度分布に広がりがあるため、従
来使用されているシリカ粒子等の流動化剤ではトナーの
凝集防止効果が十分とはいえない。 特に、解像力・階
調性等を向上させた高画質のトナー像を得ようとする場
合、体積平均粒径が例えば８μｍ以下の小粒径トナー粒
子を用いる必要があるが、このような場合、トナー粒子
の流動性は著しく低下するため、従来の流動化剤ではト
ナーの凝集を防止することが困難である。 このため、
カブリが増加し、画像濃度が低下し、感光体のクリーニ
ング性も低下する。 また、トナーの機内飛散、トナー
補給の際のトラブルも発生し易くなる。The individual particles of the toner obtained by this manufacturing method are generally amorphous and have a wide particle size distribution, so although the conventionally used fluidizing agents such as silica particles are sufficient to prevent toner agglomeration. do not have. In particular, when trying to obtain a high-quality toner image with improved resolution, gradation, etc., it is necessary to use small-sized toner particles with a volume average particle size of, for example, 8 μm or less. Since the fluidity of toner particles is significantly reduced, it is difficult to prevent toner agglomeration using conventional fluidizing agents. For this reason,
Fog increases, image density decreases, and the cleanability of the photoreceptor also decreases. Furthermore, toner scattering within the machine and troubles during toner replenishment are more likely to occur.
具体的には、０．５μｍ以上の粒径のシリカ粒子を流動
化剤として用いる場合、シリカ粒子自身の帯電量は低い
ので電気的凝集の防止効果はあるが、トナーに付着して
いる場合、シリカ粒子の表面積が小さくなることからト
ナー粒子が互いに反発しに（くなり、凝集が防止できず
、流動性が低下してしまう。Specifically, when silica particles with a particle size of 0.5 μm or more are used as a fluidizing agent, the amount of charge of the silica particles themselves is low, so there is an effect of preventing electrical aggregation, but if they are attached to the toner, Since the surface area of the silica particles becomes smaller, the toner particles tend to repel each other, making it impossible to prevent agglomeration and reducing fluidity.
また、０．１μｍ以下の粒径のシリカ粒子を流動化剤と
して用いる場合、感光体のクリーニング性が低下し、感
光体表面を傷っけ易くなる。 しかも、流動化剤として
用いられるシリカ粒子は粒径が小さいものほど帯電量が
大きくなるため、凝集を電気的に防止する効果が低い。Furthermore, when silica particles having a particle size of 0.1 μm or less are used as a fluidizing agent, the cleaning properties of the photoreceptor are reduced and the surface of the photoreceptor is easily damaged. Moreover, the smaller the particle size of the silica particles used as the fluidizing agent, the greater the amount of charge, so the effect of electrically preventing agglomeration is low.
したがって、この程度の粒径のシリカ粒子をトナーに
添加した場合、トナー凝集防止効果は期待されるほど向
上しない。Therefore, when silica particles having a particle size of this size are added to a toner, the toner aggregation prevention effect is not improved as much as expected.
また、１成分系現像用トナーの帯電は、磁性トナー粒子
と、これが接触するブレード・トナー担持体等との摩擦
、あるいは磁性トナー粒子同士との摩擦により行なわれ
る。 しかし、このような摩擦による帯電では、すべて
のトナー粒子を同一極性に帯電させることが難しく、ま
た、トナー自体の帯電も不安定であるため、トナー粒子
の凝集が生じ易くなる。Further, the one-component developing toner is charged by friction between the magnetic toner particles and a blade, toner carrier, etc. with which they come into contact, or by friction between the magnetic toner particles. However, in such frictional charging, it is difficult to charge all the toner particles to the same polarity, and since the toner itself is unstable in charging, toner particles tend to aggregate.
また、トナーの帯電制御・抵抗制御等のために、添加剤
として種々の材質の機能性粒子（例えば、酸化チタン・
ＰＭＭＡ微粒子等）をトナー粒子に外添することがある
が、これらの添加剤は物理的凝集防止効果は殆どなく、
その性質・粒径等、あるいは保存条件によってはトナー
の流動性を低下させることがある。In addition, functional particles of various materials (e.g., titanium oxide, titanium oxide,
PMMA fine particles, etc.) are sometimes externally added to toner particles, but these additives have little effect on preventing physical aggregation.
Depending on its properties, particle size, etc., or storage conditions, the fluidity of the toner may be reduced.
本発明は電子写真用トナーにおける上記問題を解決する
ためになされたものであり、小粒径のトナー粒子を用い
た場合であっても流動性が良好で、高画質のトナー像を
得ることができ、機内飛散のない電子写真用トナーおよ
び電子写真用現像剤を提供することを目的とする。The present invention has been made to solve the above-mentioned problems in electrophotographic toners, and even when using toner particles with a small particle size, it has good fluidity and it is possible to obtain high-quality toner images. An object of the present invention is to provide an electrophotographic toner and an electrophotographic developer that can be used in a machine without scattering.
〈課題を解決するための手段〉 上記目的は、下記の本発明により達成される。〈Means for solving problems〉 The above objects are achieved by the present invention as described below.
すなわち、本発明は、下記（１）〜（６）である。That is, the present invention includes the following (1) to (6).
（１）体積平均粒径が０．０１〜５．０ＬＬｍである微
粒子と、この微粒子より体積平均粒径の小さいシリカ微
粒子とを、固着一体化した凝集防止剤と、
荷電性トナー粒子とを含有することを特徴とする電子写
真用トナー
（２）前記シリカ微粒子の体積平均粒径が０．５μｍ以
下である上記（１）に記載の電子写真用トナー
（３）前記凝集防止剤がシリカ微粒子を４０〜９５ｗｔ
％含有する上記（１）または（２）に記載の電子写真用
トナー
（４）前記荷電性トナー粒子１００重量部に対し、前記
凝集防止剤が０．０５〜１０重量部含有される上記（１
）ないしく３）のいずれかに記載の電子写真用トナー
（５）前記荷電性トナー粒子が磁性トナー粒子であり、
１成分系電子写真用現像剤として用いられる上記（１）
ないしく４）のいずれかに記載の電子写真用トナー
（６）上記（１）ないしく４）のいずれかに記載の電子
写真用トナーと、キャリア粒子とを含有する電子写真用
現像剤。(1) Contains an anti-aggregation agent in which fine particles having a volume average particle size of 0.01 to 5.0 LLm and silica fine particles having a smaller volume average particle size than the fine particles are fixed and integrated, and charged toner particles. (2) The toner for electrophotography as described in (1) above, wherein the silica fine particles have a volume average particle size of 0.5 μm or less. (3) The aggregation prevention agent comprises silica fine particles. 40~95wt
(4) The toner for electrophotography according to (1) or (2) above, which contains 0.05 to 10 parts by weight of the anti-aggregation agent per 100 parts by weight of the charged toner particles (1).
