JPH01105264A - Carrier for developing electrostatic latent image - Google Patents
Carrier for developing electrostatic latent imageInfo
- Publication number
- JPH01105264A JPH01105264A JP62276839A JP27683987A JPH01105264A JP H01105264 A JPH01105264 A JP H01105264A JP 62276839 A JP62276839 A JP 62276839A JP 27683987 A JP27683987 A JP 27683987A JP H01105264 A JPH01105264 A JP H01105264A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- resistance
- comparative example
- coating layer
- resin
- 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
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000011247 coating layer Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims description 7
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007771 core particle Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 79
- 239000011162 core material Substances 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 80
- 239000000203 mixture Substances 0.000 description 64
- 238000009472 formulation Methods 0.000 description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 41
- 229920001225 polyester resin Polymers 0.000 description 37
- 239000004645 polyester resin Substances 0.000 description 37
- 239000011248 coating agent Substances 0.000 description 31
- 238000000576 coating method Methods 0.000 description 31
- 229920001577 copolymer Polymers 0.000 description 29
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 239000007788 liquid Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 20
- 229910000859 α-Fe Inorganic materials 0.000 description 20
- 239000000969 carrier Substances 0.000 description 18
- 235000014692 zinc oxide Nutrition 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 229920002050 silicone resin Polymers 0.000 description 12
- 235000013980 iron oxide Nutrition 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 238000011088 calibration curve Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012050 conventional carrier Substances 0.000 description 3
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 2
- -1 chloropolystyrene Polymers 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101710105807 UDP-N-acetylglucosamine 1-carboxyvinyltransferase 1 Proteins 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LBVWYGNGGJURHQ-UHFFFAOYSA-N dicarbon Chemical compound [C-]#[C+] LBVWYGNGGJURHQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-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
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1131—Coating methods; Structure of coatings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は静電潜像現像用キャリアに関し、より詳しくは
トナーのスペント化が防止された樹脂被覆静電潜像現像
用キャリアに関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a carrier for developing electrostatic latent images, and more particularly to a resin-coated carrier for developing electrostatic latent images that prevents toner from becoming spent.
従来、電子写真法としては、米国特許筒２，２９７，６
９１号明細書、特公昭４９−２３９１０号公報、及び特
公昭４３−２４７４８号公報等に各種の方法が記載され
ているが、一般には光導電性物質を利用し、種々の手段
により感光体上に定記的潜像を形成し、次いで該潜像を
トナーを用いて現像し、必要に応じて紙等に粉像を転写
した後、加熱あるいは溶剤蒸気等により定着し、コピー
を得るものである。Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,6
Although various methods are described in Japanese Patent Publication No. 91, Japanese Patent Publication No. 49-23910, and Japanese Patent Publication No. 43-24748, etc., generally a photoconductive substance is used and a photoreceptor is coated by various means. A fixed latent image is formed on the paper, and then the latent image is developed using toner, and if necessary, the powder image is transferred to paper, etc., and then fixed by heating or solvent vapor, etc., to obtain a copy. be.
電気的潜像を現像する方式には、大別して絶縁性有機液
体中に各種の顔料や染料を微細に分散させた現像剤を用
いる液体現像方式とカスケード法、磁気ブラシ法、パウ
ダークラウド法などの天然または合成の樹脂にカーボン
ブラック等の着色剤を分散せしめたトナーを用いる所謂
乾式現像方法とがあり、本発明は後者の乾式現像方法に
おいて使用するキャリアに関し、さらに詳しくは導電性
微粉末を含有する樹脂で表面を被覆させた乾式二成分＠
像方法において使用するキャリアの改良に関する。Methods for developing electrical latent images can be roughly divided into liquid development methods, which use a developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, and methods such as the cascade method, magnetic brush method, and powder cloud method. There is a so-called dry developing method that uses a toner in which a colorant such as carbon black is dispersed in a natural or synthetic resin. Dry two-component surface coated with resin
This invention relates to improvements in carriers used in imaging methods.
との二成分系乾式現像剤は、比較的大きなキャリア粒子
表面上に微小なトナー粒子が雨粒子の摩擦により発生し
た電気力により保持されており、静電潜像に近接される
と静電潜像が形成する電界によるトナー粒子に対する該
潜像方向への吸引力が、トナー粒子とキャリア粒子間の
結合力に打ち勝ってトナー粒子は静電潜像上に吸引付着
されて静電潜像が可視化されるものである。そして、現
像剤は現像によって消耗されたトナーを補充しながら反
復使用される。In the two-component dry developer, minute toner particles are held on the surface of relatively large carrier particles by the electric force generated by the friction of rain particles, and when brought close to an electrostatic latent image, the electrostatic latent image is released. The attraction force on the toner particles in the direction of the latent image due to the electric field formed by the image overcomes the bonding force between the toner particles and carrier particles, and the toner particles are attracted and adhered onto the electrostatic latent image, making the electrostatic latent image visible. It is something that will be done. The developer is used repeatedly while replenishing the toner consumed by development.
従って、キャリアは長期間の使用中、常にトナー粒子を
所望とする極性で、かつ十分な帯１！量に摩擦帯電しな
ければならない。しかしながら従来の現像剤は１粒子間
の衝突または粒子と現像機械との衝突等の機械的衝突又
はこれらによる発熱でキャリア表面にトナー膜が形成さ
れ、所謂スペント化が生じ、キャリアの帯電特性が使用
時間と共に低下し、現像剤全体を取換える必要が生じる
。Therefore, during long-term use, the carrier always maintains the desired polarity and sufficient band of toner particles. amount must be triboelectrically charged. However, with conventional developers, a toner film is formed on the carrier surface due to mechanical collisions such as collisions between particles or collisions between particles and a developing machine, or heat generated by these, resulting in so-called spent state, and the charging characteristics of the carrier are used. It decreases over time, requiring the entire developer to be replaced.
この様なスペント化を防止するため、従来よりキャリア
表面に種々の樹脂を被覆する方法が提案されている。In order to prevent such a spent state, methods have been proposed in which the surface of the carrier is coated with various resins.
例えばスチレン・メタクリート共重合体、ポリスチレン
、シリコーン樹脂、クロロポリスチレン、スチレン−ブ
タジェン共重合体、メチルメタクリレート共重合体など
である。Examples include styrene-methacrylate copolymer, polystyrene, silicone resin, chloropolystyrene, styrene-butadiene copolymer, and methyl methacrylate copolymer.
しかしながらこれらの樹脂を被覆したキャリアは、樹脂
自体が高抵抗であるため、現像剤の抵抗が高くなり、そ
の結果、コピー画像の大面積の画像面では、中央部の画
像濃度が非常に薄く、端縁のみが濃く表現される所謂エ
ツジ効果の鋭く利いた表現となる。複写体が文字や細線
のときはこのエツジ効果のため鮮明な画像となるが、被
写体が写真のように中間調の場合には非常に再現性の悪
い画像となる欠点がある。また、現像剤の帯電量につい
ても同様なことがいえ、抵抗の低いキャリアに比べ抵抗
の高いキャリアでは帯電量が高くなり、その結果得られ
るコピーは鋭くエツジ効果の効いた表現となる。つまり
、スペント化防止のため表面に樹脂を被覆したキャリア
は、抵抗のアップ、帯電量のアップにり、非常にエツジ
効果の効いたものとなる。これらの問題を解決するため
に樹脂被膜中に導電性微粉末を添加することが提案され
ている。しかし導電性微粉末を樹脂被膜中に添加し、キ
ャリア抵抗を下げようとした場合、相当量を添加しなく
てはならないため、樹脂被膜表面に導電性微粉末が露出
してしまい樹脂のスペント防止効果を損なってしまう。However, in carriers coated with these resins, the resin itself has high resistance, so the resistance of the developer is high, and as a result, on a large area image surface of a copy image, the image density in the center is very low. This creates a sharp, so-called edge effect where only the edges are expressed darkly. When the object to be copied is text or thin lines, the edge effect produces a clear image, but when the object is in halftones, such as a photograph, the image has very poor reproducibility. The same thing can be said about the amount of charge of the developer; a carrier with a high resistance has a higher charge amount than a carrier with a low resistance, and the resulting copy has a sharp edge effect. In other words, a carrier whose surface is coated with a resin to prevent it from becoming spent has an increased resistance and an increased amount of charge, resulting in a very effective edge effect. In order to solve these problems, it has been proposed to add conductive fine powder to the resin coating. However, when attempting to lower carrier resistance by adding conductive fine powder to a resin coating, a considerable amount must be added, which exposes the conductive fine powder to the resin coating surface and prevents the resin from spending. This will reduce the effectiveness.