(5) The electrophotographic toner according to any one of ) to 3), wherein the charged toner particles are magnetic toner particles;
The above (1) used as a one-component electrophotographic developer
Electrophotographic toner according to any one of (6) to (4) above. An electrophotographic developer containing the electrophotographic toner according to any one of (1) to 4) above and carrier particles.
以下、本発明の具体的構成を詳細に説明する。Hereinafter, the specific configuration of the present invention will be explained in detail.
本発明において、上記微粒子の材質に特に制限はないが
、トナーの帯電制御・抵抗制御、流動性向上等のはたら
きを有する機能性粒子を用いることが好ましい。 特に
、この微粒子と一体化して用いられる後述のシリカ微粒
子は比較的高い帯電量を有するため、このシリカ微粒子
よりも低い帯電量を有する粒子を選択することが好まし
い。In the present invention, there is no particular restriction on the material of the fine particles, but it is preferable to use functional particles that have functions such as controlling charge and resistance of the toner and improving fluidity. In particular, since the silica fine particles described below used in combination with the fine particles have a relatively high charge amount, it is preferable to select particles having a lower charge amount than the silica fine particles.
本発明に好適に用いられる機能性粒子の材質としては、
例えば下記のようなものが挙げられる。The materials of the functional particles suitably used in the present invention include:
Examples include the following:
酸化ケイ素、酸化チタン、酸化亜鉛、アルミナ、ケイ酸
カルシウム等の酸化物；
炭化ケイ素、炭酸カルシウム、炭酸バリウム等の無機化
合物；
ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレン
、ナイロン、シリコーン樹脂、フェノール樹脂、ベンゾ
グアナミン、ポリエステル等の有機高分子化合物；
ポリテトラフルオロエチレン、フッ化ビニリデン等の含
フツ素有機高分子化合物；
ステアリン酸亜鉛、ステアリン酸マグネシウム等の脂肪
酸金属塩；
クロム錯塩型染料、ニグロシン染料等の荷電制御剤；
これら抵抗制御剤、流動化剤、荷電制御剤等の他、着色
剤を上記微粒子として用いてもよい。 すなわち、上記
微粒子として好適に用いられる着色剤としては、下記の
ものが挙げられる。Oxides such as silicon oxide, titanium oxide, zinc oxide, alumina, calcium silicate; Inorganic compounds such as silicon carbide, calcium carbonate, barium carbonate; Polymethyl methacrylate (PMMA), polyethylene, nylon, silicone resin, phenolic resin, benzoguanamine , organic polymer compounds such as polyester; fluorine-containing organic polymer compounds such as polytetrafluoroethylene and vinylidene fluoride; fatty acid metal salts such as zinc stearate and magnesium stearate; charged chromium complex dyes, nigrosine dyes, etc. Control agent: In addition to these resistance control agents, fluidizing agents, charge control agents, etc., colorants may be used as the fine particles. That is, examples of colorants suitably used as the above-mentioned fine particles include the following.
カーボンブラック、アセチレンブラック、チャンネルブ
ラック、アニリンブラック等の黒色顔料；
ダイヤライトエローＧＲ，バリオトールエロー１０９０
等の黄色顔料；
パーマネントレッドＥ５Ｂ、ローダミン２Ｂ等の赤色顔
料；
銅フタロシアニン、コバルトブルー等の青色顔料；
ピグメントグリーンＢ等の緑色顔料；
ピラゾロンオレンジ等の榎色顔料；
以上に挙げた各種機能性粒子のうち、本発明で特に好適
に用いられるのは、金属酸化物および脂肪酸金属塩であ
る。Black pigments such as carbon black, acetylene black, channel black, aniline black; Dialite Yellow GR, Variotol Yellow 1090
Red pigments such as Permanent Red E5B and Rhodamine 2B; Blue pigments such as copper phthalocyanine and cobalt blue; Green pigments such as Pigment Green B; Eko-colored pigments such as pyrazolone orange; Various functional particles listed above Among these, metal oxides and fatty acid metal salts are particularly preferably used in the present invention.
これらの微粒子は、用いるトナー粒子の帯電極性・帯電
量等の帯電特性、あるいは用いる感光体の種類等により
、適当なものを選択すればよい。These fine particles may be appropriately selected depending on the charging characteristics such as the polarity and amount of charge of the toner particles used, the type of photoreceptor used, and the like.
本発明において、上記微粒子の体積平均粒径は、０．０
１〜５μｍ、好ましくは０．０４〜４μｍである。 粒
径が上記範囲未満であると凝集防止効果が不十分となり
、流動性が悪化する。 上記範囲を超えるとカブリや解
像力等の画質劣化の要因となる。In the present invention, the volume average particle diameter of the fine particles is 0.0
The thickness is 1 to 5 μm, preferably 0.04 to 4 μm. If the particle size is less than the above range, the agglomeration prevention effect will be insufficient and fluidity will deteriorate. Exceeding the above range may cause image quality deterioration such as fogging and resolution.
本発明では、体積平均粒径が上記微粒子より小さいシリ
カ微粒子を、流動化剤として用いる。 このシリカ微粒
子の体積平均粒径は、好ましくは０，５μｍ以下、より
好ましくは０．００１〜０．５μｍ、さらに好ましくは
０．０１〜０．１μｍである。 体積平均粒径が上記範
囲を外れると、電気的凝集を防止することが困難となる
。In the present invention, silica fine particles having a volume average particle size smaller than the above-mentioned fine particles are used as a fluidizing agent. The volume average particle diameter of the silica fine particles is preferably 0.5 μm or less, more preferably 0.001 to 0.5 μm, and still more preferably 0.01 to 0.1 μm. When the volume average particle diameter is outside the above range, it becomes difficult to prevent electrical aggregation.
また、このシリカ微粒子は、様々な環境条件下での安定
性の面から、表面処理を施すことにより疎水性としたも
のであることが好ましい。Further, from the viewpoint of stability under various environmental conditions, the silica fine particles are preferably made hydrophobic by surface treatment.
本発明において好適に用いられるシリカ微粒子としては
、日本アエロジル社製のＲ−９７２、Ｒ−９７４、Ｒ−
９７６、ＲＸ−２００等がある。The silica fine particles preferably used in the present invention include R-972, R-974, and R-972 manufactured by Nippon Aerosil Co., Ltd.
976, RX-200, etc.
本発明では、上記したような微粒子およびシリカ微粒子
を固着一体化し、凝集防止剤とする。In the present invention, the above-mentioned fine particles and silica fine particles are fixed and integrated to form an anti-agglomeration agent.
本発明において微粒子とシリカ微粒子とを固着一体化す
るとは、微粒子表面にシリカ微粒子が埋め込まれた状態
にすることを意味する。In the present invention, the term "fixing and integrating fine particles and fine silica particles" means that the fine particles are embedded in the surface of the fine particles.