本発明は上記の点に鑑みなされたもので、その目的はト
ナーのスペント化を防止するためにキャリアの表面に樹
脂を被覆しても現像剤の抵抗が高くならず、中間調再現
性の非常に優れた画像を得ることができ、また、キャリ
ア上の被覆層に添加する導電性微粉末の添加量が少なく
て済み、スペント防止効果を損なうことがなく、長期間
の繰り返し使用によっても現像剤劣化がなく安定した画
像品質を得ることができる静電潜像現像用キャリアを提
供することにある。The present invention has been made in view of the above points, and its purpose is to prevent the resistance of the developer from increasing even if the surface of the carrier is coated with resin to prevent toner from becoming spent, and to improve halftone reproducibility. In addition, the amount of conductive fine powder added to the coating layer on the carrier is small, the spent prevention effect is not impaired, and the developer can be easily used even after repeated use over a long period of time. An object of the present invention is to provide a carrier for developing an electrostatic latent image, which is free from deterioration and can provide stable image quality.
本発明によれば、芯材粒子の表面に被覆層を設けたキャ
リアであって、該被覆層が互いに非相溶の複数種の樹脂
と導電性微粉末とを含有することを特徴とする静電潜像
現像用キャリアが提供される。According to the present invention, there is provided a carrier in which a coating layer is provided on the surface of core material particles, and the coating layer contains a plurality of types of resins that are incompatible with each other and conductive fine powder. A carrier for electrolatent image development is provided.
本発明の静電潜像現像用キャリアの抵抗低下作用を図面
により説明する。The resistance lowering effect of the carrier for developing electrostatic latent images of the present invention will be explained with reference to the drawings.
第１図は本発明のキャリアを示し、第２図は従来のキャ
リアを示す。非相溶の樹脂中に導電性微粉末を含有せし
めた場合、第１図に示されるように、樹脂Ａと樹脂Ｂ（
樹脂Ａと非相溶）界面に導電性微粉末２が集中するため
キャリア１の表面に導電回路が形成され、キャリア抵抗
が低下し、かつ導電性微粒子の量は少なくて済むのであ
る。これに対し、従来のキャリアでは導電性微粉末２は
芯材３の外側の被覆層の樹脂ａ中に非局在化して分布す
るため導電性を確保するためには多量使用する必要が生
じ、既述の問題を生じさせてしまう。FIG. 1 shows a carrier of the present invention, and FIG. 2 shows a conventional carrier. When conductive fine powder is contained in incompatible resins, resin A and resin B (
Since the conductive fine powder 2 is concentrated at the interface (incompatible with the resin A), a conductive circuit is formed on the surface of the carrier 1, the carrier resistance is reduced, and the amount of conductive fine particles can be reduced. On the other hand, in conventional carriers, the conductive fine powder 2 is delocalized and distributed in the resin a of the outer coating layer of the core material 3, so it is necessary to use a large amount to ensure conductivity. This will cause the problem mentioned above.
以下本発明をより詳細に説明すると、本発明で用いられ
る被覆用樹脂としては、例えば、ポリスチレン、クロロ
ポリ〈４レン、ポリ−α−メチルスチレン、スチレン−
クロロスチレン共重合体、スチレン−プロピレン共重合
体、スチレンーブタジェン共重合体、スチレン−塩化ビ
ニル共重合体、スチレン−酢酸ビニル共重合体、スチレ
ン−マレイン酸共重合体、スチレン−アクリル酸エステ
ル共重合体（スチレン−アクリル酸メチル共重合体、ス
チレン−アクリル酸エチル共重合体、スチレン−アクリ
ル酸ブチル共重合体、スチレン−アクリル酸オクチル共
重合体、スチレン−アクリル酸フェニル共重合体等）、
スチレン−メタクリル酸エステル共重合体（スチレン−
メタクリル酸メチル共重合体、スチレン−メタクリル酸
エチル共重合体、スチレン−メタクリル酸ブチル共重合
体、スチレン−メタクリル酸フェニル共重合体等）、ス
チレン−α−クロルアクリル酸メチル共重合体、スチレ
ン−アクリロニトリル−アクリル酸エステル共重合体等
のスチレン系樹脂（スチレン又はスチレン置換体を含む
単重合体または共重合体）、塩化ビニル樹脂、スチレン
−酢酸ビニル共重合体、ロジン変性マレイン酸樹脂、フ
ェニール樹脂、エポキシ樹脂、ポリエステル樹脂、アイ
オノマー樹脂、ポリウレタン樹脂、シリコーン樹脂、ケ
トン樹脂、エチレン−エチルアクリレート共重合、キシ
レン樹脂、ポリビニルブチラール樹脂等があるが、これ
らの樹脂は必ず二種以上の非相溶の組合せで用いる。ま
た、その比率は重量比でｌ：９９〜５０：５０．望まし
くは５：９５〜３０ニア０である。To explain the present invention in more detail below, the coating resin used in the present invention includes, for example, polystyrene, chloropoly<4-lene, poly-α-methylstyrene, styrene-
Chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester Copolymers (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.) ,
Styrene-methacrylic acid ester copolymer (styrene-
methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-methyl chloroacrylate copolymer, styrene- Styrenic resins such as acrylonitrile-acrylic acid ester copolymers (unipolymers or copolymers containing styrene or styrene substitutes), vinyl chloride resins, styrene-vinyl acetate copolymers, rosin-modified maleic acid resins, phenyl resins , epoxy resins, polyester resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymerization, xylene resins, polyvinyl butyral resins, etc., but these resins always contain two or more types of incompatible resins. Use in combination. Also, the ratio is 1:99 to 50:50 by weight. The ratio is preferably 5:95 to 30 near 0.
キャリア芯材としては、平均粒径が２０−１０００μ。As a carrier core material, the average particle size is 20-1000μ.
好ましくは５０−５００μのコバルト、鉄、銅、ニッケ
ル、亜鉛、アルミニウム、フェライト、マグネタイト、
黄銅、ガラス等の非金属や金属、金属合金等従来使用さ
れている材料が広く用いられる。Preferably 50-500 μ of cobalt, iron, copper, nickel, zinc, aluminum, ferrite, magnetite,
Conventionally used materials such as nonmetals such as brass and glass, metals, and metal alloys are widely used.
導電性微粉末としてはカーボンブラック、銅、酸化亜鉛
、チタンブラック、酸化鉄、チタン酸バリウム、酸化チ
タン、酸化スズ、酸化アンチモン等の公知の材料が使用
できる。As the conductive fine powder, known materials such as carbon black, copper, zinc oxide, titanium black, iron oxide, barium titanate, titanium oxide, tin oxide, and antimony oxide can be used.
本発明で用いる導電性粉末の具体例を述べれば、カーボ
ンブラックとしては、たとえばＢｌａｃｋ Ｐｅａｒｌ
ｓ２０００（キャボット社）、ＶＵＬＣＡＮ ＸＣ−１
２Ｃキ’ｒポット社）、ケッチエンブラックＥＣ（ライ
オンアクゾ社）、ケッチエンブラックＤＪ５０Ｑ（ライ
オンアクゾ社）、コンダクテックス９７５（コロンビア
カーボン社）、コンダクテックスＳＣ（コロンビアカー
ボン社）が、酸化亜鉛としては、たとえば２３Ｋ（白水
化学社）、導電性亜鉛華Ｎａ １（本荘ケミカル社）、
導電性亜鉛華Ｎα２（本荘ケミカル社）が、チタンブラ
ックとしては。To give specific examples of the conductive powder used in the present invention, examples of carbon black include Black Pearl.
s2000 (Cabot), VULCAN XC-1
As zinc oxide For example, 23K (Hakusui Chemical Co., Ltd.), conductive zinc white Na 1 (Honjo Chemical Co., Ltd.),
Conductive zinc white Nα2 (Honjo Chemical Co., Ltd.) is used as titanium black.
２０Ｍ（三菱金属社）や１２Ｓ（三菱金属社）が、酸化
鉄としてはフェライト、たとえば戸田工業社製のＥＰＴ
−５００、ＥＰＴ−１０００、ＭＡＴ−２１０，ＭＡＴ
−３０５、ＭＡＹ−２２２、ＭＡＴ−７４０やチタン工
業社製のＢＬ−１００、ＢＬ−２００、ＢＬ−２２０、
ＢＬ−２５０、ＲＢ−ＢＬ等が挙げられる。またチタン
酸バリウムとしては富士チタン工業社製のＢＴ−１００
Ｐ、ＢＴ−１００Ｇ、 ＢＴ−１００に、 ＢＴ−ＬＯ
ＯＭ、ＢＴ−１０１等が、酸化チタンとしては、チタン
工業社製のＥＣＴ−５２、ＫＶ−４００、ＥＣＲ−７２
、ＥＣＴＲ−８２や石原産業社製（７） ５００１ｉ１
．３００Ｌ Ｓ−１あるいは三菱金属社のＷ−１０が、
酸化スズとしてはト１（三菱金属社製）やＭＥＣ−３０
０（帝国化工社）、 ＭＥＣ５００（帝国化工社）等が
挙げられる。20M (Mitsubishi Metals Co., Ltd.) and 12S (Mitsubishi Metals Co., Ltd.) are iron oxides such as ferrite, such as EPT manufactured by Toda Kogyo Co., Ltd.
-500, EPT-1000, MAT-210, MAT
-305, MAY-222, MAT-740 and BL-100, BL-200, BL-220 manufactured by Titan Kogyo Co., Ltd.
Examples include BL-250 and RB-BL. In addition, as barium titanate, BT-100 manufactured by Fuji Titanium Industry Co., Ltd.
P, BT-100G, BT-100, BT-LO
OM, BT-101, etc., and titanium oxides include ECT-52, KV-400, and ECR-72 manufactured by Titan Kogyo Co., Ltd.
, ECTR-82 and Ishihara Sangyo Co., Ltd. (7) 5001i1
．． 300L S-1 or Mitsubishi Metals W-10,
Examples of tin oxide include To1 (manufactured by Mitsubishi Metals) and MEC-30.
0 (Teikoku Kakosha), MEC500 (Teikoku Kakosha), etc.
上記導電性微粉末を前記樹脂に分散する方法は、溶剤に
樹脂（非相溶な２種以上）を溶解した後、導電性微粉末
を添加し、ホモミキサー等で分散する。The method for dispersing the conductive fine powder in the resin is to dissolve the resin (two or more incompatible types) in a solvent, then add the conductive fine powder and disperse with a homomixer or the like.
被覆層の形成方法としては流動床法、噴霧法等の従来公
知の手段で前記導電性微粉末の分散液をキャリア芯材に
塗布すればよい。The coating layer may be formed by applying a dispersion of the conductive fine powder to the carrier core material by a conventionally known method such as a fluidized bed method or a spraying method.
樹脂に対する導電性微粉末の添加量は０．５〜３０重量
部、好ましくは２〜２０重量部である。The amount of conductive fine powder added to the resin is 0.5 to 30 parts by weight, preferably 2 to 20 parts by weight.
前記本発明キャリアとともに用いられるトナーとしては
、従来より公知の方法で得られたものが用いられ、具体
的には樹脂成分、通常可視像の形成に必要なカーボンブ
ラック等の着色剤をよく混合し、熱ロールミルで混練し
た後、冷却、固化後粉砕１分級して得られる。The toner used with the carrier of the present invention is one obtained by a conventionally known method, and specifically, a resin component and a coloring agent such as carbon black, which is usually necessary for forming a visible image, are thoroughly mixed. The mixture is kneaded in a hot roll mill, cooled, solidified, and then crushed and classified into 1 class.
キャリア並びにトナーの使用量としてはトナー粒子がキ
ャリア粒子の樹脂表面に付着してその表面積の３０〜９
０％を占める程度に両粒子を混合するのが好ましい。The amount of carrier and toner used is that the toner particles adhere to the resin surface of the carrier particles and cover 30 to 9 of the surface area.
It is preferable that both particles are mixed to the extent that they account for 0%.
以下、本発明を実施例を挙げて説明する。 Hereinafter, the present invention will be explained by giving examples.
実施例１、比較例１．２
導電性微粉末二カーボンブラック（フンダクテックスＳ
Ｃ、コロンビアカーボン社製）８ｇメチルエチルケトン
１８００ ｇ上記処方をホモミキサ
ーで１０分間分散し、被覆層形成液を調合した。Example 1, Comparative Example 1.2 Conductive fine powder dicarbon black (Fundactex S
C, manufactured by Columbia Carbon Co., Ltd.) 8 g Methyl ethyl ketone 1800 g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒機７０μの球状酸化鉄粉７０００ Ｋ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed with spherical iron oxide powder of 70μ average particle size at 7000 K.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
また、比較のため
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ ｇとしたキャ
リア（比較例１）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
カーボンブラックを増したキャリアを（比較例２）作成
した。For comparison, (1) styrene-n was added by removing the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 1) (2) A carrier was prepared in which carbon black was increased so as to have the same resistance as the carrier of the above formulation (Comparative Example 2).
これらキャリア粒子の抵抗を電極面積２０ａ＆、電極間
距離２ｆｌｌ！１１のセルにキャリア粒子を充填し、１
００Ｖ印加したときの抵抗値として測定した。The resistance of these carrier particles is the electrode area 20a & the distance between the electrodes 2fl! 11 cells were filled with carrier particles, 1
The resistance value was measured when 00V was applied.
また上記キャリア粒子９５ｇとトナー（商品名買ＰＥ６
６００■リコー製）５ｇを１００ｍ Ｑステンレスポッ
トに入れ２４時間撹拌し、その後、ブローオフして電気
的に付着しているトナー除き、そのキャリア粒子２ｇに
対し溶剤１０ｇを加えてよく撹拌した後、溶剤の透過率
を測定し、予め求めておいた検量線からトナーのスペン
ト化量を求めたところ下記の結果となった。In addition, 95g of the above carrier particles and toner (trade name: PE6)
600 (manufactured by Ricoh) was placed in a 100 m Q stainless steel pot, stirred for 24 hours, then blown off to remove electrically adhered toner, and 10 g of solvent was added to 2 g of the carrier particles, stirred thoroughly, and the solvent The transmittance of the toner was measured, and the spent amount of the toner was determined from a calibration curve determined in advance, resulting in the following results.
以上の如く本発明のキャリアは少量の導電性微粉末の添
加で大きく抵抗が低下し、しかもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of conductive fine powder, and the amount of spent is also small.
実施例２、比較例３．４
導電性微粉末、チタン酸バリウム（０，６μ）１５ｇス
チレン樹脂（Ｄ−１２５エッソ社ｉ２） ６０ｇ
ポリエステル樹脂（数平均分子量４０００） ２５
ｇトルエン １０００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。この溶液を平均粒径１００μ球状フェ
ライト粉５ｏｏｏ ｇの表面に流動床型コーティング装
置を用いて被覆層を形成してキャリアを得た。Example 2, Comparative Example 3.4 Conductive fine powder, barium titanate (0.6 μ) 15 g Styrene resin (D-125 Esso i2) 60 g
Polyester resin (number average molecular weight 4000) 25
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid. This solution was used to form a coating layer on the surface of 500 g of spherical ferrite powder with an average particle size of 100 μm using a fluidized bed coating device to obtain a carrier.
また、比較のため
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例３）（４）上記処方
のキャリア抵抗と同じキャリア抵抗となるようチタン酸
バリウムを増したキャリア（比較例４）を作成した。For comparison, (3) a carrier with 85 g of styrene resin excluding the polyester resin from the above formulation (Comparative Example 3); and (4) a carrier with increased barium titanate so as to have the same carrier resistance as the carrier resistance of the above formulation. Comparative Example 4) was created.
以上のごとく本発明のキャリアは少量の導電性微粉末の
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of conductive fine powder, and the amount of spent is also small.
実施例３．比較例５．６
ポリエステル樹脂（数平均分子量４０００） １５
ｇトルエン ｔｏｏｏ
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。この溶液を平均粒径１００μの球状フ
ェライト粉５０００ｇの表面に流動床型コーティング装
置を用いて被覆層を形成してキャリアを得た。Example 3. Comparative Example 5.6 Polyester resin (number average molecular weight 4000) 15
gToluene too
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid. This solution was used to form a coating layer on the surface of 5,000 g of spherical ferrite powder having an average particle size of 100 μm using a fluidized bed coating device to obtain a carrier.
また、比較のため
（５）上記処方よりポリエステル樹脂を除いてシリコー
ン樹脂７５０ ｇとしたキャリア（比較例５）（６）上
記処方のキャリア抵抗と同じキャリア抵抗となるようカ
ーボンブラックの添加量を増したキャリア（比較例６）
を作成した。For comparison, (5) polyester resin was removed from the above formulation and 750 g of silicone resin was used as a carrier (Comparative Example 5). (6) The amount of carbon black added was increased to achieve the same carrier resistance as the carrier resistance of the above formulation. carrier (comparative example 6)
It was created.
二九らのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent state of the carrier of Niku et al. were measured in the same manner as in Example 1.
以上のごとく本発明のキャリアは少量の導電性微粉末の
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of conductive fine powder, and the amount of spent is also small.
実施例４、比較例７．８
銅微粉末（分級粒径１．０μ） ３０ｇ
メチルエチルケトン １８００ ｇ上
記処方をホモミキサーで１０分間分散し、被覆層形成液
を調合した。Example 4, Comparative Example 7.8 Fine copper powder (classified particle size 1.0μ) 30g
Methyl ethyl ketone (1800 g) The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。又、比較のため（１）上記処方
よりエポキシ樹脂を除いてスチレン−ｎ−ブチルメタク
リレート共重合体１９２ ｇとしたキャリア（比較例７
）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
銅微粉を増したキャリアを作成した。（比較例８）
これらキャリア粒子の抵抗を電極面積２０ｃｄ、電極間
距１１１１２ｍｍのセルにキャリア粒子を充填し、 １
００Ｖ印加したときの抵抗値として測定した。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device. For comparison, (1) the epoxy resin was removed from the above recipe to give 192 g of styrene-n-butyl methacrylate copolymer (Comparative Example 7).