すなわち、電子顕微鏡による観察したとき、微粒子表面
にシリカ微粒子が埋め込まれた状態であることが確認で
き、固着一体化したものについて分離することはきわめ
て困難であり、実質的に一体化している状態を保つもの
である。In other words, when observed using an electron microscope, it can be confirmed that the silica particles are embedded in the surface of the particles, and it is extremely difficult to separate the silica particles that are firmly integrated. It is something to keep.
このような構成を有する凝集防止剤は、下記のような理
由によりきわめて優れた凝集防止効果を発揮すると考え
られる。It is thought that the anti-aggregation agent having such a structure exhibits an extremely excellent anti-aggregation effect for the following reasons.
上記したような体積平均粒径な有し、しかも疎水性であ
るシリカ微粒子は、トナー粒子の凝集を物理的に防止す
る効果が高く、しかも、高温・高湿下でもその効果が低
下しにくい。 しかし、上記したように、このようなシ
リカ微粒子はトナー粒子の凝集を電気的に防止する効果
が低い。Silica fine particles having the above-mentioned volume average particle diameter and being hydrophobic have a high effect of physically preventing aggregation of toner particles, and moreover, the effect is not easily reduced even under high temperature and high humidity. However, as described above, such fine silica particles have a low effect of electrically preventing aggregation of toner particles.
一方、上記のような微粒子は、トナー粒子の凝集を物理
的に防止する効果は殆どなく、また、その材質によって
は高温・高湿下では不安定な性質を示すが、体積平均粒
径が上記シリカ微粒子より大きいため帯電量が上記シリ
カ微粒子より低く、トナー粒子の電気的凝集を防止する
効果が高い。 特に、微粒子として上記のような帯電制
御剤を用いる場合、この電気的凝集防止効果は高いもの
となる。On the other hand, the fine particles mentioned above have almost no effect on physically preventing the aggregation of toner particles, and depending on the material they are made of, they exhibit unstable properties under high temperature and high humidity. Since it is larger than the silica fine particles, the amount of charge is lower than the above-mentioned silica fine particles, and it is highly effective in preventing electrical aggregation of toner particles. In particular, when the above-mentioned charge control agent is used as the fine particles, the effect of preventing electrical aggregation is high.
したがって、微粒子表面に埋め込まれたシリカ微粒子は
トナー粒子の凝集を物理的に防止し、しかも高温・高湿
下においてもその効果は安定である。 そして、微粒子
はシリカ微粒子の帯電量を低下させることにより凝集防
止剤全体の帯電量を低下させ、トナー粒子の電気的な凝
集を防止する。Therefore, the silica particles embedded in the surface of the particles physically prevent the toner particles from agglomerating, and the effect is stable even under high temperature and high humidity conditions. The fine particles reduce the charge amount of the silica fine particles, thereby reducing the charge amount of the entire anti-aggregation agent, thereby preventing electrical aggregation of toner particles.
また、このような構成にすることにより、シリカ微粒子
のみで本発明と同程度の流動性な得ようとする場合に比
ベシリカ微粒子の使用量を抑えることができるため、ク
リーニング性が低下しにくく、また、感光体に傷をつけ
ることも少ない。In addition, by adopting such a configuration, when trying to obtain the same level of fluidity as the present invention using only silica particles, the amount of silica particles used can be reduced, so cleaning performance is less likely to deteriorate. Furthermore, the photoreceptor is less likely to be damaged.
さらに、本発明において微粒子は必ずしもトナーの物理
的凝集の防止効果を有する必要がないため、上記したよ
うな種々の機能性粒子を用いることができる。 したが
って、帯電極性・帯電量等の帯電特性が不安定となり易
いためトナー粒子の凝集を生じ易い１成分系現像剤にお
いて、上記凝集防止剤はトナー粒子の電気的凝集および
物理的凝集のいずれをも効果的に防止することができる
。Further, in the present invention, the fine particles do not necessarily have to have the effect of preventing physical aggregation of the toner, so various functional particles as described above can be used. Therefore, in a one-component developer that tends to cause aggregation of toner particles because the charging characteristics such as charge polarity and amount of charge are likely to become unstable, the above-mentioned aggregation preventing agent prevents both electrical aggregation and physical aggregation of toner particles. It can be effectively prevented.
微粒子とシリカ微粒子とを一体化するためには、微粒子
とシリカ微粒子とを混合する際に圧力を印加することが
好ましい。 圧力印加手段に特に制限はなく、上記のよ
うな一体化された状態とすることができればどのような
圧力印加手段を用いてもよいが、本発明では微粒子を乾
式の状態で使用でき、しかもコスト的に有利であること
から、機械的な歪力を印加する手段を用いることが好ま
しい。In order to integrate the fine particles and the fine silica particles, it is preferable to apply pressure when mixing the fine particles and the fine silica particles. There is no particular restriction on the pressure application means, and any pressure application means may be used as long as it can achieve the above-mentioned integrated state. However, in the present invention, fine particles can be used in a dry state, and the cost is low. It is preferable to use means for applying mechanical strain force because it is economically advantageous.
機械的な歪力とは、衝撃力を主体とする機械的エネルギ
ーを与え、メカノケミカル的な反応を起こさせるもので
ある。 このような機械的な歪力を印加する装置として
は、例えば、特開昭６３−４２７２８号公報に記載され
ているような粉粒体処理装置であり、具体的にはホンカ
ワミクロン社製のメカノフュージョンシステムや奈良機
械製作所社製のハイブリダイゼーションシステム等が好
適である。Mechanical strain force is something that applies mechanical energy, mainly impact force, to cause a mechanochemical reaction. An example of a device that applies such a mechanical strain force is a powder processing device as described in Japanese Patent Application Laid-Open No. 63-42728, and specifically, a device for processing powder and granular material such as that described in Japanese Patent Application Laid-Open No. 63-42728. Mechanofusion system, hybridization system manufactured by Nara Kikai Seisakusho Co., Ltd., etc. are suitable.
このようにして得られる凝集防止剤中のシリカ微粒子の
含有量は、好ましくは４０〜９５ｗｔ％、より好ましく
は５０〜８０ｗｔ％である。The content of silica fine particles in the anti-aggregation agent thus obtained is preferably 40 to 95 wt%, more preferably 50 to 80 wt%.
シリカ微粒子の含有量が上記範囲未満となると凝集防止
が不十分であり、上記範囲を超えると画質の経時変化や
クリーニング不良が発生する。When the content of silica fine particles is less than the above range, prevention of aggregation is insufficient, and when it exceeds the above range, image quality changes over time and cleaning defects occur.