) (2) A carrier was prepared with increased copper fine powder so as to have the same resistance as the carrier of the above formulation. (Comparative Example 8) The resistance of these carrier particles was determined by filling a cell with an electrode area of 20 cd and an inter-electrode distance of 11112 mm, and 1
The resistance value was measured when 00V was applied.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ ｆｔ＄ｌリコー製）５ｇを１００＋ａ Ｑ
Ｘ テ’Ｊ １７ スポットに入れ２４時間攪拌し、
その後ブローオフして電気的に付着しているトナーを除
き、そのキャリア粒子２ｇに対し、溶剤１０ｇを加え、
よく攪拌した後、溶剤の透過率を測定し、予め求めてお
いた検量線からトナーのスペント化量を求めたところ下
記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
E6600 ft$l Ricoh) 5g to 100+a Q
X Te'J 17 Place in the spot and stir for 24 hours.
After that, remove the electrically attached toner by blowing it off, and add 10 g of solvent to 2 g of the carrier particles.
After stirring thoroughly, the transmittance of the solvent was measured, and the amount of spent toner was determined from a previously determined calibration curve, and the results were as follows.
以上の如く本発明のキャリアは少量の銅微粉末の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of fine copper powder, and the amount of spent is also small.
実施例５、比較例９．１０
銅微粉末（分級０．８μ）１０ｇ
スチレン樹脂（Ｄ−１２５工ツソ社）９０ｇポリエステ
ル樹脂（数平均分子量４０００） ３７．５ ｇトル
エン １０００ｇ上記処方
をホモミキサーで１０分間分散し、被覆層形成液を調合
した。この溶液を平均粒径１００μ球状フェライト粉５
ｏｏｏ ｇの表面に流動床型コーティング装置を用いて
被覆層を形成してキャリアを得た。又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例９）（４）上記処方
のキャリア抵抗と同じキャリア抵抗となるよう銅微粉末
を増したキャリア（比較例１ｏ）を作成した。Example 5, Comparative Example 9.10 Copper fine powder (classified 0.8 μ) 10 g Styrene resin (D-125 Tsuso Co., Ltd.) 90 g Polyester resin (number average molecular weight 4000) 37.5 g Toluene 1000 g The above formulation was mixed with a homomixer. After dispersing for 10 minutes, a coating layer forming solution was prepared. Add this solution to spherical ferrite powder with an average particle size of 100μ
A carrier was obtained by forming a coating layer on the surface of ooog using a fluidized bed coating device. For comparison, (3) A carrier with 85 g of styrene resin except the polyester resin from the above formulation (Comparative Example 9) (4) A carrier with increased copper fine powder so as to have the same carrier resistance as the carrier resistance of the above formulation. (Comparative Example 1o) was created.
これらのキャリアの抵抗とスペントを実施例１と同様に
測定した。The resistance and spent of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の銅微粉末の添加で
大きく抵抗が低下し、しがもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of copper fine powder, and the resistance and spent are small.
実施例６、比較例１１．１２
銅微粉末（分級１．２μ） ２ｏｇ
ポリエステル樹脂（数平均分子量４０００） ３０
ｇトルエン １０００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。この溶液を平均粒径１００μ球状フェ
ライト粉５０００ ｇの表面に流動床型コーティング装
置を用いて被覆層を形成してキャリアを得た。又、比較
のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ ｇとしたキャリア（比較例１１）（６）上
記処方のキャリア抵抗と同じキャリア抵抗となるよう銅
微粉末を増したキャリア（比較例１２）を作成した。Example 6, Comparative Example 11.12 Copper fine powder (classification 1.2μ) 2og
Polyester resin (number average molecular weight 4000) 30
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid. This solution was used to form a coating layer on the surface of 5,000 g of spherical ferrite powder having an average particle size of 100 μm using a fluidized bed coating device to obtain a carrier. Also, for comparison, (5) Polyester resin was removed from the above recipe and the carrier was made into 750 g of silicone resin (Comparative Example 11) (6) Copper fine powder was increased to have the same carrier resistance as the carrier resistance of the above recipe. A carrier (Comparative Example 12) was created.
これらのキャリアの抵抗とスペントを実施例１と同様に
測定した。The resistance and spent of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の銅微粉末の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of fine copper powder, and the amount of spent is also small.
実施例７、比較例１３．１４
導電性酸化亜鉛２３Ｋ（白水化学社製）１０ｇメチルエ
チルケトン １８００ ｇ上記処方を
ホモミキサーで１０分間分散し、被覆層形成液を調合し
た。この溶液を平均粒径７０μの球状酸化鉄粉７０００
ｇの表面に流動床型コーティング装置を用いて被覆層
を形成してキャリアを得た。Example 7, Comparative Example 13.14 Conductive Zinc Oxide 23K (manufactured by Hakusui Chemical Co., Ltd.) 10 g Methyl ethyl ketone 1800 g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid. This solution was mixed with 7,000 spherical iron oxide powders with an average particle size of 70μ.
A coating layer was formed on the surface of G using a fluidized bed coating device to obtain a carrier.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ ｇとしたキャ
リア（比較例１３）
（２）上記処方のキャリア抵抗と同じキャリア抵抗とな
るよう導電性酸化亜鉛２３Ｋを増したキャリア（比較例
１４）を作成した。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 13) (2) A carrier was prepared in which conductive zinc oxide 23K was increased to have the same carrier resistance as the carrier resistance of the above formulation (Comparative Example 14).
これらのキャリア粒子の抵抗を電極面積２０ａ＆、電極
間距離２ｍｍのセルにキャリア粒子を充填し、１００ｖ
印加したときの抵抗値として測定した。The resistance of these carrier particles was determined by filling a cell with an electrode area of 20a and an inter-electrode distance of 2mm with the carrier particles at 100V.
It was measured as the resistance value when the voltage was applied.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ ｆｌｉリコー製）５ｇを１００ｍ Ｑステ
ンレスポットに入れ２４時間撹拌し、その後ブローオフ
して電気的に付着しているトナーを除き、そのキャリア
粒子２ｇに対し溶剤１０ｇを加え、よく撹拌した後、溶
剤の透過率を測定し、予め求めておいた検量線からトナ
ーのスペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
Pour 5 g of E6600 fli (manufactured by Ricoh) into a 100 m Q stainless steel pot and stir for 24 hours, then blow off to remove electrically attached toner, add 10 g of solvent to 2 g of the carrier particles, stir well, and remove the solvent. The transmittance of the toner was measured, and the spent amount of the toner was determined from a calibration curve determined in advance, resulting in the following results.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of zinc oxide, and the amount of spent is also small.
実施例８、比較例１５．１６
導電性亜鉛華、Ｎα１（本荘ケミカル社製） ５ｇ
スチレン樹脂（Ｄ−１２５エツゾＩｔＪａ） ６
０ｇポリエステル樹脂（数平均分子量４０００）
２５ｇトルエン １０００
ｇ上記処方をホモミキサ−で１０分間分散し、被覆層形
成液を調合した。この溶液を平均粒径１００μ球状フェ
ライト粉５０００ ｇの表面に流動床型コーティング装
置を用いて被覆層を形成してキャリアを得た。Example 8, Comparative Example 15.16 Conductive zinc white, Nα1 (manufactured by Honjo Chemical Co., Ltd.) 5 g
Styrene resin (D-125 Etsuzo ItJa) 6
0g polyester resin (number average molecular weight 4000)
25g toluene 1000
g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid. This solution was used to form a coating layer on the surface of 5,000 g of spherical ferrite powder having an average particle size of 100 μm using a fluidized bed coating device to obtain a carrier.
また、比較のため
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしてキャリア（比較例１５）（４）上記処
方のキャリア抵抗と同じキャリア抵抗となるよう導電性
亜鉛華Ｎα１（比較例１６）を増したキャリアを作成し
た。For comparison, (3) the polyester resin was removed from the above formulation and 85 g of styrene resin was used as a carrier (Comparative Example 15); (4) the conductive zinc white Nα1 (Comparative Example 16) was prepared to have the same carrier resistance as the carrier resistance of the above formulation; ) created a career with more.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上のごとく本発明のキャリアは少量の導電性微粉末の
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of conductive fine powder, and the amount of spent is also small.
実施例９．比較例１７．１８
導電性亜鉛華、Ｎａ ２ （本荘ケミカル社製）２０ｇ
ポリエステル樹脂（数平均分子量４０００） １５
ｇトルエン １０００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。この溶液を平均粒径１００μの球状フ
ェライト粉５０００ ｇの表面に流動床型コーティング
装置を用いて被覆層を形成してキャリアを得た。Example 9. Comparative Example 17.18 Conductive zinc white, Na 2 (manufactured by Honjo Chemical Co., Ltd.) 20 g
Polyester resin (number average molecular weight 4000) 15
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid. This solution was used to form a coating layer on the surface of 5,000 g of spherical ferrite powder having an average particle size of 100 μm using a fluidized bed coating device to obtain a carrier.
また、比較のため
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例１７）（６）上記
処方のキャリア抵抗と同じキャリア抵抗となるよう導電
性亜鉛華Ｎα２を増したキャリア（比較例１８）を作成
した。For comparison, (5) polyester resin was removed from the above recipe and 750 g of silicone resin was used as a carrier (Comparative Example 17) (6) conductive zinc white Nα2 was increased so that the carrier resistance was the same as that of the above recipe. A carrier (Comparative Example 18) was created.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上のごとく本発明のキャリアは少量の導電性微粉末の
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of conductive fine powder, and the amount of spent is also small.