本発明の電子写真用トナーに含有される荷電性トナー粒
子に特に制限はな（，１成分系現像剤用あるいは２成分
系現像剤用の公知の荷電性トナー粒子のいずれを用いた
場合であっても、上記凝集防止剤のはたらきによりトナ
ー粒子の凝集は効果的に防止されるが、上記のような理
由から、本発明はｌ成分系現像剤に適用する場合に特に
高い効果を発揮する。There are no particular limitations on the chargeable toner particles contained in the electrophotographic toner of the present invention. However, for the above-mentioned reasons, the present invention exhibits particularly high effects when applied to l-component type developers.
用いる１成分系現像剤用のトナー粒子に特に制限はない
が、画像濃度、解像力、階調性等の優れた高画質のトナ
ー像を得るために、下記のような磁性トナー粒子を用い
ることが好ましい。There are no particular restrictions on the toner particles for the one-component developer used, but in order to obtain high-quality toner images with excellent image density, resolution, gradation, etc., it is recommended to use the following magnetic toner particles. preferable.
体積平均粒径は、５〜１５μｍ、特に６〜９μｍである
ことが好ましい。 この値が上記範囲未満であると、カ
ブリの悪化、クリーニング不良が発生し、コスト的にも
不利となる。 また、上記範囲を超えると、解像力の悪
化、トナー飛散が問題となる。The volume average particle diameter is preferably 5 to 15 μm, particularly 6 to 9 μm. If this value is less than the above range, worsening of fog and poor cleaning will occur, which will also be disadvantageous in terms of cost. Moreover, when the above range is exceeded, problems arise such as deterioration of resolution and toner scattering.
磁性トナー粒子の帯電極性は、用いる感光体の材質や現
像プロセス等により適当な極性を選択すればよい。The charging polarity of the magnetic toner particles may be appropriately selected depending on the material of the photoreceptor used, the developing process, etc.
磁性トナー粒子は磁性粉および着色剤を含有する樹脂か
ら構成され、必要に応じて荷電制御剤、ワックス、抵抗
調整剤等がさらに含有される。The magnetic toner particles are composed of a resin containing magnetic powder and a colorant, and further contain a charge control agent, wax, resistance adjuster, etc., if necessary.
磁性トナー粒子に用いる樹脂は、加熱あるいは圧着等の
定着方法に応じて公知の樹脂から選択すればよ（、特に
制限はなく、例えば以下に挙げるものである。The resin used for the magnetic toner particles may be selected from known resins depending on the fixing method such as heating or pressure bonding (there are no particular restrictions, and examples include those listed below).
オレフィン樹脂、アクリル樹脂、スチレン共重合体、ビ
ニル樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹
脂、ポリエステル樹脂等の各種樹脂の１種以上。One or more types of resins such as olefin resins, acrylic resins, styrene copolymers, vinyl resins, polyamide resins, alkyd resins, epoxy resins, and polyester resins.
これらの樹脂のうち、スチレン−アクリル樹脂、ポリエ
ステル樹脂が好ましく、特にスチレン−アクリル樹脂を
用いることが好ましい。Among these resins, styrene-acrylic resins and polyester resins are preferred, and styrene-acrylic resins are particularly preferred.
着色剤は、目的に応じて選択すればよく、特に制限はな
い。 好適な着色剤としては、例えば、前記した着色剤
が挙げられる。The colorant may be selected depending on the purpose and is not particularly limited. Suitable colorants include, for example, the colorants described above.
このような着色剤の含有量は、磁性トナー粒子の樹脂１
００重量部に対し１〜１０重量部程度であることが好ま
しい。The content of such a colorant is based on the resin 1 of the magnetic toner particles.
The amount is preferably about 1 to 10 parts by weight per 00 parts by weight.
なお、これらのような着色剤を用いず、後述する磁性粉
を着色剤として用いてもよい。Note that instead of using these colorants, magnetic powder described below may be used as the colorant.
荷電制御剤は、帯電極性、帯電量等を制御するために必
要に応じて添加される。 本発明では、目的とする極性
、帯電量等に応じて公知の適当な帯電制御剤を選択すれ
ばよく、特に制限はない。 例えば、金−属錯塩アゾ系
染料、ニグロシン系染料等が挙げられるが、これらは要
求特性に応じて選択されるものである。A charge control agent is added as necessary to control charge polarity, charge amount, etc. In the present invention, a known appropriate charge control agent may be selected depending on the intended polarity, amount of charge, etc., and there are no particular limitations. Examples include metal complex salt azo dyes, nigrosine dyes, etc., which are selected depending on the required characteristics.
このような荷電制御剤の含有量は、磁性トナー粒子の樹
脂１００重量部に対し０．３〜５重量部程度であること
が好ましい。The content of such a charge control agent is preferably about 0.3 to 5 parts by weight based on 100 parts by weight of the resin of the magnetic toner particles.
ワックスは離型剤として、オフセット防止のために必要
に応じて添加される。 本発明では用いるワックスに特
に制限はな（、公知の種々のワックス、例えば、ポリエ
チレンワックス、ポリプロピレンワックス、シリコンワ
ックス等を用いればよいが、これらは要求特性に応じて
選択されるものである。 このようなワックスの含有量
は、非磁性トナー粒子の樹脂１００重量部に対し１〜７
重量部程度であることが好ましい。Wax is added as a mold release agent as necessary to prevent offset. The wax used in the present invention is not particularly limited (although various known waxes such as polyethylene wax, polypropylene wax, silicone wax, etc. may be used, these are selected depending on the required characteristics. The content of the wax is 1 to 7 parts by weight per 100 parts by weight of the resin of the non-magnetic toner particles.
Preferably, it is about parts by weight.
磁性トナー粒子に含有される磁性粉に特に制限はなく、
公知の磁性粉、例えば、マグネタイト、各種フェライト
等を用いればよいが、これらは要求特性に応じて選択さ
れるものである。There is no particular restriction on the magnetic powder contained in the magnetic toner particles.
Known magnetic powders such as magnetite and various ferrites may be used, but these are selected depending on the required characteristics.
このような磁性粉は、磁性トナー粒子に必要とされる磁
気特性が得られるように含有されればよく、磁性粉の種
類によっても異なるが、例えば、磁性トナー粒子の樹脂
１００重量部に対し５〜７０重量部程度含有されること
が好ましい。Such magnetic powder may be contained in such a way that the magnetic properties required for the magnetic toner particles can be obtained, and although it varies depending on the type of magnetic powder, for example, 5 parts by weight of the resin of the magnetic toner particles is used. It is preferable to contain about 70 parts by weight.
なお、磁性トナー粒子には、これらの他、抵抗調整剤が
含有されていてもよい。In addition to these, the magnetic toner particles may also contain a resistance adjuster.
磁性トナー粒子は、通常のトナー製造法により製造すれ
ばよ（、例えば、下記のようにして製造される。The magnetic toner particles may be manufactured by a conventional toner manufacturing method (for example, as described below).