実施例１０、比較例１９．２１
メチルエチルケトン １８００ ｇ上
記処方をホモミキサーで１０分間分散し、被覆層形成液
を調合した。Example 10, Comparative Example 19.21 Methyl ethyl ketone 1800 g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例１９）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
ケッチエンブラックＥＣＤＪ−６００を増したキャリア
（比較例２０）を作成した。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 19) (2) A carrier (Comparative Example 20) was prepared in which Ketchen Black ECDJ-600 was increased so as to have the same resistance as the carrier of the above formulation.
これらキャリア粒子の抵抗を電極面積２０ｃＪ、電極間
距離２ｍｍのセルにキャリア粒子を充填し、１００Ｖ印
加したときの抵抗値として測定した。The resistance of these carrier particles was measured as a resistance value when 100V was applied to a cell with an electrode area of 20 cJ and an inter-electrode distance of 2 mm filled with the carrier particles.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ ％リコー製）５ｇをＬｏｏｍ Ｑステンレ
スボッ１−に入れ２４時間撹拌し、その後ブローオフし
て電気的に付着しているトナーを除き、そのキャリア粒
子２ｇに対し溶剤１０ｇを加え、よく撹拌した後、溶剤
の透過率を測定し、予め求めておいた検量線からトナー
のスペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
E6600% (manufactured by Ricoh) 5g was placed in a Loom Q stainless steel bottle and stirred for 24 hours, then blown off to remove electrically attached toner, 10g of solvent was added to 2g of the carrier particles, and stirred well. The transmittance of the solvent was measured, and the amount of spent toner was determined from a calibration curve determined in advance, resulting in the following results.
以上の如く本発明のキャリアは少量の多孔性カーボンブ
ラックの添加で大きく抵抗が低下し、しかもスペントも
少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of porous carbon black, and the amount of spent is also small.
実施例１１、比較例２１．２２
スチレン樹脂（Ｄ−１２５工ツソ社製）６０ｇポリエス
テル樹脂（数平均分子量４０００） ２５ ｇトルエ
ン １０００ ｇ上記処方
をホモミキサーで１０分間分散し、被覆層形成液を調合
した。Example 11, Comparative Example 21.22 Styrene resin (D-125 manufactured by Tsuso Co., Ltd.) 60 g Polyester resin (number average molecular weight 4000) 25 g Toluene 1000 g The above formulation was dispersed in a homomixer for 10 minutes, and the coating layer forming liquid was mixed. I mixed it.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例２１）（４）上記処
方のキャリアの抵抗と同じ抵抗となるようコンダクテッ
クスＳＣを増したキャリア（比較例２２）を作成した。For comparison, (3) A carrier with 85 g of styrene resin except the polyester resin from the above formulation (Comparative Example 21) (4) A carrier with increased Conductex SC to have the same resistance as the carrier with the above formulation. (Comparative Example 22) was created.
これらキャリアの抵抗とスペント化を実施例１と同様に
８１１１定した。The resistance and spent characteristics of these carriers were determined in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の多孔性カーボンブ
ラックの添加で大きく抵抗が低下し、しかもスペントも
少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of porous carbon black, and the amount of spent is also small.
実施例１２．比較例２３．２４
ブラックパールズ２０００ （キャボット社１ｔｌ）ｔ
ｏｇシリコン樹脂 ６００ｇ
（ＳＲ２４０６トーレシリコーン社製樹脂分２０ｗｔ％
）ポリエステル樹脂（数平均分子量４０００） １５
ｇトルエン １０００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。Example 12. Comparative Example 23.24 Black Pearls 2000 (Cabot 1tl) t
og silicone resin 600g
(SR2406 manufactured by Toray Silicone Co., Ltd. Resin content 20wt%
) Polyester resin (number average molecular weight 4000) 15
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例２３）（６）上記
処方のキャリアの抵抗と同じ抵抗となるようブラックパ
ールズ２０００を増したキャリア（比較例２４）を作成
した。For comparison, (5) A carrier with 750 g of silicone resin excluding the polyester resin from the above recipe (Comparative Example 23) (6) A carrier with Black Pearls 2000 added to have the same resistance as the carrier with the above recipe. (Comparative Example 24) was created.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の多孔性カーボンブ
ラックの添加で大きく抵抗が低下し、しかもスペントも
少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of porous carbon black, and the amount of spent is also small.
実施例１３、比較例２５．２６
チタンブラック２０Ｍ（三菱金属社Ｍｌ） ５ｇ
スチレン−〇−ブチルメタクリレート １５２ｇ共
重合体（３８Ｍ７３：三洋化成社製）メチルエチルケト
ン １８００ ｇ上記処方をホモミキ
サーで１０分間分散し、被覆層形成液を調合した。Example 13, Comparative Example 25.26 Titanium Black 20M (Mitsubishi Metals Ml) 5g
Styrene-〇-butyl methacrylate 152 g Copolymer (38M73: manufactured by Sanyo Chemical Co., Ltd.) Methyl ethyl ketone 1800 g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため。Also, for comparison.
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例２５）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
ト２０を増したキャリア（比較例２６）を作成した。(1) Styrene-n excluding the epoxy resin from the above formulation
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 25) (2) A carrier (Comparative Example 26) was prepared in which the amount of 20 was increased so as to have the same resistance as the carrier of the above formulation.
これらキャリア粒子の抵抗を電極面積２０ｄ、電極間距
離２ｍｍのセルにキャリア粒子を充填し、１００Ｖ印加
したときの抵抗値として測定した。The resistance of these carrier particles was measured as a resistance value when 100V was applied to a cell with an electrode area of 20 d and an inter-electrode distance of 2 mm filled with the carrier particles.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ ｆｔ＄ｌリコー製）５ｇをＬｏｏｍ Ｑス
テンレスポットに入れ２４時間撹拌し、その後ブローオ
フして電気的に付着しているトナーを除き、そのキャリ
ア粒子２ｇに対し溶剤１０ｇを加え、よく撹拌した後、
溶剤の透過率を測定し、予め求めておいた検基線からト
ナーのスペント化量を求めたところ下記の結果となった
。In addition, 95 g of the above carrier particles and toner (product name TYP
Put 5g of E6600 ft$ (manufactured by Ricoh) into a Loom Q stainless steel pot and stir for 24 hours, then blow off to remove electrically attached toner, add 10g of solvent to 2g of carrier particles, and stir well. ,
When the transmittance of the solvent was measured and the amount of spent toner was determined from a reference line determined in advance, the following results were obtained.
以上の如く本発明のキャリアは少量のチタンブラックの
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of titanium black, and the amount of spent is also small.
実施例１４、比較例２７．２８
チタンブラック１２Ｓ（三菱金属社Ｗ） １０ｇ
スチレン樹脂（Ｄ−１２５工ツソ社Ｗ） ６０
ｇポリエステル樹脂（数平均分子ｆＡ４０００） ２
５ｇトルエン １０００ｇ
上記処方をホモミキサーで１０分間分散し、被覆層形成
液を調合した。Example 14, Comparative Example 27.28 Titanium Black 12S (Mitsubishi Metals W) 10g
Styrene resin (D-125 Tsusosha W) 60
g Polyester resin (number average molecule fA4000) 2
5g toluene 1000g
The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例２７）（４）上記処
方のキャリアの抵抗と同じ抵抗となるよう１２Ｓを増し
たキャリア（比較例２８）を作成した。For comparison, (3) A carrier with 85 g of styrene resin excluding the polyester resin from the above formulation (Comparative Example 27) (4) A carrier with increased 12S so as to have the same resistance as the carrier with the above formulation (Comparison) Example 28) was created.
これらのキャリアのスペント化を実施例１と同様に測定
した。Spent conversion of these carriers was measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量のチタンブラックの
添加で大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of titanium black, and the amount of spent is also small.
実施例１５．比較例２９．３０
チタンブラック２０Ｍ（三菱金属社製）１５ｇポリエス
テル樹脂（数平均分子量４０００） １５ ｇトルエ
ン １０００ ｇ上記処方
をホモミキサーで１０分間分散し、被覆層形成液を調合
した。Example 15. Comparative Example 29.30 Titanium Black 20M (manufactured by Mitsubishi Metals) 15 g Polyester resin (number average molecular weight 4000) 15 g Toluene 1000 g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５ｏｏ
ｏ ｇの表面に流動床型コーティング装置を用いて被７
１を形成してキャリアを得た。This solution was mixed with 5 oz of spherical ferrite powder with an average particle size of 100 μm.
The surface of the o g was coated using a fluidized bed coating device.
1 and got a carrier.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例２９）（６）上記
処方のキャリアの抵抗と同じ抵抗となるよう２０Ｍの添
加量を増したキャリア（比較例３０）を作成した。Also, for comparison, (5) The polyester resin was removed from the above recipe and the carrier was made into 750 g of silicone resin (Comparative Example 29) (6) The amount of 20M added was increased so that the resistance was the same as that of the carrier in the above recipe. A carrier (Comparative Example 30) was created.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しがもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of zinc oxide, and the resistance and spent are small.
実施例１６、比較例３１．３２
フェライトＥＰＴ−５００（戸田工業社製） ３
０ｇメチルエチルケトン １８００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。Example 16, Comparative Example 31.32 Ferrite EPT-500 (manufactured by Toda Kogyo Co., Ltd.) 3
0g methyl ethyl ketone 1800
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例３１）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
にＥＰＴ−５００を増したキャリア（比較例３２）を作
成した。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 31) (2) A carrier (Comparative Example 32) was prepared in which EPT-500 was increased so as to have the same resistance as the carrier of the above formulation.
これらキャリア粒子の抵抗を電極面積２０ａＪ、電極間
距離２ｍｍのセルにキャリア粒子を充填し、１０゜Ｖ印
加したときの抵抗値として測定した。The resistance of these carrier particles was measured as the resistance value when a cell with an electrode area of 20 aJ and an inter-electrode distance of 2 mm was filled with the carrier particles and 10°V was applied.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００−リコー製）５ｇを１００ｍ Ｑステンレス
ポットに入れ２４時間撹拌し、その後ブローオフして電
気的に付着しているトナーを除き、そのキャリア粒子２
ｇに対し溶剤１０ｇを加え、よく撹拌した後、溶剤の透
過率を測定し、予め求めておいた検量線からトナーのス
ペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
E6600 (manufactured by Ricoh)) was placed in a 100 m Q stainless steel pot, stirred for 24 hours, and then blown off to remove the electrically attached toner, and the carrier particles 2
After adding 10 g of solvent to 100 g and stirring well, the transmittance of the solvent was measured, and the amount of spent toner was determined from a previously determined calibration curve, and the following results were obtained.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of zinc oxide, and the amount of spent is also small.
実施例１７、比較例３３．３４
フェライトＢＬ−１００（チタン工業社ｍｌ）
２０ｇスチレン樹脂（Ｄ−１２５工ツソ社製）
６０ｇポリエステル樹脂（数平均分子量４０００）
２５ ｇトルエン １０
００ ｇ上記処方をホモミキサーで１０分間分散し、被
覆層形成液を調合した。Example 17, Comparative Example 33.34 Ferrite BL-100 (Titan Kogyo Co., Ltd. ml)
20g styrene resin (manufactured by D-125 Tsuso Co., Ltd.)
60g polyester resin (number average molecular weight 4000)
25 g toluene 10
00 g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例３３）（４）上記処
方のキャリアの抵抗と同じ抵抗となるようＢＬ−１００
を増したキャリア（比較例３４）を作成した。Also, for comparison, (3) A carrier made of 85 g of styrene resin by excluding the polyester resin from the above recipe (Comparative Example 33) (4) BL-100 was added to have the same resistance as the carrier with the above recipe.
A carrier (Comparative Example 34) with increased
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of zinc oxide, and the amount of spent is also small.
実施例１８、比較例３５．３６
フェライトＥＰＴ−１０００（戸田工業社製）１０ｇポ
リエステル樹脂（数平均分子量４０００） １５ ｇ
トルエン １０００ ｇ上
記処方をホモミキサーで１０分間分散し、被覆層形成液
を調合した。Example 18, Comparative Example 35.36 Ferrite EPT-1000 (manufactured by Toda Kogyo Co., Ltd.) 10 g Polyester resin (number average molecular weight 4000) 15 g
Toluene (1000 g) The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例３５）（６）上記
処方のキャリアの抵抗と同じ抵抗となるようＥＰＴ−１
０００の添加量を増したキャリア（比較例３６）を作成
した。For comparison, (5) A carrier made of 750 g of silicone resin by excluding the polyester resin from the above recipe (Comparative Example 35) (6) EPT-1 was added to have the same resistance as the carrier with the above recipe.
A carrier (Comparative Example 36) was prepared in which the amount of 000 added was increased.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量のＦｅ３Ｏ４微粉末
の添加で大きく抵抗が低下し、しかもスペントも少ない
。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of Fe3O4 fine powder, and the amount of spent is also small.
実施例１９．比較例３７．３８
メチルエチルケトン １８００ ｇ上
記処方をホモミキサーで１０分間分散し、被覆層形成液
を調合した。Example 19. Comparative Example 37.38 Methyl ethyl ketone 1800 g The above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例３７）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
うＢＴ−１００Ｐを増したキャリア（比較例３８）を作
成した。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 37) (2) A carrier (Comparative Example 38) was prepared in which BT-100P was increased so as to have the same resistance as the carrier of the above formulation.
これらの粒子の抵抗を電極面積２０ｃＪ、電極間距離２
ｍｍのセルにキャリア粒子を充填し、１ｏｏｖ印加した
ときの抵抗値として測定した。The resistance of these particles is determined by the electrode area: 20 cJ and the distance between the electrodes: 2
A cell of 1.0 mm in diameter was filled with carrier particles, and the resistance value was measured when a 100V voltage was applied.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ Ｂリコー製）５ｇを１００ｍ ｆｌステン
レスボットに入れ２４時間撹拌し、その後ブローオフし
て電気的に付着しているトナーを除き、そのキャリア粒
子２ｇに対し溶剤１０ｇを加え、よく撹拌した後、溶剤
の透過率を測定し、予め求めておいた検量線からトナー
のスペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
E6600B (manufactured by Ricoh) 5g was placed in a 100m fl stainless steel bot and stirred for 24 hours, then blown off to remove electrically attached toner, 10g of solvent was added to 2g of the carrier particles, stirred well, and the solvent was removed. The transmittance of the toner was measured, and the spent amount of the toner was determined from a calibration curve determined in advance, resulting in the following results.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しがもスペントも少ない。As described above, in the carrier of the present invention, the resistance is greatly reduced by adding a small amount of zinc oxide, and the resistance and spent are small.
実施例２０、比較例３９．４゜
スチレン樹脂（Ｄ−１２５工ツソ社ｍ） ６０
ｇポリエステル樹脂（数平均分子量４０００） ２５
ｇトルエン １０００
ｇ上記処方をホモミキサーで１ｏ分間分散し、被覆層形
成液を調合した。Example 20, Comparative Example 39.4° Styrene resin (D-125 Tsuso Co., Ltd.) 60
g Polyester resin (number average molecular weight 4000) 25
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例３９）（４）上記処
方のキャリアの抵抗と同じ抵抗となるようＢＴ−１００
Ｋを増したキャリア（比較例４０）を作成した。For comparison, (3) A carrier made of 85 g of styrene resin by excluding the polyester resin from the above formulation (Comparative Example 39) (4) BT-100 was used to obtain the same resistance as the carrier of the above formulation.
A carrier with increased K (Comparative Example 40) was created.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量のチタン酸バリウム
の添加で大きく抵抗が低下し、しかもスペントも少ない
。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of barium titanate, and the amount of spent is also small.
実施例２１、比較例４１．４２
ポリエステル樹脂（数平均分子量４０００） １５
ｇトルエン １０００ｇ上
記処方をホモミキサーで１０分間分散し、被覆層形成液
を調合した。Example 21, Comparative Example 41.42 Polyester resin (number average molecular weight 4000) 15
g Toluene 1000g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例４１）（６）上記
処方のキャリアの抵抗と同じ抵抗となるようＩＩＰＢＴ
−１０００の添加量を増したキャリア（比較例４２）を
作成した。For comparison, (5) A carrier made of 750 g of silicone resin by excluding the polyester resin from the above recipe (Comparative Example 41) (6) IIPBT was added so that the resistance was the same as that of the carrier with the above recipe.
A carrier (Comparative Example 42) was prepared in which the amount of -1000 added was increased.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量のチタン酸バリウム
の添加で大きく抵抗が低下し、しかもスペントも少ない
。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of barium titanate, and the amount of spent is also small.
実施例２２、比較例４３．４４
酸化チタンＥＣＴ−５２（チタン工業社製） １
０ｇメチルエチルケトン １８００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。Example 22, Comparative Example 43.44 Titanium oxide ECT-52 (manufactured by Titanium Kogyo Co., Ltd.) 1
0g methyl ethyl ketone 1800
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例４３）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
ＥＣＴ−５２を増したキャリア（比較例４４）を作成し
た。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 43) (2) A carrier (Comparative Example 44) was prepared in which ECT-52 was increased so as to have the same resistance as the carrier of the above formulation.
これらキャリア粒子の抵抗を電極面積２０ａＩ、電極間
距離２ｍｍのセルにキャリア粒子を充填し、１００Ｖ印
加したときの抵抗値として測定した。The resistance of these carrier particles was measured as the resistance value when 100V was applied to a cell with an electrode area of 20aI and an inter-electrode distance of 2mm filled with the carrier particles.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００■リコー製）５ｇを１００ｍ Ｑステンレス
ポットに入れ２４時間撹拌し、その後ブローオフして電
気的に付着しているトナーを除き、そのキャリア粒子２
ｇに対し溶剤Ｌｏｇを加え、よく撹拌した後、溶剤の透
過率を測定し、予め求めておいた検量線からトナーのス
ペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
E6600 (manufactured by Ricoh) 5g was placed in a 100m Q stainless steel pot, stirred for 24 hours, and then blown off to remove electrically adhered toner and the carrier particles 2
After adding the solvent Log to g and stirring thoroughly, the transmittance of the solvent was measured, and the spent amount of the toner was determined from a previously determined calibration curve, and the following results were obtained.