上記したような着色剤・荷電制御剤・ワックス・磁性粉
・その他の添加剤等のうちから必要なものを選択し、こ
れらの所定量と樹脂とを溶融・混練し、冷却後、ハンマ
ーミル、カッターミル等により粗粉砕する。 次いで、
ジェットミル、オングミル等により微粉砕した後、好ま
しくは上記体積平均粒径範囲になるように分級して磁性
トナー粒子を得る。Select the necessary additives from the above-mentioned colorants, charge control agents, waxes, magnetic powders, other additives, etc., melt and knead predetermined amounts of these and the resin, and after cooling, use a hammer mill, Coarsely grind using a cutter mill, etc. Then,
After finely pulverizing the particles using a jet mill, an ong mill, etc., the particles are classified to preferably fall within the volume average particle size range described above to obtain magnetic toner particles.
このようにして得られた磁性トナー粒子は、上記の凝集
防止剤とヘンシェルミキサー、グラインドミキサー等に
より混合され、磁性トナー粒子表面に凝集防止剤が付着
した状態にされて、電子写真用トナーとして用いられる
。The magnetic toner particles thus obtained are mixed with the above-mentioned agglomeration preventive agent using a Henschel mixer, a grind mixer, etc., and the agglomeration preventive agent is attached to the surface of the magnetic toner particles, and then used as an electrophotographic toner. It will be done.
本発明の電子写真用トナー中の磁性トナー粒子および凝
集防止剤の含有量は、磁性トナー粒子１００重量部に対
し、好ましくは凝集防止剤が０．０５〜１０重量部、よ
り好ましくは０．１〜３重量部である。 凝集防止剤の
含有量が上記範囲未満となると凝集防止が不十分であり
、上記範囲を超えると画質の経時変化が問題となる。The content of the magnetic toner particles and anti-aggregation agent in the electrophotographic toner of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0.1 parts by weight, based on 100 parts by weight of the magnetic toner particles. ~3 parts by weight. If the content of the anti-aggregation agent is less than the above range, prevention of aggregation will be insufficient, and if it exceeds the above range, changes in image quality over time will become a problem.
このような本発明の電子写真用トナーは、１成分系現像
剤として、特公昭４１−９４７５号公報、同４５−２８
７７号公報、同５４−３６２４号公報、米国特許第２８
９５８４７号明細書、同３１５２０１２号明細書等に記
載されているジャンピング法、インプレッション法、タ
ッチダウン法等に好適に用いることができる。 さらに
、特開昭５７−１１４１６３号公報に記載されているＦ
ＥＥＤ現像法にも好適に用いることができる。Such an electrophotographic toner of the present invention is used as a one-component developer as described in Japanese Patent Publications Nos. 41-9475 and 45-28.
No. 77, No. 54-3624, U.S. Patent No. 28
It can be suitably used in the jumping method, impression method, touchdown method, etc. described in Japanese Patent No. 95847, Japanese Patent No. 3152012, and the like. Furthermore, F
It can also be suitably used in the EED development method.
本発明の電子写真用トナーは、この他、キャリア粒子と
混合して２成分系現像剤として用いることもできる。In addition, the electrophotographic toner of the present invention can also be mixed with carrier particles and used as a two-component developer.
２成分系現像剤として用いる場合、荷電性トナー粒子と
して非磁性トナー粒子を用いる。When used as a two-component developer, non-magnetic toner particles are used as the charged toner particles.
非磁性トナー粒子としては、磁性粉を含有しない他は上
記したような磁性トナー粒子とほぼ同様の組成・性状の
粒子を用いることが好ましい。As the non-magnetic toner particles, it is preferable to use particles having substantially the same composition and properties as the above-mentioned magnetic toner particles, except that they do not contain magnetic powder.
用いるキャリア粒子には特に制限はな（、Ｆｅ、各種フ
ェライト等から構成される装置キャリア粒子を用いれば
よいが、帯電制御が容易であることからフェライトを用
いることが好ましい。There are no particular restrictions on the carrier particles to be used (although device carrier particles composed of Fe, various ferrites, etc. may be used; however, it is preferable to use ferrite because charging can be easily controlled).
本発明において、キャリア粒子の体積平均粒径は、好ま
しくは３０〜１２０μｍ、さらに好ましくは３５〜５５
μｍである。In the present invention, the volume average particle diameter of the carrier particles is preferably 30 to 120 μm, more preferably 35 to 55 μm.
It is μm.
このようなキャリア粒子と上記の電子写真用トナーとか
ら構成される本発明の電子写真用現像剤中において、電
子写真用トナーの含有量は、好ましくは２〜１２ｗｔ％
、より好ましくは８〜１０ｗｔ％である。In the electrophotographic developer of the present invention comprising such carrier particles and the above electrophotographic toner, the content of the electrophotographic toner is preferably 2 to 12 wt%.
, more preferably 8 to 10 wt%.
このような本発明の電子写真用現像剤は、磁気ブラシ現
像法、カスケード法、毛ブラシ法、パウダークラウド法
などの乾式現像法に用いられて所定の効果を発揮する。Such an electrophotographic developer of the present invention exhibits a predetermined effect when used in a dry developing method such as a magnetic brush developing method, a cascade method, a bristle brush method, or a powder cloud method.
〈実施例〉
以下、本発明の具体的実施例を挙げ、本発明をさらに詳
細に説明する。<Example> Hereinafter, the present invention will be explained in further detail by giving specific examples of the present invention.
［実施例１］
スチレン−アクリル樹脂
（日本カーバイド工業社製）４９重量部マグネタイト
（ティーデイ−ケイ株式会社製ＴＦＰ−２）４５重量部
ポリプロピレンワックス
（三菱化成工業社製ビスコール５５０Ｐ）３．５重量部
カーボンブラック
（三菱化成工業社製ＭＡ−１００）
０．５重量部
荷電制御剤
（保土谷化学社製ＴＲＨ） ２重量部を溶解・混
練後、冷却し、ハンマーミルにて粗粉砕した。 次いで
ジェットミルにて微粉砕し、分級して体積平均粒径８．
５μｍの磁性トナー粒子を作製した。[Example 1] 49 parts by weight of styrene-acrylic resin (manufactured by Nippon Carbide Industries, Ltd.) 45 parts by weight of magnetite (TFP-2, manufactured by TDC Co., Ltd.) 3.5 parts by weight of polypropylene wax (Viscol 550P, manufactured by Mitsubishi Chemical Industries, Ltd.) After dissolving and kneading 0.5 parts by weight of carbon black (MA-100 manufactured by Mitsubishi Chemical Industries, Ltd.) and 2 parts by weight of a charge control agent (TRH manufactured by Hodogaya Chemical Co., Ltd.), the mixture was cooled and coarsely pulverized using a hammer mill. Next, it is finely pulverized with a jet mill and classified to a volume average particle size of 8.
Magnetic toner particles of 5 μm were prepared.