以上の如く本発明のキャリアは少量の酸化チタンの添加
で大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of titanium oxide, and the amount of spent is also small.
実施例２３、比較例４５．４６
酸化チタンｓｏｏｗ （石原産業製）１０ｇスチレン樹
脂（Ｄ−１２５工ツソ社製） ６０ｇポリエス
テル樹脂（数平均分子量４０００） ２５ ｇトルエ
ン １０００ ｇ上記処方
をホモミキサーで１０分間分散し、被覆層形成液を調合
した。Example 23, Comparative Example 45.46 Titanium oxide soow (manufactured by Ishihara Sangyo) 10 g Styrene resin (manufactured by D-125 Tsuso Co., Ltd.) 60 g Polyester resin (number average molecular weight 4000) 25 g Toluene 1000 g The above formulation was mixed with a homomixer for 10 g. After dispersing for a minute, a coating layer forming solution was prepared.
この溶液を平均粒径１００μの球状フェライト粉５ｏｏ
ｏ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 5 oz of spherical ferrite powder with an average particle size of 100 μm.
A carrier was obtained by forming a coating layer on the surface of the o g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例４５）（４）上記処
方のキャリアの抵抗と同じ抵抗となるよう５００ｖを増
したキャリア（比較例４６）を作成した。For comparison, (3) A carrier with 85 g of styrene resin except the polyester resin from the above recipe (Comparative Example 45) (4) A carrier with an increased resistance of 500 V to have the same resistance as the carrier with the above recipe (Comparative Example 45) Example 46) was created.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化チタンの添加
で大きく抵抗が低下し、しがもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of titanium oxide, and the resistance and spent are small.
実施例２４、比較例４７．４８
酸化チタント１０（三菱金属社製） ８ｇポ
リエステル樹脂（数平均分子量４０００） １５ ｇ
トルエン １０００ ｇ上
記処方をホモミキサーで１ｏ分間分散し、被覆層形成液
を調合した。Example 24, Comparative Example 47.48 Titanium oxide 10 (manufactured by Mitsubishi Metals) 8 g Polyester resin (number average molecular weight 4000) 15 g
Toluene (1000 g) The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ ｇとしたキャリア（比較例４７）（６）上
記処方のキャリアの抵抗と同じ抵抗となるようト１０の
添加量を増したキャリア（比較例４８）を作成した。For comparison, (5) The polyester resin was removed from the above recipe and the carrier was made into 750 g of silicone resin (Comparative Example 47). A carrier (Comparative Example 48) was prepared.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化チタンの添加
で大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of titanium oxide, and the amount of spent is also small.
実施例２５．比較例４９．５０
酸化スズド１（三菱金属社製）１５ｇ
メチルエチルケトン １８００ ｇ
上記処方をホモミキサーで１０分間分散し、被覆層形成
液を調合した。Example 25. Comparative example 49.50 Tin oxide 1 (manufactured by Mitsubishi Metals) 15 g Methyl ethyl ketone 1800 g
The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径７０μの球状酸化鉄粉７０００ ｇ
の表面に流動床型コーティング装置を用いて被覆層を形
成してキャリアを得た。This solution was mixed into 7000 g of spherical iron oxide powder with an average particle size of 70μ.
A carrier was obtained by forming a coating layer on the surface of the carrier using a fluidized bed coating device.
又、比較のため、
（１）上記処方よりエポキシ樹脂を除いてスチレン−ｎ
−ブチルメタクリレート共重合体１９２ｇとしたキャリ
ア（比較例４９）
（２）上記処方のキャリアの抵抗と同じ抵抗となるよう
トｌを増したキャリア（比較例５０）を作成した。Also, for comparison, (1) Styrene-n was added by excluding the epoxy resin from the above formulation.
A carrier containing 192 g of -butyl methacrylate copolymer (Comparative Example 49) (2) A carrier (Comparative Example 50) was prepared with an increased torque so as to have the same resistance as the carrier of the above formulation.
これらキャリア粒子の抵抗を電極面積２０ａ＃、電極間
比１１２ｍｍのセルにキャリア粒子を充填し、１００Ｖ
印加したときの抵抗値として測定した。The resistance of these carrier particles was determined by filling a cell with an electrode area of 20a# and an electrode-to-electrode ratio of 112mm, and 100V.
It was measured as the resistance value when the voltage was applied.
また、上記キャリア粒子９５ｇとトナー（商品名ＴＹＰ
Ｅ６６００ ｔｍｍココ−）５ｇをＬｏｏｍ Ｑステン
レスポットに入れ２４時間撹拌し、その後ブローオフし
て電気的に付着しているトナーを除き、そのキャリア粒
子２ｇに対し溶剤ｌｏｇを加え、よく撹拌した後、溶剤
の透過率を測定し、予め求めておいた検量線からトナー
のスペント化量を求めたところ下記の結果となった。In addition, 95 g of the above carrier particles and toner (product name TYP
Put 5g of E6600 tmm Coco) into a Loom Q stainless steel pot and stir for 24 hours, then blow off to remove electrically attached toner, add log of solvent to 2g of carrier particles, stir well, and remove the solvent. The transmittance of the toner was measured, and the spent amount of the toner was determined from a calibration curve determined in advance, resulting in the following results.
以上の如く本発明のキャリアは少量の酸化スズの添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of tin oxide, and the amount of spent is also small.
実施例２６、比較例５１．５２
酸化スズＭＥＣ３００（帝国化工社製）１０ｇスチレン
樹脂（Ｄ−１２５工ツソ社製）６０ｇポリエステル樹脂
（数平均分子量４０００） ２５ ｇトルエン
１０００ ｇ上記処方をホモミ
キサーで１０分間分散し、被覆層形成液を調合した。Example 26, Comparative Example 51.52 Tin oxide MEC300 (manufactured by Teikoku Kako Co., Ltd.) 10 g Styrene resin (D-125 manufactured by Tsuso Co., Ltd.) 60 g Polyester resin (number average molecular weight 4000) 25 g Toluene
1000 g of the above formulation was dispersed in a homomixer for 10 minutes to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（３）上記処方よりポリエステル樹脂を除いてスチレン
樹脂８５ｇとしたキャリア（比較例５１）（４）上記処
方のキャリアの抵抗と同じ抵抗となるようＭＥＣ３００
を増したキャリア（比較例５２）を作成した。For comparison, (3) A carrier with 85 g of styrene resin except for the polyester resin from the above formulation (Comparative Example 51) (4) MEC300 was used to obtain the same resistance as the carrier with the above formulation.
A carrier (Comparative Example 52) with increased
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化スズの添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of tin oxide, and the amount of spent is also small.
実施例２７、比較例５３．５４
酸化スズＭＥＣ５００（帝国１化社製） ５
ｇポリエステル樹脂（数平均分子量４０００） １５
ｇトルエン １０００
ｇ上記処方をホモミキサーで１０分間分散し、被覆層形
成液を調合した。Example 27, Comparative Example 53.54 Tin oxide MEC500 (manufactured by Teikoku Ikasha) 5
g Polyester resin (number average molecular weight 4000) 15
g toluene 1000
g The above formulation was dispersed for 10 minutes using a homomixer to prepare a coating layer forming liquid.
この溶液を平均粒径１００μの球状フェライト粉５００
０ ｇの表面に流動床型コーティング装置を用いて被覆
層を形成してキャリアを得た。This solution was mixed with 500 pieces of spherical ferrite powder with an average particle size of 100μ.
A carrier was obtained by forming a coating layer on the surface of 0 g using a fluidized bed coating device.
又、比較のため、
（５）上記処方よりポリエステル樹脂を除いてシリコン
樹脂７５０ｇとしたキャリア（比較例５３）（６）上記
処方のキャリアの抵抗と同じ抵抗となるようＭＥＣ５０
０の添加量を増したキャリア（比較例５４）を作成した
。For comparison, (5) A carrier made of 750 g of silicone resin by excluding the polyester resin from the above formulation (Comparative Example 53) (6) MEC50 was added to have the same resistance as the carrier with the above formulation.
A carrier (Comparative Example 54) was prepared in which the amount of 0 added was increased.
これらのキャリアの抵抗とスペント化を実施例１と同様
に測定した。The resistance and spent properties of these carriers were measured in the same manner as in Example 1.
以上の如く本発明のキャリアは少量の酸化亜鉛の添加で
大きく抵抗が低下し、しかもスペントも少ない。As described above, the resistance of the carrier of the present invention is greatly reduced by adding a small amount of zinc oxide, and the amount of spent is also small.