次いで、下記の凝集防止剤を作製した。Next, the following anti-aggregation agent was prepared.
（凝集防止剤Ｎｏ、１）
微粒子として体積平均粒径０．０４μｍの酸化チタン粒
子（日本アエロジル社製Ｐ−２５）４０重量部、シリカ
微粒子として体積平均粒径０．０２μｍのシリカ粒子（
日本アエロジル社製ＲＸ−２００）６０重量部を用い、
これらに前述したような機械的な歪力を印加しながら混
合・一体化して、凝集防止剤とした。 混合時間は５分
間とした。(Anti-agglomeration agent No. 1) 40 parts by weight of titanium oxide particles (P-25 manufactured by Nippon Aerosil Co., Ltd.) with a volume average particle size of 0.04 μm as fine particles, and silica particles with a volume average particle size of 0.02 μm as fine silica particles (
Using 60 parts by weight of RX-200 (manufactured by Nippon Aerosil Co., Ltd.),
These were mixed and integrated while applying mechanical strain as described above to form an anti-agglomeration agent. The mixing time was 5 minutes.
（凝集防止剤Ｎｏ、２）
微粒子として体積平均粒径１．０μｍのシリカ粒子（日
本シリカニ業社製ニップシール５Ｓ−６０）２５重量部
、シリカ微粒子として体積平均粒径０．０１μｍのシリ
カ粒子（日本アエロジル社製Ｒ−９７２）７５重量部を
用い、これらに前述のような機械的歪力を印加しながら
混合・一体化して、凝集防止剤とした。(Agglomeration inhibitor No. 2) 25 parts by weight of silica particles with a volume average particle size of 1.0 μm (Nip Seal 5S-60 manufactured by Nippon Silikani Gyo Co., Ltd.) as fine particles, silica particles with a volume average particle size of 0.01 μm as silica fine particles (Japan Using 75 parts by weight of R-972 (manufactured by Aerosil), these were mixed and integrated while applying the mechanical strain as described above to obtain an anti-agglomeration agent.
混合時間は７分間とした。The mixing time was 7 minutes.
（凝集防止剤Ｎｏ、３）
微粒子として体積平均粒径４μｍに粉砕・分級したステ
アリン酸亜鉛（日東化成工業社製ジンクステアレート６
０１）２０重量部、シリカ微粒子として体積平均粒径０
．０２μｍのシリカ粒子（日本アエロジル社製ＲＸ−２
００）８０重量部を用い、これらに前述のような機械的
歪力を印加しながら混合・一体化して、凝集防止剤とし
た。 混合時間は５分間とした。(Agglomeration inhibitor No. 3) Zinc stearate pulverized and classified into fine particles with a volume average particle diameter of 4 μm (Zinc Stearate 6 manufactured by Nitto Kasei Kogyo Co., Ltd.)
01) 20 parts by weight, volume average particle size 0 as silica fine particles
．． 02 μm silica particles (RX-2 manufactured by Nippon Aerosil Co., Ltd.)
00) were mixed and integrated while applying the mechanical strain as described above to obtain an anti-agglomeration agent. The mixing time was 5 minutes.
凝集防止剤Ｎｏ、１〜３の断面を透過型電子顕微鏡およ
び走査型電子顕微鏡にて観察した結果、微粒子表面にシ
リカ微粒子が埋め込まれていることが確認された。As a result of observing the cross sections of anti-aggregation agents Nos. 1 to 3 using a transmission electron microscope and a scanning electron microscope, it was confirmed that silica fine particles were embedded in the fine particle surfaces.
上記磁性トナー粒子と凝集防止剤Ｎｏ、１〜３のそれぞ
れとをヘンシェルミキサーにて混合し、本発明の電子写
真用トナーＮｏ、１〜３を得た。 これらを透過型電子
顕微鏡および走査型電子顕微鏡により観察した結果、磁
性トナー粒子表面に凝集防止剤が付着していることが確
認された。 なお、磁性トナー粒子は負荷電性であり、
凝集防止剤も同荷電性であった。The above magnetic toner particles and anti-aggregation agents Nos. 1 to 3 were mixed in a Henschel mixer to obtain electrophotographic toners Nos. 1 to 3 of the present invention. As a result of observing these using a transmission electron microscope and a scanning electron microscope, it was confirmed that an anti-aggregation agent was attached to the surface of the magnetic toner particles. Note that magnetic toner particles are negatively charged,
The anti-agglomerating agent was also similarly charged.
各トナ゛−中における磁性トナー粒子１００重置部に対
する凝集防止剤の含有量を、表１に示す。Table 1 shows the content of the anti-aggregation agent per 100 stacked portions of magnetic toner particles in each toner.
また、比較のために、上記凝集防止剤Ｎｏ。In addition, for comparison, the above-mentioned agglomeration inhibitor No.
１に用いた微粒子およびシリカ微粒子をヘンシェルミキ
サーにより混合し、凝集防止剤Ｎｏ、１１を得た。 こ
れを透過型電子顕微鏡および走査型電子顕微鏡により観
察した結果、微粒子表面にシリカ微粒子が付着している
状態であって、埋め込まれた状態とはなっていなかった
。 この凝集防止剤Ｎｏ、１１と上記磁性トナーとをヘ
ンシェルミキサーにより混合し、電子写真用トナーＮｏ
、１１を作製した。The fine particles used in Example 1 and the fine silica particles were mixed using a Henschel mixer to obtain anti-agglomeration agent No. 11. When this was observed using a transmission electron microscope and a scanning electron microscope, it was found that the silica fine particles were attached to the surface of the fine particles and were not embedded. This anti-aggregation agent No. 11 and the above magnetic toner were mixed using a Henschel mixer, and electrophotographic toner No.
, 11 were produced.
さらに、体積平均粒径１．Ｏｕｍのシリカ微粒子（日本
シリカニ業社製ニップシール５Ｓ−６０）を凝集防止剤
として用い、これと上記磁性トナー粒子とをヘンシェル
ミキサーにより混合して電子写真用トナーＮｏ、１１１
を作製した。Furthermore, the volume average particle size is 1. Oum's silica fine particles (Nip Seal 5S-60, manufactured by Nippon Silikani Gyo Co., Ltd.) were used as an anti-aggregation agent, and the above magnetic toner particles were mixed with a Henschel mixer to produce electrophotographic toner No. 111.
was created.
これらの電子写真用トナーに対し、下記の流動性試験を
行った。The following fluidity test was conducted on these electrophotographic toners.
（流動性試験）
トナーＬｏｇを１００メツシユの篩上で振動させ、１０
秒後に篩上に残存しているトナー量を測定することによ
りトナーの流動性を評価した。 測定にはホソカワミク
ロン社製パウダーテスターを用いた。(Flowability test) Toner Log was vibrated on a 100 mesh sieve,
The fluidity of the toner was evaluated by measuring the amount of toner remaining on the sieve after seconds. A powder tester manufactured by Hosokawa Micron was used for the measurement.
表１に示す評価の詳細を下記に示す。Details of the evaluation shown in Table 1 are shown below.
○：０．５ｇ以下
Ｘ：０．５ｇ超
表 １
電子写真用 凝集防止剤 流動性トナーＮｏ、
含有量 試 験１
１ 。○: 0.5g or less
Content test 1
1.
２ ０ 。2 0.
３ ０ 。3 0.
１１（比較） １゜
１１１ （比較） ０゜
０重量部 ０
５重量部 ０
６重量部 ○
０重量部 ×
５重量部 ×
［実施例２］
実施例１で作製した各種電子写真用トナーに対し、下記
の連続耐刷試験を行なった。11 (Comparison) 1゜111 (Comparison) 0゜0 parts by weight 0 5 parts by weight 0 6 parts by weight ○ 0 parts by weight × 5 parts by weight × [Example 2] For various electrophotographic toners produced in Example 1 , the following continuous printing test was conducted.
（連続耐刷試験）
連続耐刷試験用パターンを作製し、このパターンを用い
て市販の電子写真式レーザービームプリンタ（京セラ株
式会社製）を使用し、２万枚の連続耐刷試験を行なった
。 なお、試験は、３０℃、７５％ＲＨの条件下にて行
なった。(Continuous printing durability test) A continuous printing durability test pattern was prepared, and using this pattern, a 20,000-sheet continuous printing durability test was conducted using a commercially available electrophotographic laser beam printer (manufactured by Kyocera Corporation). . Note that the test was conducted under conditions of 30° C. and 75% RH.
この結果、電子写真用トナーＮｏ、１〜３では、２万枚
耐刷試験後においても画質の経時変化は少なく、クリー
ニング性も良好であることがわかった。 また、感光体
に傷は観察されなかった。 さらに、機内飛散もきわめ
て少なく、トナー補給時にも問題は発生しなかった。As a result, it was found that for electrophotographic toner Nos. 1 to 3, there was little change in image quality over time even after the 20,000-sheet printing test, and the cleanability was also good. Further, no scratches were observed on the photoreceptor. Furthermore, there was very little scattering inside the machine, and no problems occurred when replenishing toner.
これに対し、電子写真用トナーＮｏ、１１およびＮｏ、
１１１では、層乱れ、カブリといった画質劣化やクリー
ニング不良や感光体劣化の問題が発生した。On the other hand, electrophotographic toner No. 11 and No.
No. 111 had problems with image quality deterioration such as layer disturbance and fog, poor cleaning, and photoreceptor deterioration.
［実施例３］
スチレン−アクリル樹脂
（三井東圧化学社製）
ポリプロピレンワックス
８８重量部
（三菱化成工業社製ビスコール５５０Ｐ）３重量部
カーボンブラック
（三菱化成工業社製ＭＡ−１００）
７重量部
荷電制御剤
（オリエント化学社製） ２重量部を溶解・混線
後、冷却し、ハンマーミルにて粗粉砕した。 次いでジ
ェットミルにて微粉砕し、分級して体積平均粒径８．０
μｍの非磁性トナー粒子を作製した。[Example 3] Styrene-acrylic resin (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 88 parts by weight of polypropylene wax (Viscol 550P, manufactured by Mitsubishi Chemical Industries, Ltd.) 3 parts by weight Carbon black (manufactured by Mitsubishi Chemical Industries, Ltd. MA-100) 7 parts by weight Charge After dissolving and mixing 2 parts by weight of a control agent (manufactured by Orient Chemical Co., Ltd.), the mixture was cooled and coarsely ground using a hammer mill. Next, it is finely pulverized with a jet mill and classified to a volume average particle size of 8.0.
Non-magnetic toner particles of μm size were produced.
上記非磁性トナー粒子と凝集防止剤Ｎｏ。The above non-magnetic toner particles and anti-aggregation agent No.
１〜３のそれぞれとをヘンシェルミキサーにて混合し、
本発明の電子写真用トナーＮ００４〜６を得た。 これ
らを透過型電子顕微鏡および走査型電子顕微鏡により観
察した結果、非磁性トナー粒子表面に凝集防止剤が付着
していることが確認された。 なお、非磁性トナー粒子
は負荷電性であり、凝集防止剤と同荷電性であった。Mix each of 1 to 3 with a Henschel mixer,
Electrophotographic toners N004-6 of the present invention were obtained. As a result of observing these using a transmission electron microscope and a scanning electron microscope, it was confirmed that an anti-aggregation agent was attached to the surface of the nonmagnetic toner particles. Note that the nonmagnetic toner particles were negatively charged, and had the same chargeability as the anti-aggregation agent.
各トナー中における非磁性トナー粒子１００重量部に対
する凝集防止剤の含有量を、表２に示す。Table 2 shows the content of anti-aggregation agent per 100 parts by weight of non-magnetic toner particles in each toner.
また、比較のために、上記凝集防止剤Ｎｏ。In addition, for comparison, the above-mentioned agglomeration inhibitor No.
１１と上記非磁性トナーとをヘンシェルミキサーにより
混合し、電子写真用トナーＮｏ。11 and the above-mentioned non-magnetic toner were mixed using a Henschel mixer to obtain toner No. 1 for electrophotography.
２１を作製した。21 was produced.
さらに、体積平均粒径１．０μｍのシリカ微粒子（日本
シリカニ業社製ニップシール５Ｓ−６０）を凝集防止剤
として用い、これと上記非磁性トナー粒子とをヘンシェ
ルミキサーにより混合して電子写真用トナーＮｏ、２１
１を作製した。Furthermore, using silica fine particles (Nip Seal 5S-60 manufactured by Nippon Silikani Gyo Co., Ltd.) with a volume average particle diameter of 1.0 μm as an anti-aggregation agent, this and the above-mentioned non-magnetic toner particles were mixed with a Henschel mixer to form electrophotographic toner No. , 21
1 was produced.
これらの電子写真用トナーに対し、実施例１と同様にし
て流動性試験を行った。A fluidity test was conducted on these electrophotographic toners in the same manner as in Example 1.
結果を表２に示す。The results are shown in Table 2.
表 電子写真用 トナーＮｏ。table for electrophotography Toner No.
凝集防止剤
含有量
流動性
試 験
４ １．０重量部 ０
５ ０．５重量部 ０
６ ０．６重量部 ０
２１（比較） １．０重量部 ×２１１（比較
） ０．５重量部 ×［実施例４］
実施例３で作製した各種電子写真用トナーとＭｇ−Ｃｕ
−Ｚｎフェライト製キャリア粒子（ティーデイ−ケイ株
式会社製ＴＦＣ５４０）とを混合し、それぞれトナーを
１０ｗｔ％含有する２成分系の電子写真用現像剤を得た
。Anti-aggregation agent content fluidity test 4 1.0 parts by weight 0 5 0.5 parts by weight 0 6 0.6 parts by weight 0 21 (comparison) 1.0 parts by weight × 211 (comparison) 0.5 parts by weight × [Example 4] Various electrophotographic toners produced in Example 3 and Mg-Cu
-Zn ferrite carrier particles (TFC540 manufactured by TDC Co., Ltd.) were mixed to obtain two-component electrophotographic developers each containing 10 wt % of toner.
これらの２成分系現像剤を用いてデータクエストチャー
ト、電子写真チャートおよびランニングチャートを複写
原稿とし、５万枚の連続複写試験を行なった。 なお、
複写機は、市販の電子写真式複写機（三田工業社製）を
使用した。Using these two-component developers, a continuous copying test of 50,000 sheets was conducted using Dataquest charts, electrophotographic charts, and running charts as copy originals. In addition,
A commercially available electrophotographic copying machine (manufactured by Sanda Kogyo Co., Ltd.) was used as a copying machine.
この結果、電子写真用トナーＮｏ、４〜６を含有する現
像剤は、画質の経時変化が少なく、また、機内飛散もき
わめて少なく、さらに、トナー補給時のトラブルも発生
しなかった。As a result, the developers containing electrophotographic toners Nos. 4 to 6 had little change in image quality over time, had very little scattering in the machine, and did not cause any trouble during toner replenishment.
これに対し、電子写真用トナーＮｏ、２１を含有する現
像剤および電子写真用トナーＮｏ。On the other hand, the developer containing electrophotographic toner No. 21 and the electrophotographic toner No.
２１１を含有する現像剤は、帯電の経時変化が太き（、
画質の劣化が発生し、また、機内飛散も大きかった。The developer containing 211 has a large charge change over time (,
Image quality deteriorated, and there was also a large amount of flying debris inside the aircraft.
以上の実施例から、本発明の効果が明らかである。The effects of the present invention are clear from the above examples.
であっても流動性が良好で、解像力・階調性等が優れた
高画質のトナー像を得ることができる。 また、機内飛
散もきわめて少ない。Even if it is, a high-quality toner image with good fluidity and excellent resolution, gradation, etc. can be obtained. In-flight scattering is also extremely low.
〈発明の効果〉<Effect of the invention>
Claims (1)
、この微粒子より体積平均粒径の小さいシリカ微粒子と
を、固着一体化した凝集防止剤と、 荷電性トナー粒子とを含有することを特徴とする電子写
真用トナー。 （２）前記シリカ微粒子の体積平均粒径が ０．５μｍ以下である請求項１に記載の電子写真用トナ
ー。 （３）前記凝集防止剤がシリカ微粒子を４０〜９５ｗｔ
％含有する請求項１または２に記載の電子写真用トナー
。 （４）前記荷電性トナー粒子１００重量部に対し、前記
凝集防止剤が０．０５〜１０重量部含有される請求項１
ないし３のいずれかに記載の電子写真用トナー。 （５）前記荷電性トナー粒子が磁性トナー粒子であり、
１成分系電子写真用現像剤として用いられる請求項１な
いし４のいずれかに記載の電子写真用トナー。 （６）請求項１ないし４のいずれかに記載の電子写真用
トナーと、キャリア粒子とを含有する電子写真用現像剤
。[Scope of Claims] (1) An anti-aggregation agent in which fine particles having a volume average particle size of 0.01 to 5 μm and silica fine particles having a smaller volume average particle size than these fine particles are fixed and integrated, and a charged toner. An electrophotographic toner characterized by containing particles. (2) The electrophotographic toner according to claim 1, wherein the silica fine particles have a volume average particle diameter of 0.5 μm or less. (3) The anti-aggregation agent contains 40 to 95 wt of silica fine particles.
% of the electrophotographic toner according to claim 1 or 2. (4) 0.05 to 10 parts by weight of the anti-aggregation agent is contained with respect to 100 parts by weight of the chargeable toner particles.
3. The electrophotographic toner according to any one of 3 to 3. (5) the charged toner particles are magnetic toner particles;
5. The electrophotographic toner according to claim 1, which is used as a one-component electrophotographic developer. (6) An electrophotographic developer comprising the electrophotographic toner according to any one of claims 1 to 4 and carrier particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63197556A JP2784924B2 (en) | 1988-08-08 | 1988-08-08 | Electrophotographic toner and electrophotographic developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63197556A JP2784924B2 (en) | 1988-08-08 | 1988-08-08 | Electrophotographic toner and electrophotographic developer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0246469A true JPH0246469A (en) | 1990-02-15 |
| JP2784924B2 JP2784924B2 (en) | 1998-08-13 |
Family
ID=16376459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63197556A Expired - Lifetime JP2784924B2 (en) | 1988-08-08 | 1988-08-08 | Electrophotographic toner and electrophotographic developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2784924B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0421861A (en) * | 1990-05-17 | 1992-01-24 | Canon Inc | Toner and image forming method |
| JPH04337738A (en) * | 1991-05-14 | 1992-11-25 | Fuji Xerox Co Ltd | Electrophotographic developer composition |
| WO2007006780A2 (en) * | 2005-07-11 | 2007-01-18 | Akzo Nobel Coatings International B.V. | Toner powders and process for their preparation |
| US7245859B2 (en) | 2005-06-17 | 2007-07-17 | Kabushiki Kaisha Toshiba | Image forming apparatus having a rotary developing device with plural developing units |
| US7972660B2 (en) | 2005-07-11 | 2011-07-05 | Akzo Nobel Coatings International B.V. | Electrostatic fluidised powder bed coating process |
-
1988
- 1988-08-08 JP JP63197556A patent/JP2784924B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0421861A (en) * | 1990-05-17 | 1992-01-24 | Canon Inc | Toner and image forming method |
| JPH04337738A (en) * | 1991-05-14 | 1992-11-25 | Fuji Xerox Co Ltd | Electrophotographic developer composition |
| US7245859B2 (en) | 2005-06-17 | 2007-07-17 | Kabushiki Kaisha Toshiba | Image forming apparatus having a rotary developing device with plural developing units |
| US7376372B2 (en) | 2005-06-17 | 2008-05-20 | Kabushiki Kaisha Toshiba | Image forming apparatus and method for forming image |
| WO2007006780A2 (en) * | 2005-07-11 | 2007-01-18 | Akzo Nobel Coatings International B.V. | Toner powders and process for their preparation |
| WO2007006780A3 (en) * | 2005-07-11 | 2008-07-03 | Akzo Nobel Coatings Int Bv | Toner powders and process for their preparation |
| US7972660B2 (en) | 2005-07-11 | 2011-07-05 | Akzo Nobel Coatings International B.V. | Electrostatic fluidised powder bed coating process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2784924B2 (en) | 1998-08-13 |
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