〔効 果］
以上の説明で明らかなように本発明の静電潜像現像用キ
ャリアは、キャリアの表面に樹脂を被覆しても現像剤の
抵抗が高くならず、中間調再現性の非常に優れた画像を
得ることができ、また、導電性微粉末の添加量が少なく
て済み、スペント化防止効果を損うことがなく、長期間
の繰り返し使用によっても現像剤劣化がなくて安定した
画像品質を得ることができる。[Effects] As is clear from the above explanation, the carrier for developing electrostatic latent images of the present invention does not increase resistance of the developer even if the surface of the carrier is coated with resin, and has excellent halftone reproducibility. Excellent images can be obtained, the amount of conductive fine powder added is small, the spent prevention effect is not impaired, and the developer does not deteriorate even after repeated use over a long period of time, resulting in stable images. You can get quality.
第１図は本発明のキャリアを示す説明図、第２図は従来
のキャリアを示す説明図である。
１・・・キャリア、２・・・導電性微粉末、３・・・芯
材、ａ・・・樹脂、Ａ・・・樹脂、Ｂ・・・（樹脂Ａと
非相溶）
特許出願人 株式会社 リ コ −FIG. 1 is an explanatory diagram showing a carrier of the present invention, and FIG. 2 is an explanatory diagram showing a conventional carrier. DESCRIPTION OF SYMBOLS 1... Carrier, 2... Conductive fine powder, 3... Core material, a... Resin, A... Resin, B... (Incompatible with resin A) Patent applicant Stock Company Rico −
Claims (2)
て、該被覆層が互いに非相溶の複数種の樹脂と導電性微
粉末とを含有することを特徴とする静電潜像現像用キャ
リア。(1) An electrostatic latent image carrier having a coating layer provided on the surface of core particles, the coating layer containing a plurality of types of mutually incompatible resins and conductive fine powder. Carrier for development.
、チタンブラック、酸化鉄、チタン酸バリウム、酸化チ
タン及び酸化スズから選ばれる少くとも１種である特許
請求の範囲第１項記載の静電潜像現像用キャリア。(2) The static electricity according to claim 1, wherein the conductive fine powder is at least one selected from carbon black, copper, zinc oxide, titanium black, iron oxide, barium titanate, titanium oxide, and tin oxide. Carrier for electrolatent image development.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62276839A JP2714590B2 (en) | 1987-07-27 | 1987-10-30 | Carrier for electrostatic latent image development |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-187033 | 1987-07-27 | ||
| JP18703387 | 1987-07-27 | ||
| JP62276839A JP2714590B2 (en) | 1987-07-27 | 1987-10-30 | Carrier for electrostatic latent image development |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01105264A true JPH01105264A (en) | 1989-04-21 |
| JP2714590B2 JP2714590B2 (en) | 1998-02-16 |
Family
ID=26504107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62276839A Expired - Lifetime JP2714590B2 (en) | 1987-07-27 | 1987-10-30 | Carrier for electrostatic latent image development |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2714590B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04288556A (en) * | 1990-01-23 | 1992-10-13 | Ricoh Co Ltd | Dry two-component developer for electrostatic latent image |
| JPH04324869A (en) * | 1991-04-25 | 1992-11-13 | Fuji Xerox Co Ltd | Manufacture of electrostatic image developing carrier |
| JPH0926675A (en) * | 1995-07-13 | 1997-01-28 | Fuji Xerox Co Ltd | Photographic carrier and its production and electrostatic charge imparting member |
| US5663617A (en) * | 1995-03-07 | 1997-09-02 | Mitsubishi Denki Kabushiki Kaisha | Parabolic-wave shaping circuit for focus-correction |
| JPH09319161A (en) * | 1996-05-29 | 1997-12-12 | Fuji Xerox Co Ltd | Carrier for electrostatic latent image developer electrostatic later image developer, image forming method and image forming device |
| JPH09319225A (en) * | 1996-05-29 | 1997-12-12 | Fuji Xerox Co Ltd | Image forming method and image forming device |
| JPH10186731A (en) * | 1996-12-25 | 1998-07-14 | Fuji Xerox Co Ltd | Electrostatic image developing carrier, electrostatic image developer, and image forming method |
| US5821023A (en) * | 1996-05-27 | 1998-10-13 | Fuji Xerox Co., Ltd. | Developer of electrostatic latent image, carrier therefor, method for forming image and image forming apparatus thereby |
| US5849448A (en) * | 1996-04-01 | 1998-12-15 | Fuji Xerox Co., Ltd. | Carrier for developer of electrostatic latent image, method for making said carrier |
| JPH11231574A (en) * | 1998-02-10 | 1999-08-27 | Ricoh Co Ltd | Carrier for developing electrostatic latent image and its production |
| JP2000298380A (en) * | 1999-04-14 | 2000-10-24 | Ricoh Co Ltd | Electrophotographic carrier and its production |
| US6677093B2 (en) | 2000-11-01 | 2004-01-13 | Fuji Xerox Co., Ltd. | Electrophotographic black toner, electrophotographic developer and image forming method |
| JP2005345999A (en) * | 2004-06-07 | 2005-12-15 | Sharp Corp | Carrier and two-component developer |
| US7393622B2 (en) | 2004-06-02 | 2008-07-01 | Sharp Kabushiki Kaisha | Two-component developing agent for electrophotography |
| JP2009093135A (en) * | 2007-09-18 | 2009-04-30 | Ricoh Co Ltd | Electrophotographic carrier, electrophotographic developer, and image forming method |
| JP2018146786A (en) * | 2017-03-06 | 2018-09-20 | 株式会社リコー | Carrier, developer, developer for replenishment, image forming apparatus, process cartridge, and image forming method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5675659A (en) * | 1979-11-27 | 1981-06-22 | Canon Inc | Carrier material |
-
1987
- 1987-10-30 JP JP62276839A patent/JP2714590B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5675659A (en) * | 1979-11-27 | 1981-06-22 | Canon Inc | Carrier material |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04288556A (en) * | 1990-01-23 | 1992-10-13 | Ricoh Co Ltd | Dry two-component developer for electrostatic latent image |
| JPH04324869A (en) * | 1991-04-25 | 1992-11-13 | Fuji Xerox Co Ltd | Manufacture of electrostatic image developing carrier |
| US5663617A (en) * | 1995-03-07 | 1997-09-02 | Mitsubishi Denki Kabushiki Kaisha | Parabolic-wave shaping circuit for focus-correction |
| US5760549A (en) * | 1995-03-07 | 1998-06-02 | Mitsubishi Denki Kabushiki Kaisha | Parabolic-wave shaping circuit for focus-correction |
| US5764005A (en) * | 1995-03-07 | 1998-06-09 | Mitsubishi Denki Kabushiki Kaisha | Parabolic-wave shaping circuit for focus-correction |
| JPH0926675A (en) * | 1995-07-13 | 1997-01-28 | Fuji Xerox Co Ltd | Photographic carrier and its production and electrostatic charge imparting member |
| US5849448A (en) * | 1996-04-01 | 1998-12-15 | Fuji Xerox Co., Ltd. | Carrier for developer of electrostatic latent image, method for making said carrier |
| US5821023A (en) * | 1996-05-27 | 1998-10-13 | Fuji Xerox Co., Ltd. | Developer of electrostatic latent image, carrier therefor, method for forming image and image forming apparatus thereby |
| JPH09319161A (en) * | 1996-05-29 | 1997-12-12 | Fuji Xerox Co Ltd | Carrier for electrostatic latent image developer electrostatic later image developer, image forming method and image forming device |
| JPH09319225A (en) * | 1996-05-29 | 1997-12-12 | Fuji Xerox Co Ltd | Image forming method and image forming device |
| JPH10186731A (en) * | 1996-12-25 | 1998-07-14 | Fuji Xerox Co Ltd | Electrostatic image developing carrier, electrostatic image developer, and image forming method |
| JPH11231574A (en) * | 1998-02-10 | 1999-08-27 | Ricoh Co Ltd | Carrier for developing electrostatic latent image and its production |
| JP2000298380A (en) * | 1999-04-14 | 2000-10-24 | Ricoh Co Ltd | Electrophotographic carrier and its production |
| US6677093B2 (en) | 2000-11-01 | 2004-01-13 | Fuji Xerox Co., Ltd. | Electrophotographic black toner, electrophotographic developer and image forming method |
| US7393622B2 (en) | 2004-06-02 | 2008-07-01 | Sharp Kabushiki Kaisha | Two-component developing agent for electrophotography |
| JP2005345999A (en) * | 2004-06-07 | 2005-12-15 | Sharp Corp | Carrier and two-component developer |
| US7455945B2 (en) | 2004-06-07 | 2008-11-25 | Sharp Kabushiki Kaisha | Coated carrier and two-component developing agent |
| JP2009093135A (en) * | 2007-09-18 | 2009-04-30 | Ricoh Co Ltd | Electrophotographic carrier, electrophotographic developer, and image forming method |
| JP2018146786A (en) * | 2017-03-06 | 2018-09-20 | 株式会社リコー | Carrier, developer, developer for replenishment, image forming apparatus, process cartridge, and image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2714590B2 (en) | 1998-02-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |